Pub Date : 2024-06-20DOI: 10.1038/s44160-024-00568-8
Yongxiang Liang, Feng Li, Rui Kai Miao, Sunpei Hu, Weiyan Ni, Shuzhen Zhang, Yanjiang Liu, Yang Bai, Haoyue Wan, Pengfei Ou, Xiao-Yan Li, Ning Wang, Sungjin Park, Fengwang Li, Jie Zeng, David Sinton, Edward H. Sargent
Electrochemical reduction of carbon monoxide is a promising carbonate-free approach to produce ethylene using renewable electricity. However, the performance of this process suffers from low selectivity and energy efficiency. A priority has been to weaken water dissociation with the aim of inhibiting the competing hydrogen evolution reaction but when this path was examined by replacing H2O with D2O, a further-reduced selectivity toward ethylene was observed. Here we examine approaches to promote water adsorption and to decrease the energy barrier to the ensuing water dissociation step, which could promote C–O cleavage in *CHCOH hydrogenation to *CCH. We modified a copper catalyst with the strong electron acceptor 7,7,8,8-tetracyanoquinodimethane, which made the catalyst surface electron deficient. The observed ethylene Faradaic efficiency was 75%, 1.3 times greater than that of unmodified copper control catalysts. A full-cell energy efficiency of 32% was achieved for a total projected energy cost of 154 GJ t−1 in ethylene electrosynthesis in a membrane electrode assembly. CO electroreduction is a promising carbonate-free approach to produce ethylene, but suffers from limited selectivity and low energy efficiency. By modifying copper with a strong electron acceptor, 7,7,8,8-tetracyanoquinodimethane, the water dissociation step is accelerated, leading to excellent ethylene selectivity and full-cell energy efficiency in CO electroreduction.
{"title":"Efficient ethylene electrosynthesis through C–O cleavage promoted by water dissociation","authors":"Yongxiang Liang, Feng Li, Rui Kai Miao, Sunpei Hu, Weiyan Ni, Shuzhen Zhang, Yanjiang Liu, Yang Bai, Haoyue Wan, Pengfei Ou, Xiao-Yan Li, Ning Wang, Sungjin Park, Fengwang Li, Jie Zeng, David Sinton, Edward H. Sargent","doi":"10.1038/s44160-024-00568-8","DOIUrl":"10.1038/s44160-024-00568-8","url":null,"abstract":"Electrochemical reduction of carbon monoxide is a promising carbonate-free approach to produce ethylene using renewable electricity. However, the performance of this process suffers from low selectivity and energy efficiency. A priority has been to weaken water dissociation with the aim of inhibiting the competing hydrogen evolution reaction but when this path was examined by replacing H2O with D2O, a further-reduced selectivity toward ethylene was observed. Here we examine approaches to promote water adsorption and to decrease the energy barrier to the ensuing water dissociation step, which could promote C–O cleavage in *CHCOH hydrogenation to *CCH. We modified a copper catalyst with the strong electron acceptor 7,7,8,8-tetracyanoquinodimethane, which made the catalyst surface electron deficient. The observed ethylene Faradaic efficiency was 75%, 1.3 times greater than that of unmodified copper control catalysts. A full-cell energy efficiency of 32% was achieved for a total projected energy cost of 154 GJ t−1 in ethylene electrosynthesis in a membrane electrode assembly. CO electroreduction is a promising carbonate-free approach to produce ethylene, but suffers from limited selectivity and low energy efficiency. By modifying copper with a strong electron acceptor, 7,7,8,8-tetracyanoquinodimethane, the water dissociation step is accelerated, leading to excellent ethylene selectivity and full-cell energy efficiency in CO electroreduction.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510628","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 : 2024-06-18DOI: 10.1038/s44160-024-00576-8
Yuki Haruta, Hanyang Ye, Paul Huber, Nicholas Sandor, Antoine Pavesic Junior, Sergey Dayneko, Shuang Qiu, Vishal Yeddu, Makhsud I. Saidaminov
Controlling the linear growth rate, a critical factor that determines crystal quality, has been a challenge in solution-grown single crystals due to complex crystallization kinetics influenced by multiple parameters. Here we introduce a flux-regulated crystallization (FRC) method to directly monitor and feedback-control the linear growth rate, circumventing the need to control individual growth conditions. When applied to metal halide perovskites, the FRC maintains a stable linear growth rate for over 40 h in synthesizing CH3NH3PbBr3 and CsPbBr3 single crystals, achieving outstanding crystallinity (quantified by a full width at half-maximum of 15.3 arcsec in the X-ray rocking curve) in a centimetre-scale single crystal. The FRC is a reliable platform for synthesizing high-quality crystals essential for commercialization and systematically exploring crystallization conditions, maintaining a key parameter—the linear growth rate—constant, which enables a comprehensive understanding of the impact of other influencing factors. Controlling linear growth rate is challenging in solution-grown single crystals. Now, flux-regulated crystallization (FRC) is developed to directly feedback-control the growth rate. When applied to metal halide perovskites, FRC achieves reproducible high crystallinity, offering a platform for synthesizing high-quality single crystals and exploring crystallization conditions.
{"title":"Reproducible high-quality perovskite single crystals by flux-regulated crystallization with a feedback loop","authors":"Yuki Haruta, Hanyang Ye, Paul Huber, Nicholas Sandor, Antoine Pavesic Junior, Sergey Dayneko, Shuang Qiu, Vishal Yeddu, Makhsud I. Saidaminov","doi":"10.1038/s44160-024-00576-8","DOIUrl":"10.1038/s44160-024-00576-8","url":null,"abstract":"Controlling the linear growth rate, a critical factor that determines crystal quality, has been a challenge in solution-grown single crystals due to complex crystallization kinetics influenced by multiple parameters. Here we introduce a flux-regulated crystallization (FRC) method to directly monitor and feedback-control the linear growth rate, circumventing the need to control individual growth conditions. When applied to metal halide perovskites, the FRC maintains a stable linear growth rate for over 40 h in synthesizing CH3NH3PbBr3 and CsPbBr3 single crystals, achieving outstanding crystallinity (quantified by a full width at half-maximum of 15.3 arcsec in the X-ray rocking curve) in a centimetre-scale single crystal. The FRC is a reliable platform for synthesizing high-quality crystals essential for commercialization and systematically exploring crystallization conditions, maintaining a key parameter—the linear growth rate—constant, which enables a comprehensive understanding of the impact of other influencing factors. Controlling linear growth rate is challenging in solution-grown single crystals. Now, flux-regulated crystallization (FRC) is developed to directly feedback-control the growth rate. When applied to metal halide perovskites, FRC achieves reproducible high crystallinity, offering a platform for synthesizing high-quality single crystals and exploring crystallization conditions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00576-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530223","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 : 2024-06-14DOI: 10.1038/s44160-024-00563-z
Antonio Angelastro, Alexey Barkhanskiy, Toby Journeaux, Rohan Sivapalan, Thomas A. King, Laura Rodríguez Pérez, William R. F. Goundry, Perdita Barran, Sabine L. Flitsch
Chemo-selective modifications of proteins are fundamental to the advancement of biological and pharmaceutical sciences. The search for biocompatible chemical reactions has prompted us to investigate Horner–Wadsworth–Emmons (HWE) olefinations, iconic reactions in organic synthesis that would give rise to new selective protein olefinations. Our choice of HWE olefinations was inspired by the growing number of methods for generating aldehydes as transient reactive groups in proteins and the potential for mild and simple reaction conditions. Here we show that HWE olefination reactions on aldehydes, produced by both chemical and enzymatic methods, are compatible with physiological conditions and highly selective in small and large proteins, including therapeutic antibodies and stable recombinant proteins exemplified by green fluorescent protein. Reaction kinetics can be fine-tuned over orders of magnitude both by judicious use of substituents and pH regulation. The electrophilic nature of the HWE olefination products can be tuned to allow for subsequent nucleophilic additions, including thiol- and phospha-Michael additions. Our results demonstrate that HWE olefination of aldehydes in proteins provides efficient and selective bioconjugation chemistries that are orthogonal to existing methods. Aldehyde-bearing proteins are shown to be suitable substrates for Horner–Wadsworth–Emmons reactions. Applying this process to proteins and glycoproteins enables site-specific bioconjugation with tunable reaction kinetics.
{"title":"Horner–Wadsworth–Emmons olefination of proteins and glycoproteins","authors":"Antonio Angelastro, Alexey Barkhanskiy, Toby Journeaux, Rohan Sivapalan, Thomas A. King, Laura Rodríguez Pérez, William R. F. Goundry, Perdita Barran, Sabine L. Flitsch","doi":"10.1038/s44160-024-00563-z","DOIUrl":"10.1038/s44160-024-00563-z","url":null,"abstract":"Chemo-selective modifications of proteins are fundamental to the advancement of biological and pharmaceutical sciences. The search for biocompatible chemical reactions has prompted us to investigate Horner–Wadsworth–Emmons (HWE) olefinations, iconic reactions in organic synthesis that would give rise to new selective protein olefinations. Our choice of HWE olefinations was inspired by the growing number of methods for generating aldehydes as transient reactive groups in proteins and the potential for mild and simple reaction conditions. Here we show that HWE olefination reactions on aldehydes, produced by both chemical and enzymatic methods, are compatible with physiological conditions and highly selective in small and large proteins, including therapeutic antibodies and stable recombinant proteins exemplified by green fluorescent protein. Reaction kinetics can be fine-tuned over orders of magnitude both by judicious use of substituents and pH regulation. The electrophilic nature of the HWE olefination products can be tuned to allow for subsequent nucleophilic additions, including thiol- and phospha-Michael additions. Our results demonstrate that HWE olefination of aldehydes in proteins provides efficient and selective bioconjugation chemistries that are orthogonal to existing methods. Aldehyde-bearing proteins are shown to be suitable substrates for Horner–Wadsworth–Emmons reactions. Applying this process to proteins and glycoproteins enables site-specific bioconjugation with tunable reaction kinetics.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00563-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141342629","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 : 2024-06-14DOI: 10.1038/s44160-024-00571-z
Yimon Aye
Through site-specific generation of intermediary reactive aldehydes, Horner–Wadsworth–Emmons olefination can now deliver selective functionalization of stable recombinant proteins and monoclonal antibodies, whilst preserving protein integrity.
{"title":"Horner–Wadsworth–Emmons olefination for bioconjugation","authors":"Yimon Aye","doi":"10.1038/s44160-024-00571-z","DOIUrl":"10.1038/s44160-024-00571-z","url":null,"abstract":"Through site-specific generation of intermediary reactive aldehydes, Horner–Wadsworth–Emmons olefination can now deliver selective functionalization of stable recombinant proteins and monoclonal antibodies, whilst preserving protein integrity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141339838","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 : 2024-06-12DOI: 10.1038/s44160-024-00553-1
Liyan Zhao, Yanling Wang, Shoutong Jin, Ning An, Mi Yan, Xiaochen Zhang, Zijian Hong, Shikuan Yang
Electrochemical deposition has been widely used to prepare conformal coatings but has rarely been used to design well-defined micro/nanostructures. Here we report electrochemical synthesis of complex, hierarchical inorganic microarchitectures simply via programming the applied potential waveforms. We identify two distinct electrochemical growth modes—the stacking mode and the flattening mode—under different potential waveforms. We demonstrate how these growth modes can work individually or cooperatively to design previously inaccessible microarchitectures. Each specific potential waveform corresponds to a specific microarchitecture, allowing us to prepare a rich library of microarchitectures. The designed microarchitectures can be converted into other materials by simple redox-potential-driven chemical reactions. We preliminarily studied the applications of converted nanoporous silver microscale torpedoes as high-performance surface-enhanced Raman spectroscopy (SERS) sensing substrates. The reported method opens up a new concept to design complex inorganic microarchitectures with promising applications in metamaterials, chemically or magnetically propelled microrobotics, and miniaturized devices. Rational design of the morphology of inorganic microstructures is challenging. Now an electrochemical method is reported for designing the morphology of inorganic microarchitectures via programming of the potential waveforms applied during microstructure growth. These microstructures have potential application as SERS sensors.
{"title":"Rational electrochemical design of hierarchical microarchitectures for SERS sensing applications","authors":"Liyan Zhao, Yanling Wang, Shoutong Jin, Ning An, Mi Yan, Xiaochen Zhang, Zijian Hong, Shikuan Yang","doi":"10.1038/s44160-024-00553-1","DOIUrl":"10.1038/s44160-024-00553-1","url":null,"abstract":"Electrochemical deposition has been widely used to prepare conformal coatings but has rarely been used to design well-defined micro/nanostructures. Here we report electrochemical synthesis of complex, hierarchical inorganic microarchitectures simply via programming the applied potential waveforms. We identify two distinct electrochemical growth modes—the stacking mode and the flattening mode—under different potential waveforms. We demonstrate how these growth modes can work individually or cooperatively to design previously inaccessible microarchitectures. Each specific potential waveform corresponds to a specific microarchitecture, allowing us to prepare a rich library of microarchitectures. The designed microarchitectures can be converted into other materials by simple redox-potential-driven chemical reactions. We preliminarily studied the applications of converted nanoporous silver microscale torpedoes as high-performance surface-enhanced Raman spectroscopy (SERS) sensing substrates. The reported method opens up a new concept to design complex inorganic microarchitectures with promising applications in metamaterials, chemically or magnetically propelled microrobotics, and miniaturized devices. Rational design of the morphology of inorganic microstructures is challenging. Now an electrochemical method is reported for designing the morphology of inorganic microarchitectures via programming of the potential waveforms applied during microstructure growth. These microstructures have potential application as SERS sensors.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141350998","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 : 2024-06-12DOI: 10.1038/s44160-024-00565-x
Conor L. Rooney, Hailiang Wang
Implementing a chemical C–N coupling step to intercept reactive intermediates in electrocatalytic CO2 or NOxy– reduction reactions is an emerging approach to sustainable electrosynthesis of organonitrogen compounds from cheap and abundant feedstocks.
{"title":"Electrocatalytic methylation and amination reactions with CO2 and NOxy–","authors":"Conor L. Rooney, Hailiang Wang","doi":"10.1038/s44160-024-00565-x","DOIUrl":"10.1038/s44160-024-00565-x","url":null,"abstract":"Implementing a chemical C–N coupling step to intercept reactive intermediates in electrocatalytic CO2 or NOxy– reduction reactions is an emerging approach to sustainable electrosynthesis of organonitrogen compounds from cheap and abundant feedstocks.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352852","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 : 2024-06-11DOI: 10.1038/s44160-024-00601-w
Wesley Wang, Nicholas H. Angello, Daniel J. Blair, Theodore Tyrikos-Ergas, William H. Krueger, Kameron N. S. Medine, Antonio J. LaPorte, Joshua M. Berger, Martin D. Burke
{"title":"Publisher Correction: Rapid automated iterative small-molecule synthesis","authors":"Wesley Wang, Nicholas H. Angello, Daniel J. Blair, Theodore Tyrikos-Ergas, William H. Krueger, Kameron N. S. Medine, Antonio J. LaPorte, Joshua M. Berger, Martin D. Burke","doi":"10.1038/s44160-024-00601-w","DOIUrl":"10.1038/s44160-024-00601-w","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00601-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141973733","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 : 2024-06-10DOI: 10.1038/s44160-024-00556-y
Methods for the asymmetric functionalization of unstrained C(sp3)–C(sp3) bonds are rare. Now, strategies are developed for the enantioselective functionalization of allylic C(sp3)–C(sp3) bonds with a palladium catalyst through either kinetic resolution or dynamic kinetic asymmetric transformation.
{"title":"Asymmetric allylic C(sp3)–C(sp3) bond functionalization","authors":"","doi":"10.1038/s44160-024-00556-y","DOIUrl":"10.1038/s44160-024-00556-y","url":null,"abstract":"Methods for the asymmetric functionalization of unstrained C(sp3)–C(sp3) bonds are rare. Now, strategies are developed for the enantioselective functionalization of allylic C(sp3)–C(sp3) bonds with a palladium catalyst through either kinetic resolution or dynamic kinetic asymmetric transformation.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141365602","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}
The selective one-step CO2 electroreduction reaction (CO2RR) to acetate and propanol has garnered intense interest. Here we report the design of self-pressurizing nanoscale capsule catalysts for the CO2RR. A high-pressure CO intermediate environment is created around copper catalysts by a permselective enclosure. Microkinetic modelling, 13CO2/12CO co-feed experiments and in situ Raman spectroscopy confirm that a unique CO–CO2 coupling path is involved, which is only initiated at high CO intermediate pressure. This pathway benefits acetate production due to the kinetic and energetic advantages of COCO2*. The acetate Faradaic efficiency is 38.5 ± 2.2% (8 times higher than that achieved without enclosure) and the acetate partial current density is 328 ± 19 mA cm−2, which surpasses the performance of previous CO2RR catalysts. In situ investigation indicates that the CO pressure inside the nanoscale capsule catalysts can reach 8 ± 3 bar. Furthermore, self-pressurizing nanoscale capsule catalysts with a CuI-derived core can reduce CO2 to propanol with a Faradaic efficiency of 25.7 ± 1.2% and a conversion rate of 155 ± 3 mA cm−2. CO2 electroreduction to multicarbon products is desirable but challenging. Now, self-pressurizing nanoscale capsule catalysts are synthesized. The self-pressurising capsules harness high-pressure CO environments for selective acetate or propanol production via a CO–CO2 coupling pathway.
一步法选择性 CO2 电还原反应（CO2RR）生成醋酸酯和丙醇引起了人们的浓厚兴趣。在此，我们报告了用于 CO2RR 的自加压纳米级胶囊催化剂的设计。铜催化剂周围通过包覆选择性形成了高压 CO 中间环境。微动力学建模、13CO2/12CO 共馈实验和原位拉曼光谱证实，其中涉及一种独特的 CO-CO2 耦合途径，该途径仅在高 CO 中间压力下启动。由于 COCO2* 在动力学和能量方面的优势，这一途径有利于醋酸盐的生产。醋酸酯法拉第效率为 38.5 ± 2.2%（是无封闭情况下的 8 倍），醋酸酯部分电流密度为 328 ± 19 mA cm-2，超过了以往 CO2RR 催化剂的性能。原位研究表明，纳米胶囊催化剂内部的 CO 压力可达 8 ± 3 巴。此外，以 CuI 为核心的自加压纳米级胶囊催化剂可将二氧化碳还原为丙醇，其法拉第效率为 25.7 ± 1.2%，转化率为 155 ± 3 mA cm-2。将 CO2 电还原为多碳产品是一种理想但具有挑战性的方法。现在，我们合成了自加压纳米级胶囊催化剂。自加压胶囊利用高压 CO 环境，通过 CO-CO2 偶联途径选择性地生产醋酸或丙醇。
{"title":"Self-pressurizing nanoscale capsule catalysts for CO2 electroreduction to acetate or propanol","authors":"Yanming Cai, Ruixin Yang, Jiaju Fu, Zhe Li, Liangyiqun Xie, Kai Li, Yu-Chung Chang, Shichao Ding, Zhaoyuan Lyu, Jian-Rong Zhang, Jun-Jie Zhu, Yuehe Lin, Wenlei Zhu","doi":"10.1038/s44160-024-00552-2","DOIUrl":"10.1038/s44160-024-00552-2","url":null,"abstract":"The selective one-step CO2 electroreduction reaction (CO2RR) to acetate and propanol has garnered intense interest. Here we report the design of self-pressurizing nanoscale capsule catalysts for the CO2RR. A high-pressure CO intermediate environment is created around copper catalysts by a permselective enclosure. Microkinetic modelling, 13CO2/12CO co-feed experiments and in situ Raman spectroscopy confirm that a unique CO–CO2 coupling path is involved, which is only initiated at high CO intermediate pressure. This pathway benefits acetate production due to the kinetic and energetic advantages of COCO2*. The acetate Faradaic efficiency is 38.5 ± 2.2% (8 times higher than that achieved without enclosure) and the acetate partial current density is 328 ± 19 mA cm−2, which surpasses the performance of previous CO2RR catalysts. In situ investigation indicates that the CO pressure inside the nanoscale capsule catalysts can reach 8 ± 3 bar. Furthermore, self-pressurizing nanoscale capsule catalysts with a CuI-derived core can reduce CO2 to propanol with a Faradaic efficiency of 25.7 ± 1.2% and a conversion rate of 155 ± 3 mA cm−2. CO2 electroreduction to multicarbon products is desirable but challenging. Now, self-pressurizing nanoscale capsule catalysts are synthesized. The self-pressurising capsules harness high-pressure CO environments for selective acetate or propanol production via a CO–CO2 coupling pathway.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141373860","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 : 2024-06-07DOI: 10.1038/s44160-024-00559-9
Ting Guo, Jinghao Li, Zhangkai Cui, Zefan Wang, Hongjian Lu
The nitrogen deletion of secondary amines has emerged as an effective strategy for direct molecular skeletal editing and carbon–carbon bond formation. However, current methods are often limited to acyclic bis(α-primary) amines and cyclic amines, which possess two stabilizing elements at the α-position of amine. Here we report the use of O-diphenylphosphinylhydroxylamine as a reagent for nitrogen deletion of secondary amines to form C(sp3)–C(sp3) bonds. This method overcomes substrate requirements of other methods and tolerates a range of secondary amine substrates. The process can be readily applied to multiple nitrogen deletion processes, is tolerant of both air and water, forms water-soluble byproducts and can be readily scaled to a hundred-gram scale. The versatility of the method is further showcased through the direct editing of natural products, pharmaceutical compounds, N-coordinated ligands, a three-dimensional amine cage and the synthesis of several bioactive compounds. Methods for nitrogen deletion of secondary amines are often limited by substrate structure requirements. Now the use of O-diphenylphosphinylhydroxylamine for nitrogen deletion of a range of secondary amines is reported. The developed process is tolerant of both air and water and can be scaled easily.
{"title":"C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine","authors":"Ting Guo, Jinghao Li, Zhangkai Cui, Zefan Wang, Hongjian Lu","doi":"10.1038/s44160-024-00559-9","DOIUrl":"10.1038/s44160-024-00559-9","url":null,"abstract":"The nitrogen deletion of secondary amines has emerged as an effective strategy for direct molecular skeletal editing and carbon–carbon bond formation. However, current methods are often limited to acyclic bis(α-primary) amines and cyclic amines, which possess two stabilizing elements at the α-position of amine. Here we report the use of O-diphenylphosphinylhydroxylamine as a reagent for nitrogen deletion of secondary amines to form C(sp3)–C(sp3) bonds. This method overcomes substrate requirements of other methods and tolerates a range of secondary amine substrates. The process can be readily applied to multiple nitrogen deletion processes, is tolerant of both air and water, forms water-soluble byproducts and can be readily scaled to a hundred-gram scale. The versatility of the method is further showcased through the direct editing of natural products, pharmaceutical compounds, N-coordinated ligands, a three-dimensional amine cage and the synthesis of several bioactive compounds. Methods for nitrogen deletion of secondary amines are often limited by substrate structure requirements. Now the use of O-diphenylphosphinylhydroxylamine for nitrogen deletion of a range of secondary amines is reported. The developed process is tolerant of both air and water and can be scaled easily.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141372954","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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