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Deciphering 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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High 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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Facilitating 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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A 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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Photocatalytic 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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Nanoparticles 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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Reverse 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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Constructing regulable supports via non-stoichiometric engineering to stabilize ruthenium nanoparticles for enhanced pH-universal water splitting
Establishing optimal metal-support interactions is crucial for creating efficient catalysts for water splitting. Here, stable Ti–O–Ru interface formation and minimal work function difference between Ru nanoparticles and non-stoichiometric Ti4O7 lead to exceptional bifunctional activity of Ru/Ti4O7 for both HER and OER across pH-universal environments, maintaining stable operation for 500 h.
- Sheng Zhao
- , Sung-Fu Hung
- & Shengjie Peng
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Water-participated mild oxidation of ethane to acetaldehyde
The direct conversion of low alkane-like ethane into high-value chemicals has posed a significant challenge. Herein, the authors successfully accomplish a one-step conversion of ethane to C2 oxygenates using a Rh single-atom catalyst under mild conditions.
- Bin Li
- , Jiali Mu
- & Yunjie Ding
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Spectroscopic visualization of reversible hydrogen spillover between palladium and metal–organic frameworks toward catalytic semihydrogenation
The authors report an in situ investigation of interfacial hydrogen spillover in Pd/ZIF-8 structures with X-ray and Raman techniques. A mechanistic picture of how Pd/ZIF-8 catalyst mediate alkyne semihydrogenation to alkynes is described.
- Qiaoxi Liu
- , Wenjie Xu
- & Yujie Xiong
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Bubble-water/catalyst triphase interface microenvironment accelerates photocatalytic OER via optimizing semi-hydrophobic OH radical
Temperature has demonstrated the potential to regulate the photocatalytic oxygen evolution reaction (OER). This study confirms that the temperature-induced bubble-water/catalyst triphase interface microenvironment significantly enhances OER by optimizing the formation and deprotonation of semi-hydrophobic OH radicals.
- Guanhua Ren
- , Min Zhou
- & Haifeng Wang
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Tailoring d-band center of high-valent metal-oxo species for pollutant removal via complete polymerization
Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) allows for sustainable contamination abatement and resource recovery. Here, authors achieved pollutant removal via complete polymerization by tailoring d-band center of high-valent metal-oxo species.
- Hong-Zhi Liu
- , Xiao-Xuan Shu
- & Han-Qing Yu
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Cobalt 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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Surface 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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Interrogating 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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Dual-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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A 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
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Potential 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
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Tuning oxidant and antioxidant activities of ceria by anchoring copper single-site for antibacterial application
Nanozymes used for antibacterial therapy conventionally have complex catalytic activities that cause multiple pathways in parallel and unwanted outcome. Here, the authors report a Cu-CeO2 single site nanozyme in which Cu single site modification can enhance the peroxidase-like activity and inhibit the hydroxyl radical antioxidant capacity of CeO2 to optimise the antibacterial effects.
- Peng Jiang
- , Ludan Zhang
- & Yuguang Wang
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Unraveling the rate-determining step of C2+ products during electrochemical CO reduction
The electrochemical reduction of CO for sustainable fuel production has gained attention, but the reaction mechanism needs further clarification. Here the authors delve into the discussion regarding whether the rate-determining step for the generation of multi-carbon products is the C-C coupling or the hydrogenation of CO, and provide evidence for dimerization of two *CO as the pivotal step in this process.
- Wanyu Deng
- , Peng Zhang
- & Jinlong Gong
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A contact-electro-catalysis process for producing reactive oxygen species by ball milling of triboelectric materials
Through contact-electro-catalysis (CEC), reactive oxygen species can be produced by chemically inert triboelectric materials in ball milling, enabling mechanoredox reactions with a broad selection of abundant triboelectric materials
- Ziming Wang
- , Xuanli Dong
- & Zhong Lin Wang
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Regulating Au coverage for the direct oxidation of methane to methanol
The direct oxidation of methane to methanol occurs in two steps that are difficult to control. Here, the authors use the OH binding strength as a descriptor to optimize the trade-off effect between the two pathways over PdxAuy catalysts.
- Yueshan Xu
- , Daoxiong Wu
- & Quanbing Liu
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Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides
Zhu et al. report a quantitative and time-resolved analysis of hydrogen activation on Ga2O3, specifically shedding light on the long-standing puzzle of homolytic dissociation as opposed to the heterolytic pathway on oxides.
- Chengsheng Yang
- , Sicong Ma
- & Xinhe Bao
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Oxophilic Ce single atoms-triggered active sites reverse for superior alkaline hydrogen evolution
The Ru single atom-nanocluster alkaline hydrogen evolution catalyst suffers from that hydrogen forms on its less active single atom side. Here, the authors report that oxophilic Ce single atom can reverse the hydrogen formation site to more active Ru nanocluster, enabling enhanced hydrogen evolution capabilities.
- Fengyi Shen
- , Zhihao Zhang
- & Kebin Zhou
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Designing Cu0−Cu+ dual sites for improved C−H bond fracture towards methanol steam reforming
Cu-based catalysts are widely considered to be effective materials for H2 production via methanol steam reforming. Herein, the authors explore a series of catalysts containing Cu0−Cu+ dual sites for facilitating C-H bond breaking and H2 evolution.
- Hao Meng
- , Yusen Yang
- & Min Wei
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Mechanistic manifold in a hemoprotein-catalyzed cyclopropanation reaction with diazoketone
Hemoproteins have recently emerged as promising biocatalysts for carbene transfer reactions but mechanistic understanding of the interplay between productive and unproductive pathways in these processes is limited. Here, the authors use a combination of spectroscopic, crystallographic, and computational tools to elucidate the mechanism of a recently reported myoglobin-catalyzed cyclopropanation reaction with diazoketones.
- Donggeon Nam
- , John-Paul Bacik
- & Rudi Fasan
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Nonredox trivalent nickel catalyzing nucleophilic electrooxidation of organics
A good understanding of the mechanism behind organic electrooxidation is crucial for the development of efficient energy conversion technology. Here, the authors find that trivalent nickel is capable of oxidizing organics through a nucleophilic attack and electron transfer via a non-redox process.
- Yuandong Yan
- , Ruyi Wang
- & Zhigang Zou
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Enabling direct-growth route for highly efficient ethanol upgrading to long-chain alcohols in aqueous phase
Achieving efficient carbon chain propagation remains a grand challenge for ethanol upgrading. Here, the authors report sulfur doped Ni@C-Sx catalysts with controllably exposed nickel sites that can dramatically improve direct-growth probability towards long-chain alcohols production.
- Juwen Gu
- , Wanbing Gong
- & Yujie Xiong
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Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
Ligands capable of accelerating and inducing enantioselectivity in C–H activations with base metal catalysts have remained elusive. Here, the authors report a ligand-accelerated enantioselective C–H alknylation, using a chiral BINOL ligand with a copper catalyst.
- Xin Kuang
- , Jian-Jun Li
- & Jin-Quan Yu
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Balancing elementary steps enables coke-free dry reforming of methane
High-temperature hydrocarbon conversions often face issues like coke buildup and catalyst deactivation. Here, the authors show a general approach: balancing key reaction steps to achieve coke-free processes, exemplified in a 1000-hour coke-free dry reforming of methane process by optimizing C-H activation and C removal steps.
- Jiaqi Yu
- , Tien Le
- & Wenyu Huang
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Direct time-resolved observation of surface-bound carbon dioxide radical anions on metallic nanocatalysts
Understanding the activity and selectivity of metal catalysts requires elucidating the dynamics of CO2•− radicals bound to the surface. Here, the authors use pulse radiolysis to directly observe the stabilization process of CO2•− radicals at nanoscale metallic sites from nanoseconds to seconds.
- Zhiwen Jiang
- , Carine Clavaguéra
- & Mehran Mostafavi
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Nickel-catalyzed acylzincation of allenes with organozincs and CO
The development of carbonylative reactions with CO gas under mild conditions are important in organic synthesis. Here, the authors demonstrate an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence of allene and alkylzinc reagent with 1 atm of CO.’
- Xianqing Wu
- , Chenglong Wang
- & Yifeng Chen
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Revealing the role of double-layer microenvironments in pH-dependent oxygen reduction activity over metal-nitrogen-carbon catalysts
By combining theoretical simulations and spectroscopic measurements, Peng Li et al. demonstrated that distinct interfacial double-layer structures play a key role in the pH-dependent oxygen reduction kinetics over metal-nitrogen-carbon catalysts.
- Peng Li
- , Yuzhou Jiao
- & Shengli Chen
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A tautomerized ligand enabled meta selective C–H borylation of phenol
Remote meta selective C–H Functionalization of aromatic compounds remains challenging in chemical synthesis. Here, the authors report an iridium catalyst bearing a bidentate pyridine-pyridone ligand framework that efficiently catalyzes this meta selective borylation reaction.
- Saikat Guria
- , Mirja Md Mahamudul Hassan
- & Buddhadeb Chattopadhyay
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Electrochemical carbon–carbon coupling with enhanced activity and racemate stereoselectivity by microenvironment regulation
Positioning multiple components in a confined space increases the efficiency of many transformations catalyzed by enzymes but achieving such configuration in artificial catalysts remains challenging. Here, the authors demonstrate that modifying carbon paper with hexadecyltrimethylammonium cations can position reactants for efficient electrochemical carbon–carbon coupling of benzaldehyde with enhanced racemate stereoselectivity.
- Kejian Kong
- , An-Zhen Li
- & Haohong Duan
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Elucidating the active phases of CoOx films on Au(111) in the CO oxidation reaction
Supported CoOx catalysts display higher reactivities towards CO oxidation, yet, corresponding catalytically active phases are still unclear, especially under reaction conditions. Here, by means of in-situ APXPS and ResPES, the authors demonstrate that the topographic restructuring and chemical restructuring occur on these CoOx working catalysts, and also highlight the unique catalytic properties of Co3+ sites.
- Hao Chen
- , Lorenz J. Falling
- & Miquel Salmeron
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Constructing asymmetric double-atomic sites for synergistic catalysis of electrochemical CO2 reduction
Elucidating the synergistic catalytic mechanism involving multiple active centers is of great significance for heterogeneous catalysis. Here the authors construct an asymmetric TeN2–CuN3 double atomic site catalyst featuring synergistic CO2 activation and H2O dissociation for CO2 electroreduction.
- Jiqing Jiao
- , Qing Yuan
- & Tongbu Lu
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Methyl radical chemistry in non-oxidative methane activation over metal single sites
Understanding of the direct methane conversion mechanism is essential for further development of efficient catalysts. Here, authors demonstrate a general methyl radical chemistry for metal single site catalysis regardless of the support (either zeolite or SiO2) in non-oxidative methane activation.
- Xin Huang
- , Daniel Eggart
- & Xinhe Bao
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Article
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Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination
Carbon is a key support for metal-catalyzed acetylene hydrochlorination to vinyl chloride but its role remains elusive. Here, the authors, by means of operando spectroscopy, demonstrate the co-catalytic function of neighboring carbon and isolated metal atoms, constituting the active ensemble.
- Vera Giulimondi
- , Andrea Ruiz-Ferrando
- & Javier Pérez-Ramírez
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Heterogeneity in M. tuberculosis β-lactamase inhibition by Sulbactam
Here, the reaction of the suicide inhibitor sulbactam with the M. tuberculosis β-lactamase (BlaC) is investigated with time-resolved crystallography. Singular Value Decomposition is implemented to extract kinetic information despite changes in unit cell parameters during the time-course of the reaction.
- Tek Narsingh Malla
- , Kara Zielinski
- & Marius Schmidt
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Metallic W/WO2 solid-acid catalyst boosts hydrogen evolution reaction in alkaline electrolyte
The high cost and low abundance of noble metals largely restrict practical applications for electrochemical hydrogen production. Here, the authors prepare ultrasmall tungsten nanoparticles on metallic tungsten dioxide nanorods and demonstrate excellent activities for the alkaline hydrogen evolution reaction.
- Zhigang Chen
- , Wenbin Gong
- & Yi Cui
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Article
| Open Access
Streamlining the synthesis of amides using Nickel-based nanocatalysts
The synthesis of amides is a key technology for the preparation of fine and bulk chemicals in industry. Here, the authors present the reductive amidation of esters with nitro compounds under additivesfree conditions as a robust methodology for amide synthesis.
- Jie Gao
- , Rui Ma
- & Matthias Beller
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Article
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Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface
The authors report selective nucleophilic α-C alkylation of phenols with alcohols catalyzed by anatase titanium dioxide. Experimental and computational studies reveal the formation of Ti=Cα intermediate with the primary carbon of alkyl group at oxygen vacancies of anatase titanium dioxide.
- Xinze Du
- , Hongjun Fan
- & Z. Conrad Zhang
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Article
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Fluorocarbonylation via palladium/phosphine synergistic catalysis
Despite the growing importance of fluorinated organic compounds introduction of fluorine into organic molecules is still challenging. Here, the authors present the development of palladium and phosphine synergistic redox catalysis of fluorocarbonylation of potassium aryl/alkyl trifluoroborate.
- Mingxin Zhao
- , Miao Chen
- & Pingping Tang
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Article
| Open Access
Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis
Unveiling catalytic mechanisms at a molecular level aids selectivity control of lignin catalytic fast pyrolysis. Here authors show that the suppression of highly reactive ketenes is responsible for the five-fold phenol selectivity increase.
- Zeyou Pan
- , Allen Puente-Urbina
- & Patrick Hemberger
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Article
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Synergy of dual-atom catalysts deviated from the scaling relationship for oxygen evolution reaction
The utilization of dual-atom catalysts holds the potential in surpassing single-atom catalysts for oxygen evolution reactions. Here, the authors examine the mechanism of dual-atom catalysts for oxygen evolution reaction and identify catalyst optimization recipes via large-scale computations.
- Cong Fang
- , Jian Zhou
- & Xiaoyan Sun
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Article
| Open Access
Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands
Noble metals have been extensively employed in a variety of hydrotreating catalyst systems. Here, the authors demonstrate that coordinating Pd with alkenyl-type ligands creates an electron-rich environment for Pd entity to weaken the interaction between Pd and unsaturated C for selective hydrogenation.
- Jianghao Zhang
- , Wenda Hu
- & Yong Wang
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Designing main-group catalysts for low-temperature methane combustion by ozone
Automated reaction route mapping is used to design catalysts for low-temperature CH4 combustion with ozone. A suitable proton-type zeolite catalyst with Brønsted acid sites was predicted and shown to have superior performance in CH4 combustion.
- Shunsaku Yasumura
- , Kenichiro Saita
- & Ken-ichi Shimizu
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Lattice oxygen-mediated electron tuning promotes electrochemical hydrogenation of acetonitrile on copper catalysts
While copper is active for electrocatalytic nitriles hydrogenation, the correlation between the local structures and catalytic activity is still illusive. Here, the authors report that residual lattice oxygen in oxide-derived copper nanowires plays vital roles in boosting the hydrogenation activity.
- Cong Wei
- , Yanyan Fang
- & Gongming Wang
Atomically dispersed MoNi alloy catalyst for partial oxidation of methane