摘要
Sn-based electrocatalysts have been gaining increasing attention due to their potential contribution in the conversion of CO2 into HCOOH driven by sustainable energy sources;however,their actual capability to catalyze CO2 reduction reaction(CO2RR)still cannot meet the requirements of commercial-scale applications.Therefore developing Snbased catalyst is of vital importance.Herein,the sheet-like heterophase Sn O2/Sn3O4 with a high density of phase interfaces has been first engineered by a facile hydrothermal process,with Sn3O4 as the dominant phase.The evidences from experiments and theoretical simulation indicate that the charge redistribution and built-in electric field at heterophase interfaces boost CO2 adsorption and HCOO*formation,accelerate the charge transfer between the catalysts and reactants,and ultimately greatly elevate the intrinsic activity of the heterophase Sn O2/Sn3O4 towards CO2 RR.Meanwhile,the in-situ generated porous structure and metal Sn during CO2 RR improve the mass transmission within the interlayer volume and the conductivity of Sn O2/Sn3O4.The heterophase Sn O2/Sn3O4 displays high activity and selectivity for CO2 RR,achieving an improvement in CO2 reduction current density,88.3%Faradaic efficiency of HCOOH conversion at-0.9 VRHE,along with a long-term tolerance in CO2 RR.This study demonstrates that heterophase interface engineering is an efficient strategy to regulate advanced catalysts for different applications.
锡(Sn)基电催化剂可以以可持续能源为动力将二氧化碳转化为甲酸,因而获得越来越多的关注,但其催化二氧化碳还原反应(CO2RR)的能力仍然达不到商业应用要求,因此开发高效Sn基催化剂极为重要.本文利用简单的水热过程,首次设计合成得到以Sn3O4为主的具有高密度相界面的片状Sn O2/Sn3O4异相催化剂.实验和理论模拟结果表明,异相界面的电荷再分布和内建电场促进了CO2的吸附和HCOO*的形成,加速了催化剂和反应物之间的电荷转移,最终大大提高了Sn O2/Sn3O4异相催化剂对CO2RR的内在活性.同时,在CO2RR过程中原位生成的多孔结构和金属Sn改善了反应物和电子在Sn O2/S n3O4片内的传质和传荷.Sn O2/S n3O4异相催化剂对CO2RR表现出较高的活性和选择性,提高了CO2还原电流密度.在-0.9 VRHE时甲酸的法拉第效率为88.3%,且对CO2RR具有长期的耐受性.该研究结果表明,异相界面工程是调节先进催化剂性能的一种有效策略.
作者
Jun Wu
Ying Xie
Shichao Du
Zhiyu Ren
Peng Yu
Xiuwen Wang
Guiling Wang
Honggang Fu
吴君;谢颖;杜世超;任志宇;于鹏;王秀文;王贵领;付宏刚(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;Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education of China,School of Chemistry and Materials Science,Heilongjiang University,Harbin 150080,China)
基金
the National Natural Science Foundation of China(21573062,21631004 and 21901065)
the Natural Science Foundation of Heilongjiang Province(B2018008)
the Youth Science and Technology Innovation Team Project of Heilongjiang Province(2018-KYYWF-1593)
the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2018009)。
作者简介
Corresponding author:王贵领,email:wangguiling@hrbeu.edu.cn,received his PhD in 2006 from the Institute of Chemical Engineering,Harbin En-gineering University.He became a full professor at the College of Material Science and Chemical Engineering,Harbin Engineering University in 2007.His research interests focus on the design and controlled synthesis of electrode materials of NaBH4 fuel cells,H2O2 fuel cell,supercapacitors and lithium ion batteries;Corresponding author:付宏刚,email:fuhg@vip.sina.com,received his BSc degree in 1984 and MSc degree in 1987 from Jilin University.Then,he joined Heilongjiang University as an assistant professor.In 1999,he received his PhD degree from Harbin Institute of Technology.He became a full professor in 2000.Currently,he is a Cheung Kong Scholar.His interest focuses on the oxide-based semiconductor nanomaterials for solar energy conversion and photocatalysis,car-bon-based nanomaterials for energy conversion and storage,and W(Mo,V)-based catalysts for HER and OER.Up to now,he has published over 300 peer reviewed papers as corresponding author with more than 13,000 citations and H-index of 60;Corresponding author:任志宇,email:zyren@hlju.edu.cn,received her BSc degree in 2001 and MSc degree in 2004 from Heilongjiang Uni-versity.Then,she joined Heilongjiang University as an assistant professor.In 2008,she received her PhD degree from Jilin University.She be-came a full professor in 2014.Her interest fo-cuses on the surface crystal engineering and defect regulation of advanced transition metal-based compounds and carbon-based nano-composites for electrocatalysis(e.g,,water split-ting,carbon dioxide reduction,and organic small molecule oxidation);吴君,received her BSc and MSc degrees from Heilongjiang University in 2013 and 2016,re-spectively.She is currently a PhD candidate in material science and engineering under the su-pervision of Prof.Guiling Wang and Prof.Honggang Fu at Harbin Engineering University.Her current research focuses on the design and synthesis of nanomaterials for energy conversion.
