Efficient charge relay steering in Pd nanoparticles coupled with the heterojunction for boosting CO_(2)photoreduction to C_(2)H_(6)  

耦合异质结和Pd纳米颗粒的高效电荷接力促进CO_(2)光还原为C_(2)H_(6)

作　　者：Jiaojiao Fang Chengyang Zhu Lincan Fang Yukai Chen Huiling Hu Yan Wu Qingqing Chen Junjie Mao 方姣姣;朱成洋;方林灿;陈雨凯;胡慧玲;吴艳;陈庆庆;毛俊杰(Key Laboratory of Functional Molecular Solids,Ministry of Education,College of Chemistry and Materials Science,Anhui Normal University,Wuhu,241002,China;Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology,Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,School of Petrochemical Engineering,Changzhou University,Changzhou,213164,China)

机构地区：[1]Key Laboratory of Functional Molecular Solids,Ministry of Education,College of Chemistry and Materials Science,Anhui Normal University,Wuhu,241002,China [2]Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology,Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,School of Petrochemical Engineering,Changzhou University,Changzhou,213164,China

出　　处：《Science China Materials》2024年第9期2949-2956,共8页中国科学（材料科学）（英文版）

基　　金：supported by the National Natural Science Foundation of China(22302002,22375006);the University Science Research Project of Anhui Province(2022AH050182,2022AH020020)。

摘　　要：Solar-driven CO_(2)conversion to prepare value-added products is highly desirable but challenging.Central to the achievement of multi-carbon products via CO_(2)photoconversion is to break the bottlenecks of C-C coupling and multi-electron transfer.Herein,a charge relay system consisting of Pd-decorated BiOCl-wrapped CuBi_(2)O_(4)is reported by taking advantage of the synergy of Pd nanoparticles(PdNPs)and heterojunction for efficient CO_(2)-to-C_(2)H_(6)photoconversion.The C_(2)H_(6)production rate reached 167.1µmol g^(-1)h^(-1)with the electron selectivity of 81.1%in the absence of any sacrificial agents.The spectroscopic characterizations indicated that BiOCl nanosheets,acting as the charge relay,directionally transferred the photogenerated electrons from itself and CuBi2O4 nanorods to PdNPs for C-C coupling.The coordinated ensemble of PdNPs and heterojunction significantly elevated the charge separation and transfer efficiency.Moreover,the in-situ spectroscopic analysis supported by theoretical simulations demonstrated that the electron-rich PdNPs generated by the charge relay of PdNPs and heterojunction optimized the CO_(2)-to-C_(2)H_(6)reaction pathway and reduced the energy barrier of the key*CHOCO intermediates.This work develops an innovative strategy to design the multifunctional catalysts for the photoconversion of CO_(2)to value-added carbon products.太阳能驱动CO_(2)转换制备高附加值产品是实现碳中和的路径之一,但具有挑战性.CO_(2)光转化实现多碳产物的关键是打破C-C耦合难和多电子转移效率低的瓶颈.本文报道了一种由Pd修饰的BiOCl包裹CuBi_(2)O_(4)组成的电荷接力系统,利用PdNPs和异质结的协同作用实现CO_(2-)C_(2)H_(6)的高效光转换.在无牺牲剂条件下,C_(2)H_(6)产率达到167.1μmol g^(-1)h^(-1),电子选择性为81.1%.光谱研究表明,BiOCl纳米片作为电荷中继站,将光生电子从自身和CuBi_(2)O_(4)纳米棒定向转移到Pd纳米颗粒(PdNPs)上进行C-C耦合.PdNPs与异质结的协同作用显著提高了电荷的分离和转移效率.原位表征和理论模拟均表明,由PdNPs和异质结组成的电荷接力系统产生的富电子PdNPs,优化了CO_(2)到C_(2)H_(6)反应路径,降低了中间体*CHOCO的能垒.这项工作为发展高效的CO_(2)光催化材料提供了思路.

关 键 词：charge relay Pd nanoparticles HETEROJUNCTION CO_(2)photoreduction C_(2)H_(6) 

分 类 号：O643.36[理学—物理化学] TQ221.211[理学—化学] O644.1[化学工程—有机化工]