NiN4/Cr修饰的石墨烯电化学固氮电极

doi:10.15541/jim20220033

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1141-1148.DOI: 10.15541/jim20220033 CSTR: 32189.14.10.15541/jim20220033

• 研究快报 • 上一篇

NiN₄/Cr修饰的石墨烯电化学固氮电极

吴静¹(), 余立兵¹, 刘帅帅¹, 黄秋艳¹, 姜姗姗¹, ANTON Matveev², 王连莉³, 宋二红⁴(), 肖蓓蓓¹()

1.江苏科技大学能源与动力学院, 镇江 212003
2.莫尔多瓦州立大学, 萨兰斯克430005, 俄罗斯
3.西安科技大学材料科学与工程学院, 西安 710054
4.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050

收稿日期:2022-01-20 修回日期:2022-04-06 出版日期:2022-10-20 网络出版日期:2022-05-09
通讯作者: 肖蓓蓓, 副教授. E-mail: xiaobb11@mails.jlu.edu.cn;
宋二红, 副研究员. E-mail: ehsong@mail.sic.ac.cn
作者简介:吴静(1998-), 女, 硕士研究生. E-mail: wjjust20@163.com

NiN₄/Cr Embedded Graphene for Electrochemical Nitrogen Fixation

WU Jing¹(), YU Libing¹, LIU Shuaishuai¹, HUANG Qiuyan¹, JIANG Shanshan¹, ANTON Matveev², WANG Lianli³, SONG Erhong⁴(), XIAO Beibei¹()

1. School of Energy and Power Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
2. National Research Ogarev Mordovia State University, Saransk 430005, Russia
3. School of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an 710054, China
4. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2022-01-20 Revised:2022-04-06 Published:2022-10-20 Online:2022-05-09
Contact: XIAO Beibei, associate professor. E-mail: xiaobb11@mails.jlu.edu.cn;
SONG Erhong, associate professor. E-mail: ehsong@mail.sic.ac.cn
About author:WU Jing(1998-), female, Master candidate. E-mail: wjjust20@163.com
Supported by:
National Natural Science Foundation of China(21503097);Natural Science Foundation of Shaanxi Province(2018JQ5181);Science and Technology Commission of Shanghai Municipality(21ZR1472900)

摘要/Abstract

摘要：

工业上应用哈伯工艺法合成氨过程要求严苛, 需要消耗大量能源且二氧化碳排放量大。因此, 开发在常规环境条件下通过电催化氮还原反应的清洁技术, 对未来可持续的能源转化进程具有重要意义。本研究采用密度泛函理论计算方法, 对TM₁N₄/TM₂嵌入石墨烯的氮还原反应进行了全面研究。在充分考虑活性和稳定性的情况下, 研究结果表明, NiN₄/Cr锚定石墨烯通过酶促反应途径表现出最佳的催化活性, 其中第一次加氢为电位决定步骤, 起始电位为0.57 V, 优于商业Ru基材料。此外, 与单一的Cr原子修饰的石墨烯相比, 引入NiN₄官能团降低了ΔG_max并提高了电催化性能。根据Mulliken电荷分析, 催化剂的催化活性主要来源于载体和反应中间体之间的电子转移。上述结果为高效合成氨提供了电极候选材料, 进一步深化了相应的电催化机理。

关键词: 氮气还原反应, 石墨烯, 密度泛函原理, 电催化, 热力学

Abstract:

Owing to the heavy energy consumption and the massive CO₂ emission during ammonia synthesis via Haber-Bosch process, a clean technology of nitrogen reduction electrocatalysis under ambient conditions is of significance for the sustainable energy conversion progress in future. In the study, the nitrogen reduction reaction of TM₁N₄/TM₂ embedded graphene is comprehensively investigated using density functional theory calculations. Fully considering the activity and stability, our results reveal that NiN₄/Cr anchored graphene exhibits the best catalytic activity via the enzymatic reaction pathway wherein the potential determining step is located at the first hydrogenation with an onset potential of 0.57 V, being superior to the commercial Ru-based material. Furthermore, compared with the isolated Cr atom decorated nitrogen functionalized graphene, the introduction of NiN₄ moiety decreases ΔG_max and enhances the electrocatalytic performance. According to the Mulliken charge analysis, the physical origin of the catalytic activity is ascribed to the electron transition between the supports and reaction intermediates. Overall, these results pave a way for the design of the high efficient electrode material for ammonia synthesis and provide a fundamental insight into the electrocatalysis.

Key words: nitrogen reduction reaction, graphene, density functional theory, electrocatalysis, thermodynamic

中图分类号:

TQ174

吴静, 余立兵, 刘帅帅, 黄秋艳, 姜姗姗, ANTON Matveev, 王连莉, 宋二红, 肖蓓蓓. NiN₄/Cr修饰的石墨烯电化学固氮电极[J]. 无机材料学报, 2022, 37(10): 1141-1148.

WU Jing, YU Libing, LIU Shuaishuai, HUANG Qiuyan, JIANG Shanshan, ANTON Matveev, WANG Lianli, SONG Erhong, XIAO Beibei. NiN₄/Cr Embedded Graphene for Electrochemical Nitrogen Fixation[J]. Journal of Inorganic Materials, 2022, 37(10): 1141-1148.

图/表 19

参考文献 47

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3d	Sc	Ti	V	Cr	Mn	Fe	Co	Ni
E_ads(TM₂) N₂ end-on	-0.22	-0.36	-0.62	-0.72	-1.02	-1.07	-0.89	-0.59
E_ads(TM₂) N₂ side-on	0.12	-0.02	-1.17	-0.35	-0.59	-0.51	-0.33	-0.19
E_ads(TM₂) H	0.75	0.20	-0.18	-0.14	-0.19	-0.20	-0.22	-0.38
4d	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd
E_ads(TM₂) N₂ end-on	-0.14	-0.22	-1.05	-0.70	-0.73	-0.99	-0.73	-1.30
E_ads(TM₂) N₂ side-on	-0.13	0.11	-0.42	-0.43	-0.47	-0.44	-0.25	-0.96
E_ads(TM₂) H	0.78	0.25	-0.87	-0.38	0.51	-0.11	-0.33	-1.06
5d	Lu	Hf	Ta	W	Re	Os	Ir	Pt
E_ads(TM₂) N₂ end-on	-0.21	-0.35	-0.60	-1.57	-1.23	-1.30	-1.08	-0.52
E_ads(TM₂) N₂ side-on	0.07	0.02	-0.32	-1.48	-0.88	-0.68	-0.44	-0.23
E_ads(TM₂) H	0.65	-0.01	-1.33	-0.92	-0.88	-0.81	-0.87	-0.99

3d	Sc	Ti	V	Cr	Mn	Fe	Co	Ni
E_ads(TM₂) N₂ end-on	-0.22	-0.36	-0.62	-0.72	-1.02	-1.07	-0.89	-0.59
E_ads(TM₂) N₂ side-on	0.12	-0.02	-1.17	-0.35	-0.59	-0.51	-0.33	-0.19
E_ads(TM₂) H	0.75	0.20	-0.18	-0.14	-0.19	-0.20	-0.22	-0.38
4d	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd
E_ads(TM₂) N₂ end-on	-0.14	-0.22	-1.05	-0.70	-0.73	-0.99	-0.73	-1.30
E_ads(TM₂) N₂ side-on	-0.13	0.11	-0.42	-0.43	-0.47	-0.44	-0.25	-0.96
E_ads(TM₂) H	0.78	0.25	-0.87	-0.38	0.51	-0.11	-0.33	-1.06
5d	Lu	Hf	Ta	W	Re	Os	Ir	Pt
E_ads(TM₂) N₂ end-on	-0.21	-0.35	-0.60	-1.57	-1.23	-1.30	-1.08	-0.52
E_ads(TM₂) N₂ side-on	0.07	0.02	-0.32	-1.48	-0.88	-0.68	-0.44	-0.23
E_ads(TM₂) H	0.65	-0.01	-1.33	-0.92	-0.88	-0.81	-0.87	-0.99

3d	Sc	Ti	V	Cr	Mn	Fe	Co	Ni
E_ads(TM₂) N₂ end-on	-0.21	-0.75	-0.26	-0.52	-0.94	-1.06	-0.88	-0.53
E_ads(TM₂) N₂ side-on	-0.21	-0.37	-0.35	-0.41	-0.59	-0.54	-0.25	-0.56
E_ads(TM₂) H	0.93	0.33	0.27	-0.02	-0.14	-0.25	-0.11	-0.37
4d	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd
E_ads(TM₂) N₂ end-on	-0.14	-0.22	-0.20	-0.62	-0.88	-0.96	-0.76	-0.49
E_ads(TM₂) N₂ side-on	0.22	-0.20	-0.20	0.01	-0.58	-0.41	-0.27	0.01
E_ads(TM₂) H	0.90	0.21	0.17	-0.23	-0.12	-0.12	-0.09	-0.33
5d	Lu	Hf	Ta	W	Re	Os	Ir	Pt
E_ads(TM₂) N₂ end-on	-0.20	-0.31	-0.64	-0.91	-1.15	-1.27	-1.09	-0.26
E_ads(TM₂) N₂ side-on	-0.20	0.07	-0.49	-0.77	-0.94	-0.68	-0.48	0.22
E_ads(TM₂) H	0.77	0.01	-0.73	-0.84	-0.68	-0.78	-0.72	-0.99

3d	Sc	Ti	V	Cr	Mn	Fe	Co	Ni
E_ads(TM₂) N₂ end-on	-0.21	-0.75	-0.26	-0.52	-0.94	-1.06	-0.88	-0.53
E_ads(TM₂) N₂ side-on	-0.21	-0.37	-0.35	-0.41	-0.59	-0.54	-0.25	-0.56
E_ads(TM₂) H	0.93	0.33	0.27	-0.02	-0.14	-0.25	-0.11	-0.37
4d	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd
E_ads(TM₂) N₂ end-on	-0.14	-0.22	-0.20	-0.62	-0.88	-0.96	-0.76	-0.49
E_ads(TM₂) N₂ side-on	0.22	-0.20	-0.20	0.01	-0.58	-0.41	-0.27	0.01
E_ads(TM₂) H	0.90	0.21	0.17	-0.23	-0.12	-0.12	-0.09	-0.33
5d	Lu	Hf	Ta	W	Re	Os	Ir	Pt
E_ads(TM₂) N₂ end-on	-0.20	-0.31	-0.64	-0.91	-1.15	-1.27	-1.09	-0.26
E_ads(TM₂) N₂ side-on	-0.20	0.07	-0.49	-0.77	-0.94	-0.68	-0.48	0.22
E_ads(TM₂) H	0.77	0.01	-0.73	-0.84	-0.68	-0.78	-0.72	-0.99

3d	Sc	Ti	V	Cr	Mn	Fe	Co	Ni
E_ads(TM₂) N₂ end-on	-0.21	-0.37	-0.68	-0.84	-1.01	-1.05	-0.85	-0.46
E_ads(TM₂) N₂ side-on	-0.20	-0.37	-0.29	-0.51	-0.64	-0.53	-0.26	-0.56
E_ads(TM₂) H	1.02	0.37	-0.09	-0.08	-0.36	-0.13	-0.07	-0.28
4d	Y	Zr	Nb	Mo	Tc	Ru	Rh	Pd
E_ads(TM₂) N₂ end-on	-0.12	-0.19	-0.44	-0.61	-0.82	-0.93	-0.75	-0.48
E_ads(TM₂) N₂ side-on	-0.13	-0.20	-0.03	-0.29	-0.57	-0.42	-0.25	-0.48
E_ads(TM₂) H	1.03	0.42	-0.12	-0.22	-0.07	-0.07	-0.03	-0.26
5d	Lu	Hf	Ta	W	Re	Os	Ir	Pt
E_ads(TM₂) N₂ end-on	-0.20	-0.29	-0.62	-0.86	-1.08	-1.23	-1.07	-0.49
E_ads(TM₂) N₂ side-on	-0.21	-0.29	-0.28	-0.63	-0.89	-0.67	-0.46	-0.48
E_ads(TM₂) H	0.82	0.23	-0.50	-0.75	-0.63	-0.72	-0.69	-0.87

NiN₄/Cr修饰的石墨烯电化学固氮电极

NiN₄/Cr Embedded Graphene for Electrochemical Nitrogen Fixation

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System	Mechanisms	N₂ adsorption	R₁	R₂	R₃	R₄	R₅	R₆	NH₃ desorption
NiN₄/Cr	Distal	-0.41	0.98	-0.28	0.17	-1.08	-1.09	-0.23	1.04
	Alternating	-0.41	0.98	0.05	-0.31	-0.25	-1.29	-0.71	1.04
	Enzymatic	-0.10	0.57	0.16	-0.56	-0.12	-1.51	-0.38	1.04
NiN₄/Mo	Distal	-0.27	0.92	-0.08	-0.22	-1.14	-0.71	-0.20	1.04
	Alternating	-0.27	0.92	0.16	-0.56	0.06	-1.52	-0.49	1.04
	Enzymatic	-0.11	0.60	0.18	-0.89	0.50	-1.54	-0.44	1.04
NiN₄/Ta	Distal	-0.18	0.69	-0.37	-0.06	-1.22	-1.02	0.22	1.04
	Alternating	-0.18	0.69	0.05	-0.88	0.11	-1.78	0.05	1.04
	Enzymatic	0.04	0.11	-0.23	-0.70	0.58	-1.70	-0.04	1.04

	Distal		Alternating		Enzymatic
	RDS	ΔG_max	RDS	ΔG_max	RDS	ΔG_max
Cr	N₂+H→NNH	1.03	N₂+H→NNH	1.03	NN+H→NNH	0.66
NiN₄/Cr	N₂+H→NNH	0.98	N₂+H→NNH	0.98	NN+H→NNH	0.57
Mo	N₂+H→NNH	1.27	N₂+H→NNH	1.27	NN+H→NNH	0.43
NiN₄/Mo	N₂+H→NNH	0.92	N₂+H→NNH	0.92	NN+H→NNH	0.60
Ta	NNH₂+H→N	0.72	N₂+H→NNH	0.66	NHNH₂+H→NH₂NH₂	0.49
NiN₄/Ta	N₂+H→NNH	0.69	N₂+H→NNH	0.69	NHNH₂+H→NH₂NH₂	0.58

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