Ni单原子催化剂表面CO2电还原动力学的电化学谱学解析

doi:10.7503/cjcu20190699

摘要/Abstract

摘要：

针对Ni单原子催化剂表面的CO₂电还原反应(CO₂RR), 提出了以Ni为活性位点的“单中心”机理以及同时借助Ni位点还原和碳氮锚定位水解的“双功能”机理. 依据稳态极化的实验结果, 开展了CO₂RR的动力学解析与模型参数的敏感性分析; 借助暂态模型方程, 分别获取可表达CO₂RR线性与非线性频响特征的电化学阻抗谱(EIS)与总谐波失真(THD)谱. 研究结果表明, CO₂的溶解分压对CO₂RR活性影响最显著. 若CO₂RR遵循“单中心”机理, Ni位点COOH_ads的形成为速率控制步骤; 但若为“双功能”机理, 碳氮锚定位的水解与Ni位点的CO_2,ads还原同为速率控制步骤. EIS理论上可用于区分CO₂RR的“单中心”机理与“双功能”机理; 与之相比, THD谱在CO₂RR的机理识别中并无优势.

关键词: 二氧化碳电还原反应机理, 电化学阻抗谱, 非线性频响分析, 总谐波失真谱

Abstract:

Single site mechanism and bi-function mechanism were both put forward for CO₂ electro-reduction reaction(CO₂RR) on the carbon-nitride anchoring Ni single atoms catalysts. The former is specific to the CO₂RR only on the active site Ni and the latter considers both reductions on the Ni site and water spitting on the anchoring carbon nitride site. Kinetic analysis of the CO₂RR as well as sensitivity analysis for the model parameters were both performed by means of static CO₂RR models and experimental polarizations. Electrochemical impedance spectroscopy(EIS) and total harmonic distortion(THD) spectroscopy were also simulated using dynamic CO₂RR models to explore its linear and nonlinear frequency response behaviors, respectively. It is suggested that CO₂ concentration is the most sensitive parameters to CO₂RR performance. The elemental step to form COOH_ads is the rate determines step as the CO₂RR follows the single site mechanism. As for the bi-function mechanism, both CO_2,ads electro-reduction on the Ni site and water splitting on the carbon nitride site are rate-determining steps of the CO₂RR. Transient simulation of CO₂RR reveals that the EIS is able to tell the difference of the single site mechanism from the bi-function mechanism theoretically over the THD spectroscopy.

Key words: CO₂ Electro-reduction reaction(CO₂RR) mechanism, Electrochemical impedance spectroscopy(EIS), Nonlinear frequency response analysis, Total harmonic distortion(THD) spectroscopy

中图分类号:

O646

TrendMD:

毛庆,赵健,刘松,郭唱,李冰玉,徐可一,曹自强,黄延强. Ni单原子催化剂表面CO₂电还原动力学的电化学谱学解析. 高等学校化学学报, 2020, 41(5): 1058.

MAO Qing,ZHAO Jian,LIU Song,GUO Chang,LI Bingyu,XU Keyi,CAO Ziqiang,HUANG Yanqiang. Electrochemical Spectroscopy Analysis for Kinetics of the CO₂ Electroreduction Reaction on Ni Single Atom Catalysts ^†. Chem. J. Chinese Universities, 2020, 41(5): 1058.

图/表 10

Fig.1 Faraday efficiency of CO and H2 at different CO2RR potential(A) and IR and current corrected polarization of CO2RR(B)

Table 1 Kinetic parameters of the CO2RR with single site mechanism and bi-function mechanism

Mechanism	K₁₀₁	K₁₀₂	K₂₀₁	K₂₀₂	K₃₀₁	K₃₀₂
Single site mechanism	6.5×10¹	9.3×10⁰	6.3×10^-6	6.9×10^-15	1.6×10^-3	6.0×10^-12
bi-Function mechanism	6.6×10²	4.2×10²	2.5×10^-5	5.9×10^-5	3.0×10^-5	4.3×10^-2

Fig.2 Comparison between simulated steady state V-j curve of the CO2RR and the experimental data(A) and simulated coverage of intermediates CO2,ads(B) and COOHads(C) adopting single site mechanism

Fig.3 Comparison between simulated steady state V-j curve of the CO2RR and the experimental data(A) and simulated coverage of intermediates CO2,ads(B) and Hads(C) adopting bi-function mechanism

Table 2 Sensitivity coefficients of parameters in the CO2RR model adopting single site mechanism

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ COOH$	$E c$
CO₂ concentration	-0.7357	-0.7357	0.1745
KHCO₃ concentration	0	0	-0.0152
CO concentration	0	0	-0.0079
Limiting coverage of active site Ni	-0.5	-0.5	0.0396

Table 2 Sensitivity coefficients of parameters in the CO2RR model adopting single site mechanism

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ COOH$	$E c$
CO₂ concentration	-0.7357	-0.7357	0.1745
KHCO₃ concentration	0	0	-0.0152
CO concentration	0	0	-0.0079
Limiting coverage of active site Ni	-0.5	-0.5	0.0396

Table 3 Sensitivity coefficients of parameters in the CO2RR model adopting bi-function mechanism

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ H$	$E c$
CO₂ concentration	-0.7563	0.0294	0.1779
KHCO₃ concentration	0	0	-0.0153
CO concentration	0	0	-0.0079
Limiting coverage of active site N	0	-0.5	0.0316
Limiting coverage of active site Ni	-0.5	0.0193	0.0308

Table 3 Sensitivity coefficients of parameters in the CO2RR model adopting bi-function mechanism

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ H$	$E c$
CO₂ concentration	-0.7563	0.0294	0.1779
KHCO₃ concentration	0	0	-0.0153
CO concentration	0	0	-0.0079
Limiting coverage of active site N	0	-0.5	0.0316
Limiting coverage of active site Ni	-0.5	0.0193	0.0308

Fig.4 Simulated EIS(A) and THD(B) spectroscopy with different CO2 concentrations for the CO2RR adopting single site mechanism CO2 conc./(mol·m-3): a. 33.9; b. 27.1; c. 20.3; d. 17.0; e. 15.3; f. 14.4.

Fig.5 Simulated EIS(A) and THD(B) spectroscopy with different CO2 concentrations for the CO2RR adopting bi-function mechanism CO2 conc./(mol·m-3): a. 33.9; b. 27.1; c. 20.3; d. 17.0; e. 15.3; f. 14.4.

Fig.6 Simulated EIS(A) and THD(B) spectroscopy with different current density for the CO2RR adopting single site mechanism jdc/(A·m-2): a. 50; b. 100; c. 150; d. 200; e. 250; f. 270.

Fig.7 Simulated EIS(A) and THD(B) spectroscopy with different current densities for the CO2RR adopting bi-function mechanism jdc/(A·m-2): a. 50; b. 100; c. 150; d. 200; e. 250; f. 270.

参考文献 19

[1]	Friedlingstein P., Andrew R. M., Rogelj J., Peters G. P., Canadell J. G., Knutti R., Luderer G., Raupach M. R., Schaeffer M., van Vuuren D. P., Le Quéré C., Nat. Geosci., 2014,7, 709—715
[2]	Hori Y ., Modern Aspects of Electrochemistry, Springer, New York, 2008, 89—189
[3]	Jing W. Y., Mao Q., Shi Y., Du Z. L., Xiao Y., Liu S., Xu J. M., Huang Y. Q., Chem. Ind. Eng. Prog., 2017,36(5), 2150—2157
	( 景维云, 毛庆, 石越, 杜兆龙, 肖宇, 刘松, 徐金铭, 黄延强 . 化工进展, 2017,36(5), 2150—2157)
[4]	Back S., Lim J., Kim N. Y., Kim Y. H., Jung Y., Chem. Sci., 2017,8, 1090—1096 doi: 10.1039/c6sc03911a URL pmid: 28451248
[5]	Zhao C. M., Dai X. Y., Yao T., Chen W. X., Wang X. Q., Wang J., Yang J., Wei S. Q., Wu Y. E., Li Y. D., J. Am. Chem. Soc., 2017,139, 8078—8081 doi: 10.1021/jacs.7b02736 URL pmid: 28595012
[6]	Pan F. P., Zhang H. G., Liu K. X., Cullen D., More K., Wang M. Y., Feng Z. X., Wang G. F., Wu G., Li Y., ACS Catal., 2018,8, 3116—3122
[7]	Yang H. B., Hung S. F., Liu S., Yuan K., Miao S., Zhang L., Huang X., Wang H. Y., Cai W., Chen R., Gao J., Yang X., Chen W., Huang Y., Chen H. M., Li C. M., Zhang T., Liu B., Nat . Energy, 2018,3(2), 140—147
[8]	Liu S., Yang H. B., Hung S. F., Ding J., Cai W. Z., Liu L. H., Gao J. J., Li X. N., Ren X. Y., Kuang Z. C., Huang Y. Q., Zhang T., Liu B., Angew. Chem. Int. Ed., 2020,59, 798—803 doi: 10.1002/anie.201911995 URL pmid: 31657106
[9]	Li X. G., Bi W. T., Chen M. L., Sun Y. X., Ju H. X., Yan W. S., Zhu J. F., Wu X. J., Chu W. Z., Xie Y., J. Am. Chem. Soc., 2017,139(42), 14889—14892 doi: 10.1021/jacs.7b09074 URL pmid: 28992701
[10]	Zheng T. T., Jiang K., Ta N., Hu Y. F., Zeng J., Liu J. Y., Wang H. T., Joule, 2019,3(1), 265—278
[11]	Mao Q., Li B. Y., Jing W. Y., Zhao J., Liu S., Huang Y. Q., Du Z. L., J. Electrochem., 2019, DOI: 10.13208/j.electrochem.190305
	( 毛庆, 李冰玉, 景维云, 赵健, 刘松, 黄延强, 杜兆龙 . 电化学, 2019, DOI: 10.13208/j.electrochem.190305)
[12]	Li B. Y., Mao Q., Zhao J., Du Z. L., Liu S., Huang Y. Q., Chem. Ind. & Eng. Pro., 2019,38(11), 4901—4910
	( 李冰玉, 毛庆, 赵健, 杜兆龙, 刘松, 黄延强 . 化工进展, 2019,38(11), 4901—4910)
[13]	Liu S., Yang H. B., Su X., Ding J., Mao Q., Huang Y. Q., Zhang T., Liu B., J. Energ. Chem., 2019,36, 95—105
[14]	Yang D. W., Li L., Wang Q., Wang X. C., Li Q. Y., Shi J., Chem. J. Chinese Universities, 2016,37(1), 94—99
	( 杨冬伟, 李露, 王琴, 王晓春, 李青远, 施锦 . 高等学校化学学报, 2016,37(1), 94—99)
[15]	Mao Q., Jing W. Y., Shi Y., Process. Chem., 2017,29(2/3), 210—215
	( 毛庆, 景维云, 石越 . 化学进展, 2017,29(2/3), 210—215)
[16]	Mao Q., Krewer U ., Electrochimica Acta, 2013,103, 188—198
[17]	Mao Q., Krewer U ., Electrochimica Acta, 2012,68, 60—68
[18]	Mao Q., Krewer U., Hanke-Rauschenbach R., Electrochem. Commun, 2010,12(11), 1517—1519
[19]	Shi Y., Mao Q., Xiao C., Jing W. Y., Zhang X. Y., Chem. J. Chinese Universities, 2018,39(9), 2017—2024
	( 石越, 毛庆, 肖成, 景维云, 张学元 . 高等学校化学学报, 2018,39(9), 2017—2024)

Ni单原子催化剂表面CO₂电还原动力学的电化学谱学解析

Electrochemical Spectroscopy Analysis for Kinetics of the CO₂ Electroreduction Reaction on Ni Single Atom Catalysts ^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 19

相关文章 14

编辑推荐

Metrics

本文评价

[1]	石越, 毛庆, 肖成, 景维云, 张学元. PtRu/C表面甲醇电催化氧化动力学的非线性谱学分析[J]. 高等学校化学学报, 2018, 39(9): 2017.
[2]	宗美荣, 何辉超, 董发勤, 何平, 孙仕勇, 刘明学, 聂小琴. 钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究[J]. 高等学校化学学报, 2016, 37(9): 1701.
[3]	吕江维, 曲有鹏, 冯玉杰, 刘峻峰. 硼掺杂金刚石薄膜电极上二氯酚的电化学阻抗谱研究[J]. 高等学校化学学报, 2016, 37(1): 142.
[4]	樊小勇孙世刚王晶晶李严黄令李东林. 电化学阻抗谱法研究温度对三维多孔Cu6Sn5合金电极嵌锂过程的影响[J]. 高等学校化学学报, 2011, 32(4): 934.
[5]	田雷雷庄全超王蓉崔永丽方亮强颖怀. Li₂CO₃添加剂对石墨电极性能的影响[J]. 高等学校化学学报, 2010, 31(12): 2468.
[6]	张伟, 王佳, 赵增元, 姜晶. 有机涂层失效过程的电化学阻抗和电位分布响应特征[J]. 高等学校化学学报, 2009, 30(4): 762.
[7]	庄全超,许金梅,田景华,樊小勇,董全峰,孙世刚 . 石墨负极电化学扫描循环过程的EIS、Raman光谱和XRD研究[J]. 高等学校化学学报, 2008, 29(5): 973.
[8]	文莉,林仲华,翁少煌,周剑章 . 自组装金团簇电极库仑台阶现象和电化学阻抗谱研究[J]. 高等学校化学学报, 2008, 29(2): 350.
[9]	金宝舵, 郭建伟, 谢晓峰, 王树博, 王金海. 操作条件对DMFC阴极电化学阻抗谱参数的影响[J]. 高等学校化学学报, 2008, 29(11): 2258.
[10]	柳英姿, 肖丽平, 张凯, 赵淑凤, 张静波, 陆嘉星. 离子液体BMIMBF₄-H₂O中邻氯硝基苯的电化学还原性能[J]. 高等学校化学学报, 2008, 29(10): 2059.
[11]	孙向英, 翁文婷. 荧光性自组装双层膜的制备及其性能研究[J]. 高等学校化学学报, 2005, 26(6): 1030.
[12]	丁艳君, 王桦, 李继山, 沈国励, 俞汝勤. 纳米金-蛋白A介导抗体定向固定的压电传感及电化学特性研究[J]. 高等学校化学学报, 2005, 26(2): 222.
[13]	庄全超, 陈作锋, 董全峰, 姜艳霞, 周志有, 孙世刚. 锂离子电池电解液中甲醇杂质对石墨电极性能影响机制的电化学阻抗谱研究[J]. 高等学校化学学报, 2005, 26(11): 2073.
[14]	罗小雯, 陈月辉, 李善君, 周伟舫. 电化学阻抗法研究环氧膜的吸水性能[J]. 高等学校化学学报, 1996, 17(2): 329.