Pub Date : 2024-11-08DOI: 10.1038/s41929-024-01249-7
Yaguang Li, Bang Liu, Dachao Yuan, Haixiao Wang, Qixuan Wu, Yachuan Wang, Junwei Wang, Xingyuan San, Yanhong Luo, Jinhua Ye
High-purity carbon monoxide (CO), crucial for various high-tech industries, requires complex purification and further energy input. Here we show that pure fluorite ZrO2 can produce clean CO without purification by driving formic acid dehydration and completely shutting off the formic acid dehydrogenation pathway. An explosion method is developed for synthesizing pristine fluorite ZrO2 nanosheets that achieve a pure CO production rate of 55 mmol g−1 h−1 at 250 °C. Integrated with a homemade photothermal reactor, the fluorite ZrO2 nanosheets show a pure CO productivity of 83 mmol g−1 h−1 under 0.5 sun irradiation and a photochemical energy conversion efficiency of 12.3%. Moreover, this system generates over 1,538 l m−2 of pure CO per day under outdoor sunlight irradiation. This work charts a promising course for purification-free pure CO generation without secondary energy input. Obtaining high-purity CO requires energy-intensive purification processes. Here metastable fluorite ZrO2 is prepared that can catalyse thermal and photothermal formic acid dehydration to CO while completely shutting off the impurity-generating dehydrogenation pathway.
高纯度一氧化碳（CO）对各种高科技产业至关重要，但需要复杂的提纯过程和进一步的能源投入。在这里，我们展示了纯净的萤石 ZrO2 可通过驱动甲酸脱水并完全关闭甲酸脱氢途径来生产清洁的一氧化碳，而无需提纯。我们开发了一种爆炸方法，用于合成纯净的萤石 ZrO2 纳米片，该纳米片在 250 °C 下的纯 CO 生成率达到 55 mmol g-1 h-1。与自制的光热反应器集成后，萤石 ZrO2 纳米片在 0.5 太阳光照射下的纯 CO 生产率为 83 mmol g-1 h-1，光化学能量转换效率为 12.3%。此外，在室外阳光照射下，该系统每天可产生超过 1,538 升 m-2 的纯 CO。这项工作为无需二次能源输入的无净化纯 CO 发电技术指明了一条前景广阔的道路。
{"title":"High-purity carbon monoxide production via photothermal formic acid decomposition over fluorite ZrO2","authors":"Yaguang Li, Bang Liu, Dachao Yuan, Haixiao Wang, Qixuan Wu, Yachuan Wang, Junwei Wang, Xingyuan San, Yanhong Luo, Jinhua Ye","doi":"10.1038/s41929-024-01249-7","DOIUrl":"10.1038/s41929-024-01249-7","url":null,"abstract":"High-purity carbon monoxide (CO), crucial for various high-tech industries, requires complex purification and further energy input. Here we show that pure fluorite ZrO2 can produce clean CO without purification by driving formic acid dehydration and completely shutting off the formic acid dehydrogenation pathway. An explosion method is developed for synthesizing pristine fluorite ZrO2 nanosheets that achieve a pure CO production rate of 55 mmol g−1 h−1 at 250 °C. Integrated with a homemade photothermal reactor, the fluorite ZrO2 nanosheets show a pure CO productivity of 83 mmol g−1 h−1 under 0.5 sun irradiation and a photochemical energy conversion efficiency of 12.3%. Moreover, this system generates over 1,538 l m−2 of pure CO per day under outdoor sunlight irradiation. This work charts a promising course for purification-free pure CO generation without secondary energy input. Obtaining high-purity CO requires energy-intensive purification processes. Here metastable fluorite ZrO2 is prepared that can catalyse thermal and photothermal formic acid dehydration to CO while completely shutting off the impurity-generating dehydrogenation pathway.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1350-1358"},"PeriodicalIF":42.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598074","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 : 2024-11-01DOI: 10.1038/s41929-024-01248-8
Yigao Yuan, Jingyi Zhou, Aaron Bayles, Hossein Robatjazi, Peter Nordlander, Naomi J. Halas
Steam methane reforming (SMR) is the major industrial process for hydrogen production. It currently relies on high-temperature operating conditions and is associated with high carbon intensity. Photocatalytic SMR could provide greener and potentially more efficient H2 production. Here we demonstrate a plasmonic photocatalytic approach based on a Cu–Rh antenna–reactor photocatalyst for highly reactive, selective and stable SMR due to plasmon-mediated hot carrier contributions. We observe that the photocatalyst is intrinsically stable in photocatalysis but deactivates under thermocatalysis; however, the thermally deactivated catalyst can be regenerated by resonant illumination. The regeneration mechanism is studied in detail and found to be caused by plasmon-induced associative desorption of oxygen and carbon species. Catalysts used for steam methane reforming frequently suffer from deactivation by coking and oxidation. Here an active Cu–Rh plasmonic antenna–reactor photocatalyst is selective and stable under illumination but deactivates under purely thermal conditions. The thermally deactivated catalyst can then be regenerated under illumination.
{"title":"Steam methane reforming using a regenerable antenna–reactor plasmonic photocatalyst","authors":"Yigao Yuan, Jingyi Zhou, Aaron Bayles, Hossein Robatjazi, Peter Nordlander, Naomi J. Halas","doi":"10.1038/s41929-024-01248-8","DOIUrl":"10.1038/s41929-024-01248-8","url":null,"abstract":"Steam methane reforming (SMR) is the major industrial process for hydrogen production. It currently relies on high-temperature operating conditions and is associated with high carbon intensity. Photocatalytic SMR could provide greener and potentially more efficient H2 production. Here we demonstrate a plasmonic photocatalytic approach based on a Cu–Rh antenna–reactor photocatalyst for highly reactive, selective and stable SMR due to plasmon-mediated hot carrier contributions. We observe that the photocatalyst is intrinsically stable in photocatalysis but deactivates under thermocatalysis; however, the thermally deactivated catalyst can be regenerated by resonant illumination. The regeneration mechanism is studied in detail and found to be caused by plasmon-induced associative desorption of oxygen and carbon species. Catalysts used for steam methane reforming frequently suffer from deactivation by coking and oxidation. Here an active Cu–Rh plasmonic antenna–reactor photocatalyst is selective and stable under illumination but deactivates under purely thermal conditions. The thermally deactivated catalyst can then be regenerated under illumination.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1339-1349"},"PeriodicalIF":42.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561801","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 : 2024-10-28DOI: 10.1038/s41929-024-01238-w
M. Klingenhof, H. Trzesniowski, S. Koch, J. Zhu, Z. Zeng, L. Metzler, A. Klinger, M. Elshamy, F. Lehmann, P. W. Buchheister, A. Weisser, G. Schmid, S. Vierrath, F. Dionigi, P. Strasser
Recent efforts in anion-exchange membrane water electrolysis (AEMWE) focus on developing superior catalysts and membrane electrode assemblies to narrow the performance gaps compared with proton-exchange membrane water electrolysis (PEMWE). Here we present and characterize Ir-free AEMWE cells with NiX (X = Fe, Co or Mn) layered double hydroxide (LDH) catalyst-coated membranes with polarization characteristics and hydrogen productivities approaching those of acidic PEMWE cells, achieving >5 A cm−2 at <2.2 V. Operando spectroscopy revealed a correlation between Ni4+ centres and redox-active O ligands with an O K-edge feature, attributed to µ3-O ligands in the γ-LDH catalytic phase via density functional theory calculations. This computational–experimental study challenges the previously assumed correlation between spectral O K-edge features and oxygen evolution reaction performance in Ni-based LDH catalysts and provides insights from the molecular to the technological level demonstrating how redox-active Ni–O species and innovative catalyst-coated membrane preparation boost AEMWE performance to values rivalling state-of-the-art PEMWE cell technology. Anion-exchange membrane water electrolysers have the potential to rival more costly acidic proton-exchange membrane electrolysers, but their performance and efficiency commonly still fall short. Now an anion-exchange membrane water electrolyser is prepared with a NiFe layered double hydroxide catalyst-coated membrane that achieves high current densities above 2 A cm−2 at 1.8 V and operando X-ray absorption spectroscopy is used to track the formation of the catalytically active γ-LDH phase.
最近，阴离子交换膜水电解法（AEMWE）的研究重点是开发优质催化剂和膜电极组件，以缩小与质子交换膜水电解法（PEMWE）的性能差距。在这里，我们介绍并表征了采用 NiX（X = 铁、钴或锰）层状双氢氧化物（LDH）催化剂涂层的无 Ir AEMWE 电池，其极化特性和氢气生产率接近酸性 PEMWE 电池，在 2.2 V 时达到 5 A cm-2。运算光谱显示了 Ni4+ 中心与氧化还原活性 O 配体之间的相关性，通过密度泛函理论计算，在 γ-LDH 催化阶段，O K 边特征归因于 µ3-O 配体。这项计算-实验研究挑战了之前假设的镍基 LDH 催化剂中 O K-edge 光谱特征与氧进化反应性能之间的相关性，并提供了从分子到技术层面的见解，展示了氧化还原活性 Ni-O 物种和创新的催化剂涂层膜制备如何将 AEMWE 性能提升到可与最先进的 PEMWE 电池技术相媲美的数值。
{"title":"High-performance anion-exchange membrane water electrolysers using NiX (X = Fe,Co,Mn) catalyst-coated membranes with redox-active Ni–O ligands","authors":"M. Klingenhof, H. Trzesniowski, S. Koch, J. Zhu, Z. Zeng, L. Metzler, A. Klinger, M. Elshamy, F. Lehmann, P. W. Buchheister, A. Weisser, G. Schmid, S. Vierrath, F. Dionigi, P. Strasser","doi":"10.1038/s41929-024-01238-w","DOIUrl":"10.1038/s41929-024-01238-w","url":null,"abstract":"Recent efforts in anion-exchange membrane water electrolysis (AEMWE) focus on developing superior catalysts and membrane electrode assemblies to narrow the performance gaps compared with proton-exchange membrane water electrolysis (PEMWE). Here we present and characterize Ir-free AEMWE cells with NiX (X = Fe, Co or Mn) layered double hydroxide (LDH) catalyst-coated membranes with polarization characteristics and hydrogen productivities approaching those of acidic PEMWE cells, achieving >5 A cm−2 at <2.2 V. Operando spectroscopy revealed a correlation between Ni4+ centres and redox-active O ligands with an O K-edge feature, attributed to µ3-O ligands in the γ-LDH catalytic phase via density functional theory calculations. This computational–experimental study challenges the previously assumed correlation between spectral O K-edge features and oxygen evolution reaction performance in Ni-based LDH catalysts and provides insights from the molecular to the technological level demonstrating how redox-active Ni–O species and innovative catalyst-coated membrane preparation boost AEMWE performance to values rivalling state-of-the-art PEMWE cell technology. Anion-exchange membrane water electrolysers have the potential to rival more costly acidic proton-exchange membrane electrolysers, but their performance and efficiency commonly still fall short. Now an anion-exchange membrane water electrolyser is prepared with a NiFe layered double hydroxide catalyst-coated membrane that achieves high current densities above 2 A cm−2 at 1.8 V and operando X-ray absorption spectroscopy is used to track the formation of the catalytically active γ-LDH phase.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 11","pages":"1213-1222"},"PeriodicalIF":42.8,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519246","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 : 2024-10-23DOI: 10.1038/s41929-024-01226-0
Estíbaliz Merino
Typically, active acyl intermediates are quenched with nucleophiles to complete carbonylation. Now, a visible-light-induced radical relay enables CO insertion and selective (hetero)aryl group migration without nucleophiles.
通常情况下，活性酰基中间体会被亲核物淬灭以完成羰基化。现在，一种由可见光诱导的自由基中继技术无需亲核剂即可实现 CO 插入和选择性（杂）芳基迁移。
{"title":"Synergistic role for CO","authors":"Estíbaliz Merino","doi":"10.1038/s41929-024-01226-0","DOIUrl":"10.1038/s41929-024-01226-0","url":null,"abstract":"Typically, active acyl intermediates are quenched with nucleophiles to complete carbonylation. Now, a visible-light-induced radical relay enables CO insertion and selective (hetero)aryl group migration without nucleophiles.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1058-1059"},"PeriodicalIF":42.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487904","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 : 2024-10-23DOI: 10.1038/s41929-024-01246-w
Davide Esposito
{"title":"Blowing in the tube","authors":"Davide Esposito","doi":"10.1038/s41929-024-01246-w","DOIUrl":"10.1038/s41929-024-01246-w","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1053-1053"},"PeriodicalIF":42.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487870","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 : 2024-10-23DOI: 10.1038/s41929-024-01235-z
Sukriyo Chakraborty, Akkattu T. Biju
Thiamine, a common enzymatic cofactor, catalyses the benzoin condensation. From 1943, a panoply of mechanistic proposals were invoked to explain the intriguing transformation until two seminal papers by Ronald Breslow about 15 years after the discovery of this reaction helped resolve the mechanistic conundrum and heralded the birth of NHC-organocatalysis.
{"title":"Birth of organocatalysis by N-heterocyclic carbenes","authors":"Sukriyo Chakraborty, Akkattu T. Biju","doi":"10.1038/s41929-024-01235-z","DOIUrl":"10.1038/s41929-024-01235-z","url":null,"abstract":"Thiamine, a common enzymatic cofactor, catalyses the benzoin condensation. From 1943, a panoply of mechanistic proposals were invoked to explain the intriguing transformation until two seminal papers by Ronald Breslow about 15 years after the discovery of this reaction helped resolve the mechanistic conundrum and heralded the birth of NHC-organocatalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1060-1062"},"PeriodicalIF":42.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487875","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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