Electrocatalytic Hydrogen Evolution Performance of Two-dimensional Mo2CTx MXene Materials: A Review from Preparation to Application

doi:10.15541/jim20250023

Abstract

Abstract:

MXenes, an emerging family of two-dimensional (2D) materials with high electronic conductivity, large specific surface area, good hydrophilicity, and regulable surface functional groups, have shown broad application potential across the domains of energy, catalysis, corrosion prevention, and electromagnetic shielding. Among numerous MXenes, Mo₂CT_x MXene has attracted much attention due to its excellent electrocatalytic hydrogen evolution activity. This paper aims to systematically review its preparation and current research status in the field of electrocatalytic hydrogen evolution, providing a comprehensive and clear reference framework for further in-depth study. The synthesis methodologies and exfoliation techniques in recent years are comprehensively reviewed, the important role as an electrocatalyst for hydrogen evolution reaction (HER) is summarized, and the optimization strategies for improving catalytic performance of HER are addressed from perspectives of terminated group modification, elemental doping, and hybridization. Finally, a prospective outlook regarding Mo₂CT_x MXene-based composites in the realm of electrocatalytic hydrogen evolution is presented. Despite significant research advancements on Mo₂CT_x MXene, the absence of eco-friendly and scalable preparation methodologies remains a critical challenge, contributing to elevated production costs. Additionally, the delayed progress in catalytic mechanism investigations hinders the formulation of rational design strategies. Henceforth, efforts should focus on developing green, fluorine-free synthetic approaches to facilitate large-scale material production, concurrently enhancing catalytic activity and catalyst stability, and accelerating the exploration of catalytic mechanisms. These endeavors are critical to advancing the practical application of Mo₂CT_x and its composite materials in the field of electrocatalytic hydrogen evolution.

Key words: MXene, Mo₂CT_x, electrocatalytic hydrogen evolution, review

CLC Number:

TB34

ZOU Minmin, LIU Jingxin, HU Haolin, ZENG Dongmei, ZHANG Ting, ZHANG You. Electrocatalytic Hydrogen Evolution Performance of Two-dimensional Mo₂CT_x MXene Materials: A Review from Preparation to Application[J]. Journal of Inorganic Materials, 2025, 40(11): 1173-1187.

Figures/Tables 10

Fig. 1 Main synthesis techniques of Mo2CTx

Table 1 Experimental parameters of Mo2CTx prepared by different etching methods[11,31,34 -44]

Method	MAX	Etching solution	Temperature/℃	Time/h	Ref.
Fluoride etching	Mo₂Ga₂C	50% HF	50	3	[34]
		LiF+HCl	35	384	[35]
		HF	55	158.4	[35]
		LiF+HCl, NaF+HCl, KF+HCl & NH₄F+HCl	140	24	[31]
		48% HF	140	96	[42]
	Mo₂SnC	HF	60	72	[43]
Alkali etching	Mo₃AlC₂	NaOH+Na₂S	220	2	[38]
Alkali etching	Mo₂Ga₂C	20 mol/L NaOH	180	24	[44]
Molten salt etching	Mo₂Ga₂C	NaCl, KCl & CuCl₂	600	0.5	[11]
Molten salt etching	Mo inks	KCl salt template	900	3	[40]
UV induced etching	Mo₂Ga₂C	UV+H₂PO₄	RT	3-5	[36]
UV induced etching	Mo-In-C	85% H₃PO₄+UV	RT	3-5	[37]
Other etching	Mo₂Ga₂C	CTAB+HCl	160	24	[39]
		HBr	220	72	[41]
		LiBr+HBr, NaBr+HBr & NH₄Br+HBr	180	24	[41]

Fig. 2 Preparation of Mo2CTx by the top-down method[34,39 -40] (a) XRD patterns and (b, c) TEM images of Mo2C prepared by HF etching[34]; (d) Representative AFM images of 2D Mo2C flakes of different thicknesses[40]; (e) Polarization curves obtained from 2D Mo2C microcell devices with flake thickness from 10 layers down to monolayer[40]; (f) Schematic diagram of the preparation of Mo2C MXene by CTAB etching[39]

Fig. 3 Preparation of Mo2CTx by the bottom-up method[50,53,55] (a) Synthesis of Mo2C by CVD[50]; (b) Optical microscopy image of Mo2C[53]; (c) Optical microscopy images of 2D ultrathin α-Mo2C crystals with a uniform thickness of ~3 nm[53]; (d) LSV curves and (e) Tafel plots of Mo2CTx/G[50]; (f, g) Cross-sectional HRTEM images of (f) Mo2C-MoS2 junction and (g) fully converted Mo2C[55]

Fig. 4 Schematic diagram of etching, intercalation and exfoliation processes of Mo2CTx

Table 2 Electrocatalytic hydrogen evolution performance of Mo2CTx and its composites[14,20 -21,23 -24,38,61 -73]

Electrocatalyst	Electrolyte	Overpotential@ 10 mA·cm^-2/mV	Tafel slope/(mV·dec^-1)	Ref.
Mo₂CT_x	0.5 mol/L H₂SO₄	283	-	[14]
Mo₂CT_x-F	0.5 mol/L H₂SO₄	189	75	[20]
P-Mo₂CT_x	0.5 mol/L H₂SO₄	186	-	[21]
N-Mo₂CT_x	1 mol/L KOH	191	88	[61]
Ru/Mo₂CT_x	1 mol/L PBS	73	57	[62]
Co-MoS₂/Mo₂CT_x	1 mol/L KOH	112	82	[63]
MoS₂/Mo₂CT_x	1 mol/L KOH	176	-	[23]
MoS₂/Mo₂CT_x	1 mol/L KOH	110±7	65	[38]
Mo₂CT_x/2H-MoS₂	0.5 mol/L H₂SO₄	119	60	[64]
MoS₂/Mo₂CT_x	1 mol/L KOH	150	70	[65]
MoS₂/Mo₂CT_x	0.5 mol/L H₂SO₄	243	81	[66]
MoSe₂/Mo₂CT_x	0.5 mol/L H₂SO₄	108.3	70.7	[24]
Pt/NBF-ReS₂/Mo₂CT_x	0.5 mol/L H₂SO₄	29	24	[67]
Pt/NBF-ReS₂/Mo₂CT_x	1 mol/L KOH	37	36	[67]
NBF-CoSe/Mo₂CT_x	0.5 mol/L H₂SO₄	70	30	[68]
NBF-CoSe/Mo₂CT_x	1 mol/L KOH	81	29	[68]
Ru/NBF-NiSe₂/Mo₂CT_x	0.5 mol/L H₂SO₄	30	25	[69]
Ru/NBF-NiSe₂/Mo₂CT_x	1 mol/L KOH	39	29	[69]
NiS/Mo₂CT_x	0.5 mol/L H₂SO₄	157	77	[70]
CoP/Mo₂CT_x	1 mol/L KOH	78	66	[71]
NBF-BiOBr/Bi₂Se₃/Mo₂CT_x	0.5 mol/L H₂SO₄	109	36	[72]
Mo₂CT_x/PDTDA/rGO	1 mol/L KOH	59	44	[73]

Fig. 5 Characterization of heteroatom-doped Mo2CTx materials[21,61] (a) XRD patterns, (b) LSV curves and (c) Nyquist plots of P-Mo2CTx[21]; (d) LSV curves of N-Mo2CTx[61]; (e) H atoms free energy barriers for different structures[61]

Fig. 6 Characterization of Mo2CTx/precious metal hybrid materials[62,76] (a) SEM image, (b) LSV curves and (c) Tafel plots of Ru/Mo2CTx[62]; (d-f) Top and side views of the geometry of Pd4-6 on bare Mo2C, Mo2CO2 and Mo2CF2 with blue, red, purple, brown, and cyan dots representing Pd, O, F, C, and Mo atoms, respectively[76]; (g-i) Top and side views of the geometry of Au4-6 on bare Mo2C, Mo2CO2 and Mo2CF2 with yellow, red, purple, brown, and cyan dots representing Au, O, F, C, and Mo atoms, respectively[76]

Fig. 7 Characterization of Mo2CTx/transition metal compound hybrid materials[24,38,63 -64,66,71] (a) LSV curves of Co-MoS2/Mo2CTx[63]; (b) Stability of Co-MoS2/Mo2CTx nano-arrays measured by chronocurrent method[63]; (c) Polarization curves of Co-MoS2/Mo2CTx electrode before and after 1000 CV cycles at 100 mV·s-1[63]; (d) HER polarization curves after 10 and 3000 cycles of Mo2CTx and MoS2/Mo2CTx[38]; (e) Schematic diagram of Mo2CTx/2H-MoS2 synthesis[64]; (f) SEM image of MoS2/Mo2CTx[66]; (g) HRTEM image of MoSe2/Mo2CTx@C nanohybrids[24]; (h) HER and (i) OER polarization curves of CoP/Mo2CTx[71]

Fig. 8 Characterization of other Mo2CTx-based hybrid materials[72-73] (a) HRTEM image, (b) LSV curves and (c) Tafel plots of NBF-BiOBr/Bi2Se3/Mo2CTx[72]; (d) SEM image, (e) LSV curves and (f) Tafel plots of Mo2CTx/PDTDA/rGO[73]

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Electrocatalytic Hydrogen Evolution Performance of Two-dimensional Mo₂CT_x MXene Materials: A Review from Preparation to Application

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