{"title":"光致晶格压缩Cu促进CO2制乙烯","authors":"Zhenyao Li, Wei Wei, Xuli Hu, Zhen Zhang, Yangshun Hu, Yushan Wu, Yao Wang, Junchen Xu, Mingyue Ding","doi":"10.1002/adfm.202422898","DOIUrl":null,"url":null,"abstract":"<p>While engineering lattice strain has been proven effective in enhancing the electrochemical CO<sub>2</sub> reduction performance of a catalyst, the correlation between strain effect and the intrinsic catalytic mechanism has remained elusive. Herein, a photolithography-inspired method is proposed to regulate Cu(111) lattice strain. By irradiating the photosensitive Cu(Acac) sol–gel, Acac chelate bond undergoes π→π<sup>*</sup> electronic transition, and the ring-closed Cu(Acac) decompose into the stabilized Cu(Acac) mesh which presents as nanospots embedded onto the surface of the Cu cluster. The photoinduced nanospots serve to exert compressive strain to the Cu(111) lattice in which the lattice distance is reduced by 5.7–11.4%. Herein, the catalyst with 11.4% lattice compression exhibits enhanced C<sub>2</sub>H<sub>4</sub> production capabilities, reaching a maximal Faradaic efficiency of 57.00%, and a high partial current density of 456.01 mA cm<sup>−2</sup>. Theoretical calculations reveal that the compressed Cu(111) lattice exhibits reduced surface energies, leading to a significant drop in the C─C coupling reaction free energy from 1.16 eV over the pristine lattice, to 0.57 eV over the 10% compressed lattice. Additionally, the 10% compressed lattice facilitates spontaneous *O splitting immediately after OC─CHO coupling which leads to the generation of C<sub>2</sub>H<sub>4</sub>-favoring *CCH intermediate.</p>","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"35 17","pages":""},"PeriodicalIF":19.0000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoinduced Lattice Compression of Cu for Enhanced Production of Ethylene from CO2\",\"authors\":\"Zhenyao Li, Wei Wei, Xuli Hu, Zhen Zhang, Yangshun Hu, Yushan Wu, Yao Wang, Junchen Xu, Mingyue Ding\",\"doi\":\"10.1002/adfm.202422898\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>While engineering lattice strain has been proven effective in enhancing the electrochemical CO<sub>2</sub> reduction performance of a catalyst, the correlation between strain effect and the intrinsic catalytic mechanism has remained elusive. Herein, a photolithography-inspired method is proposed to regulate Cu(111) lattice strain. By irradiating the photosensitive Cu(Acac) sol–gel, Acac chelate bond undergoes π→π<sup>*</sup> electronic transition, and the ring-closed Cu(Acac) decompose into the stabilized Cu(Acac) mesh which presents as nanospots embedded onto the surface of the Cu cluster. The photoinduced nanospots serve to exert compressive strain to the Cu(111) lattice in which the lattice distance is reduced by 5.7–11.4%. Herein, the catalyst with 11.4% lattice compression exhibits enhanced C<sub>2</sub>H<sub>4</sub> production capabilities, reaching a maximal Faradaic efficiency of 57.00%, and a high partial current density of 456.01 mA cm<sup>−2</sup>. Theoretical calculations reveal that the compressed Cu(111) lattice exhibits reduced surface energies, leading to a significant drop in the C─C coupling reaction free energy from 1.16 eV over the pristine lattice, to 0.57 eV over the 10% compressed lattice. Additionally, the 10% compressed lattice facilitates spontaneous *O splitting immediately after OC─CHO coupling which leads to the generation of C<sub>2</sub>H<sub>4</sub>-favoring *CCH intermediate.</p>\",\"PeriodicalId\":112,\"journal\":{\"name\":\"Advanced Functional Materials\",\"volume\":\"35 17\",\"pages\":\"\"},\"PeriodicalIF\":19.0000,\"publicationDate\":\"2024-12-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Functional Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/adfm.202422898\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/adfm.202422898","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
虽然工程晶格应变已被证明能有效提高催化剂的电化学CO2还原性能,但应变效应与内在催化机制之间的关系尚不明确。本文提出了一种光刻启发的方法来调节Cu(111)晶格应变。通过对光敏Cu(Acac)溶胶-凝胶的辐照,Acac螯合键发生π→π*电子跃迁,环封闭的Cu(Acac)分解成稳定的Cu(Acac)网状结构,并以纳米斑点的形式嵌入在Cu簇表面。光致纳米点对Cu(111)晶格施加压缩应变,使晶格距离减小了5.7% ~ 11.4%。其中,当晶格压缩率为11.4%时,催化剂的C2H4生成能力增强,最大法拉第效率达到57.00%,分电流密度高达456.01 mA cm−2。理论计算表明,压缩Cu(111)晶格表面能降低,导致C─C耦合反应自由能从原始晶格的1.16 eV显著下降到压缩10%晶格的0.57 eV。此外,10%的压缩晶格有利于OC─CHO耦合后的自发*O分裂,从而生成有利于C2H4‐的*CCH中间体。
Photoinduced Lattice Compression of Cu for Enhanced Production of Ethylene from CO2
While engineering lattice strain has been proven effective in enhancing the electrochemical CO2 reduction performance of a catalyst, the correlation between strain effect and the intrinsic catalytic mechanism has remained elusive. Herein, a photolithography-inspired method is proposed to regulate Cu(111) lattice strain. By irradiating the photosensitive Cu(Acac) sol–gel, Acac chelate bond undergoes π→π* electronic transition, and the ring-closed Cu(Acac) decompose into the stabilized Cu(Acac) mesh which presents as nanospots embedded onto the surface of the Cu cluster. The photoinduced nanospots serve to exert compressive strain to the Cu(111) lattice in which the lattice distance is reduced by 5.7–11.4%. Herein, the catalyst with 11.4% lattice compression exhibits enhanced C2H4 production capabilities, reaching a maximal Faradaic efficiency of 57.00%, and a high partial current density of 456.01 mA cm−2. Theoretical calculations reveal that the compressed Cu(111) lattice exhibits reduced surface energies, leading to a significant drop in the C─C coupling reaction free energy from 1.16 eV over the pristine lattice, to 0.57 eV over the 10% compressed lattice. Additionally, the 10% compressed lattice facilitates spontaneous *O splitting immediately after OC─CHO coupling which leads to the generation of C2H4-favoring *CCH intermediate.
期刊介绍:
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