The 100 most-cited articles in Angewandte Chemie, 2018

Abstract Two‐dimensional (2D) titanium carbide (Ti 3 C 2 ) is emerging as an important member of the MXene family. However, fluoride‐based synthetic procedures remain an impediment to the practical applications of this promising class of materials. Here we demonstrate an efficient fluoride‐free etching method based on the anodic corrosion of titanium aluminium carbide (Ti 3 AlC 2 ) in a binary aqueous electrolyte. The dissolution of aluminium followed by in situ intercalation of ammonium hydroxide results in the extraction of carbide flakes (Ti 3 C 2 T x , T=O, OH) with sizes up to 18.6 μm and high yield (over 90 %) of mono‐ and bilayers. All‐solid‐state supercapacitor based on exfoliated sheets exhibits high areal and volumetric capacitances of 220 mF cm −2 and 439 F cm −3 , respectively, at a scan rate of 10 mV s −1 , superior to those of LiF/HCl‐etched MXenes. Our strategy paves a safe way to the scalable synthesis and application of MXene materials.

Abstract Conjugated carbon nitride (CN) is an emerging and promising semiconductor photocatalyst for water photolysis owing to its unique properties. However, the traditional thermally induced polymerization of N‐containing precursors typically produces melon‐based CN solids with amorphous or semi‐crystalline structures with only moderate photocatalytic performance. Many strategies have been developed to prepare crystalline CNs (CCNs), such as high‐temperature and high‐pressure routes, ionothermal synthesis, and microwave‐assisted synthesis. In this Minireview, we summarize the progress that has been made in the synthesis of CCNs and their application in photocatalytic water splitting reactions. Three kinds of CCNs are mainly discussed according to their polymeric subunits. Challenges associated with CCNs and their future development are also included.

Abstract Die Photokatalyse mit sichtbarem Licht hat sich im letzten Jahrzehnt zu einer breit angewandten Methode in der organischen Synthese entwickelt. Für viele wichtige Reaktionen, wie Kreuzkupplungen, α‐Amino‐Funktionalisierungen, Cycloadditionen, ATRA‐Reaktionen oder Fluorierungen, wurden photokatalytische Varianten berichtet. Um Chemiker bei der Auswahl photokatalytischer Methoden für ihre Synthesen zu unterstützen, vergleichen wir in diesem Aufsatz klassische und photokatalytische Verfahren für ausgewählte Reaktionsklassen und zeigen deren Vorteile und Grenzen auf. In vielen Fällen verlaufen die photokatalytischen Reaktionen unter milderen Reaktionsbedingungen, typischerweise bei Raumtemperatur, und stöchiometrische Reagenzien werden durch einfache Oxidanzien oder Reduktionsmittel wie Luft, Sauerstoff oder Amine ersetzt. Beeinflusst die Photokatalyse mit sichtbarem Licht die organische Synthese? Die Aussicht, Elektronen zu Substraten und Zwischenprodukten hin‐ und herzuschieben oder Energie selektiv durch einen sichtbares Licht absorbierenden Photokatalysatoren zu übertragen,…

Abstract Spontaneously solar‐driven water splitting to produce H2 and O2, that is, the conversion of solar energy to chemical energy is a dream of mankind. However, it is difficult to make overall water splitting feasible without using any sacrificial agents and external bias. Drawing inspiration from nature, a new artificial Z‐scheme photocatalytic system has been designed herein based on the two‐dimensional (2D) heterostructure of black phosphorus (BP)/bismuth vanadate (BiVO4). An effective charge separation makes possible the reduction and oxidation of water on BP and BiVO4, respectively. The optimum H2 and O2 production rates on BP/BiVO4 were approximately 160 and 102 μmol g−1 h−1 under irradiation of light with a wavelength longer than 420 nm, without using any sacrificial agents or external bias.

Abstract MXenes, 2D compounds generated from layered bulk materials, have attracted significant attention in energy‐related fields. However, most syntheses involve HF, which is highly corrosive and harmful to lithium‐ion battery and supercapacitor performance. Here an alkali‐assisted hydrothermal method is used to prepare a MXene Ti3C2Tx (T=OH, O). This route is inspired from a Bayer process used in bauxite refining. The process is free of fluorine and yields multilayer Ti3C2Tx with ca. 92 wt % in purity (using 27.5 m NaOH, 270 °C). Without the F terminations, the resulting Ti3C2Tx film electrode (ca. 52 μm in thickness, ca. 1.63 g cm−3 in density) is 314 F g−1 via gravimetric capacitance at 2 mV s−1 in 1 m H2SO4. This surpasses (by ca. 214 %) that of the multilayer Ti3C2Tx prepared via HF treatments. This fluorine‐free method also provides an alkali‐etching strategy for exploring new MXenes for which the interlayer amphoteric/acidic atoms from the pristine MAX phase must be removed.

Abstract Die direkte Nutzung von Elektrizität für die organische Synthese erlebt derzeit eine Renaissance. Von den eher syntheseorientierten Laboratorien, die auf diesem Gebiet arbeiten, werden neuartige oder althergebrachte Konzepte genutzt, um den Weg von der Nischentechnologie zu breiteren Anwendungen zu ebnen. Da nur Elektronen als Reagens genutzt werden, wird die Bildung von Abfallreagentien effizient vermieden. Darüber hinaus können stöchiometrische Reagentien regeneriert werden und ermöglichen eine elektrokatalysierte Umsetzung. Die Anwendung von elektroorganischen Transformationen ist jedoch mehr als nur die Minimierung des Abfallaufkommens; sie führt vielmehr zu inhärent sicheren Prozessen, zur Abkürzung vieler Synthesestufen, zu milderen Reaktionsbedingungen, zu alternativen Zugängen zu gewünschten Struktureinheiten sowie zur Schaffung neuer Bereiche für geistiges Eigentum (Patente). Wenn die verwendete Elektrizität aus regenerativen Ressourcen stammt, kann dieser Stromüberschuss direkt als terminales Oxidations‐ oder Reduktionsmittel eingesetzt werden, was eine äußerst…

Abstract Chemodynamic therapy (CDT) utilizes iron‐initiated Fenton chemistry to destroy tumor cells by converting endogenous H2O2 into the highly toxic hydroxyl radical (.OH). There is a paucity of Fenton‐like metal‐based CDT agents. Intracellular glutathione (GSH) with .OH scavenging ability greatly reduces CDT efficacy. A self‐reinforcing CDT nanoagent based on MnO2 is reported that has both Fenton‐like Mn2+ delivery and GSH depletion properties. In the presence of HCO3−, which is abundant in the physiological medium, Mn2+ exerts Fenton‐like activity to generate .OH from H2O2. Upon uptake of MnO2‐coated mesoporous silica nanoparticles (MS@MnO2 NPs) by cancer cells, the MnO2 shell undergoes a redox reaction with GSH to form glutathione disulfide and Mn2+, resulting in GSH depletion‐enhanced CDT. This, together with the GSH‐activated MRI contrast effect and dissociation of MnO2, allows MS@MnO2 NPs to achieve MRI‐monitored chemo–chemodynamic combination therapy.

Abstract Die stoffliche Nutzung von Elektrizität anstelle stöchiometrischer Mengen an Oxidations‐ oder Reduktionsmitteln ist ökonomisch und ökologisch sehr attraktiv und stellt eine wichtige Triebkraft für die Forschungen in der Elektrosynthese dar. Um den Elektronentransfer an der Elektrode für eine organische Umsetzung zu nutzen, müssen die intermediär gebildeten Radikalspezies stabilisiert werden. Die Kombination der Elektrosynthese mit anderen Ansätzen der organischen Chemie oder aktuellen Synthesekonzepten ermöglicht die Entwicklung effizienter Synthesewege. Die zentrale Aufgabe des 21. Jahrhunderts besteht darin, möglichst wenig fossilen Kohlenstoff zu verwenden, weshalb die Nutzung erneuerbarer Energien immer wichtiger wird. Von steigendem Interesse ist auch die direkte Umsetzung erneuerbarer Rohstoffe, die zuvor hauptsächlich verbrannt wurden. Dieser Aufsatz gibt einen Überblick über viele der wichtigsten, zukunftsweisenden Entwicklungen der letzten Zeit, welche die Zukunft dieses sich rasch entwickelnden Feldes bestimmen werden.

Abstract Tailored to the specific tumour microenvironment, which involves acidity and the overproduction of hydrogen peroxide, advanced nanotechnology has been introduced to generate the hydroxyl radical ( . OH) primarily for tumour chemodynamic therapy (CDT) through the Fenton and Fenton‐like reactions. Numerous studies have investigated the enhancement of CDT efficiency, primarily the increase in the amount of . OH generated. Notably, various strategies based on the Fenton reaction have been employed to enhance . OH generation, including nanomaterials selection, modulation of the reaction environment, and external energy fields stimulation, which are discussed systematically in this Minireview. Furthermore, the potential challenges and the methods used to facilitate CDT effectiveness are also presented to support this cutting‐edge research area.

Abstract Halide perovskite quantum dots (QDs) have great potential in photocatalytic applications if their low charge transportation efficiency and chemical instability can be overcome. To circumvent these obstacles, we anchored CsPbBr 3 QDs (CPB) on NH x ‐rich porous g‐C 3 N 4 nanosheets (PCN) to construct the composite photocatalysts via N−Br chemical bonding. The 20 CPB‐PCN (20 wt % of QDs) photocatalyst exhibits good stability and an outstanding yield of 149 μmol h −1 g −1 in acetonitrile/water for photocatalytic reduction of CO 2 to CO under visible light irradiation, which is around 15 times higher than that of CsPbBr 3 QDs. This study opens up new possibilities of using halide perovskite QDs for photocatalytic application.

Abstract Rechargeable batteries have been used to power various electric devices and store energy from renewables, but their toxic components (namely, electrode materials, electrolyte, and separator) generally cause serious environment issues when disused. Such toxicity characteristic makes them difficult to power future wearable electronic devices. Now an environmentally friendly and highly safe rechargeable battery, based on a pyrene‐4,5,9,10‐tetraone (PTO) cathode and zinc anode in mild aqueous electrolyte is presented. The PTO‐cathode shows a high specific capacity (336 mAh g−1) for Zn2+ storage with fast kinetics and high reversibility. Thus, the PTO//Zn full cell exhibits a high energy density (186.7 Wh kg−1), supercapacitor‐like power behavior and long‐term lifespan (over 1000 cycles). Moreover, a belt‐shaped PTO//Zn battery with robust mechanical durability and remarkable flexibility is first fabricated to clarify its potential application in wearable electronic devices.

Abstract Constructing efficient catalysts for the N2 reduction reaction (NRR) is a major challenge for artificial nitrogen fixation under ambient conditions. Herein, inspired by the principle of “like dissolves like”, it is demonstrated that a member of the nitrogen family, well‐exfoliated few‐layer black phosphorus nanosheets (FL‐BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 μg h−1 mg−1cat. under ambient conditions. Density functional theory calculations reveal that the active orbital and electrons of zigzag and diff‐zigzag type edges of FL‐BP NSs enable selective electrocatalysis of N2 to NH3 via an alternating hydrogenation pathway. This work proves the feasibility of using a nonmetallic simple substance as a nitrogen‐fixing catalyst and thus opening a new avenue towards the development of more efficient metal‐free catalysts.

Abstract The development of new nonlinear optical (NLO) materials for deep‐ultraviolet (DUV) applications is in great demand. However, the synthesis of an ideal DUV NLO crystal is a serious challenge. Herein, three new alkali‐metal fluorooxoborates, AB 4 O 6 F (A=K, Rb, and Cs, and a mixed cation between two of them), were successfully synthesized by cation regulation. It is found that all reported compounds exhibit short UV absorption edges (<190 nm), and show second harmonic generation (SHG) responses ranging from 0.8 to 1.9 KH 2 PO 4 (KDP). Interestingly, by judicious selection of the A‐site alkali‐metal cations, the arrangement of NLO‐active structural units is fine‐tuned to an optimal configuration, which contributes to large SHG responses.

Abstract A novel fluorescent probe was developed by integrating chlorinated coumarin and benzothiazolylacetonitrile and exploited for simultaneous detection of cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). Featuring four binding sites and different reaction mechanisms for different biothiols, this probe exhibited rapid fluorescence turn‐on for distinguishing Cys, Hcy, and GSH with 108‐, 128‐, 30‐fold fluorescence increases at 457, 559, 529 nm, respectively, across different excitation wavelengths. Furthermore, the probe was successfully applied to the fluorescence imaging of endogenous Cys and GSH and exogenous Cys, Hcy, and GSH in living cells.

Abstract N2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH3 production, which still heavily relies on the Haber–Bosch process at the cost of huge energy and massive production of CO2. A noble‐metal‐free Bi4V2O11/CeO2 hybrid with an amorphous phase (BVC‐A) is used as the cathode for electrocatalytic NRR. The amorphous Bi4V2O11 contains significant defects, which play a role as active sites. The CeO2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi4V2O11 for rapid interfacial charge transfer. Remarkably, BVC‐A shows outstanding electrocatalytic NRR performance with high average yield (NH3: 23.21 μg h−1 mg−1cat., Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi4V2O11/CeO2 hybrid with crystalline phase (BVC‐C) counterpart.

Abstract Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing picture for the conversion of N 2 into NH 3 . However, electrocatalytic NRR mainly relies on metal‐based catalysts, and it remains a grand challenge in enabling effective N 2 activation on metal‐free catalysts. Here we report a defect engineering strategy to realize effective NRR performance (NH 3 yield: 8.09 μg h −1 mg −1 cat. , Faradaic efficiency: 11.59 %) on metal‐free polymeric carbon nitride (PCN) catalyst. Illustrated by density functional theory calculations, dinitrogen molecule can be chemisorbed on as‐engineered nitrogen vacancies of PCN through constructing a dinuclear end‐on bound structure for spatial electron transfer. Furthermore, the N−N bond length of adsorbed N 2 increases dramatically, which corresponds to “strong activation” system to reduce N 2 into NH 3 . This work also highlights the significance of defect engineering for improving electrocatalysts with weak N 2 adsorption and activation ability.

Abstract As electron transfer to CO2 is generally considered to be the critical step during the activation of CO2, it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO2 activation by introducing oxygen vacancies into electrocatalysts with electronic‐rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of −16.1 mA cm−2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO2. Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO2 and the eased CO2 activation.

Abstract Until now, MXenes could only be produced from MAX phases containing aluminum, such as Ti 3 AlC 2 . Here, we report on the synthesis of Ti 3 C 2 (MXene) through selective etching of silicon from titanium silicon carbide—the most common MAX phase. Liters of colloidal solutions of delaminated Ti 3 SiC 2 ‐derived MXene (0.5–1.3 mg mL −1 ) were produced and processed into flexible and electrically conductive films, which show higher oxidation resistance than MXene synthesized from Ti 3 AlC 2 . This new synthesis method greatly widens the range of precursors for MXene synthesis.

Abstract Lead‐free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb 2+ cation with a divalent cation or substituting three Pb 2+ cations with two trivalent cations. The substitution of two Pb 2+ cations with one monovalent Ag + and one trivalent Bi 3+ cations was used to synthesize Cs 2 AgBiX 6 (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs 2 AgBiBr 6 NCs exhibit ultrafast hot‐carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs 2 AgBiCl 6 NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.

Abstract Solar CO 2 reduction efficiency is largely limited by poor photoabsorption, sluggish electron–hole separation, and a high CO 2 activation barrier. Defect engineering was employed to optimize these crucial processes. As a prototype, BiOBr atomic layers were fabricated and abundant oxygen vacancies were deliberately created on their surfaces. X‐ray absorption near‐edge structure and electron paramagnetic resonance spectra confirm the formation of oxygen vacancies. Theoretical calculations reveal the creation of new defect levels resulting from the oxygen vacancies, which extends the photoresponse into the visible‐light region. The charge delocalization around the oxygen vacancies contributes to CO 2 conversion into COOH* intermediate, which was confirmed by in situ Fourier‐transform infrared spectroscopy. Surface photovoltage spectra and time‐resolved fluorescence emission decay spectra indicate that the introduced oxygen vacancies promote the separation of carriers. As a result, the oxygen‐deficient BiOBr atomic layers achieve visible‐light‐driven CO 2 reduction with a CO…

Abstract Endowing materials with specific functions that are not readily available is always of great importance, but extremely challenging. Co4N, with its beneficial metallic characteristics, has been proved to be highly active for the oxidation of water, while it is notoriously poor for catalyzing the hydrogen evolution reaction (HER), because of its unfavorable d‐band energy level. Herein, we successfully endow Co4N with prominent HER catalytic capability by tailoring the positions of the d‐band center through transition‐metal doping. The V‐doped Co4N nanosheets display an overpotential of 37 mV at 10 mA cm−2, which is substantially better than Co4N and even close to the benchmark Pt/C catalysts. XANES, UPS, and DFT calculations consistently reveal the enhanced performance is attributed to the downshift of the d‐band center, which helps facilitate the H desorption. This concept could provide valuable insights into the design of other catalysts for HER and beyond.

Chemical modification of phenothiazine-benzophenone derivatives tunes the emission behavior from triplet states by selecting the geometry of the intramolecular charge transfer (ICT) state. A fundamental principle of planar ICT (PICT) and twisted ICT (TICT) is demonstrated to obtain selectively either room temperature phosphorescence (RTP) or thermally activated delayed fluorescence (TADF), respectively. Time-resolved spectroscopy and time-dependent density functional theory (TD-DFT) investigations on polymorphic single crystals demonstrate the roles of PICT and TICT states in the underlying photophysics. This has resulted in a RTP molecule OPM, where the triplet states contribute with 89 % of the luminescence, and an isomeric TADF molecule OMP, where the triplet states contribute with 95 % of the luminescence.

Abstract Cost‐effective aqueous rechargeable batteries are attractive alternatives to non‐aqueous cells for stationary grid energy storage. Among different aqueous cells, zinc‐ion batteries (ZIBs), based on Zn 2+ intercalation chemistry, stand out as they can employ high‐capacity Zn metal as the anode material. Herein, we report a layered calcium vanadium oxide bronze as the cathode material for aqueous Zn batteries. For the storage of the Zn 2+ ions in the aqueous electrolyte, we demonstrate that the calcium‐based bronze structure can deliver a high capacity of 340 mA h g −1 at 0.2 C, good rate capability, and very long cycling life (96 % retention after 3000 cycles at 80 C). Further, we investigate the Zn 2+ storage mechanism, and the corresponding electrochemical kinetics in this bronze cathode. Finally, we show that our Zn cell delivers an energy density of 267 W h kg −1 at a power density of 53.4 W kg −1 .

Abstract Photokatalyse mit sichtbarem Licht ist eine sich schnell entwickelnde und wirksame Strategie zur Initiierung organischer Umwandlungen, und sie folgt den Prinzipien einer grünen und nachhaltigen Chemie. Im Allgemeinen verlaufen die Reaktionspfade der meisten durch sichtbares Licht induzierten photokatalytischen Reaktionen über einen Einelektronentransfer (single‐electron transfer, SET). Neuerdings erfahren auch Energietransferreaktionen (EnT‐Reaktionen), welche durch sichtbares Licht induziert werden, beträchtliche Aufmerksamkeit, da diese Strategie einen spezifischen Reaktionsweg aufweist und bemerkenswerte Fortschritte in diesem Feld erzielt wurden. In diesem Aufsatz diskutieren wir die neuesten Fortschritte im Bereich der durch sichtbares Licht induzierten EnT‐Reaktionen.

Abstract Rechargeable aqueous zinc batteries are promising energy‐storage systems for grid applications. Highly conductive polyaniline (PANI) is a potential cathode, but it tends to deactivate in electrolytes with low acidity (i.e. pH >1) owing to deprotonation of the polymer. In this study, we synthesized a sulfo‐self‐doped PANI electrode by a facile electrochemical copolymerization process. The −SO3− self‐dopant functions as an internal proton reservoir to ensure a highly acidic local environment and facilitate the redox process in the weakly acidic ZnSO4 electrolyte. In a full zinc cell, the self‐doped PANI cathode provided a high capacity of 180 mAh g−1, excellent rate performance of 70 % capacity retention with a 50‐fold current‐density increase, and a long cycle life of over 2000 cycles with coulombic efficiency close to 100 %. Our study opens a door for the use of conducting polymers as cathode materials for high‐performance rechargeable zinc batteries.

Abstract It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed‐ligand strategy to afford high‐content (1.76 wt %) single‐atom (SA) iron‐implanted N‐doped porous carbon (Fe SA ‐N‐C) via pyrolysis. Thanks to the single‐atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe SA ‐N‐C exhibits excellent oxygen reduction activity and stability, surpassing almost all non‐noble‐metal catalysts and state‐of‐the‐art Pt/C, in both alkaline and more challenging acidic media. More far‐reaching, this MOF‐based mixed‐ligand strategy opens a novel avenue to the precise fabrication of efficient single‐atom catalysts.

Abstract Tough hydrogels, polymeric network structures with excellent mechanical properties (such as high stretchability and toughness), are emerging soft materials. Despite their remarkably mechanical features, tough hydrogels exhibit two flaws (freezing around the icing temperatures of water and drying under arid conditions). Inspired by cryoprotectants (CPAs) used in the inhibition of the icing of water in biological samples, a versatile and straightforward method is reported to fabricate extreme anti‐freezing, non‐drying CPA‐based organohydrogels with long‐term stability by partially displacing water molecules within the pre‐fabricated hydrogels. CPA‐based Ca‐alginate/polyacrylamide (PAAm) tough hydrogels were successfully fabricated with glycerol, glycol, and sorbitol. The CPA‐based organohydrogels remain unfrozen and mechanically flexible even up to −70 °C and are stable under ambient conditions or even vacuum.

Abstract Oxygen vacancy (VO) engineering is an effective method to tune the photoelectrochemical (PEC) performance, but the influence of VO on photoelectrodes is not well understood. Using hematite as a prototype, we herein report that VO functions in a more complicated way in PEC process than previously reported. Through a comprehensive analysis of the key charge transfer and surface reaction steps in PEC processes on a hematite photoanode, we clarify that VO can facilitate surface electrocatalytic processes while leading to severe interfacial recombination at the semiconductor/electrolyte (S‐E) interface, in addition to the well‐reported improvements in bulk conductivity. The improved bulk conductivity and surface catalysis are beneficial for bulk charge transfer and surface charge consumption while interfacial charge transfer deteriorates because of recombination through VO‐induced trap states at the S‐E interface.

Abstract A small‐molecule fluorophore FD‐1080 with both excitation and emission in the NIR‐II region has been successfully synthesized for in vivo imaging. A heptamethine structure is designed to shift the absorption and emission into NIR‐II region. Sulphonic and cyclohexene groups are introduced to enhance its water solubility and stability. The quantum yield of FD‐1080 is 0.31 %, and can be increased to 5.94 % after combining with fetal bovine serum (FBS). Significantly, 1064 nm NIR‐II excitation was demonstrated with the high tissue penetration depth and superior imaging resolution compared to previously reported NIR excitation from 650 nm to 980 nm. FD‐1080 is not only capable of realizing non‐invasive high‐resolution deep‐tissue hindlimb vasculature and brain vessel bioimaging, but also quantifying the respiratory rate based on the dynamic imaging of respiratory craniocaudal motion of the liver for the awake and anaesthetized mouse.

Abstract Photocatalytic water splitting requires separation of the mixed H2 and O2 products and is often hampered by the sluggish O2‐producing half reaction. An approach is now reported to address these issues by coupling the H2‐producing half reaction with value‐added benzylamine oxidation reaction using metal–organic framework (MOF) composites. Upon MOF photoexcitation, the electrons rapidly reduce the protons to generate H2 and the holes promote considerable benzylamine oxidation to N‐benzylbenzaldimine with high selectivity. Further experimental characterizations and theoretical calculation reveal that the highly conjugated s‐triazine strut in the MOF structure is crucial to the efficient charge separation and excellent photocatalytic activity.

Abstract Die sich rasant entwickelnden Felder der Photo‐ und Photoredoxkatalyse bieten neue Gelegenheiten, das Potential der synthetisch‐organischen Chemie zu erweitern. Fortschritte bei photokatalytischen Prozessen haben sich bisher vor allem aus empirischen Entdeckungen und der Suche nach neuen Reaktionen ergeben. Die allgemeine Wahrnehmung jedoch ist, dass die Photokatalyse in eine reifere Phase eintritt, in der die Kombination experimenteller und mechanistischer Studien eine Vorreiterrolle für weitere Innovationen spielt. Dieser Aufsatz beschreibt die mechanistischen Schlüsselstudien, die bei der Entwicklung photochemischer Prozesse in Betracht gezogen werden sollten, sowie die geeignetsten verfügbaren Techniken zur Gewinnung relevanter Informationen. Die Diskussion verweist auf ausgewählte Fallstudien, um zu zeigen, wie mechanistische Untersuchungen eine instrumentelle Rolle bei der Entdeckung und Entwicklung synthetisch nützlicher, photokatalytischer Transformationen spielen können.

Abstract Single Fe atoms dispersed on hierarchically structured porous carbon (SA‐Fe‐HPC) frameworks are prepared by pyrolysis of unsubstituted phthalocyanine/iron phthalocyanine complexes confined within micropores of the porous carbon support. The single‐atom Fe catalysts have a well‐defined atomic dispersion of Fe atoms coordinated by N ligands on the 3D hierarchically porous carbon support. These SA‐Fe‐HPC catalysts are comparable to the commercial Pt/C electrode even in acidic electrolytes for oxygen reduction reaction (ORR) in terms of the ORR activity (E1/2=0.81 V), but have better long‐term electrochemical stability (7 mV negative shift after 3000 potential cycles) and fuel selectivity. In alkaline media, the SA‐Fe‐HPC catalysts outperform the commercial Pt/C electrode in ORR activity (E1/2=0.89 V), fuel selectivity, and long‐term stability (1 mV negative shift after 3000 potential cycles). Thus, these nSA‐Fe‐HPCs are promising non‐platinum‐group metal ORR catalysts for fuel‐cell technologies.

Abstract Potassium‐ion batteries (KIBs) are plagued by a lack of materials for reversible accommodation of the large‐sized K + ion. Herein we present, the Bi anode in combination with the dimethoxyethane‐(DME) based electrolyte to deliver a remarkable capacity of ca. 400 mAh g −1 and long cycle stability with three distinct two‐phase reactions of Bi↔ KBi 2 ↔K 3 Bi 2 ↔K 3 Bi. These are ascribed to the gradually developed three‐dimensional (3D) porous networks of Bi, which realizes fast kinetics and tolerance of its volume change during potassiation and depotassiation. The porosity is linked to the unprecedented movement of the surface Bi atoms interacting with DME molecules, as suggested by DFT calculations. A full KIB of Bi//DME‐based electrolyte//Prussian blue of K 0.72 Fe[Fe(CN) 6 ] is demonstrated to present large energy density of 108.1 Wh kg −1 with average discharge voltage of 2.8 V and capacity retention of 86.5 % after 350 cycles.

Abstract The lithium metal anode is regarded as a promising candidate in next‐generation energy storage devices. Lithium nitrate (LiNO 3 ) is widely applied as an effective additive in ether electrolyte to increase the interfacial stability in batteries containing lithium metal anodes. However, because of its poor solubility LiNO 3 is rarely utilized in the high‐voltage window provided by carbonate electrolyte. Dissolution of LiNO 3 in carbonate electrolyte is realized through an effective solvation regulation strategy. LiNO 3 can be directly dissolved in an ethylene carbonate/diethyl carbonate electrolyte mixture by adding trace amounts of copper fluoride as a dissolution promoter. LiNO 3 protects the Li metal anode in a working high‐voltage Li metal battery. When a LiNi 0.80 Co 0.15 Al 0.05 O 2 cathode is paired with a Li metal anode, an extraordinary capacity retention of 53 % is achieved after 300 cycles (13 % after 200 cycles for LiNO 3 ‐free electrolyte) and a very high average Coulombic efficiency above 99.5 % is achieved at 0.5 C. The solvation chemistry of LiNO 3…

Abstract Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite‐free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first‐principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal…

Abstract The application of photochemistry to polymer and material science has led to the development of complex yet efficient systems for polymerization, polymer post‐functionalization, and advanced materials production. Using light to activate chemical reaction pathways in these systems not only leads to exquisite control over reaction dynamics, but also allows complex synthetic protocols to be easily achieved. Compared to polymerization systems mediated by thermal, chemical, or electrochemical means, photoinduced polymerization systems can potentially offer more versatile methods for macromolecular synthesis. We highlight the utility of light as an energy source for mediating photopolymerization, and present some promising examples of systems which are advancing materials production through their exploitation of photochemistry.

Abstract The low structural stability of hydrogen‐bonded organic frameworks (HOFs) is a thorny issue retarding the development of HOFs. A rational design approach is now proposed for construction of a stable HOF. The resultant HOF (PFC‐1) exhibits high surface area of 2122 m 2 g −1 and excellent chemical stability (intact in concentrated HCl for at least 117 days). A new method of acid‐assisted crystalline redemption is used to readily cure the thermal damage to PFC‐1. With periodic integration of photoactive pyrene in the robust framework, PFC‐1 can efficiently encapsulate Doxorubicin (Doxo) for synergistic chemo‐photodynamic therapy, showing comparable therapeutic efficacy with the commercial Doxo yet considerably lower cytotoxicity. This work demonstrates the notorious stability issue of HOFs can be properly addressed through rational design, paving a way to develop robust HOFs and offering promising application perspectives.

Abstract Learning from natural mineral structures is an efficient way to develop potential host lattices for applications in phosphor converted (pc)LEDs. A narrow‐band blue‐emitting silicate phosphor, RbNa3(Li3SiO4)4:Eu2+ (RNLSO:Eu2+), was derived from the UCr4C4‐type mineral model. The broad excitation spectrum (320–440 nm) indicates this phosphor can be well matched with the near ultraviolet (n‐UV) LED chip. Owing to the UCr4C4‐type highly condensed and rigid framework, RNLSO:Eu2+ exhibits an extremely small Stokes shift and an unprecedented ultra‐narrow (full‐width at half‐maximum, FWHM=22.4 nm) blue emission band (λem=471 nm) as well as excellent thermal stability (96 %@150 °C of the initial integrated intensity at 25 °C). The color gamut of the as‐fabricated (pc)LEDs is 75 % NTSC for the application in liquid crystal displays from the prototype design of an n‐UV LED chip and the narrow‐band RNLSO:Eu2+ (blue), β‐SiAlON:Eu2+ (green), and K2SiF6:Mn4+ (red) components as RGB emitters.

Abstract Dieser Aufsatz fast die jüngsten Fortschritte in der Chemie gekrümmter aromatischer Moleküle zusammen. Mit dem Schwerpunkt auf den wesentlichen Erfolgen des vergangenen Jahrzehnts stellen wir einen allgemeinen Überblick über die Synthesemethoden zur Verfügung, die eine effiziente Induktion von interner Spannung in π‐konjugierten Strukturen ermöglichen. Dieser Aufsatz ist gemäß der am spannungsinduzierenden Reaktionsschritt (Cyclisierungen, Eliminierungen, Ringexpansionen und –kontraktionen) beteiligten Topologieänderung gegliedert und unterstreicht die bemerkenswerte Vielfalt an Strukturen, die mit modernen Synthesemethoden erzielt werden kann.

Abstract NH3 synthesis by the electrocatalytic N2 reduction reaction (NRR) under ambient conditions is an appealing alternative to the currently employed industrial method—the Haber–Bosch process—that requires high temperature and pressure. We report single Mo atoms anchored to nitrogen‐doped porous carbon as a cost‐effective catalyst for the NRR. Benefiting from the optimally high density of active sites and hierarchically porous carbon frameworks, this catalyst achieves a high NH3 yield rate (34.0±3.6 μg h−1 mgcat.−1) and a high Faradaic efficiency (14.6±1.6 %) in 0.1 m KOH at room temperature. These values are considerably higher compared to previously reported non‐precious‐metal electrocatalysts. Moreover, this catalyst displays no obvious current drop during a 50 000 s NRR, and high activity and durability are achieved in 0.1 m HCl. The findings provide a promising lead for the design of efficient and robust single‐atom non‐precious‐metal catalysts for the electrocatalytic NRR.

Abstract Energy efficient buildings require materials with a low thermal conductivity and a high fire resistance. Traditional organic insulation materials are limited by their poor fire resistance and inorganic insulation materials are either brittle or display a high thermal conductivity. Herein we report a mechanically resilient organic/inorganic composite aerogel with a thermal conductivity significantly lower than expanded polystyrene and excellent fire resistance. Co‐polymerization and nanoscale phase separation of the phenol‐formaldehyde‐resin (PFR) and silica generate a binary network with domain sizes below 20 nm. The PFR/SiO 2 aerogel can resist a high‐temperature flame without disintegration and prevents the temperature on the non‐exposed side from increasing above the temperature critical for the collapse of reinforced concrete structures.

Abstract Single atoms immobilized on metal–organic frameworks (MOFs) with unique nanostructures have drawn tremendous attention in the application of catalysis but remain a great challenge. Various single noble‐metal atoms have now been successfully anchored on the well‐defined anchoring sites of the zirconium porphyrin MOF hollow nanotubes, which are probed by aberration‐corrected scanning transmission electron microscopy and synchrotron‐radiation‐based X‐ray absorption fine‐structure spectroscopy. Owing to the hollow structure and excellent photoelectrochemical performance, the HNTM‐Ir/Pt exhibits outstanding catalytic activity in the visible‐light photocatalytic H2 evolution via water splitting. The single atom immobilized on MOFs with hollow structures are expected to pave the way to expand the potential applications of MOFs.

Abstract Pure organic, heavy‐atom‐free room‐temperature phosphorescence (RTP) materials have attracted much attention and have potential applications in photoelectric and biochemical material fields owing to their rich excited state properties. They offer long luminescent lifetime, diversified design, and facile preparation. However, recent achievements of efficient phosphorescence under ambient conditions mainly focus on ordered crystal lattices or embedding into rigid matrices, which require strict growth conditions and have poor reproducibility. Herein, we developed a concise approach to give RTP with a decent quantum yield and ultralong phosphorescence lifetime in the amorphous state by radical binary copolymerization of acrylamide and different phosphors with oxygen‐containing functional groups. The cross‐linked hydrogen‐bonding networks between the polymeric chains immobilize phosphors to suppress non‐radiative transitions and provide a microenvironment to shield quenchers.

Abstract The potassium aluminyl complex K[Al(NONAr)] (NON=NONAr=[O(SiMe2NAr)2]2−, Ar=2,6‐iPr2C6H3) reacts with 1,3,5,7‐cyclooctatetraene (COT) to give K[Al(NONAr)(COT)]. The COT‐ligand is present in the asymmetric unit as a planar μ2‐η2:η8‐bridge between Al and K, with additional K⋅⋅⋅π‐aryl interactions to neighboring molecules that generate a helical chain. DFT calculations indicate significant aromatic character, consistent with reduction to [COT]2−. Addition of 18‐crown‐6 causes a rearrangement of the C8‐carbocycle to form the isomeric 9‐aluminabicyclo[4.2.1]nona‐2,4,7‐triene anion.

Abstract In situ and operando spectroscopic and microscopic methods were used to gain insight into the correlation between the structure, chemical state, and reactivity of size‐ and shape‐controlled ligand‐free Cu nanocubes during CO2 electroreduction (CO2RR). Dynamic changes in the morphology and composition of Cu cubes supported on carbon were monitored under potential control through electrochemical atomic force microscopy, X‐ray absorption fine‐structure spectroscopy and X‐ray photoelectron spectroscopy. Under reaction conditions, the roughening of the nanocube surface, disappearance of the (100) facets, formation of pores, loss of Cu and reduction of CuOx species observed were found to lead to a suppression of the selectivity for multi‐carbon products (i.e. C2H4 and ethanol) versus CH4. A comparison with Cu cubes supported on Cu foils revealed an enhanced morphological stability and persistence of CuI species under CO2RR in the former samples. Both factors are held responsible for the higher C2/C1 product ratio observed for the Cu cubes/Cu as compared to Cu cubes/C. Our…

Abstract Fluorooxoborates, benefiting from the large optical band gap, high anisotropy, and ever‐greater possibility to form non‐centrosymmetric structures activated by the large polarization of [BOxF4−x](x+1)− building blocks, have been considered as the new fertile fields for searching the ultraviolet (UV) and deep‐UV nonlinear optical (NLO) materials. Herein, we report the first asymmetric alkaline‐earth metal fluorooxoborate SrB5O7F3, which is rationally designed by taking the classic Sr2Be2B2O7 (SBBO) as a maternal structure. Its [B5O9F3]6− fundamental building block with near‐planar configuration composed by two edge‐sharing [B3O6F2]5− rings in SrB5O7F3 has not been reported in any other borates. Solid state 19F and 11B magic‐angle spinning NMR spectroscopy verifies the presence of covalent B−F bonds in SrB5O7F3. Property characterizations reveal that SrB5O7F3 possesses the optical properties required for deep‐UV NLO applications, which make SrB5O7F3 a promising crystal that could produce deep‐UV coherent light by the direct SHG process.

Abstract Pyrolysis of a bimetallic metal–organic framework (MIL‐88‐Fe/Ni)‐dicyandiamide composite yield a Fe and Ni containing carbonaceous material, which is an efficient bifunctional electrocatalyst for overall water splitting. FeNi3 and NiFe2O4 are found as metallic and metal oxide compounds closely embedded in an N‐doped carbon–carbon nanotube matrix. This hybrid catalyst (Fe‐Ni@NC‐CNTs) significantly promotes the charge transfer efficiency and restrains the corrosion of the metallic catalysts, which is shown in a high OER and HER activity with an overpotential of 274 and 202 mV, respectively at 10 mA cm−2 in alkaline solution. When this bifunctional catalyst was further used for H2 and O2 production in an electrochemical water‐splitting unit, it can operate in ambient conditions with a competitive gas production rate of 1.15 and 0.57 μL s−1 for hydrogen and oxygen, respectively, showing its potential for practical applications.

Abstract Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe‐LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe‐O‐Fe moieties. These Fe2+‐containing NiFe‐LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm−2, which is among the best OER catalytic performance to date. In‐situ X‐ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe‐O‐Fe motifs could stabilize high‐valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.

Abstract The development of efficient and low energy‐consumption catalysts for CO2 conversion is desired, yet remains a great challenge. Herein, a class of novel hollow porous carbons (HPC), featuring well dispersed dopants of nitrogen and single Zn atoms, have been fabricated, based on the templated growth of a hollow metal–organic framework precursor, followed by pyrolysis. The optimized HPC‐800 achieves efficient catalytic CO2 cycloaddition with epoxides, under light irradiation, at ambient temperature, by taking advantage of an ultrahigh loading of (11.3 wt %) single‐atom Zn and uniform N active sites, high‐efficiency photothermal conversion as well as the hierarchical pores in the carbon shell. As far as we know, this is the first report on the integration of the photothermal effect of carbon‐based materials with single metal atoms for catalytic CO2 fixation.

Abstract Circulating tumor cell (CTC)‐enrichment by using aptamers has a number of advantages, but the issue of compromised binding affinities and stabilities in real samples hinders its wide applications. Inspired by the high efficiency of the prey mechanism of the octopus, we engineered a deterministic lateral displacement (DLD)‐patterned microfluidic chip modified with multivalent aptamer‐functionalized nanospheres (AP‐Octopus‐Chip) to enhance capture efficiency. The multivalent aptamer–antigen binding efficiency improves 100‐fold and the capture efficiency is enhanced more than 300 % compared with a monovalent aptamer‐modified chip. Moreover, the captured cancer cells can be released through a thiol exchange reaction with up to 80 % efficiency and 96 % viability, which is fully compatible with downstream mutation detection and CTC culture. Using the chip, we were able to find CTCs in all cancer samples analyzed.

Abstract In den letzten Jahren hat das Interesse an katalytischen Reaktionen zum Einbau von CO2 als allgegenwärtigem und preisgünstigem C1‐Rohstoff in organischen Stoffen aufs Neue zugenommen. Obgleich C‐C‐Kupplungen durch katalytische CO2‐Fixierung für lange Zeit eher begrenzt waren, zeigt die nähere Betrachtung der neueren Literatur, dass katalytische Carboxylierungen in eine Epoche exponentiellen Wachstums eingetreten sind. Es ist das Entstehen einer umfassenden Disziplin abzusehen, die eine Optimierung der Synthese von Carbonsäuren erlaubt, welche äußerst wichtige Zwischenprodukte in industriellen Prozessen darstellen. Die neuen Strategien sind generell breit anwendbar und leicht durchzuführen, jedoch bestehen nach wie vor erhebliche Herausforderungen. Aus diesem Grund werden die metallkatalysierten Carboxylierungen hier auf konzeptionelle und übersichtliche Weise abgehandelt, um ihre grundlegenden Prinzipien aufzuzeigen.

Abstract Halogen‐ and chalcogen‐based σ‐hole interactions have recently received increased interest in non‐covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and monodentate pnictogen‐bonding catalysts. Solution and in silico binding studies, together with high catalytic activity in chloride abstraction reactions, yield compelling evidence for operational pnictogen bonds. The depth of the σ holes is easily varied with different substituents. Comparison with homologous halogen‐ and chalcogen‐bonding catalysts shows an increase in activity from main group VII to V and from row 3 to 5 in the periodic table. Pnictogen bonds from antimony thus emerged as by far the best among the elements covered, a finding that provides most intriguing perspectives for future applications in catalysis and beyond.

Abstract Two‐dimensional (2D) materials and ultrathin nanosheets are advantageous for elevating the catalysis performance and elucidating the catalysis mechanism of heterogeneous catalysts, but they are mostly restricted to inorganic or organic materials based on covalent bonds. We report an electrochemical/chemical exfoliation strategy for synthesizing metal–organic 2D materials based on coordination bonds. A catechol functionalized ligand is used as the redox active pillar to construct a pillared‐layer framework. When the 3D pillared‐layer MOF serves as an electrocatalyst for water oxidation (pH 13), the pillar ligands can be oxidized in situ and removed. The remaining ultrathin (2 nm) nanosheets of the metal–organic layers are an efficient catalyst with overpotentials as low as 211 mV at 10 mA cm−2 and a turnover frequency as high as 30 s−1 at an overpotential of 300 mV.

Abstract Transition‐metal sulfides (TMSs) have emerged as important candidates for oxygen evolution reaction (OER) electrocatalysts. Now a hybrid nanostructure has been decorated with CeOx nanoparticles on the surface of ZIF‐67‐derived hollow CoS through in situ generation. Proper control of the amount of CeOx on the surface of CoS can achieve precise tuning of Co2+/Co3+ ratio, especially for the induced defects, further boosting the OER activity. Meanwhile, the formation of protective CeOx thin layer effectively inhibits the corrosion by losing cobalt ion species from the active surface into the solution. It is thus a rare example of a hybrid hetero‐structural electrocatalyst with CeOx NPs to improve the performance of the hollow TMS nanocage.

Abstract All‐inorganic perovskite solar cells with high efficiency and improved stability are promising for commercialization. A multistep solution‐processing method was developed to fabricate high‐purity inorganic CsPbBr3 perovskite films for use in efficient solar cells. By tuning the number of deposition cycles (n) of a CsBr solution, the phase conversion from CsPb2Br5 (n ≤3), to CsPbBr3 (n=4), and Cs4PbBr6 (n≥5) was optimized to achieve vertical‐ and monolayer‐aligned grains. Upon interfacial modification with graphene quantum dots, the all‐inorganic perovskite solar cell (without a hole‐transporting layer) achieved a power conversion efficiency (PCE) as high as 9.72 % under standard solar illumination conditions. Under challenging conditions, such as 90 % relative humidity (RH) at 25 °C or 80 °C at zero humidity, the optimized device retained 87 % PCE over 130 days or 95 % over 40 days, compared to the initial efficiency.

Abstract Enzyme gewinnen immer mehr Bedeutung als Katalysatoren für organische Oxidationsreaktionen. Mit Oxidoreduktasen stehen dem Chemiker vielseitige Werkzeuge für selektive und effiziente Oxidationsreaktionen zur Verfügung. Ihr Spektrum reicht von einfachen Alkoholoxidationen bis hin zur stereoselektiven Halogenierung nicht‐aktivierter C‐H‐Bindungen. Für viele biokatalytische Oxidationen ist bisher kein chemisches Pendant bekannt. Daher ermöglichen Oxidoreduktasen kürzere Syntheserouten. Darüber hinaus sind die generell milderen Reaktionsbedingungen biokatalytischer Oxidationen attraktiv. In diesem Aufsatz fassen wir einige aktuelle Entwicklungen im Bereich der biokatalytischen Oxidation zusammen. Wir beschreiben auch derzeitige Grenzen und vielversprechende Lösungsansätze.

Abstract Transition‐metal phosphides have stimulated great interest as catalysts to drive the hydrogen evolution reaction (HER), but their use as bifunctional catalytic electrodes that enable efficient neutral‐pH water splitting has rarely been achieved. Herein, we report the synthesis of ternary Ni0.1Co0.9P porous nanosheets onto conductive carbon fiber paper that can efficiently and robustly catalyze both the HER and water oxidation in 1 m phosphate buffer (PBS; pH 7) electrolyte under ambient conditions. A water electrolysis cell comprising the Ni0.1Co0.9P electrodes demonstrates remarkable activity and stability for the electrochemical splitting of neutral‐pH water. We attribute this performance to the new ternary Ni0.1Co0.9P structure with porous surfaces and favorable electronic states resulting from the synergistic interplay between nickel and cobalt. Ternary metal phosphides hold promise as efficient and low‐cost catalysts for neutral‐pH water splitting devices.

Abstract An enantioselective C−H arylation of phosphine oxides with o‐quinone diazides catalyzed by an iridium(III) complex bearing an atropchiral cyclopentadienyl (Cpx) ligand and phthaloyl tert‐leucine as co‐catalyst is reported. The method allows access to a) P‐chiral biaryl phosphine oxides, b) atropo‐enantioselective construction of sterically demanding biaryl backbones, and also c) selective assembly of axial and P‐chiral compounds in excellent yields and diastereo‐ and enantioselectivities. Enantiospecific reductions provide monodentate chiral phosphorus(III) compounds having structures and biaryl backbones with proven importance as ligands in asymmetric catalysis.

Abstract Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture, one of the most important while challenging industrial separation processes, is mainly through energy‐intensive cryogenic distillation. Now a family of gallate‐based metal–organic framework (MOF) materials is presented, M‐gallate (M=Ni, Mg, Co), featuring 3D interconnected zigzag channels, the aperture sizes of which (3.47–3.69 Å) are ideally suitable for molecular sieving of ethylene (3.28×4.18×4.84 Å 3 ) and ethane (3.81×4.08×4.82 Å 3 ) through molecular cross‐section size differentiation. Co‐gallate shows an unprecedented IAST selectivity of 52 for C 2 H 4 over C 2 H 6 with a C 2 H 4 uptake of 3.37 mmol g −1 at 298 K and 1 bar, outperforming the state‐of‐the‐art MOF material NOTT‐300. Direct breakthrough experiments with equimolar C 2 H 4 /C 2 H 6 mixtures confirmed that M‐gallate is highly selective for ethylene. The adsorption structure and mechanism of ethylene in the M‐gallate was further studied through neutron diffraction experiments.

Abstract Separation of propyne/propylene (C3H4/C3H6) is more difficult and challenging than that of acetylene/ethylene (C2H2/C2H4) because of their closer molecular sizes. A comprehensive screening of a series of metal–organic frameworks with broad types of structures, pore sizes, and functionalities was carried out. UTSA‐200 was identified as the best separating material for the removal of trace C3H4 from C3H4/C3H6 mixtures. Gas sorption isotherms reveal that UTSA‐200 exhibits by far the highest C3H4 adsorption capacity (95 cm3 cm−3 at 0.01 bar and 298 K) and record C3H4/C3H6 selectivity, which was mainly attributed to the suitable dynamic pore size to efficiently block the larger C3H6 molecule whilst the strong binding sites and pore flexibility capture smaller C3H4. This material thus provides record purification capacity for the removal of C3H4 from a 1:99 (or 0.1:99.9, v/v) C3H4/C3H6 mixture to produce 99.9999 % pure C3H6 with a productivity of 62.0 (or 142.8) mmol g−1.

Abstract Graphite carbon nitride (g‐C 3 N 4 ) is a promising candidate for photocatalytic hydrogen production, but only shows moderate activity owing to sluggish photocarrier transfer and insufficient light absorption. Herein, carbon quantum dots (CQDs) implanted in the surface plane of g‐C 3 N 4 nanotubes were synthesized by thermal polymerization of freeze‐dried urea and CQDs precursor. The CQD‐implanted g‐C 3 N 4 nanotubes (CCTs) could simultaneously facilitate photoelectron transport and suppress charge recombination through their specially coupled heterogeneous interface. The electronic structure and morphology were optimized in the CCTs, contributing to greater visible light absorption and a weakened barrier of the photocarrier transfer. As a result, the CCTs exhibited efficient photocatalytic performance under light irradiation with a high H 2 production rate of 3538.3 μmol g −1 h −1 and a notable quantum yield of 10.94 % at 420 nm.

Abstract Optical multiplexing plays an important role in fields ranging from advanced biological assays to security. However, conventional codes based on fluorescent color and intensity are limited to spectral overlap and background interference. Herein, we present a new multiplexing concept by manipulating the luminescence emission color and decay lifetimes of upconversion nanoparticles (τλ‐UCNPs) separately for the first time through designing the core/multi‐shell structure and controlled energy relay method. This new color/lifetime binary strategy exhibits exponentially scalable encoding capacity (>105), three orders of magnitudes higher than that of conventional color/intensity way. The strategy enables the multiplexed detection of human papilloma virus (HPV) subtypes in patient samples and robust anti‐counterfeiting. This work opens new opportunities for optical multiplexing with luminescent materials.

Abstract Die Verbindung von Photoredox‐ und Nickel‐Katalyse führte zu einer Renaissance in der Radikalchemie und bei nickelkatalysierten Umsetzungen, insbesondere für die Kohlenstoff‐Kohlenstoff‐Bindungsbildung. Gemeinsam unterstützen diese Entwicklungen die Lösung des seit langem bestehenden Problems der Kreuzkupplung funktionalisierter Alkylfragmente in späten Synthesestadien. Basierend auf der Vorstellung, dass photokatalytisch erzeugte Alkylradikale leicht von Ni‐Komplexen eingefangen werden können, sind gänzlich neue Ausgangsstoffe für die Kreuzkupplung denkbar. In diesem Kurzaufsatz werden die neuesten Entwicklungen für mehrere Arten von Alkyl‐Kreuzkupplungen beleuchtet, die ausschließlich durch diesen Ansatz verwirklicht werden können.

Abstract Mesoporous carbon nitrides (MCN) with C3N4 stoichiometry could find applications in fields ranging from catalysis, sensing, and adsorption–separation to biotechnology. The extension of the synthesis of MCN with different nitrogen contents and chemical structures promises access to a wider range of applications. Herein we prepare mesoporous C3N5 with a combined triazole and triazine framework via a simple self‐assembly of 5‐amino‐1H‐tetrazole (5‐ATTZ). We are able to hybridize these nanostructures with graphene by using graphene–mesoporous‐silica hybrids as a template to tune the electronic properties. DFT calculations and spectroscopic analyses clearly demonstrate that the C3N5 consists of 1 triazole and 2 triazine moieties. The triazole‐based mesoporous C3N5 and its graphene hybrids are found to be highly active for oxygen reduction reaction (ORR) with a higher diffusion‐limiting current density and a decreased overpotential than those of bulk g‐C3N4.

Abstract Three coordination polymers (CPs) have been synthesized based on a [Co(bpy)(H2O)4]2+ chain (bpy=4,4′‐bipyridine) by a template approach. The frameworks are neutralized by different templated polycarboxylate anions (furan di‐carboxylate (fdc) in Co‐fdc, benzene tri‐carboxylate (btc) in Co‐tri and benzene tetra‐carboxylate (btec) in Co‐tetra). These templates with different degrees of protonation and ionic carrier concentration played significant role on crystal packing as well as formation of well‐directed H‐bonded networks which made these CPs perform well in proton conduction (PC). The PC value reaches to 1.49×10−1 S cm−1 under 80 °C and 98 % relative humidity (R.H.) for Co‐tri, which is the highest among CPs/MOFs/COFs and is an example of conductivity in the order of 10−1 S cm−1. Co‐tri and Co‐tetra are excellent proton conductors at mild temperature (40 °C) and 98 % R.H. (conductivities up to 2.92×10−2 and 1.38×10−2 S cm−1, respectively).

Abstract Eosin Y, a well‐known economical alternative to metal catalysts in visible‐light‐driven single‐electron transfer‐based organic transformations, can behave as an effective direct hydrogen‐atom transfer catalyst for C−H activation. Using the alkylation of C−H bonds with electron‐deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y‐based photocatalytic hydrogen‐atom transfer strategy is promising for diverse functionalization of a wide range of native C−H bonds in a green and sustainable manner.

Abstract The electrochemical reduction reaction of carbon dioxide (CO2RR) to carbon monoxide (CO) is the basis for the further synthesis of more complex carbon‐based fuels or attractive feedstock. Single‐atom catalysts have unique electronic and geometric structures with respect to their bulk counterparts, thus exhibiting unexpected catalytic activities. A nitrogen‐anchored Zn single‐atom catalyst is presented for CO formation from CO2RR with high catalytic activity (onset overpotential down to 24 mV), high selectivity (Faradaic efficiency for CO (FECO) up to 95 % at −0.43 V), remarkable durability (>75 h without decay of FECO), and large turnover frequency (TOF, up to 9969 h−1). Further experimental and DFT results indicate that the four‐nitrogen‐anchored Zn single atom (Zn‐N4) is the main active site for CO2RR with low free energy barrier for the formation of *COOH as the rate‐limiting step.

Abstract Polymeric carbon nitride (PCN), in either triazine or heptazine form, has been regarded as a promising metal‐free, environmentally benign, and sustainable photocatalyst for solar hydrogen production. However, PCN in most cases only exhibits moderate activity owing to its inherent properties, such as rapid charge carrier recombination. Herein we present a triazine–heptazine copolymer synthesized by simple post‐calcination of PCN in eutectic salts, that is, NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of an internal triazine–heptazine donor–acceptor (D‐A) heterostructure was affirmed to significantly accelerate interface charge transfer (CT) and thus boost the photocatalytic activity (AQY=60 % at 420 nm). This study highlights the construction of intermolecular D‐A copolymers in NaCl/KCl molten salts with higher melting points but in the absence of lithium to modulate the chemical structure and properties of PCN.

Abstract A two‐dimensional (2D) sp2‐carbon‐linked conjugated polymer framework (2D CCP‐HATN) has a nitrogen‐doped skeleton, a periodical dual‐pore structure and high chemical stability. The polymer backbone consists of hexaazatrinaphthalene (HATN) and cyanovinylene units linked entirely by carbon–carbon double bonds. Profiting from the shape‐persistent framework of 2D CCP‐HATN integrated with the electrochemical redox‐active HATN and the robust sp2 carbon‐carbon linkage, 2D CCP‐HATN hybridized with carbon nanotubes shows a high capacity of 116 mA h g−1, with high utilization of its redox‐active sites and superb cycling stability (91 % after 1000 cycles) and rate capability (82 %, 1.0 A g−1 vs. 0.1 A g−1) as an organic cathode material for lithium‐ion batteries.

Abstract Chemical functionalization of covalent organic frameworks (COFs) is critical for tuning their properties and broadening their potential applications. However, the introduction of functional groups, especially to three‐dimensional (3D) COFs, still remains largely unexplored. Reported here is a general strategy for generating a 3D carboxy‐functionalized COF through postsynthetic modification of a hydroxy‐functionalized COF, and for the first time exploration of the 3D carboxy‐functionalized COF in the selective extraction of lanthanide ions. The obtained COF shows high crystallinity, good chemical stability, and large specific surface area. Furthermore, the carboxy‐functionalized COF displays high metal loading capacities together with excellent adsorption selectivity for Nd3+ over Sr2+ and Fe3+ as confirmed by the Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. This study not only provides a strategy for versatile functionalization of 3D COFs, but also opens a way to their use in environmentally related applications.

Abstract Considering the potential applications of all‐polymer solar cells (all‐PSCs) as wearable power generators, there is an urgent need to develop photoactive layers that possess intrinsic mechanical endurance, while maintaining a high power‐conversion efficiency (PCE).Herein a strategy is demonstrated to simultaneously control the intercalation behavior and nanocrystallite size in the polymer–polymer blend by using a newly developed, high‐viscosity polymeric additive, poly(dimethylsiloxane‐co‐methyl phenethylsiloxane) (PDPS), into the TQ‐F:N2200 all‐PSC matrix. A mechanically robust 10wt% PDPS blend film with a great toughness was obtained. Our results provide a feasible route for producing high‐performance ductile all‐PSCs, which can potentially be used to realize stretchable all‐PSCs as a linchpin of next‐generation electronics.

Abstract Maximizing the platinum utilization in electrocatalysts toward oxygen reduction reaction (ORR) is very desirable for large‐scale sustainable application of Pt in energy systems. A cost‐effective carbon‐supported carbon‐defect‐anchored platinum single‐atom electrocatalysts (Pt1/C) with remarkable ORR performance is reported. An acidic H2/O2 single cell with Pt1/C as cathode delivers a maximum power density of 520 mW cm−2 at 80 °C, corresponding to a superhigh platinum utilization of 0.09 gPt kW−1. Further physical characterization and density functional theory computations reveal that single Pt atoms anchored stably by four carbon atoms in carbon divacancies (Pt‐C4) are the main active centers for the observed high ORR performance.

Abstract A zinc–iodine flow battery (ZIFB) with long cycle life, high energy, high power density, and self‐healing behavior is prepared. The long cycle life was achieved by employing a low‐cost porous polyolefin membrane and stable electrolytes. The pores in the membrane can be filled with a solution containing I3− that can react with zinc dendrite. Therefore, by consuming zinc dendrite, the battery can self‐recover from micro‐short‐circuiting resulting from overcharging. By using KI, ZnBr2, and KCl as electrolytes and a high ion‐conductivity porous membrane, a very high power density can be achieved. As a result, a ZIFB exhibits an energy efficiency (EE) of 82 % at 80 mA cm−2, which is 8 times higher than the currently reported ZIFBs. Furthermore, a stack with an output of 700 W was assembled and continuously run for more than 300 cycles. We believe this ZIFB can lead the way to development of new‐generation, high‐performance flow batteries.

Abstract Persistent luminescence from purely organic materials is basically triggered by light and electricity, which largely confines its practical applications. A purely organic AIEgen exhibits not only persistent photoluminescence, but also transient and persistent room‐temperature mechanoluminescence. By simply turning on and off a UV lamp, tricolor emission switching between blue, white, and yellow was achieved. The data from single‐crystal structure analysis and theoretical calculation suggest that mechanism of the observed persistent mechanoluminescence (pML) is correlated with the strong spin–orbit coupling of the bromine atom, as well as the formation of H‐aggregates and restriction of intramolecular motions in noncentrosymmetric crystal structure. These results outline a fundamental principle for the development of new pML materials, providing an important step forward in expanding the application scope of persistent luminescence.

Abstract Multi‐resonance induced by boron and nitrogen atoms in opposite resonance positions endows a thermally activated delayed fluorescence (MR‐TADF) emitter with a strikingly small full width at half maximum of only 26 nm and excellent photoluminescence quantum yield of up to 97.48 %. The introduction of a carbazole unit in the para position of the B‐substituted phenyl‐ring can significantly boost up the resonance effect without compromising the color fidelity, subsequently enhancing the performances of the corresponding pure blue TADF‐OLED, with an outstanding external quantum efficiency (EQE) up to 32.1 % and low efficiency roll‐off, making it one of the best TADF‐OLEDs in the blue region to date. Furthermore, utilizing this material as host for a yellow phosphorescent emitter, the device also shows a significantly reduced turn‐on voltage of 3.2 V and an EQEmax of 22.2 %.

Abstract Trotz ihres Potentials für klinische Anwendungen besitzt die photodynamische Therapie einen entscheidenden Nachteil, der mit der inhärenten Abhängigkeit von Sauerstoff einhergeht und ihre Effektivität bei der Behandlung hypoxischer Tumore einschränkt. Des Weiteren befördern sowohl der Sauerstoffverbrauch als auch die Schädigung der Mikrovaskulatur die Tumorhypoxie und beeinträchtigen daher den möglichen Therapieerfolg. In den letzten Jahren widmeten sich zahlreiche Untersuchungen der Entwicklung innovativer Methoden, um diese Schwierigkeiten zu überwinden und die Einschränkungen der PDT im Zusammenhang mit Hypoxie zu umgehen. Die Ergebnisse dieser Studien werden in diesem Kurzaufsatz zusammengefasst.

Abstract For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value‐added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (−CH2−NH2) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that NiII/NiIII may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram‐scale synthesis.

Abstract Highly selective separation and/or purification of acetylene from various gas mixtures is a relevant and difficult challenge that currently requires costly and energy‐intensive chemisorption processes. Two ultramicroporous metal–organic framework physisorbents, NKMOF‐1‐M (M=Cu or Ni), offer high hydrolytic stability and benchmark selectivity towards acetylene versus several gases at ambient temperature. The performance of NKMOF‐1‐M is attributed to their exceptional acetylene binding affinity as revealed by modelling and several experimental studies: in situ single‐crystal X‐ray diffraction, FTIR, and gas mixture breakthrough tests. NKMOF‐1‐M exhibit better low‐pressure uptake than existing physisorbents and possesses the highest selectivities yet reported for C2H2/CO2 and C2H2/CH4. The performance of NKMOF‐1‐M is not driven by the same mechanism as current benchmark physisorbents that rely on pore walls lined by inorganic anions.

Abstract Poor mechanical stability of the polymer electrolyte membranes remains one of the bottlenecks towards improving the performance of the proton exchange membrane (PEM) fuel cells. The present work proposes a unique way to utilize crystalline covalent organic frameworks (COFs) as a self‐standing, highly flexible membrane to further boost the mechanical stability of the material without compromising its innate structural characteristics. The as‐synthesized p ‐toluene sulfonic acid loaded COF membranes (COFMs) show the highest proton conductivity (as high as 7.8×10 −2 S cm −1 ) amongst all crystalline porous organic polymeric materials reported to date, and were tested under real PEM operating conditions to ascertain their practical utilization as proton exchange membranes. Attainment of 24 mW cm −2 power density, which is the highest among COFs and MOFs, highlights the possibility of using a COF membrane over the other state‐of‐the‐art crystalline porous polymeric materials reported to date.

Abstract The synthesis and characterization of an enantiopure superhelicene nanographene is reported in which two saddle‐shaped and one planar hexabenzocoronene (HBC) units are arranged in a helicoidal shape to form an undecabenzo[7]carbohelicene. The described compound is the first fully π‐extended [7]helicene. Racemic resolution of the helical nanographene permitted analysis of the chiroptical properties and revealed dissymmetry factors in the range of 2×10−3 both in the absorption and in the emission measurements. Remarkably, non‐linear photophysical analysis demonstrated a two‐photon absorption cross‐section of 870 GM at 800 nm and a perfect overlap between linear, non‐linear, and chiral emissions.

Abstract In den letzten Jahrzehnten haben sich “unübliche” nichtkovalente Wechselwirkungen wie Anion‐π oder Halogenbrücken in vielen Forschungsbereichen zu interessanten Alternativen zu den allgegenwärtigen Wasserstoffbrücken entwickelt. Dies trifft – zu einem etwas geringeren Grad – auch auf Chalkogenbrücken zu, die nichtkovalenten Wechselwirkungen Lewis‐acider Chalkogenzentren. Dieser Kurzaufsatz soll einen Überblick über den Einsatz von Chalkogenbrücken in der kondensierten Phase geben, mit einem Fokus auf den neuesten Entwicklungen bei der Anwendung intermolekularer Chalkogenbrücken in Lösung. Im Festkörper wurden Chalkogenbrücken zum Aufbau nanoskaliger Strukturen und für die Selbstorganisation ausgefeilter selbstkomplementärer Komplexe verwendet. Bis vor kurzem konzentrierten sich die Anwendungen in Lösung vor allem auf intramolekulare Wechselwirkungen, welche die Konformation von Intermediaten oder Reagentien stabilisierten. In den letzten Jahren wurden nun aber auch intermolekulare Chalkogenbrücken zunehmend in Lösung eingesetzt, besonders für Anionenerkennung und ‐transport…

Abstract Electrochemical reduction of CO2 to CH3OH is of great interest. Aerogels have fine inorganic superstructure with high porosity and are known to be exceptional materials. Now a Pd−Cu bimetallic aerogel electrocatalyst has been developed for conversion of CO2 into CH3OH. The current density and Faradaic efficiency of CH3OH can be as high as 31.8 mA cm−2 and 80.0 % over the Pd83Cu17 aerogel at a very low overpotential (0.24 V). The superior performance of the electrocatalyst results from efficient adsorption and stabilization of the CO2 radical anion, high Pd0/PdII and CuI+Cu0/CuII ratios, and sufficient Pd/Cu grain boundaries of aerogel nanochains.

Abstract Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H 2 evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH 2 ‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H 2 evolution under visible light irradiation. Especially, NH 2 ‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H 2 evolution rate of 23.41 mmol g −1 h −1 (with the TOF of 402.36 h −1 ), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H 2 evolution among various MOF‐ and COF‐based photocatalysts.

Abstract Nanomaterials with enzyme‐like activity (nanozymes) attract significant interest owing to their applications in biomedical research. Particularly, redox nanozymes that exhibit glutathione peroxidase (GPx)‐like activity play important roles in cellular signaling by controlling the hydrogen peroxide (H2O2) level. Herein we report, for the first time, that the redox properties and GPx‐like activity of V2O5 nanozyme depends not only on the size and morphology, but also on the crystal facets exposed on the surface within the same crystal system of the nanomaterials. These results suggest that the surface of the nanomaterials can be engineered to fine‐tune their redox properties to act as “nanoisozymes” for specific biological applications.

Abstract Cysteine‐based chiral optically active carbon dots (CDs) and their effects on cellular energy metabolism, which is vital for essential cellular functions, have been barely reported. A green and effective synthesis strategy for chiral N‐S‐doped CDs (fluorescence quantum yield ca. 41.26 %) based on hydrothermal treatment of l‐ or d‐cysteine at as low as 60 °C has been developed. This suggested that cysteine was instable in aqueous solutions and acts as a warning for high‐temperature synthesis of nanomaterials using cysteine as stabilizer. Human bladder cancer T24 cells treated with l‐CDs showed up‐regulated glycolysis, while d‐CDs had no similar effects. In contrast, no disturbance to the basal mitochondrial aerobic respiration of T24 cells was caused by either chiral CD.

Die Unterdrückung der Linkerbeweglichkeit und die Anpassung der Aperturgröße einer MOF-Membran sind wichtige Faktoren, um eine gute Gastrennleistung zu erreichen. In ihrer Zuschrift auf S. 333 beschreiben Y. Wei, J. Caro, H. Wang und Mitarbeiter eine doppelte Strategie des “Versteifens und Verengens”, um eine circa 500 nm dünne hybride Mixed-Linker-ZIF-7×-8-Membran mit unterdrückter Flexibilität und verengter Apertur durch eine schnelle stromgetriebene Synthese (FCDS) innerhalb von 20 min herzustellen, die eine deutlich gesteigerte CO2/CH4-Trennung mit einem Trennfaktor von bis zu 25 zeigt.

Abstract Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE ST ) and pure ππ* configuration of the lowest triplet state (T 1 ) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE ST and pure ππ* configuration of T 1 .

Abstract The removal of C2H2 and C2H6 from C2H4 streams is of great significance for feedstock purification to produce polyethylene and other commodity chemicals but the simultaneous adsorption of C2H6 and C2H2 over C2H4 from a ternary mixture has never been realized. Herein, a robust metal–organic framework, TJT‐100, was designed and synthesized, which demonstrates remarkably selective adsorption of C2H2 and C2H6 over C2H4. Breakthrough experiments show that TJT‐100 can be used as an adsorbent for high‐performance purification of C2H4 from a ternary mixture of C2H2/C2H4/C2H6 (0.5:99:0.5) to afford a C2H4 purity greater than 99.997 %, beyond that required for ethylene polymerization. Computational studies reveal that the uncoordinated carboxylate oxygen atoms and coordinated water molecules pointing towards the pore can trap C2H2 and C2H6 through the formation of multiple C−H⋅⋅⋅O electrostatic interactions, while the corresponding C2H4–framework interaction is unfavorable.

Abstract Creating CsPbBr3 perovskite nanocrystals with bright blue emission is challenging because their optical properties depend sensitively on structure. Growing perovskites in mesoporous templates bypasses some of these purification issues because the size of the nanocrystal is governed by the dimensions of the pores. Mesoporous silica consisting of aligned channels with tunable diameter can be easily synthesized and used as a template. When the perovskite solution evaporates and retreats, some of the liquid remains trapped in the interconnecting pores by discontinuous dewetting. The precursor crystallizes, generating stable ca. 3.1 nm blue‐emitting perovskite nanocrystals. The mesoporous template also serves as a protective barrier to preserve the optical properties of the CsPbBr3 from atmospheric conditions. Compared to the bulk crystals and the powder composite, the strong blue‐shift of the emission peak in the film is accompanied by a decrease in the longer lifetime component and an 8‐fold increase in the external quantum efficiency.

Abstract Separation of acetylene from carbon dioxide and ethylene is challenging in view of their similar sizes and physical properties. Metal–organic frameworks (MOFs) in general are strong candidates for these separations owing to the presence of functional pore surfaces that can selectively capture a specific target molecule. Here, we report a novel 3D microporous cationic framework named JCM‐1. This structure possesses imidazolium functional groups on the pore surfaces and pyrazolate as a metal binding group, which is well known to form strong metal‐to‐ligand bonds. The selective sorption of acetylene over carbon dioxide and ethylene in JCM‐1 was successfully demonstrated by equilibrium gas adsorption analysis as well as dynamic breakthrough measurement. Furthermore, its excellent hydrolytic stability makes the separation processes highly recyclable without a substantial loss in acetylene uptake capacity.

Abstract The electrochemical CO 2 reduction (ECDRR), as a key reaction in artificial photosynthesis to implement renewable energy conversion/storage, has been inhibited by the low efficiency and high costs of the electrocatalysts. Herein, we synthesize a fluorine‐doped carbon (FC) catalyst by pyrolyzing commercial BP 2000 with a fluorine source, enabling a highly selective CO 2 ‐to‐CO conversion with a maximum Faradaic efficiency of 90 % at a low overpotential of 510 mV and a small Tafel slope of 81 mV dec −1 , outcompeting current metal‐free catalysts. Moreover, the higher partial current density of CO and lower partial current density of H 2 on FC relative to pristine carbon suggest an enhanced inherent activity towards ECDRR as well as a suppressed hydrogen evolution by fluorine doping. Fluorine doping activates the neighbor carbon atoms and facilitates the stabilization of the key intermediate COOH* on the fluorine‐doped carbon material, which are also blocked for competing hydrogen evolution, resulting in superior CO 2 ‐to‐CO conversion.

Abstract Theranostics provides opportunities for precision cancer therapy. However, theranostic probes that simultaneously turn on their diagnostic signal and pharmacological action only in respond to a targeted biomarker have been less exploited. We herein report the synthesis of a macrotheranostic probe that specifically activates its near‐infrared fluorescence (NIRF), photoacoustic (PA), and photothermal signals in the presence of a cancer‐overexpressed enzyme for imaging‐guided cancer therapy. Superior to the small‐molecule counterpart probe, the macrotheranostic probe has ideal biodistribution and renal clearance, permitting passive targeting of tumors, in situ activation of multimodal signals, and effective photothermal ablation. Our study thus provides a macromolecular approach towards activatable multimodal phototheranostics.

Abstract A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near‐infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self‐assemble into new cocrystals through non‐covalent interactions. The strong D–A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest‐lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency ( η =18.8 %), which is due to the active non‐radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications.

Abstract Hydrothermally stable, acid‐resistant nickel catalysts are highly desired in hydrogenation reactions, but such a catalyst remains absent owing to the inherent vulnerability of nickel under acidic conditions. An ultra‐durable Ni‐N‐C single‐atom catalyst (SAC) has now been developed that possesses a remarkable Ni content (7.5 wt %) required for practical usage. This SAC shows not only high activities for hydrogenation of various unsaturated substrates but also unprecedented durability for the one‐pot conversion of cellulose under very harsh conditions (245 °C, 60 bar H2, presence of tungstic acid in hot water). Using integrated spectroscopy characterization and computational modeling, the active site structure is identified as (Ni‐N4)⋅⋅⋅N, where significantly distorted octahedral coordination and pyridinic N constitute a frustrated Lewis pair for the heterolytic dissociation of dihydrogen, and the robust covalent chemical bonding between Ni and N atoms accounts for its ultrastability.

Abstract Nanoparticles for photothermal therapy: Real‐time temperature monitoring is critical to reduce the nonspecific damage during photothermal therapy (PTT); however, PTT agents that can emit temperature‐related signals are rare and limited to few inorganic nanoparticles. We herein synthesize a semiconducting polymer nanococktail (SPNCT) that can not only convert photo‐energy to heat but also emit temperature‐correlated luminescence after cessation of light excitation. Such an afterglow luminescence of the SPNCT detects tumors more sensitively than fluorescence as a result of the elimination of tissue autofluorescence, while its temperature‐dependent nature allows tumor temperature to be optically monitored under near‐infrared (NIR) laser irradiation. Thus, SPNCT represents the first organic optical nanosystem that enables optical‐imaging guided PTT without real‐time light excitation.

Abstract A covalent organic framework integrating naphthalenediimide and triphenylamine units (NT‐COF) is presented. Two‐dimensional porous nanosheets are packed with a high specific surface area of 1276 m 2 g −1 . Photo/electrochemical measurements reveal the ultrahigh efficient intramolecular charge transfer from the TPA to the NDI and the highly reversible electrochemical reaction in NT‐COF. There is a synergetic effect in NT‐COF between the reversible electrochemical reaction and intramolecular charge transfer with enhanced solar energy efficiency and an accelerated electrochemical reaction. This synergetic mechanism provides the key basis for direct solar‐to‐electrochemical energy conversion/storage. With the NT‐COF as the cathode materials, a solar Li‐ion battery is realized with decreased charge voltage (by 0.5 V), increased discharge voltage (by 0.5 V), and extra 38.7 % battery efficiency.

Abstract In den letzten Jahren sind die Vermüllung durch Kunststoffe und deren Persistenz in der Umwelt zu einem Schwerpunkt in Forschung und Nachrichten geworden. Bioabbaubare Polymere wie Polymilchsäure gelten als geeignete Alternativen zu Standardkunststoffen. Polymilchsäure ist jedoch im Meerwasser grundsätzlich nur schlecht abbaubar. In ähnlicher Weise hängt die Abbaurate von anderen bioabbaubaren Polymeren auch entscheidend von der Umgebung ab, in der sie enden. Dieser Kurzaufsatz zeigt, dass Abbautests unter Laborbedingungen nicht auf reale Bedingungen übertragbar sind und daher ökologisch authentische und relevante Feldtestbedingungen erforderlich sind. Zudem werden ökotoxikologische Folgen von bioabbaubaren Polymeren erwogen. Auch soziale Aspekte werden betrachtet, und die Frage wird gestellt, wie bioabbaubare Polymere das Konsumverhalten und die kommunale Abfallwirtschaft beeinflussen. Dies soll einen Beitrag zur Bewertung des Potenzials bioabbaubarer Polymere als alternative Materialien zu Standardkunststoffen leisten.

Abstract Die Modifikation von strukturell komplexen Peptiden im späten Stadium der Synthese birgt großes Potenzial unter anderem für die Wirkstoffforschung, den Pflanzenschutz und die Pharmaindustrie. Während sich traditionelle Ansätze bisher weitgehend auf Vorfunktionalisierungen stützten, hat sich die C‐H‐Aktivierungskatalyse in den letzten Jahren als immer leistungsfähigere Methode für posttranslationale Peptid‐Modifikationen mit kürzeren Syntheserouten herausgestellt. Dieser Kurzaufsatz präsentiert zusammenfassend die jüngsten Erfolge in der metallorganischen C‐H‐Aktivierung an Peptiden bis Juni 2018, unter anderem mit positions‐ und chemoselektiven Palladium‐, Ruthenium‐ und Mangankatalysatoren.

Abstract A ligand‐controlled system that enables regioselective trifluoromethylcyanation of 1,3‐enynes has been identified, which provides access to a variety of CF3‐containing tri‐ and tetrasubstituted allenyl nitriles. We disclose that the involved propargylic radicals can be selectively trapped by (Box)CuII cyanide, while the tautomerized allenyl radicals are trapped by (phen)CuII cyanide (Box= bisoxazoline, phen=phenanthroline). In addition, the reaction features broad substrate scope and excellent functional group compatibility. Moreover, this protocol represents a novel regioselectivity‐tunable functionalization of 1,3‐enynes via radicals, which we believe will have great implications for the development of catalytic systems for selectivity control in radical and organometallic chemistry.

Abstract The presence of electrocatalysis in lithium–sulfur batteries has been proposed but not yet sufficiently verified. In this study, molybdenum phosphide (MoP) nanoparticles are shown to play a definitive electrocatalytic role for the sulfur cathode working under lean electrolyte conditions featuring a low electrolyte/active material ratio: the overpotentials for the charging and discharging reactions are greatly decreased. As a result, sulfur electrodes containing MoP nanoparticles show faster kinetics and more reversible conversion of sulfur species, leading to improvements in charging/discharging voltage profiles, capacity, rate performance, and cycling stability. Taking advantage of the electrocatalytic properties of MoP, high‐performance sulfur electrodes were successfully realized that are steadily cyclable at a high areal capacity of 5.0 mAh cm−2 with a challenging electrolyte/sulfur (E/S) ratio of 4 μLE mg−1S .