利用过渡金属氧化物调控金属铋纳米片的p轨道从而实现CO_(2)的高效电还原  

Regulating p-orbital of metallic bismuth nanosheets via transition-metal oxides enables advanced CO_(2) electroreduction

作　　者：尹伟勃 刘博文 王晓蕾 王文倩 宋子辰 任志宇 付宏刚 Weibo Yin;Bowen Liu;Xiaolei Wang;Wenqian Wang;Zichen Song;Zhiyu Ren;Honggang Fu(Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education of China,School of Chemistry and Materials Science,Heilongjiang University,Harbin 150080,China;Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education,College of Materials Science and Chemical Engineering,Harbin Engineering University,Harbin 150001,China)

机构地区：[1]Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education of China,School of Chemistry and Materials Science,Heilongjiang University,Harbin 150080,China [2]Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education,College of Materials Science and Chemical Engineering,Harbin Engineering University,Harbin 150001,China

出　　处：《Science China Materials》2024年第6期1965-1974,共10页中国科学（材料科学）（英文版）

基　　金：the support of this research by the National Natural Science Foundation of China (U20A20250 and 22179035);the Science Fund for Distinguished Young Scholars of Heilongjiang Province (JQ2022B001);the Fundamental Research Funds for Youth Science and Technology Innovation Team Project of Heilongjiang Province (2021-KYYWF-0030);the China Postdoctoral Science Foundation (2019M651313);the Universities Fundamental Research Funds of Heilongjiang Province (RCCXYJ201806 and 2022-KYYWF-1063);University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (UNPYSCT-2020006)。

摘　　要：p-d轨道之间的相互作用是一种提升电催化性能的有效方法.然而,其对主族金属的电催化CO_(2)还原(eCO_(2)RR)的增强机制尚不清晰.因此,我们向金属Bi纳米片中引入了一系列过渡金属氧化物(TMO:Fe_(2)O_(3)、Co_(3)O_(4)、NiO),并以此研究引入TMO对Bi物种eCO_(2)RR性能的影响.根据原位傅里叶变换红外光谱(FTIR)和CO_(2)-程序升温脱附(TPD)的结果,Bi/TMO中的TMO可以增强CO_(2)的吸附和活化能力.密度泛函理论(DFT)计算结果表明,Bi活性位点^(*)OCHO吸附能及p轨道的优化可以降低CO_(2)到^(*)OCHO过程和^(*)OCHO到HCOOH过程的理论过电位.同时,由于Bi与TMO之间因复合而发生的电子重排也促进了催化剂与反应物之间的电子传输.因此,在热力学和动力学的双重作用下,Bi/TMO中的Bi活性位点表现出最佳的催化能力,在更宽的电位区间内实现了更高的催化活性和甲酸选择性.其中,Bi/Fe_(2)O_(3)的增强效果最为显著.在500 mV的宽电位区间内达到较高的甲酸的法拉第效率(>90%),在-0.8 VRHE时,甲酸的法拉第效率达到最大值99.7%(Bi的1.11倍),甲酸局部电流密度达到12.65 mA cm^(-2)(Bi的1.86倍).这一研究不仅建立了eCO_(2)RR性能增强与引入TMO之间的关系,也为理性设计高性能电催化剂提供了一条实用的、可扩展的途径.The interaction of p-d orbitals can be used to efficiently improve electrocatalytic performance.However,the enhanced mechanism of electrocatalytic CO_(2) reduction reac-tion(eCO_(2)RR)on main group metals inspired by the p-d orbital interactions is still unclear.Herein,a series of transi-tion-metal oxides(TMOs:Fe_(2)O_(3),Co_(3)O_(4),and NiO)are in-troduced to metallic bismuth(Bi)nanosheets(NSs),which is proposed as a proof of concept for investigating the effect of introduced TMOs on the eCO_(2)RR performance for Bi.Based on the results from in-situ Fourier transform infrared(FTIR)spectra and CO_(2)-temperature programmed deposition(TPD),the TMOs in the Bi/TMOs NSs can enhance the adsorption and/or activation ability of CO_(2).Density functional theory(DFT)calculations reveal that the regulated adsorption energy of^(*)OCHO and p-orbital of Bi sites can decrease theoretical overpotentials for both the CO_(2)-to-^(*)OCHO process and the^(*)OCHO-to-HCOOH process.Moreover,the electron re-arrangement that occurred due to the contact between Bi and TMO can also promote electron transport between the cata-lyst and reactants.Therefore,under the dual positive effect of thermodynamics and kinetics,the Bi sites in Bi/TMO NSs exhibit the maximum catalytic ability,realizing high catalytic activity and selectivity for HCOOH over a wider potential region.In particular,Bi/Fe_(2)O_(3) NSs can present the most sig-nificant enhancement effect.It can yield a wide potential re-gion of 500 mV with a high FEHCOOH(>90%)and achieve a maximum FEHCOOH of 99.7%(1.11 times that of Bi)at-0.8 VRHE with the HCOOH partial current density of 12.65 mA cm^(-2)(1.86 times that of Bi).This study establishes a relationship between the enhanced performance and the in-troduced TMOs and provides a practicable and scalable ave-nue for rationally engineering high-powered electrocatalysts.

关 键 词：transition metal oxides Bi/Fe_(2)O_(3)nanosheets elec-trocatalytic CO_(2)reduction HCOOH p-orbital regulation 

分 类 号：TQ426[化学工程] TB383.1[一般工业技术—材料科学与工程] X701[环境科学与工程—环境工程]