TY - JOUR
T1 - Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels
AU - Ren, Dan
AU - Gao, Jing
AU - Pan, Linfeng
AU - Wang, Zaiwei
AU - Luo, Jingshan
AU - Zakeeruddin, Shaik M.
AU - Hagfeldt, Anders
AU - Grätzel, Michael
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/10/14
Y1 - 2019/10/14
N2 - Electrochemical reduction of carbon dioxide, if powered by renewable electricity, could serve as a sustainable technology for carbon recycling and energy storage. Among all the products, ethanol is an attractive liquid fuel. However, the maximum faradaic efficiency of ethanol is only ≈10 % on polycrystalline Cu. Here, CuZn bimetallic catalysts were synthesized by in situ electrochemical reduction of ZnO-shell/CuO-core bi-metal-oxide. Dynamic evolution of catalyst was revealed by STEM-EDS mapping, showing the migration of Zn atom and blending between Cu and Zn. CuZn bimetallic catalysts showed preference towards ethanol formation, with the ratio of ethanol/ethylene increasing over five times regardless of applied potential. We achieved 41 % faradaic efficiency for C2+ liquids with this catalyst. Transitioning from H-cell to an electrochemical flow cell, we achieved 48.6 % faradaic efficiency and −97 mA cm−2 partial current density for C2+ liquids at only −0.68 V versus reversible hydrogen electrode in 1 m KOH. Operando Raman spectroscopy showed that CO binding on Cu sites was modified by Zn. Free CO and adsorbed *CH3 are believed to combine and form *COCH3 intermediate, which is exclusively reduced to ethanol.
AB - Electrochemical reduction of carbon dioxide, if powered by renewable electricity, could serve as a sustainable technology for carbon recycling and energy storage. Among all the products, ethanol is an attractive liquid fuel. However, the maximum faradaic efficiency of ethanol is only ≈10 % on polycrystalline Cu. Here, CuZn bimetallic catalysts were synthesized by in situ electrochemical reduction of ZnO-shell/CuO-core bi-metal-oxide. Dynamic evolution of catalyst was revealed by STEM-EDS mapping, showing the migration of Zn atom and blending between Cu and Zn. CuZn bimetallic catalysts showed preference towards ethanol formation, with the ratio of ethanol/ethylene increasing over five times regardless of applied potential. We achieved 41 % faradaic efficiency for C2+ liquids with this catalyst. Transitioning from H-cell to an electrochemical flow cell, we achieved 48.6 % faradaic efficiency and −97 mA cm−2 partial current density for C2+ liquids at only −0.68 V versus reversible hydrogen electrode in 1 m KOH. Operando Raman spectroscopy showed that CO binding on Cu sites was modified by Zn. Free CO and adsorbed *CH3 are believed to combine and form *COCH3 intermediate, which is exclusively reduced to ethanol.
KW - carbon dioxide
KW - electrocatalysis
KW - ethanol
KW - flow cell
KW - operando Raman spectroscopy
UR - https://www.scopus.com/pages/publications/85072047000
U2 - 10.1002/anie.201909610
DO - 10.1002/anie.201909610
M3 - 文章
C2 - 31433551
AN - SCOPUS:85072047000
SN - 1433-7851
VL - 58
SP - 15036
EP - 15040
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 42
ER -
