MXene基材料在电催化领域的研究进展

王利萌; 李亚如; 任永鹏; 潘昆明; 赵帅凯; 吕贝贝

MXene基材料在电催化领域的研究进展

王利萌¹,
李亚如^{1, 2},
任永鹏^{1, 2, 3, ,},
潘昆明^{1, 2, 3},
赵帅凯¹,
吕贝贝¹

1.
河南科技大学　材料科学与工程学院, 洛阳 471000
2.
河南省高温结构与功能材料重点实验室河南科技大学金属材料磨损控制与成型技术国家地方联合工程研究中心, 洛阳 471000
3.
龙门实验室, 洛阳 471000

基金项目: 国家自然科学基金(No. 51901069)；河南省高校科技创新人才项目(22HASTIT1006)；中原英才计划(ZYYCYU202012172)；新加坡教育部(AcRF Tier 1, Grant No. RG70/20)

详细信息

通讯作者:
任永鹏，博士，讲师，硕士生导师，研究方向为材料冶金、功能材料　E-mail: Ren_YP123@163.com

中图分类号: TB331
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- HTML全文浏览量: 45
- 被引次数: 0
出版历程
- 收稿日期: 2023-01-06
- 修回日期: 2023-04-06
- 录用日期: 2023-04-08
- 网络出版日期: 2023-04-24

Research progress of MXene based materials in the field of electrocatalysis

Limeng WANG¹,
Yaru LI^{1, 2},
Yongpeng REN^{1, 2, 3
, ,},
Kunming PAN^{1, 2, 3},
Shuaikai ZHAO¹,
Beibei LV¹

1.
School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China
2.
National and Local Jocal Engineering Research Center for Wear Control and Forming Technology of Metal Materials at Henan University of Science and Technology, Henan Provincial Key Laboratory of High Temperature Structural and Functional Materials, Luoyang 471000, China
3.
Longmen Laboratory, Luoyang 471000, China

Funds: National Natural Science Foundation of China (No. 51901069); The Program for Science & Technology Innovation Talents in the University of Henan Province (22HASTIT1006); The Program for Central Plains Talents (ZYYCYU202012172); The Ministry of Education, Singapore (AcRF Tier 1, Grant No. RG70/20);

摘要

摘要: 目的电催化是未来新能源存储与转化技术的关键，主要应用于电解水制氢和燃料电池等氢能产业。效果较好的催化剂是贵金属基材料(如Pt、Ir、Ru)，然而贵金属具有高成本、低储量的特点，限制了生产中的大规模推广应用。而MXene材料具有高电导率、大比表面积、良好的电荷转移能力以及丰富可控的表面官能团的优势，作为电催化材料的活性物质或载体时均表现出良好的电催化性能。鉴于此，本文综述了近年来国内外MXenes基复合材料电催化剂在析氢反应(HER)、析氧反应(OER)、氧还原反应(ORR)等催化反应中的研究进展，最后总结并展望了MXenes基复合材料未来的发展前景。方法通过搜集整理并分析现有文献，从MXene的晶体结构和微观形貌出发，总结了MXenes基复合材料在电催化领域中具有亲水性、导电性和离子传输、层状结构富含大量的缺陷的优势，通过掺杂或负载金属、非金属、过渡金属化合物的方法，将MXenes与其他材料复合，或在MXenes表面引入缺陷、增加活性位点，有效提升电催化性能，证明了其在催化领域的发展潜力。结果重点综述了近年来MXene基材料在HER、OER、ORR、CORR、NRR、MOR等催化反应中的研究进展，对比了MXenes基复合材料和其他材料的催化性能，并展望其在催化领域的研究方向与应用前景。结论探索MXenes基复合材料催化剂依然存在挑战，未来研究可从以下几方面进行深入研究：(1)代替HF刻蚀MAX的方法有LiF与HCl混合、电化学刻蚀、水热法碱刻蚀等新的无氟刻蚀方法，但进一步探索无氟环保刻蚀剂及制备方法，是确保MXenes能持续发展的重要任务之一。(2)目前，已制备出60多种MXenes材料，但Ti基过渡金属碳化物占绝大部分，其他新型MXenes材料的物理化学性能和机制有待进一步探索。(3) MXenes材料表面官能团丰富，可通过选择路易斯酸的种类控制终端基的类型，但并不能确定所有类型终端基的性质，故对官能团的具体调控机制和方法还需进一步研究。
- MXene /
- 二维材料 /
- 复合材料 /
- 层状结构 /
- 电催化
Abstract: Electrocatalysis is the key technology of new energy storage and conversion in the future, which is mainly used in hydrogen energy industries such as hydrogen production by water electrolysis and fuel cells. MXene is a general term for two-dimensional layered transition metal carbides, nitrides and carbonitrides. It has high conductivity, large specific surface area, good charge transfer ability as well as rich and controllable surface functional groups, which has been widely used in the field of electrochemical catalysis in recent years. In this paper, the multiple structures of two-dimensional MXene are described firstly, and then the advantages of MXene based electrocatalytic materials in hydrophilicity, conductivity, ion transport and surface defects are summarized, with emphasis on the application and progress of MXene based materials in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and other catalytic reactions in recent years, The relationship between MXene structure and performance is revealed. Finally, the future development prospect is summarized and prospected.
- MXene /
- two dimensional materials /
- compound material /
- layered structure /
- electrocatalysis

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图 1 MXene的晶体结构^[24]

Figure 1. Crystal structure of MXene^[24]

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图 2 MAX (a)、MXene(b)和d-MXene(c)的SEM图像；(d)MAX、MXene、d-MXene的XRD图谱^[26]

Figure 2. SEM images of MAX (a)、 MXene(b) and d-MXene (c); (d)XRD patterns of MAX, MXene and d-MXene^[26]

d-MXene—MXene solution with few peeled layers

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图 3 MXene在电催化中的潜在应用^[50]

Figure 3. Potential application of MXene in electrocatalysis^[50]

CO₂RR—Carbon dioxide reduction); NRR—Nitrogen reduction; MOR—Methanol oxidation; hydrogen evolution reaction (HER); OER—Oxygen evolution reaction: ORR—oxygen reduction reaction

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图 4 (a)Mo₂C/Ti₃C₂T_x@NC的合成示意图^[63]；(b)p-N-C—吡啶氮掺杂石墨烯、g-N-C—石墨氮掺杂的石墨烯、Mo₂C、Ti₃C₂T_x及其异质结构的ΔGH值^[63]；(c) Co_xMo_2−xC/MXene/NC合成示意图^[65]；(d)在10 mV/s的扫描速率下，在1.0 mol/L KOH中Co_0.31Mo_1.69C/MXene/NC、Mo₂C/MXene/NC、Co_0.35Mo_1.65C/NC、Co/MXene/NC、MXene/NC和20%Pt/C的HER极化曲线^[65]；(e)在pH值为0.3–13.8的情况下，在ηj=20时，Co_0.31Mo_1.69C/MXene/NC和20%Pt/C之间的比较^[65]

Figure 4. (a)Synthetic schematic diagram of Mo₂C/Ti₃C₂T_x@NC^[63]; (b) The ΔGH of p-N-C—pyridinic N doped graphene、g-N-C—graphitic N doped graphene、Mo₂C、Ti₃C₂T_xand their heterostructures^[63]; (c) Schematic diagram of Co_xMo_2−xC/MXene/NC^[65]; (d) At a scanning rate of 10 mV/s, the HER polarization curves ofCo_0.31Mo_1.69C/MXene/NC、Mo₂C/MXene/NC、Co_0.35Mo_1.65C/NC、Co/MXene/NC、MXene/NCand 20% Pt/C in 1.0 mol/L KOH^[65]; (e) At pH 0.3-13.8 and ηj=20, the comparison between Co_0.31Mo_1.69C/MXene/NC and 20% Pt/C^[65]

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图 5 (a)Co-CNT/Ti₃C₂的合成示意图^[69]；(b)Co-CNT/Ti₃C₂、Pt/C、ZIF-800和Ti₃C₂的LSV曲线^[69]；(c)Co-CNT Ti₃C₂-60和Pt/C的计时电流曲线^[69]；(d)NiCoS/Ti₃C₂T_x合成示意图^[75]；在ηj=10时，NiCoS/Ti₃C₂T_x、NiCoS、NiCo-LDH/Ti₃C₂T_x、NiCo-LDH和RuO₂的(e)LSV曲线和(f)Tafel图^[75]；(g)η=350和400 mV时的TOF值^[75]

Figure 5. (a)Synthesis diagram of Co-CNT/Ti₃C₂^[69]; (b) LSV curves of Co-CNT/Ti₃C₂、Pt/C、ZIF-800 and Ti₃C₂^[69]; (c) Timing current curve of Co-CNT Ti₃C₂-60 and Pt/C^[69]; (d) Schematic diagram of NiCoS/Ti₃C₂T_x synthesis^[75]; (e) LSV curve and (f) Tafel diagram of NiCoS/Ti₃C₂T_x、NiCoS、NiCo-LDH/Ti₃C₂T_x、NiCo-LDH and RuO₂ when ηj=10^[75]; (g) TOF value at η=350 and 400 mV^[75]

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图 6 (a)CeO₂/MXene复合材料的合成示意图^[81]；(b)无氟Ti₃C₂T_x纳米片(50-100 nm)的合成示意图^[85]；(c)NaOH–Ti₃C₂T_x/CC在不同电位下NH₃产率和法拉第效率^[85]；(d)NaOH-Ti₃C₂T_x/CC在重复NRR过程中的稳定性试验中的NH₃产率和法拉第效率^[85]；(e)50 mV/s的扫描速率下,在0.5 mol/L H₂SO₄+0.5 mol/L CH₃OH溶液中Pt/Ti₃C₂ MXene和商用Pt/C的MOR的CV曲线^[92]；(f)在0.5 mol/L H₂SO₄+0.5 mol/L CH₃OH溶液中,0.6 V条件下进行的Pt/Ti₃C₂-MXene的EIS光谱^[92]；(g)Pt/Ti₃C₂ MXene和商业Pt/C在0.5 mol/L H₂SO₄溶液中的线性扫描伏安曲线^[92]

Figure 6. (a)Schematic diagram of the synthesis of CeO₂/MXene composite^[76]; (b) Schematic diagram of the synthesis of fluorine-free Ti₃C₂T_x nanosheet (50-100 nm)^[85]; (c) The NH₃ yield and Faraday efficiency of NaOH–Ti₃C₂T_x/CC at different potentials^[85]; (d) NH₃ yield and Faraday efficiency in the stability test of NaOH–Ti₃C₂T_x/CC in the repeated NRR process^[85]; (e) CV curve of MOR of Pt/Ti₃C₂ MXene and commercial Pt/C in 0.5 mol/L H₂SO₄+0.5 mol/L CH₃OH solution at a scanning rate of 50 mV/s^[92]; (f) EIS spectrum of Pt/Ti₃C₂-MXene in 0.5 mol/L H₂SO₄+0.5 mol/L CH₃OH solution at 0.6 V^[92]; (g) Linear sweep voltammetric curves of Pt/Ti₃C₂ MXene and commercial Pt/C in 0.5 mol/L H₂SO₄ solution^[92]

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表 1 酸性和碱性电解质中的HER反应机制

Table 1. HER reaction mechanism in acidic and alkaline electrolytes

	Acidic electrolyte	Alkaline electrolyte
Volmer reaction	H₃O⁺+e⁻→H_ads+H₂O	H₂O+e⁻→OH⁻+H_ads
Heyrovsky reaction	H_ads+H⁺+e⁻→H₂	H_ads+H₂O+e⁻→OH⁻+H₂
Tafel reaction	H_ads+H_ads→H₂	H_ads+H_ads→H₂
Catalytic mechanism
Notes：H_ads are the adsorbed hydrogen atoms.

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表 2 酸性和碱性电解质中的ORR反应机制

Table 2. ORR reaction mechanism in acidic and alkaline electrolytes

Reaction pathway	Acidic electrolyte	Alkaline electrolyte
Four electrons reaction	O₂+4 H⁺+4 e⁻→2 H₂O	O₂+2 H₂O+4 e⁻→4 OH⁻
Two electrons reaction	O₂+2 H⁺+2 e⁻→H₂O₂H₂O₂→1/2 O₂+H₂O	O₂+2 H₂O+2 e⁻→HO₂⁻+OH⁻HO₂⁻→1/2 O₂+OH⁻

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表 3 酸性和碱性电解质中的OER反应机制

Table 3. HER reaction mechanism in acidic and alkaline electrolytes

	Acidic electrolyte	Alkaline electrolyte
Reaction pathway	H₂O→OH_ads+H⁺+e⁻OH_ads→O_ads+H⁺+e⁻O_ads+H₂O→OOH_ads+H⁺+e⁻OOH_ads→O₂+H⁺+e⁻2 O_ads→O₂	OH⁻→OH_ads+e⁻OH_ads+OH⁻→O_ads+H₂O+e⁻O_ads+OH⁻→OO_ads+e⁻OO_ads+OH⁻→O₂+H₂O+e⁻2 O_ads→O₂
Catalytic mechanism
Notes: O_ads, OH_ads, and OOH_ads are three different oxygen-containing intermediatesH_ads is the adsorbed hydrogen atom. O_ads are oxygen groups; OH_ads are hydroxide groups; OOH_ads are hydroperoxide groups

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表 4 MXene基复合材料和其他常见催化剂的催化性能对比

Table 4. Comparison of catalytic performance between MXene based composite materials and other common catalysts

Classification	Electrocatalyst	Electrolyte	Application	Overpotential^a/mV	Tafel slope/mV·dec⁻¹	Ref.
MXene based composite materials	Pt-Ti₃C₂T_x	0.5 mol/L H₂SO₄	HER	55	65	[54]
	Pt_3.21Ni@Ti₃C₂	0.5 mol/L H₂SO₄	HER	18.55	13.37	[56]
	Ni_0.9Co_0.1@NTM	l .0 mol/L KOH	HER	43.4	116	[58]
	MoS₂⊥Ti₃C₂T_x	0.5 mol/L H₂SO₄	HER	95	40	[59]
	Co-MoS₂ /Mo₂CT_x	1.0 mol/L KOH	HER	112	85.7	[60]
	1 T/2 H MoSe₂-Ti₃C₂T_x	1.0 mol/L KOH	HEROER	95340	9190	[61]
	Mo₂TiC₂T_x-Pt_SA	0.5 mol/L H₂SO₄	HER	30	30	[62]
	Mo₂C/Ti₃C₂T_x@NC	0.5 mol/L H₂SO₄	HER	53	40	[63]
	Co-CNT/Ti₃C₂	0.1 mol/L KOH	ORR	—	63	[69]
	TCCN	0.1 mol/L KOH	ORR	—	74.6	[73]
	CoNi-LDH/Ti₃C₂T_x	1.0 mol/L KOH	OER	257.4^b	68	[74]
	NiCoS/Ti₃C₂T_x	1.0 mol/L KOH	OER	365	58.2	[75]
	BP QDs/MXene	1.0 mol/L KOH	HEROER	190360	8364.3	[76]
Other materials	Ti₃C₂@mNiCoP NS	1.0 mol/L KOH	HEROER	127237	103104	[77]
	Al-Ni₃S₂/NF	1.0 mol/L KOH	HEROER	86223	7537	[93]
	Ni-Fe-W-LDHs/NF	1.0 mol/L KOH	OER	247^b	55	[94]
	NiO/NiCoP	1.0 mol/L KOH	HER	112	56	[95]
	Mo₂C/CNT-GR	0.5 mol/L H₂SO₄	HER	130	58	[96]
	W₂C/MWNT	0.5 mol/L H₂SO₄	HER	123	45	[97]
	FeCoNiCuPtIr	1.0 mol/L KOH	HEROER	21255	54.561.7	[98]
Notes：NTM—Nb-doped Ti₃C₂T_x MXene nanohybrids; Pt_SA—A single Pt atom is fixed at a molybdenum vacancy; NC—Nitrogen doped carbon layer packaging; CNT—Carbon nanotube; TCCN—Overlapped g-C₃N₄ and Ti₃C₂ nanosheets; LDH—Layer double hydroxides; BP QDs—Black phosphorus quantum dots; NS—Nanosheets; NF—Nickel foam; GR—Graphene; MWNT—Multi-walled carbon nanotubes; ^a The overpotential and cell voltage are obtained at the current density of 10 mA·cm^-2; ^b The overpotential and cell voltage are obtained at the current density of 100 mA·cm^-2.

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