Pub Date : 2024-03-25DOI: 10.1038/s41929-024-01135-2
Dongxiao Chen, Lin Chen, Qian-Cheng Zhao, Zheng-Xin Yang, Cheng Shang, Zhi-Pan Liu
Ag-catalysed ethene epoxidation is the only viable route for making ethene oxide (EO) in industry, but the active site remains elusive due to the lack of tools to probe this reaction under high temperature and high-pressure conditions. Here, aided by advanced machine-learning grand canonical global structure exploration and in situ experiments, we identify a unique surface oxide phase, namely O5 phase, grown on Ag(100) under industrial catalytic conditions. This phase features square-pyramidal subsurface O and strongly adsorbed ethene, which can selectively convert ethene to EO. The other Ag surface facets, although also reconstructing to surface oxide phases, only contain surface O and produce CO2. The complex in situ surface phases with distinct selectivity contribute to an overall medium (50%) selectivity of Ag catalyst to EO. Our further catalysis experiments with in situ infra-red spectroscopy confirm the theory-predicted infra-red-active C=C vibration of adsorbed ethene on O5 phase and the microkinetics simulation results. Ethylene oxide is a key platform chemical that is produced industrially from the epoxidation of ethylene on silver catalysts, but the precise mechanism remains elusive. Now, in a joint computational–experimental effort, a phase of the silver catalyst grown on (100) facets that contains square-pyramidal subsurface oxygens and is stabilized by strongly adsorbed ethylene is identified as the active phase, and the mechanism is revealed.
银催化的乙烯环氧化反应是工业上制造氧化乙烯（EO）的唯一可行途径，但由于缺乏在高温高压条件下探测该反应的工具，活性位点仍然难以捉摸。在这里，借助先进的机器学习大规范全局结构探索和原位实验，我们确定了一种独特的表面氧化物相，即在工业催化条件下生长在 Ag(100) 上的 O5 相。该相具有方锥体次表面 O 和强吸附乙烯的特点，可选择性地将乙烯转化为环氧乙烷。其他的 Ag 表面虽然也会重构为表面氧化物相，但只含有表面 O 并产生 CO2。复杂的原位表面相具有不同的选择性，使得银催化剂对环氧乙烷的选择性总体处于中等水平（50%）。我们利用原位红外光谱进行的进一步催化实验证实了理论预测的 O5 相上吸附乙烯的红外活性 C=C 振动以及微动力学模拟结果。
{"title":"Square-pyramidal subsurface oxygen [Ag4OAg] drives selective ethene epoxidation on silver","authors":"Dongxiao Chen, Lin Chen, Qian-Cheng Zhao, Zheng-Xin Yang, Cheng Shang, Zhi-Pan Liu","doi":"10.1038/s41929-024-01135-2","DOIUrl":"10.1038/s41929-024-01135-2","url":null,"abstract":"Ag-catalysed ethene epoxidation is the only viable route for making ethene oxide (EO) in industry, but the active site remains elusive due to the lack of tools to probe this reaction under high temperature and high-pressure conditions. Here, aided by advanced machine-learning grand canonical global structure exploration and in situ experiments, we identify a unique surface oxide phase, namely O5 phase, grown on Ag(100) under industrial catalytic conditions. This phase features square-pyramidal subsurface O and strongly adsorbed ethene, which can selectively convert ethene to EO. The other Ag surface facets, although also reconstructing to surface oxide phases, only contain surface O and produce CO2. The complex in situ surface phases with distinct selectivity contribute to an overall medium (50%) selectivity of Ag catalyst to EO. Our further catalysis experiments with in situ infra-red spectroscopy confirm the theory-predicted infra-red-active C=C vibration of adsorbed ethene on O5 phase and the microkinetics simulation results. Ethylene oxide is a key platform chemical that is produced industrially from the epoxidation of ethylene on silver catalysts, but the precise mechanism remains elusive. Now, in a joint computational–experimental effort, a phase of the silver catalyst grown on (100) facets that contains square-pyramidal subsurface oxygens and is stabilized by strongly adsorbed ethylene is identified as the active phase, and the mechanism is revealed.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140291527","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}
Pub Date : 2024-03-25DOI: 10.1038/s41929-024-01119-2
Yu Shan, Xiao Zhao, Maria Fonseca Guzman, Asmita Jana, Shouping Chen, Sunmoon Yu, Ka Chon Ng, Inwhan Roh, Hao Chen, Virginia Altoe, Stephanie N. Gilbert Corder, Hans A. Bechtel, Jin Qian, Miquel B. Salmeron, Peidong Yang
The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO2-to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience. Nanoparticles are often stabilized by capping ligands but the specific role of such ligands during catalytic processes is often ignored. Now, in situ techniques including spatially resolved infrared nanospectroscopy reveal the ligand-assisted formation of a catalytic microenvironment on the surface of silver nanoparticles with nanoscale precision during CO2 electroreduction.
纳米粒子（NPs）表面配体对外界刺激的动态反应决定了 NP-配体系统的功能。例如，在电催化过程中，NP 表面配体的集体解离可导致 NP/配体间层的产生，这种微环境对 CO2 到 CO 的转化具有高度活性和选择性。然而，由于缺乏高空间分辨率的原位表征技术，阻碍了对夹层形成机理的分子层面的全面了解。在这里，我们利用原位红外纳米光谱学和表面增强拉曼光谱，揭示了电化学偏压诱导的表面配体连续键裂解机制，从而导致 NP/被缚配体夹层的形成。这种实时的分子洞察力可影响多种催化系统中封闭局部场的设计。此外，所展示的捕捉纳米分辨动态分子尺度事件的能力为利用受控局部分子行为实现纳米科学多个研究领域所需的功能带来了希望。
{"title":"Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface","authors":"Yu Shan, Xiao Zhao, Maria Fonseca Guzman, Asmita Jana, Shouping Chen, Sunmoon Yu, Ka Chon Ng, Inwhan Roh, Hao Chen, Virginia Altoe, Stephanie N. Gilbert Corder, Hans A. Bechtel, Jin Qian, Miquel B. Salmeron, Peidong Yang","doi":"10.1038/s41929-024-01119-2","DOIUrl":"10.1038/s41929-024-01119-2","url":null,"abstract":"The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO2-to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience. Nanoparticles are often stabilized by capping ligands but the specific role of such ligands during catalytic processes is often ignored. Now, in situ techniques including spatially resolved infrared nanospectroscopy reveal the ligand-assisted formation of a catalytic microenvironment on the surface of silver nanoparticles with nanoscale precision during CO2 electroreduction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140209849","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}
The lithium-mediated nitrogen reduction reaction (LiNRR) produces ammonia in ambient conditions. This electrochemical pathway is dependent on a catalytic solid–electrolyte interphase—a nanoscale passivation layer formed from reductive electrolyte decomposition on the surface of lithium metal. The catalytic solid–electrolyte interphase is a unique nanostructured environment that exists on reactive metal surfaces and intimately influences product selectivity. Here we explore recent progress made in the field of lithium-mediated nitrogen reduction to ammonia, especially in light of growing knowledge about the nature of the catalytic solid–electrolyte interphase. We systematically analyse the observed chemical species and reactions that occur within the solid–electrolyte interphase. We also summarize key developments in kinetic and transport models, as well as highlight the cathodic and complementary anodic reactions. Trends in ammonia selectivities and rates with varying electrolyte compositions, cell designs and operating conditions are extracted and used to articulate a path forward for continued development of lithium-mediated nitrogen reduction to ammonia. The electrochemical synthesis of ammonia via the lithium-mediated reduction of N2 holds great promise to replace the carbon- and energy-intensive Haber–Bosch process. This Review discusses this approach and examines the critical role of the catalytic solid–electrolyte interphase formed on the electrode.
{"title":"Lithium-mediated nitrogen reduction to ammonia via the catalytic solid–electrolyte interphase","authors":"Wesley Chang, Anukta Jain, Fateme Rezaie, Karthish Manthiram","doi":"10.1038/s41929-024-01115-6","DOIUrl":"10.1038/s41929-024-01115-6","url":null,"abstract":"The lithium-mediated nitrogen reduction reaction (LiNRR) produces ammonia in ambient conditions. This electrochemical pathway is dependent on a catalytic solid–electrolyte interphase—a nanoscale passivation layer formed from reductive electrolyte decomposition on the surface of lithium metal. The catalytic solid–electrolyte interphase is a unique nanostructured environment that exists on reactive metal surfaces and intimately influences product selectivity. Here we explore recent progress made in the field of lithium-mediated nitrogen reduction to ammonia, especially in light of growing knowledge about the nature of the catalytic solid–electrolyte interphase. We systematically analyse the observed chemical species and reactions that occur within the solid–electrolyte interphase. We also summarize key developments in kinetic and transport models, as well as highlight the cathodic and complementary anodic reactions. Trends in ammonia selectivities and rates with varying electrolyte compositions, cell designs and operating conditions are extracted and used to articulate a path forward for continued development of lithium-mediated nitrogen reduction to ammonia. The electrochemical synthesis of ammonia via the lithium-mediated reduction of N2 holds great promise to replace the carbon- and energy-intensive Haber–Bosch process. This Review discusses this approach and examines the critical role of the catalytic solid–electrolyte interphase formed on the electrode.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140114712","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}
Pub Date : 2024-03-11DOI: 10.1038/s41929-024-01120-9
Congjun Yu, Zining Zhang, Guangbin Dong
Constructive functionalization of unstrained aryl–aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows twofold arylation with diverse aryl iodides through cleaving unstrained aryl–aryl bonds of common 2,2′-biphenols. The reaction is catalysed by a rhodium complex and promoted by a removable phosphinite directing group and an organic reductant such as tetrakis(dimethylamino)ethylene. The combined experimental and computational mechanistic studies reveal a turnover-limiting reductive elimination step that can be accelerated by a Lewis acid co-catalyst. The utility of this coupling method has been illustrated in the modular and simplified syntheses of unsymmetrical 2,6-diarylated phenols and skeletal insertion of phenylene units. Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.
{"title":"Split cross-coupling via Rh-catalysed activation of unstrained aryl–aryl bonds","authors":"Congjun Yu, Zining Zhang, Guangbin Dong","doi":"10.1038/s41929-024-01120-9","DOIUrl":"10.1038/s41929-024-01120-9","url":null,"abstract":"Constructive functionalization of unstrained aryl–aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows twofold arylation with diverse aryl iodides through cleaving unstrained aryl–aryl bonds of common 2,2′-biphenols. The reaction is catalysed by a rhodium complex and promoted by a removable phosphinite directing group and an organic reductant such as tetrakis(dimethylamino)ethylene. The combined experimental and computational mechanistic studies reveal a turnover-limiting reductive elimination step that can be accelerated by a Lewis acid co-catalyst. The utility of this coupling method has been illustrated in the modular and simplified syntheses of unsymmetrical 2,6-diarylated phenols and skeletal insertion of phenylene units. Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140135940","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}
Constructing well-defined heterostructure interfaces in catalysts is an efficient strategy to break the so-called scaling relationships and to accelerate the reactions involving multiple intermediates. Here a cluster–cluster heterostructure catalyst composed of crystalline ruthenium cluster and amorphous chromium oxide cluster is designed to realize high-performance alkaline hydrogen electrocatalysis. The strongly coupled cluster–cluster heterostructure interface induces a unique interfacial interpenetration effect, which simultaneously optimizes the adsorption of intermediates on each cluster. The resulting catalyst exhibits impressive catalytic activities for the hydrogen oxidation reaction (exchange current density of 2.8 A mg−1Ru) and the hydrogen evolution reaction (mass activity of 23.0 A mg−1Ru at the overpotential of 100 mV) in alkaline media. The hydroxide exchange membrane fuel cell delivers a mass activity of 22.4 A mg−1Ru at 0.65 V and outstanding durability with no voltage loss over 105 h operation at 500 mA cm−2. The present work demonstrates the superiority of cluster–cluster heterostructure interface towards the development of advanced catalysts. The synthesis of well-defined heterostructure interfaces can be leveraged to design advanced catalysts. Now a catalyst consisting of carbon-supported Janus particles with crystalline Ru and amorphous CrOx sides is shown to achieve high performance for both alkaline hydrogen oxidation and evolution reactions due to the synergy between both sides.
在催化剂中构建定义明确的异质结构界面是一种有效的策略，可以打破所谓的比例关系，加速涉及多种中间体的反应。本文设计了一种由结晶钌簇和无定形氧化铬簇组成的簇-簇异质结构催化剂，以实现高性能碱性氢气电催化。强耦合的簇-簇异质结构界面产生了独特的界面互穿效应，同时优化了每个簇上中间产物的吸附。由此产生的催化剂在碱性介质中的氢氧化反应（交换电流密度为 2.8 A mg-1Ru）和氢进化反应（过电位为 100 mV 时的质量活性为 23.0 A mg-1Ru）中表现出惊人的催化活性。氢氧化物交换膜燃料电池在 0.65 V 电压下的质量活度为 22.4 A mg-1Ru，在 500 mA cm-2 下运行 105 小时无电压损失，具有出色的耐用性。本研究成果证明了簇-簇异质结构界面在开发先进催化剂方面的优越性。
{"title":"A strongly coupled Ru–CrOx cluster–cluster heterostructure for efficient alkaline hydrogen electrocatalysis","authors":"Bingxing Zhang, Jianmei Wang, Guimei Liu, Catherine M. Weiss, Danqing Liu, Yaping Chen, Lixue Xia, Peng Zhou, Mingxia Gao, Yongfeng Liu, Jian Chen, Yushan Yan, Minhua Shao, Hongge Pan, Wenping Sun","doi":"10.1038/s41929-024-01126-3","DOIUrl":"10.1038/s41929-024-01126-3","url":null,"abstract":"Constructing well-defined heterostructure interfaces in catalysts is an efficient strategy to break the so-called scaling relationships and to accelerate the reactions involving multiple intermediates. Here a cluster–cluster heterostructure catalyst composed of crystalline ruthenium cluster and amorphous chromium oxide cluster is designed to realize high-performance alkaline hydrogen electrocatalysis. The strongly coupled cluster–cluster heterostructure interface induces a unique interfacial interpenetration effect, which simultaneously optimizes the adsorption of intermediates on each cluster. The resulting catalyst exhibits impressive catalytic activities for the hydrogen oxidation reaction (exchange current density of 2.8 A mg−1Ru) and the hydrogen evolution reaction (mass activity of 23.0 A mg−1Ru at the overpotential of 100 mV) in alkaline media. The hydroxide exchange membrane fuel cell delivers a mass activity of 22.4 A mg−1Ru at 0.65 V and outstanding durability with no voltage loss over 105 h operation at 500 mA cm−2. The present work demonstrates the superiority of cluster–cluster heterostructure interface towards the development of advanced catalysts. The synthesis of well-defined heterostructure interfaces can be leveraged to design advanced catalysts. Now a catalyst consisting of carbon-supported Janus particles with crystalline Ru and amorphous CrOx sides is shown to achieve high performance for both alkaline hydrogen oxidation and evolution reactions due to the synergy between both sides.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140114713","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}
Pub Date : 2024-02-27DOI: 10.1038/s41929-024-01129-0
Correlating structure and activity is a very important research goal in catalysis. This Editorial reflects on this topic, taking inspiration from examples in the current issue.
{"title":"The quest for correlations","authors":"","doi":"10.1038/s41929-024-01129-0","DOIUrl":"10.1038/s41929-024-01129-0","url":null,"abstract":"Correlating structure and activity is a very important research goal in catalysis. This Editorial reflects on this topic, taking inspiration from examples in the current issue.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01129-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139987496","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}
{"title":"Retraction Note: A universal principle for a rational design of single-atom electrocatalysts","authors":"Haoxiang Xu, Daojian Cheng, Dapeng Cao, Xiao Cheng Zeng","doi":"10.1038/s41929-024-01125-4","DOIUrl":"10.1038/s41929-024-01125-4","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01125-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139987490","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}
The notion of descriptors has been widely used for assessing structure–activity relationships for many types of heterogenous catalytic reaction, as well as in searching for highly active single-atom catalysts (SACs). Here, with the aid of a machine-learning model for identifying key intrinsic properties of SACs, we revisit our previous descriptor φ [ , 339–348 (2018) ] and present φ′ to correlate the activity of graphene-based SACs for the oxygen reduction reaction, oxygen evolution reaction and hydrogen evolution reaction. The descriptor φ′ not only captures the activity trend among experimentally reported SACs, but can also help with the search for SACs to replace precious-metal-based commercial catalysts (for example Pt/C and IrO2), including Fe-pyridine/pyrrole-4N for the oxygen reduction reaction and Co-pyridine/pyrrole-4N for the oxygen evolution reaction (discovered in previous experimental studies). More importantly, we show that the descriptor φ′ can be broadly applicable to correlate SACs embedded in small-, mid- and large-sized macrocyclic complexes, so long as the active metal centre has the same local coordination environment. In 2018 a descriptor was put forward to correlate the activity of various electrocatalytic reactions on carbon-based single-atom catalysts, but some data the work was based on were later found to be incorrect. This work revisits and amends the original 2018 study while presenting a modified version of the φ descriptor.
{"title":"Revisiting the universal principle for the rational design of single-atom electrocatalysts","authors":"Haoxiang Xu, Daojian Cheng, Dapeng Cao, Xiao Cheng Zeng","doi":"10.1038/s41929-023-01106-z","DOIUrl":"10.1038/s41929-023-01106-z","url":null,"abstract":"The notion of descriptors has been widely used for assessing structure–activity relationships for many types of heterogenous catalytic reaction, as well as in searching for highly active single-atom catalysts (SACs). Here, with the aid of a machine-learning model for identifying key intrinsic properties of SACs, we revisit our previous descriptor φ [ , 339–348 (2018) ] and present φ′ to correlate the activity of graphene-based SACs for the oxygen reduction reaction, oxygen evolution reaction and hydrogen evolution reaction. The descriptor φ′ not only captures the activity trend among experimentally reported SACs, but can also help with the search for SACs to replace precious-metal-based commercial catalysts (for example Pt/C and IrO2), including Fe-pyridine/pyrrole-4N for the oxygen reduction reaction and Co-pyridine/pyrrole-4N for the oxygen evolution reaction (discovered in previous experimental studies). More importantly, we show that the descriptor φ′ can be broadly applicable to correlate SACs embedded in small-, mid- and large-sized macrocyclic complexes, so long as the active metal centre has the same local coordination environment. In 2018 a descriptor was put forward to correlate the activity of various electrocatalytic reactions on carbon-based single-atom catalysts, but some data the work was based on were later found to be incorrect. This work revisits and amends the original 2018 study while presenting a modified version of the φ descriptor.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139987503","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}
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