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.
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)
基金
supported by the National Natural Science Foundation of China(22302002,22375006)
the University Science Research Project of Anhui Province(2022AH050182,2022AH020020)。
