The 100 most-cited articles in Inorganic Chemistry, 2024

Here, we report ternary COFs@MoS 2 -Pd hybrids with an innovative self-sacrificial approach. MoO 3 @Covalent organic frameworks (COFs) microcables were first prepared and then two-dimensional MoS 2 nanosheets (NSs) were integrated onto the surface of COFs, as COFs@MoS 2, after treatment with hydrothermal reaction. The MoS 2 NSs were used as an excellent support to introduce Pd nanoparticles (NPs) thanks to their reducing ability for the formation of the ternary COFs@MoS 2 -Pd hybrids. While COF microtubes improved the electrical conductivity of the hybrid materials, they also decreased the aggregation of MoS 2 NSs, as a contribution to the enhanced catalytic performance. The mild reaction between MoS 2 and Pd 2+ ions realized the dense distribution of Pd NPs onto COFs@MoS 2 for abundant active sites to further improve the catalytic performance. Thus, the hierarchical MoS 2 -based ternary hybrids were prepared with the enhanced catalytical performance as validated with the enzyme-like catalysis and the reduction of 4-nitrophenol.

Several measures, including crude oil recovery improvement and carbon dioxide (CO2) conversion into valuable chemicals, have been considered to decrease the greenhouse effect and ensure a sustainable low-carbon future. The Knoevenagel condensation and CO2 fixation have been introduced as two principal solutions to these challenges. In the present study for the first time, bio-metal–organic frameworks (MOF)­(Cu)/graphene oxide (GO) nanocomposites have been used as catalytic agents for these two reactions. In view of the attendance of amine groups, biological MOFs with NH2 functional groups as Lewis base sites protruding on the channels’ internal surface were used. The bio-MOF­(Cu)/20%GO performs efficaciously in CO2 fixation, leading to more than 99.9% conversion with TON = 525 via a solvent-free reaction under a 1 bar CO2 atmosphere. It has been shown that these frameworks are highly catalytic due to the Lewis basic sites, i.e., NH2, pyrimidine, and CO groups. Besides, the Lewis base active sites exert synergistic effects and render bio-MOF­(Cu)/10%GO nanostructures as highly…

The urea oxidation reaction (UOR) is an alternative anodic reaction for hydrogen generation via water splitting. The significance of UOR lies in both H 2 production and the decontamination of urea-containing wastewater. Commercial electrocatalysts in this field are generally based on noble metals and show several limitations. Bimetal–organic frameworks (BMOFs) can be excellent candidates for the replacement of noble-metal-based catalysts beacuse of their promising features, such as a tunable structure, high surface area, and abundant sites for electrocatalysis. In this study, a series of nickel–cobalt BMOFs (Ni x -Co y -BMOFs: x and y refer to a molar fraction of Ni and Co) were synthesized and applied as electrocatalysts in UOR. In particular, a Ni 0.15 Co 0.85 -MOF material with a structure similar to that of its parent Co-MOF, revealed exceptional electrocatalytic performance, as evidenced by low values of overpotential (1.33 V vs RHE at 10 mA cm –2 ), TOF (0.47 s –1 ), and Tafel slope (125 mV dec –1 ). At a 40 mA cm –2 current density, Ni 0.15 Co 0.85 -MOF also showed excellent…

Continuous increase in carbon dioxide (CO 2 ) emissions are causing imbalances in the environment, which impact biodiversity and human health. The conversion of CO 2 to cyclic carbonates by means of metal–organic frameworks (MOFs) as a heterogeneous catalyst is a prominent strategy for rectifying this imbalance. Herein, we have developed nitrogen-rich Zn (II) based metal–organic framework, [Zn(CPMT)(bipy)] n (CPMT = 1-(4-carboxyphenyl)-5-mercapto-1 H -tetrazole; bipy = 4,4′-bipyridine), synthesized via a mixed ligand strategy. This Zn-MOF showed high chemical stability in both acidic and basic conditions, and in organic solvents for a long time. On account of the concurrent presence of acid–base active sites and strong chemical stability under abrasive conditions, this Zn-MOF was employed as an effective catalyst for the coupling of CO 2 and epoxides, under atmospheric pressure, mild temperature, and neat conditions. This Zn-MOF shows remarkable activity by producing high yields of epichlorohydrin carbonate (98%) and styrene carbonate (82%) at atmospheric CO 2 pressure, 70 °C…

High Resolution Image Download MS PowerPoint Slide The recent discovery of superconductivity in the Ruddlesden–Popper bilayer nickelate, specifically La 3 Ni 2 O 7, has generated significant interest in the exploration of high-temperature superconductivity within this material family. In this study, we present the crystallographic and electrical resistivity properties of two distinct Ruddlesden–Popper nickelates: the bilayer La 3 Ni 2 O 7 (referred to as 2222-phase) and a previously uncharacterized phase, La 3 Ni 2 O 7 (1313-phase). The 2222-phase is characterized by a pseudo F -centered orthorhombic lattice, featuring bilayer perovskite [LaNiO 3 ] layers interspaced by rock salt [LaO] layers, forming a repeated ...2222... sequence. Intriguingly, the 1313-phase, which displays semiconducting properties, crystallizes in the Cmmm space group and exhibits a pronounced predilection for a C -centered orthorhombic lattice. Within this structure, the perovskite [LaNiO 3 ] layers exhibit a distinctive long-range ordered arrangement, alternating between single- and trilayer configurations,…

Urea oxidation reaction (UOR) is one of the potential routes in which urea-rich wastewater is used as a source of energy for hydrogen production. Metal–organic frameworks (MOFs) have promising applications in electrocatalytic processes, although there are still challenges in identifying the MOFs’ molecular regulation and obtaining practical catalytic systems. The current study sought to synthesize [Zn 6 (IDC) 4 (OH) 2 (Hprz) 2 ] n (Zn-MOF) with three symmetrically independent Zn(II) cations connected via linear N-donor piperazine (Hprz), rigid planar imidazole-4,5-dicarboxylate (IDC 3– ), and −OH ligands, revealing the 3,4T1 topology. The optimized noble-metal-free Zn 0.33 V 0.66 -MOF/NF electrocatalysts show higher robustness and performance compared to those of the parent Zn monometallic MOF/NF electrode and other bimetallic MOFs with different Zn–V molar ratios. The low potential of 1.42 V (vs RHE) at 50 mA cm –2 in 1.0 M KOH with 0.33 M urea required by the developed Zn 0.33 V 0.66 -MOF electrode makes its application in the UOR more feasible. The availability of more exposed…

Defect engineering is an extremely effective strategy for modifying metal–organic frameworks (MOFs), which can break through the application limitations of traditional MOFs and enhance their functionality. Herein, we report a highly robust nanoporous thulium(III)–organic framework, {[Tm 2 (BDCP)(H 2 O) 5 ](NO 3 )·3DMF·2H 2 O} n ( NUC-105 ), with [Tm(COO) 2 (H 2 O)] n chains and [Tm 2 (COO) 4 (H 2 O) 8 ] dinuclears as metal nodes and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (BDCP) linkers. In NUC-105, each of the four chains of [Tm(COO) 2 ] n and the two rows of [Tm 2 (COO) 4 (H 2 O) 8 ] units is unified by the organic skeleton, resulting in a rectangular nanochannel with dimensions of 15.35 Å × 11.29 Å, which leads to a void volume of 50%. It is worth mentioning that the [Tm 2 (COO) 4 (H 2 O) 8 ] cluster is very rare in terms of its higher level of associated water molecules, implying that the activated host framework can serve as a strong Lewis acid. NUC-105a exhibited great heterogeneous catalytic performance for CO 2 cycloaddition with epoxides under the…

Constructing a phosphor with multifunctional applications is an imperative challenge. Especially, highly thermostable luminescence of phosphor is indispensable for stable white-light-emitting diodes (LEDs). Nevertheless, good thermal quenching resistance behavior is unfavorable for a fluorescence intensity ratio (FIR)-based optical temperature sensor. Herein, a highly thermostable Ba 3 (ZnB 5 O 10 )PO 4 (BZBP)-based phosphor is successfully achieved via replacing Ba 2+ with Dy 3+, demonstrating simultaneously promising lighting and thermometry utilizations. Under the excitation of 350 nm, the title phosphor only loses 12% of the initial intensity when the temperature is up to 473 K, ensuring sufficient luminescence thermostability for white-LED lighting. The white-LED device fabricated using the title phosphor emits high-quality white light with a high color rendering index ( R a = 93) and low correlated color temperature (CCT = 3996 K). Meanwhile, the yellow and blue emission intensities demonstrate a downtrend difference with rising temperature. Temperature sensing properties are…

The development of heterogeneous catalysts with abundant active sites is pivotal for enhancing the efficiency of photothermal CO 2 conversion. Herein, we report the construction of Co 2 N 0.67 @ZIF-67 through the in situ pyrolysis of ZIF-67 under low-temperature pyrolysis conditions. During the pyrolysis process, the crystal structure of ZIF-67 is predominantly preserved concurrently with the formation of Co 2 N 0.67 nanoparticles (NPs) within the ZIF-67 pores. The optimal catalyst Co 2 N 0.67 @ZIF-67(450,2) not only possesses high photothermal efficiency but also can efficiently activate CO 2 . Benefiting from these characteristics, Co 2 N 0.67 @ZIF-67(450,2) exhibited significant catalytic activity in the photocatalytic cycloaddition of CO 2 and epichlorohydrin. The yield of (chloromethyl)ethylene carbonate reached 95%, which is more than 4 times higher than that of ZIF-67 under visible light irradiation (300 W·m 2 Xe lamp, 3 h). This study could offer an alternative approach to enhance the photocatalytic activity of MOFs through low-temperature pyrolysis.

Phosphor-converted white-light-emitting diodes (WLEDs) with superhigh color rendering index (CRI) are the ongoing pursuit of next-generation solid-state lighting. One of the most important challenges is the limited improvement in CRI on account of the absence of a cyan component in the typical commercial combination. Here, a bright broad-band cyan-green-emitting phosphor with cubic garnet structure, SrLu 2 Al 3 ScSiO 12:Ce 3+ (SLASSO:Ce 3+ ), was successfully reported, which can compensate for the absence of cyan cavity in the 480–520 nm blue-green emission region. With 439 nm blue-light irradiation, the as-fabricated SLASSO:Ce 3+ phosphor yields a broad-band cyan-green emission with the maximum emission peak positioned at 525 nm and an appropriate full width at half-maximum (fwhm) of 111 nm, capable of providing more cyan emission component without sacrificing green emission. Meanwhile, the optimal SLASSO:2%Ce 3+ phosphor features CIE color coordinates of (0.3254, 0.5470) with cyan-green hue, along with a high internal quantum efficiency of up to 93%. Additionally, thermal…

Global clean energy demands can be effectively addressed using the promising approach of hydrogen energy generation combined with less energy consumption. Hydrogen can be generated, and urea-rich wastewater pollution can be mitigated in a low-energy manner using the urea oxidation reaction (UOR). This paper seeks to assemble a unique electrocatalyst of a pristine 2D MOF, [Co(HBTC)(DMF)] n (Co-MUM-3), from 1,3,5-benzenetricarboxylate (BTC) to oxidize urea in simulated seawater. Ni foam (NF)-based working electrodes were fabricated by incorporating a series of heterometallic CuCo-MUM-3 frameworks (Cu 0.1 Co 0.9 -MUM-3, Cu 0.2 Co 0.8 -MUM-3, Cu 0.3 Co 0.7 -MUM-3, and Cu 0.4 Co 0.6 -MUM-3), after which their application in the urea oxidation reaction was examined. A very low required overpotential [1.26 V vs reversible hydrogen electrode (RHE) in 1 M KOH + 0.5 M NaCl (simulated seawater) + 0.33 M urea] and a Tafel slope of 112 mV dec –1 could be observed for the Cu 0.3 Co 0.7 -MUM-3 electrocatalyst, ensuring the achievement of urea electro-oxidation and hydrogen evolution reactions at a…

Currently, near-infrared (NIR) light-emitting materials have been widely used in many fields, such as night vision, bioimaging, and nondestructive analysis. However, it is difficult to achieve multifunction in certain NIR light emitting phosphor. Herein, we propose a new near-infrared phosphor Mg 3 Ga 2 GeO 8:Cr 3+,Ni 2+ that can be applied to at least three fields, i.e., identification of compounds, temperature sensing, anticounterfeiting, and other applications. The multifunctional material exhibited efficient broadband emission of 650–1650 nm under 420 nm excitation. The emission intensity of Ni 2+ in Mg 3 Ga 2 GeO 8:Cr 3+,Ni 2+ is enhanced by two times compared with that of Ni 2+ in Mg 3 Ga 2 GeO 8:Ni 2+ due to the energy transfer process. Compared with phosphor single doped with Ni 2+, Mg 3 Ga 2 GeO 8:Cr 3+,Ni 2+ is more convincing in organic compound recognition because it is based on two emission bands: 600–1100 nm and 1100–1650 nm. As a temperature sensor, Mg 3 Ga 2 GeO 8:Cr 3+,Ni 2+ is an ideal temperature-sensing material. This work not only provides a super broadband NIR…

Photocatalytic coupling technologies have emerged as popular strategies to increase the treatment efficiency of dye-containing wastewater. Herein, the Z-scheme Co 3 O 4 /BiOBr heterojunction (Z-CBH) was constructed and developed as a photocatalytic peroxydisulfate (PDS) activator for the degradation of high-concentration Rhodamine B (RhB). Multiple testing techniques were employed to confirm the formation of Z-CBHs. When 0.1 g·L –1 of Z-CBH20 and 1.0 mmol·L –1 of PDS were added simultaneously under simulated sunlight irradiation, the RhB degradation efficiency could approach 91.3%. Its reaction rate constant (0.01231 min –1 ) was much beyond the sum of those in the Z-CBH20/light system (0.00436 min –1 ) and the PDS/light system (0.0062 min –1 ). h +, • OH, • O 2 –, SO 4 •–, and 1 O 2 were detected as the dominant reactive species for RhB degradation. The potential mechanism of photocatalytic PDS oxidation was proposed. The possible intermediates were determined by high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry assisted with density functional…

The immobilization of tiny active species within inert mesoporous silica imparts a range of functions, enhancing their applicability. A significant obstacle is the spontaneous migration and aggregation of these species within the mesopores, which threaten their uniform distribution. To address this, we propose a postmodification method that involves grafting transition metal oxide nanoclusters into silica mesopores via interfacial condensation, catalyzed by acetate ions. Specifically, CuO nanoclusters, in the form of oligomeric [O 1– x –Cu 2 –(OH) 2 x ] n 2+, have a strong interaction with the silica framework. This interaction inhibits their growth and prevents mesopore blockage. Theoretical calculation results reveal that the acetate ion promotes proton transfer among various hydroxy species, lowering the free energy and thereby facilitating the formation of Cu–O–Si bonds. This technique has also been successfully applied to the encapsulation of four other types of transition metal oxide nanoclusters. Our encapsulation strategy effectively addresses the challenge of dispersing…

A three-dimensional (3D) Ni-MOF of the formula [Ni(C 4 H 4 N 2 )(CHO 2 ) 2 ] n, has been reported, which shows a capacitance of 2150 F/g at a current density of 1A/g in a three-electrode setup (5.0 M KOH). Post-mortem analysis of the sample after three-electrode measurements revealed the bias-induced transformation of Ni-MOF to Ni(OH) 2, which has organic constituents intercalated within the sample exhibiting better storage performance than bulk Ni(OH) 2 . Afterward, the synthesized MOF and reduced graphene (rGO) were used as the anode and cathode electrode material, respectively, and a two-electrode asymmetric supercapacitor device (ASC) setup was designed that exhibited a capacitance of 125 F/g (at 0.2 A/g) with a high energy density of 50.17 Wh/kg at a power density of 335.1 W/kg. The ASC further has a very high reversibility (97.9% Coulombic efficiency) and cyclic stability (94%) after 5000 constant charge–discharge cycles. Its applicability was also demonstrated by running a digital watch. Using sophisticated density functional theory simulations, the electronic properties,…

Three new POM-based compounds, with formulae [Na 0.63 Ag 3 (Htba) 2.37 (tba) 0.63 (H 2 O) 2 (PMo 12 O 40 )]·4H 2 O ( Ag 3 PMo ), [Ag 4 (Htba) 4 (H 2 O) 2 (PMo 12 O 40 )](NO 3 )·H 2 O ( Ag 4 PMo ), and [Ag 3 (Htba) 2 (tba)(PW 12 O 40 ) 0.5 ](NO 3 ) 0.5 ·13H 2 O ( Ag 3 PW ), were prepared with a 3-(4 H -1,2,4-triazol-4-yl)benzoic acid (Htba) ligand, Keggin-type anions ([PMo 12 O 40 ] 3– /[PW 12 O 40 ] 3– ), and a silver ion (Ag + ). The structural features of these compounds are particularly different from the multinuclear subunits, which are [Ag 3 (tba) 3 ] clusters in Ag 3 PMo, [Ag 4 (tba) 3 ] chains in Ag 4 PMo, and [Ag 3 (tba) 3 ] 2 clusters in Ag 3 PW, connected by multidonor atom tba ligands and Ag + ions. Meanwhile, in these compounds, polyanions act as polydentate ligands to link adjacent Ag-tba metal–organic units and expand their spatial dimensions. These compounds, as heterogeneous catalysts, exhibit high stability and excellent catalytic activity to construct benzimidazoles. Ag 3 PMo could efficiently catalyze the condensation of benzene-1,2-diamines and benzaldehydes and…

Four Co(II)-based metal–organic frameworks (MOFs) were constructed by a mixed ligand strategy under solvothermal conditions. The controllable modification of the bridging groups in the secondary building units was realized by changing the anions in MOFs 1 – 3 . The MOF 4 with 3D framework structure was obtained by regulating the solvent ratio following the synthesis process of MOF 3 . Furthermore, the MOFs 1 – 4 exhibited efficient photocatalytic activity for the degradation of malachite green (MG) dye without any photosensitizer or cocatalyst under a low-energy light source, the decolorization ratio of MG all reached more than 96.0% within 60 min, and maximal degradation was obtained to be 99.4% ( MOF 4 ). The recycling experiments showed that the degradation rate of MG was still higher than 91% after 10 cycles. In the MOF 4 as representation, the photocatalytic process was explored systematically. The possible mechanism of catalytic degradation was discussed, which proved the existence of efficient oxidation active factors ( • O 2 –, • OH, and h + ). The possible intermediates and…

The synthesis of two versatile fluorescent metal–organic frameworks (MOFs), [Eu(4-NCP)(1,4-bdc)] n ·0.5H 2 O ( 1 ) and [Eu(4-NCP)(4,4′-bpdc)] n ·0.75H 2 O ( 2 ) (HNCP = 2-(4-carboxyphenyl)imidazo(4,5- f )-(1,10)phenanthroline, 1,4-H 2 bdc = benzene-1,4-dicarboxylic acid, 4,4′-H 2 bpdc = 4,4′-biphenyldicarboxylic acid), was carried out using a hydrothermal method. These MOFs were characterized through various advanced technologies to determine their structural information. The results indicate that both MOFs exhibited 3D network structures with specific topologies. Furthermore, these MOFs demonstrated exceptional thermal stabilities and adsorption capabilities. Additionally, complex 2 was utilized for studying the fluorescence sensing properties of various micronutrients including metal ions, nitro aromatic compounds, and biological small molecules. Notably, complex 2 showed promising potential as a multifunctional sensor for selectively detecting Fe 3+, nitrobenzene, and ascorbic acid in aqueous solutions through fluorescence quenching with low limits of detection (LODs ∼ 10 –7 M)…

In this study, the novel Pt-embedded mesoporous CeO 2 hollow nanospheres (Pt-MS-CeO 2 -H) with varying Pt contents (0.5–3.0 wt %) were facilely prepared. The Pt nanoparticles were one-pot embedded within the mesoporous shell of Pt-MS-CeO 2 -H and assisted with the reduction Ostwald ripening process. The traditional preparation methods often face challenges, such as the uneven distribution or aggregation of nanoparticles, as well as difficulty in maintaining high catalytic activity at low Pt content. Compared with the traditional supported Pt/MS-CeO 2 catalyst, the embedding strategy facilitated precise control over the position, distribution, and uniformity of Pt nanoparticles within the CeO 2 mesoporous shell. Additionally, the encapsulation process of Pt nanoparticles played a pivotal role in generating oxygen vacancies and activating surface chemical adsorption of oxygen. Resultantly, the toluene oxidation performances of 1Pt-MS-CeO 2 -H catalyst showed much lower T 90 (171 °C) than 1Pt/MS-CeO 2 (311 °C). To elucidate the underlying reasons, in situ diffuse reflectance infrared…

It is a challenging task to design a piezoelectric photocatalyst with excellent performance under mechanical agitation instead of ultrasonic irradiation. Integrating vacancy defects into a heterojunction seems to be an effective strategy for synergistically increasing its piezo-photocatalytic performance. For this goal, a two-step hydrothermal method was adopted to architect a type-I oxygen-vacancy-rich BaTiO 3 /BiOBr heterojunction to surge the degradation of Rhodamine B (RhB) under the combined action of simulated sunlight irradiation and mechanical agitation. Various instrumental techniques demonstrated the formation of a BaTiO 3 /BiOBr heterojunction with high crystallinity. The existence of surface oxygen vacancies was confirmed by XPS and EPR tests. PFM results manifested that this heterojunction had excellent piezoelectric properties, with a piezoelectric response value of 30.31 pm V –1 . Comparative experiments indicated that RhB degradation efficiency under piezo-photocatalysis over this heterojunction largely exceeded the total sum of those under piezocatalysis and…

A novel doubly interpenetrated indium-organic framework of 1 has been assembled by In3+ ions and highly conjugated biquinoline carboxylate-based bitopic connectors (H2L). The isolated 1 exhibits an anionic framework possessing channel-type apertures repleted with exposed quinoline N atoms and carboxyl O atoms. Owing to the unique architecture, 1 displays a durable photoluminescence effect and fluorescence quenching sensing toward CrO42–, Cr2O72–, and Cu2+ ions with reliable selectivity and anti-interference properties, fairly high detection sensitivity, and rather low detection limits. Ligand-to-ligand charge transition (LLCT) was identified as the essential cause of luminescence by modeling the ground state and excited states of 1 using DFT and TD-DFT. In addition, the negatively charged framework has the ability to rapidly capture single cationic MB, BR14, or BY24 and their mixture, including the talent to trap MB from the (MB + MO) system with high selectivity. Moreover, intrinsic light absorption capacity and band structure feature endow 1 with effective photocatalytic…

Inorganic phosphor materials often face the common phenomenon of luminescence thermal quenching (TQ), which deteriorates their device performance and consequently limits their applicability for broad applications. Thus, exploring thermally stable and even anti-TQ phosphors is viable to meet the urgent requirements of lighting technology and many other luminescence-based applications. One of the emerging approaches devoted to solving the TQ issue of phosphors, especially at elevated temperatures, is to employ negative thermal expansion (NTE) properties occurring in some unique inorganic materials. The present Review focuses on the progress of exploring NTE-based inorganic phosphor materials that have demonstrated unusual negative TQ with enhancing upconversion and downshift luminescence upon elevating temperature. We have also provided a brief history of exploring NTE phosphors for thermally stable and enhanced emission along with the investigation methods and proposed mechanisms of these unusual phenomena. To summarize, we have further discussed some opportunities and challenges…

Compared with monometallic metal–organic frameworks (MOFs), the synergistic effect of multiple metals significantly enhances the catalytic performance of the CO 2 cycloesterification reaction, leading to improved CO 2 adsorption and catalytic conversion capabilities. To investigate this concept, a high-entropy MOF-74 (HE-MOF-74) with a uniform distribution of five distinct metal ions (Zn 2+, Mg 2+, Ni 2+, Co 2+, and Cu 2+ ) was successfully synthesized using a straightforward mechanical ball milling technique and comprehensively characterized (including structural, morphological, and physicochemical properties). The results reveal that HE-MOF-74 exhibits significantly increased specific surface area and CO 2 adsorption capacity compared with those of monometallic MOF-74. The presence of multiple unsaturated metal centers as Lewis acid sites, oxygen atoms linking the metals, and ligand-based hydroxyl groups serving as base sites enable efficient immobilization of CO 2 into cyclic carbonate. This study introduces a novel synthetic approach for the green and efficient production of…

Two two-dimensional (2D) layered metal–organic frameworks (MOFs), namely, {[Yb( L )(H 2 O) 2 NO 3 ]·2H 2 O} n (Yb-MOF) and [Er( L )(H 2 O) 3 Cl] n (Er-MOF) (H 2 L = 5-((6 H -purin-6-yl)amino)isophthalic acid), were constructed by a solvothermal method and characterized. The catalytic performance study showed that the Yb-MOF could efficiently catalyze the oxidation of sulfides to sulfoxides under 15 W light-emitting diode (LED) blue light irradiation. Electron paramagnetic resonance spectroscopy and free-radical trapping experiments demonstrated that the photocatalytic reaction process involved • O 2 –, and the corresponding mechanism was proposed. Moreover, Er-MOF exhibited good catalytic efficiency and excellent substrate tolerance in the cycloaddition reaction of CO 2, and the reaction conditions were mild. After 5 cycles, the catalytic activities of two MOFs did not significantly decrease, and the framework structures remained unchanged. Therefore, the Yb-MOF and Er-MOF were considered efficient and stable heterogeneous catalysts.

Similar to GaN and SiC semiconductors, GaC may be a potential semiconductor because of the mixed elemental features of Ga and C. Unfortunately, the phase stability and mechanical and physical properties of GaC are unknown. To search for novel third-generation semiconductors, the present study delves into an in-depth analysis of the structural stability and electronic and optical properties of GaC by DFT calculations. Similar to GaN, three GaC phases are discussed. It is found that three GaC phases (two cubic phases and one hexagonal phase) are first predicted. The band gaps of Fm 3̅ m, F 4̅ 3m, and hexagonal GaC are 0.449, 2.733, and 3.340 eV, respectively. In particular, the band gap of F 4̅ 3m GaC and hexagonal GaC is bigger than that of GaN. Compared to GaN semiconductors, the C-2 p state is in the valence band region across the Fermi level, which is beneficial to electronic mobility and electronic transport capacity near the Fermi level. In addition, three GaC phases exhibit ultraviolet properties. The first peak of three GaC phases produces the right migration compared to the…

Benefiting from the unique photoluminescence behavior of the lanthanide­(III) ions and organic ligands, a lanthanide­(III) metal–organic framework (Ln-MOF) material can simultaneously demonstrate photoluminescence of lanthanide­(III) cations and organic molecules and endow its superior applications of fluorescence sensing behaviors. Herein, we present a europium­(III) MOF material {[Eu2(BPTA)·(CH3COO)2·3DMA]·0.5DMA·3H2O}n (1) (where H4BPTA is 3,3′,5,5′-biphenyltetracarboxylic acid) for photoluminescence performance of quantitatively sensing the inflammatory marker neopterin (Neo). The obtained 1 comprises Eu2(COO)4 paddlewheel secondary building units, which could be bridged by BPTA4– ligands to extend a 2D framework. The fluorescence titration indicates 1 can achieve simultaneous fluorescence behavior of Eu3+ ions and Neo via on–off ratiometric effects and thus could be exploited as the ratiometric fluorescence sensor matrix. Such a fluorescence phenomenon of 1 as a ratiometric sensor for quantitative detection of Neo via an on–off ratiometric effect is never observed in MOF…

Developing high-performance electrodes for flexible antifreezing energy storage devices has been a significant challenge with the increasing demand for portable components. In this work, Cr-substituted SrCoO 3-δ perovskites were first proposed as potential low-temperature supercapacitor electrode materials. The high-valence Cr 6+ ([Ne]3s 2 3p 6 ) substitution favors a high-spin state of Co ions with enhanced electronic repulsion effect, ultimately forming a stable cubic structure with high conductivity. Accordingly, the modification strategies of SrCoO 3 through the p6 configuration cation substitution have been improved. As a result, the asymmetric SrCo 0.95 Cr 0.05 O 3-δ @CC//PPy@CC device exhibited a high energy density of 44.90 Wh kg –1 at 902.01 W kg –1 and maintained a 95.8% specific capacitance after 10,000 cycles, demonstrating an ultralong cyclic stability. The dramatically improved electrochemical performance was attributed to the stabilized crystal structure, increased oxygen vacancy, and accelerated oxygen diffusion rate. Furthermore, a quasi-solid-state supercapacitor…

Carbon dioxide (CO 2 ) cycloaddition not only produces highly valued cyclic carbonate but also utilizes CO 2 as C1 resources with 100% atomic efficiency. However, traditional catalytic routes still suffer from inferior catalytic efficiency and harsh reaction conditions. Developing multienergy-field catalytic technology with expected efficiency offers great opportunity for satisfied yield under mild conditions. Herein, Zn 3 In 2 S 6 with sulfur vacancies (S v ) was fabricated with the assistance of cetyltrimethylammonium bromide (CTAB), which is further employed for photothermally driven CO 2 cycloaddition first. Photoluminescence spectroscopy and photoelectrochemical characterization demonstrated its superior separation kinetics of photoinduced carriers induced by defect engineering. The temperature-programmed desorption (TPD) technique indicated its excellent Lewis acidity–basicity characters. Due to the combination of above merits from photocatalysis and thermal catalysis, defective Zn 3 In 2 S 6 -S v achieved a yield as high as 73.2% for cyclic carbonate at 80 °C under blue LED…

The increasing demands in optoelectronic applications have driven the advancement of organic–inorganic hybrid metal halides (OIMHs), owing to their exceptional optical and scintillation properties. Among them, zero-dimensional (0D) low-toxic manganese-based scintillators have garnered significant interest due to their exceptional optical transparency and elevated photoluminescence quantum yields (PLQYs), making them promising for colorful light-emitting diodes and X-ray imaging applications. In this study, two OIMH single crystals of (Br-PrTPP) 2 MnBr 4 (Br-PrTPP = (3-bromopropyl) triphenylphosphonium) and (Br-BuTPP) 2 MnBr 4 (Br-BuTPP = (4-bromobutyl) triphenylphosphonium) were prepared via a facile saturated crystallization method. Benefiting from the tetrahedrally coordinated [MnBr 4 ] 2– polyhedron, both of them exhibited strong green emissions peaked at 517 nm owing to the d–d electron transition of Mn 2+ with near-unity PLQYs of 99.33 and 86.85%, respectively. Moreover, benefiting from the high optical transparencies and remarkable luminescence properties, these manganese…

A series of Ca 3 Al 2 Ge 3 O 12: x Dy 3+, y Eu 3+ phosphors were successfully prepared by the high-temperature solid-phase method. The phase and morphology of the phosphors were studied by means of Rietveld refinement and scanning electron microscopy. The results show that the phase is pure, and the crystal structure is the Ia 3̅ d space group. In the Ca 3 Al 2 Ge 3 O 12: x Dy 3+ phosphors, using 380 nm excitation, phosphors showed blue ( 4 F 9/2 → 6 H 15/2 ) and yellow ( 4 F 9/2 → 6 H 13/2 ) emission peaks at 481 and 581 nm, respectively. In Ca 3 Al 2 Ge 3 O 12: x Dy 3+, y Eu 3+ phosphors, the energy transfer was inferred by the spectrum overlap of Dy 3+ and Eu 3+, and the lifetime attenuation was analyzed from the perspective of dynamics; finally, the band gap structure of the phosphors was analyzed by combining diffuse reflection spectra with the first principle, and the energy transfer mechanism and luminescence mechanism were elaborated by combining theory and practice. The transition from blue white light to red light can be achieved by tuning the range of y in Ca 3 Al 2 Ge 3…

Constructing a Z-scheme heterostructure on a metal–organic framework (MOF) composite with an explicit charge transfer mechanism at the interface is considered to be an effective strategy for improving the photocatalytic performance of MOFs. Herein, an internal electric field (IEF)-induced Z-scheme heterostructure on the ZnIn 2 S 4 @NH 2 -MIL-125 composite is designed and fabricated by a facile electrostatic self-assembly process. Systematic investigations reveal that close interfacial contact and difference in work function between NH 2 -MIL-125 and ZnIn 2 S 4 enable the formation of the IEF, which drives the Z-scheme charge transfer as revealed by the in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), photoirradiated Kelvin probe force microscope (KPFM) measurement, electron paramagnetic resonance (EPR) radical trapping experiment, as well as density functional theory (DFT) calculation; meanwhile, directions of the interfacial IEFs are determined. Benefiting from the unique merit of IEF-induced Z-scheme charge transfer, the optimized ZnIn 2 S 4 @NH 2 -MIL-125 composite…

In this study, a chiral [Cu( l -proline) 2 ] complex-modified Fe 3 O 4 @SiO 2 @UiO-66-NH 2 (Zr) metal–organic framework [Fe 3 O 4 @SiO 2 @UiO-66-NH-Cu( l -proline) 2 ] via multifunctionalization strategies was designed and synthesized. One simple approach to chiralize an achiral MOF-structure that cannot be directly chiralized using a chiral secondary agent like 4-hydroxy- l -proline. Therefore, this chiral catalyst was synthesized with a simple and multistep method. Accordingly, Fe 3 O 4 @SiO 2 @UiO-66-NH 2 has been synthesized via Fe 3 O 4 modification with tetraethyl orthosilicate and subsequently with ZrCl 4 and 2-aminoterephthalic acid. The presence of the silica layer helps to stabilize the Fe 3 O 4 core, while the bonding between Zr 4+ and the –OH groups in the silica layer promotes the development of Zr-MOFs on the Fe 3 O 4 surface, and then the surfaces of the synthesized magnetic MOFs composite are functionalized with 1,2-dichloroethane and Cu(II) complex with 4-hydroxy- l -proline, [Cu( l -proline) 2 ] to afford the magnetically chiral nanocatalyst. Multiple techniques…

We synthesized a stable and reusable Schiff base complex of copper immobilized on core–shell magnetic nanoparticles [Cu(II)-SB/GPTMS@SiO 2 @Fe 3 O 4 ] with simple, efficient, and available materials. A variety of characterization analyses including Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET), thermogravimetric analysis (TGA), X-ray diffraction (XRD), vibrating-sample magnetometry (VSM), energy-dispersive X-ray spectrometry (EDX), and inductively coupled plasma (ICP) confirm that our synthesized nanocatalyst was obtained. The particle size distribution from the TEM image was obtained in the range of 42–55 nm. The existence of cupric species (Cu 2+ ) in the catalyst was determined with XPS analysis and clearly indicated two peaks at 933.7 and 953.7 eV for Cu 2p 3/2 and Cu 2p 1/2, respectively. BET results showed that our catalyst synthesized with a mesoporous structure and with a specific area of 48.82 m 2 g –1 . After detailed…

The development of efficient urea oxidation reaction (UOR) catalysts helps UOR replace the oxygen evolution reaction (OER) in hydrogen production from water electrolysis. Here, we prepared Fe-doped Ni 2 P/NiSe 2 composite catalyst (Fe–Ni 2 P/NiSe 2 -12) by using phosphating-selenizating and acid etching to increase the intrinsic activity and active areas. Spectral characterization and theoretical calculations demonstrated that electrons flowed through the Ni–P–Fe–interface–Ni–Se–Fe, thus conferring high UOR activity to Fe–Ni 2 P/NiSe 2 -12, which only needed 1.39 V vs RHE to produce the current density of 100 mA cm –2 . Remarkably, this potential was 164 mV lower than that required for the OER under the same conditions. Furthermore, EIS demonstrated that UOR driven by the Fe–Ni 2 P/NiSe 2 -12 exhibited faster interfacial reactions, charge transfer, and current response compared to OER. Consequently, the Fe–Ni 2 P/NiSe 2 -12 catalyst can effectively prevent competition with OER and NSOR, making it suitable for efficient hydrogen production in UOR-assisted water electrolysis. Notably,…

The tubular architecture with multiple components can bring synergistic effects to improve the enzyme-like activity of molybdenum-based nanomaterials. Here, a facile polypyrrole (PPy)-protected hydrothermal sulfidation process was implemented to engineer MoS 2 /Ag 2 S heterointerfaces encapsulated in one-dimensional (1D) PPy nanotubes with MoO 3 @Ag nanorods as the self-sacrificing precursor. Notably, the sulfidation treatment led to the generation of MoS 2 nanosheets (NSs) and Ag 2 S nanoparticles (NPs) and the creation of a tubular structure with a “kill three birds with one stone” role. The Ag 2 S/MoS 2 @PPy nanotubes showed the synergistic combined effects of Ag 2 S NPs, MoS 2 NSs, and the 1D tube-like nanostructure. Based on the synergistic effects from these multiple components and the tubular structure, Ag 2 S/MoS 2 @PPy nanocomposites were used as a colorimetric sensing platform for detecting H 2 O 2 . Moreover, the reduction of 4-nitrophenol (4-NP) revealed excellent catalytic activity in the presence of NaBH 4 and Ag 2 S/MoS 2 @PPy nanocomposites. This work highlights the…

Photocatalysis is an eco-friendly and significant perspective for generating hydrogen. Our study investigated the ZnO/ZnIn2S4 heterojunction photocatalytic system prepared through hydrothermal technique. Accordingly, the ZnIn2S4 nanofibers loaded with 11 mol % ZnO exhibited the hydrogen evolution rate of about 1998 μmol g–1 h–1, which was 2.6 times higher than the pristine ZnIn2S4. In situ electron paramagnetic resonance results proved the S-scheme photocarrier transport route, and in situ KPFM further characterized the internal electric field between ZnO and ZnIn2S4. The development of S-scheme heterojunctions allows for the spatial segregation and transport of charges by preserving photoexcited holes and electrons with a tremendous redox potential. Furthermore, the photoelectrochemical analysis demonstrated that the S-scheme heterojunction could also be employed for the separation of photoexcited species.

High Resolution Image Download MS PowerPoint Slide The present study outlines the synthesis of cadmium sulfide-metal–organic framework (CdS-MOF) MIL-101 (Fe) heterojunctions achieved via fast microwave-assisted reactions. Thus, different CdS-MOF MIL-101 (Fe) ratios were prepared to study their effectiveness as photocatalysts. These compounds were employed in the photocatalytic degradation of methylene blue (MB) under UV and visible irradiation. Structural, morphological, textural, compositional, and optical properties of the synthesized compounds determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–vis spectroscopy, Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy were utilized to characterize the structural, morphological, textural, compositional, and optical properties. Electrochemical impedance spectroscopy (EIS) was also employed to determine photovoltage and photocurrent densities. The resulting valence band offset ( V fb ) and band gap energy values were utilized to construct an energy band…

Photocatalytic for hydrogen peroxide (H 2 O 2 ) production is thought as a promising technology owing to its clean and green properties with the cheap and easily available raw materials of H 2 O and O 2 . Herein, Pt/g-C 3 N 4 Schottky junction photocatalysts with ultralow Pt contents (0.025–0.1 wt %) were successfully fabricated by an impregnation-reduction method. It can efficiently reduce O 2 to generate H 2 O 2 without a sacrificial agent under visible-light irradiation. The yield of H 2 O 2 produced over Pt0.05/g-C 3 N 4 with the optimal 0.05 wt % Pt reached 31.82 μM, which was 2.46 times that of g-C 3 N 4 and higher than most of those in the literature. It also showed good stability in three repeated tests. The deposition of highly dispersed metal Pt nanoparticles with low and limited content can expose enough active Pt atoms, significantly enhance the separation efficiency of photogenerated carriers, and reduce its negative effect on H 2 O 2 decomposition, resulting in improved and outstanding efficiency of H 2 O 2 production. The ·O 2 – radicals were found to be the main…

The exploration of smart sensors is of great significance for the selectivity, sensitivity, and ability to show the low detection limit for the target analyte. Here, we have used the linker H 2 L (5-((anthracen-9-ylmethyl)amino)isophthalic acid) for the construction of {[Cd(L)(DMF)(H 2 O) 2 ]·H 2 O} n ( 1 ) which is in order with the chromophore anthracene moiety and the free −NH functionality as a guest interaction site. This framework showed the luminescence recovery “turn-on” detection of the Al 3+ ion in an aqueous solution. An exhaustive mechanism study disclosed that the Lewis acid–base-type interaction between the Al 3+ ion and the –NH functionality of the linker in the framework revealed that the absorbance caused an enhancement for the “turn-on” sensing event. Besides the “turn-on” sensing event, the “turn-off” sensing phenomenon of 1 is also noticed when it detects the hazardous oxo-anions (MnO 4 – and CrO 4 2– ) with limit of detection values of 17.08 and 19.91 ppb, respectively. The detection of these diverse analytes are very fast (10 s) and they can also be recognized…

The introduction of transition metal (TM) ions into polyoxometalates (POMs) cannot only bring about interesting structural diversities but also enable changes in properties. However, TM-containing Silverton-type polyoxomolybdates are still lacking in terms of structural diversity and application development. Herein, two Zn(II)-containing Silverton-type {UMo 12 O 42 }-based polyoxomolybdates, H 1.89 Na 4.11 (H 2 O) 9 Zn[UMo 12 O 42 ]·4.5H 2 O ( Zn-1 ) and H 1.8 Na 4.2 (H 2 O) 12 Zn[UMo 12 O 42 ] ( Zn-2 ) were hydrothermally synthesized, demonstrating a practical strategy to assembly of TM-containing Silverton-type POMs. Zn-1 is proven to be an excellent and recyclable heterogeneous catalyst in cross-dehydrogenation coupling of 1,4-naphthoquinones with amines reactions, and a series of 2-amino-1,4-naphthoquinones with potential medicinal value have been constructed.

The relentless increase in drug resistance of platinum-based chemotherapeutics has opened the scope for other new cancer therapies with novel mechanisms of action (MoA). Recently, photocatalytic cancer therapy, an intrusive catalytic treatment, is receiving significant interest due to its multitargeting cell death mechanism with high selectivity. Here, we report the synthesis and characterization of three photoresponsive Ru(II) complexes, viz., [Ru(ph-tpy)(bpy)Cl]PF 6 ( Ru1 ), [Ru(ph-tpy)(phen)Cl]PF 6 ( Ru2 ), and [Ru(ph-tpy)(aip)Cl]PF 6 ( Ru3 ), where, ph-tpy = 4′-phenyl-2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, and aip = 2-(anthracen-9-yl)-1 H -imidazo[4,5- f ][1,10] phenanthroline, showing photocatalytic anticancer activity. The X-ray crystal structures of Ru1 and Ru2 revealed a distorted octahedral geometry with a RuN 5 Cl core. The complexes showed an intense absorption band in the 440–600 nm range corresponding to the metal-to-ligand charge transfer (MLCT) that was further used to achieve the green light-induced photocatalytic anticancer…

Piezoelectric–photocatalysis is distinguished by its piezoelectricity as an external force that induces deformation within the catalyst to engender a polarized electric field compared to conventional photocatalysis. Herein, the piezoelectric photocatalyst BiOBr has been expertly synthesized via a plasma process and applied for piezoelectric–photocatalysis removal of uranium(VI) for the first time. The abundant surface oxygen vacancies (OVs) could induce a dipole moment and built-in electric field, which endows BiOBr with excellent separation and transport efficiency of photogenerated charges to actuate more charges to participate in the piezoelectric–photocatalytic reduction process. Consequently, under visible light and ultrasound (150 W and 40 kHz), the removal rate constant of OVs-BiOBr-30 (0.0306 min –1 ) was 2.4, 30.6, and 6 times higher than those of BiOBr (0.01273 min –1 ), ultrasound, or photocatalysis, respectively. The piezoelectric–photocatalytic synergy is also universal for BiOX (X = Cl, Br, or I) to accelerate the reduction rate of uranium(VI). This work highlights the…

Herein, Bi 3+ /Mn 4+ doped Ca 2 LaTaO 6 phosphors with a double-perovskite structure were successfully synthesized with solid-state reaction at high temperature. The photoluminescence (PL) performances were investigated in detail. The blue radiation (∼465 nm) from the Bi 3+ ion and the red radiation (∼686 nm) originating from the Mn 4+ ion were obtained under 313 nm excitation. Especially, the pathway of energy transfer (Bi 3+ → Mn 4+ ) contributes to enhance the red emission intensity (Mn 4+: ∼686 nm) in Ca 2 LaTaO 6:Bi 3+ /Mn 4+ system. The PL mechanism of Ca 2 LaTaO 6:Bi 3+ /Mn 4+ was analyzed through luminescence lifetimes and PL spectra. Moreover, the emitting bands of Ca 2 LaTaO 6:Bi 3+ /Mn 4+ were primarily matched with the absorbing bands of carotenoids and phytochrome P FR on behalf of plant growth, so the phosphors were suitable for the design of a plant growth light under near-ultraviolet to blue excitation. At last, the optical temperature dependent performances of the Ca 2 LaTaO 6:Bi 3+ /Mn 4+ were analyzed with luminescence intensity ratio technology. The sample has…

An exceptional Zinc(II)-organic framework with the formula [{Zn( L 4-py )(bdc)}·DMF] n ( Zn-MOF ) has been constructed solvothermally using a novel linker L 4-py {2,7-bis(3-(pyridin-4-ylethynyl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2 H,7 H )-tetraone}, coligand H 2 bdc (1,4-benzenedicarboxylic acid), and ZnBF 4 · x H 2 O. The ligand L 4-py has been fabricated after functionalization of NDA (1,4,5,8-naphthalenetetracarboxylic dianhydride) core with 3-(pyridin-4-ylethynyl)phenyl group. The single-crystal X-ray analysis reveals that Zn-MOF exhibits a comprehensive three-dimensional (3D) framework architecture and features (4)-connected uninodal dia; 4/6/c1; sqc6 topology with point symbol {6 6 } and two-dimensional (2D) + 2D, parallel polycatenation. Notably, Zn-MOF displayed excellent fluorescence phenomenon and stability in water as well as in methanol solvents and was harnessed as a versatile sensor, demonstrating selective and sensitive molecular recognition of flame retardants and antibiotics. Notably, Zn-MOF displayed 57 and 49.5% quenching efficiency for the…

Improving the practicality of rechargeable zinc–air batteries relies heavily on the development of oxygen electrode catalysts that are low-cost, durable, and highly efficient in performing dual functions. In the present study, a catalyst with atomic Ce and Co distribution on a nitrogen-doped carbon substrate was prepared by doping the rare earth elements Ce and Co into a metal–organic framework precursor. Rare earth element Ce, known for its unique structure and excellent oxygen affinity, was utilized to regulate the catalytic activity. The catalyst prepared in this study demonstrated an exceptional electrocatalytic performance. At a current density of 10 mA cm –2, the catalyst exhibited an overpotential of 340 mV for the oxygen evolution reaction (OER), which was lower than that of commercial IrO 2 (370 mV), while achieving a half-wave potential of 0.79 V for the process of oxygen reduction reaction (ORR), exhibiting a similar level of effectiveness as commercially accessible Pt/C catalysts (0.8 V). The catalyst’s porous structure, interconnected three-dimensional carbon network,…

Developing low-cost electrocatalysts with excellent activity and durability in urea-assisted water splitting is urgently needed in order to achieve sustainable hydrogen production. Herein, we in situ synthesized a robust coupled heterostructured electrocatalyst (CoP/MoO 2 ) on a nickel foam (NF) substrate and explored its electrocatalytic performances in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). The overpotential of CoP/MoO 2 /NF is found to be only 11 mV at 10 mA cm –2 during the HER process, which is significantly lower than that of commercial Pt/C. Meanwhile, the UOR catalytic performance of CoP/MoO 2 /NF indicates fast reaction kinetics, along with a considerable low driving potential (1.26 V) compared to that of the OER (1.51 V). In situ and ex situ techniques demonstrate that these excellent electrocatalytic properties are mainly ascribed to the effective synergistic coupled effect and strong electronic interactions between single-component CoP and MoO 2, which can tune electronic states of Co and Mo, expose more…

A variety of new inorganic and organic materials have emerged to advance laser technologies and optical engineering. A rational design approach can contribute significantly to fabricating nonlinear optically active metal–organic frameworks (MOFs) by considering the underlying structure–property linkage. Here, it has been embarked on a study of novel samarium(III) MOF, ([Sm 2 (ata) 3 (DMF) 4 ]·DMF (ata 2–: 2-aminoterephthalate), abbreviated as NH 2 -Sm-MUM-4) with enhanced nonlinear optical (NLO) properties. The crystal structure of this MOF represents a 6-connected framework with a pcu topology and distinctive characteristics, including open metal sites, free amine groups, and great stability, making it suitable for third-order NLO activity. The nonlinear index of refraction ( n 2 ) revealed the self-focusing impacts of NH 2 -Sm-MUM-4 at different incident intensities. The highest value of n 2 and β related to 10 mw power of incident intensity are 5.15 cm 2 /W and 2.65 cm/W, respectively. As far as the authors know, this is the first study examining the potential systematic…

Metalo hydrogen-bonded organic frameworks (MHOFs) have received growing interest in designing crystalline functional materials. However, reports on bifunctional MHOFs showing magnetic and proton-conductive properties are extremely limited and their design is challenging. Herein, we investigated the magnetic and proton-conductive properties of two sulfonated CoHOF and MnHOF, {M(H 2 O) 2 (abs) 2 } n (M = Co 2+ and Mn 2+, Habs = 4-aminoazobenzene-4’-sulfonic anion), constructed by coordination chains. The supramolecular frameworks sustained by H bonds between −SO 3 – and coordinated water show directional ladder-type H bonds with hydrophilic nanochannels, leading to high proton conduction with exceptionally high conductivity around 10 –2 S cm –1 at 100 °C under 97% relative humidity. In particular, the maximum σ value of CoHOF, 2.11 × 10 –2 S cm –1, recorded the highest value among the reported proton-conducting materials showing slow magnetic relaxation. Meanwhile, the molecular structure of organosulfonate enables the magnetic isolation of high-spin Co 2+ and Mn 2+ centers in the…

Conductive metal–organic frameworks (cMOFs), as a kind of porous material, are considered to be highly promising materials in the field of electrochemistry due to their excellent conductivity. However, due to the low specific capacitance of pure cMOFs, their application in supercapacitors is limited. By virtue of the high theoretical capacity and excellent chemical stability of Co-based compounds, in this work, cMOFs’ M-HHTP (M = Ni, Co, NiCo, HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) are grown in situ on Co(OH) 2, CoP, and Co 3 O 4 nanosheets, resulting in a series of electroactive compounds as electrode materials used in supercapacitors. Among all of the compounds, Ni-HHTP@Co(OH) 2 shows the most excellent energy storage performance and outstanding cyclic stability in the application of aqueous asymmetric supercapacitors.

Near-infrared (NIR) phosphor conversion light-emitting diodes (pc-LEDs) have great application potential as NIR light sources in many fields such as food analysis, night vision illumination, and bioimaging for noninvasive medical diagnosis. In general, phosphors synthesized by a high-temperature solid-phase method have large particle sizes and have to be processed to fine powders by a grinding process, which may introduce surface defects and lower the luminous efficiency. Here, we report a sol–gel sintering method with ammonium nitrate and citric acid as the sacrificing agents to synthesize high purity, nanosized (less than 50 nm) Zr 4+ /Ni 2+ codoped MgAl 2 O 4 spinel NIR phosphors, in which MgAl 2 O 4 spinel is the matrix, Ni 2+ is the luminous center, and Zr 4+ acts as the charge compensator. We systematically characterized the crystal structures and NIR luminescence properties of the Ni 2+ -doped MgAl 2 O 4 and the Zr 4+ /Ni 2+ codoped MgAl 2 O 4 . Under 390 nm light excitation, the emission spectrum of the Ni 2+ -doped MgAl 2 O 4 phosphor covers 900–1600 nm, the half-peak width…

The utilization of multivalence ionic metal species generated through a peroxymonosulfate (PMS)-assisted photocatalytic system is a promising platform for the selective degradation of water contaminants. However, achieving an effective electron transport and enhanced separation efficiency for these metal species is a daunting challenge. Thus, our current study addresses this challenge by using a Co–Fe-based layered-double-hydroxide template to synthesize a Co 3 O 4 /FeCo 2 O 4 p–n heterojunction composite via a simple monosynthetic route. The resultant composite is thoroughly validated through advanced characterization techniques that efficiently activate PMS for sulfadiazine (SDZ) degradation under visible light, achieving a remarkable degradation efficiency of up to 90%. This accomplishment is attributed to factors including intimate interfacial contact, excellent light harvesting, mesoporosity, and oxygen vacancies within the composite. The formation of a distinct p–n heterojunction following the S-scheme charge dynamic significantly enhances photogenerated carrier separation and…

Ethylene glycol (EG) is one of the most attractive platform molecules derived from biomass and waste plastics. Thus, the selective electrooxidation of ethylene glycol (EGOR) into value-added chemicals (especially glycolic acid (GA)) can promote its recycling and upgrading. However, the understanding of the EG-to-GA process on Pt-group metal (PGM) electrodes is far limited now. It has been shown that the Pt and Pd electrodes could show considerable EGOR activity but not Rh and Ir electrodes. Meanwhile, EGOR mainly produces the glycolate, oxalate, and formate on Pt and Pd electrodes, whereas it can obtain minute amounts of glycolate and oxalate on Rh and Ir electrodes. Impressively, the selectivity of glycolate on Pt and Pd electrodes can be over 85% (apparent Faradaic efficiency) in alkaline media, although the stability should be further improved through interfacial tuning and/or engineering. This work might deepen the fundamental understanding of the EGOR process on the nature of PGM electrodes.

Four self-assembled inorganic–organic hybrid materials, namely, H{Na(H 2 O) 3 [Gd(PDA)(H 2 O) 2 ] 3 [BW 12 O 40 ]}·4H 2 O ( 1 ), H{Na(H 2 O) 3 [Tb(PDA)(H 2 O) 2 ] 3 [BW 12 O 40 ]}·3H 2 O ( 2 ), H{Na(H 2 O) 3 [Er(PDA)(H 2 O) 3 ] 3 [BW 12 O 40 ]}·H 2 O ( 3 ) (PDA = 1,10-phenanthroline-2,9-dicarboxylate), and [Pr 3 (H 2 O) 13 (pydc–OH) 2 ][BW 12 O 40 ]·12H 2 O ( 4 ) (pydc–OH = 4-hydroxy-2,6-pyridinedicarboxylate), were hydrothermally synthesized and structurally characterized. Hybrids 1 – 3 are isostructural and contain a Keggin unit, which is linked to lanthanoids to produce distinct trinuclear lanthanoid building blocks. The fragments are connected by anion−π and hydrogen bonding interactions to create 3D networks. In hybrid 4, a trimeric Pr-organic species bearing a Keggin unit forms a 2D coordination polymer, and then hydrogen bonding interactions between 2D layers lead to the formation of a 3D structure. These polyoxometalate-based frameworks were used as sorbents for the dispersive microsolid-phase extraction (D-μSPE) of two anticancer drugs (doxorubicin and epirubicin) in human…

One 3D Cd-MOF, namely, {[(HDMA) 2 ][Cd 3 (L) 2 ]·5H 2 O·2DMF} n ( LCU-124, LCU indicates Liaocheng University), was synthesized from an ether-containing ligand 1,3-bis(3,5-dicarboxylphenoxy)benzene (H 4 L). Its Ln 3+ -postmodified samples, Eu 3+ @LCU-124 and Tb 3+ @LCU-124, were obtained through cation exchange of dimethylamine cation (HDMA) with Eu 3+ and Tb 3+ . The successful entry of rare earth into LCU-124 by cation exchange modification was verified by IR, XRD, XPS, EDS mapping, and luminescence spectra. The proportion of Eu 3+ /Tb 3+ was adjusted during the modification process, leading to fluorescent materials with different emissions. Luminescence measurements indicated that these complexes exhibited interesting multiresponsive sensing activities toward biomarkers urine acid (UA), quinine (QN), and quinidine (QND). First, LCU-124 has a pronounced quenching effect toward UA with the detection limit of 31.01 μM. After modification, the visualization of the detection was improved significantly and the detection limit of Eu 3+ @LCU-124 was reduced to 0.868 μM. Second, when QN…

Low phonon tantalate-based phosphors with a layer structure are considered to have excellent upconversion luminescence (UCL) intensity, which could be reduced due to the existence of impure phase defects and inappropriate doped rare earth ions. To improve their UCL performance, we have prepared single-phase CaTa 4 O 11:Er 3+ /Yb 3+ samples by a molten salt synthesis (MSS) using KCl as the reaction medium and compared its UCL properties with counterparts made by a conventional solid-state reaction (SSR) in this study. We have demonstrated that the MSS samples have a much higher UCL intensity under 980 nm laser excitation than the SSR ones due to accurate replacement of Ca 2+ sites by Er 3+ /Yb 3+ in high-purity single-phase MSS samples. We have further enhanced the green UCL intensity of the MSS samples by 1.57 times via acid picking (AP). Under 980 nm laser excitation at a high powder density of 61.3 W/cm 2, the green UCL intensity of the MSS-AP samples can reach 3.72 times that of the SSR-AP samples. For potential luminescence thermometry applications, the maximum absolute…

In this research, a range of Pt/CeO 2 catalysts featuring varying Pt–O–Ce bond contents were developed by modulating the oxygen vacancies of the CeO 2 support for toluene abatement. The Pt/CeO 2 –HA catalyst generated a maximum quantity of Pt–O–Ce bonds (possessed the strongest metal–support interaction), as evidenced by the visible Raman results, which demonstrated outstanding toluene catalytic performance. Additionally, the UV Raman results revealed that the strong metal–support interaction stimulated a substantial increase in oxygen vacancies, which could facilitate the activation of gaseous oxygen to generate abundant reactive oxygen species accumulated on the Pt/CeO 2 –HA catalyst surface, a conclusion supported by the H 2 -TPR, XPS, and toluene-TPSR results. Furthermore, the results from quasi- in situ XPS, in situ DRIFTS, and DFT indicated that the Pt/CeO 2 –HA catalyst with a strong metal–support interaction led to improved mobility of reactive oxygen species and lower oxygen activation energies, which could transfer a large number of activated reactive oxygen species to the…

Benefiting from highly tunable pore environments, some metal–organic frameworks (MOFs) have recently shown promising prospects in the separation of methanol-to-olefin (MTO) products (mainly C 3 H 6 and C 2 H 4 ). However, the “trade-off” between gas storage capacity and selectivity always results in inefficient separation. In addition, poor stability of MOFs also limits practical separation applications. Herein, we have successfully assembled a layered Y-MOF ( FJI-W9 ) with bent diisophthalate ligands (H 4 L), Y–O chains, and 2-fluorobenzoic acids. As expected, FJI-W9 not only exhibits good chemical stability but also shows significant potential for C 3 H 6 /C 2 H 4 separation. For FJI-W9, the C 3 H 6 uptake at 298 K and 10 kPa is 63 cm 3 /g, and the IAST selectivity of FJI-W9 for C 3 H 6 /C 2 H 4 (V/V = 50/50) is calculated to be 20.5. To the best of our knowledge, both C 3 H 6 uptake and selectivity of FJI-W9 surpass most porous materials. GCMC simulation indicates that the special supramolecular binding sites in FJI-W9 have much stronger interactions with C 3 H 6 than C 2 H 4…

There is long-standing interest in nonaqueous uranium chemistry because of fundamental questions about uranium's variable chemical bonding and the similarities of this pseudo-Group 6 element to its congener d-block elements molybdenum and tungsten. To provide historical context, with reference to a conference presentation slide presented around 1988 that advanced a defining collection of top targets, and the challenge, for synthetic actinide chemistry to realize in isolable complexes under normal experimental conditions, this Viewpoint surveys progress against those targets, including (i) CO and related π-acid ligand complexes, (ii) alkylidenes, carbynes, and carbidos, (iii) imidos and terminal nitrides, (iv) homoleptic polyalkyls, -alkoxides, and -aryloxides, (v) uranium-uranium bonds, and (vi) examples of topics that can be regarded as branching out in parallel from the leading targets. Having summarized advances from the past four decades, opportunities to build on that progress, and hence possible future directions for the field, are highlighted. The wealth and diversity of…

A long-term goal of rechargeable zinc–air batteries (ZABs) has always been to design bifunctional electrocatalysts that are robust, effective, and affordable for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It has become a feasible method to construct metal/metal oxide interfaces to achieve superior electrocatalytic performance for ORR and OER by enhanced charge transfer. In this study, Co/Co 3 O 4 heterojunctions were successfully prepared and encased in porous N-doped mesoporous carbon (Co/Co 3 O 4 @NC) via a simple condensation-carbonization-etching method. The extensive specific surface area of Co/Co 3 O 4 @NC facilitates effective interaction between the electrolyte and the catalyst, thereby enabling sufficient exposure of active sites for the ORR and the OER, consequently enhancing the rate of transport of active species. The well-designed Co/Co 3 O 4 @NC delivers superior ORR catalytic activity with a half-wave potential of 0.82 V (vs RHE) and a low overpotential of 347 mV at 10 mA cm –2 for OER in alkaline solution. The power density of Co/Co 3 O…

Phenanthroline diamide ligands have been widely used in the separation of trivalent actinides and lanthanides, but little research has focused on extractants with asymmetrical substitutes. Two novel asymmetrical phenanthroline-based ligands N 2, N 2, N 9 -triethyl- N 9 -tolyl-1,10-phenanthroline-2,9-dicarboxamide (DE-ET-DAPhen) and N 2 -ethyl- N 9, N 9 -dioctyl- N 2 -tolyl-1,10-phenanthroline-2,9-dicarboxamide (DO-ET-DAPhen) were first synthesized in this work, whose extraction ability and complexation mechanism to trivalent actinides [An(III)] and lanthanides [Ln(III)] were systematically investigated. The ligands dissolved in n-octanol exhibit good extraction ability and high selectivity toward Am(III) in acidic solutions. The complexation mechanism of the ligands with Ln(III) in solution and solid state was analyzed using slope analysis, 1 H NMR spectrometric titration, ESI-MS, and calorimetric titration. It is revealed that the ligands complex with Am(III)/Eu(III) with 1:1 stoichiometry. The stability constant (log β) of the complexation reaction of Eu(III) with DE-ET-DAPhen…

Colorimetry based on the bioenzyme inhibition strategy holds promising application prospects in the field of organophosphorus pesticide (OPs) detection. However, overcoming the challenges of the high cost and low stability of bioenzymes remains crucial. In this study, we successfully synthesized a peroxidase vanadium-based metal-organic framework (MOF) nanozyme named MIL-88B(V) and employed its mediated bioenzyme-free colorimetric strategy for direct OPs detection. The experimental results demonstrated that MIL-88B(V) exhibited a remarkable affinity and a remarkable catalytic rate. When the OPs target is added, it can be anchored on the MOF surface through a V-O-P bond, effectively inhibiting the MOF's activity. Subsequently, leveraging the advantages of smartphones such as convenience, speed, and sensitivity, we developed a paper sensor integrated into a smartphone for efficient OPs detection. The as-designed nanozyme-based colorimetric assay and paper sensor presented herein offer notable advantages, including affordability, speed, stability, wide adaptability, low cost, and…

Indium phosphide (InP) quantum dots (QDs) have become the most recognized prospect to be less-toxic surrogates for Cd-based optoelectronic systems. Due to the particularly dangling bonds (DBs) and the undesirable oxides, the photoluminescence performance and stability of InP QDs remain to be improved. Previous investigations largely focus on eliminating P-DBs and resultant surface oxidation states; however, little attention has been paid to the adverse effects of the surface In-DBs on InP QDs. This work demonstrates a facile one-step surface peeling and passivation treatment method for both In- and P-DBs for InP QDs. Meanwhile, the surface treatment may also effectively support the encapsulation of the ZnSe shell. Finally, the generated InP/ZnSe QDs display a narrower full width at half-maximum (fwhm) of ∼48 nm, higher photoluminescence quantum yields (PLQYs) of ∼70%, and superior stability. This work enlarges the surface chemistry engineering consideration of InP QDs and considerably promotes the development of efficient and stable optoelectronic devices.

High Resolution Image Download MS PowerPoint Slide Developing efficient and robust electrode materials for electrochemical sensors is critical for real-time analysis. In this paper, a hierarchical holmium vanadate/phosphorus-doped graphitic carbon nitride (HoVO 4 /P-CN) nanocomposite is synthesized and used as an electrode material for electrochemical detection of hydrogen peroxide (H 2 O 2 ). The HoVO 4 /P-CN nanocomposite exhibits superior electrocatalytic activity at a peak potential of −0.412 V toward H 2 O 2 reduction in alkaline electrolytes while compared with other reported electrocatalysts. The HoVO 4 /P-CN electrochemical platform operated under the optimized conditions shows excellent analytical performance for H 2 O 2 detection with a linear concentration range of 0.009–77.4 μM, a high sensitivity of 0.72 μA μM –1 cm –2, and a low detection limit of 3.0 nΜ. Furthermore, the HoVO 4 /P-CN-modified electrode exhibits high selectivity, remarkable stability, good repeatability, and satisfactory reproducibility in detecting H 2 O 2 . Its superior performance can be attributed…

Five- and six-membered heterocycles containing nitrogen or oxygen have been considered as privileged scaffolds in organic chemistry and the chemical industry because of their usage in high-value commodities. Herein, we report a two-dimensional (2D) Cu(II)-based MOF catalyst, IITKGP-40, via the strategic employment of ample Lewis acid–base bifunctional sites (open metal nodes and free pyrazine moieties) along the pore wall. IITKGP-40 could convert toxic CO 2 to cyclic carbonates in an atom-economical manner under solvent-free conditions and aromatic aldehyde to bioactive 1,4-DHPs via Hantzsch condensation. Exceptional catalytic performance (99%) and turnover number under mild reaction conditions for CO 2 fixation using sterically hindered styrene oxide, and good-to-excellent yields for a wide range of aromatic aldehydes toward 1,4-dihydropyridines (1,4-DHPs) make IITKGP-40 promising as a multipurpose heterogeneous catalyst. Moreover, to demonstrate the practical utility of the catalyst, two biologically important drug molecules, diludine and nitrendipine analogue, have also been…

Decomposing extended structures into smaller, molecular, even functional groups or simple fragments has a long tradition in chemistry because it allows for understanding certain electronic peculiarities in truly chemical terms. By doing so, invaluable property information is chemically accessible, for example, needed to rationalize catalytic or magnetic or optical nature. In order to also follow that train of thought for periodic materials, we have developed a tool which in a straightforward manner derives fragment molecular orbitals from plane-wave electronic-structure data of whatever kind of solid-state material. We here report on the mathematical apparatus of the method dubbed linear combination of fragment orbitals (LCFO) used for that purpose, implemented within the LOBSTER code. The method is illustrated from various sorts of molecular entities contained in such crystalline materials, together with an assessment of both accuracy and robustness of the new tool.

Selective oxidation of sulfides to sulfoxides is of great significance in the synthesis of pharmaceuticals, desulfurization of fuels, and detoxification of sulfur mustard chemical warfare agents. Designing selective catalysts to achieve the efficient transformation of sulfides to sulfoxides is thus highly desired. Herein, we report three transition metal-complex-functionalized polyoxovanadates, [Zn 2 (BPB) 2 ][V 4 O 12 ]·0.5BPB·H 2 O ( 1 ), [Ni(BPB)(H 2 O)][V 2 O 6 ]·2H 2 O ( 2 ), and [Co(HBPB) 2 ][V 4 O 12 ] ( 3 ) (BPB = 1,4-bis(pyrid-4-yl)benzene)), and explore their applications for selective oxidation of sulfides using H 2 O 2 as an oxidant. All three compounds were catalytically effective for the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide, with 1 being best-performing with complete conversion and a selectivity of 96.7%. In the selective oxidation of a series of aromatic and aliphatic sulfides to corresponding sulfoxides, 1 also showed satisfactory performance; in particular, the chemical warfare agent stimulant 2-chloroethyl ethyl sulfide can be completely…

Exploring highly effective bifunctional electrocatalysts with surface structural advantages and synergistic optimization effects among multimetals is greatly important for overall water splitting. Herein, we successfully synthesized Pt-loaded NiFe-metal-organic framework nanosheet arrays grown on nickel foam (Pt–NiFe-MOF/NF) via a facile hydrothermal-electrodeposition process. Benefiting from large exposed specific surface, optimal electrical conductivity and efficient metal-support interaction endow Pt–NiFe-MOF/NF with highly catalytic performance, exhibiting small overpotential of 261 mV toward oxygen evolution reaction and 125 mV toward hydrogen evolution reaction at a current density of 100 mA cm –2 in alkaline medium. More significantly, the assembled water electrolyzer comprising the Pt–NiFe-MOF/NF//Pt–NiFe-MOF/NF couple demands a low cell voltage of 1.45 V to reach 10 mA cm –2 . This work renders a viable approach to design dual-functional electrocatalysts with exceptional electrocatalytic activity and stability at high current density, showing the great prospect of water…

Quick and easy synthetic methods and highly efficient catalytic performance are equally important to anodic oxygen evolution reaction (OER) electrocatalysts for alkaline seawater electrolysis. Herein, we report a facile one-step route to in situ growing PO 4 3– intercalated NiFe layered double hydroxides (NiFe-LDH) on Ni foam (denoted as NiFe-P/NF) by a room-temperature immersion for several minutes. This ultrafast approach transforms the NF surface into a rough PO 4 3– intercalated NiFe-LDH overlayer, which demonstrates outstanding OER performance in both alkaline simulated and natural seawaters owing to good hydrophilic interface and the electrostatic repulsion of PO 4 3– against Cl – anions. Density functional theory calculations reveal that the intercalated PO 4 3– can not only promote electron transfer but also prevent Cl – from entering the interlayer and simultaneously inhibit the migration of Cl – over the NiFe-LDH surface. In alkaline simulated and natural seawater electrolytes, NiFe-P/NF needs low overpotentials of 248 and 298 mV to achieve a current density of 100 mA cm…

Ba 3 Lu(BO 3 ) 3 (BLB):Ce 3+,Tb 3+ /Mn 2+ phosphors were designed to explore effective and multifunctional applications. Under the excitation of near-ultraviolet (n-UV) light, the BLB:Ce 3+ phosphor showed broad-band blue emission. After codoping with Mn 2+ ions, the single-phase white light phosphor is achieved through the energy transfer (ET) between Ce 3+ and Mn 2+ . In addition, thermal stability is significantly enhanced by the addition of Tb 3+ (BLB:0.02Ce 3+,0.20Tb 3+ ) compared to that codoped with Mn 2+ (BLB:0.02Ce 3+,0.10Mn 2+ ). The light-emitting diode (LED) device with warm white light emission is fabricated with UV-chip-coated BLB:0.02Ce 3+,0.05Tb 3+ and Sr 2 Si 5 N 8:Eu 2+ phosphors, showing a good potential application value for LEDs. Additionally, the spectral properties of borate-based phosphors (BLB:0.02Ce 3+ ) under high pressure were studied for the first time. Surprisingly, the change of pressure enabled the emission peak of BLB:0.02Ce 3+ to be tuned from 485 to 552 nm, and dλ/d P is 3.51 nm GPa –1 . The color changes from blue to yellow with an increase of…

Semiconductor materials based on bismuth metal have been extensively explored for their potential in photocatalytic applications owing to their distinctive crystal structure. Herein, we present the development of a hybrid photocatalyst, CAU-17/BiOCl, featuring a flower-like nanosheet morphology tailored for the photocatalytic degradation of organic contaminants such as rhodamine B (RhB) and tetracycline hydrochloride (TCH). The composite material is obtained by growing thin CAU-17 layers directly onto the host flower-like BiOCl nanosheets under solvothermal conditions. The optimized CAU-17/BiOCl composite possesses excellent photocatalytic performance, achieving a notable 96.0% removal rate for RhB and 78.4% for TCH after 60 and 90 min of LED light irradiation, respectively. This boosted activity is attributed to the heightened absorption of visible light caused by BiOCl and the provision of additional reaction sites due to the thin CAU-17 layers. Furthermore, the establishment of an S-scheme heterojunction mechanism enables efficient charge separation between CAU-17 and BiOCl,…

Ceramic capacitors have great potential for application in power systems due to their fantastic energy storage performance (ESP) and wide operating temperature range. In this study, the (1 – x )Bi 0.5 Na 0.47 Li 0.03 Sn 0.01 Ti 0.99 O 3 - x KNbO 3 (BNLST- x KN) energy storage ceramics were synthesized through the solid-phase reaction method. The addition of KN disrupts the long-range ferroelectric order of the BNLST ceramic, inducing the emergence of polar nanoregions (PNRs), which enhances the ESP of the ceramics. The BNLST-0.2KN ceramic demonstrates a high recovered energy density ( W rec ∼ 3.66 J/cm 3 ) and efficiency (η ∼ 85.8%) under a low electric field of 210 kV/cm. Meantime, it exhibits a large current density ( C D ∼ 831.74 A/cm 2 ), high power density ( P D ∼ 78.86 MW/cm 3 ), and fast discharge rate ( t 0.9 ∼ 0.1 μs), along with good temperature stability and excellent fatigue stability. These properties make the BNLST-0.2KN ceramic a promising candidate for energy storage applications in low electric fields.

Znln 2 S 4 has great prospects for photocatalytic water splitting to hydrogen by visible light. Herein, a novel Znln 2 S 4 –In-MOF (ZnIn M S 4 ) photocatalyst is elaborately synthesized by in situ method with In-MOF as the template and In 3+ as the source. ZnIn M S 4 overcomes the fast interface charge recombination and a sluggish charge lifetime via the formed heterojunctions. Photoelectrochemical measurements reveal that the charge-transfer kinetics is enhanced since In-MOF is introduced to act as a reliable charge-transport channel. ZnIn M S 4 exhibits outstanding cocatalyst-free H 2 evolution rate of 70 μmol h –1 under irradiation (λ > 420 nm), which is 3.2-fold higher than that of Znln 2 S 4 . In addition, the ZnIn M S 4 photocatalyst shows good stability in the 16 h continuous reaction. This work illustrates the feasibility of the MOF precursor instead of inorganic salts to directly synthesize photocatalysts with high performance.

High Resolution Image Download MS PowerPoint Slide Layered double hydroxides (LDHs) exhibit diverse chemical compositions and are being designed for promising applications such as CO 2 adsorbents. Although many researchers have analyzed CO 2 gas evolution and structural transformation behavior at elevated temperatures, there are still inconsistencies in results on the effect of different metal ions in LDHs. In this study, on the basis of atomic/molecular-level findings from our previous study on multistep structural/chemical transformation of Mg–Al LDHs, we analyzed the quantitative gas evolution behavior and structural transformations of M –Al–CO 3 LDHs with different divalent metal ions ( M = Mg, Zn, or Co, M /Al = 2) at elevated temperatures. Our quantitative analysis revealed that all three LDH samples undergo the three-step chemical transformations: release of interlayer water, partial dehydroxylation of the hydroxyl layers, and complete dehydroxylation of layers and decomposition of interlayer CO 3 2– . However, the temperature range for each step differs, as do the structural…

The rational design of nitrite sensors has attracted significant research interest due to their widespread use and the associated risks of methemoglobinemia and carcinogenicity. The undisclosed nitrite-sensing performance of the spinel cobaltite MnCo 2 O 4 (MCO) prepared by an oxalate-assisted coprecipitation method is reported in this study. Spectroscopy and microscopy investigations revealed the formation of uniform MCO nanorods with a high aspect ratio. The electrocatalytic nitrite oxidation at the MCO-coated glassy carbon electrode (MCO/GCE) indicated the promising performance of the synthesized material for nitrite sensing. MCO/GCE detects nitrite in a concentration range of 5 μM to 3 mM and has a limit of detection of 0.95 μM with a higher sensitivity of 857 μA mM –1 cm –2 in a response time of 4 s. In MCO, the mixed-valence states of Co 2+ /Co 3+ confer a high electrical conductivity, and higher valent redox couples of Mn and Co impart remarkable electrocatalytic activity toward nitrite oxidation. MCO spinel undergoes facile and ultrafast faradaic reactions to mediate nitrite…

Single-atom catalysts (SACs) present substantial potential in electrocatalytic CO 2 reduction reactions; however, inferior accessibility of single-atom sites to CO 2 limits the overall CO 2 RR performances. Herein, we propose to improve the accessibility between In sites and CO 2 through the construction of a three-dimensional (3D) porous indium single-atom catalyst (In 1 /NC-3D). The NaCl template-mediated synthesis strategy generates the unique 3D porous nanostructure of In 1 /NC-3D. Multiple characterizations validate that In 1 /NC-3D exhibits increased exposure of active sites and enhanced CO 2 transport/adsorption capacity compared to the bulk In 1 /NC, thus improving accessibility of active sites to CO 2 . As a result, the In 1 /NC-3D presents superior CO 2 RR performance to the bulk In 1 /NC, with a partial current density of formate of 67.24 mA cm –2 at −1.41 V, relative to a reversible hydrogen electrode (vs RHE). The CO 2 RR performances with high formate selectivity at a large current density also outperform most reported In-based SACs. Importantly, the In 1 /NC-3D is…

Constructing high-efficiency composite photocatalysts with enhanced charge transfer and a rapid surface catalytic reaction has recently received significant attention. Herein, a hydrochar-mediated NiFe 2 O 4 nanosheet (C/NFO) composite was rationally constructed by a simple hydrothermal method. Intimate interface contacts and chemical interactions between hydrochar and NFO were formed. The prepared C/NFO samples exhibited remarkable visible-light-driven catalytic CO 2 reduction properties under mild reaction conditions with Ru(bpy) 3 2+ sensitization. As the optimized sample, 16%-C/NFO achieved a 4-fold enhancement of CO production (17.49 μmol/h) compared with that of pure NFO. The C/NFO samples demonstrated good activity and structural stability in the CO 2 photoreduction system. The carbon source of CO derived from CO 2 was verified through isotopic labeling experiments using 13 CO 2 . In situ photoluminescence and electrochemical characterizations confirmed the role of electron transfer intermediates of C/NFO. The synergistic effect of the nanosheet-like structure of NFO,…

It is an important strategy to design composite materials with a special microstructure and a tunable electronic structure through structural compatibility. In this work, a novel hexagonal/cubic ZnIn 2 S 4 polymorphic heterophase junction with a three-dimensional multihierarchical structure is successfully constructed by in situ growth of hexagonal ZnIn 2 S 4 nanosheets on the surface of cubic ZnIn 2 S 4 flower-like microspheres prepared by topological chemical synthesis. On the one hand, the multihierarchical architecture provides large specific surface area, abundant active sites, and excellent light trapping capability. On the other hand, the construction of a direct S-scheme heterophase junction enables the formation of a special charge-transfer channel under the force of a built-in electric field, which not only improves the separation efficiency of carriers but also ensures the stronger reaction activity of charges. The prepared ZnIn 2 S 4 heterophase junction composite photocatalyst exhibits greatly boosted photocatalytic efficiency in rhodamine B degradation, hexavalent…

The zero-valent iron (ZVI) has attracted increasing attention due to the enhanced reactivity of ZVI to uranium wastewater. However, ZVI practical application is hampered due to its susceptibility to oxidation and the formation of passivation layers during storage and in situ restoration. To address these issues, we used a biosulfuration approach to modify ZVI for application in uranium ore wastewater treatment. A series of physicochemical characterization tools and photoelectronic analyses showed that BS-ZVI considerably increased carrier separation efficiency and visible light absorption capacity, resulting in a significant photoassisted enhancement effect on uranium extraction. Accordingly, the uranium removal efficiency of BS-ZVI reached 91% within 60 min, and its maximum adsorption capacity was 336.3 mg/g. By analyzing the mechanism, the improved U(VI) removal performance was mostly responsible on the dissolution of the passivation layer on the surface of ZVI, the generation of Fe(II) and FeS, and the important role of Shewanella putrefaciens extracellular polymers (EPS).…

Bifunctional electrocatalysts, capable of efficiently driving both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), are crucial for advancing electrochemical processes. While noble-metal-based catalysts are widely recognized for their role in oxygen processes, current state-of-the-art designs are limited to either ORR or OER activity, presenting a notable research gap. In addressing this challenge, we have developed a novel Ni/NiO-C nanocomposite catalyst derived from a nickel-based metal–organic framework ( Ni-SKU-5 ). For the ORR, the Ni/NiO-C catalyst exhibits an onset potential of 0.95 V vs RHE in a 1.0 M KOH solution, coupled with a Tafel slope of −99 mV dec –1 at 1600 rpm. Moreover, the catalyst displays excellent stability, maintaining a performance of over 90% after 10 h of continuous reaction. Furthermore, the catalyst proves effective in the OER, boasting an overpotential of 370 mV (at 10 mA cm –2 ) and a Tafel slope of 114 mV dec –1, highlighting its bifunctionality. The bifunctional overpotential of the Ni/NiO-C composite is measured at 820…

The core principles of multicomponent interface and electronic structure engineering are essential in designing high-performance catalysts for the oxygen evolution reaction (OER). However, combining these aspects within a catalyst is a significant challenge. In this investigation, a novel approach involving the development of hybrid Ir-doped CoMO 4 –Co(OH) 2 (M = W and Mo) hollow nanoboxes was introduced, enabling remarkably efficient water oxidation electrocatalysis. Constructed from ultrathin nanosheet-assembled hollow nanoboxes, these structures boast a wealth of active centers for intermediate species, which in turn enhance both charge transfer and mass transport capabilities. Moreover, the compelling electronic and synergistic effects arising from the interaction between CoMO 4 and Co(OH) 2 significantly bolster OER electrocatalysis by facilitating efficient electron transfer. The introduction of Ir atoms serves to strategically adjust the electronic structure, fine-tune its electronic state, and operate as active centers to enhance OER electrocatalysis, thus diminishing the…

Monitoring levels of excessive aluminum ions (Al 3+ ) is crucial as it can harm the immune system, reduce enzyme activity, cause cell death, and damage environmental and biological systems. Developing a fast and efficient Al 3+ ion determination method is the key to addressing this issue. In this work, red-emitting fluorescent copper nanoclusters (CuNCs) were synthesized using N -acetyl- l -cysteine (NAC) as a ligand and CuCl 2 ·2H 2 O through a facile procedure. The NAC-CuNCs exhibited a large Stokes shift and displayed remarkable luminescence properties. A method for detecting Al 3+ through a fluorescence probe was proposed. Its fluorescence mechanism was also explored. The probe showed rapid responsiveness (within 1 min) to Al 3+ ion determination. The detection limit for Al 3+ was found to be 19.7 nM, which is significantly lower than the WHO’s value and most reports, with a linear range of 0–52.9 μM. The determination of Al 3+ concentrations in actual water using the fluorescence probe yielded satisfactory outcomes. Moreover, the visual detection of Al 3+ ions was also achieved…

Development of a simple, cost-efficient, and portable UO 2 2+ sensory probe with high selectivity and sensitivity is highly desirable in the context of monitoring radioactive contaminants. Herein, we report a luminescent Co-based metal–organic framework (MOF), {[Me 2 NH 2 ] 0.5 [Co(DATRz) 0.5 (NH 2 BDC)]· x G} n ( 1 ), equipped with abundant amino functionalities for the selective detection of uranyl cations. The ionic structure consists of two types of channels decorated with plentiful Lewis basic amino moieties, which trigger a stronger acid–base interaction with the diffused cationic units and thus can selectively quench the fluorescence intensity in the presence of other interfering ions. Furthermore, the limit of detection for selective UO 2 2+ sensing was achieved to be as low as 0.13 μM (30.94 ppb) with rapid responsiveness and multiple recyclabilities, demonstrating its excellent efficacy. Density functional theory (DFT) calculations further unraveled the preferred binding sites of the UO 2 2+ ions in the tubular channel of the MOF structure. Orbital hybridization between NH…

A series of Ru(II) complexes incorporating two 4,4′-bis(trifluoromethyl)-2,2′-bipyridine (4,4′-btfmb) coligands and thienyl-appended imidazo[4,5- f ][1,10]phenanthroline (IP- n T) ligands was characterized and assessed for phototherapy effects toward cancer cells. The [Ru(4,4′-btfmb) 2 (IP- n T)] 2+ scaffold has greater overall redox activity compared to Ru(II) polypyridyl complexes such as [Ru(bpy) 3 ] 2+ . Ru-1T – Ru-4T have additional oxidations due to the n T group and additional reductions due to the 4,4′-btfmb ligands. Ru-2T – Ru-4T also exhibit n T-based reductions. Ru-4T exhibits two oxidations and eight reductions within the potential window of −3 to +1.5 V. The lowest-lying triplets (T 1 ) for Ru-0T – 2T are metal-to-ligand charge-transfer ( 3 MLCT) excited states with lifetimes around 1 μs, whereas T 1 for Ru-3T – 4T is longer-lived (∼20–24 μs) and of significant intraligand charge-transfer ( 3 ILCT) character. Phototoxicity toward melanoma cells (SK-MEL-28) increases with n, with Ru-4T having a visible EC 50 value as low as 9 nM and PI as large as 12,000. Ru-3T and Ru-4T…

Doping metals and constructing heterostructures are pivotal strategies to enhance the electrocatalytic activity of metal–organic frameworks (MOFs). Nevertheless, effectively designing MOF-based catalysts that incorporate both doping and multiphase interfaces poses a significant challenge. In this study, a one-step Co-doped and Co 3 O 4 -modified Ni-MOF catalyst (named Ni NDC-Co/CP) with a thickness of approximately 5.0 nm was synthesized by a solvothermal-assisted etching growth strategy. Studies indicate that the formation of the Co–O–Ni–O-Co bond in Ni NDC-Co/CP was found to facilitate charge density redistribution more effectively than the Co–O–Ni bimetallic synergistic effect in NiCo NDC/CP. The designating Ni NDC-Co/CP achieved superior oxygen evolution reaction (OER) activity (245 mV @ 10 mA cm –2 ) and robust long stability (100 h @ 100 mA cm –2 ) in 1.0 M KOH. Furthermore, the Ni NDC-Co/CP (+) ||Pt/C/CP (−) displays pregnant overall water splitting performance, achieving a current density of 10 mA cm –2 at an ultralow voltage of 1.52 V, which is significantly lower than that…

Four kinds of polyoxometalate (POM)-viologen compounds were synthesized by hydrothermal method, namely (1–cby) 2 ·[H 2 (SiMo 12 O 40 )]·2H 2 O ( 1 ), (1–cby) 2 ·[H 2 (SiW 12 O 40 )]·2H 2 O ( 2 ), (1–cby) 2 ·(1,1′–bcby) 2 ·{H 4 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]}·12H 2 O ( 3 ), (1–cby)·(1,1′–bcby)·[H(α–PW 11 O 39 )Co II (1–cby)]·8H 2 O ( 4 ) (1–cby·Br = 1–Cyclopropylmethyl–[4,4′]bipyridinyl–1–ium bromide, 1,1′–bcby·Br = 1,1′–Bis-cyclopropylmethyl–[4,4′]bipyridinyl–1–ium bromide). These four POM-viologen compounds exhibit one-dimensional supramolecular network structures. Especially, compound 3 contains a rare sandwich POM subunit {Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 } 10– . These four compounds can be used as color-changing materials, and they all exhibit noticeable color changes upon exposure to light, heat, and electricity. The discoloration mechanism involves viologen derivatives with electron-deficient properties accepting electrons from POM with electron-rich properties under external stimulation, leading to the formation of viologen free radicals. Among them, compounds 1 and 2 also…

The constant demand for eco-friendly methods of synthesizing complex organic compounds inspired researchers to design and develop modern, highly efficient heterogeneous catalytic systems. Herein, In-HCPCP metal–organic framework (SRMIST–1), a heterogeneous Lewis acid catalyst containing less toxic indium and eco-friendly robust cyclotriphosphazene and exhibiting notable chemical and thermal stability, durable catalytic activity, and exceptional reusability was produced through the reaction between indium(III) nitrate hydrate and hexakis(4-carboxylatophenoxy)-cyclotriphosphazene. In the SRMIST–1 structure, secondary building units {InO 7 } are assembled by a connection of η 2 - and η 1 -carboxylic oxo atoms from different HCPCP ligands, forming a three-dimensional network. The occurrence of regularly distributed In(III) sites in SRMIST–1 confers superior reactivity on the catalyst toward the synthesis of 2,3-dihydroquinazolin-4(1 H )-ones and 3,4-dihydro-2 H -1,2,4-benzothiadiazine-1,1-dioxides by the cyclization reaction of 2-aminobenzamides and 2-aminobenzenesulphonamides with…

Posttreatment of pristine metal–organic frameworks (MOFs) with suitable vapor may be an effective way to regulate their structures and properties but has been less explored. Herein, we report an interesting example in which a crystalline nonporous Eu(III)-MOF was transferred to a porous amorphous MOF (aMOF) via iodine vapor adsorption–desorption posttreatment, and the resulting aMOF showed improved turn-on sensing properties with respect to Ag + ions. The crystalline Eu-MOF, namely, Eu-IPDA, was assembled from Eu(III) and 4,4′-{4-[4-(1 H -imidazol-1-yl)phenyl]pyridine-2,6-diyl}dibenzoic acid (H 2 IPDA) and exhibited a two-dimensional (2D) coordination network based on one-dimensional secondary building blocks. The close packing of the 2D networks gives rise to a three-dimensional supramolecular framework without any significant pores. Interestingly, the nonporous Eu-IPDA could absorb iodine molecules when Eu-IPDA crystals were placed in iodine vapor at 85 °C, and the adsorption capacity was 1.90 g/g, which is comparable to those of many MOFs with large BET surfaces. The adsorption…

Chalcogenide perovskites (CPs) have recently attracted interest as a class of materials with practical potential in optoelectronics and have been suggested as a more thermally stable alternative to intensely studied halide perovskites (HPs). Here we report a comparative study of the thermal stability of representative HPs, MAPbI 3 (MA = CH 3 NH 3 +, methylammonium) and CsPbI 3, and a series of CPs with compositions BaZrS 3, β-SrZrS 3, BaHfS 3, SrHfS 3 . Changes in the crystal structure, chemical composition, and optical properties upon heating in air up to 800 °C were studied using thermogravimetric analysis, temperature-dependent X-ray diffraction, energy-dispersive X-ray spectroscopy, and diffuse reflectance spectroscopy. While HPs undergo phase transitions and thermally decompose at temperatures below 300 °C, the CPs show no changes in crystal phase or composition when heated up to at least 450 °C. At 500 °C CPs oxidize on time scales of several hours, forming oxides and sulfates. The structural origins of the higher thermal and phase stability of the CPs are discussed.

Metal halides have drawn great interest as luminescent materials and scintillators due to their outstanding optical properties. Exploring new types of phosphors with easy production processes, excellent photophysical properties, high light yields, and environmentally friendly compositions is crucial and quite challenging. Herein, a novel Mn(II)-based metal halide (4-BTP) 2 MnBr 4 was produced using a facile solvent evaporation method, which exhibited a strong green emission peaking at 524 nm from the d–d transition of tetrahedral-coordinated Mn 2+ ion and a near-unity quantum yield. The prepared white light-emitting diode device has a wide color gamut of 100.7% NTSC with CIE chromaticity coordinates of (0.32, 0.32). In addition, (4-BTP) 2 MnBr 4 demonstrates excellent characteristics in X-ray scintillation, including a high light yield of 98 000 photons/MeV, a sensitive detection limit of 37.4 nGy/s, excellent resistance to radiation damage, and successful demonstration of X-ray imaging with high resolution at 21.3 lp/mm, revealing the potential for application in diagnostic X-ray…

In this study, we synthesized and characterized a series of cobalt(II) complexes bearing linear tetradentate N4 ligands. These Co(II)–N4 complexes proved to be efficient catalysts for the cycloaddition reaction between carbon dioxide and epoxides even at room temperature and 1 bar pressure of carbon dioxide without the need for solvents or cocatalysts. Furthermore, when combined with (triphenylphosphoranylidene)ammonium chloride (PPNCl) as a cocatalyst, the Co–N4 catalysts exhibited an impressive turnover frequency of up to 41,000 h –1 for coupling of epichlorohydrin/CO 2 . These Co(II)–N4 catalysts were found to have excellent stability and reusability, retaining their catalytic activity after they were recycled seven times. Density functional theory (DFT) calculations provided a comprehensive mechanism for the cycloaddition reaction, indicating that the rate-determining step is the epoxide ring opening, in both the presence and absence of PPNCl. Further kinetic studies allow us to determine the activation parameters (Δ H ‡, Δ S ‡, and Δ G ‡ at 25 °C) of the coupling reaction using…

High-power LED lighting is a crucial challenge due to the notorious thermal quenching (TQ) effect of traditional phosphors at high operating currents, which would result in poor device performance and hamper practical optoelectronic application. Herein, we demonstrate ligand engineering of a cubane- versus staircase-like [Cu4I4] conformer as a node in coordination polymers, which remarkably suppresses the TQ effect of cluster-based photoluminescence. For complex 1 (the formula [Cu4I4(bbimb)2]n) with the cubane-like [Cu4I4] conformer as a node, the metallophilicity interaction enables ultrabright triplet emission with a photoluminescence quantum yield over 82%, and the phonon-assisted detrapping process of excitons effectively suppresses the TQ effect in the wide temperature range. In contrast, the staircase-like [Cu4I4] conformer as a node in complex 2 (the formula [Cu4I4(bbtmb)2]n) exhibits a serious TQ effect over the investigated temperature. Phosphor-converted white LEDs (pc-wLEDs) were fabricated by integrating the cluster-based coordination polymers as a color converter, and…

High Resolution Image Download MS PowerPoint Slide Pure and Pr 3+ -doped BaYF 5 nanoparticles were synthesized by the microwave hydrothermal method. The nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and optical spectroscopy. The XRD and TEM confirm that the average size of nanoparticles is in the range of 26–37 nm. The optical excitation and luminescence spectra of BaYF 5:Pr 3+ nanoparticles are presented in the visible and ultraviolet (UV) range. It has been verified that Pr 3+ ions are capable of emitting UV-C photons when excited by a 444 nm laser. This emission arises from a two-photon energy-transfer upconversion mechanism. The concentration dependence of the upconversion luminescence of BaYF 5:Pr 3+ was studied.

Hematite (α-Fe 2 O 3 ) photoanode is a promising candidate for efficient PEC solar energy conversion. However, the serious charge recombination together with the sluggish water oxidation kinetics of α-Fe 2 O 3 still restricts its practical application in renewable energy systems. In this work, a CoOOH/α-Fe 2 O 3 /SnO 2 photoanode was fabricated, in which the ultrathin SnO 2 underlayer is deposited on the fluorine-doped tin oxide (FTO) substrate, α-Fe 2 O 3 nanorod array is the absorber layer, and CoOOH nanosheet is the surface modifier, respectively. The resulting CoOOH/α-Fe 2 O 3 /SnO 2 exhibited excellent PEC water splitting with a high photocurrent density of 2.05 mA cm –2 at 1.23 V vs RHE in the alkaline electrolyte, which is ca. 3.25 times that of bare α-Fe 2 O 3 . PEC characterizations demonstrated that SnO 2 not only could block hole transport from α-Fe 2 O 3 to FTO substrate but also could efficiently enhance the light-harvesting property and reduce the surface states by controlling the growth process of α-Fe 2 O 3, while the CoOOH overlayer as cocatalysts could rapidly…

Bifunctional materials have attracted ongoing interest in the field of detection and removal of contaminants because of their integration of two functions, but they exhibit commonly exceptional performance in only one of these two aspects. The interaction between the two functional units of the bifunctional materials may compromise their sensing and adsorption abilities. Guided by the concept of domain building blocks (DBBs), a hierarchical metal–organic framework (MOF)-on-MOF hybrid was designed by growing gold nanoclusters (AuNCs)-embedded zeolitic imidazolate framework 8 (AuNCs/ZIF-8) on the surface of Zr-MOF (UiO-66-NH 2 ) for the simultaneous detection and removal of Hg 2+ . In the hybrid, the amino groups (−NH 2 ) and AuNCs─which were the adsorption groups and sensing units, respectively, were isolated from each other. Specifically, the adsorption groups (−NH 2 ) were assembled in the inner UiO-66-NH 2 layer, while the sensing units (AuNCs) were confined in the outer ZIF-8 layer. This hierarchical structure not only spatially hindered the electron transfer between these two…

The conversion of CO 2 to generate high-value-added chemicals has become one of the hot research topics in green synthesis. Thereinto, the cyclization reaction of propargylic amines with CO 2 is highly attractive because the resultant oxazolidinones are widely found in pharmaceutical chemistry. Cu(I)-based metal–organic frameworks (MOFs) as catalysts exhibit promising application prospects for CO 2 conversion. However, their practical application was greatly limited due to Cu(I) being liable to disproportionation or oxidization. Herein, the solid copper(I) iodide thorium-based porous framework {[Cu 5 I 6 Th 6 (μ 3 -O) 4 (μ 3 –OH) 4 (H 2 O) 10 (L) 10 ]·OH·4DMF·H 2 O} n ( 1 ) (HL = 2-methylpyridine-4-carboxylic acid) constructed by [Th 6 ] clusters and [Cu x I y ] subunits was successfully prepared and structurally characterized. To our knowledge, this is the first copper(I) iodide-based actinide organic framework. Catalytic investigations indicate that 1 can effectively catalyze the cyclization of propargylic amines with CO 2 under ambient conditions, which can be reused at least…

The lead-free halide perovskites possess nontoxicity and excellent chemical stability, whereas relatively weak luminescence intensity limits their potential in practical applications. Therefore, strengthening the luminescence intensity and expanding application fields are urgent tasks for the development of lead-free halide perovskites. In this paper, antimony-doped Cs 2 NaScCl 6 crystals synthesized by a solvothermal method emit bright, deep blue photoluminescence at 447 nm. The photoluminescence (PL), photoluminescence excitation (PLE), and absorption spectra demonstrate that Sb 3+ doping effectively activate the intrinsic “dark self-trapped exciton (STE),” leading to an impressive photoluminescence quantum yield (PLQY) value of 78.31% for 1% Sb 3+ doping. Furthermore, the luminescence intensity remains above 92% compared with the fresh sample without secondary phases detected even after 90 days under environmental conditions. To expand the emission spectra, rare-earth Sm 3+ is further incorporated into Cs 2 NaScCl 6:1% Sb 3+ crystals. The results show that Sb ions not only…

Given the escalating significance of near-infrared (NIR) spectroscopy across industries, agriculture, and various domains, there is an imminent need to address the development of a novel generation of intelligent NIR light sources. Here, a series of Cr 3+ -doped BaLaMgNbO 6 (BLMN) ultrabroadband NIR phosphor with a coverage range of 650–1300 nm were developed. The emission peak locates at 830 nm with a full width at half maximum of 210 nm. This ultrabroadband emission originates from the 4 T 2 → 4 A 2 transition of Cr 3+ and the simultaneous occupation of [MgO 6 ] and [NbO 6 ] octahedral sites confirmed by low photoluminescence spectra (77–250 K), time-resolved photoluminescence spectra, and electron paramagnetic resonance spectra. The fluxing strategy improves the luminescence intensity and thermal stability of BLMN:0.02Cr 3+ phosphors. The internal quantum efficiency (IQE) is 51%, external quantum efficiency (EQE) can reach 33%, and thermal stability can be maintained at 60%@100 °C. Finally, we successfully demonstrated the application of BLMN:Cr 3+ ultrabroadband in the…

NaH 2 SIP was selected as an organic ligand (NaH 2 SIP = 5-sulfoisophthalic acid monosodium salt). We successfully constructed a new class of lanthanide coordination polymers Ln-HS ([Ln(SIP)(DMF)(H 2 O) 4 ]DMF·H 2 O; Ln = Eu, Tb, Sm, and Dy) by a simple solvothermal synthesis method. They exhibited excellent photoluminescence properties for Ln 3+ ions, where Eu-HS and Tb-HS exhibited high quantum yields of 13.70 and 42.38%, respectively. The codoped lanthanide coordination polymers obtained by doping with different ratios of Eu 3+ /Tb 3+ serve as excellent ratiometric thermometers with high sensitivities in the physiological temperature range, with values of 16.8, 7.0, and 14.5%·K –1, respectively. The luminescent colors of Tb 0.95 Eu 0.05 -HS and Tb 0.94 Eu 0.06 -HS exhibit variations from green to yellow to orange, achieving visualized luminescence in a narrow temperature range. The composite film material Tb 0.94 Eu 0.06 -HS@PMMA demonstrates this color variation. Next, Tb 0.5 Sm 0.5 -HS obtained by Tb 3+ /Sm 3+ codoping was investigated. The difference in the luminescence colors…

High Resolution Image Download MS PowerPoint Slide The two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used in various electrochemical applications, such as electrocatalysts, sensors, and energy storage. They have been potentially demonstrated not only as catalysts but also as supporting materials for boosting catalytic performance and durability. However, the different types of TMD nanosheets (transition metals and chalcogenide atoms) for supporting nanoparticles have not yet been investigated for electrocatalytic performance. Herein, we provide mechanistic insights into the hydrogen evolution reaction (HER) of various TMDs (i.e., MoS 2, MoSe 2, and WSe 2 ) as catalyst supports for the decoration of gold nanoparticles (AuNPs), which represent an active catalyst. Among various TMD supports, it was found that the MoS 2 supports with an optimal amount of AuNPs loading (MoS 2 /AuNPs) exhibited excellent catalytic activity (low overpotential and Tafel slope), which is better than that of other TMD supports and the previously reported TMD-based support. This…

Achieving high-efficiency tunable emission in a single phosphor remains a significant challenge. Herein, we report a series of Sb 3+ -doped all-inorganic double perovskites, Sb 3+:Cs 2 NaScCl 6, with efficient excitation-dependent emission. In 0.5%Sb 3+:Cs 2 NaScCl 6, strong blue emission with a high photoluminescence quantum yield (PLQY) of 85% is obtained under 265 nm light irradiation, which turns into bright neutral white light with a PLQY of 56% when excited at 303 nm. Spectroscopic and computational investigations were performed to reveal the mechanism of this excitation-dependent emission. Sb 3+ doping induces two different excitation channels: the internal transition of Sb 3+: 5s 2 → 5s5p and the electron transfer transition of Sb 3+: 5s → Sc 3+ 3d. The former one generates excited Sb 3+ ions, which can undergo efficient energy transfer to populate the host self-trapped exciton (STE) state, yielding enhanced blue emission. The latter one leads to the formation of a new STE state with the hole localized on Sb 3+ and the electron delocalized on the nearest Sc 3+, which…