金属掺杂SnO2电化学还原CO2制甲酸的计算研究

doi:10.1016/S1872-2067(23)64476-6

摘要/Abstract

摘要：

CO₂电化学还原为甲酸(HCOOH)作为可再生氢的液体载体, 有助于可再生能源的转变. 本文使用密度泛函理论和微观动力学模拟研究了SnO₂电极上CO₂高效催化还原为HCOOH的要求. 表面羟基化是实现高活性的先决条件, 预测的电流密度与实验值的趋势相同. 所得到的羟基化表面对HCOOH的产生具有高选择性, 析氢反应的贡献可以忽略不计. 机理研究结果表明, 反应首先将吸附的CO₂加氢为羧酸盐(COOH), 然后进一步加氢获得所需产物. 通过采用常用元素(Bi, Pd, Ni和Cu)对表面进行掺杂, 确定Bi掺杂可以显著提高电流密度. 根据该机理中的两个关键步骤建立了Brønsted-Evans-Polanyi关系. 总之, 羧酸盐的形成是速率控制步骤. 将两个质子化步骤的自由能作为两个描述符, 分析了CO₂还原活性, 结果表明Bi掺杂SnO₂电极具有最高活性.

关键词: CO₂还原, 甲酸, SnO₂, 助剂, 密度泛函理论

Abstract:

Electrochemical reduction of CO₂ to formic acid (HCOOH) can contribute to the renewable energy transition as a liquid carrier of renewably hydrogen. Here, we investigated the catalytic requirements of SnO₂ electrodes for efficient CO₂ reduction to HCOOH using density functional theory and microkinetics simulations. Hydroxylation of the surface is a prerequisite to achieve a high activity with predicted current densities in agreement with experiment. The resulting surface is selective to HCOOH production with a negligible contribution of the hydrogen evolution reaction. Mechanistically, it is found that the reaction proceeds via hydrogenation of adsorbed CO₂ to carboxylate (COOH), which is then further hydrogenated to the desired product. Doping of the surface by commonly used elements (Bi, Pd, Ni and Cu) identifies Bi as the preferred promoter to substantially improve the current density. Brønsted-Evans-Polanyi relations are established for the two key steps in the mechanism. Overall, carboxylate formation is the rate-controlling step. The CO₂ reduction activity is analyzed in terms of two descriptors, namely the free energies for the two protonation steps, showing that Bi presents the highest activity.

Key words: CO₂ reduction, Formic acid, SnO₂, Promoters, Density functional theory

刘赵春, 宗雪, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. 金属掺杂SnO₂电化学还原CO₂制甲酸的计算研究[J]. 催化学报, 2023, 50: 249-259.

Zhaochun Liu, Xue Zong, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂[J]. Chinese Journal of Catalysis, 2023, 50: 249-259.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64476-6

https://www.cjcatal.com/CN/Y2023/V50/I7/249

图/表 10

Fig. 1. Top view (a) and side view (b) of the SnO2?x(OH)4 model, top view (c) and side view (d) of the most stable adsorption configuration of CO2 on SnO2?x(OH)4 (gray = Sn, red = O atoms of SnO2?x(OH)4, orange = O of CO2, black = C, white = H).

Fig. 3. Top view of the most stable adsorption configuration of CO2RR on SnO2?x(OH)4 (gray = Sn, red = O atoms of SnO2?x(OH)4, orange = O of CO2, black = C, white = H).

Fig. 2. Reaction energy diagram for CO2RR on the SnO2?x(OH)4 surface at standard conditions (T = 298.15 K, P = 1 bar, pH = 0, and 0 V vs. RHE).

Fig. 4. Reaction energy diagram for CO2RR on metal-doped SnO2?x(OH)4 surface at standard conditions (T = 298.15 K, P = 1 bar, pH = 0, and 0 V vs. RHE).

Fig. 5. Br?nsted-Evans-Polanyi plots for CO2 to COOH* step (a) and COOH* to HCOOH step (b) on metal-doped (metal = Ni, Pd, Bi, and Cu) SnO2?x(OH)4 surfaces.

Fig. 6. Correlation matrix between properties of the dopant metal and the reaction energy and activation barrier for the elementary reaction step CO2* + H* → COOH* + *. Positive values indicate positive correlations, while negatives ones anticorrelations between the parameters.

Fig. 7. Microkinetics simulations of electrochemical CO2RR on undoped and Bi-doped SnO2?x(OH)4 surfaces using a reaction-diffusion model pertaining to a rotating disc electrode setup operated at 100 r/min with a bulk pH of 6.8. (a) Total electrochemical current; (b) Near-surface concentration of CO2; (c) Near-surface concentration of H+; (d) Faradaic efficiency of various product.

Fig. 8. Evolution of surface coverages during electrochemical CO2RR on the SnO2?x(OH)4 surface on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

Fig. 9. The degree of rate control coefficients during electrochemical CO2RR on the SnO2?x(OH)4 surface on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

Fig. 10. Heatmap of the TOF as a function of ΔG*COOH ? ΔG*CO2 and ΔG*HCOOH ? ΔG*COOH adsorption energies for electrocatalytic CO2RR on metal doped SnO2?x(OH)4 surface based on DFT-based microkinetic simulations at ?0.2 V vs. RHE. Reaction conditions are T = 300 K on a rotating disc electrode at 100 r/min and a bulk pH of 6.8.

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金属掺杂SnO₂电化学还原CO₂制甲酸的计算研究

A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂

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