Continuous constant potential model for describing the potential-dependent energetics of CO2RR on single atom catalysts

Lv，Xin Mao; Zhao，Hong Yan; Wang，Yang Gang

2023-09-07

10.1063/5.0164869

Journal of Chemical Physics   Impact Factor & Quartile

0021-9606

1089-7690

In this work, we have proposed a Continuous Constant Potential Model (CCPM) based on grand canonical density functional theory for describing the electrocatalytic thermodynamics on single atom electrocatalysts dispersed on graphene support. The linearly potential-dependent capacitance is introduced to account for the net charge variation of the electrode surface and to evaluate the free energetics. We have chosen the CO electro-reduction reaction on single-copper atom catalysts, dispersed by nitrogen-doped graphene [CuN@Gra ( = 2, 4)], as an example to show how our model can predict the potential-dependent free energetics. We have demonstrated that the net charges of both catalyst models are quadratically correlated with the applied potentials and, thus, the quantum capacitance is linearly dependent on the applied potentials, which allows us to continuously quantify the potential effect on the free energetics during the carbon dioxide reduction reaction instead of confining it to a specific potential. On the CuN@Gra model, it is suggested that CO adsorption, coupled with an electron transfer, is a potential determining step that is energetically unfavorable even under high overpotentials. Interestingly, the hydrogen adsorption on CuN@Gra is extremely easy to occur at both the Cu and N sites, which probably results in the reconstruction of the CuN@Gra catalyst, as reported by many experimental observations. On CuN@Gra, the CORR is found to exhibit a higher activity at the adjacent C site, and the potential determining step is shifted to the *CO formation step at a wide potential range. In general, CCPM provides a simple method for studying the free energetics for the electrocatalytic reactions under constant potential.

SCI

English

First

This work was financially supported by the National Key Ramp;amp;D Program of China (Grant No. 2022YFA1503102), NSFC (Grant Nos. 22022504 and 22373045), Science, Technology and Innovation Commission of Shenzhen Municipality (Grant Nos. JCYJ202208181004100[22022504] ; National Key Ramp;amp;D Program of China["22373045","JCYJ20220818100410023"] ; NSFC["JCYJ20210324103608023","KCXST20221021111207017","2019QN01L353"] ; Science, Technology and Innovation Commission of Shenzhen Municipality[2020B121201002] ; null[2022YFA1503102]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:001063795300003

AIP Publishing

CHEMISTRY

2-s2.0-85169763450

Scopus

Department of Chemistry,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China

Lv，Xin Mao,Zhao，Hong Yan,Wang，Yang Gang. Continuous constant potential model for describing the potential-dependent energetics of CO2RR on single atom catalysts[J]. Journal of Chemical Physics,2023,159(9).

Lv，Xin Mao,Zhao，Hong Yan,&Wang，Yang Gang.(2023).Continuous constant potential model for describing the potential-dependent energetics of CO2RR on single atom catalysts.Journal of Chemical Physics,159(9).

Lv，Xin Mao,et al."Continuous constant potential model for describing the potential-dependent energetics of CO2RR on single atom catalysts".Journal of Chemical Physics 159.9(2023).