商用氧化铟锡玻璃: 室温高效还原氮气的催化剂电极

doi:10.1016/S1872-2067(20)63704-4

催化学报 ›› 2021, Vol. 42 ›› Issue (6): 1024-1029.DOI: 10.1016/S1872-2067(20)63704-4

商用氧化铟锡玻璃: 室温高效还原氮气的催化剂电极

王婷^a,†, 李绍雄^a,†, 赫丙玲^b, 朱晓娟^a, 罗永岚^a^,^*(), 刘倩^c, 李廷帅^c, 卢思宇^d, 叶晨^e, Abdullah M.Asiri^f, 孙旭平^c^,^#()

^a西华师范大学化学合成与污染控制四川省重点实验室, 四川成都637002, 中国
^b新乡大学物理与电子工程学院, 河南新乡453003, 中国
^c电子科技大学基础与前沿研究院, 四川成都610054, 中国
^d郑州大学化学学院绿色催化中心, 河南郑州450001, 中国
^e四川大学化学学院, 四川成都610064, 中国
^f阿卜杜勒阿齐兹国王大学科学学院和先进材料研究卓越中心, 吉达21589, 沙特阿拉伯

收稿日期:2020-03-22 接受日期:2020-07-27 出版日期:2021-06-18 发布日期:2021-01-30
通讯作者: 罗永岚,孙旭平
作者简介:
^†共同第一作者.

Commercial indium-tin oxide glass: A catalyst electrode for efficient N₂ reduction at ambient conditions

Ting Wang^a,†, Shaoxiong Li^a,†, Bingling He^b, Xiaojuan Zhu^a, Yonglan Luo^a^,^*(), Qian Liu^c, Tingshuai Li^c, Siyu Lu^d, Chen Ye^e, Abdullah M. Asiri^f, Xuping Sun^c^,^#()

^aChemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, Sichuan, China
^bCollege of Physics and Electronic Engineering, Xinxiang University, Xinxiang 453003, Henan, China
^cInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^dGreen Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
^eCollege of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China
^fChemistry Department, Faculty of Science & Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia

Received:2020-03-22 Accepted:2020-07-27 Online:2021-06-18 Published:2021-01-30
Contact: Yonglan Luo,Xuping Sun
About author:^# E-mail: xpsun@uestc.edu.cn
^*E-mail: luoylcwnu@hotmail.com;
First author contact:
^† Contributed equally to this work.

摘要/Abstract

摘要：

NH₃作为一种必需的活化氮源, 在化肥、染料、爆炸物和药物等的制造中起到了关键作用; 同时, 它也是一种在交通运输领域具有吸引力的无碳能源载体. 工业上生产氨气使用典型的哈伯-博世工艺, 但是此工艺涉及大量的能源消耗和碳排放, 给环境带来巨大的压力. 电化学氮还原反应(NRR)能够在温和环境下实现环境友好、节能的氨合成, 但此过程需要高效的电催化剂. 高效的NRR催化剂(Au、Ag、Pd和Ru)储量少、成本高, 阻碍了它的实际应用. 因此, 设计和开发由地球上丰富的元素制成的具有成本效益的催化剂来代替NRR催化剂意义重大. 本课题组最近的研究(Chem. Commun., 2018, 54, 12966-12969)表明, SnO₂在环境条件下具有电催化氧化活性, 但其低电导率限制了其性能, 可通过氟掺杂或石墨烯杂化予以解决. 氧化铟锡(ITO)作为一种含SnO₂的材料, 导电性好, 可望用于NRR的高效电催化剂中. 因此, 本文采用商用氧化铟锡玻璃(ITO/G)作为催化剂电极, 在温和环境条件下进行N₂-NH₃的电化学转化, 并呈现出对生成氨气有较高的选择性. XRD和XPS结果表示, 商用ITO/G中存在In, Sn和O元素; SEM显示ITO/G具有清晰的纳米薄膜结构和267 nm的截面厚度; 相应的EDX谱图显示In, Sn和O元素分布均匀, 且原子比为32.11:3.16:64.74. 采用紫外-可见光谱及线性扫描伏安和恒电位极化等电化学测试研究了商用ITO/G的NRR活性. 在0.5 M LiClO₄电解液中测试时, 于-0.40 V vs. RHE条件下, ITO/G的NH₃产率为1.06 × 10^-10 mol s^-1 cm^-2, 其法拉第效率为6.17%. ¹⁵N同位素标记实验证实了所测到的NH₃是由ITO/G催化的N₂电还原反应生成的. 利用第一性原理计算探讨了在ITO催化剂上可能的NRR反应机理, 确定了ITO催化剂的NRR活性位点、N₂化学吸附活性位点以及NRR的反应途径. 此外, 24 h恒电位(-0.40 V vs. RHE)极化测试和2 h恒电位极化(-0.40 V vs. RHE)测试后的XRD和SEM结果表明, 该催化剂具有较高的电化学稳定性. 综上所述, 商用ITO/G用作在环境条件下将N₂转化为NH₃的有效催化剂电极, 将为开发人工固定氮气的ITO基纳米结构提供一种研究途径.

关键词: N₂还原反应, NH₃, 铟-锡氧化物, 电催化剂, 环境条件, 密度泛函理论

Abstract:

The typical Haber technical process for industrial NH₃ production involves plenty of energy-consumption and large quantities of greenhouse gas emission. In contrast, electrochemical N₂ reduction proffers environment-friendly and energy-efficient avenues to synthesize NH₃ at mild conditions but demands efficient electrocatalysts for the N₂ reduction reaction (NRR). Herein we report for the first time that commercial indium-tin oxide glass (ITO/G) can be used as a catalyst electrode toward artificial N₂ fixation, as it demonstrates excellent selectivity at mild conditions. Such ITO/G delivers excellent NRR performance with a NH₃ yield of 1.06 × 10^-10 mol s^-1 cm^-2 and a faradaic efficiency of 6.17% at -0.40 V versus the reversible hydrogen electrode (RHE) in 0.5 M LiClO₄. Furthermore, the ITO/G also possesses good electrochemical stability and durability. Finally, the possible reaction mechanism for the NRR on the ITO catalysts was explored using first-principles calculations.

Key words: N₂ reduction reaction, NH₃, Indium-tin oxide, Electrocatalyst, Ambient conditions, Density functional theory

王婷, 李绍雄, 赫丙玲, 朱晓娟, 罗永岚, 刘倩, 李廷帅, 卢思宇, 叶晨, Abdullah M.Asiri, 孙旭平. 商用氧化铟锡玻璃: 室温高效还原氮气的催化剂电极[J]. 催化学报, 2021, 42(6): 1024-1029.

Ting Wang, Shaoxiong Li, Bingling He, Xiaojuan Zhu, Yonglan Luo, Qian Liu, Tingshuai Li, Siyu Lu, Chen Ye, Abdullah M. Asiri, Xuping Sun. Commercial indium-tin oxide glass: A catalyst electrode for efficient N₂ reduction at ambient conditions[J]. Chinese Journal of Catalysis, 2021, 42(6): 1024-1029.

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图/表 6

Fig. 1. (a) XRD pattern of ITO/G; (b,c) SEM images of ITO/G; (d) SEM and corresponding EDX elemental mapping images of In, Sn, and O elements for ITO/G.

Fig. 2. (a) XPS survey spectrum for ITO/G; XPS spectra of ITO/G in the In 3d (b), Sn 3d (c), and O 1s (d) regions.

Fig. 3. (a) LSV curves of ITO/G in Ar- and N2-saturated 0.5 M LiClO4 with a scan rate of 2 mV s-1; (b) Chronoamperometry curves of ITO/G at various potentials for 2 h; (c) UV-Vis absorption spectra of the electrolytes colored with indophenol indicator; (d) Corresponding NH3 yields and FEs for ITO/G at all potentials.

Fig. 4. (a) UV-Vis absorption spectra of the electrolytes stained with indophenol indicator at -0.40 V under different electrochemical conditions using ITO/G; (b) NH3 yields and FEs of ITO/G at -0.40 V with alternating at the interval of 2 h cycles between Ar-saturated and N2-saturated electrolytes; (c) Cycling stability over ITO/G at -0.40 V; (d) NH3 yields and FEs at -0.40 V for 2 h over initial ITO/G and ITO/G subjected to 24 h operation.

Fig. 5. (a) XRD pattern and (b) SEM images of ITO/G after stability test.

Fig. 6. Free energy (in eV) diagrams and the local atomic structures of the reaction intermediates for the NRR on the ITO (400) surface through the alternating pathway. The blue, green, pink, red, and grey spheres represent the N, H, In, O, and Sn atoms, respectively.

参考文献

[1]	R. Schlögl, Angew. Chem. Int. Ed., 2003,42, 2004-2008.
[2]	A. Klerke, C. H. Christensen, J. K. Nørskov, T. Vegge, J. Mater. Chem., 2008,18, 2304-2310.
[3]	I. Dybkjaer, Springer: Berlin Heidelberg, 1995, 199-308.
[4]	S. Gao, Y. Zhu, Y. Chen, M. Tian, Y. Yang, T. Jiang, Z. Wang, Mater. Today 2019,28, 17-24.
[5]	X. Zhu, S. Mou, Q. Peng, Q. Liu, Y. Luo, G. Chen, S. Gao, X. Sun, J. Mater. Chem. A, 2020,8, 1545-1556.
[6]	C. Guo, J. Ran, A. Vasileff, S. Qiao, Energy Environ. Sci., 2018,11, 45-56.
[7]	Z. Wang, Y. Li, H. Yu, Y. Xu, H. Xue, X. Li, H. Wang, L. Wang, ChemSusChem, 2018,11, 3480-3485.
[8]	M. Shi, D. Bao, B. Wulan, Y. Li, Y. Zhang, J. Yan, Q. Jiang, Adv. Mater., 2017,29, 1606550.
[9]	Y. Li, H. Yu, Z. Wang, S. Liu, Y. Xu, X. Li, L. Wang, H. Wang, Chem. Commun., 2019,55, 14745-14748.
[10]	J. Wang, L. Yu, L. Hu, G. Chen, H. Xin, X. Feng, Nat. Commun., 2018,9, 1795.
[11]	G. Deng, T. Wang, A. A. Alshehri, K. A. Alzahrani, Y. Wang, H. Ye, Y. Luo, X. Sun, J. Mater. Chem. A, 2019,7, 21674-21677.
[12]	H. Xie, Q. Geng, X. Zhu, Y. Luo, L. Chang, X. Niu, X. Shi, A. M. Asiri, S. Gao, Z. Wang, X. Sun, J. Mater. Chem. A, 2019,7, 24760-24764.
[13]	V. Kordali, G. Kyriacou, Ch. Lambrou, Chem. Commun., 2000, 1673-1674.
[14]	R. Zhao, C. Liu, X. Zhang, X. Zhu, P. Wei, L. Ji, Y. Guo, S. Gao, Y. Luo, Z. Wang, X. Sun, J. Mater. Chem. A, 2020,8, 77-81.
[15]	Y. Liu, M. Han, Q. Xiong, S. Zhang, C. Zhao, W. Gong, G. Wang, H. Zhang, H. Zhao, Adv. Energy Mater., 2019,9, 1803935.
[16]	T. Wu, X. Zhu, Z. Xing, S. Mou, C. Li, Y. Qiao, Q. Liu, Y. Luo, X. Shi, Y. Zhang, X. Sun, Angew. Chem. Int. Ed., 2019,58, 18449-18453.
[17]	Q. Qin, Y. Zhao, M. Schmallegger, T. Heil, J. Schmidt, R. Walczak, G. Demner, H. Jiao, M. Oschatz, Angew. Chem. Int. Ed., 2019,58, 13101-13106.
[18]	T. Wu, H. Zhao, X. Zhu, Z. Xing, Q. Liu, T. Liu, S. Gao, S. Lu, G. Chen, A. M. Asiri, Y. Zhang, X. Sun, Adv. Mater., 2020,32, 2000299.
[19]	S. Chen, S. Perathoner, C. Ampelli, C. Mebrahtu, D. Su, G. Centi, Angew. Chem. Int. Ed., 2017,56, 2699-2703.
[20]	X. Lv, F. Wang, J. Du, Q. Liu, Y. Luo, S. Lu, G. Chen, S. Gao, B. Zheng, X. Sun, Sustain. Energy Fuels, 2020,4, 4469-4472
[21]	B. Ma, J. Liang, T. Li, Q. Liu, Y. Luo, S. Lu, A. M. Asiri, D. Ma, X. Sun, Nano Res. 2020, DOI: / 10.1007/s12274-020-3049-5.
[22]	L. Hu, A. Khaniya, J. Wang, G. Chen, W. E. Kaden, X. Feng, ACS Catal., 2018,8, 9312-9319.
[23]	W. Xiong, X. Cheng, T. Wang, Y. Luo, J. Feng, S. Lu, A. M. Asiri, W. Li, Z. Jiang, X. Sun, Nano Res., 2020,13, 1008-1012.
[24]	H. Jin, L. Li, X. Liu, C. Tang, W. Xu, S. Chen, L. Song, Y. Zheng, S. Qiao, Adv. Mater., 2019,31, 1902709.
[25]	X. Cheng, J. Wang, W. Xiong, T. Wang, T. Wu, S. Lu, G. Chen, S. Gao, X. Shi, Z. Jiang, X. Niu, X. Sun, ChemNanoMat, 2020,6, 1315-1319.
[26]	Y. Luo, G. Chen, L. Ding, X. Chen, L. Ding, H. Wang, Joule, 2019,3, 279-289.
[27]	T. Wu, M. Han, X. Zhu, G. Wang, Y. Zhang, H. Zhang, H. Zhao, J. Mater. Chem. A, 2019,7, 16969-16978.
[28]	L. Xia, B. Li, Y. Zhang, R. Zhang, L. Ji, H. Chen, G. Cui, H. Zheng, X. Sun, F. Xie, Q. Liu, Inorg. Chem., 2019,58, 2257-2260.
[29]	L. Li, C. Tang, B. Xia, H. Jin, Y. Zheng, S. Qiao, ACS Catal., 2019,9, 2902-2908.
[30]	C. Li, D. Ma, S. Mou, Y. Luo, B. Ma, S. Lu, G. Cui, Q. Li, Q. Liu, X. Sun, J. Energy Chem., 2020,50, 402-408.
[31]	K. Chu, Y. Liu, Y. Li, H. Zhang, Y. Tian, J. Mater. Chem. A, 2019,7, 4389-4394.
[32]	T. Xu, D. Ma, Ch. Li, Q. Liu, S. Lu, A. M. Asiri, C. Yang, X. Sun, Chem. Commun., 2020,56, 3673-3676.
[33]	K. Chu, Y. Liu, J. Wang, H. Zhang, ACS Appl. Energy Mater., 2019,2, 2288-2295.
[34]	F. Wang, X. Lv, X. Zhu, J. Du, S. Lu, A. A. Alshehri, K. A. Alzahrani, B. Zheng, X. Sun, Chem. Commun., 2020,56, 2107-2110.
[35]	C. Li, J. Yu, L., J. Zhao, W. Kong, T. Wang, A. M. Asiri, Q. Li, X. Sun, Inorg. Chem., 2019,58, 9597-9601.
[36]	X. Zhao, X. Lan, D. Yu, H. Fu, Z. Liu, T. Mu, Chem. Commun., 2018,54, 13010-13013.
[37]	L. Zhang, X. Ji, X. Ren, Y. Ma, X. Shi, Z. Tian, A. M. Asiri, L. Chen, B. Tang, X. Sun, Adv. Mater., 2018,30, 1800191.
[38]	J. Gao, X. Lv, F. Wang, Y. Luo, S. Lu, G. Chen, S. Gao, B. Zhong, X. Guo, X. Sun, J. Mater. Chem. A, 2020,8, 17956-17959.
[39]	J. Han, Z. Liu, Y. Ma, G. Cui, F. Xie, F. Wang, Y. Wu, S. Gao, Y. Xu, X. Sun, Nano Energy, 2018,52, 264-270.
[40]	X. Yang, J. Nash, J. Anibal, M. Dunwell, S. Kattel, E. Stavitski, K. Attenkofer, J. G. Chen, Y. Yan, B. Xu, J. Am. Chem. Soc., 2018,140, 13387-13391.
[41]	L. Zhang, X. Ren, Y. Luo, X. Shi, A. M. Asiri, T. Li, X. Sun, Chem. Commun., 2018,54, 12966-12969.
[42]	Y. Liu, D. Li, J. Yu, B. Ding, Angew. Chem. Int. Ed., 2019,58, 16439-16444.
[43]	Y. Liu, Y. Li, H. Zhang, K. Chu, Inorg. Chem., 2019,58, 10424-10431.
[44]	K. Chu, Y. Liu, Y. Li, J. Wang, H. Zhang, ACS Appl. Mater. Interfaces, 2019,11, 31806-31815.
[45]	G. Bühler, D. Thölmann, C. Feldmann, Adv. Mater., 2007,19, 2224-2227.
[46]	J. H. Lee, A. B. M. H. Islam, T. K. Kim, Y. Cha, J. S. Kwak, Photon. Res., 2020,8, 1049-1058.
[47]	J. Li, L. Wang, W. You, M. Liu, L. Zhang, X. Sang, Chin. J. Catal., 2018,39, 534-541.
[48]	D. Zhu, L. Zhang, R. E. Ruther, R. J. Hamers, Nat. Mater., 2013,12, 836-841.
[49]	G. W. Watt, J. D. Chrisp, Anal. Chem., 1952,24, 2006-2008.
[50]	X. Li, X. Xu, X. Yin, C. Li, J. Zhang, Particuology, 2011,9, 471-474.
[51]	B. Koo, H. Ahn, Ceram. Int., 2016,42, 509-517.
[52]	W. Chang, C. Kuo, C. Juan, P. Lee, Y. Chueh, S. Lin, Nanoscale Res. Lett., 2012,7, 684-684.
[53]	W. Qiu, X. Xie, J. Qiu, W. Fang, R. Liang, X. Ren, X. Ji, G. Cui, A. M. Asiri, G. Cui, B. Tang, X. Sun, Nat. Commun., 2018,9, 3485.
[54]	X. Ren, J. Zhao, Q. Wei, Y. Ma, H. Guo, Q. Liu, Y. Wang, G. Cui, A. M. Asiri, B. Li, B. Tang, X. Sun, ACS Central Sci., 2019,5, 116-121.
[55]	P.-R. Huang, Y. He, C. Cao, Z.-H. Lu, NPG Asia Mater., 2013,5, 57-57.
[56]	D. Ma, Z. Zeng, L. Liu, X. Huang, Y. Jia, J. Phys. Chem. C, 2019,123, 19066-19076.
[57]	X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Qiao, J. Am. Chem. Soc., 2019,141, 9664-9672.

商用氧化铟锡玻璃: 室温高效还原氮气的催化剂电极

Commercial indium-tin oxide glass: A catalyst electrode for efficient N₂ reduction at ambient conditions

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商用氧化铟锡玻璃: 室温高效还原氮气的催化剂电极

Commercial indium-tin oxide glass: A catalyst electrode for efficient N2 reduction at ambient conditions

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Commercial indium-tin oxide glass: A catalyst electrode for efficient N₂ reduction at ambient conditions