Solar-driven CO_(2) conversion to methane and methanol using different nanostructured Cu_(2)O-based catalysts modified with Au nanoparticles  

作　　者：João Angelo Lima Perini Lilian D.Moura Torquato Juliana Fde Brito Gustavo A.Andolpho Mateus A.Gonçalves Leonardo D.De Angelis Lucas D.Germano Susana I.Córdoba de Torresi Teodorico C.Ramalho Maria V.Boldrin Zanoni 

机构地区：[1]São Paulo State University(UNESP),Institute of Chemistry,Rua Prof.Francisco Degni,55,Araraquara,SP 14800-060,Brazil [2]National Institute of Alternative Technologies for Detection,Toxicological Evaluation and Removal of Micropollutants and Radioactive Substances(INCT-DATREM),São Paulo State University(UNESP),Institute of Chemistry,Rua Prof.Francisco Degni,55,Araraquara,SP 14800-060,Brazil [3]Laboratory of Molecular Modelling,Department of Chemistry,Natural Sciences Institute,Federal University of Lavras,Lavras,MG 37200-900,Brazil [4]Department of Chemistry,Faculty of Science,University of Hradec Králové,Hradec Králové50003,Czech Republic [5]Instituto de Química,Universidade de São Paulo,Av.Prof.Lineu Prestes 74805508-080,São Paulo,SP,Brazil

出　　处：《Journal of Energy Chemistry》2024年第4期287-298,共12页能源化学（英文版）

基　　金：FAPESP,Brazil(#2023/10027-5,#2014/50945-4,#2020/15230-5,and#2021/000675-4);CNPq,Brazil(#465571/2014-0,#303269/2021-9,and#307837/2014-9);Instituto Serrapilheira(grant number Serra-2211-41925);FAPEMIG,Brazil(#PPM-00831-15)for support of this work;CNPq,Brazil(#105944/2022-0)and PROPEUNESP(13/2022);FAPESP(#2019/00463-7,#2018/22845-6,and#2021/08007-0,respectively)for scholarships;the National Institute for Alternative Technologies of Detection,Toxicological Evaluation and Removal of Micropollutants and Radioactives(INCT-DATREM);the support of the Research Centre for Greenhouse Gas Innovation(RCGI),hosted by the University of Sao Paulo(USP)and sponsored by FAPESP and Shell Brasil;the strategic support given by ANP,Brazil(Brazilian National Oil,Natural Gas,and Biofuels Agency)through the R&D levy regulation。

摘　　要：This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.

关 键 词：Cu_(2)O nanocubes PHOTOELECTROCATALYSIS POLYDOPAMINE CO_(2) photoelectroreduction DFT calculations 

分 类 号：TQ221.11[化学工程—有机化工] TQ223.121[理学—物理化学] O643.36[理学—化学]