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| Open AccessPhotocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers
By introducing Ni dopants into monolayer Bi2WO6, Bi/O frustrated Lewis pairs, unsaturated W atoms, and Ni active units are formed. The authors show that these units facilitate oxygen species transfer and enhance photocatalytic toluene oxidation.
- Yingzhang Shi
- , Peng Li
- & Xianzhi Fu
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Article
| Open AccessAtroposelective synthesis of biaxial bridged eight-membered terphenyls via a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization of phenols
Biaryl compounds with an axial chirality are valuable architectures but few methods have been developed for the construction of bridged biaryls, a subclass of these compounds that bear a tether to connect the two arenes and form a medium-sized ring. Here, the authors design a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization sequence of prochiral phenols for the enantioselective synthesis of biaxial bridged m-terphenyls embedded in an azocane.
- Shuang-Hu Wang
- , Shi-Qiang Wei
- & Tong-Mei Ding
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Article
| Open AccessCO electrolysis to multicarbon products over grain boundary-rich Cu nanoparticles in membrane electrode assembly electrolyzers
Producing valuable chemicals like ethylene via catalytic CO conversion is an important nonpetroleum route. Here, authors demonstrate high-rate electrosynthesis of multicarbon chemicals via CO electrolysis, with a multicarbon product partial current density of 4.35 A cm−2 at a cell voltage of 2.78 V.
- Hefei Li
- , Pengfei Wei
- & Xinhe Bao
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Article
| Open AccessCatalytic asymmetric synthesis of planar-chiral dianthranilides via (Dynamic) kinetic resolution
Chirality has long fascinated chemists, but asymmetric synthesis has largely focused on central, axial, and helical chirality to date. Here, the authors synthesize dianthranilides with planar chirality, via cinchona alkaloid-catalyzed (dynamic) kinetic resolution.
- Chun-Yan Guan
- , Shuai Zou
- & Guang-Jian Mei
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Article
| Open AccessCatalytic asymmetric [4 + 2] dearomative photocycloadditions of anthracene and its derivatives with alkenylazaarenes
While significant progress has been made in classical Diels-Alder reactions, the use of simple and inert feedstock chemicals under mild reaction conditions still remains challenging. Here the authors present the development of catalytic asymmetric [4 + 2] dearomative photocycloaddition involving anthracene and its derivatives with alkenylazaarenes.
- Dong Tian
- , Wenshuo Shi
- & Zhiyong Jiang
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Article
| Open AccessEmergence of a short peptide based reductase via activation of the model hydride rich cofactor
Biological cofactors such as dihydronicotinamides are exploited by extant enzymes as hydride transfer agents and electron carriers but are generally inefficient to facilitate any reactions on their own. Here, the authors report short peptide-based amyloid nanotubes featuring exposed arrays of cationic and hydrophobic residues that can bind small hydride transfer agents (NaBH4) to facilitate efficient reduction of ester substrates in water.
- Ayan Chatterjee
- , Surashree Goswami
- & Dibyendu Das
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Article
| Open AccessCobalt-catalyzed cross-electrophile coupling of alkynyl sulfides with unactivated chlorosilanes
Transition-metal catalyzed cross-electrophile coupling (XEC) is a powerful tool for the construction of molecules but XEC between carbon electrophile and chlorosilanes to access organosilicon compounds remains underdeveloped. Here the authors disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of a broad range of unactivated chlorosilanes with alkynyl sulfides as a stable and practical alkynyl electrophiles.
- Donghui Xing
- , Jinlin Liu
- & Liangbin Huang
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Article
| Open AccessEnantioselective nickel-catalyzed anodic oxidative dienylation and allylation reactions
Precision control of stereochemistry in radical reactions remains a formidable challenge. Here the authors demonstrate an electricity driven asymmetric Lewis acid catalysis to facilitate asymmetric dienylation and allylation reactions, resulting in the formation of all-carbon quaternary stereocenters.
- Qinglin Zhang
- , Jiayin Zhang
- & Chang Guo
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Article
| Open AccessIn-situ noncovalent interaction of ammonium ion enabled C–H bond functionalization of polyethylene glycols
The noncovalent interaction of ammonium ion with multidentate oxygen-based host serving as a key reacting center in catalytic reactions is rare. In this work, the authors report a noncovalent interaction of ammonium ion enabled reactivity enhancement process, achieving the C–H functionalization of polyethylene glycols with acrylates.
- Zongnan Zhang
- , Xueli Lv
- & Rong Zeng
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Article
| Open AccessUnusual facet and co-catalyst effects in TiO2-based photocatalytic coupling of methane
Designing photocatalysts to enhance the efficiency of non-oxidative coupling of methane is a challenging task. Here, the authors report that the anatase TiO2 with exposed {101} facets and Pd co-catalyst enables efficient and selective methane coupling to ethane via a heterogeneous-homogeneous hybrid reaction pathway.
- Huizhen Zhang
- , Pengfei Sun
- & Ye Wang
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Article
| Open AccessTitanium catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]-butanes with 1,3-dienes for efficient synthesis of stilbene bioisosteres
Natural stilbenes show significant potential in the prevention and treatment of diseases due to their diverse pharmacological activities. Here the authors present a mild and effective Ti-catalyzed intermolecular radical-relay cycloaddition reaction with good regio- and trans-selectivity offering rapid access to structurally diverse stilbene bioisosteres.
- Yonghong Liu
- , Zhixian Wu
- & Lei Shi
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Article
| Open AccessA rationally designed miniature of soluble methane monooxygenase enables rapid and high-yield methanol production in Escherichia coli
Soluble methane monooxygenase (sMMO) is a potentially value biocatalyst, but production of active recombinant sMMO is very challenging. Here the authors report the rational design and construction of a catalytically active miniature sMMO which enables high-yield production of methanol in E. coli.
- Yeonhwa Yu
- , Yongfan Shi
- & Jeewon Lee
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Article
| Open AccessOrganocatalytic skeletal reorganization for enantioselective synthesis of S-stereogenic sulfinamides
The enantioselective synthesis of S-stereogenic sulfinamides has garnered considerable attention due to their unique structural and physicochemical properties but catalytic asymmetric synthesis of sulfinamides still remains challenging. Here, the authors present the synthesis of S-stereogenic sulfinamides through the peptide-mimic phosphonium salt-catalyzed asymmetric skeletal reorganization of simple prochiral and racemic sulfoximines.
- Zanjiao Liu
- , Siqiang Fang
- & Tianli Wang
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Article
| Open AccessDiastereoselective dearomatization of indoles via photocatalytic hydroboration on hydramine-functionalized carbon nitride
Dearomative hydroboration of predominantly existing indole derivatives provides a straightforward strategy to synthesize boryl indolines, but developing eco-friendly methods for remains challenging. Here, the authors develop a method for heterogeneous photocatalytic trans-hydroboration of indole derivatives with NHC-borane.
- Qiao Zhang
- , Wengang Xu
- & Mingbo Wu
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Article
| Open AccessObservation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry
Allylic substitution reaction of alkenes has been well-developed, but it has limitations, partly due to the intrinsic predilection for an inner-sphere mechanism. Herein, the authors present an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates.
- Yaxin Zeng
- , Han Gao
- & Ying Xia
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Article
| Open AccessAtomically dispersed Iridium on Mo2C as an efficient and stable alkaline hydrogen oxidation reaction catalyst
High-performance hydroxide exchange membrane fuel cells rely on the anode loading of platinum-group metals. Here, the authors report a highly active hydrogen oxidation electrocatalyst which contains atomically dispersed Ir on Mo2C nanoparticles supported on a carbon substrate.
- Jinjie Fang
- , Haiyong Wang
- & Zhongbin Zhuang
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Article
| Open AccessSingle-zinc vacancy unlocks high-rate H2O2 electrosynthesis from mixed dioxygen beyond Le Chatelier principle
The principle of Le Chatelier is a fundamental concept in textbooks, serving as a guiding principle for controlling chemical and catalytic systems. In this study, the authors present an oxygen electroreduction system based on a single zinc vacancy catalyst, which operates in a manner that extends “beyond” Le Chatelier’s principle.
- Qi Huang
- , Baokai Xia
- & Sheng Chen
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Article
| Open AccessRedox-induced controllable engineering of MnO2-MnxCo3-xO4 interface to boost catalytic oxidation of ethane
The exploration of heterogeneous interfaces between metal oxides has received limited attention. Here the authors demonstrated the creation of MnO2-MnxCo3-xO4 interfaces through controlled chemical reduction processes, effectively altering electron distribution and yielding a superior catalyst for ethane oxidation.
- Haiyan Wang
- , Shuang Wang
- & Xinwen Guo
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Article
| Open AccessAsymmetric C–H Dehydrogenative Alkenylation via a Photo-induced Chiral α‑Imino Radical Intermediate
The direct alkenylation with simple alkenes stands out as the most ideal yet challenging strategy for obtaining high-valued desaturated alkanes. Herein, the authors present a direct asymmetric dehydrogenative α-C(sp3)-H alkenylation of carbonyls based on synergistic photoredox-cobalt-chiral primary amine catalysis under visible light.
- Zongbin Jia
- , Liang Cheng
- & Sanzhong Luo
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Article
| Open AccessAtomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media
The relationship between the structural configurations of M-N-C electrocatalysts and their performances in neutral environments has been insufficiently investigated. Here the authors demonstrate that an ultralow metal-loaded Co-N-C electrocatalyst, featuring the asymmetric Co-C/N/O configuration, exhibit exceptional efficiency in electrochemically producing hydrogen peroxide under neutral conditions.
- Longxiang Liu
- , Liqun Kang
- & Guanjie He
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Article
| Open AccessRapid and scalable photocatalytic C(sp2)–C(sp3) Suzuki−Miyaura cross-coupling of aryl bromides with alkyl boranes
In recent years a growing demand for drug design approaches that incorporate a higher number of sp3-hybridized carbons fuelled the development of innovative cross-coupling strategies to reliably introduce aliphatic fragments. Here, the authors present a powerful approach for the light-mediated B-alkyl Suzuki−Miyaura crosscoupling between alkyl boranes and aryl bromides.
- Ting Wan
- , Luca Capaldo
- & Timothy Noël
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Article
| Open AccessSynergistic growth of nickel and platinum nanoparticles via exsolution and surface reaction
Utilizing “Chemistry at a point”, Ni is exsolved from a perovskite lattice under deposited Pt nanoparticles. This yields even smaller Ni Pt alloy nanoparticles on a perovskite nanofiber structure, exhibiting high catalytic activity.
- Min Xu
- , Yukwon Jeon
- & John T. S. Irvine
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Article
| Open AccessOperando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction
Controlling the selectivity of the electroreduction of CO2 to value-added products is challenging. Here, authors use sub-second operando Raman spectroscopy to analyze Cu catalyst surfaces and discover the pivotal role of co-adsorbed OH and CO in enhancing ethanol selectivity.
- Antonia Herzog
- , Mauricio Lopez Luna
- & Beatriz Roldan Cuenya
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Article
| Open AccessDeciphering complexity in Pd–catalyzed cross-couplings
Knowledge about the full reaction signature, such as the complete profile of products and side-products is important in accelerating discovery chemistry. Here, the authors report a methodology using high-throughput experimentation and multivariate data analysis to examine Palladium- catalyzed cross-coulpling reactions.
- George E. Clarke
- , James D. Firth
- & Ian J. S. Fairlamb
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Article
| Open AccessBicontinuous RuO2 nanoreactors for acidic water oxidation
Developing stable water oxidation catalysts is of great importance for proton-exchange membrane water electrolyzers. Here the authors report a bicontinuous nanoreactor composed of multiscale defected RuO2 nanocrystals for robust acidic water oxidation reactivity.
- Ding Chen
- , Ruohan Yu
- & Shichun Mu
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Article
| Open AccessVisualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis
Industrial methanol synthesis uses materials based on Cu and ZnO. We present high-resolution imaging of active surfaces which reveals how Zn species are transported at the active Cu interface in diffusion processes controlled by the reactant gas composition.
- Sigmund Jensen
- , Mathias H. R. Mammen
- & Jeppe V. Lauritsen
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Article
| Open Access“On-Water” accelerated dearomative cycloaddition via aquaphotocatalysis
Developing water compatible synthetic methods for Sulfur(VI) fluoride exchange (SuFEx) chemistry is of paramount importance. Here the authors demonstrate a catalytic dearomative [2+2] photocycloaddition that significantly speeds up the synthesis of heterocyclic alkyl SuFEx hubs, leveraging the unique reactivity at the water-oil interface.
- Soo Bok Kim
- , Dong Hyeon Kim
- & Han Yong Bae
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Article
| Open AccessHigh yield electrosynthesis of oxygenates from CO using a relay Cu-Ag co-catalyst system
Using CO and H2O to electrosynthesize oxygenates is a possible low-carbon synthetic route. Here, the authors study the CO adsorption behavior on Ag catalysts and design a Cu-Ag nanostructure catalyst with a relay mechanism that enhances the electrosynthesis of oxygenates.
- Nannan Meng
- , Zhitan Wu
- & Kian Ping Loh
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Article
| Open AccessInterplay of structural preorganization and conformational sampling in UDP-glucuronic acid 4-epimerase catalysis
Enzymes involve structural flexibility in their function, but understanding enzyme catalysis as connected to protein motions is a major challenge. Here, the authors obtain energetic description of C-H activation in nicotinamide coenzyme-dependent UDP-glucuronic acid C4 epimerase based on temperature kinetic studies and isotope effect measurements.
- Christian Rapp
- , Annika Borg
- & Bernd Nidetzky
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Article
| Open AccessCapture of single Ag atoms through high-temperature-induced crystal plane reconstruction
Terminal hydroxyl groups on γ-Al2O3 surfaces serve as anchoring sites for Ag. Based on the surface energy of different crystal planes of γ-Al2O3 at various temperatures, the authors propose a high-temperature-induced crystal plane transformation method to construct terminal hydroxyl anchoring sites.
- Jiaxin Li
- , Kai Li
- & Hong He
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Article
| Open AccessElectrochemical C−H deuteration of pyridine derivatives with D2O
Despite the established C − H deuteration of pyridine derivatives synthetic methods with good D-incorporation, under milder conditions with easy operation procedures is still on the way. Here, the authors develop a straightforward, metal-free, and acid-/base-free electrochemical C4-selective C − H deuteration of pyridine derivatives with high selectivity and excellent D-incorporation at room temperature, which use D2O as economic and convenient D-source.
- Zhiwei Zhao
- , Ranran Zhang
- & Youai Qiu
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Article
| Open AccessIn-silico-assisted derivatization of triarylboranes for the catalytic reductive functionalization of aniline-derived amino acids and peptides with H2
Machine learning has not been strategically applied to design main-group catalysts. Here, the authors built an in-silico library of triarylboranes, which was used to identify reactive catalysts for functionalizing amino acids and peptides with H2.
- Yusei Hisata
- , Takashi Washio
- & Yoichi Hoshimoto
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Article
| Open AccessEnantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch
Catalytic and enantioselective construction of chiral α,α-dialkyl indoles represents an important yet challenging objective to be developed. Herein the authors describe a cobalt catalyzed enantioselective anti-Markovnikov alkene hydroalkylation via the remote stereocontrol for the synthesis of α,α-dialkyl indoles and other N-heterocycles.
- Jiangtao Ren
- , Zheng Sun
- & Zhihui Shao
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Article
| Open AccessFacilitating the dry reforming of methane with interfacial synergistic catalysis in an Ir@CeO2−x catalyst
Dry reforming of methane is an attractive route to convert greenhouse gases into valuable syngas. Here, the authors demonstrate design strategy to prepare efficient catalysts towards activation of both C–H and C = O bonds and provide atomic-level insights into interfacial synergistic catalysis.
- Hui Wang
- , Guoqing Cui
- & Min Wei
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Article
| Open AccessCarbon–nitrogen transmutation in polycyclic arenol skeletons to access N-heteroarenes
Developing skeletal editing tools, especially to realize the single-atom transmutation in a ring system without altering the ring size is challenging. Here, the authors introduce a skeletal editing strategy that enables polycyclic arenols to be readily converted into N-heteroarenes through carbon–nitrogen transmutation.
- Hong Lu
- , Yu Zhang
- & Hao Wei
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Article
| Open AccessSelective production of methylindan and tetralin with xylose or hemicellulose
Indan and tetralin are used as fuel additives and intermediates in the manufacture of many products, including thermal-stable jet fuel. Here the authors report a route for the synthesis of methylindan and tetralin by the hydrogenolysis of xylose or hemicellulose over a non-noble metal catalyst, followed by further reaction over zeolite H-ZSM-5. Reviewer recognition:
- Zhufan Zou
- , Zhenjie Yu
- & Ning Li
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Article
| Open AccessDinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes
The widespread use of organoboronic acids has prompted the development of synthetic methodologies to meet the demands on structural diversity and functional group tolerance. Herein, the authors disclose a divergent radical dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation.
- Cheng-Long Ji
- , Hongliang Chen
- & Jin Xie
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Article
| Open AccessA human-machine interface for automatic exploration of chemical reaction networks
Automated reaction exploration is the key to systematic elucidation of chemical mechanisms. Here, the authors introduce a generally applicable algorithm to steer an automated exploration towards region of interest in chemical reaction space.
- Miguel Steiner
- & Markus Reiher
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Article
| Open AccessDiastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction
Developing an efficient method for the stereocontrolled synthesis of all stereoisomers of chiral hindered ethers is highly desirable but challenging. Here, the authors report an asymmetric cascade reaction catalyzed by a bimetallic catalytic system with control over the configuration of the stereocenters of tetra-aryl substituted ethers.
- Xiangfeng Lin
- , Xia Mu
- & Can Li
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Article
| Open AccessThe role of charge in microdroplet redox chemistry
Redox reactions exhibit different thermodynamics and kinetics in water microdroplets compared to the bulk. Here, the authors use reactive molecular dynamics to show the importance of charged reactive species in explaining reactivity under confinement.
- Joseph P. Heindel
- , R. Allen LaCour
- & Teresa Head-Gordon
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Article
| Open AccessCatalytic 1,1-diazidation of alkenes
Compared to well-developed catalytic 1,2-diazidation of alkenes, the corresponding catalytic 1,1-diazidation of alkenes has not been realized. Here, the authors report an efficient approach for catalytic 1,1-diazidation of alkenes by redox-active selenium catalysis.
- Wangzhen Qiu
- , Lihao Liao
- & Xiaodan Zhao
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Article
| Open AccessIn situ enzymatic control of colloidal phoresis and catalysis through hydrolysis of ATP
The design of synthetic systems that can sense chemical gradients and respond with directional motility and chemical activity is of interest. Here, the authors realize and control such behaviors in a synthetic system by tailoring multivalent interactions of adenosine nucleotides with catalytic microbeads.
- Ekta Shandilya
- , Bhargav Rallabandi
- & Subhabrata Maiti
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Article
| Open AccessAllotrope-dependent activity-stability relationships of molybdenum sulfide hydrogen evolution electrocatalysts
The stability of non-noble catalysts is key for their use in proton exchange membrane water electrolysers. Here, authors study activity-stability relationships of MoSx allotropes for H2 production, reporting allotrope-dependent stabilities and dissolution pathways, and propose operation guidelines.
- Daniel Escalera-López
- , Christian Iffelsberger
- & Serhiy Cherevko
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Article
| Open AccessMolecular tuning boosts asymmetric C-C coupling for CO conversion to acetate
This work presents a general surface molecular tuning strategy to promote the electrochemical reduction of CO.
- Jie Ding
- , Fuhua Li
- & Bin Liu
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Article
| Open AccessSpatial decoupling of bromide-mediated process boosts propylene oxide electrosynthesis
The practical application of electrosynthesis of propylene oxide is hindered by limited performance. Here, the authors report a spatial decoupling strategy by utilizing the bromide mediator to link propylene and anode within separated reactors, realizing high-performance electrosynthesis of propylene oxide.
- Mingfang Chi
- , Jingwen Ke
- & Jie Zeng
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Article
| Open AccessEfficient tandem electroreduction of nitrate into ammonia through coupling Cu single atoms with adjacent Co3O4
An optimal catalyst for nitrate electroreduction should satisfy the simultaneously optimized adsorption of intermediates. Here, the authors report a tandem electrocatalyst by combining Cu single atoms with Co3O4 nanosheets, enhancing the binding with NO2−, thus promoting nitrate electroreduction to NH3.
- Yan Liu
- , Jie Wei
- & Jie Zeng
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Article
| Open AccessPlasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NOx
Achieving supported nanoclusters with unique geometric and electronic structures continues to pose a challenge. Here, the authors introduce a plasma-assisted treatment approach for generating supported metal oxide nanoclusters, facilitated by the rapid transformation of monomeric dispersed metal oxides.
- Yong Yin
- , Bingcheng Luo
- & Xiang Li
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Article
| Open AccessIron-catalyzed stereoselective C–H alkylation for simultaneous construction of C–N axial and C-central chirality
A highly efficient stereoselective C−H alkylation of indoles with aryl alkenes is achieved by sustainable iron catalysis, leading to atropoenriched and enantioenriched substituted indoles with high structural diversity. Detailed mechanistic studies by experiment, Mössbauer spectroscopy and computation reveal the origin of the catalytic efficacy and stereoselectivity.
- Zi-Jing Zhang
- , Nicolas Jacob
- & Lutz Ackermann
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Perspective
| Open AccessEmerging trends in chiral inorganic nanomaterials for enantioselective catalysis
Considerable attention has been directed towards chiral nanocatalysts due to their significant role in facilitating asymmetric organic transformations. Here the authors highlight the recent advancements and notable examples in the field of chiral inorganic nanocatalysts.
- Si Li
- , Xinxin Xu
- & Chuanlai Xu