Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles.
Size effect has been regularly utilized to tune the catalytic activity and selectivity of metal nanoparticles (NPs). Yet, there is a lack of understanding of the size effect in the electrocatalytic reduction of CO2, an important reaction that couples with intermittent renewable energy storage and carbon cycle utilization. We report here a prominent size-dependent activity/selectivity in the electrocatalytic reduction of CO2 over differently sized Pd NPs, ranging from 2.4 to 10.3 nm. The Faradaic efficiency for CO production varies from 5.8% at -0.89 V (vs reversible hydrogen electrode) over 10.3 nm NPs to 91.2% over 3.7 nm NPs, along with an 18.4-fold increase in current density. Based on the Gibbs free energy diagrams from density functional theory calculations, the adsorption of CO2 and the formation of key reaction intermediate COOH* are much easier on edge and corner sites than on terrace sites of Pd NPs. In contrast, the formation of H* for competitive hydrogen evolution reaction is similar on all three sites. A volcano-like curve of the turnover frequency for CO production within the size range suggests that CO2 adsorption, COOH* formation, and CO* removal during CO2 reduction can be tuned by varying the size of Pd NPs due to the changing ratio of corner, edge, and terrace sites.
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.|§University of Chinese Academy of Sciences, Beijing 100039, China.
Dunfeng
D
Gao
‡College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
Hu
H
Zhou
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.|§University of Chinese Academy of Sciences, Beijing 100039, China.
Jing
J
Wang
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Shu
S
Miao
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Fan
F
Yang
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Guoxiong
G
Wang
‡College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
Jianguo
J
Wang
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Xinhe
X
Bao