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| 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
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Article
| Open AccessEfficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions
The conversion of atmospheric N2 into NH3 under ambient pressure is highly interesting but very challenging. In this study, the authors present a tandem air-NOx and NOx-NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx−reduction, resulting in a high NH3 yield from N2 under ambient pressure conditions.
- Wei Liu
- , Mengyang Xia
- & Guidong Yang
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Article
| Open AccessHighly defective ultra-small tetravalent MOF nanocrystals
Crystalline materials’ properties are highly dependent on their size. Here authors report a general synthesis of ultrasmall (4–6 nm) and highly defective Zr/Hf-Metal Organic Frameworks nanoparticles that present enhanced peptide hydrolysis performance.
- Shan Dai
- , Charlotte Simms
- & Christian Serre
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Article
| Open AccessPathway-divergent coupling of 1,3-enynes with acrylates through cascade cobalt catalysis
The development of divergent reaction pathways controlled by different ligands is a critical goal. Here the authors describe a cobalt-catalyzed strategy for cascade coupling of 1,3-enynes with two molecules of acrylates through three reaction modes.
- Heng Wang
- , Xiaofeng Jie
- & Fanke Meng
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Article
| Open AccessHighly efficient anion exchange membrane water electrolyzers via chromium-doped amorphous electrocatalysts
Modulating the electronic structure of active metal sites is crucial to enhance the activity of anion-exchange membrane water electrolyzers. Here, the authors elaborate Cr-doped amorphous metal oxide catalysts with excellent activity and stability.
- Sicheng Li
- , Tong Liu
- & Tao Yao
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Article
| Open AccessLate-stage meta-C–H alkylation of pharmaceuticals to modulate biological properties and expedite molecular optimisation in a single step
Installation of small aliphatic motifs within pharmaceuticals provides a medicinally relevant tool in drug discovery programmes. Here, the authors report a late-stage meta-C–H alkylation method facilitating the biological properties modulation of therapeutic agents.
- Lucas Guillemard
- , Lutz Ackermann
- & Magnus J. Johansson
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Article
| Open AccessElectric-field-assisted proton coupling enhanced oxygen evolution reaction
Manganese complexes have long been utilized by nature to catalyze the oxygen evolution reaction (OER) but mirroring their efficiency in artificial electrochemical systems has proven difficult. This study centers on alpha-manganese dioxide (α-MnO2), which closely mimics natural MnIV-O-MnIII-HxO motifs, presenting a novel method for manipulating proton coupling within the OER process using an external electric field.
- Xuelei Pan
- , Mengyu Yan
- & Liqiang Mai
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Article
| Open AccessNoncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation
Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.
- Yushu Jin
- , Boobalan Ramadoss
- & Laurean Ilies
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Article
| Open AccessPhotocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks
The stereospecific Z/E isomerization of tetrasubstituted alkenes remains underdeveloped, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Here, authors report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by the photocatalyzed Z/E isomerization.
- Jie Wang
- , Jun Gu
- & Ying He
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Article
| Open AccessNanoparticles as an antidote for poisoned gold single-atom catalysts in sustainable propylene epoxidation
The poisoning of single-atom catalysts hampers their performance. Here, the authors propose Au nanoparticles as an antidote for poisoned Au single-atom catalysts, with trace addition shown to reinforce and sustain propylene epoxidation.
- Qianhong Wang
- , Keng Sang
- & Xuezhi Duan
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Article
| Open AccessElectrocatalytic hydrogenation of acetonitrile to ethylamine in acid
Proton exchange membrane electrolyzers hold promise for ethylamine synthesis from acetonitrile, yet local acidity fosters proton reduction. Here, authors systematically screen metal catalysts, verifying their effectiveness in such electrolyzers.
- Chongyang Tang
- , Cong Wei
- & Xiangfeng Duan
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Article
| Open AccessSolvent-free selective hydrogenation of nitroaromatics to azoxy compounds over Co single atoms decorated on Nb2O5 nanomeshes
Single atom catalysts can endow exceptional activity and selectively. Here, the authors report a single atom Co catalyst and reveal the importance of geometric and electronic properties for synthesizing azoxy compounds under solvent-free conditions.
- Zhijun Li
- , Xiaowen Lu
- & Yu Wang
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Article
| Open AccessFrustrated Lewis pair catalyst realizes efficient green diesel production
The commercial production of green diesel suffers from the requirement for continuous sulfur replenishment to maintain catalytic activity. Here, the authors report a sulfur-free catalytic system that can efficiently produce green diesel from various feedstocks over long periods of operation.
- De-Chang Li
- , Zhengyi Pan
- & Guang-Hui Wang
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Article
| Open AccessOrganocatalytic desymmetrization provides access to planar chiral [2.2]paracyclophanes
Planar chiral [2.2]paracyclophanes have a wide range of applications in asymmetric synthesis and materials science. However, they are accessed via time-consuming chiral separations or kinetic resolution approaches. Here, the authors report a simple, metal-free protocol for organocatalytic desymmetrization of prochiral diformyl[2.2]paracyclophanes.
- Vojtěch Dočekal
- , Filip Koucký
- & Jan Veselý
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Article
| Open AccessThermally stable Ni foam-supported inverse CeAlOx/Ni ensemble as an active structured catalyst for CO2 hydrogenation to methane
An inverse CeAlOx/Ni/Ni-foam structured catalyst with high thermal stability and water resistance is shown to be effective at CO2 methanation across a wide temperature range because of efficient heat/mass transport.
- Xin Tang
- , Chuqiao Song
- & Lili Lin
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Article
| Open AccessReverse water gas-shift reaction product driven dynamic activation of molybdenum nitride catalyst surface
Catalyst activation commonly occurs during reactions. This study demonstrates that the surface’s active structure in nitride catalysts during the reverse water gas-shift reaction varies with the partial pressure of reaction products, resulting in enhanced catalytic activity through positive feedback between catalytic activity and the evolution of MoNx’s active structure.
- Hui Xin
- , Rongtan Li
- & Xinhe Bao
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Article
| Open AccessLow-nuclearity CuZn ensembles on ZnZrOx catalyze methanol synthesis from CO2
The ideal metal selection and atomic-level arrangement for catalysts in CO2 hydrogenation are still uncertain. Here, copper is identified as the most effective promoter for enhancing ZnZrOx catalysts when precisely structured into CuZn ensembles, offering new insights for designing superior catalysts for CO2-based methanol synthesis.
- Thaylan Pinheiro Araújo
- , Georgios Giannakakis
- & Javier Pérez-Ramírez