The 100 most-cited articles in Chemical Communications, 2018

We report a low-cost water-in-salt electrolyte, of 30 m ZnCl2, which enables a dendrite-free Zn metal anode to possess a high coulombic efficiency (CE). In asymmetric Zn‖Zn cells with a limited mass of plated Zn as the working electrode, the ZnCl2 WiSE improves the average CE of the Zn anode to 95.4% from 73.2% in 5 m ZnCl2.

Two-dimensional (2D) conductive metal-organic frameworks (MOFs) have emerged as a unique class of multifunctional materials due to their compositional and structural diversity accessible through bottom-up self-assembly. This feature article summarizes the progress in the development of 2D conductive MOFs with emphasis on synthetic modularity, device integration strategies, and multifunctional properties. Applications spanning sensing, catalysis, electronics, energy conversion, and storage are discussed. The challenges and future outlook in the context of molecular engineering and practical development of 2D conductive MOFs are addressed.

Nucleation of new peptide and protein aggregates on the surfaces of amyloid fibrils of the same peptide or protein has emerged in the past two decades as a major pathway for both the generation of molecular species responsible for cellular toxicity and for the autocatalytic proliferation of peptide and protein aggregates. A key question in current research is the molecular mechanism and driving forces governing such processes, known as secondary nucleation. In this context, the analogies with other self-assembling systems for which monomer-dependent secondary nucleation has been studied for more than a century provide a valuable source of inspiration. Here, we present a short overview of this background and then review recent results regarding secondary nucleation of amyloid-forming peptides and proteins, focusing in particular on the amyloid β peptide (Aβ) from Alzheimer's disease, with some examples regarding α-synuclein from Parkinson's disease. Monomer-dependent secondary nucleation of Aβ was discovered using a combination of kinetic experiments, global analysis, seeding…

Chiral spirooxindoles are privileged heterocyclic motifs, which are widely found in natural alkaloids and pharmaceuticals. Moreover, the construction of chiral spiro-cyclic frameworks is a long-lasting challenge in organic synthesis. The past four years have witnessed significant developments in this field, and this feature article outlines the recent progress in the catalytic asymmetric synthesis of spirooxindoles, including the contributions of our group. The catalytic asymmetric construction of spirooxindoles has greatly benefited from the utilization of oxindole derivatives as starting materials, including isatin derivatives, methyleneindolinones, indolin-2-one derivatives and isatin-derived 3-indolylmethanols. This article is divided into sections according to the size and type of the generated spiro-ring fused at the C3-position of the oxindole core (from three-membered to seven-membered spiro-rings), and representative examples are given with illustrations. In addition, the enantioselective construction of bispirooxindole frameworks is also discussed in the last section.

Rechargeable aqueous zinc ion batteries (ZIBs) are highly desirable for large-scale energy storage due to their advantages of safety and low-cost. Development of advanced cathodes for use in aqueous ZIBs is urgently needed. Herein, we report a low-cost rechargeable aqueous Zn-V2O5 cell with 3 M ZnSO4 electrolyte that demonstrates high zinc storage capability. We also investigated the effect of different types/concentrations of the aqueous electrolytes on the performance of the Zn-V2O5 cells.

Polyoxometalates (POMs) are, mostly anionic, metal oxide compounds that span a wide range of tunable physical and chemical features rendering them very interesting for biological purposes, an continuously emerging but little explored field. Due to their biological and biochemical effects, including antitumor, -viral and -bacterial properties, POMs and POM-based systems are considered as promising future metallodrugs. In this article, we focus on the antibacterial activity of POMs and their therapeutic potential in the battle against bacteria and their increasing resistance against pharmaceuticals. Recent advances in the synthesis of POMs are highlighted, with emphasis on the development and properties of biologically active POM-based hybrid and nanocomposite structures. By analysing the antibacterial activity and structure of POMs, putative mode of actions are provided, including potential targets for POM-protein interactions, and a structure-activity-relationship was established for a series of POMs against two bacteria, namely Helicobacter pylori and Streptococcus pneumoniae.

The interest in organic molecules exhibiting thermally activated delayed fluorescence (TADF) has been reinvigorated in recent years owing to their potential to be exploited as emitters in highly efficient purely organic light emitting diodes (OLEDs). However, designing new molecules that exhibit efficient TADF is a non-trivial task because they would appear to require the optimisation of a number of contrasting properties. For example these molecules must exhibit rapid conversion between the singlet and triplet manifolds without the use of heavy elements to enhance spin-orbit coupling. They should also display a large fluorescence rate, but simultaneously a small energy gap between low lying singlet and triplet states. Consequently to achieve systematic material design, a detailed understanding of the fundamental factors influencing the photophysical behaviour of TADF emitters is essential. Towards achieving this goal, theory and computation is playing a crucial role. In this feature article the recent progress in the theory of organic TADF molecules in the context of OLEDs is…

A highly attractive, but still a key challenge, is the development of earth-abundant electrocatalysts for efficient NH3 electrosynthesis via the N2 reduction reaction (NRR). In this communication, we report the development of a Mo2N nanorod as a highly efficient and selective NRR electrocatalyst for artificial N2 fixation in acidic electrolytes under ambient conditions. In 0.1 M HCl, this catalyst achieved a high Faradaic efficiency of 4.5% with a NH3 yield of 78.4 μg h-1 mgcat.-1 at -0.3 V vs. a reversible hydrogen electrode, thus outperforming most reported NRR electrocatalysts under ambient conditions and some under harsh conditions. Density functional theory calculations revealed that the free energy barrier of the potential determining step of NRR on MoO2 decreases dramatically after nitrogenization.

More than 20 000 MOFs have been reported to date, with different combinations of metal ions/centers and organic linkers, and they can be grown into various 3D, 2D, 1D and 0D morphologies. The flexibility in control over varying length scales from atomic scale up to bulk structure allows access to an almost endless variety of MOF-based and MOF-derived materials. Indeed, MOFs themselves have been studied as a class of useful functional materials. More remarkably, extensive research conducted in recent years has shown that MOFs are exceptionally good precursors for a large variety of nanohybrids as active materials in both electrocatalysis and energy storage. As they already contain both carbon and well-dispersed metal atoms, MOFs can be converted to conductive carbons decorated with active metal species and doping elements through appropriate pyrolysis. Due to the great diversity accessible in the composition, structure, and morphology of MOFs, several types of MOF-derived nanohybrids are now among the best performing materials both for electrocatalysts and electrodes in various…

In this Feature Article, we highlight our recent efforts toward stable open-shell singlet diradicaloids and polyradicaloids. A brief review on the historical works in the area is introduced first, followed by discussion on the fundamental electronic and physical properties of open-shell singlet diradicaloids. Then, the structure-diradical character relationships based on our recently developed diradicaloids are presented. Next, the challenges and solutions toward stable polyradicaloids and 3D π-conjugated diradicaloids are discussed. Finally, their preliminary material applications are introduced and a perspective view of the area is given.

Atomically dispersed Fe-N4 sites anchored on N-doped porous carbon materials (Fe-SAs/NC) can mimic two antioxidative enzymes of catalase (CAT) and superoxide dismutase (SOD), and therefore serves as a bifunctional single-atom-based enzyme (SAzyme) for scavenging reactive oxygen species (ROS) to remove excess ROS generated during oxidative stress in cells.

The strong π-π interactions in the stacking layers of two-dimensional covalent organic frameworks (2D-COFs), together with rotationally labile imine linkages, make most of the solid state imine-linked COFs non-fluorescent due to fluorescence quenching processes. Here, we report the successful synthesis of highly photoluminescent imine-based 2D-COFs by integrating a non-planar building unit with a pyrene-based unit and transforming the COF into spherical, sub-micron particles. High photoluminescence quantum yields (PLQY) were achieved with COF sub-micron particles dispersed in organic solvents. The as-prepared COF sub-micron particles can be used as a chemical sensor for the detection of explosive chemicals, with high sensitivity and selectivity (up to ppm level).

Metal-organic frameworks (MOFs) have emerged as attractive electrode materials for applications in energy storage and conversion, owing to their high porosity and surface area. In this communication, we report a hierarchically structured Co-MOF supported on nickel foam (Co-MOF/NF) serving as a high-performance electrode material for supercapacitors. The as-obtained Co-MOF/NF exhibits an ultrahigh areal specific capacitance of 13.6 F cm-2 at 2 mA cm-2 in 2 M KOH, exceeding those of the previously reported MOF-based materials. It also shows an excellent rate performance of 79.4% at a current density of 20 mA cm-2. An asymmetric supercapacitor (ASC) device employing Co-MOF/NF as the positive electrode and activated carbon (AC) as the negative electrode achieves a high energy density of 1.7 mW h cm-2 at a power density of 4.0 mW cm-2 with a capacitance retention of 69.7% after 2000 cycles.

The industrial-scale NH3 production still heavily depends on the Haber-Bosch process which demands not only high energy consumption but emits a large amount of CO2. Electrochemical fixation of N2 to NH3 under ambient conditions is regarded as an eco-friendly and sustainable approach, but stable and efficient electrocatalysts are demanded for the N2 reduction reaction (NRR). In this work, we report our recent finding that an Ag nanosheet acts as a high-performance NRR electrocatalyst at room temperature and pressure. Electrochemical tests in 0.1 M HCl reveal that such a catalyst achieves a high Faradaic efficiency of 4.8% and a NH3 yield rate of 4.62 × 10-11 mol s-1 cm-2 at -0.60 V vs. reversible hydrogen electrode (RHE), rivaling the performances of most of the reported aqueous-based NRR electrocatalysts. Additionally, the Ag nanosheet also shows excellent selectivity, strong long-term electrochemical stability and durability.

Zeolite-templated carbons (ZTCs) are ordered microporous carbons synthesized by using zeolite as a sacrificial template. Unlike well-known ordered mesoporous carbons obtained by using mesoporous silica templates, ZTCs consist of curved and single-layer graphene frameworks, thereby affording uniform micropore size (ca. 1.2 nm), developed microporosity (∼1.7 cm3 g-1), very high surface area (∼4000 m2 g-1), good compatibility with chemical modification, and remarkable softness/elasticity. Thus, ZTCs have been used in many applications such as hydrogen storage, methane storage, CO2 capture, liquid-phase adsorption, catalysts, electrochemical capacitors, batteries, and fuel cells. Herein, the relevant research studies are summarized, and the properties as well as the performances of ZTCs are compared with those of other materials including metal-organic frameworks, to elucidate the intrinsic advantages of ZTCs and their future development.

Cobalt-doped MoS2 nanosheets were prepared via a facile hydrothermal method, exhibiting bifunctional activities of hydrogen and oxygen evolution reactions in both acidic and alkaline media. Cobalt doping not only improves the conductivity, decreasing the hydrogen adsorption free energy of MoS2 for HER, but also contributes catalytic active sites for OER.

A general outlook of the changing face of chemical synthesis is provided in this article through recent applications of continuous flow processing in both industry and academia. The benefits, major challenges and limitations associated with the use of this mode of processing are also given due attention as an attempt to put into perspective the current position of continuous flow processing, either as an alternative or potential combinatory technology for batch processing.

Stable cycling of a 4 V-class potassium-ion battery is demonstrated with a highly concentrated potassium bis(fluorosulfonyl)amide 1,2-dimethoxyethane solution as an electrolyte. Not only graphite and K2Mn[Fe(CN)6] half cells but also graphite//K2Mn[Fe(CN)6] full cells filled with the electrolyte exhibit higher coulombic efficiency and better cyclability than those of KPF6/carbonate ester solutions.

The LUMO levels of rylene diimides are highly comparable to those of fullerenes but this class of molecules offers tunability of both HOMO and LUMO levels and the related band gap by either simple substitution at the aromatic core or annulation to give expanded π-scaffolds. In this article we highlight the most outstanding achievements during the last decade in terms of charge carrier mobility for organic thin-film and single crystal field-effect transistors as well as photovoltaic performance for both small molecule and polymeric compounds.

In the period 1985 to 1995 applications of biocatalysis, driven by the need for more sustainable manufacture of chemicals and catalytic, (enantio)selective methods for the synthesis of pharmaceutical intermediates, largely involved the available hydrolases. This was followed, in the next two decades, by revolutionary developments in protein engineering and directed evolution for the optimisation of enzyme function and performance that totally changed the biocatalysis landscape. In the same period, metabolic engineering and synthetic biology revolutionised the use of whole cell biocatalysis in the synthesis of commodity chemicals by fermentation. In particular, developments in the enzymatic enantioselective synthesis of chiral alcohols and amines are highlighted. Progress in enzyme immobilisation facilitated applications under harsh industrial conditions, such as in organic solvents. The emergence of biocatalytic or chemoenzymatic cascade processes, often with co-immobilised enzymes, has enabled telescoping of multi-step processes. Discovering and inventing new biocatalytic…

The necessity of sustainable development in the chemical industry has continuously drawn attention to find safe, environmentally friendly and atom-economic chemical processes, which is defined in the 12 principles of green chemistry. Merging photoredox catalysis and reversible addition-fragmentation chain transfer (RAFT) polymerisation, the photoinduced electron/energy transfer (PET)-RAFT process has opened up a new way of performing reversible deactivation radical polymerisation for well-defined polymer synthesis using light as an external stimulus. While providing an increased level of control (spatiotemporal, wavelength, and intensity control) over the polymerisation, PET-RAFT has many attractive attributes (abundant catalyst availability, catalyst recyclability, selectivity and oxygen tolerance) to be green and sustainable, which is intriguing for precision polymer manufacturing in industry.

Recent advances in the sulfonylation reactions by using inorganic sulfites as the source of sulfonyl group are reported. The approaches employing inorganic sulfites as sulfur dioxide surrogates are attractive and promising for the synthesis of sulfonyl compounds since inorganic sulfites are abundant, easily available and cheap. The transformations using inorganic sulfites as the source of sulfonyl group work efficiently, providing diverse sulfonyl compounds including sulfones and sulfonamides. The sulfonylation reactions can be performed under transition metal catalysis or through radical processes under catalyst- and additive-free conditions. In some cases, a photocatalyst is employed under visible-light irradiation to facilitate the transformation. For the sulfur dioxide surrogate of inorganic sulfites, potassium metabisulfite or sodium metabisulfite has been broadly used in various transformations. However, the reactivities of inorganic sulfites in organic reactions still need to be explored.

The development of a sustainable route to ammonia production is one of the most attractive targets in chemistry. The primary method of ammonia production, Haber-Bosch process, can bring about excessive consumption of fossil fuels and large CO2 emission. In this communication, we develop a VN nanowire array on carbon cloth (VN/CC) as a high-performance catalyst for the nitrogen reduction reaction (NRR) under ambient conditions. Such an electrocatalyst achieves high ammonia yield (2.48 × 10-10 mol-1 s-1 cm-2) and faradaic efficiency (3.58%) at -0.3 V versus RHE in 0.1 M HCl, outperforming most reported results for N2 fixation under ambient conditions, and even comparing favorably with those obtained under high temperatures and/or pressures. This work not only provides us an attractive catalyst material for the NRR in acidic media, but would also open up an exciting new avenue to the rational design and fabrication of transition metal nitrides for the NRR.

Unlike typical polycyclic aromatic hydrocarbons, such as coronene, which are flat and planar, corannulene is a molecular bowl of carbon. It can be imagined as the cap region of fullerene C60 or an end of a single-walled carbon nanotube. This structural distinction manifests itself in unique properties. For example, corannulene exhibits bowl-flipping dynamics, electron accepting capability, and formation of a ball-in-socket type of interaction with C60. These varied properties allow for application of corannulene in a myriad of disciplines ranging from organic electronics and sensing to energy storage and self-assembly. In this feature article, our goal is to discuss the major synthetic developments in corannulene chemistry which allow the scientific community access to this beautiful molecule in a practical fashion, the unique properties of the corannulene nucleus that sets it apart from the planar polynuclear aromatic hydrocarbons, and lastly its applications in the arena of materials chemistry.

Recent advances in the sulfonylation of alkenes via the insertion of sulfur dioxide are summarized. The sulfur dioxide surrogate of DABCO·(SO2)2 or inorganic sulfites is used in the transformation through a radical process. Two strategies for the sulfonylation of alkenes with the insertion of sulfur dioxide have been developed. In most cases, the vicinal difunctionalization of alkenes is initiated by the arylsulfonyl radical generated in situ. Although the sulfonylation of alkenes with the insertion of sulfur dioxide is efficient, the asymmetric versions are still challenging and less to be explored. It is expected that the asymmetric vicinal difunctionalization of alkenes with the insertion of sulfur dioxide will be developed rapidly in the near future.

Lithium metal-based batteries offer promising prospects as alternatives to today's lithium-ion batteries, due to their ultra-high energy density. Unfortunately, the application of lithium metal is full of challenges and has puzzled researchers for more than 40 years. In this feature article, we describe the history of the development of lithium metal batteries and their existing key challenges, which include non-uniform electrodeposition, volume expansion, high reactivity of the lithium metal/unstable solid electrolyte interphase (SEI), and the shuttling of active cathode materials. Then, we focus on the growth mechanisms of uneven lithium electrodeposition and extend the discussion to the approaches to inhibit lithium dendrites. Finally, we discuss future directions that are expected to drive progress in the development of lithium metal batteries.

Metal halide double perovskites (DPs) are being explored as stable and non-toxic alternatives of Pb-halide perovskites. Typically DPs exhibit a wide (>2.5 eV) and/or indirect bandgap, limiting their applications in the visible region. Here we impart the visible-light emission property in direct bandgap Cs2AgInCl6 DPs by doping Mn2+ ions. Synthesis, characterization and luminescence of metal halide double perovskites are reported.

Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

The construction of C-C and C-X (X = hetero atom) bonds is the core aspect for the assembly of molecules. In this regard, late transition-metal-catalyzed cross-coupling reactions have retained their dominance for decades. Lately, gold catalysts have been emerging as a reliable contender for such transformations owing to the recent findings that reveal gold's potential beyond carbophilic π-Lewis acid. The newfound ability of gold to undergo redox transformations under certain circumstances has allowed us to explore gold catalysts as a viable alternative to other late transition-metals for efficient construction of cross-coupled products. This feature article critically presents an overview of all the redox neutral cross-coupling reactions enabled by gold catalysis, which we believe would stimulate further research activities in this promising area.

This feature article focuses on the bottom-up approaches (solution-phase) based on organic synthesis for the preparation of saddle-shaped distorted polycyclic aromatic hydrocarbons (PAHs). We summarise the recent progress on the synthetic strategies followed to obtain well-defined nanographenes containing heptagonal and octagonal carbocycles, highlighting the novel strategy developed by our group together with our recent contributions in the area of distorted aromatics. The presence of seven- or eight-membered rings induces a saddle-shape curvature in the planar network pushing the structure out of the plane, which influences the physical properties exhibited. Some brief details on the optical and electronic properties of these curved nanostructures are also discussed.

Recent advances in the sulfonylation of C–H bonds with the insertion of sulfur dioxide are summarized. C–H bond sulfonylation under transition metal catalysis or through a radical process has been developed. In some cases, the sulfonylation can be performed under catalyst- and additive-free conditions, or can be facilitated by visible light irradiation. The efficiency is also studied by merging the radical process and metal catalysis.

Over the past years, impressive progress has been made on the development of the chemoselective and direct formation of carbon-carbon and carbon-heteroatom bonds involving internal alkynes under catalytic oxidative systems. These transformations heavily rely on the in situ generation of reactive radical intermediates that are initiated by oxidants, visible light photocatalysis, or electrocatalysis and so on. Numerous chemically and biomedically important building blocks have been synthesized, and will continue to be obtained by taking advantage of the radical transformation of internal alkynes in the following years. In this review, we highlight the recent progress in this rapidly growing area by presenting a series of catalytic oxidative reactions, mechanisms and applications which have appeared in the most recent literature.

Rhodium-catalyzed and acid-controlled chemodivergent annulations between N -methoxybenzamides and sulfoxonium ylides have been realized.

Correction for 'Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction' by Diyang Zhang et al., Chem. Commun., 2018, DOI: 10.1039/c8cc00988k.

The MS-c anion has been encapsulated in cationic EB-COF to obtain Mo 3 S 13 @EB-COF, an efficient, stable and recyclable photocatalytic material. This encapsulation also achieved the conversion of a homogeneous catalyst to a heterogeneous one.

As a powerful synthon, pyrazolone has widely been exploited for the construction of various chiral pyrazoles/pyrazolones which hold great potential in the development of pharmaceutical chemistry, coordination chemistry and functional materials. Benefited from the diversity and multiple active sites of the starting materials, such as 4-nonsubstituted/4-monosubstituted pyrazolones and α,β-unsaturated pyrazolones, large numbers of strategies for the asymmetric synthesis of various pyrazoles/pyrazolones have been developed successfully in the past few years. This feature article summarizes these excellent research studies since 2015, including some efforts by our group. Based on the structural feature of the final products, this feature article is divided into four sections, including the catalytic asymmetric synthesis of 4-monosubstituted, 4-disubstituted, fused and spiro pyrazoles/pyrazolones. Schematic illustrations are given for some representative examples in each section.

A high voltage (1.38 V) total organic aqueous redox flow battery is reported using 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr)2V) as an anolyte and 4-trimethylammonium-TEMPO chloride (NMe-TEMPO) as a catholyte. The exceptional radical stability of [(NPr)2V]+˙ enabled the flow battery in achieving 97.48% capacity retention for 500 cycles and a power density of 128.2 mW cm-2.

A facile water bath method was developed to synthesize layered iron vanadate Fe 5 V 15 O 39 (OH) 9 ·9H 2 O (FVO) nanosheets. As a cathode material FVO delivers a high capacity of 385 mA h g −1 at 0.1 A g −1 due to the high proportion of variable valence elements (Fe and V). A remarkable cycling performance at a high current density is achieved in a Zn(TFSI) 2 electrolyte.

Renewable energy-driven hydrogen production from electrocatalytic and photocatalytic water splitting has been widely recognized as a promising approach to utilize green energy resources and hence reduces our dependence on legacy fossil fuels as well as alleviates net carbon dioxide emissions. The realization of large-scale water splitting, however, is mainly impeded by its slow kinetics, particularly because of its sluggish anodic half reaction, the oxygen evolution reaction (OER), whose product O2 is ironically not of high value. In fact, the co-production of H2 and O2 in conventional water electrolysis may result in the formation of explosive H2/O2 gas mixtures due to gas crossover and reactive oxygen species (ROS); both pose safety concerns and shorten the lifetimes of water splitting cells. With these considerations in mind, replacing the OER with thermodynamically more favorable organic oxidation reactions is much more preferred, which will not only substantially reduce the voltage input for H2 evolution from water and avoid the generation of H2/O2 gas mixtures and ROS, but…

This Feature Article is aimed at highlighting the recent developments in the transition-metal-free molecular rearrangements involving arynes. The chemistry of arynes has shown incredible developments especially in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions in the last three decades. The rapid growth in this field is mainly due to the development of mild methods for the generation of arynes. One aspect of the recent developments in the chemistry of arynes involves the molecular rearrangements proceeding via this electrophilic intermediate. The molecular rearrangements have provided direct access to a library of valuable molecules, which cannot be accessed in a single step through other synthetic routes. Herein, we present a concise account on the developments that occurred in this field over the last three decades.

The dominant charge transfer mechanism in a vast number of metal-organic frameworks (MOFs) is that of redox hopping, a process best explained through the motion of electrons via self-exchange reactions between redox centers coupled to the motion of counter-balancing ions. Mechanistic studies of redox hopping transport in MOFs reveal characteristics that recall pioneering studies in linear redox polymers. When MOFs are employed as electrocatalysts, consideration must be given to both the catalytic properties - turn-over frequency (TOF) and energetic requirements (overpotential, TON) - and the charge transport properties - rate of charge hopping, measured via an apparent diffusion coefficient (Dapp). Herein, we provide a mathematical framework to provide constraints to MOF catalyst development by relating Dapp, TOF, and film thickness in the context of providing 10 mA cm-2 of catalytic current. Lastly with the mechanistic studies discussed as a foundation, design rules for future MOF electrocatalysts are provided and the challenges to the community to optimize MOF charge transport are…

We prepare a totally nonflammable phosphate-based electrolyte composed of 5 mol L-1 (M) Li bis(fluorosulfonyl) imide (LiFSI) in a trimethyl phosphate (TMP) solvent. The concentrated 5 M LiFSI/TMP electrolyte shows good compatibility with graphite and no Al corrosion. More attractively, such a concentrated electrolyte can effectively suppress the growth of Li dendrites in Li metal batteries because of a stable LiF-rich SEI layer. Therefore, this highly concentrated electrolyte is promising for safe Li batteries.

We present a novel strategy for constructing three-dimensional (3D) porous Ti3C2Tx (MXene) networks by alkali-induced crumpling of Ti3C2Tx nanosheets. The 3D porous Ti3C2Tx networks display high capacity and outstanding rate performance as anode materials for sodium-ion batteries.

A PVP-assisted pyrolysis strategy that can simply but efficiently transform zeolitic imidazolate framework-67 (ZIF-67) into a Co-embedded N-enriched meso/microporous carbon material (Co-NC) is reported for the first time. Without further acid treatment, Co-NC can reach an excellent electroactivity and long-term durability toward the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER).

Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and fatty acids, were used for the extraction and separation of Cu(ii) from other transition metals in mildly acidic solutions. Multiple parameters were evaluated for metal extraction and the hydrophobic eutectic solvent was successfully recovered and reused.

, respectively. Furthermore, the electrocatalytic NRR mechanism on the NPC electrode was undoubtedly confirmed by electrochemical in situ Fourier transform infrared spectroscopy, and follows an associative pathway. These results are predicted to offer a new platform in the rational design and synthesis of highly efficient electrocatalysts for the NRR under ambient conditions.

Supramolecular delivery systems (SDSs) fabricated via molecular assembly, which conveniently allow integration of multiple functions in a single system and structural diversity of systems, are a very active research area due to their enormous potential in biomedical applications, including drug delivery, cell imaging, diagnosis, and release monitoring. Pillararenes, a novel type of macrocyclic molecule, are gaining increasing interest as an important component in the construction of SDSs due to their unique structural and chemical properties. This feature article summarizes pillararene-based SDSs constructed via host-guest interactions via four strategies: (1) supramolecular host-guest complexation; (2) self-assembly of supramolecular amphiphiles; (3) self-assembly of amphiphilic supramolecular polymer conjugates; (4) hybridization with other porous materials, such as inorganic materials and metal-organic frameworks (MOFs). The various SDSs based on pillararenes for the delivery of different cargoes from anti-cancer drugs, fluorescent molecules, siRNAs, and insulin to antibiotics…

Poly (ADP-ribose) polymerase-1 (PARP1) is a major member of the PARP superfamily that is involved in DNA damage signalling and other important cellular processes. Here we report the development of a small molecule targeting PARP1 based on the PROTAC strategy. In the MDA-MB-231 cell line, the representative compound 3 can induce significant PARP1 cleavage and programmed cell death.

A promising UV nonlinear optical material, beryllium-free nitrate Ba2NO3(OH)3, has been synthesized via modified high-temperature solid state reactions in a self-made high-pressure apparatus which exhibits a perfect balance of a large second harmonic generation coefficient, an appropriate birefringence for phase matching, a short UV absorption cutoff edge and physicochemical stabilities.

C-F bond activation has drawn a lot of attention in the past, and the case of C(sp3)-F bonds is particularly interesting as those are the strongest single bonds carbon makes with any other element. This Feature Article aims at highlighting our work and that of others on the successful approaches that led to the activation of such C-F bonds at benzylic, allylic, propargylic and allenylic positions, for both mono- and polyfluorides. We now hope that this will set ground for discussions, contribute to fostering new ideas, and thus help in pushing current frontiers further.

We report the synthesis of nanostructured Fe3S4 from deep eutectic solvents via a one-step solvothermal method. The as-obtained Fe3S4 catalyst was capable of electrochemically reducing N2 to NH3 under ambient conditions, and exhibits a high NH3 yield (75.4 μg h-1 mg-1cat.) and faradaic efficiency (6.45%) at -0.4 V vs. a reversible hydrogen electrode.

Here we report a flexible and rechargeable aqueous Zn-iodine battery with an iodine/carbon cloth cathode. Combined experimental and computational studies suggest that the battery undergoes a reversible reaction of Zn + I2 ↔ ZnI2 with suppressed I3- formation by confining iodine species in porous carbon.

Herein the first sustainable synthesis of quinoxalines, pyrazines and benzothiazoles catalysed by a phosphine free Mn(i) complex via acceptorless dehydrogenative coupling (ADC) is reported. This method is also applied successfully to synthesize quinolines via the dehydrogenation (removal of H2) and condensation (removal of H2O) reaction between 2-aminobenzyl alcohols and secondary alcohols.

A water-stable cationic MOF could be used as a single crystal container to capture Cr(vi)-oxyanions via ion exchange with high capacity and selectivity. It is the first report that demonstrates that CrO42- ions could be traced and confirmed via a single-crystal to single-crystal (SC-SC) pattern.

The radical copolymerization of the thionolactone dibenzo[c,e]oxepane-5-thione with acrylates, acrylonitrile, and N,N-dimethylacrylamide afforded copolymers containing a controllable amount of backbone thioesters which could be selectively cleaved. The process is compatible with RAFT polymerization and promising for the development of advanced degradable polymers.

A blue light-promoted cross-coupling of two distinct diazo compounds was described. The reaction produces E-configured trisubstituted alkenes in good yields in the absence of catalysts and additives. The reactive free carbene intermediates were generated via selective photolysis of one of the two diazo compounds upon blue light irradiation.

CO2 is a vital compond for life, and its concentration significantly affects the living environment of the Earth. Extensive effort has been devoted to balance its concentration. Among the developed approaches, photocatalytic CO2 conversion is considered as an ideal option. Previous reports suggest polymeric carbon nitride (PCN) can be effectively used as a metal-free photocatalyst to convert CO2. Herein, the recent developments of PCN and the related photocatalysts for CO2 conversion are summarized from the fundamental of using PCN, and their extended applications through molecular modification and physical/chemical coupling with other substances. The concluding remarks finally indicate the future challenges of using PCN materials for relevant solar-driven applications.

The free energy landscape concept that describes enzymes as an ensemble of differently populated conformational sub-states in dynamic equilibrium is key for evaluating enzyme activity, enantioselectivity, and specificity. Mutations introduced in the enzyme sequence can alter the populations of the pre-existing conformational states, thus strongly modifying the enzyme ability to accommodate alternative substrates, revert its enantiopreferences, and even increase the activity for some residual promiscuous reactions. In this feature article, we present an overview of the current experimental and computational strategies to explore the conformational free energy landscape of enzymes. We provide a series of recent publications that highlight the key role of conformational dynamics for the enzyme evolution towards new functions and substrates, and provide some perspectives on how conformational dynamism should be considered in future computational enzyme design protocols.

Deep eutectic solvents (DESs) have been considered as a new class of green solvents with tunable physical properties based on the selective combination of their individual components. As the liquid window of a DES identifies the range of feasible applications, it is essential to determine, quantify, and predict their phase behavior. Phase diagrams were measured for systems consisting of tetrapentylammonium bromide and erythritol or succinic acid. Regular solution theory is applied to quantitatively describe the liquid window of DESs. The succinic acid mixture shows a larger deviation from ideal behavior, caused by the stronger hydrogen bond forming acid groups. The interaction parameter between the two DES components in regular solution theory could be determined directly from the eutectic temperature of the mixture and this enables quantification of the degree of non-ideality of DESs.

Recent years have witnessed the exploration and synthesis of an increasing number of metal-organic frameworks (MOFs). The utilization of stable MOFs as a platform for catalysis and biomimetics is discussed. This Feature Article will provide insights into the rational design and synthesis of three types of stable MOF catalysts on the basis of structural features of MOFs, that is, (i) MOF catalysts with catalytic sites on metal nodes, (ii) MOF catalysts with catalytic sites immobilized in organic struts, and (iii) MOF catalysts with catalytic centres encapsulated in the pores. Then, MOFs used in biomimetics including biomimetic mineralization, biosensors and biomimetic replication are introduced. Finally, a discussion on the challenges that must be addressed for successful implementation of MOFs in catalysis and biomimetics is presented.

A fluorescent covalent organic framework (COF), featuring precise distribution of thioether pendant arms inside the cavity, was designed. The thioether-functionalized COF exhibits selective sensing and capture of Au ions at ultra-trace levels in water with high sensitivity, selectivity and adsorption capacity, which makes it an excellent candidate for selective detection and recovery of Au.

Perovskite solar cells (PSCs) reached a certified 23.7% efficiency in 2018 by boosting their surprisingly high open-circuit voltage (VOC) and photocurrent. The suppressed recombination in PSCs significantly cut down the voltage loss between the bandgap energy and VOC, which encouraged the VOC to reach closer to the bandgap. In addition, the photocurrent is considerably closer to the theoretical value at a given bandgap, leaving almost no room for further improvement. This remarkable development in the performance of PSCs is mainly ascribed to high-quality perovskite material being consistently tailored in the progress of technology. At the beginning of the progress, the morphology of the perovskite was a major target for improvement to enhance the crystal quality. The need for compositional engineering of the perovskite was raised in later stages of the progress by considering the benefits from different compositions of perovskites and their structural stability. Here we review the overall progress in perovskite materials from two perspectives: morphological progress and…

A hierarchical NiO/C hollow sphere composite (NiO/C-HS) was prepared via semi-sacrificial template-assisted hydrothermal and calcination methods. NiO/C-HS, with well-dispersed NiO nanosheets supported by carbon hollow spheres, exhibited excellent electrochemical performance. The method was heuristic for the design of other composites and suitable for ameliorating the poor stability of transition metal oxides.

As a promising low-cost solar energy conversion technique, dye-sensitized solar cells have undergone spectacular development since 1991. For practical applications, improvement of power conversion efficiency has always been one of the major research topics. Porphyrins are outstanding sensitizers endowed with strong sunlight harvesting ability in the visible region and multiple reaction sites available for functionalization. However, judicious molecular design in consideration of light-harvest, energy levels, operational dynamics, adsorption geometry and suppression of back reactions is specifically required for achieving excellent photovoltaic performance. This feature article highlights some of the recently developed porphyrin sensitizers, especially focusing on the systematic dye structure optimization approach in combination with coadsorption and cosensitization methods in pursuing higher efficiencies. Herein, we expect to provide more insights into the structure-performance correlation and molecular engineering strategies in a stepwise manner.

Alkaline water splitting offers a simple method for the mass production of hydrogen but suffers from the sluggish kinetics of the anodic oxygen evolution reaction (OER). Here, we report on the development of an Fe-doped NiCr2O4 nanoparticle film on Ni foam (Fe-NiCr2O4/NF) as a non-noble-metal OER electrocatalyst with superior catalytic activity at alkaline pH. Such Fe-NiCr2O4/NF demands overpotentials as low as 228 and 318 mV to drive current densities of 20 and 500 mA cm-2, respectively, in 1.0 M KOH. Notably, it also shows strong long-term electrochemical durability with its activity being retained for at least 60 h.

We introduce a novel strategy to enhance the fluorescence brightness of organic-molecule-based nanoparticles in the second near-infrared window (NIR-II, 1000-1700 nm) by fabricating J-aggregate nanoparticles SQP-NPs(J). Our prepared J-aggregate nanoparticles SQP-NPs(J) show an emission maximum near 1100 nm, and the emission intensity is 4.8-fold higher than that of H-aggregate SQP-NPs(H). In addition, SQP-NPs(J) can be used for NIR-II imaging guided photothermal therapy on MCF-7 tumor-bearing mice due to the fact that SQP-NPs(J) have highly effective photothermal properties, which are significant for precise tumor diagnostics and treatments.

Inert chemical bond cleavage and functionalization reactions provide expedient synthetic routes and are fundamental in organic synthesis. Alkoxyl radicals enable inert chemical bond cleavages by hydrogen atom transfer and β-fragmentation reactivity; however their further synthetic transformations and functional group compatibility are limited by traditional alkoxyl radical generation methods. Recently, visible-light-induced alkoxyl radical generation methods have emerged and led to new advancements in inert chemical bond cleavage reactions and subsequent functionalization, with excellent chemoselectivity and functional group compatibility. In this Feature Article, the generation of alkoxyl radicals by different visible-light-induced methods and their common or distinct reactivity are discussed, which are categorized by C(sp3)-H, C(sp3)-C(sp3), and C(sp3)-X bond cleavages and subsequent transformations.

C7-Decorated indoles are important structural motifs present in a plethora of bioactive and pharmaceutical compounds. Early stage developments for C7 modifications were realized through directed metallation (DOM) and subsequent quenching with suitable electrophiles or by halogenation with Cu(ii) halides. Direct C-7 functionalization of indoles is comparatively difficult compared to functionalization at C-2 and C-3 positions owing to the inherent reactivity of the pyrrole-type ring. However, recently transition-metal-catalyzed auxiliary assisted site-selective C-7 functionalization of indoles has emerged as an elegant synthetic tool for carbon-carbon and carbon-heteroatom bond formation to diversify the indoles. This article covers the advancement, application and mechanistic underpinnings of the evolved transformations of the otherwise inert C7-H bond up to October 2018.

Recent advances in transition metal-catalyzed selective C-H functionalization of indoles have garnered tremendous attention. Great efforts have been devoted to C2 and C3 arylation because of the inherent reactivity of the pyrrole ring. Until recently, elegant methods have been developed to enable selective direct arylation on the benzenoid moiety at C4, C5, C6, and C7. This review highlights the contributions made in benzenoid direct arylation of indoles and presents their potential in organic synthesis.

Timely detection of toxic vapor is vital for safeguarding people's lives. Herein, we design a plasmonic nose based on a zeolitic imidazolate framework (ZIF)-encapsulated Ag nanocube array for ultratrace recognition of VOC vapor. The plasmonic nose enables in situ adsorption kinetics and recognition of various VOCs at ppm levels, eliminating false positives. Our approach provides a paradigm shift to next-generation, effective and specific gas sensors.

Synthetic macrocyclic receptors generally display unique geometries, preorganized cavities, and tunable binding affinities, which facilitate their application in numerous fields including molecular recognition and self-assembly. Calix[n]arenes and pillar[n]arenes are very prevalent synthetic macrocyclic arenes, whose syntheses, host-guest properties, and supramolecular functions have been intensively studied. In recent years, some new families of synthetic macrocyclic arenes closely related to calix[n]arenes and pillar[n]arenes have emerged and represent new opportunities in modern supramolecular chemistry. Therefore, in this feature article, we present a comprehensive discussion on some newly designed, versatile macrocyclic arene receptors that sprang up during the past decade, focusing on their syntheses, structures, functionalization, and host-guest properties. Future perspectives of synthetic macrocyclic arene chemistry are also given. We hope that this feature article will be a timely and useful reference for those who are exploring new opportunities in functional macrocycles.

Nanozymes have been viewed as the next generation of artificial enzymes due to their low cost, large specific surface area, and good robustness under extreme conditions. However, the moderate activity and limited selectivity of nanozymes have impeded their usage. To overcome these shortcomings, integrated nanozymes (INAzymes) have been developed by encapsulating two or more different biocatalysts (e.g., natural oxidases and peroxidase mimics) together within confined frameworks. On the one hand, with the assistance of natural enzymes, INAzymes are capable of specifically recognizing targets. On the other hand, nanoscale confinement brought about by integration significantly enhances the cascade reaction efficiency. In this Feature Article, we highlight the newly developed INAzymes, covering from synthetic strategies to versatile applications in biodetection and therapeutics. Moreover, it is predicted that INAzymes with superior activities, specificity, and stability will enrich the research of nanozymes and pave new ways in designing multifunctional nanozymes.

Platinum(iv) prodrugs of clinically used cisplatin and oxaliplatin with two axial long lipid chains were developed for nanoparticle delivery to combat cisplatin resistance.

Negative thermal expansion (NTE), whereby lattices contract upon heating, is of considerable interest for its wide applications in many fields. Molecular materials have been widely investigated as catalysts, sensors, etc., which usually endure temperature vibration. NTE can become a substantial means for controlling the coefficients of thermal expansion. Molecular materials possess plentiful structures and can be easily decorated, making them ideal platforms for thermal expansion modification. In this feature article, we provide an overview of the recent developments in utilizing NTE in molecular materials and summarize some mechanisms leading to NTE. The discussion of NTE in molecular materials concerns many factors, including transverse vibration, geometric flexibility, host-guest interactions, spin crossover, molecular packing rearrangement and molecular conformational changes.

NH3 is one of the most important chemicals with a wide range of applications. NH3 is mainly produced via the Haber-Bosch process, which leads to large energy consumption and carbon emission. Electrochemical reduction has emerged as an environmentally-benign and sustainable alternative for artificial N2 fixation under ambient conditions, but needs materials to effectively catalyze the N2 reduction reaction (NRR). In this communication, we report that β-FeOOH nanorods behave as an efficient and durable NRR electrocatalyst. In 0.5 M LiClO4, such an electrocatalyst achieves a high NH3 yield of 23.32 μg h-1 mgcat.-1 and a faradaic efficiency of 6.7%, outperforming most reported aqueous-based NRR electrocatalysts under ambient conditions. Notably, this catalyst also shows good electrochemical stability and excellent selectivity. The catalytic mechanism of the NRR on the FeOOH(110) surface is further discussed using density functional theory calculations.

A new phosphine-free Co(ii) complex-catalyzed synthesis of various quinoxalines via dehydrogenative coupling of vicinal diols with both o-phenylenediamines and 2-nitroanilines is reported. This complex was also effective for the synthesis of quinolines. The practical aspect of this catalytic system was revealed by the one-pot synthesis of 2-alkylaminoquinolines.

Photocatalytic H2O2 production via two-electron reduction of O2 was realized by visible-light irradiation of a metal-organic framework, MIL-125-NH2, in the presence of TEOA and benzylalcohol. Deposition of NiO nanoparticles onto MIL-125-NH2 dramatically enhanced the catalytic activity. Further studies suggested that fast disproportionation of the O2˙- intermediate to H2O2 resulted in the enhancement.

A ZnCrOx-ZnZSM-5 composite catalyst was used for CO2 hydrogenation into hydrocarbons especially aromatics (Aro). 81.1% Aro selectivity in C5+ hydrocarbons (mainly C5-11) was obtained at 320 °C, corresponding to 19.9% CO2 conversion, 29.8% total hydrocarbons (HCt) selectivity and 69.7% C5+ selectivity in HCt. Our optimized STY of Aro is the highest ever reported.

A label-free nanozyme MIL-53(Fe) with the dual-function of catalyzing and emitting fluorescence was utilized for turn-on fluorescence detection of hydrogen peroxide and glucose. The proposed strategy provides a cost-effective, safe and sensitive method for the design and development of multiple enzyme cascade assays for various biomolecules.

[FeFe]-Hydrogenases are the most efficient enzymes for catalytic hydrogen turnover. Their H2 production efficiency is hitherto unrivalled. However, functional details of the catalytic machinery and possible modes of application are discussed controversially. The incorporation of synthetically modified cofactors and utilization of semi-artificial enzymes only recently allowed us to shed light on key steps of the catalytic cycle. Herein, we summarize the essential findings regarding the redox chemistry of [FeFe]-hydrogenases and discuss their catalytic hydrogen turnover. We furthermore will give an outlook on potential research activities and exploit the utilization of synthetic cofactor mimics.

NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

From discrete and dispersed to condensed and organized, directed assembly provides a link between molecular structure and macroscopic properties. If we are able to combine several different molecular entities within the same crystalline lattice and make co-crystals, then we can also access a wider chemical space whilst circumventing the need for complex covalent synthesis. Co-crystal technology can offer versatile avenues for the design and preparation of new solid forms that have tunable physical properties. All of this, however, requires an improved understanding of intermolecular interactions-over the full range of molecular size and structure. In this perspective, we highlight some strategies and protocols that have been developed in order to synthesize co-crystals with predetermined and desirable structural features.

Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent of that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters and the distinct nature of boron-halogen/boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can…

Carbon dots have a wide range of applications in biological and medical fields as an alternative to quantum dots because of their low toxicity and excellent luminescence properties. To date, a large number of carbon dots have been prepared and they were consequently reviewed according to their synthetic method, luminescence properties and related applications. The dispersibility of carbon dots in aqueous and/or organic solvents could actually play a significant role in the properties and various application fields, however, such a perspective is ignored by most of the reviewed literature studies. Thus in this minireview, we focus on the surfactant groups of carbon dots which could be classified as hydrophilic, hydrophobic and amphiphilic types. They have accordingly a marked impact on the dispersibility of carbon dots in different solvents as well as the further advantage in those imaging studies in vitro and in vivo.

Diabetes is a global epidemic that threatens the health and well-being of hundreds of millions of people. The first step in patient treatment is to monitor glucose levels. Currently this is most commonly done using enzymatic strips. This approach suffers from several limitations, namely it requires a blood sample and is therefore invasive, the quality and the stability of the enzymatic strips vary widely, and the patient is burdened by performing the measurement themselves. This results in dangerous fluctuations in glucose levels often going undetected. There is currently intense research towards new approaches in glucose detection that would enable non-invasive continuous glucose monitoring (CGM). In this review, we explore the state-of-the-art in glucose detection technologies. In particular, we focus on the physical mechanisms behind different approaches, and how these influence and determine the accuracy and reliability of glucose detection. We begin by reviewing the basic physical and chemical properties of the glucose molecule. Although these play a central role in detection,…

A robust fluorescent probe CTPA has been rationally designed for cancer diagnosis by monitoring lipid drop (LD) polarity and number variation. With the outstanding properties of CTPA, we have shown that the diagnosis of cancer can be achieved not only at the cellular levels but also in organs and living mice for the first time.

The majority of known chemiluminescent compounds produce light through oxidation-dependent mechanisms. The unique notion of triggering chemiluminescence by a chemical reaction other than oxidation was first introduced by Schaap in 1987 with the development of chemically and enzymatically activated phenoxy-dioxetanes. Such dioxetanes are distinctive among chemiluminescent molecules since the oxidized high-energy species, the dioxetane, is stable for years at room temperature. Light emission is selectively activated by deprotection of the phenol-protecting group. The chemiluminescence quantum yields of such dioxetanes are relatively high in organic solvents like DMSO. In aqueous solution, however, light emission efficiency drops by approximately 10 000-fold due to energy loss to water molecules. As we sought to understand the low light emission efficiency in water, we realized that the dioxetane chemiexcitation leads to the release of an excited state benzoate molecule, which is a very weak emitter under aqueous conditions. Thus, we reasoned that emission in aqueous solution could be…

in deep tissues and eradicate tumors with high efficacy. This platform paves the way for the application of 2D semiconductors in sonodynamic cancer therapy.

The first examples of through-space conjugated thermally activated delayed fluorescence (TADF) emitters based on a [2.2]paracyclophane (PCP) skeleton with stacked (coplanar) donor-acceptor groups have been synthesized. The optoelectronic properties are studied by the relative configuration, cis (pseudo-geminal) and trans (pseudo-para), of the donor and acceptor groups.

We report an in situ analysis of nano-micro sodium deposition in an ester-based electrolyte using atomic force microscopy. It is found that sodium dendrites are effectively suppressed by adding fluoroethylene carbonate (FEC) as an electrolyte additive. The decomposition of FEC provides a NaF-containing solid electrolyte interphase with homogenous morphology and high modulus, leading to stable sodium deposition and high Coulombic efficiency (88% over 50 cycles) of the sodium metal anode.

The synthesis of core/shell perovskite nanocrystals was demonstrated for the first time by applying a seeded growth approach. The obtained core/shell nanocrystals were shown to consist of a light-emitting CsPbX3 core with a narrow band gap and a Cs4PbX6 passivating shell with a large band gap (>3.2 eV), and to therefore display an improved photoluminescence quantum yield.

Electrochemical N2-to-NH3 fixation under ambient conditions is emerging as a promising alternative to the energy-intensive and CO2-emitting Haber-Bosch process. However, this process involves difficulty in N2 activation, underlining the demand of electrocatalysts for the N2 reduction reaction (NRR). In this work, cubic sub-micron SnO2 particles on carbon cloth (SnO2/CC) are proposed as an efficient NRR electrocatalyst for ambient N2 conversion to NH3 with excellent selectivity. Electrochemical tests reveal that SnO2/CC attains a large NH3 yield of 1.47 × 10-10 mol s-1 cm-2 at -0.8 V vs. reversible hydrogen electrode (RHE) and a high Faradaic efficiency of 2.17% at -0.7 V vs. RHE in 0.1 M Na2SO4, outperforming most reported aqueous-based NRR electrocatalysts. Notably, it also shows strong electrochemical stability.

In this communication, we demonstrate the development of hierarchical CoTe2-MnTe2 hybrid nanowires grown on Ti mesh (CoTe2-MnTe2/TM) as an electrocatalyst for the oxygen evolution reaction. The catalyst exhibits excellent conductivity and exposes sufficient active sites derived from its favorable composition and structure, which only needs an overpotential of 310 mV to drive a current density of 50 mA cm-2 in 1.0 M KOH.

Cs3Bi2Br9 quantum dots (QDs) with photoluminescence quantum yields (PLQYs) of up to 22% were prepared through the steady binding of octylammonium bromide and oleic acid. Excellent thermal stability and good luminescence properties have been achieved as intrinsic features of the inorganic halide perovskites, as well as the effective passivation of surface trap-states.

In this study, metal-organic frameworks, as an interfacial layer, were introduced into perovskite solar cells (PSCs) for the first time. An interface modified with the metal-organic framework ZIF-8 efficiently enhanced perovskite crystallinity and grain sizes, and the photovoltaic performance of the PSCs was significantly improved, resulting in a maximum PCE of 16.99%.

A novel room temperature phosphorescent material has been developed by the use of luminescent organic rigid poly-imidazole moieties coordinating to a zinc phosphite framework, which shows excellent thermal and mechanical stability.

Resonant acoustic mixing (RAM) is a new technology designed for intensive mixing of powders that offers the capability to process powders with minimal damage to particles. This feature is particularly important for mixing impact-sensitive materials such as explosives and propellants. While the RAM technique has been extensively employed for the mixing of powders and viscous polymers, comparatively little is known about its use for mechanosynthesis. We present here the first in situ study of RAM-induced co-crystallisation monitored using synchrotron X-ray powder diffraction. The phase profile of the reaction between nicotinamide and carbamazepine in the presence of a small amount of water was monitored at two different relative accelerations of the mixer. In marked contrast to ball-milling techniques, the lack of milling bodies in the RAM experiment does not hinder co-crystallisation of the two starting materials, which occurred readily and was independent of the frequency of oscillation. The reaction could be optimised by enhancing the number of reactive contacts through mixing and…

mp-MXene/TiO2-x nanodots (NDs) structurally composed of microporous MXene monolayers embedded with Ti3+-doped TiO2 nanodots were developed for the first time. The drastically enhanced catalytic efficiency (as much as 13 times higher than that of P25) in degrading dye molecules over mp-MXene/TiO2-x NDs is due to a synergistic effect of the pseudo-Fenton reaction and photocatalysis.

This feature article summarizes the recent progress in porous perovskite oxides as advanced catalysts for both energy conversion applications and various heterogeneous reactions. Recently, research has been focused on specifically designing porous perovskite materials so that large surface areas can be harnessed and surface properties can be improved. Numerous potential applications of porous perovskites have been investigated, including heterogeneous catalysis and air battery applications that rely on interactions and/or reactions of other components with porous perovskites. The main objective of this article is to examine the progress of recent research studies on porous perovskite nanomaterials, including the preparation methods and their applications in catalysis and batteries. The wide variety of the related knowledge on porous mixed oxides can provide guidance for researchers with interests ranging from the design of functionalized materials to the field of heterogeneous catalysis and electrochemical applications.

This review describes how one can perform nanometer (nm)-scale SECM experiments through advances in tip fabrication and positioning and instrumentation design. Basic SECM methodology including instrumentation and feedback and generation/collection modes are discussed. Aspects of nanoscale SECM including fabrication of nm-sized electrodes and nano SECM instrumentation are also described. State of the art applications related to nanogaps (i.e., rapid homogeneous reactions and short-lived intermediates; heterogeneous electron transfer kinetics; nanoparticles (NPs) and clusters) and nanoscale imaging (e.g., single NPs, single biological samples, combined methods) are described. Future possibilities and prospects are suggested that might lead to even better resolution, thus introducing SECM electrochemical imaging to the single atom level.