Featured
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Article
| Open AccessCobalt catalyzed practical hydroboration of terminal alkynes with time-dependent stereoselectivity
Stereodefined vinylboron compounds are important organic synthons, but the selective generation of the thermodynamically unfavorable Z-isomers remains challenging. Here, the authors develop a cobalt catalytic system, enabling the transformation of terminal alkynes with excellent Z-selectivity, even in the presence of bulky substituents.
- Jinglan Wen
- , Yahao Huang
- & Peng Hu
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Article
| Open AccessLiquid metals for boosting stability of zeolite catalysts in the conversion of methanol to hydrocarbons
For the methanol-to-hydrocarbons process, coke build can rapidly deactivate the zeolite catalyst. Here the authors show that the addition of liquid metal gallium can reduce coke deposition and increase catalyst lifetime.
- Yong Zhou
- , Sara Santos
- & Vitaly V. Ordomsky
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Article
| Open AccessSpatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation
Integrating heterogeneous single atom nanozyme (SAzyme) configurations and homogeneous enzyme-like mechanism is promising for optimizing SAzymes but elusive. Here the authors address this issue by developing a spatial engineering strategy to fabricate dual-sites SAzymes incorporating single atom Fe active centers (Fe–N4) and Cu atomic sites (Cu–N4) in a vertically stacked Fe–N4 and Cu–N4 geometry.
- Ying Wang
- , Vinod K. Paidi
- & Kwok-Yin Wong
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Article
| Open AccessEnantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution
Site- and stereoselective C–H functionalization is challenging in the synthetic chemistry, and the catalytic enantioselective C(sp3)–H functionalization based on vinyl cations has scarcely explored. Here, the authors report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp3)–H insertion reaction via a kinetic resolution.
- Yang-Bo Chen
- , Li-Gao Liu
- & Long-Wu Ye
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Article
| Open AccessSelective hydrodeoxygenation of α, β-unsaturated carbonyl compounds to alkenes
The selective reduction of α, β-unsaturated carbonyls remains a challenge. Here the authors report a zinc-based catalyst for this reaction, converting α, β-unsaturated carbonyl compounds into unsaturated alcohols followed by hydrodeoxygenation to form alkenes.
- Tianjiao Wang
- , Yu Xin
- & Buxing Han
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Article
| Open AccessA Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol
Carbon dioxide hydrogenation is an important industrial reaction. Here, the authors design a CeCuZn catalyst through a metal organic framework template for CO2 hydrogenation to methanol with excellent methanol yield and stability.
- Runping Ye
- , Lixuan Ma
- & Jian Liu
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Article
| Open AccessSurface hydrophobization of zeolite enables mass transfer matching in gas-liquid-solid three-phase hydrogenation under ambient pressure
A modified zeolite nanoreactor with organosilanes boosts hydrogenation of aldehydes/ketones in water at ambient pressure. This method, promoting H2 and substrate mass transfer, achieves a 4.3-fold increase in reaction rate, offering a sustainable approach for organic synthesis under mild conditions.
- Shuai Wang
- , Riming Hu
- & Guozhu Chen
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Article
| Open AccessInterrogating site dependent kinetics over SiO2-supported Pt nanoparticles
Kim and co-workers introduce a new ‘kinetic site deconvolution’ method to identify active sites on heterogeneous catalysts by linking reaction rates to specific adsorption environments.
- Taek-Seung Kim
- , Christopher R. O’Connor
- & Christian Reece
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Article
| Open AccessDesymmetric homologating annulation to access chiral pentafulvenes and their application in bioimaging
Polycyclic/multisubstituted pentafulvenes are of interest as they frequently occur in biologically relevant motifs, electrochromic dyes, and solar cells. Here, the authors report an enantioselective homologating annulation of cyclopent-4-ene-dione with 3-cyano-4-methylcoumarins through L-tert-leucine derived thiourea catalysis, affording a wide range of enantioenriched polycyclic multi-substituted embedded aminopentafulvenes.
- Sanjay Singh
- , Ravi Saini
- & Ravi P. Singh
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Article
| Open AccessCopper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a stable and selective CO2 hydrogenation catalyst
Here, authors report an inter-site structural heterogeneity induced effect of hierarchical single atom Fe catalysts for robust oxygen reduction. Dynamic evolutions and insights into structure-activity relationship are presented.
- Vijay K. Velisoju
- , Jose L. Cerrillo
- & Pedro Castaño
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Article
| Open AccessWood-inspired metamaterial catalyst for robust and high-throughput water purification
Continuous industrialization and human activities have led to severe water quality deterioration. Here, a structure-function integrated system is developed by Douglas fir wood inspired metamaterial catalysts with robust and high throughput water purification performances.
- Lei Zhang
- , Hanwen Liu
- & Jian Lu
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Article
| Open AccessIdentification of a potent palladium-aryldiphosphine catalytic system for high-performance carbonylation of alkenes
The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Here, the authors develop an aryldiphosphine ligand, used in palladium-catalyzed regioselective carbonylation of alkenes, exhibiting high catalytic performance and strong oxygen-resistance stability.
- Kang Zhao
- , Hongli Wang
- & Feng Shi
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Article
| Open AccessA non-canonical nucleophile unlocks a new mechanistic pathway in a designed enzyme
The authors previously showed that a histidine nucleophile and a flexible arginine can work in synergy to accelerate the Morita Baylis-Hillman (MBH) reaction. Here, they report another efficient MBHase that employs a non-canonical Nδ-methylhistidine nucleophile paired with a catalytic glutamate, providing an alternative mechanistic solution for MBH catalysis.
- Amy E. Hutton
- , Jake Foster
- & Anthony P. Green
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Article
| Open AccessSilver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
Epoxides are prominent small-ring O-heterocycles found in a variety of bioactive natural products and pharmaceuticals. Here, the authors report a silver carbene strategy to achieve O-to-C atom exchange of epoxides in a single step, affording diverse fluoroalkylcyclopropanes.
- Linxuan Li
- , Paramasivam Sivaguru
- & Xihe Bi
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Article
| Open AccessInfluence of electric double layer rigidity on CO adsorption and electroreduction rate
High-pressure infrared spectroscopy shows concentrated cations suppress CO adsorption. Here the authors report two electrochemical interfaces forming distinct double layer structures and reaction rates at elevating pressure and various potentials.
- Jiajie Hou
- , Bingjun Xu
- & Qi Lu
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Article
| Open AccessDioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation
The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.
- Jialiang Wei
- , Junhong Meng
- & Ning Jiao
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Article
| Open AccessCharging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction
The catalytic efficacy of covalent organic frameworks (COFs) is constrained by their restricted electro-transfer capability and weak binding affinities for reaction intermediates. Here the authors report COFs with various pyridinic-based units for tuning their catalytic activity towards oxygen reduction reaction.
- Xiubei Yang
- , Qizheng An
- & Gaofeng Zeng
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Article
| Open AccessSingle-atom tailored atomically-precise nanoclusters for enhanced electrochemical reduction of CO2-to-CO activity
Tailoring catalytic performance of atomically-precise metal nanoclusters catalysts is of great interest but remains challenging. Here, the authors report a co-eletropolymerization strategy to modify well-defined Au8 nanoclusters by single-atom sites to enhance its electrocatalytic activity for the reduction of CO2 towards CO.
- Yi-Man Wang
- , Fang-Qin Yan
- & Shuang-Quan Zang
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Article
| Open AccessZirconium and hafnium catalyzed C–C single bond hydroboration
Selective cleavage and subsequent functionalization of C−C single bonds present a fundamental challenge, and the use of inexpensive and Earth-abundant group IV metals for catalytic C−C single-bond cleavage is largely underdeveloped. Here, the authors report zirconium-catalyzed C−C single-bond cleavage and subsequent hydroboration reactions.
- Sida Li
- , Haijun Jiao
- & Lipeng Wu
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Article
| Open AccessTuning light-driven oxidation of styrene inside water-soluble nanocages
Selective functionalization of C(sp2)–H bonds under ambient conditions is a persistent synthetic challenge in organic chemistry. Here the authors combine host-guest charge-transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration.
- Souvik Ghosal
- , Ankita Das
- & Jyotishman Dasgupta
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Article
| Open AccessContinuous strain tuning of oxygen evolution catalysts with anisotropic thermal expansion
Tuning compressive strain is an effective way to accelerate the oxygen evolution reaction kinetics. Here the authors show that anisotropic thermal expansion induces compressive strains on IrO6 octahedron in Sr2IrO4, shifting its d-band center downward and accelerating water oxidation kinetics beyond traditional thermal diffusion effects.
- Yu Du
- , Fakang Xie
- & Zhigang Zou
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Article
| Open AccessNickel-catalyzed electrophiles-controlled enantioselective reductive arylative cyclization and enantiospecific reductive alkylative cyclization of 1,6-enynes
Transition metal-catalyzed asymmetric cyclization of 1,6-enynes is a powerful tool for the construction of chiral nitrogen-containing heterocycles, but limiting to the use of aryl or alkenyl metal reagents. Here, the authors report Ni-catalyzed enantioselective anti-arylative cyclization and enantiospecific cis-alkylative cyclization of 1,6-enynes.
- Wenfeng Liu
- , Yunxin Xing
- & Kun Shen
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Article
| Open AccessDual-site segmentally synergistic catalysis mechanism: boosting CoFeSx nanocluster for sustainable water oxidation
Efficient oxygen evolution reaction electrocatalysts are essential for sustainable clean energy conversion. Here, the authors propose a Co-Fe dual-site to facilitate the ferromagnetic O-O bond coupling to achieve a great balance between activity and stability.
- Siran Xu
- , Sihua Feng
- & Jia-Nan Zhang
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Article
| Open AccessDistance effect of single atoms on stability of cobalt oxide catalysts for acidic oxygen evolution
Dissolution of Co atoms in acidic media impedes the application of cobalt oxides in proton exchange membrane water electrolyzers. Here, the authors reveal a stabilizing effect induced by Ir single atoms on cobalt oxides that suppress Co dissolution.
- Zhirong Zhang
- , Chuanyi Jia
- & Jie Zeng
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Article
| Open AccessRemote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins
The synthesis of highly substituted olefins has been pursued for decades. Here, the authors show a carbonyl-directed sequential Heck/isomerization/C–H arylation of alkenes for modular synthesis of stereodefined all-carbon tetrasubstituted olefins.
- Runze Luan
- , Ping Lin
- & Weiping Su
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Article
| Open AccessNanocurvature-induced field effects enable control over the activity of single-atom electrocatalysts
Modulating interfacial electric fields provides a means to control electrocatalyst activity for a broad range of reactions. Here the authors show that this can be achieved by tuning the nanocurvature of carbon supported single-atom catalysts.
- Bingqing Wang
- , Meng Wang
- & Yanwei Lum
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Article
| Open AccessCoverage enhancement accelerates acidic CO2 electrolysis at ampere-level current with high energy and carbon efficiencies
The increased surface coverage of CO2 electroreduction (CO2R) intermediates promotes CO2R at high operating current densities under strongly acidic conditions. Here the authors report a 77.4% single-pass carbon efficiency for conversion of acidic CO2R to pure formic acid.
- Xiaohan Yu
- , Yuting Xu
- & Miao Zhong
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Article
| Open AccessIn situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction
The electrochemical oxygen reduction reaction plays an important role in new energy technologies such as fuel cells and metal-air batteries. Here the authors present a cobalt catalyst with a symmetry-broken Cl−Co−N4 moiety capable of dynamically modulating electron occupancy at active sites during practical reaction conditions to optimize oxygen reduction performance.
- Meihuan Liu
- , Jing Zhang
- & Qinghua Liu
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Article
| Open AccessSuperexchange-stabilized long-distance Cu sites in rock-salt-ordered double perovskite oxides for CO2 electromethanation
Cu-oxide-based catalysts are promising for CO2 electromethanation but suffer from inevitable reduction and structural collapse. Here the authors report a Cu-based rock-salt-ordered double perovskite oxide with superexchange-stabilized long-distance Cu sites for efficient and stable CO2 methanation.
- Jiawei Zhu
- , Yu Zhang
- & Heqing Jiang
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Article
| Open AccessCooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline
The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.
- Le Wang
- , Cheng-Long Wang
- & Shu-Yu Zhang
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Article
| Open AccessMetal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes
Enhancing the sp3-hybridized character of molecular structures in drug discovery is paramount. Here, the authors introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation.
- Stefano Bonciolini
- , Antonio Pulcinella
- & Timothy Noël
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Review Article
| Open AccessChallenges and recent advancements in the synthesis of α,α-disubstituted α-amino acids
α,α-Disubstituted α-amino acids (α-AAs) have improved properties compared to other amino acids. Here, the authors provide an overview of the recent advancements since 2015 and discuss existing challenges for their synthesis.
- Yu Zhang
- , Jaro Vanderghinste
- & Shoubhik Das
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Article
| Open AccessIron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay
Stoichiometric amounts of metal reductant and the requirement of a directing group limit the application of transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides. Here, the authors report a reductive difunctionalization of alkenes via a radical-anion relay with Na2S2O4 as both reductant and sulfone-source.
- Xiaoya Hou
- , Hongchi Liu
- & Hanmin Huang
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Article
| Open AccessOxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy
Direct use of flue gas for the electrocatalytic CO2 reduction reaction is desirable but severely limited by the thermodynamically favorable oxygen reduction reaction. Here the authors report an oxygen passivation strategy to improve electrocatalytic CO2 reduction reaction under aerobic conditions using a covalent organic frameworks with a photoswitching unit.
- Hong-Jing Zhu
- , Duan-Hui Si
- & Yuan-Biao Huang
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Article
| Open AccessAccessing ladder-shape azetidine-fused indoline pentacycles through intermolecular regiodivergent aza-Paternò–Büchi reactions
Conformationally rigid 3D molecules are of high interest. Here the authors develop intermolecular aza-Paternò-Büchi reactions to access ladder-shape azetidine-fused indoline pentacycles with excellent regiodivergency and stereoselectivity.
- Jianjian Huang
- , Tai-Ping Zhou
- & Fangrui Zhong
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Article
| Open AccessIntegrating hydrogen utilization in CO2 electrolysis with reduced energy loss
Electrochemical CO2 reduction is a promising method of producing sustainable chemicals and fuels, yet is highly energy intensive. Here, the authors couple CO2 electrolysis with hydrogen oxidation using a Ni(OH)2/NiOOH auxiliary electrode to enhance energy efficiency.
- Xiaoyi Jiang
- , Le Ke
- & Ning Yan
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Article
| Open AccessCharacterization of A π–π stacking cocrystal of 4-nitrophthalonitrile directed toward application in photocatalysis
Photoexcitation of the electron-donor-acceptor (EDA) complexes are an effective approach to achieve radicals by triggering electron transfer but the catalytic version of EDA complex photoactivation remains underdeveloped. Here, the authors introduce 4-nitrophthalonitrile as an electron acceptor to facilitate π-stacking with electron-rich aromatics to form EDA complexes.
- Ting Xue
- , Cheng Ma
- & Rong Zeng
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Article
| Open AccessElectrocatalytic water oxidation with manganese phosphates
Understanding water oxidation on Mn-based catalysts remains a long-standing challenge. Here, the authors use homologous KMnPO4 and KMnPO4•H2O as model catalyst to show that Mn(V)=O is responsible for O−O bond formation and its concentration determines the intrinsic activity.
- Shujiao Yang
- , Kaihang Yue
- & Wei Zhang
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Article
| Open AccessIn-situ formatting donor-acceptor polymer with giant dipole moment and ultrafast exciton separation
Donor-acceptor polymers have potential for application in photocatalysis, but often harsh synthetic conditions are required. Here, the authors report a post-synthetic method for conversion to donor-acceptor states, to give a polymer capable of enhancing photocatalytic hydrogen peroxide synthesis.
- Chang Cheng
- , Jiaguo Yu
- & Mietek Jaroniec
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Article
| Open AccessMicroenvironment reconstitution of highly active Ni single atoms on oxygen-incorporated Mo2C for water splitting
The comprehensive understanding of complex catalytic mechanisms under harsh reaction conditions for efficient bifunctional single-atom electrocatalysts remain challenging. Here the authors found microenvironment reconsitution of highly active Ni single atoms on oxygen-incorporated Mo2C for water splitting.
- Mengyun Hou
- , Lirong Zheng
- & Chen Chen
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Article
| Open AccessA nonmetallic plasmonic catalyst for photothermal CO2 flow conversion with high activity, selectivity and durability
In this work, the authors design a Mo2N/MoO2-x nonmetallic plasmonic catalyst by regulating synergy between two specific active sites. Highly efficient, selective, and durable CO2 hydrogenation under relatively mild reaction conditions is achieved
- Xueying Wan
- , Yifan Li
- & Yujie Xiong
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Article
| Open AccessSustainable conversion of alkaline nitrate to ammonia at activities greater than 2 A cm−2
Alkaline nitrate electroreduction to ammonia is restricted by insufficient H+ supply. Here, the authors propose a halogen-mediated H+ feeding strategy, by triggering dangling O-H water dissociation and fast *H desorption for *NO intermediate hydrogenation, to enhance the formation of ammonia.
- Wanru Liao
- , Jun Wang
- & Min Liu
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Article
| Open AccessA surface strategy boosting the ethylene selectivity for CO2 reduction and in situ mechanistic insights
The electrochemical reduction of CO2 into multi-carbon product is interesting yet requires further research. Here, the authors develop a surface strategy to achieve high CO2-to-ethylene selectivity by dodecanethiol modification CuO electrode and show that dodecanethiol facilitates CO2 transfer, enhances *CO coverage and stabilize Cu(100) facet.
- Yinchao Yao
- , Tong Shi
- & Zhuo Chen
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Article
| Open AccessMediating trade-off between activity and selectivity in alkynes semi-hydrogenation via a hydrophilic polar layer
The semi-hydrogenation of alkynes faces the trade-off between activity and selectivity due to undesirable over-hydrogenation. Here the authors report an efficient additive-free WO3-based single-atom Pd catalytic system with a vertical size effect of hydrogen spillover to mediate the trade-off between activity and selectivity.
- Jinqi Xiong
- , Shanjun Mao
- & Yong Wang
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Article
| Open AccessAcidic media enables oxygen-tolerant electrosynthesis of multicarbon products from simulated flue gas
Direct electroreduction of dilute CO2 in flue gas streams is challenging due to the presence of O2 impurities. Here the authors demonstrate that an acidic electrolyte can overcome this challenge, enabling the generation of multicarbon products from simulated flue gas at reasonable rates.
- Meng Wang
- , Bingqing Wang
- & Yanwei Lum
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Article
| Open AccessGenerating active metal/oxide reverse interfaces through coordinated migration of single atoms
Steam treatment transforms inactive Pd1/CeO2 catalyst into a highly reactive one by forming a Ce2O3-Pd nanoparticle interface. This domain interface is created by the coordinated migration of Ce and Pd atoms on the atom trapped Pd1/CeO2.
- Lina Zhang
- , Shaolong Wan
- & Haifeng Xiong
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Article
| Open AccessOne-pot redox cascade paired electrosynthesis of gamma-butyrolactone from furoic acid
Paired electrolysis is challenging without membrane and redox mediators. The authors developed a one-pot, mediator-free, and scalable e-synthesis of γ-butyrolactone (GBL) from furoic acid with high yield and selectivity in an aqueous electrolyte.
- Shengqin Liu
- , Yangxin Jin
- & Jason Chun-Ho Lam
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Article
| Open AccessTuning the apparent hydrogen binding energy to achieve high-performance Ni-based hydrogen oxidation reaction catalyst
Nickel-based electrocatalysts for the hydrogen oxidation reaction in hydroxide exchange membrane fuel cells show promise, but their activity requires further enhancement. Here, the authors report NiCuCr alloy with high activity, owing to the efficient tuning of both hydrogen and water binding on Ni sites by alloying with Cu and Cr.
- Xingdong Wang
- , Xuerui Liu
- & Zhongbin Zhuang
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Article
| Open AccessPotential and electric double-layer effect in electrocatalytic urea synthesis
Electrochemical urea synthesis presents a promising alternative to conventional synthesis methods, yet the elusive mechanism hindered its development. Here, the authors take copper as an example to explore the potential and electric double-layer effect in electrocatalytic urea synthesis, and reveal two essential strategies to promote the efficiency of urea synthesis.
- Qian Wu
- , Chencheng Dai
- & Zhichuan J. Xu