Nature Catalysis最新文献_第5页

Iron-catalysed alkenylzincation of allenes via electrophilicity reversal 通过亲电性反转铁催化烯基锌化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-02-07 DOI: 10.1038/s41929-025-01293-x

Jun-Jia Chen, Mu-Han Guan, Peng He, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu

{"title":"Iron-catalysed alkenylzincation of allenes via electrophilicity reversal","authors":"Jun-Jia Chen, Mu-Han Guan, Peng He, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu","doi":"10.1038/s41929-025-01293-x","DOIUrl":"10.1038/s41929-025-01293-x","url":null,"abstract":"Given the structural characteristics of allenes, nucleophilic additions usually occur at the electron-deficient central carbon atom of allene. Here we report an iron-catalysed alkenylzincation reaction of terminal allenes that shows abnormal regioselectivity, wherein the electrophilic zinc moiety from an organozinc reagent is incorporated at the electron-deficient central carbon atom of the allene. This alkenylzincation reaction shows broad functional group compatibility and excellent regio- and stereoselectivities. Using this method, we accessed cis-1,4-dienylzinc reagents and their corresponding polysubstituted 1,4-diene derivatives, which are notoriously challenging to prepare via conventional routes. Mechanistic studies revealed that an unexpected reversal of the electrophilicity of the allene carbons is realized through the electron donation from the Fe(0) to the allene via π back-bonding, resulting in the observed abnormal regioselectivity. Allenes are versatile substrates in synthetic chemistry. Now an iron catalyst enables unusual regioselectivity by mediating an electrophilicity reversal of allenes for stereoselective alkenylzincation reactions affording 1,4-diene zinc products.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"178-186"},"PeriodicalIF":42.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Identifying a highly efficient molecular photocatalytic CO2 reduction system via descriptor-based high-throughput screening 通过基于描述符的高通量筛选，确定了一种高效的分子光催化CO2还原系统

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-02-07 DOI: 10.1038/s41929-025-01291-z

Yangguang Hu, Can Yu, Song Wang, Qian Wang, Marco Reinhard, Guozhen Zhang, Fei Zhan, Hao Wang, Dean Skoien, Thomas Kroll, Peiyuan Su, Lei Li, Aobo Chen, Guangyu Liu, Haifeng Lv, Dimosthenis Sokaras, Chao Gao, Jun Jiang, Ye Tao, Yujie Xiong

{"title":"Identifying a highly efficient molecular photocatalytic CO2 reduction system via descriptor-based high-throughput screening","authors":"Yangguang Hu, Can Yu, Song Wang, Qian Wang, Marco Reinhard, Guozhen Zhang, Fei Zhan, Hao Wang, Dean Skoien, Thomas Kroll, Peiyuan Su, Lei Li, Aobo Chen, Guangyu Liu, Haifeng Lv, Dimosthenis Sokaras, Chao Gao, Jun Jiang, Ye Tao, Yujie Xiong","doi":"10.1038/s41929-025-01291-z","DOIUrl":"10.1038/s41929-025-01291-z","url":null,"abstract":"Molecular metal complexes offer opportunities for developing artificial photocatalytic systems. The search for efficient molecular photocatalytic systems, which involves a vast number of photosensitizer–catalyst combinations, is extremely time consuming via a conventional trial and error approach, while high-throughput virtual screening has not been feasible owing to a lack of reliable descriptors. Here we present a machine learning-accelerated high-throughput screening protocol for molecular photocatalytic CO2 reduction systems using multiple descriptors incorporating the photosensitization, electron transfer and catalysis steps. The protocol rapidly screened 3,444 molecular photocatalytic systems including 180,000 conformations of photosensitizers and catalysts during their interaction, enabling the prediction of six promising candidates. Then, we experimentally validated the screened photocatalytic systems, and the optimal one achieved a turnover number of 4,390. Time-resolved spectroscopy and first-principles calculation further validated not only the relevance of the descriptors within certain screening scopes but also the role of dipole coupling in triggering dynamic catalytic reaction processes. High-throughput computational screening of multicomponent molecular photocatalytic systems offers a strategy to minimize the screening of large numbers of photosensitizer–catalyst combinations. Here a machine learning-accelerated approach using multiple descriptors shows strong predictive power in experimentally validated systems for CO2 reduction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"126-136"},"PeriodicalIF":42.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Iminium catalysis in natural Diels–Alderase 天然Diels-Alderase的氨催化作用

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-02-06 DOI: 10.1038/s41929-025-01294-w

Zuodong Sun, Xin Zang, Qingyang Zhou, Masao Ohashi, K. N. Houk, Jiahai Zhou, Yi Tang

{"title":"Iminium catalysis in natural Diels–Alderase","authors":"Zuodong Sun, Xin Zang, Qingyang Zhou, Masao Ohashi, K. N. Houk, Jiahai Zhou, Yi Tang","doi":"10.1038/s41929-025-01294-w","DOIUrl":"10.1038/s41929-025-01294-w","url":null,"abstract":"Iminium-catalysed cycloaddition is one of the most prominent examples of organocatalysis, yet a biological counterpart has not been reported, despite the widespread occurrence of iminium adducts in enzymes. Here we present biochemical, structural and computational evidence for iminium catalysis by the natural Diels–Alderase SdnG, which catalyses norbornene formation in sordarin biosynthesis. A Schiff-base adduct between the ε-nitrogen of active site K127 and the aldehyde group of the enal dienophile is revealed by structural analysis and captured under catalytic conditions via borohydride reduction. This Schiff-base adduct positions the substrate into near-attack conformation and decreases the transition-state barrier of Diels–Alder cyclization by 8.3 kcal mol−1 via dienophile activation. A hydrogen-bond network consisting of a catalytic triad is proposed to facilitate the proton transfer required for iminium formation. This work establishes an intriguing mode of catalysis for Diels–Alderases and points the way to the design of iminium-based (bio)catalysts. Iminium-catalysed cycloaddition is a prominent example of organocatalytic reactivity, yet a biological counterpart has not been identified. Now, the authors report biochemical, structural and computational evidence for iminium catalysis by the natural Diels–Alderase SdnG.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 3","pages":"218-228"},"PeriodicalIF":42.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01294-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selectively monitoring the operando temperature of active metal nanoparticles during catalytic reactions by X-ray absorption nanothermometry 用x射线吸收纳米热法选择性地监测催化反应中活性金属纳米颗粒的操作温度

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-02-04 DOI: 10.1038/s41929-025-01295-9

Matthias Filez, Valentijn De Coster, Hilde Poelman, Valerie Briois, Anthony Beauvois, Jolien Dendooven, Maarten B. J. Roeffaers, Vladimir Galvita, Christophe Detavernier

{"title":"Selectively monitoring the operando temperature of active metal nanoparticles during catalytic reactions by X-ray absorption nanothermometry","authors":"Matthias Filez, Valentijn De Coster, Hilde Poelman, Valerie Briois, Anthony Beauvois, Jolien Dendooven, Maarten B. J. Roeffaers, Vladimir Galvita, Christophe Detavernier","doi":"10.1038/s41929-025-01295-9","DOIUrl":"10.1038/s41929-025-01295-9","url":null,"abstract":"Heat involved in catalytic reactions can influence the local temperature and performance of the active site, potentially causing catalyst degradation and runaway scenarios. Yet, broadly applicable thermometry methods to selectively probe the temperature of the catalytically active phase—where reactions take place—are generally lacking. Here we explore extended X-ray absorption fine-structure thermometry to monitor the operando temperature of active Ni nanoparticles, fully deconvoluted from their metal-oxide support. During dry reforming of methane, the reaction’s endothermicity causes Ni nanoparticles to become local heat sinks with their temperature deviating 90 °C from the reactor temperature. By thermometry at the single nanoparticle level, we chart the energy balance of nanoparticles and relate their temperature to reaction kinetics. Covering the full temperature range relevant to catalysis, this broadly applicable method enables temperature monitoring of individual catalyst components separately. Applying extended X-ray absorption fine-structure thermometry to existing datasets worldwide can generate enhanced understanding on reaction-induced temperature phenomena in heterogeneous catalysis. Monitoring the temperature of a catalyst’s active site during reactions can offer important insights into reactivity, but broadly applicable methods are lacking. Here the authors evaluate the potential of extended X-ray absorption fine-structure thermometry to observe variations in the temperature of nickel nanoparticles throughout representative gas–solid reactions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"187-195"},"PeriodicalIF":42.8,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Perovskite-driven solar C2 hydrocarbon synthesis from CO2 钙钛矿驱动的二氧化碳太阳能C2碳氢化合物合成

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-02-03 DOI: 10.1038/s41929-025-01292-y

Virgil Andrei, Inwhan Roh, Jia-An Lin, Joshua Lee, Yu Shan, Chung-Kuan Lin, Steve Shelton, Erwin Reisner, Peidong Yang

{"title":"Perovskite-driven solar C2 hydrocarbon synthesis from CO2","authors":"Virgil Andrei, Inwhan Roh, Jia-An Lin, Joshua Lee, Yu Shan, Chung-Kuan Lin, Steve Shelton, Erwin Reisner, Peidong Yang","doi":"10.1038/s41929-025-01292-y","DOIUrl":"10.1038/s41929-025-01292-y","url":null,"abstract":"Photoelectrochemistry (PEC) presents a direct pathway to solar fuel synthesis by integrating light absorption and catalysis into compact electrodes. Yet, PEC hydrocarbon production remains elusive due to high catalytic overpotentials and insufficient semiconductor photovoltage. Here we demonstrate ethane and ethylene synthesis by interfacing lead halide perovskite photoabsorbers with suitable copper nanoflower electrocatalysts. The resulting perovskite photocathodes attain a 9.8% Faradaic yield towards C2 hydrocarbon production at 0 V against the reversible hydrogen electrode. The catalyst and perovskite geometric surface areas strongly influence C2 photocathode selectivity, which indicates a role of local current density in product distribution. The thermodynamic limitations of water oxidation are overcome by coupling the photocathodes to Si nanowire photoanodes for glycerol oxidation. These unassisted perovskite–silicon PEC devices attain partial C2 hydrocarbon photocurrent densities of 155 µA cm−2, 200-fold higher than conventional perovskite–BiVO4 artificial leaves for water and CO2 splitting. These insights establish perovskite semiconductors as a versatile platform towards PEC multicarbon synthesis. Hydrocarbon selectivity in photoelectrochemical CO2 reduction has been limited due to a lack of low-overpotential catalysts and high-photovoltage semiconductors. Here Cu nanoflowers are interfaced with perovskite light absorbers for bias-free conversion of CO2 to ethane and ethylene coupled to water or glycerol oxidation.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 2","pages":"137-146"},"PeriodicalIF":42.8,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-025-01292-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reaching out 接触

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-29 DOI: 10.1038/s41929-025-01297-7

引用次数: 0

Enzymatic catalysis meets radical coupling 酶催化满足自由基偶联

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-29 DOI: 10.1038/s41929-025-01290-0

Chenyu Wang

引用次数: 0

Role of the human-in-the-loop in emerging self-driving laboratories for heterogeneous catalysis 人在环在新兴的多相催化自动驾驶实验室中的作用

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-29 DOI: 10.1038/s41929-024-01275-5

Christoph Scheurer, Karsten Reuter

{"title":"Role of the human-in-the-loop in emerging self-driving laboratories for heterogeneous catalysis","authors":"Christoph Scheurer, Karsten Reuter","doi":"10.1038/s41929-024-01275-5","DOIUrl":"10.1038/s41929-024-01275-5","url":null,"abstract":"Self-driving laboratories (SDLs) represent a cutting-edge convergence of machine learning with laboratory automation. SDLs operate in active learning loops, in which a machine learning algorithm plans experiments that are subsequently executed by increasingly automated (robotic) modules. Here we present our view on emerging SDLs for accelerated discovery and process optimization in heterogeneous catalysis. We argue against the paradigm of full automation and the goal of keeping the human out of the loop. Based on analysis of the involved workflows, we instead conclude that crucial advances will come from establishing fast proxy experiments and re-engineering existing apparatuses and measurement protocols. Industrially relevant use cases will also require humans to be kept in the loop for continuous decision-making. In turn, active learning algorithms will have to be advanced that can flexibly deal with corresponding adaptations of the design space and varying information content and noise in the acquired data. Uses of machine learning and automation are increasing and these techniques are becoming popular in catalysis research. This Perspective discusses how active learning workflows and human intervention should be optimized to ensure the most efficient progress for emerging self-driving laboratories performing heterogeneous catalysis research.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"13-19"},"PeriodicalIF":42.8,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Clarifying cation control 澄清控制

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-29 DOI: 10.1038/s41929-024-01284-4

Michael J. Janik

引用次数: 0

Molecular basis of activity changes in acid catalysis within nanoconfined water 纳米密闭水中酸催化活性变化的分子基础

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-29 DOI: 10.1038/s41929-025-01296-8

引用次数: 0