过渡金属电催化剂在硅基光阳极分解水产氧中的作用

doi:10.1016/S1872-2067(20)63647-6

催化学报 ›› 2021, Vol. 42 ›› Issue (8): 1387-1394.DOI: 10.1016/S1872-2067(20)63647-6

过渡金属电催化剂在硅基光阳极分解水产氧中的作用

RajenderBoddula^a, 谢关才^a^,^b, 郭北斗^a^,^b, 宫建茹^a^,^b^,^*()

^a国家纳米科学中心, 中国科学院纳米系统与多级次重点实验室, 中国科学院纳米科学卓越创新中心, 北京 100190
^b中国科学院大学, 北京 100049

收稿日期:2020-02-28 接受日期:2020-03-23 出版日期:2021-08-18 发布日期:2021-03-18
通讯作者: 宫建茹
作者简介:^*. 电话: (010)82545649; 传真: (010)62656765; 电子信箱: gongjr@nanoctr.cn
第一联系人：
^† 共同第一作者.
基金资助:
中国科学院战略性先导科技专项(B类)资助(XDB36000000);国家自然科学基金(21422303);国家自然科学基金(21573049);国家自然科学基金(21872043);国家自然科学基金(22002028);中国科学院青年创新促进会; 中国科学院“一带一路”专项; 中国科学院“国际人才计划”, 北京市自然科学基金(2142036)

Role of transition-metal electrocatalysts for oxygen evolution with Si-based photoanodes

Rajender Boddula^a, Guancai Xie^a^,^b, Beidou Guo^a^,^b, Jian Ru Gong^a^,^b^,^*()

^aChinese Academy of Sciences (CAS) Center for Excellence in Nanoscience, CAS Key Laboratory of Nanosystem and Hierarchy Fabrication, National Center for Nanoscience and Technology, Beijing 100190, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-02-28 Accepted:2020-03-23 Online:2021-08-18 Published:2021-03-18
Contact: Jian Ru Gong
About author:^*. Tel: +86-10-82545649; Fax: +86-10-62656765; E-mail: gongjr@nanoctr.cn
First author contact:
^† These authors contributed equally to this paper.
Supported by:
This work was supported by the Strategic Priority Research Program of CAS(XDB36000000);National Natural Science Foundation of China(21422303);National Natural Science Foundation of China(21573049);National Natural Science Foundation of China(21872043);National Natural Science Foundation of China(22002028);Beijing Natural Science Foundation, Youth Innovation Promotion Association of CAS, the Belt and Road Special Program of CAS, and CAS President’s International Fellowship Initiative(2142036)

摘要/Abstract

摘要：

光电化学分解水可将太阳能转换为绿色的氢能, 为目前的能源危机和环境问题提供了一种理想的解决方案. 在分解水反应中, 涉及四空穴过程的产氧半反应是制约性能的关键步骤, 往往需要在半导体表面沉积电催化剂以加速产氧反应动力学. 因此, 全面理解电催化剂在光电化学分解水体系中的作用至关重要. 在目前的产氧电催化剂中, 过渡金属羟基氧化物电催化剂(MOOH, M = Fe, Co, Ni)因其环保、廉价、高效以及稳定的特性, 已被广泛用于半导体光阳极分解水器件中. 而且, MOOH可用简单的电沉积方法沉积在光电极表面, 易于大面积制备. 然而, 电沉积法制备的MOOH具有复杂的结构, 对其作用机制的全面理解更加困难. 因此, 本文以电沉积MOOH修饰的硅基光阳极(n ⁺p-Si/SiO_x/Fe/FeOx/MOOH)作为模型, 研究了不同电催化剂对硅光阳极光电化学产氧性能的影响. 实验发现电催化剂的界面优化在电催化剂修饰的光电极中发挥着重要作用, 这是因为优化的界面可以提升界面电荷传输, 提供更多的催化反应活性位点以及更高的本征催化活性, 从而更有利于光解水性能的提升. 该项研究揭示了电催化剂在光解水器件中的作用, 并为今后高效光解水器件的设计提供了一定指导.
首先在多晶n ⁺p-Si基底上热蒸镀了一层30 nm的金属Fe膜, 并通过电化学活化将Fe膜表面转换为FeO_x得到Fe/FeO_x(记作aFe)界面层, 然后利用电沉积方法制备MOOH表面修饰层, 最终得到n ⁺p-Si/SiO_x/aFe:MOOH光阳极. X射线光电子能谱、拉曼光谱以及扫描电子显微镜表面元素成像的表征结果均证实电极表面由于界面层金属Fe元素的掺杂而形成了Fe_1‒_xNi_xOOH. 在模拟太阳光下用于光解水产氧时, n ⁺p-Si/SiO_x/aFe:NiOOH电极的起始电位为~1.01 V_RHE (相对于可逆氢电极的电势), 在1.23 V_RHE下的光电流为38.82 mA cm ^-2, 显著优于n ⁺p-Si/SiO_x/aFe、n ⁺p-Si/SiO_x/aFe:FeOOH以及n ⁺p-Si/SiO_x/aFe:CoOOH三个对比样品, 且其稳定性达到75 h. 另外, 我们发现n ⁺p-Si/SiO_x/aFe:MOOH电极的光电化学产氧性能均显著高于n ⁺p-Si/SiO_x/aFe电极, 且p ⁺⁺-Si/SiO_x/aFe:MOOH的电催化产氧性能也高于p ⁺⁺-Si/SiO_x/MOOH, 不仅证明了aFe界面层对Si与MOOH层之间的界面接触作用的有效调控, 而且表明双电催化剂体系(aFe:MOOH)的电催化产氧活性高于单电催化剂(MOOH). 热力学分析表明, n ⁺p-Si/SiO_x/aFe:MOOH光阳极的光电压大小与其光解水产氧性能并不一致, 从而排除了热力学因素对性能的关键影响. 进一步从塔菲尔斜率、电化学活性表面积和电化学阻抗谱对各电极的动力学进行了分析, 证明了动力学因素在上述光阳极产氧性能中的主导作用. 同时发现, 由于aFe:NiOOH双电催化剂具有更高的本征电催化产氧性能, 提供了更多的表面活性位点以及更有效地促进了光生载流子的传输, 对动力学的提升效果更显著, 从而使n ⁺p-Si/SiO_x/aFe:NiOOH光阳极表现出最高的光解水产氧性能.

关键词: 光解水, 人工光合作用, 产氧反应, 光阳极, 界面工程, 过渡金属电催化剂

Abstract:

A comprehensive understanding of the role of the electrocatalyst in photoelectrochemical (PEC) water splitting is central to improving its performance. Herein, taking the Si-based photoanodes (n ⁺p-Si/SiO_x/Fe/FeO_x/MOOH, M = Fe, Co, Ni) as a model system, we investigate the effect of the transition-metal electrocatalysts on the oxygen evolution reaction (OER). Among the photoanodes with the three different electrocatalysts, the best OER activity, with a low-onset potential of ∼1.01 V_RHE, a high photocurrent density of 24.10 mA cm ^-2 at 1.23 V_RHE, and a remarkable saturation photocurrent density of 38.82 mA cm ^-2, was obtained with the NiOOH overlayer under AM 1.5G simulated sunlight (100 mW cm ^-2) in 1 M KOH electrolyte. The optimal interfacial engineering for electrocatalysts plays a key role for achieving high performance because it promotes interfacial charge transport, provides a larger number of surface active sites, and results in higher OER activity, compared to other electrocatalysts. This study provides insights into how electrocatalysts function in water-splitting devices to guide future studies of solar energy conversion.

Key words: Solar water splitting, Artificial photosynthesis, Oxygen evolution reaction, Photoanode, Interfacial engineering, Transition-metal electrocatalyst

RajenderBoddula, 谢关才, 郭北斗, 宫建茹. 过渡金属电催化剂在硅基光阳极分解水产氧中的作用[J]. 催化学报, 2021, 42(8): 1387-1394.

Rajender Boddula, Guancai Xie, Beidou Guo, Jian Ru Gong. Role of transition-metal electrocatalysts for oxygen evolution with Si-based photoanodes[J]. Chinese Journal of Catalysis, 2021, 42(8): 1387-1394.

×
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(20)63647-6

https://www.cjcatal.com/CN/Y2021/V42/I8/1387

图/表 3

Fig. 1. (a) Schematic configuration of n+p-Si/SiOx/aFe:MOOH (M = Fe, Co, Ni) photoanodes; (b) cross-sectional SEM image and (c) XPS profiles of Ni 2p, Fe 2p, and O 1s for the n+p-Si/SiOx/aFe:NiOOH photoanode.

Fig. 2. (a) CV curves of n+p-Si/SiOx/aFe:MOOH photoanodes (dotted lines shows dark conditions: aFe (black); aFe:FeOOH (blue); aFe:CoOOH (yellow); and aFe:NiOOH (red)); (b) O2 production measured (black line) and calculated based on the charge passed assuming 100% faradaic efficiency (red line); and (c) ABPE for the n+p-Si/SiOx/aFe:NiOOH photoanode conducted in 1 M KOH electrolyte under illumination at 100 mW cm-2 (AM 1.5 G).

Fig. 3. (a) Tafel plots extracted from the current density-voltage (J-V) measurements at a scan rate of 50 mV s-1; (b) Capacitive currents at different scan rates (The linear slope, equivalent to twice of the double-layer capacitance Cdl, is used to represent the ECSA); and (c) impedance Nyquist plots measured at 1.23 VRHE for the n+p-Si/SiOx/aFe photoanodes with and without the MOOH overlayer for experiments conducted in 1 M KOH under irradiation at 100 mW cm-2 (AM 1.5 G).

参考文献

[1]	M. G. Walter, E. L. Warren, J. R. McKone, S. W. Boettcher, Q. Mi, E. A. Santori, N. S. Lewis , Chem. Rev., 2010,110, 6446-6473.
[2]	Z. Chen, Q. Huang, B. Huang, F. Zhang, C. Li , Chin. J. Catal., 2019,40, 38-42.
[3]	P. Kuang, B. Zhu, Y. Li, H. Liu, J. Yu, K. Fan , Nanoscale Horiz., 2018,3, 317-326.
[4]	P. Li, W. Chen , Chin. J. Catal., 2019,40, 4-22.
[5]	P. Kuang, M. He, H. Zou, J. Yu, K. Fan , Appl. Catal. B, 2019,254, 15-25.
[6]	X. Li, J. Yu, M. Jaroniec, X. Chen , Chem. Rev., 2019,119, 3962-4179.
[7]	R. Shen, J. Xie, Q. Xiang, X. Chen, J. Jiang, X. Li , Chin. J. Catal., 2019,40, 240-288.
[8]	W. Zhang, H. Zhang, J. Xu, H. Zhuang, J. Long , Chin. J. Catal., 2019,40, 320-325.
[9]	K. He, J. Xie, X. Luo, J. Wen, S. Ma, X. Li, Y. Fang, X. Zhang , Chin. J. Catal., 2017,38, 240-252.
[10]	S. Hu, M. R. Shaner, J. A. Beardslee, M. Lichterman, B. S. Brunschwig, N. S. Lewis , Science, 2014,344, 1005-1009.
[11]	M. J. Kenney, M. Gong, Y. Li, J. Z. Wu, J. Feng, M. Lanza, H. Dai , Science, 2013,342, 836-840.
[12]	A. G. Scheuermann, J. P. Lawrence, K. W. Kemp, T. Ito, A. Walsh, C. E. Chidsey, P. K. Hurley, P. C. McIntyre , Nat. Mater., 2016,15, 99-105.
[13]	G. Xie, S. U. Jan, Z. Dong, Y. Dai, R. Boddula, Y. Wei, C. Zhao, Q. Xin, J.-N. Wang, Y. Du , Chin. J. Catal., 2020,41, 2-8.
[14]	J. Yang, K. Walczak, E. Anzenberg, F. M. Toma, G. Yuan, J. Beeman, A. Schwartzberg, Y. Lin, M. Hettick, A. Javey , J. Am. Chem. Soc., 2014,136, 6191-6194.
[15]	Y. W. Chen, J. D. Prange, S. Dühnen, Y. Park, M. Gunji, C. E. Chidsey, P. C. McIntyre , Nat. Mater., 2011,10, 539-544.
[16]	B. Mei, B. Seger, T. Pedersen, M. Malizia, O. Hansen, I. Chorkendorff, P. C. Vesborg , J. Phys. Chem. Lett., 2014,5, 1948-1952.
[17]	M. Mikolasek, K. Frohlich, K. Husekova, J. Racko, V. Rehacek, F. Chymo, M. Tapajna, L. Harmatha , Appl. Surf. Sci., 2018,461, 48-53.
[18]	J. Yang, D. Wang, H. Han, C. Li , Acc. Chem. Res., 2013,46, 1900-1909.
[19]	I. A. Digdaya, G. W. Adhyaksa, B. J. Trześniewski, E. C. Garnett, W. A. Smith, Nat. Commun., 2017, 8, 15968/1-15968/8.
[20]	X. Zhou, R. Liu, K. Sun, K. M. Papadantonakis, B. S. Brunschwig, N. S. Lewis , Energy Environ. Sci., 2016,9, 892-897.
[21]	R. Fan, Z. Mi, M. Shen , Opt. Express, 2019,27, A51-A80.
[22]	B. Guo, A. Batool, G. Xie, R. Boddula, L. Tian, S. U. Jan, J. R. Gong , Nano Lett., 2018,18, 1516-1521.
[23]	R. Boddula, B. Guo, A. Ali, G. Xie, Y. Dai, C. Zhao, Y. Wei, S. U. Jan, J. R. Gong , ACS Appl. Energy Mater., 2019,2, 7256-7262.
[24]	K. Sun, S. Shen, Y. Liang, P. E. Burrows, S. S. Mao, D. Wang , Chem. Rev., 2014,114, 8662-8719.
[25]	L. Trotochaud, S. L. Young, J. K. Ranney, S. W. Boettcher , J. Am. Chem. Soc., 2014,136, 6744-6753.
[26]	B. M. Hunter, H. B. Gray, A. M. Muller , Chem. Rev., 2016,116, 14120-14136.
[27]	Y. Hou, X. Zhuang, X. Feng , Small Methods, 2017,1, 1700090.
[28]	C. Li, Y. Xiao, L. Zhang, Y. Li, J.-J. Delaunay, H. Zhu , Sustain. Energy Fuels, 2018,2, 663-672.
[29]	A. Singh, L. Spiccia , Coord. Chem. Rev., 2013,257, 2607-2622.
[30]	N. Wang, H. Zheng, W. Zhang, R. Cao , Chin. J. Catal., 2018,39, 228-244.
[31]	F. A. Laskowski, M. R. Nellist, J. Qiu, S. W. Boettcher , J. Am. Chem. Soc., 2018,141, 1394-1405.
[32]	J. Y. Kim, D. H. Youn, K. Kang, J. S. Lee , Angew. Chem. Int. Ed., 2016,55, 10854-10858.
[33]	W. D. Chemelewski, H.-C. Lee, J.-F. Lin, A. J. Bard, C. B. Mullins , J. Am. Chem. Soc., 2014,136, 2843-2850.
[34]	T. W. Kim, K.-S. Choi , Science, 2014,343, 990-994.
[35]	T. Yao, R. Chen, J. Li, J. Han, W. Qin, H. Wang, J. Shi, F. Fan, C. Li , J. Am. Chem. Soc., 2016,138, 13664-13672.
[36]	J. C. Hill, A. T. Landers, J. A. Switzer , Nat. Mater., 2015,14, 1150-1155.
[37]	D. Bae, B. Mei, R. Frydendal, T. Pedersen, B. Seger, O. Hansen, P. C. Vesborg, I. Chorkendorff , ChemElectroChem, 2016,3, 1546-1552.
[38]	S. Oh, S. Jung, Y. H. Lee, J. T. Song, T. H. Kim, D. K. Nandi, S.-H. Kim, J. Oh , ACS Catal., 2018,8, 9755-9764.
[39]	K. Sun, M. T. McDowell, A. C. Nielander, S. Hu, M. R. Shaner, F. Yang, B. S. Brunschwig, N. S. Lewis , J. Phys. Chem. Lett., 2015,6, 592-598.
[40]	I. Roger, M. D. Symes , J. Mater. Chem. A, 2016,4, 6724-6741.
[41]	Y. Kuang, Q. Jia, H. Nishiyama, T. Yamada, A. Kudo, K. Domen , Adv. Energy Mater., 2016,6, 1501645.
[42]	Y.-J. Shih, Y.-H. Huang, C. Huang , Electrochim. Acta, 2018,263, 261-271.
[43]	Q. Cai, W. Hong, C. Jian, J. Li, W. Liu , ACS Catal., 2017,7, 3277-3283.
[44]	S. Klaus, Y. Cai, M. W. Louie, L. Trotochaud, A. T. Bell , J. Phys. Chem. C, 2015,119, 7243-7254.
[45]	L. Trotochaud, J. K. Ranney, K. N. Williams, S. W. Boettcher , J. Am. Chem. Soc., 2012,134, 17253-17261.
[46]	L. Cai, J. Zhao, H. Li, J. Park, I. S. Cho, H. S. Han, X. Zheng , ACS Energy Lett., 2016,1, 624-632.
[47]	H. Zhou, F. Yu, Q. Zhu, J. Sun, F. Qin, L. Yu, J. Bao, Y. Yu, S. Chen, Z. Ren , Energy Environ. Sci., 2018,11, 2858-2864.
[48]	D. Tang, O. Mabayoje, Y. Lai, Y. Liu, C. B. Mullins , ChemistrySelect, 2017,2, 2230-2234.
[49]	J. Li, S. Jiang, M. Shao, M. Wei , Catalysts, 2018,8, 214.
[50]	T. Shinagawa, A. T. Garcia-Esparza, K. Takanabe , Sci. Rep., 2015,5, 13801.

过渡金属电催化剂在硅基光阳极分解水产氧中的作用

Role of transition-metal electrocatalysts for oxygen evolution with Si-based photoanodes

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 3

参考文献

相关文章 15

编辑推荐

Metrics

[1]	石靖, 郭煜华, 谢飞, 章名田, 张洪涛. 氧化还原活性配体的电子效应对钌催化水氧化反应的影响[J]. 催化学报, 2023, 52(9): 271-279.
[2]	乔玉彦, 潘艳秋, 张江威, 王彬, 武婷婷, 范文俊, 曹雨程, Rashid Mehmood, 张飞, 章福祥. 多碳界面工程用于促进NiFe纳米复合电催化剂的产氧反应[J]. 催化学报, 2022, 43(9): 2354-2362.
[3]	Karen Cristina Bedin, Beatriz Mouriño, Ingrid Rodríguez-Gutiérrez, João Batista Souza Junior, Gabriel Trindade dos Santos, Jefferson Bettini, Carlos Alberto Rodrigues Costa, Lionel Vayssieres, Flavio Leandro Souza. 基于溶液化学策略构建背接触FTO/赤铁矿光阳极界面工程的高效光催化水氧化研究[J]. 催化学报, 2022, 43(5): 1247-1257.
[4]	周志明, 陈金金, 王擎龙, 蒋兴星, 申燕. 硫化钴装饰BiVO₄光阳极提升其光电化学水分解性能[J]. 催化学报, 2022, 43(2): 433-441.
[5]	张学鹏, 王红艳, 郑浩铨, 张伟, 曹睿. 分子催化剂催化水氧化过程及其O-O成键机理[J]. 催化学报, 2021, 42(8): 1253-1268.
[6]	李佳原, 朱勇, 李斐, 刘国权, 许素显, 孙立成. 修饰吡啶衍生物的染料敏化光阳极水氧化性能的研究[J]. 催化学报, 2021, 42(8): 1352-1359.
[7]	陈齐发, 杜昊易, 章名田. 缓冲溶液阴离子对三价铜催化剂催化水氧化过程的影响[J]. 催化学报, 2021, 42(8): 1338-1344.
[8]	胡慧慧, 曾令真, 李哲, 朱天宝, 汪骋. 将铂(II)-四(4-羧基苯基)卟啉组装到光捕获金属有机框架中增强可见光驱动的产氢效能[J]. 催化学报, 2021, 42(8): 1345-1351.
[9]	李银银, 武倩楠, 步琦璟, 张凯, 林艳红, 王德军, 邹晓新, 谢腾峰. 高效的CdS/Ti-Fe₂O₃异质结光阳极: 研究Z型电荷迁移机制增强光电化学水氧化活性[J]. 催化学报, 2021, 42(5): 762-771.
[10]	李洋, 张宁斯, 刘昌昊, 张园明, 徐晓明, 王文静, 冯建勇, 李朝升, 邹志刚. 光电催化分解水稳定性达100 h的亚稳相β-Fe₂O₃光阳极[J]. 催化学报, 2021, 42(11): 1992-1998.
[11]	郭俊雄, 李奕奕, 李尚栋, 崔旭梅, 刘宇, 黄文, 毛琳娜, 魏雄邦, 张晓升. 一步法制备TiO₂/石墨烯复合多孔薄膜应用于增强光催化活性及光伏性能[J]. 催化学报, 2020, 41(8): 1208-1216.
[12]	肖静冉, 范龙龙, 黄忠亮, 钟俊, 赵飞刚, 徐凯吉, 周树锋, 詹国武. Co-Pi与FeOOH对Fe₂O₃光阳极用于光电化学氧化的协同作用原理[J]. 催化学报, 2020, 41(11): 1761-1771.
[13]	谢关才, Saad Ullah Jan, 董泽健, 代亚雯, Rajender Boddula, 魏玉轩, 赵唱, 辛琪, 王娇娜, 杜银芳, 马兰, 郭北斗, 宫建茹. GaP/GaPN核壳纳米线阵列修饰的硅光阴极的光电化学制氢反应[J]. 催化学报, 2020, 41(1): 2-8.
[14]	何菲, 孟爱云, 程蓓, Wingkei Ho, 余家国. 石墨烯修饰三氧化钨/二氧化钛S型异质结增强的光催化产氢活性[J]. 催化学报, 2020, 41(1): 9-20.
[15]	朱勇, 李斐, 孙立成. 基于分子水氧化催化剂光电分解水的研究进展[J]. 催化学报, 2019, 40(s1): 227-234.