Pub Date : 2024-10-14DOI: 10.1038/s41557-024-01656-0
Peter J. Dahl, Nikhil S. Malvankar
Hydrogen bonds get a bad rap in electronic materials because their weak, transient structure often results in poor performance. Now, this dogma has been turned on its head by intercalating molecules into two-dimensional superlattices to generate hydrogen-bonded organic–inorganic structures that feature significantly enhanced electrical conductivity.
{"title":"The Jekyll-and-Hyde electron transfer chemistry of hydrogen bonds","authors":"Peter J. Dahl, Nikhil S. Malvankar","doi":"10.1038/s41557-024-01656-0","DOIUrl":"10.1038/s41557-024-01656-0","url":null,"abstract":"Hydrogen bonds get a bad rap in electronic materials because their weak, transient structure often results in poor performance. Now, this dogma has been turned on its head by intercalating molecules into two-dimensional superlattices to generate hydrogen-bonded organic–inorganic structures that feature significantly enhanced electrical conductivity.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1746-1747"},"PeriodicalIF":19.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430560","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 : 2024-10-14DOI: 10.1038/s41557-024-01654-2
Jiahao Rao, Liang Deng
Open-shell carbenes, which feature two unpaired electrons on a carbene carbon centre, are highly unstable compounds and are usually observed as excited-state species. Now, two triplet metallocarbenes have been stabilized by transition-metal and silyl substituents; the compounds have been characterized by various techniques including single-crystal X-ray diffraction, spectroscopy and quantum-chemical analyses.
开壳碳烯的特点是碳烯碳中心有两个未成对电子，是一种极不稳定的化合物，通常以激发态形式出现。现在，两种三重金属碳烯已通过过渡金属和硅基取代基得到稳定；这些化合物已通过单晶 X 射线衍射、光谱和量子化学分析等多种技术进行了表征。
{"title":"Triplet metallocarbenes featuring carbon-centred spin localization","authors":"Jiahao Rao, Liang Deng","doi":"10.1038/s41557-024-01654-2","DOIUrl":"10.1038/s41557-024-01654-2","url":null,"abstract":"Open-shell carbenes, which feature two unpaired electrons on a carbene carbon centre, are highly unstable compounds and are usually observed as excited-state species. Now, two triplet metallocarbenes have been stabilized by transition-metal and silyl substituents; the compounds have been characterized by various techniques including single-crystal X-ray diffraction, spectroscopy and quantum-chemical analyses.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1741-1742"},"PeriodicalIF":19.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430561","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 : 2024-10-14DOI: 10.1038/s41557-024-01658-y
Xiaoqun Li, Flavio S. Brigiano, Simone Pezzotti, Xinyi Liu, Wanlin Chen, Huiling Chen, Ying Li, Hui Li, Xin Lin, Wenqi Zheng, Yuchong Wang, Yue Ron Shen, Marie-Pierre Gaigeot, Wei-Tao Liu
Oxide–water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica–water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide–water interfaces.
{"title":"Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy","authors":"Xiaoqun Li, Flavio S. Brigiano, Simone Pezzotti, Xinyi Liu, Wanlin Chen, Huiling Chen, Ying Li, Hui Li, Xin Lin, Wenqi Zheng, Yuchong Wang, Yue Ron Shen, Marie-Pierre Gaigeot, Wei-Tao Liu","doi":"10.1038/s41557-024-01658-y","DOIUrl":"https://doi.org/10.1038/s41557-024-01658-y","url":null,"abstract":"<p>Oxide–water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica–water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide–water interfaces.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"27 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430562","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}
{"title":"Author Correction: Opportunities and challenges with hyperpolarized bioresponsive probes for functional imaging using magnetic resonance","authors":"Goran Angelovski, Ben J. Tickner, Gaoji Wang","doi":"10.1038/s41557-024-01667-x","DOIUrl":"https://doi.org/10.1038/s41557-024-01667-x","url":null,"abstract":"<p>Correction to: <i>Nature Chemistry</i> https://doi.org/10.1038/s41557-023-01211-3, published online 1 June 2023.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"838 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430558","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 : 2024-10-11DOI: 10.1038/s41557-024-01616-8
Thomas D. Bennett, Satoshi Horike, John C. Mauro, Morten M. Smedskjaer, Lothar Wondraczek
Glasses are typically formed by melt-quenching, that is, cooling of a liquid on a timescale fast enough to avoid ordering to a crystalline state, and formerly thought to comprise three categories: inorganic (non-metallic), organic and metallic. Their impact is huge, providing safe containers, allowing comfortable and bright living spaces and even underlying the foundations of modern telecommunication. This impact is tempered by the inability to chemically design glasses with precise, well-defined and tunable structures: the literal quest for order in disorder. However, metal–organic or hybrid glasses are now considered to belong to a fourth category of glass chemistry. They have recently been demonstrated upon melt-quenching of coordination polymer, metal–organic framework and hybrid perovskite framework solids. In this Review, we discuss hybrid glasses through the lens of both crystalline metal–organic framework and glass chemistry, physics and engineering, to provide a vision for the future of this class of materials. Hybrid glasses are considered the fourth category of glass, and they exhibit different structures and properties to inorganic, organic or metallic glasses. This Review discusses hybrid glasses through the lens of crystalline metal–organic frameworks and glass chemistry, physics and engineering, providing a vision for the future of this class of materials.
{"title":"Looking into the future of hybrid glasses","authors":"Thomas D. Bennett, Satoshi Horike, John C. Mauro, Morten M. Smedskjaer, Lothar Wondraczek","doi":"10.1038/s41557-024-01616-8","DOIUrl":"10.1038/s41557-024-01616-8","url":null,"abstract":"Glasses are typically formed by melt-quenching, that is, cooling of a liquid on a timescale fast enough to avoid ordering to a crystalline state, and formerly thought to comprise three categories: inorganic (non-metallic), organic and metallic. Their impact is huge, providing safe containers, allowing comfortable and bright living spaces and even underlying the foundations of modern telecommunication. This impact is tempered by the inability to chemically design glasses with precise, well-defined and tunable structures: the literal quest for order in disorder. However, metal–organic or hybrid glasses are now considered to belong to a fourth category of glass chemistry. They have recently been demonstrated upon melt-quenching of coordination polymer, metal–organic framework and hybrid perovskite framework solids. In this Review, we discuss hybrid glasses through the lens of both crystalline metal–organic framework and glass chemistry, physics and engineering, to provide a vision for the future of this class of materials. Hybrid glasses are considered the fourth category of glass, and they exhibit different structures and properties to inorganic, organic or metallic glasses. This Review discusses hybrid glasses through the lens of crystalline metal–organic frameworks and glass chemistry, physics and engineering, providing a vision for the future of this class of materials.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1755-1766"},"PeriodicalIF":19.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404940","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 : 2024-10-11DOI: 10.1038/s41557-024-01653-3
Aleksandr Koronatov, Pavel Sakharov, Deepak Ranolia, Alexander Kaushansky, Natalia Fridman, Mark Gandelman
Alkenes are broadly used in synthetic applications, thanks to their abundance and versatility. Ozonolysis is one of the most canonical transformations that converts alkenes into molecules bearing carbon–oxygen motifs via C=C bond cleavage. Despite its extensive use in both industrial and laboratory settings, the aza version—cleavage of alkenes to form carbon–nitrogen bonds—remains elusive. Here we report the conversion of alkenes into valuable amines via complete C=C bond disconnection. This process, which we have termed ‘triazenolysis’, is initiated by a (3 + 2) cycloaddition of triazadienium cation to an alkene. The triazolinium salt formed accepts hydride from borohydride anion and spontaneously decomposes to create new C–N motifs upon further reduction. The developed reaction is applicable to a broad range of cyclic alkenes to produce diamines, while various acyclic C=C bonds may be broken to generate two separate amine units. Computational analysis provides insights into the mechanism, including identification of the key step and elucidating the significance of Lewis acid catalysis. Ozonolysis reactions convert alkenes into carbon–oxygen compounds via C=C bond cleavage. Now the cleavage of alkenes to form carbon–nitrogen bonds—the aza version of ozonolysis, termed triazenolysis—has been developed. The reaction produces diamines from cyclic alkenes, while acyclic C=C bonds are broken to generate two separate amine units.
{"title":"Triazenolysis of alkenes as an aza version of ozonolysis","authors":"Aleksandr Koronatov, Pavel Sakharov, Deepak Ranolia, Alexander Kaushansky, Natalia Fridman, Mark Gandelman","doi":"10.1038/s41557-024-01653-3","DOIUrl":"10.1038/s41557-024-01653-3","url":null,"abstract":"Alkenes are broadly used in synthetic applications, thanks to their abundance and versatility. Ozonolysis is one of the most canonical transformations that converts alkenes into molecules bearing carbon–oxygen motifs via C=C bond cleavage. Despite its extensive use in both industrial and laboratory settings, the aza version—cleavage of alkenes to form carbon–nitrogen bonds—remains elusive. Here we report the conversion of alkenes into valuable amines via complete C=C bond disconnection. This process, which we have termed ‘triazenolysis’, is initiated by a (3 + 2) cycloaddition of triazadienium cation to an alkene. The triazolinium salt formed accepts hydride from borohydride anion and spontaneously decomposes to create new C–N motifs upon further reduction. The developed reaction is applicable to a broad range of cyclic alkenes to produce diamines, while various acyclic C=C bonds may be broken to generate two separate amine units. Computational analysis provides insights into the mechanism, including identification of the key step and elucidating the significance of Lewis acid catalysis. Ozonolysis reactions convert alkenes into carbon–oxygen compounds via C=C bond cleavage. Now the cleavage of alkenes to form carbon–nitrogen bonds—the aza version of ozonolysis, termed triazenolysis—has been developed. The reaction produces diamines from cyclic alkenes, while acyclic C=C bonds are broken to generate two separate amine units.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"101-110"},"PeriodicalIF":19.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404941","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 : 2024-10-04DOI: 10.1038/s41557-024-01648-0
Indu Bala, Joshua T. Plank, Brandon Balamut, Drake Henry, Alexander R. Lippert, Ivan Aprahamian
The photomodulation of the helical pitch of cholesteric liquid crystals results in dynamic and coloured canvases that can potentially be used in applications ranging from energy-efficient displays to colour filters, anti-counterfeiting tags and liquid crystal (LC) lasers. Here we report on the analysis of a series of photoswitchable chiral dopants that combine the large geometrical change and bistability of hydrazone switches with the efficient helical pitch induction of the chiral motif, triptycene. We elucidate the effects that conformational flexibility, dispersion forces and π–π interactions have on the chirality transfer ability of the dopant. We then use the irradiation time with visible light (442 nm) combined with a simple digital light processing microscope projection set-up to draw numerous stable multi-coloured images on an LC canvas, showcasing the fine control this dopant yields over the LC assembly. Understanding how photoswitchable chiral dopants can control the helical pitch of host liquid crystals will aid the development of smart and adaptive soft materials. Now the molecular-level mechanisms that control the chirality transfer in chiral triptycene-containing bistable hydrazones have been elucidated. This enables the preparation of rewritable multi-coloured liquid crystal canvases.
{"title":"Multi-stage and multi-colour liquid crystal reflections using a chiral triptycene photoswitchable dopant","authors":"Indu Bala, Joshua T. Plank, Brandon Balamut, Drake Henry, Alexander R. Lippert, Ivan Aprahamian","doi":"10.1038/s41557-024-01648-0","DOIUrl":"10.1038/s41557-024-01648-0","url":null,"abstract":"The photomodulation of the helical pitch of cholesteric liquid crystals results in dynamic and coloured canvases that can potentially be used in applications ranging from energy-efficient displays to colour filters, anti-counterfeiting tags and liquid crystal (LC) lasers. Here we report on the analysis of a series of photoswitchable chiral dopants that combine the large geometrical change and bistability of hydrazone switches with the efficient helical pitch induction of the chiral motif, triptycene. We elucidate the effects that conformational flexibility, dispersion forces and π–π interactions have on the chirality transfer ability of the dopant. We then use the irradiation time with visible light (442 nm) combined with a simple digital light processing microscope projection set-up to draw numerous stable multi-coloured images on an LC canvas, showcasing the fine control this dopant yields over the LC assembly. Understanding how photoswitchable chiral dopants can control the helical pitch of host liquid crystals will aid the development of smart and adaptive soft materials. Now the molecular-level mechanisms that control the chirality transfer in chiral triptycene-containing bistable hydrazones have been elucidated. This enables the preparation of rewritable multi-coloured liquid crystal canvases.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"2084-2090"},"PeriodicalIF":19.2,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370138","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 : 2024-10-04DOI: 10.1038/s41557-024-01592-z
Yin Zheng, Tilong Yang, Ka Fai Chan, Zhenyang Lin, Zhongxing Huang
The high nitrogen content and diverse reactivity of malononitrile are widely harnessed to access nitrogen-rich fine chemicals. Although the facile substitutions of malononitrile can give structurally diverse quaternary carbons, their access to enantioenriched molecules, particularly chiral amines that are prevalent in bioactive compounds, remains rare. Here we report a cobalt-catalysed desymmetric reduction of disubstituted malononitriles to give highly functionalized β-quaternary amines. The pair of cobalt salt and sodium borohydride is proposed to generate a cobalt-hydride intermediate and initiate the reduction. Meanwhile, the enantiocontrol of the dinitrile is achieved through a tailored bisoxazoline ligand with two large flanks that create a narrow gap to host the bystanding nitrile and thus restrict the C(ipso)−C(α) bond rotation of the complexed one. Combined with the extensive derivatization possibilities of all substituents on the quaternary carbon, this asymmetric reduction unlocks pathways from malononitrile as a bulk chemical feedstock to intricate, chiral nitrogen-containing molecules. Malononitriles are widely used precursors for the synthesis of diverse enantioenriched nitrogen-containing molecules, but controlling the stereochemistry of their asymmetric transformations is challenging. Now, the desymmetric reduction of disubstituted malononitriles to chiral amines has been achieved, enabled by a bidentate ligand with extended flanks that can differentiate between the precursor’s nitrile groups through tailored steric pairings.
{"title":"Cobalt-catalysed desymmetrization of malononitriles via enantioselective borohydride reduction","authors":"Yin Zheng, Tilong Yang, Ka Fai Chan, Zhenyang Lin, Zhongxing Huang","doi":"10.1038/s41557-024-01592-z","DOIUrl":"10.1038/s41557-024-01592-z","url":null,"abstract":"The high nitrogen content and diverse reactivity of malononitrile are widely harnessed to access nitrogen-rich fine chemicals. Although the facile substitutions of malononitrile can give structurally diverse quaternary carbons, their access to enantioenriched molecules, particularly chiral amines that are prevalent in bioactive compounds, remains rare. Here we report a cobalt-catalysed desymmetric reduction of disubstituted malononitriles to give highly functionalized β-quaternary amines. The pair of cobalt salt and sodium borohydride is proposed to generate a cobalt-hydride intermediate and initiate the reduction. Meanwhile, the enantiocontrol of the dinitrile is achieved through a tailored bisoxazoline ligand with two large flanks that create a narrow gap to host the bystanding nitrile and thus restrict the C(ipso)−C(α) bond rotation of the complexed one. Combined with the extensive derivatization possibilities of all substituents on the quaternary carbon, this asymmetric reduction unlocks pathways from malononitrile as a bulk chemical feedstock to intricate, chiral nitrogen-containing molecules. Malononitriles are widely used precursors for the synthesis of diverse enantioenriched nitrogen-containing molecules, but controlling the stereochemistry of their asymmetric transformations is challenging. Now, the desymmetric reduction of disubstituted malononitriles to chiral amines has been achieved, enabled by a bidentate ligand with extended flanks that can differentiate between the precursor’s nitrile groups through tailored steric pairings.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1845-1854"},"PeriodicalIF":19.2,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370108","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 : 2024-10-04DOI: 10.1038/s41557-024-01650-6
Morgan McKee, Maximilian Kutter, Yue Wu, Hannah Williams, Marc-Antoine Vaudreuil, Mariolino Carta, Ashok Kumar Yadav, Harishchandra Singh, Jean-François Masson, Dieter Lentz, Moritz F. Kühnel, Nikolay Kornienko
Molecular catalysts offer tunable active and peripheral sites, rendering them ideal model systems to explore fundamental concepts in catalysis. However, hydrophobic designs are often regarded as detrimental for dissolution in aqueous electrolytes. Here we show that established cobalt terpyridine catalysts modified with hydrophobic perfluorinated alkyl side chains can assemble at the gas–liquid–solid interfaces on a gas diffusion electrode. We find that the self-assembly of these perfluorinated units on the electrode surface results in a catalytic system selective for electrochemical CO2 reduction to CH4, whereas every other cobalt terpyridine catalyst reported previously was only selective for CO or formate. Mechanistic investigations suggest that the pyridine units function as proton shuttles that deliver protons to the dynamic hydrophobic pocket in which CO2 reduction takes place. Finally, integration with fluorinated carbon nanotubes as a hydrophobic conductive scaffold leads to a Faradaic efficiency for CH4 production above 80% at rates above 10 mA cm−2—impressive activities for a molecular electrocatalytic system. Although molecular complexes can serve as well-defined model catalysts for CO2 electroreduction, few compounds reduce CO2 beyond two electrons. Now, hydrophobic molecular cobalt terpyridine complexes, containing perfluorinated alkyl side chains, have been shown to assemble at the gas–liquid–solid interface and to electrocatalytically reduce CO2 to methane with high efficiencies.
分子催化剂具有可调的活性和外围位点，是探索催化基本概念的理想模型系统。然而，疏水性设计通常被认为不利于在水性电解质中的溶解。在这里，我们展示了用疏水性全氟烷基侧链修饰的钴三联吡啶催化剂可以在气体扩散电极的气-液-固界面上组装。我们发现，这些全氟单元在电极表面的自组装导致催化系统对电化学 CO2 还原成 CH4 具有选择性，而之前报道的其他所有钴萜吡啶催化剂都只对 CO 或甲酸盐具有选择性。机理研究表明，吡啶单元具有质子穿梭器的功能，可将质子输送到发生 CO2 还原的动态疏水口袋中。最后，与作为疏水性导电支架的氟化碳纳米管相结合，在速率超过 10 mA cm-2 的情况下，产生 CH4 的法拉第效率超过 80%--这对于分子电催化系统来说是令人印象深刻的。
{"title":"Hydrophobic assembly of molecular catalysts at the gas–liquid–solid interface drives highly selective CO2 electromethanation","authors":"Morgan McKee, Maximilian Kutter, Yue Wu, Hannah Williams, Marc-Antoine Vaudreuil, Mariolino Carta, Ashok Kumar Yadav, Harishchandra Singh, Jean-François Masson, Dieter Lentz, Moritz F. Kühnel, Nikolay Kornienko","doi":"10.1038/s41557-024-01650-6","DOIUrl":"10.1038/s41557-024-01650-6","url":null,"abstract":"Molecular catalysts offer tunable active and peripheral sites, rendering them ideal model systems to explore fundamental concepts in catalysis. However, hydrophobic designs are often regarded as detrimental for dissolution in aqueous electrolytes. Here we show that established cobalt terpyridine catalysts modified with hydrophobic perfluorinated alkyl side chains can assemble at the gas–liquid–solid interfaces on a gas diffusion electrode. We find that the self-assembly of these perfluorinated units on the electrode surface results in a catalytic system selective for electrochemical CO2 reduction to CH4, whereas every other cobalt terpyridine catalyst reported previously was only selective for CO or formate. Mechanistic investigations suggest that the pyridine units function as proton shuttles that deliver protons to the dynamic hydrophobic pocket in which CO2 reduction takes place. Finally, integration with fluorinated carbon nanotubes as a hydrophobic conductive scaffold leads to a Faradaic efficiency for CH4 production above 80% at rates above 10 mA cm−2—impressive activities for a molecular electrocatalytic system. Although molecular complexes can serve as well-defined model catalysts for CO2 electroreduction, few compounds reduce CO2 beyond two electrons. Now, hydrophobic molecular cobalt terpyridine complexes, containing perfluorinated alkyl side chains, have been shown to assemble at the gas–liquid–solid interface and to electrocatalytically reduce CO2 to methane with high efficiencies.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"92-100"},"PeriodicalIF":19.2,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370121","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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