Pub Date : 2024-08-03DOI: 10.1038/s44160-024-00624-3
The stereoselectivity of SN1-type glycosylation reactions involving 4,6-O-benzylidene-protected sugars is determined by a glycosyl cation intermediate. However, these species are usually too unstable to be characterized directly in solution. Now, mass spectrometry is used to capture these ions in a vacuum and to analyse their structure using cryogenic infrared spectroscopy, in conjunction with computational calculations.
{"title":"Structure of the cationic intermediate in benzylidene-directed glycosylation","authors":"","doi":"10.1038/s44160-024-00624-3","DOIUrl":"10.1038/s44160-024-00624-3","url":null,"abstract":"The stereoselectivity of SN1-type glycosylation reactions involving 4,6-O-benzylidene-protected sugars is determined by a glycosyl cation intermediate. However, these species are usually too unstable to be characterized directly in solution. Now, mass spectrometry is used to capture these ions in a vacuum and to analyse their structure using cryogenic infrared spectroscopy, in conjunction with computational calculations.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141881499","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-26DOI: 10.1038/s44160-024-00619-0
Chun-Wei Chang, Kim Greis, Gurpur Rakesh D. Prabhu, Dana Wehner, Carla Kirschbaum, Katja Ober, América Y. Torres-Boy, Sabrina Leichnitz, Gerard Meijer, Gert von Helden, Peter H. Seeberger, Kevin Pagel
The stereoselective formation of 1,2-cis glycosidic linkages is challenging. The currently most widely used strategy for their installation uses 4,6-O-benzylidene-protected building blocks. The stereoselectivity of this reaction is thought to be driven by a covalent intermediate, which reacts via an SN2 mechanism. However, the role of cationic SN1-type intermediates in this reaction is unclear. Here we elucidate the structure of glycosyl cations carrying 4,6-O-benzylidene groups using cryogenic infrared ion spectroscopy and computational methods. The data reveal that the intermediates form anhydro cations, which correlates well with the stereoselective outcome of SN1-type glycosylations. The study highlights how cryogenic infrared spectroscopy can elucidate the role of intermediates in sugar chemistry and how these structural data can be linked to reactions in solution. The role of cationic intermediates in the benzylidene-directed synthesis of 1,2-cis glycosidic linkages is unclear. Now cryogenic infrared spectroscopy provides insight into the SN1 mechanism of benzylidene-directed glycosylation reactions. The analysis reveals that cationic intermediates form anhydro cations through a two-step process, which correlates with the observed stereochemical outcome.
{"title":"Mechanistic insight into benzylidene-directed glycosylation reactions using cryogenic infrared spectroscopy","authors":"Chun-Wei Chang, Kim Greis, Gurpur Rakesh D. Prabhu, Dana Wehner, Carla Kirschbaum, Katja Ober, América Y. Torres-Boy, Sabrina Leichnitz, Gerard Meijer, Gert von Helden, Peter H. Seeberger, Kevin Pagel","doi":"10.1038/s44160-024-00619-0","DOIUrl":"10.1038/s44160-024-00619-0","url":null,"abstract":"The stereoselective formation of 1,2-cis glycosidic linkages is challenging. The currently most widely used strategy for their installation uses 4,6-O-benzylidene-protected building blocks. The stereoselectivity of this reaction is thought to be driven by a covalent intermediate, which reacts via an SN2 mechanism. However, the role of cationic SN1-type intermediates in this reaction is unclear. Here we elucidate the structure of glycosyl cations carrying 4,6-O-benzylidene groups using cryogenic infrared ion spectroscopy and computational methods. The data reveal that the intermediates form anhydro cations, which correlates well with the stereoselective outcome of SN1-type glycosylations. The study highlights how cryogenic infrared spectroscopy can elucidate the role of intermediates in sugar chemistry and how these structural data can be linked to reactions in solution. The role of cationic intermediates in the benzylidene-directed synthesis of 1,2-cis glycosidic linkages is unclear. Now cryogenic infrared spectroscopy provides insight into the SN1 mechanism of benzylidene-directed glycosylation reactions. The analysis reveals that cationic intermediates form anhydro cations through a two-step process, which correlates with the observed stereochemical outcome.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00619-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-24DOI: 10.1038/s44160-024-00606-5
Zoe Ashbridge, Joost N. H. Reek
Metal–organic cages are versatile supramolecular architectures, fulfilling various distinct roles in the mediation of catalysed chemical reactions. MnL2n cages have become increasingly synthetically accessible in recent years, and their modular nature allows for precise tailoring for specific applications. Sophisticated MnL2n cages have now been deliberately designed to fulfil several roles, providing unique reactivity that begins to emulate the highly complex nature of enzyme active sites. Here we highlight the different functions played by MnL2n cages in the context of catalysed synthetic reactions: (1) protection of catalysts or substrates, (2) activation or preorganization of guests and (3) concentration enhancement of reactants or catalysts in confined space. We conclude by discussing future directions for the field, such as the potential to increase complexity further by developing stimuli-responsive, flexible or reduced-symmetry cages, ultimately progressing artificial cage catalysis towards the levels of catalytic control provided by biological host–guest architectures. MnL2n cages are versatile supramolecular architectures and have become increasingly synthetically accessible. This Review examines the multiple roles that can be filled by MnL2n cages in catalysed chemical reactions.
{"title":"The multifaceted roles of MnL2n cages in catalysis","authors":"Zoe Ashbridge, Joost N. H. Reek","doi":"10.1038/s44160-024-00606-5","DOIUrl":"10.1038/s44160-024-00606-5","url":null,"abstract":"Metal–organic cages are versatile supramolecular architectures, fulfilling various distinct roles in the mediation of catalysed chemical reactions. MnL2n cages have become increasingly synthetically accessible in recent years, and their modular nature allows for precise tailoring for specific applications. Sophisticated MnL2n cages have now been deliberately designed to fulfil several roles, providing unique reactivity that begins to emulate the highly complex nature of enzyme active sites. Here we highlight the different functions played by MnL2n cages in the context of catalysed synthetic reactions: (1) protection of catalysts or substrates, (2) activation or preorganization of guests and (3) concentration enhancement of reactants or catalysts in confined space. We conclude by discussing future directions for the field, such as the potential to increase complexity further by developing stimuli-responsive, flexible or reduced-symmetry cages, ultimately progressing artificial cage catalysis towards the levels of catalytic control provided by biological host–guest architectures. MnL2n cages are versatile supramolecular architectures and have become increasingly synthetically accessible. This Review examines the multiple roles that can be filled by MnL2n cages in catalysed chemical reactions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-18DOI: 10.1038/s44160-024-00600-x
Chenxiao Wang, Jianlong He, Younan Xia
Colloidal synthesis of metal nanocrystals often relies on using reduction kinetics to manipulate their size, shape, internal structure and composition. Whereas the first three features can all be readily manipulated, it remains challenging to control the composition of nanocrystals because the reduction rate, and thus the production rate of atoms, follows an exponential decay during the synthesis. By stabilizing the reduction rate of a precursor in the steady state, dropwise addition has emerged as a transformative route for the colloidal synthesis of nanocrystals. This Perspective highlights the advantages of dropwise addition over traditional one-shot injection for controlling the composition and elemental distribution of bi- and multi-metallic nanocrystals. Our analysis demonstrates the promise of dropwise addition for achieving the deterministic synthesis of complex nanocrystals with controlled compositions for a range of applications, especially those related to catalysis and energy conversion. By stabilizing the reduction rate of a precursor in the steady state, dropwise addition has emerged as a transformative route for the colloidal synthesis of nanocrystals. This Perspective highlights the advantages of dropwise addition over one-shot injection for controlling the composition and elemental distribution of bi- and multi-metallic nanocrystals.
{"title":"Controlling the composition and elemental distribution of bi- and multi-metallic nanocrystals via dropwise addition","authors":"Chenxiao Wang, Jianlong He, Younan Xia","doi":"10.1038/s44160-024-00600-x","DOIUrl":"10.1038/s44160-024-00600-x","url":null,"abstract":"Colloidal synthesis of metal nanocrystals often relies on using reduction kinetics to manipulate their size, shape, internal structure and composition. Whereas the first three features can all be readily manipulated, it remains challenging to control the composition of nanocrystals because the reduction rate, and thus the production rate of atoms, follows an exponential decay during the synthesis. By stabilizing the reduction rate of a precursor in the steady state, dropwise addition has emerged as a transformative route for the colloidal synthesis of nanocrystals. This Perspective highlights the advantages of dropwise addition over traditional one-shot injection for controlling the composition and elemental distribution of bi- and multi-metallic nanocrystals. Our analysis demonstrates the promise of dropwise addition for achieving the deterministic synthesis of complex nanocrystals with controlled compositions for a range of applications, especially those related to catalysis and energy conversion. By stabilizing the reduction rate of a precursor in the steady state, dropwise addition has emerged as a transformative route for the colloidal synthesis of nanocrystals. This Perspective highlights the advantages of dropwise addition over one-shot injection for controlling the composition and elemental distribution of bi- and multi-metallic nanocrystals.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalytic intermolecular [2+2+2] cycloaddition reactions of three 2π-components, such as alkynes and alkenes, are a valuable method to synthesize multi-substituted six-membered carbocycles in a single step with high atom economy. When one 2π-component reacts as a one-carbon unit, a five-membered carbocycle is accessible instead of a six-membered one. However, examples of catalytic intermolecular [2+2+1] cycloaddition reactions are scarce, and enantioselective or three different 2π-component versions remain elusive. Here we report the development of a Rh-catalysed enantioselective [2+2+1] cycloaddition reaction using three different 2π-components, cycloalkenes, acetylenecarboxylates and terminal alkynes, which can form a broad range of synthetically valuable chiral 3-methylenecyclopent-1-ene derivatives with excellent selectivity. Interestingly, the three-component cycloadducts are obtained in high selectivity, while all three 2π-components are mutually reactive. Experimental and theoretical mechanistic studies reveal that the reaction proceeds via the kinetically favoured vinylidene formation from a rhodacyclopentene and a terminal alkyne. Intermolecular [2+2+1] cycloaddition reactions are challenging owing to issues with chemoselectivity. Now a Rh-catalysed enantioselective [2+2+1] cycloaddition reaction using three different 2π-components is reported. The process can form a broad range of synthetically valuable chiral 3-methylenecyclopent-1-ene derivatives with excellent selectivity.
{"title":"Rh-catalysed enantioselective [2+2+1] cycloaddition reactions using three different 2π-components","authors":"Kaito Shibahara, Yoshihito Kayaki, Kairi Yamashiro, Yuki Nagashima, Kohei Fujii, Ken Tanaka","doi":"10.1038/s44160-024-00604-7","DOIUrl":"10.1038/s44160-024-00604-7","url":null,"abstract":"Catalytic intermolecular [2+2+2] cycloaddition reactions of three 2π-components, such as alkynes and alkenes, are a valuable method to synthesize multi-substituted six-membered carbocycles in a single step with high atom economy. When one 2π-component reacts as a one-carbon unit, a five-membered carbocycle is accessible instead of a six-membered one. However, examples of catalytic intermolecular [2+2+1] cycloaddition reactions are scarce, and enantioselective or three different 2π-component versions remain elusive. Here we report the development of a Rh-catalysed enantioselective [2+2+1] cycloaddition reaction using three different 2π-components, cycloalkenes, acetylenecarboxylates and terminal alkynes, which can form a broad range of synthetically valuable chiral 3-methylenecyclopent-1-ene derivatives with excellent selectivity. Interestingly, the three-component cycloadducts are obtained in high selectivity, while all three 2π-components are mutually reactive. Experimental and theoretical mechanistic studies reveal that the reaction proceeds via the kinetically favoured vinylidene formation from a rhodacyclopentene and a terminal alkyne. Intermolecular [2+2+1] cycloaddition reactions are challenging owing to issues with chemoselectivity. Now a Rh-catalysed enantioselective [2+2+1] cycloaddition reaction using three different 2π-components is reported. The process can form a broad range of synthetically valuable chiral 3-methylenecyclopent-1-ene derivatives with excellent selectivity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141718573","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
For over a century, scientists have been fascinated by the unique electronic, structural and bonding properties of the three isomers of benzyne, a highly reactive organic intermediate derived from benzene by removing two hydrogen atoms. Although o- and p-benzynes have been extensively studied following the establishment of reliable synthetic methods to prepare them, m-benzyne in the ground state has remained experimentally inaccessible. We report herein the room-temperature and atmospheric-pressure synthesis of m-benzyne in solution. Experimental and theoretical investigations revealed that owing to the inner bond inside the benzene ring between C1 and C3 atoms, m-benzyne behaves as a potent electrophile with a Mayr’s electrophilicity parameter E of around −2 but shows weak free-radical character. The bonding appears similar to the inverted σ-bond, the so-called charge-shift bond, in [1.1.1]propellane. By utilizing the unique bonding character of m-benzyne, we established halogenations and C–N and C–C coupling reactions, as well as a successive m-benzyne generation and trapping sequence that provides access to 1,3,5-trisubstituted benzenes. While facile methods to prepare o- and p-benzynes exist, m-benzyne in the ground state has remained experimentally inaccessible. Now, the room-temperature and atmospheric-pressure synthesis of m-benzyne in solution is reported. Experimental and theoretical investigations reveal that m-benzyne behaves as a potent electrophile but shows weak free-radical character.
{"title":"Room-temperature synthesis of m-benzyne","authors":"Kenta Koyamada, Kazunori Miyamoto, Masanobu Uchiyama","doi":"10.1038/s44160-024-00572-y","DOIUrl":"10.1038/s44160-024-00572-y","url":null,"abstract":"For over a century, scientists have been fascinated by the unique electronic, structural and bonding properties of the three isomers of benzyne, a highly reactive organic intermediate derived from benzene by removing two hydrogen atoms. Although o- and p-benzynes have been extensively studied following the establishment of reliable synthetic methods to prepare them, m-benzyne in the ground state has remained experimentally inaccessible. We report herein the room-temperature and atmospheric-pressure synthesis of m-benzyne in solution. Experimental and theoretical investigations revealed that owing to the inner bond inside the benzene ring between C1 and C3 atoms, m-benzyne behaves as a potent electrophile with a Mayr’s electrophilicity parameter E of around −2 but shows weak free-radical character. The bonding appears similar to the inverted σ-bond, the so-called charge-shift bond, in [1.1.1]propellane. By utilizing the unique bonding character of m-benzyne, we established halogenations and C–N and C–C coupling reactions, as well as a successive m-benzyne generation and trapping sequence that provides access to 1,3,5-trisubstituted benzenes. While facile methods to prepare o- and p-benzynes exist, m-benzyne in the ground state has remained experimentally inaccessible. Now, the room-temperature and atmospheric-pressure synthesis of m-benzyne in solution is reported. Experimental and theoretical investigations reveal that m-benzyne behaves as a potent electrophile but shows weak free-radical character.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141718575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-15DOI: 10.1038/s44160-024-00608-3
Taito Watanabe, Shigeyuki Masaoka
Strategic modification of molecular catalysts has led to efficient CO2 reduction in strong acid while suppressing the competing hydrogen evolution reaction.
对分子催化剂进行战略性改性，可在强酸中高效还原二氧化碳，同时抑制竞争性的氢进化反应。
{"title":"CO2 reduction in strong acid","authors":"Taito Watanabe, Shigeyuki Masaoka","doi":"10.1038/s44160-024-00608-3","DOIUrl":"10.1038/s44160-024-00608-3","url":null,"abstract":"Strategic modification of molecular catalysts has led to efficient CO2 reduction in strong acid while suppressing the competing hydrogen evolution reaction.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141644304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-15DOI: 10.1038/s44160-024-00612-7
Ryuhei Suzuki, Taiga Ando, Fritz Deufel, Kohsuke Ohmatsu, Takashi Ooi
Selective reactions between more than two molecules are governed by appropriate combinations of polar functionalities. This restriction can be ameliorated by photoredox umpolung reactivity, which enables the functionalization of unreactive bonds of chemical reagents while leaving their inherent reactive functional groups intact, paving the way for otherwise difficult multicomponent reactions. Here we report that the photocatalytic single-electron oxidation of phosphorus ylides underpins their sequential assembly with electron-rich olefins and α,β-unsaturated carbonyl compounds to form functionalized six-membered carbocycles. This three-component formal cycloaddition, featuring consecutive C–H functionalization and Wittig reaction of phosphorus ylides, offers a carbyne-like transformation that involves the conversion of inert C–H and C=P bonds into C–C and C=C bonds, respectively, as a powerful tool for the rapid construction of versatile synthetic building blocks from readily available substrates. The selective formation of C–C bonds using carbynes or carbyne equivalents is difficult due to their highly reactive nature. Now, a three-component formal cycloaddition reaction between phosphorus ylides, electron-rich olefins and electron-deficient olefins is reported, using the photocatalytic carbyne reactivity of phosphorus ylides.
{"title":"Photocatalytic carbyne reactivity of phosphorus ylides for three-component formal cycloaddition reactions","authors":"Ryuhei Suzuki, Taiga Ando, Fritz Deufel, Kohsuke Ohmatsu, Takashi Ooi","doi":"10.1038/s44160-024-00612-7","DOIUrl":"10.1038/s44160-024-00612-7","url":null,"abstract":"Selective reactions between more than two molecules are governed by appropriate combinations of polar functionalities. This restriction can be ameliorated by photoredox umpolung reactivity, which enables the functionalization of unreactive bonds of chemical reagents while leaving their inherent reactive functional groups intact, paving the way for otherwise difficult multicomponent reactions. Here we report that the photocatalytic single-electron oxidation of phosphorus ylides underpins their sequential assembly with electron-rich olefins and α,β-unsaturated carbonyl compounds to form functionalized six-membered carbocycles. This three-component formal cycloaddition, featuring consecutive C–H functionalization and Wittig reaction of phosphorus ylides, offers a carbyne-like transformation that involves the conversion of inert C–H and C=P bonds into C–C and C=C bonds, respectively, as a powerful tool for the rapid construction of versatile synthetic building blocks from readily available substrates. The selective formation of C–C bonds using carbynes or carbyne equivalents is difficult due to their highly reactive nature. Now, a three-component formal cycloaddition reaction between phosphorus ylides, electron-rich olefins and electron-deficient olefins is reported, using the photocatalytic carbyne reactivity of phosphorus ylides.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141644833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-15DOI: 10.1038/s44160-024-00607-4
Jiangwei Chang, Wen Jing, Xue Yong, Ang Cao, Jingkun Yu, Han Wu, Chengzhang Wan, Siyang Wang, Geoffrey I. N. Waterhouse, Bai Yang, Zhiyong Tang, Xiangfeng Duan, Siyu Lu
Single-atom catalysts (SACs) exhibit exceptional intrinsic activity per metal site, but are often limited by low metal loading, which compromises the overall catalytic performance. Pyrolytic strategies commonly used for synthesizing SACs generally suffer from aggregation at high metal loadings. Here we report a universal synthesis approach for ultrahigh-density metal–nitrogen–carbon (UHDM–N–C) SACs via a metal-sulfide-mediated atomization process. We show that our approach is general for transition, rare-earth and noble metals, achieving 17 SACs with metal loadings >20 wt% (including a loading of 26.9 wt% for Cu, 31.2 wt% for Dy and 33.4 wt% for Pt) at 800 °C, as well as high-entropy quinary and vicenary SACs with ultrahigh metal contents. In situ X-ray diffraction and transmission electron microscopy alongside molecular simulations reveals a dynamic nanoparticle-to-single atom transformation process, including thermally driven decomposition of the metal sulfide and the trapping of liberated metal atoms to form thermodynamically stable M–N–C moieties. Our studies indicate that a high N-doping is crucial for achieving ultrahigh-loading metal atoms and a metal-sulfide-mediated process is essential for avoiding metal aggregation at high loadings. As a demonstration, the metal-loading-dependent activity in electrocatalytic oxygen evolution reaction is demonstrated on SACs with increasing Ni content. Increasing the metal loading of single-atom catalysts (SACs) typically results in aggregation, which can have a detrimental effect on catalytic performance. Now, a nitrogen-doping-assisted atomization approach is reported that transforms metal-sulfide nanoparticles into ultrahigh-density metal–nitrogen–carbon SACs.
{"title":"Synthesis of ultrahigh-metal-density single-atom catalysts via metal sulfide-mediated atomic trapping","authors":"Jiangwei Chang, Wen Jing, Xue Yong, Ang Cao, Jingkun Yu, Han Wu, Chengzhang Wan, Siyang Wang, Geoffrey I. N. Waterhouse, Bai Yang, Zhiyong Tang, Xiangfeng Duan, Siyu Lu","doi":"10.1038/s44160-024-00607-4","DOIUrl":"10.1038/s44160-024-00607-4","url":null,"abstract":"Single-atom catalysts (SACs) exhibit exceptional intrinsic activity per metal site, but are often limited by low metal loading, which compromises the overall catalytic performance. Pyrolytic strategies commonly used for synthesizing SACs generally suffer from aggregation at high metal loadings. Here we report a universal synthesis approach for ultrahigh-density metal–nitrogen–carbon (UHDM–N–C) SACs via a metal-sulfide-mediated atomization process. We show that our approach is general for transition, rare-earth and noble metals, achieving 17 SACs with metal loadings >20 wt% (including a loading of 26.9 wt% for Cu, 31.2 wt% for Dy and 33.4 wt% for Pt) at 800 °C, as well as high-entropy quinary and vicenary SACs with ultrahigh metal contents. In situ X-ray diffraction and transmission electron microscopy alongside molecular simulations reveals a dynamic nanoparticle-to-single atom transformation process, including thermally driven decomposition of the metal sulfide and the trapping of liberated metal atoms to form thermodynamically stable M–N–C moieties. Our studies indicate that a high N-doping is crucial for achieving ultrahigh-loading metal atoms and a metal-sulfide-mediated process is essential for avoiding metal aggregation at high loadings. As a demonstration, the metal-loading-dependent activity in electrocatalytic oxygen evolution reaction is demonstrated on SACs with increasing Ni content. Increasing the metal loading of single-atom catalysts (SACs) typically results in aggregation, which can have a detrimental effect on catalytic performance. Now, a nitrogen-doping-assisted atomization approach is reported that transforms metal-sulfide nanoparticles into ultrahigh-density metal–nitrogen–carbon SACs.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141648280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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