解耦质子-电子传输促进Ru-Pb二元电催化剂上的OER动力学

doi:10.1016/S1872-2067(21)63856-1

催化学报 ›› 2022, Vol. 43 ›› Issue (1): 130-138.DOI: 10.1016/S1872-2067(21)63856-1

解耦质子-电子传输促进Ru-Pb二元电催化剂上的OER动力学

黄睿^†, 温蕴周^†, 彭慧胜, 张波^*()

复旦大学高分子科学系, 聚合物分子工程国家重点实验室, 上海200438

收稿日期:2021-05-28 接受日期:2021-06-02 出版日期:2022-01-18 发布日期:2021-06-09
通讯作者: 张波
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21875042);国家自然科学基金(21634003);国家自然科学基金(51573027);中华人民共和国科技部研发项目(2016YFA0203302);上海市科技委(18QA140080);上海市科技委(16JC1400702);上海市“东方学者”岗位计划

Improved kinetics of OER on Ru-Pb binary electrocatalyst by decoupling proton-electron transfer

Rui Huang^†, Yunzhou Wen^†, Huisheng Peng, Bo Zhang^*()

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China

Received:2021-05-28 Accepted:2021-06-02 Online:2022-01-18 Published:2021-06-09
Contact: Bo Zhang
About author:* Tel: +86-21-31242803; E-mail: bozhang@fudan.edu.cn
First author contact:
^† Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21875042);National Natural Science Foundation of China(21634003);National Natural Science Foundation of China(51573027);Ministry of Science and Technology of the People's Republic of China(2016YFA0203302);Shanghai Municipal Committee of Science and Technology(18QA140080);Shanghai Municipal Committee of Science and Technology(16JC1400702);Program for Eastern Scholars at Shanghai Institutions

摘要/Abstract

摘要：

开发酸性条件下的析氧反应(OER)电催化剂是质子交换膜(PEM)电解水技术的核心问题. Ru基催化剂作为酸性OER中的基准催化剂, 其OER活性被传统的协同质子-电子转移过程带来的比例关系所限制, 仍然存在动力学迟缓的问题. 基于荷电表面可能有利于加速OER动力学的认识, 本文将具有赝电容性质的元素Pb加入Ru基催化剂中以提升OER活性. 本文采用一种改进的溶胶-凝胶法制备得到RuPbO_x电催化剂, 用于酸性条件下高效和稳定的水氧化. 高分辨透射电镜及X射线吸收谱结果表明, RuPbO_x催化剂为约10 nm颗粒, Ru、Pb和O原子均匀分布在催化剂中, 形成原子级的混合. 电化学测试结果表明, 该催化剂达到10 mA cm^-2的过电位仅需191 ± 3 mV, 相比于商业纳米RuO₂提升了94 mV. 该催化剂的质量比活性及转化频率(TOF)相较于RuO₂提高了20倍. 经过电化学活性面积(ECSA)归一化的OER电流也显著提升, 表明Pb掺杂后提高了催化剂的本征活性. Tafel动力学研究结果表明, RuPbO_x的Tafel斜率为39 mV dec^-1, 而RuO₂的为63 mV dec^-1, 表明RuPbO_x与RuO₂决速步骤不同. 该RuPbO_x催化剂还表现出较好的稳定性, 在10 mA cm^-2电流密度下连续电解100 h后过电位仅提升85 mV. 将该催化剂应用在工业条件(80^oC)下的质子交换膜(PEM)电解装置中, 到达1 A cm^-2电流密度时全电池电压仅需2 V.
使用X射线光电子能谱(XPS)、电化学分析以及原位拉曼光谱研究了催化剂表面的化学状态. 脉冲伏安法研究表明, Pb掺杂后的催化剂具有更强的荷电能力. O 1s XPS结果表明, 反应后RuPbO_x表面被更多活性氧物种覆盖. 电化学原位拉曼光谱研究表明, 在约1158 cm^-1出现了超氧根物种的伸缩振动峰, 随着电势的增加, 超氧根物种逐渐消耗并释放出氧气. 基于以上实验结果认为, RuPbO_x催化剂在OER过程中可能经历了一个与RuO₂不同的非协同质子-电子传输路径. RuPbO_x的OER活性也表现出了pH相关性, 进一步证明了非协同质子-电子转移的发生. 原子级的Pb掺杂可以调控金红石氧化钌的局域微结构, 增加了催化剂表面的电容性荷电能力. 这种强荷电的表面可以促进含氧中间体的去质子化并稳定带电的OER前驱物(例如超氧根离子), 从而将质子-电子转移过程解耦, 打破比例关系的限制, 提升OER活性.

关键词: 电催化, 酸性析氧反应, 氧化钌, 原位拉曼, 质子-电子转移

Abstract:

The acidic oxygen evolution reaction (OER) is central to water electrolysis using proton-exchange membranes. However, even as benchmark catalysts in the acidic OER, Ru-based catalysts still suffer from sluggish kinetics owing to the scaling relationship that arises from the traditional concerted proton-electron transfer (CPET) process. Motivated by the knowledge that a charged surface may be favorable for accelerating the OER kinetics, we posited the incorporation of elements with pseudocapacitive properties into Ru-based catalysts. Herein, we report a RuPbO_x electrocatalyst for efficient and stable water oxidation in acid with a low overpotential of 191 mV to reach 10 mA cm^-2 and a low Tafel slope of 39 mV dec^-1. The combination of electrochemical analysis, X-ray photoelectron spectroscopy, and in situ Raman spectroscopy demonstrated that the improved OER kinetics was associated with the formation of superoxide precursors on the strongly charged surface after Pb incorporation, indicating a non-concerted proton-electron transfer mechanism for the OER on RuPbO_x.

Key words: Electrocatalysis, Acidic oxygen evolution reaction, Ruthenium oxide, In situ Raman, Proton-coupled electron transfer

黄睿, 温蕴周, 彭慧胜, 张波. 解耦质子-电子传输促进Ru-Pb二元电催化剂上的OER动力学[J]. 催化学报, 2022, 43(1): 130-138.

Rui Huang, Yunzhou Wen, Huisheng Peng, Bo Zhang. Improved kinetics of OER on Ru-Pb binary electrocatalyst by decoupling proton-electron transfer[J]. Chinese Journal of Catalysis, 2022, 43(1): 130-138.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63856-1

https://www.cjcatal.com/CN/Y2022/V43/I1/130

图/表 4

Fig. 1. Characterization of RuPbOx catalyst. (a) TEM image. Scale bar: 50 nm. (b) HR-TEM image. Inset: FFT pattern from the nanoparticle can be indexed to (110), (101), and (211) planes of rutile structure. Scale bar: 10 nm. (c) XRD patterns. (d-g) HADDF-STEM image and EDX element mappings. Scale bar: 50 nm. (h) Normalized Ru K-edge XANES spectra of RuPbOx, Ru powder, RuCl3, and commercial RuO2. (i) Fourier-transform EXAFS profile of Ru K-edge for RuPbOx, Ru powder, RuCl3, and commercial RuO2.

Fig. 2. Electrochemical performance. (a) OER polarization curves of different catalysts. The curves were 95% iR-compensated; (b) η10 and mass activities of different catalysts; (c) Steady-state Tafel plots for different catalysts; (d) Steady-state polarization curve of RuPbOx in PEM electrolyzer. Inset: schematic of PEM electrolyzer; (e) Chronopotentiometry stability test of RuPbOx at 10 mA cm-2.

Fig. 3. Surface chemical state of RuPbOx. (a) Cyclic voltammogram of RuPbOx in the range of 0-1.5 V vs. RHE at 200 mV s-1 scan rate; (b) Relationship between total charge and applied potential of different catalysts, measured by pulse voltammetry; (c,d) Fitted O 1s spectra for RuPbOx and RuO2 after OER. The fits are described in the text; (e,f) In situ EC-Raman spectra of RuPbOx and RuO2. * Peaks of H2SO4 electrolyte and substrate. The yellow region in (e) represents the superoxide species.

Fig. 4. Non-concerted proton-electron transfer steps on RuPbOx. (a) pH-dependent OER activity of RuPbOx and RuO2 at η = 300 mV; (b) pH-Dependence of Tafel slope of RuPbOx; (c) Schematic of the non-concerted proton-electron transfer mechanism. Brown balls: Ru, black balls: Pb, white balls: O, red ball: H. The active oxygen species are marked with yellow.

参考文献

[1]	C. Spori, J. T. H. Kwan, A. Bonakdarpour, D. P. Wilkinson, P. Strasser, Angew. Chem. Int. Ed., 2017, 56, 5994-6021.
[2]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[3]	K. Sardar, E. Petrucco, C. I. Hiley, J. D. Sharman, P. P. Wells, A. E. Russell, R. J. Kashtiban, J. Sloan, R. I. Walton, Angew. Chem. Int. Ed., 2014, 53, 10960-10964.
[4]	Y. Wen, P. Chen, L. Wang, S. Li, Z. Wang, J. Abed, X. Mao, Y. Min, C. T. Dinh, P. Luna, R. Huang, L. Zhang, L. Wang, L. Wang, R. J. Nielsen, H. Li, T. Zhuang, C. Ke, O. Voznyy, Y. Hu, Y. Li, W. A. Goddard Iii, B. Zhang, H. Peng, E. H. Sargent, J. Am. Chem. Soc., 2021, 143, 6482-6490.
[5]	Y. Liu, X. Liang, H. Chen, R. Gao, L. Shi, L. Yang, X. Zou, Chin. J. Catal., 2021, 42, 1054-1077.
[6]	L. C. Seitz, C. F. Dickens, K. Nishio, Y. Hikita, J. Montoya, A. Doyle, C. Kirk, A. Vojvodic, H. Y. Hwang, J. K. Norskov, T. F. Jaramillo, Science, 2016, 353, 1011-1014.
[7]	S. Kumari, B. P. Ajayi, B. Kumar, J. B. Jasinski, M. K. Sunkara, J. M. Spurgeon, Energy Environ. Sci., 2017, 10, 2432-2440.
[8]	L. Giordano, B. Han, M. Risch, W. T. Hong, R. R. Rao, K. A. Stoerzinger, Y. Shao-Horn, Catal. Today, 2016, 262, 2-10.
[9]	Y. Yao, S. Hu, W. Chen, Z.-Q. Huang, W. Wei, T. Yao, R. Liu, K. Zang, X. Wang, G. Wu, W. Yuan, T. Yuan, B. Zhu, W. Liu, Z. Li, D. He, Z. Xue, Y. Wang, X. Zheng, J. Dong, C.-R. Chang, Y. Chen, X. Hong, J. Luo, S. Wei, W.-X. Li, P. Strasser, Y. Wu, Y. Li, Nat. Catal., 2019, 2, 304-313.
[10]	H. Dau, C. Limberg, T. Reier, M. Risch, S. Roggan, P. Strasser, ChemCatChem, 2010, 2, 724-761.
[11]	M. T. M. Koper, Chem. Sci., 2013, 4, 2710-2723.
[12]	A. Grimaud, O. Diaz-Morales, B. Han, W. T. Hong, Y. L. Lee, L. Giordano, K. A. Stoerzinger, M. T. M. Koper, Y. Shao-Horn, Nat. Chem., 2017, 9, 457-465.
[13]	O. Diaz-Morales, D. Ferrus-Suspedra, M. T. M. Koper, Chem. Sci., 2016, 7, 2639-2645.
[14]	Y. Matsumoto, H. Manabe, E. Sato, J. Electrochem. Soc., 1980, 127, 811-814.
[15]	Y. Matsumoto, S. Yamada, T. Nishida, E. Sato, J. Electrochem. Soc., 1980, 127, 2360-2364.
[16]	Y. Hu, X. Luo, G. Wu, T. Chao, Z. Li, Y. Qu, H. Li, Y. Wu, B. Jiang, X. Hong, ACS Appl. Mater. Interfaces, 2019, 11, 42298-42304.
[17]	J. Yi, W. H. Lee, C. H. Choi, Y. Lee, K. S. Park, B. K. Min, Y. J. Hwang, H.-S. Oh, Electrochem. Commun., 2019, 104, 106469.
[18]	H. N. Nong, L. J. Falling, A. Bergmann, M. Klingenhof, H. P. Tran, C. Spöri, R. Mom, J. Timoshenko, G. Zichittella, A. Knop-Gericke, S. Piccinin, J. Pérez-Ramírez, B. R. Cuenya, R. Schlögl, P. Strasser, D. Teschner, T. E. Jones, Nature, 2020, 587, 408-413.
[19]	X. Li, D. Pletcher, F. C. Walsh, Chem. Soc. Rev., 2011, 40, 3879-3894.
[20]	Y. Yao, G. Teng, Y. Yang, C. Huang, B. Liu, L. Guo, Sep. Purif. Technol., 2019, 211, 456-466.
[21]	B. Zhang, X. Zheng, O. Voznyy, R. Comin, M. Bajdich, M. Garcia-Melchor, L. Han, J. Xu, M. Liu, L. Zheng, F. P. Garcia de Arquer, C. T. Dinh, F. Fan, M. Yuan, E. Yassitepe, N. Chen, T. Regier, P. Liu, Y. Li, P. De Luna, A. Janmohamed, H. L. Xin, H. Yang, A. Vojvodic, E. H. Sargent, Science, 2016, 352, 333-337.
[22]	C. Girardeaux, J.-J. Pireaux, Surf. Sci. Spectra, 1996, 4, 138-141.
[23]	M. Schulze, M. Lorenz, T. Kaz, Surf. Interface Anal., 2002, 34, 646-651.
[24]	R. D. Shannon, Acta Cryst. A, 1976, 32, 751-767.
[25]	J. Kim, P. C. Shih, K. C. Tsao, Y. T. Pan, X. Yin, C. J. Sun, H. Yang, J. Am. Chem. Soc., 2017, 139, 12076-12083.
[26]	T. Shinagawa, A. T. Garcia-Esparza, K. Takanabe, Sci. Rep., 2015, 5, 13801.
[27]	J. Zhang, H. B. Tao, M. Kuang, H. B. Yang, W. Cai, Q. Yan, Q. Mao, B. Liu, ACS Catal., 2020, 10, 8597-8610.
[28]	Y. H. Fang, Z. P. Liu, J. Am. Chem. Soc., 2010, 132, 18214-18222.
[29]	P. Castelli, S. Trasatti, F. H. Pollak, W. E. O'Grady, J. Electroanal. Chem. Interf. Electrochem., 1986, 210, 189-194.
[30]	Y. Lin, Z. Tian, L. Zhang, J. Ma, Z. Jiang, B. J. Deibert, R. Ge, L. Chen, Nat. Commun., 2019, 10, 162.
[31]	R. R. Rao, M. J. Kolb, L. Giordano, A. F. Pedersen, Y. Katayama, J. Hwang, A. Mehta, H. You, J. R. Lunger, H. Zhou, N. B. Halck, T. Vegge, I. Chorkendorff, I. E. L. Stephens, Y. Shao-Horn, Nat. Catal., 2020, 3, 516-525.
[32]	S. Chen, H. Huang, P. Jiang, K. Yang, J. Diao, S. Gong, S. Liu, M. Huang, H. Wang, Q. Chen, ACS Catal., 2019, 10, 1152-1160.
[33]	J. Su, R. Ge, K. Jiang, Y. Dong, F. Hao, Z. Tian, G. Chen, L. Chen, Adv. Mater., 2018, 30, e1801351.
[34]	S. H. Chang, N. Danilovic, K. C. Chang, R. Subbaraman, A. P. Paulikas, D. D. Fong, M. J. Highland, P. M. Baldo, V. R. Stamenkovic, J. W. Freeland, J. A. Eastman, N. M. Markovic, Nat. Commun., 2014, 5, 4191.
[35]	M. E. G. Lyons, S. Floquet, Phys. Chem. Chem. Phys., 2011, 13, 5314-5335.
[36]	T. Reier, D. Teschner, T. Lunkenbein, A. Bergmann, S. Selve, R. Kraehnert, R. Schlögl, P. Strasser, J. Electrochem. Soc., 2014, 161, F876-F882.
[37]	T. Reier, Z. Pawolek, S. Cherevko, M. Bruns, T. Jones, D. Teschner, S. Selve, A. Bergmann, H. N. Nong, R. Schlogl, K. J. Mayrhofer, P. Strasser, J. Am. Chem. Soc., 2015, 137, 13031-13040.
[38]	S. Y. Mar, C. S. Chen, Y. S. Huang, K. K. Tiong, Appl. Surf. Sci., 1995, 90, 497-504.
[39]	H. C. Jo, K. M. Kim, H. Cheong, S.-H. Lee, S. K. Deb, Electrochem. Solid-State Lett., 2005, 8, E39-E41.
[40]	J.-C. Dong, X.-G. Zhang, V. Briega-Martos, X. Jin, J. Yang, S. Chen, Z.-L. Yang, D.-Y. Wu, J. M. Feliu, C. T. Williams, Z.-Q. Tian, J.-F. Li, Nat. Energy, 2018, 4, 60-67.
[41]	H. Y. Wang, S. F. Hung, Y. Y. Hsu, L. Zhang, J. Miao, T. S. Chan, Q. Xiong, B. Liu, J. Phys. Chem. Lett., 2016, 7, 4847-4853.
[42]	S. A. Hunter-Saphir, J. A. Creighton, J. Raman Spectrosc., 1998, 29, 417-419.
[43]	J. Kim, A. A. Gewirth, J. Phys. Chem. B, 2006, 110, 2565-2571.

解耦质子-电子传输促进Ru-Pb二元电催化剂上的OER动力学

Improved kinetics of OER on Ru-Pb binary electrocatalyst by decoupling proton-electron transfer

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 4

参考文献

相关文章 15

编辑推荐

Metrics

[1]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[2]	张季, 俞爱民, 孙成华. 非金属掺杂石墨烯异核双原子催化剂氮还原特性研究[J]. 催化学报, 2023, 52(9): 263-270.
[3]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[4]	洪岩, 王琦, 阚子旺, 张禹烁, 郭晶, 李思琦, 刘松, 李斌. 电化学氮还原氨反应催化剂的最新研究进展[J]. 催化学报, 2023, 52(9): 50-78.
[5]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[6]	高晖, 张恭, 程东方, 王永涛, 赵静, 李晓芝, 杜晓伟, 赵志坚, 王拓, 张鹏, 巩金龙. 构建Cu台阶位促进电催化CO₂还原制醇类化学品的研究[J]. 催化学报, 2023, 52(9): 187-195.
[7]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[8]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[9]	王元男, 王立娜, 张可新, 徐靖尧, 武倩楠, 谢周兵, 安伟, 梁宵, 邹晓新. 钙钛矿氧化物在水裂解反应中的电催化研究[J]. 催化学报, 2023, 50(7): 109-125.
[10]	周纳, 王家志, 张宁, 王志, 王恒国, 黄岗, 鲍迪, 钟海霞, 张新波. 富含缺陷的Cu@CuTCNQ复合材料增强电催化硝酸盐还原成氨[J]. 催化学报, 2023, 50(7): 324-333.
[11]	李轩, 蒋兴星, 孔艳, 孙建桔, 胡琪, 柴晓燕, 杨恒攀, 何传新. GaN/In₂O₃的界面工程用于高效电催化CO₂还原制备甲酸[J]. 催化学报, 2023, 50(7): 314-323.
[12]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. 用于电化学能量转换反应的非贵金属单原子催化剂[J]. 催化学报, 2023, 50(7): 195-214.
[13]	牛青, 米林华, 陈玮, 李秋军, 钟升红, 于岩, 李留义. 基于共价有机框架的单位点光(电)催化材料的研究进展[J]. 催化学报, 2023, 50(7): 45-82.
[14]	欧阳玲, 梁杰, 罗永嵩, 郑冬冬, 孙圣钧, 刘倩, Mohamed S. Hamdy, 孙旭平, 应斌武. 电催化合成氨的研究进展[J]. 催化学报, 2023, 50(7): 6-44.
[15]	李静静, 张锋伟, 詹新雨, 郭河芳, 张涵, 昝文艳, 孙振宇, 张献明. 酞菁镍分子结构的精确设计: 优化电子和空间效应用于CO₂电还原[J]. 催化学报, 2023, 48(5): 117-126.