镍基金属有机框架及其衍生物在电催化析氧反应中的研究进展

doi:10.3866/PKU.WHXB202009074

物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2009074.doi: 10.3866/PKU.WHXB202009074

所属专题：电催化

镍基金属有机框架及其衍生物在电催化析氧反应中的研究进展

徐冰妍¹, 张应¹, 皮业灿², 邵琪², 黄小青¹^,*()

¹ 厦门大学化学化工学院，福建厦门 361005
² 苏州大学材料与化学化工学部，江苏苏州 215123

收稿日期:2020-09-23 录用日期:2020-10-26 发布日期:2020-10-30
通讯作者: 黄小青 E-mail:hxq006@xmu.edu.cn
作者简介:Dr. Xiaoqing Huang is currently a professor at College of Chemistry and Chemical Engineering, Xiamen University. He obtained his B.Sc. in chemistry education from Southwest Normal University (2005) and Ph.D. in organic chemistry from Xiamen University (2011). His current research interests are in the design of nanoscale materials for heterogenous catalysis, electrocatalysis, energy conversion and beyond
基金资助:
厦门大学高层次人才科研启动基金(0040/X2303321)

Research Progress of Nickel-Based Metal-Organic Frameworks and Their Derivatives for Oxygen Evolution Catalysis

Bingyan Xu¹, Ying Zhang¹, Yecan Pi², Qi Shao², Xiaoqing Huang¹^,*()

¹ College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, China
² College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu Province, China

Received:2020-09-23 Accepted:2020-10-26 Published:2020-10-30
Contact: Xiaoqing Huang E-mail:hxq006@xmu.edu.cn
About author:Xiaoqing Huang, Email:hxq006@xmu.edu.cn
Supported by:
the Start-Up Support from Xiamen University, China(0040/X2303321)

摘要/Abstract

摘要：

作为未来最有潜力的制氢技术之一，电解水为解决环境污染和能源危机等问题提供了一种有效的解决途径。然而，阳极析氧反应缓慢的动力学和较高的过电位使其成为电解水装置效率提升的主要瓶颈。因此，开发高活性和高稳定性的析氧反应催化剂对于电解水技术的发展具有重要意义。近年来，镍基金属有机框架材料因其具有丰富可调的拓扑结构、较大的比表面积以及多孔特性，在催化领域受到了越来越多的关注。本文综述了镍基金属有机框架及其衍生材料在析氧催化研究中的最新进展。首先简要介绍了镍基材料在析氧反应中的原理及评价析氧催化剂活性的一些重要参数，并列举了几种镍基金属有机框架材料的结构及其在催化中的优势。随后，结合近年来发表的文献，对单金属、双金属和三金属镍基金属有机框架材料及其衍生物在析氧催化中的研究进展进行了总结与讨论，重点分析了该类材料的设计策略和催化机理。最后对该领域目前所面临的主要挑战以及未来的发展趋势进行了总结与展望。

关键词: 析氧反应, 电催化, 镍基金属有机框架, 水裂解, 氧化还原活性位点

Abstract:

As one of the most promising hydrogen production technologies, electrochemical water splitting is an effective measure for solving environmental pollution and energy crises. However, the slow kinetics and high overpotential of the oxygen evolution reaction (OER) are the primary deterrents for improving the efficiency of water splitting devices. Iridium- and ruthenium-based noble metal catalysts are extremely expensive, which limits the industrial-scale development of this technology. Therefore, the development of oxygen evolution catalysts with high activity, excellent stability, and low costs is significantly important for water splitting technologies. Nickel-based materials meet the requirements of high abundance, cost-effectiveness, and high activity. In recent years, nickel-based metal organic frameworks (Ni-based MOFs) have attracted increasing research attention owing to their diverse and tunable topological structures and large specific surface areas. Furthermore, the mesoporous three-dimensional structure of MOFs can promote the diffusion of reactants, rendering them excellent candidates for catalytic applications. In order to utilize the advantages of Ni-MOFs more efficiently, the following methods are usually used to improve their catalytic performance. Owing to their unique properties, metal nodes can be replaced without affecting the MOF skeleton. As iron series metals, Co and Fe doping show unique catalytic activity and structural stability due to the synergistic effect between metal centers. Further, Ni-MOFs can simultaneously be used as precursors for oxidation, phosphating, or vulcanization to obtain Ni-MOF derivatives with different components. Among them, high-temperature carbonization treatment can make use of abundant organic ligands of Ni-MOFs to form a partially graphitized carbon-based framework, thereby augmenting conductivity, preventing the aggregation and corrosion of transition metals, and improving the overall support strength. The catalytic performance of oxygen production can be further improved by directly growing the Ni-MOFs on the substrate and introducing other active substances or conductive materials. Herein, the latest developments of Ni-based MOFs and their derivatives have been reviewed with regard to their utilization in OER catalysis, including nickel oxides, nickel hydroxides, nickel phosphides, nickel sulfides, and carbon composite materials. First, the mechanism and measurement criteria of the OER are briefly introduced. Second, the structures of several typical Ni-based MOFs (MOF-74, MILs, PBAs, and ZIFs) and their preparation methods are described. Subsequently, recent advances in the application of Ni-based MOFs and their derivatives in the OER are discussed, with an emphasis on materials design strategies and catalytic mechanisms. Finally, the main challenges and opportunities in this field are proposed.

Key words: Oxygen evolution reaction, Electrocatalysis, Nickel-based metal-organic frameworks, Water-splitting, Redox active site

徐冰妍, 张应, 皮业灿, 邵琪, 黄小青. 镍基金属有机框架及其衍生物在电催化析氧反应中的研究进展[J]. 物理化学学报, 2021, 37(7), 2009074. doi: 10.3866/PKU.WHXB202009074

Bingyan Xu, Ying Zhang, Yecan Pi, Qi Shao, Xiaoqing Huang. Research Progress of Nickel-Based Metal-Organic Frameworks and Their Derivatives for Oxygen Evolution Catalysis[J]. Acta Phys. -Chim. Sin. 2021, 37(7), 2009074. doi: 10.3866/PKU.WHXB202009074

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202009074

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I7/2009074

图/表 17

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Table 2

Table 3

Comparison of the OER performance of bimetallic and trimetallic Ni-MOFs and their derivatives materials."

	Catalyst	Substrate	Electrolyte (KOH)	η at 10 mA∙cm⁻² (mV)	Tafel slope/(mV∙dec⁻1)	Ref.
NiFe-MOF	NiFe-MOF-74	NF	1 mol∙L⁻¹	223	72	56
	FeNi-DOBDC-(Fe/Ni 3:1)	GC	1 mol∙L⁻¹	270 (at 50 mA∙cm⁻²)	49	57
	MIL-100(FeNi)	NF	1 mol∙L⁻¹	243 (at 50 mA∙cm⁻²)	30	64
	FeNi₃-BTC	NF	1 mol∙L⁻¹	236	49	59
	Fe₁Ni₄-HHTP NWAs	CC	1 mol∙L⁻¹	213	96	26
	Fe₂Ni-MIL-88B	NF	1 mol∙L⁻¹	222	42	65
	Fe_0.1-Ni-MOF/NF	NF	1 mol∙L⁻¹	243 (at 50 mA∙cm⁻²)	70	67
	NiFe-MOF/FeCH-NF	NF	1 mol∙L⁻¹	200	51	68
	NiFe-NFF	NF	1 mol∙L⁻¹	250	39	66
	Fe_0.38Ni_0.62-MOF	CC	1 mol∙L⁻¹	190	58	22
	N-Fe-MOF NSs	GC	1 mol∙L⁻¹	221	56	70
	MFN-MOF (2:1)/NF	NF	1 mol∙L⁻¹	235 (at 50 mA∙cm⁻²)	55	102
	Fe₂Ni-MIL-101	NF	1 mol∙L⁻¹	237 (at 20 mA∙cm⁻²)	44	103
	FeNi@CNF	GC	1 mol∙L⁻¹	356	63	104
NiFe-MOF derived oxides/hydroxides/carbonaceous materials	Fe-Ni-O_x	GC	0.1 mol∙L⁻¹	584	72	71
	NiFe₂O₄	NF	1 mol∙L⁻¹	293	98	72
	FeNi₃-Fe₃O₄ NPs/MOF-CNT	GC	1 mol∙L⁻¹	234	37	73
	FeNi@N-CNT	GC	1 mol∙L⁻¹	300	48	33
	Fe-Ni@NC-CNTs	NF	1 mol∙L⁻¹	274	45.5	75
	NiFe-NCs	CFP	1 mol∙L⁻¹	271	48	105
	Ni_0.5Fe_0.5-HP	NF	1 mol∙L⁻¹	280	79	106
	FeNi/NiFe₂O₄@NC	GC	1 mol∙L⁻¹	316	60	107
	NiFe@NC	GC	1 mol∙L⁻¹	360	60	108
NiFe-MOF derived phosphates/sulfides	Fe-Ni-P/rGO-400	GC	1 mol∙L⁻¹	240	63	77
	(Ni_xFe_1−x)₂P nanocubes	GC	1 mol∙L⁻¹	290	44	76
	Ni-Fe-O-P	GC	1 mol∙L⁻¹	227	50	78
	Ni-Fe-O-B	GC	1 mol∙L⁻¹	243	53	78
	Ni-Fe-O-S	GC	1 mol∙L⁻¹	272	70	78
NiCo-MOF	NiCo-UMOFNs	GC	1 mol∙L⁻¹	250	42	37
	CTGU-10c2	GC	1 mol∙L⁻¹	240	58	79
	AuNPs@CoNi-MOF	GC	1 mol∙L⁻¹	283	83	80
	M₂-(BDC)₂TED@CF	CF	1 mol∙L⁻¹	260	76	81
NiCo-MOF derived materials	Ni_xCo_3−xO₄/NF	NF	1 mol∙L⁻¹	287	88	82
	NCMC	CFP	1 mol∙L⁻¹	290	73	83
	NiCo alloy@C/Ni_xCo_1−xO/NF	NF	1 mol∙L⁻¹	300 (at 100 mA∙cm⁻²)	106	36
	Co_xNi_1−x@Co_yNi_1−yO@C	GC	0.1 mol∙L⁻¹		126	84
	CoNi₃C/Ni@C	GC	1 mol∙L⁻¹	325	68	85
	NiCo-0.8@N-CNFs-800	GC	0.1 mol∙L⁻¹	380	78	86
	Co₄Ni₁P NTs	GC	1 mol∙L⁻¹	245	61	87
	Ni_1.4Co_0.6P/NCNHMs		1 mol∙L⁻¹	320	54.5	88
	Ni_xCo_y-P	NF	1 mol∙L⁻¹	300 (at 35 mA∙cm⁻²)	71	38
	Ni₁Co₄S@C-1000	GC	1 mol∙L⁻¹		64	89
	Ni-Co-S HPNA	CC	1 mol∙L⁻¹	270	56	90
	Co/Ni@C	GC	0.1 mol∙L⁻¹	410	101	109
	Ni-doped CoS₂/CFP	CFP	1 mol∙L⁻¹	270	79	110
Other bimetallic Ni-MOFs and their derivatives	NiCu-MOFNs/NF	NF	1 mol∙L⁻¹	309 (at 100 mA∙cm⁻²)	48	92
	Ni/Ni₂P/Mo₂C@C	GC	1 mol∙L⁻¹	368	75	93
	Ni-Cu@Cu-Ni-MOF	CP	1 mol∙L⁻¹	640	98	61
	Pt-Ni@PCN920	NF	1 mol∙L⁻¹		59	111
	UiO-66-NH₂-Ni@G	GC	1 mol∙L⁻¹	370	45	112
Trimetal Ni-MOF and their derivatives	Fe/Ni_2.4/Co_0.4-MIL-53	GC	1 mol∙L⁻¹	219		94
	Co_2.36Fe_0.19Ni_0.45-btca	NF	1 mol∙L⁻¹	292	73	95
	NiCo/Fe₃O₄/MOF-74	GC	1 mol∙L⁻¹	238	29	96
	FeCo_0.5Ni_0.5-LDH	Cu foil	1 mol∙L⁻¹	248	38	97
	NCF-MOF	NF	0.1 mol∙L⁻¹	480 (at 30 mA∙cm⁻²)	49	98
	Ni₃S₂@MIL-53(NiFeCo)/NF	NF	1 mol∙L⁻¹	236 (at 50 mA∙cm⁻²)	15	99

Table 3

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Acidic electrolyte	Alkaline electrolyte
* + H₂O → OH* + H⁺ + e⁻	* + OH⁻ → OH* + e⁻
OH* → O* + H⁺ + e⁻	OH* + OH⁻ → O* + H₂O + e⁻
O* + H₂O → OOH* + H⁺ + e⁻	O* + OH⁻ → OOH* + e⁻
OOH* → O₂ + H⁺ + e⁻ + *	OOH+ OH⁻ → O₂ + H₂O + e⁻ +

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Research Progress of Nickel-Based Metal-Organic Frameworks and Their Derivatives for Oxygen Evolution Catalysis

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