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Synthesis of formate from hydrogenation of carbon dioxide (CO2) is an atom‐economic reaction but is confronted with challenges in developing high‐performance non‐precious metal catalysts for application of the process. Herein, we report a highly durable edge‐rich molybdenum disulfide (MoS2) catalyst for CO2 hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h−1 surpassing those of previously reported non‐precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS2 edges are the active sites and the selective production of formate is enabled via a completely new water‐mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO2 with residual O* reduced by hydrogen. This study provides a new route for developing low‐cost high‐performance catalysts for CO2 hydrogenation to formate. [ABSTRACT FROM AUTHOR]

The purification of p‐xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho‐ and meta‐ isomers by a microporous calcium‐based metal–organic framework material (HIAM‐203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o‐xylene (oX) and m‐xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor‐phase/liquid‐phase adsorption experiments have demonstrated the capability of HIAM‐203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism. [ABSTRACT FROM AUTHOR]

We propose an effective highest occupied d‐orbital modulation strategy engendered by breaking the coordination symmetry of sites in the atomically precise Cu nanocluster (NC) to switch the product of CO2 electroreduction from HCOOH/CO to higher‐valued hydrocarbons. An atomically well‐defined Cu6 NC with symmetry‐broken Cu−S2N1 active sites (named Cu6(MBD)6, MBD=2‐mercaptobenzimidazole) was designed and synthesized by a judicious choice of ligand containing both S and N coordination atoms. Different from the previously reported high HCOOH selectivity of Cu NCs with Cu−S3 sites, the Cu6(MBD)6 with Cu−S2N1 coordination structure shows a high Faradaic efficiency toward hydrocarbons of 65.5 % at −1.4 V versus the reversible hydrogen electrode (including 42.5 % CH4 and 23 % C2H4), with the hydrocarbons partial current density of −183.4 mA cm−2. Theoretical calculations reveal that the symmetry‐broken Cu−S2N1 sites can rearrange the Cu 3d orbitals with dx2-y2 ${d_{x^2 - y^2 } }$ as the highest occupied d‐orbital, thus favoring the generation of key intermediate *COOH instead of *OCHO to favor *CO formation, followed by hydrogenation and/or C−C coupling to produce hydrocarbons. This is the first attempt to regulate the coordination mode of Cu atom in Cu NCs for hydrocarbons generation, and provides new inspiration for designing atomically precise NCs for efficient CO2RR towards highly‐valued products. [ABSTRACT FROM AUTHOR]

The separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal‐organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Finally, we briefly discuss the existing challenges, possible solutions, and future directions of this important field. [ABSTRACT FROM AUTHOR]

We present the first example of charged imidazolium functionalized porphyrin‐based covalent organic framework (Co‐iBFBim‐COF‐X) for electrocatalytic CO2 reduction reaction, where the free anions (e.g. F−, Cl−, Br−, and I−) of imidazolium ions nearby the active Co sites can stabilize the key intermediate *COOH and inhibit hydrogen evolution reaction. Thus, Co‐iBFBim‐COF‐X exhibits higher activity than the neutral Co‐BFBim‐COF, following the trend of F−

The full separation of alkane isomers as a function of different degrees of branching remains a daunting challenge due to its stringent requirement with respect to pore dimensions of the adsorbents. In this work, we report a novel microporous coordination network built on calcium (II) and chloranilate. The compound has a flexible framework and exhibits temperature‐dependent adsorption behavior toward hexane isomers. At 30 °C, it accommodates substantial amounts of linear and monobranched hexanes but fully excludes their dibranched isomer, and at elevated temperatures such as 150 °C, it acts as a splitter for linear and branched alkanes. Its capability of efficient discrimination of hexane isomers as a function of branching is verified by experimental breakthrough measurements. Ab initio calculations have uncovered the underlying selective size‐exclusion separation mechanism. [ABSTRACT FROM AUTHOR]

High‐efficiency separation of C6 alkanes, particularly the mono‐ and dibranched isomers by using porous solids, is of paramount significance in the petrochemical industry and, remains a daunting challenge. In this work, we report the complete separation of linear/monobranched hexanes from their dibranched isomers through selective size‐exclusion by a microporous MOF, Zn‐tcpt (H3tcpt=2,4,6‐tris(4‐carboxyphenoxy)‐1,3,5‐triazine), with a two‐fold interpenetrated structure of hms nets. Importantly, its adsorption capacity and selectivity are notably higher than those of the previously reported adsorbents that can split mono‐ and dibranched alkane isomers. Dynamic breakthrough measurements verify the excellent separation of C6 alkane isomers by Zn‐tcpt, and the size‐exclusion based separation mechanism has been confirmed by ab initio materials modeling. The high‐efficiency separation of alkane isomers by Zn‐tcpt can be attributed to its optimal pore dimensions as well as high porosity. [ABSTRACT FROM AUTHOR]

The vicinal oxygen chelate (VOC) metalloenzyme superfamily catalyzes a highly diverse set of reactions with the mechanism characterized by the bidentate coordination of vicinal oxygen atoms to metal ion centers, but there remains a lack of a platform to steer the reaction trajectories, especially for o‐quinone metabolizing pathways. Herein, we present the directed‐evolution‐enabled bifunctional turnover of ChaP, which is a homotetramer and represents an unprecedented VOC enzyme class. Unlike the ChaP catalysis of extradiol‐like o‐quinone cleavage and concomitant α‐keto acid decarboxylation, a group of ChaP variants (CVs) catalyze intradiol‐like o‐quinone deconstruction and CO2 liberation from the resulting o‐hydroxybenzoic acid scaffolds with high regioselectivity. Enzyme crystal structures, labeling experiments and computational simulations corroborated that the D49L mutation allows the metal ion to change its coordination with the tyrosine phenoxy atoms in different monomers, thereby altering the reaction trajectory with the regiospecificity further improved by the follow‐up replacement of the Y92 residue with any of alanine, glycine, threonine, and serine. The study highlights the unpredicted catalytic versatility and enzymatic plasticity of VOC enzymes with biotechnological significance. [ABSTRACT FROM AUTHOR]