高暴露{111}晶面Ag2-xO用于高效电化学析氧反应及其活性和机理

doi:10.1016/S1872-2067(20)63574-4

摘要/Abstract

摘要： 析氧反应（OER）是工业上制约水裂解制氢和CO₂综合利用的瓶颈，涉及四电子、四质子耦合以及O-O键的形成，是一个复杂的、高活化能（高过电位）的动力学过程.模拟自然界光系统PS II，发展高效、稳定、经济的析氧催化剂（OEC）是一个具有挑战性的研究课题.Ag基催化剂因具有以下优势而成为候选：（1）Ag与Ru同属第五周期性质相近，且有经济性且储量丰富；（2）Ag比第三周期过渡金属具有更高的电子密度和更多可调节配位数；（3）Ag存在I，II，III多种氧化态.本课题组前期工作证明，Ag基配合物[H₃Ag^I（H₂O）PW₁₁O₃₉]^3-在酸性水溶液体系中能够形成高氧化态Ag^II和Ag^III配合物，用于OER时展现出高活性和稳定性.受此启发，我们选择简单银基氧化物用于研究电催化OER活性并探究其催化机理.
本文通过恒电流沉积法在含有Ag⁺离子的0.1 M K₂B₄O₇电解质溶液中设计合成了系列Ag_2-xO/FTO-i（i=0.5，1，2，3，4，7mA cm^-2）电极，并通过XRD，SEM和TEM方法对其组成和形貌进行了表征.XRD结果表明，电极膜由Ag₂O组成，随着沉积电流密度增加，其{111}晶面衍射峰向高角度移动，推测是由部分Ag⁺离子氧化成Ag²⁺离子所致.SEM显示，Ag_2-xO/FTO-1电极膜上Ag_2-xO主体呈现三角薄片状，拥有比其它电极Ag_2-xO/FTO-i（i=0.5，2，3，4，7）暴露更多的{111}晶面.同时，高倍TEM显示晶面间距为0.267nm，进一步证明存在较多暴露{111}晶面.线性扫描伏安曲线（LSV）显示，Ag_2-xO/FTO-1电极具有最高的OER电流密度，通过对Tafel区域进行拟合，得到Tafel方程η=0.37+0.047 log|j|，计算得出在10 mA cm^-2电流密度下Ag_2-xO/FTO-1电极具有较低的Tafel斜率47mV dec^-1和过电位417mV vs.RHE，可用作高效的OEC.电化学阻抗谱（EIS）表明，相比其它电极，Ag_2-xO/FTO-1具有最佳的电荷转移能力.电流-时间（I-t）曲线显示10 h内其电流密度仅下降4%，表明电极稳定性良好.通过XPS和拉曼光谱发现，Ag_2-xO/FTO-1经过循环伏安（CV）测试后存在O-O键，说明Ag_2-xO电催化OER过程中形成了过氧物种.XPS进一步显示催化反应前后Ag⁺和Ag²⁺峰面积比由1.46降至0.65，说明反应后Ag²⁺含量显著增加.通过对Ag_2-xO/FTO-1电极电催化OER机理的研究，我们推测其具有优异活性的原因是Ag_2-xO表面更高暴露{111}晶面有利于Ag⁺/Ag²⁺吸附OH^-和H₂O，相邻的吸附氧原子在脱去H⁺的同时，氧原子上活性电子易于转移给Ag²⁺形成O-O键和Ag⁺.电极上Ag⁺进一步被氧化生成Ag²⁺，Ag²⁺将过氧物种氧化，放出O₂，完成催化剂的循环再利用.

关键词: 氧化银, 晶面, 二价银离子, 电催化, 水氧化, 析氧反应

Abstract: A series of Ag_2-xO/FTO-i electrodes (where i denotes the current density during the electrodeposition, and i=0.5, 1, 2, 3, 4, or 7) was fabricated in 0.1 M K₂B₄O₇ electrolyte containing Ag⁺ ions by galvanostatic electrocrystallization. The electrode composition and morphology were characterized using X-ray powder diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. The results reveal that the electrode films consist of Ag₂O, but some of the Ag⁺ ions on the {111} crystal facets are oxidized into Ag²⁺ ions. Furthermore, the Ag_2-xO/FTO-1 electrode shows a triangular slice shape of a parallel matrix with a larger exposed area of {111} crystal facets than other Ag_2-xO/FTO-i (i=0.5, 2, 3, 4, or 7) electrodes. Electrocatalytic experiments prove that the Ag_2-xO/FTO-1 electrode produces the highest oxidative current density, has an overpotential of 417 mV at 10 mA cm^-2, and has a Tafel slope of 47 mV dec^-1 in 0.1 M K₂B₄O₇. Electrochemical impedance spectra indicate that Ag_2-xO/FTO-1 electrodes have the best ability for charge transfer. In addition, in the I-t test over 10 h, the current density decreased 4%. Fortunately, both O-O and Ag²⁺ species were detected after electrocatalysis and a possible mechanism for the oxygen evolution reaction is proposed in which the formation of Ag²⁺ and O-O species on {111} facets plays a critical role.

Key words: Ag₂O, Crystal facet, Ag²⁺ ions, Electrocatalysis, Water oxidation, Oxygen evolution reaction

张晓枫, 李健生, 由万胜, 朱再明. 高暴露{111}晶面Ag_2-xO用于高效电化学析氧反应及其活性和机理[J]. 催化学报, 2020, 41(11): 1706-1714.

Xiao-Feng Zhang, Jian-Sheng Li, Wan-Sheng You, Zai-Ming Zhu. Ag_2-xO with highly exposed {111} crystal facets for efficient electrochemical oxygen evolution: Activity and mechanism[J]. Chinese Journal of Catalysis, 2020, 41(11): 1706-1714.

×
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)63574-4

https://www.cjcatal.com/CN/Y2020/V41/I11/1706

参考文献

[1] C. Herrero, B. Lassalle-Kaiser, W. Leibl, A. W. Rutherford, A. Aukauloo, Acc. Chem. Res., 2008, 252, 456-468.
[2] M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy, 2013, 38, 4901-4934.
[3] X. Liu, F. Wang, Coord. Chem. Rev., 2012, 256, 1115-1136.
[4] G. C. Dismukes, R. Brimblecombe, G. A. Felton, R. S. Pryadun, J. E. Sheats, L. Spiccia, G. F. Swiegers, Acc. Chem. Res., 2009, 42, 1935-1943.
[5] I. Roger, M. A. Shipman, M. D. Symes, Nat. Rev. Chem., 2017, 1, 0003.
[6] L. Duan, F. Bozoglian, S. Mandal, B. Stewart, T. Privalov, A. Llobet, L. Sun, Nat. Chem., 2012, 4, 418-423.
[7] Z. Li, Y. Qi, W. Y. Wang, D. Li, Z. Li, Y. Xiao, G. Y. Han, J. R. Shen, C. Li, Chin. J. Catal., 2019, 40, 486-494.
[8] S. Iwata, J. Barber, Curr. Opin. Struct. Biol., 2004, 14, 447-453.
[9] M. W. Kanan, D. G. Nocera, Science, 2008, 321, 1072-1075.
[10] L. L. Huang, Y. Q. Zou, D. W. Chen, S. Y. Wang, Chin. J. Catal., 2019, 40, 1822-1840.
[11] M. D. Karkas, O. Verho, E. V. Johnston, B. Akermark, Chem. Rev., 2014, 114, 11863-12001.
[12] M. Liu, W. You, Z. Lei, G. Zhou, J. Yang, G. Wu, G. Ma, G. Luan, T. Takata, M. Hara, K. Domen, C. Li, Chem. Commun., 2004, 2192-2193.
[13] D. Wang, R. N. Sampaio, L. Troian-Gautier, S. L. Marquard, B. H. Farnum, B. D. Sherman, M. V. Sheridan, C. J. Dares, G. J. Meyer, T. J. Meyer, J. Am. Chem. Soc., 2019, 141, 7926-7933.
[14] Y. Xie, D. W. Shaffer, J. J. Concepcion, Inorg. Chem., 2018, 57, 10533-10542.
[15] J. Yano, J. Kern, K. Sauer, M. J. Latimer, Y. Pushkar, J. Biesiadka, B. Loll, W. Saenger, J. Messinger, A. Zouni, V. K. Yachandra, Science, 2006, 314, 821-825.
[16] J. Yang, Y. Xiao, Q. Zhao, G. Zhang, R. Wang, G. Teng, X. Chen, M. Weng, D. He, S. Mu, Y. Lin, F. Pan, Nano Energy, 2019, 59, 443-452.
[17] C. C. McCrory, S. Jung, I. M. Ferrer, S. M. Chatman, J. C. Peters, T. F. Jaramillo, J. Am. Chem. Soc., 2015, 137, 4347-4357.
[18] C. C. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem. Soc., 2013, 135, 16977-16987.
[19] E. Tsuji, A. Imanishi, K. I. Fukui, Y. Nakato, Electrochim. Acta, 2011, 56, 2009-2016.
[20] J. D. Blakemore, N. D. Schley, G. W. Olack, C. D. Incarvito, G. W. Brudvig, R. H. Crabtree, Chem. Sci., 2011, 2, 94-98.
[21] M. Yagi, E. Tomita, S. Sakita, T. Kuwabara, K. Nagai, J. Phys. Chem. B, 2005, 109, 21489-21491.
[22] T. Shinagawa, M. T. K. Ng, K. Takanabe, Angew. Chem. Int. Ed., 2017, 56, 5061-5065.
[23] X. L. Li, W. M. Xue, R. Mo, S. Yang, H. X. Li, J. X. Zhong, Chin. J. Catal., 2019, 40, 1576-1584.
[24] X. F. Lu, L. F. Gu, J. W. Wang, J. X. Wu, P. Q. Liao, G. R. Li, Adv. Mater., 2017, 29, 1604437.
[25] T. Y. Ma, S. Dai, M. Jaroniec, S. Z. Qiao, J. Am. Chem. Soc., 2014, 136, 13925-13931.
[26] H. Liang, F. Meng, M. Caban-Acevedo, L. Li, A. Forticaux, L. Xiu, Z. Wang, S. Jin, Nano Lett., 2015, 15, 1421-1427.
[27] Y. Zhang, Y. D. Chen, Z. Z. Liang, J. Qi, X. Q. Gao, W. Zhang, R. Cao, Chin. J. Catal., 2019, 40, 1860-1866.
[28] W. Liu, H. Liu, L. Dang, H. Zhang, X. Wu, B. Yang, Z. Li, X. Zhang, L. Lei, S. Jin, Adv. Funct. Mater., 2017, 27, 1603904.
[29] Y. Yang, L. Dang, M. J. Shearer, H. Sheng, W. Li, J. Chen, P. Xiao, Y. Zhang, R. J. Hamers, S. Jin, Adv. Energy Mater., 2018, 8, 1703189.
[30] G. F. Chen, T. Y. Ma, Z. Q. Liu, N. Li, Y. Z. Su, K. Davey, S. Z. Qiao, Adv. Funct. Mater., 2016, 26, 3314-3323.
[31] J. W. Li, Q. N. Zhuang, P. M. Xu, D. W. Zhang, L. C. Wei, D. S. Yuan, Chin. J. Catal., 2018, 39, 1403-1410.
[32] B. Q. Li, S. Y. Zhang, C. Tang, X. Cui, Q. Zhang, Small, 2017, 13, 1700610.
[33] M. R. Gao, X. Cao, Q. Gao, Y. F. Xu, Y. R. Zheng, J. Jiang, S. H. Yu, ACS Nano, 2014, 8, 3970-3978.
[34] M. Caban-Acevedo, M. L. Stone, J. R. Schmidt, J. G. Thomas, Q. Ding, H. C. Chang, M. L. Tsai, J. H. He, S. Jin, Nat. Mater., 2015, 14, 1245-1251.
[35] X. Xiao, C. T. He, S. Zhao, J. Li, W. Lin, Z. Yuan, Q. Zhang, S. Wang, L. Dai, D. Yu, Energy Environ. Sci., 2017, 10, 893-899.
[36] F. Meng, H. Zhong, D. Bao, J. Yan, X. Zhang, J. Am. Chem. Soc., 2016, 138, 10226-10231.
[37] J. M. V. Nsanzimana, Y. Peng, Y. Y. Xu, L. Thia, C. Wang, B. Y. Xia, X. Wang, Adv. Energy Mater., 2017, 1701475.
[38] Y. Cui, L. Shi, Y. Yang, W. You, L. Zhang, Z. Zhu, M. Liu, L. Sun, Dalton Trans., 2014, 43, 17406-17415.
[39] J. S. Li, L. Wang, W. S. You, M. Y. Liu, L. C. Zhang, X. J. Sang, Chin. J. Catal., 2018, 39, 534-541.
[40] D. A. House, Chem. Rev., 1962, 62, 185.
[41] M. Kimura, T. Kawajiri, M. Tanida, J. Chem. Soc., Dalton Trans., 1980, 726-730.
[42] W. Wang, Q. Zhao, J. Dong, J. Li, Int. J. Hydrogen Energy, 2011, 36, 7374-7380.
[43] Q. Zhao, Z. Yu, G. Hao, W. Yuan, J. Li, Int. J. Hydrogen Energy, 2014, 39, 1364-1370.
[44] Q. Zhao, Z. Yu, W. Yuan, J. Li, Int. J. Hydrogen Energy, 2013, 38, 5251-5258.
[45] Q. Zhao, Z. Yu, W. Yuan, J. Li, Int. J. Hydrogen Energy, 2012, 37, 13249-13255.
[46] S. Wang, G. Liu, L. Wang, Chem. Rev., 2019, 119, 5192-5247.
[47] X. Zhou, Z. Liu, Y. Wang, Y. Ding, Appl. Catal. B, 2018, 237, 74-84.
[48] L. Liu, Z. Jiang, L. Fang, H. T Xu, H. Zhang, X. Gu, Y. Wang, ACS Appl. Mater. Interfaces, 2017, 9, 27736-27744.
[49] Y. J. Chen, Y. W. Chiang, M. H. Huang, ACS Appl. Mater. Interfaces, 2016, 8, 19672-19679.
[50] X. Wang, H. F. Wu, Q. Kuang, R. B. Huang, Z. X. Xie, L. S. Zheng, Langmuir, 2010, 26, 2774-2778.
[51] L. M. Lyu, W. C. Wang, M. H. Huang, Chem. Eur. J., 2010, 16, 14167-14174.
[52] G. Wang, X. Ma, B. Huang, H. Cheng, Z. Wang, J. Zhan, X. Qin, X. Zhang, Y. Dai, J. Mater. Chem., 2012, 22, 21189-21194.
[53] L. M. Lyu, M. H. Huang, J. Phys. Chem. C, 2011, 115, 17768-17773.
[54] D. Li, C. Wei, Q. Wang, L. Liu, D. Zhong, G. Hao, Z. Zuo, Q. Zhao, J. Phys. Chem. C, 2019, 123, 10967-10973.
[55] T. Shinagawa, Y. Ida, K. Mizuno, S. Watase, M. Watanabe, M. Inaba, A. Tasaka, M. Izaki, Cryst. Growth Des., 2012, 13, 52-58.
[56] X. Wang, D. Liao, H. Yu, J. Yu, Dalton Trans., 2018, 47, 6370-6377.
[57] L. Gui, X. Miao, C. Lei, K. Wang, W. Zhou, B. He, Q. Wang, L. Zhao, Chem. Eur. J., 2019, 25, 11007-11014.
[58] D. Zhou, Z. Cai, X. Lei, W. Tian, Y. Bi, Y. Jia, N. Han, T. Gao, Q. Zhang, Y. Kuang, J. Pan, X. Sun, X. Duan, Adv. Energy Mater., 2017, 8, 1701905.
[59] S. W. Gaarenstroom, N. Winograd, J. Chem. Phys., 1977, 67, 3500-3506.
[60] G. B. Hoflund, J. F. Weaver, W. S. Epling, Surf. Sci. Spectra, 1994, 3, 163-168.
[61] G. B. Hoflund, J. F. Weaver, W. S. Epling, Surf. Sci. Spectra, 1994, 3, 157-162.
[62] Y. W. Choi, F. Scholten, I. Sinev, B. R. Cuenya, J. Am. Chem. Soc., 2019, 141, 5261-5266.
[63] R. R. Zhang, Z. T. Sun, C. C. Zong, Z. Y. Lin, H. Huang, K. Yang, J. Chen, S. Liu, M. X. Huang, Y. Yang, W. H. Zhang, Q. W. Chen, Nano Energy, 2019, 57, 753-760.
[64] B. G. Choi, H. Park, T. J. Park, M. H. Yang, J. S. Kim, S. Y. Jang, N. S. Heo, S. Y. Lee, J. Kong, W. H. Hong, ACS Nano, 2010, 4, 2910-2918.
[65] H. An, Z. Chen, J. Yang, Z. Feng, X. Wang, F. Fan, C. Li, J. Catal., 2018, 367, 53-61.
[66] J. Ghilane, F. R. F. Fan, A. J. Bard, Nano Lett., 2007, 7, 1406-1412.
[67] C. Z. Xu, M. Q. Zheng, K. Chen, H. Hu, X. H. Chen, J. Fuel. Chem. Technol., 2016, 44, 943-953.
[68] Z. Jiang, S. Huang, B. Qian, Electrochim. Acta, 1994, 39, 2465-2470.
[69] D. I. Kondarides, G. N. Papatheodorou, C. G. Vayenas, X. E. Verykios, Ber. Bunsen-Ges. Phys. Chem., 1993, 97, 709-719.