过渡金属碳氮化物在电催化领域的应用: 改性和杂化

doi:10.1016/S1872-2067(21)64030-5

摘要/Abstract

摘要：

化石能源过度消耗导致的环境污染问题使发展绿色可持续替代能源成为人们需要面对的重要问题. 寻找绿色高效的方法生产可再生燃料是一个有效的策略, 在减少二氧化碳排放的同时可满足能源需求. 电催化是一种实现清洁能源的重要途径, 可将地球上含量丰富的H₂O, N₂, CO₂和O₂等转化为燃料和化合物. 尽管贵金属Pt, RuO₂等具有优异的电催化性能, 但由于成本高、储量少限制了其大规模应用, 因此开发一种高活性且低成本的电催化剂是实现大规模应用的关键. 由于具有独特的形貌和电子结构, 石墨烯, 黑磷和二硫化钼等二维材料已经在电催化领域得到了广泛应用. 作为一种新型的二维材料, 碳化物、氮化物和碳氮化物(MXenes)不仅具有良好的机械性能和大比表面积, 其较好的导电性和基底面上丰富的活性位点在促进可持续能源发展方面发挥了更重要的作用. 自MXenes首次被用于析氢反应(HER)以来, 大量的工作预测并合成了具有多种元素的MXenes及其复合材料, 并用于电催化反应.

本文从理论和实验两方面综述了基于MXenes在HER、析氧反应(OER)和氧还原反应(ORR)方面的研究进展, 包括对原始MXenes的结构形态调控和对杂化MXenes的修饰. 简要介绍了MXenes的蚀刻合成法(氢氟酸蚀刻、熔融盐蚀刻和电化学蚀刻等), 提出了设计MXene基电催化剂的基本原则(提高稳定性、导电性和固有活性)并将其电催化性能与M, X, T和空位以及形貌的关系进行了总结. 对于HER, 原始MXene表面的氧官能团是活性位点, 通过调节M, X和空位的类型可以调节表面氧原子的电子结构, 从而使氢吸附吉布斯自由能趋于零, 提高MXene的固有活性. 对于OER和ORR, 原始MXene不具备固有催化活性, 然而某些金属(Pt, Ru等)在T位上以单原子形式掺杂从而形成的MXene基单原子催化剂表现出良好的催化性能. 在总结了原子取代、功能修饰、缺陷工程和形貌控制等方面的研究策略后, 重点讨论了MXenes与金属纳米颗粒、氧化物、氢氧化物、硫化物、磷化物等其他纳米结构异质结的构建. 最后提出了MXenes目前面临的问题和挑战, 并展望了其在电催化领域的应用前景.

关键词: 析氢反应, 过渡金属碳氮化物, 析氧反应, 氧还原反应, 水分解

Abstract:

Two-dimensional carbides, nitrides, and carbonitrides (MXenes) play important roles in promoting the development of sustainable energy because they have abundant reactive sites on their surfaces. An increasing number of MXenes with diverse elements and composites have been predicted and synthesized for electrocatalysis applications since the first report of a Ti-Mo-based MXene for the hydrogen evolution reaction (HER). Herein, we summarize the progress of MXene-based electrocatalysts for the HER, the oxygen evolution reaction, and the oxygen reduction reaction, including regulated pristine MXenes and modified hybrid MXenes, from both theoretical and experimental perspectives. A brief overview on MXene synthesis is presented first, accompanied by a discussion on the relationship between electrocatalytic properties and M, X, T, vacancies, and morphologies. After reviewing strategies in terms of atom substitution, functional modification, defect engineering, and morphology control, we emphasize the construction of heterojunctions between MXenes and other nanostructures, such as metal nanoparticles, oxides, hydroxides, sulfides, and phosphides. We finally discuss prospects for the future development of MXene-based electrocatalysts.

Key words: Hydrogen evolution reaction, MXene, Oxygen evolution reaction, Oxygen reduction reaction, Water splitting

白雪, 管景奇. 过渡金属碳氮化物在电催化领域的应用: 改性和杂化[J]. 催化学报, 2022, 43(8): 2057-2090.

Xue Bai, Jingqi Guan. MXenes for electrocatalysis applications: Modification and hybridization[J]. Chinese Journal of Catalysis, 2022, 43(8): 2057-2090.

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图/表 34

Fig. 1. Structural diagrams of typical MXenes.

Fig. 2. Theoretical calculational model of an MXene. Side (a) and top (b) views of a pristine MXene; Side views of T-doped (c), M-doped (d), and X-doped (e) MXenes; Side views of VT-MXene (f), VM-MXene (g); and VX-MXene (h).

Fig. 3. (a) Schematic diagram of the HER mechanism. (b) Top view of the structure of bare MXene with different adsorption sites. (c) HER volcano plot; (d) Enlargement of the top of the volcano. (a?d) Reprinted with permission from Ref. [26]. Copyright 2016, American Chemical Society. (e) ΔGH* under standard conditions at USHE = 0 V. (f) Band structures at each nitrogen-doping concentration. Each green solid line corresponds to the conduction band. (e,f) Reprinted with permission from Ref. [57]. Copyright 2021, American Chemical Society.

Fig. 4. Schematic diagrams showing the mechanisms associated with the OER (a) and ORR (b).

Fig. 5. Calculated stress-strain curves of 2D Ti2C (a) and 2D Ti2CO2 (c). (b) Variations in the bond lengths (Ti-C) and out-of-plane heights of Ti atoms. (d) Variations in the out-of-plane heights of Ti atoms and O atoms. Reprinted with permission from Ref. [76]. Copyright 2016, American Physical Society.

Fig. 6. (a) Schematic diagram showing the formation of an MXene by fluoride etching. Reprinted with permission from Ref. [88]. Copyright 2020, Elsevier. (b) Fluoride-free electro-etching equipment with a dual electrode system. Reprinted with permission from Ref. [95]. Copyright 2018, Wiley-VCH. (c) Schematic diagram showing the mechanism for the synthesis of an MXene in a Lewis-acid molten salt. Reprinted with permission from Ref. [97]. Copyright 2019, American Chemical Society. (d) Schematic diagram of the device used to react Ti3AlC2 in an aqueous NaOH solution. Reprinted with permission from Ref. [100]. Copyright 2018, Wiley-VCH.

Fig. 8. Feedback mode (a,c,e) and corresponding SG-TC mode (b,d,f) SECM images of three V-Ti4N3Tx samples. Reprinted with permission from Ref. [116]. Copyright 2020, WILEY-VCH. (g) In-situ Raman spectra of NiCo2O4/MXene at various applied potentials. Reprinted with permission from Ref. [118]. Copyright 2020, American Chemical Society.

Fig. 9. (a) Structure diagram for BP@MXene; Normalized Ti K-edge XANES spectra (b) and k3-weighted Fourier-transformed Ti K-edge XANES spectra (c). Reprinted with permission from Ref. [122]. Copyright 2021, American Chemical Society.

Fig. 10. LSV (a) and Tafel plots (b) of various Ti3C2Tx systems. (a,b) Reprinted with permission from Ref. [129]. Copyright 2017, American Chemical Society. (c) Optimized structures of selected MXenes. The distances between the terminators and the first Ti layer are also shown. Reprinted with permission from Ref. [133]. Copyright 2018, American Chemical Society.

Fig. 11. (a) Model of the Mo2CTx:Co structure; LSV curves (b) and Tafel plots (c). (a?c) Reprinted with permission from Ref. [137]. Copyright 2019, American Chemical Society. (d) Top and side views of transition metal carbonitride models; Values of ΔGH on the C-sides (e) and N-sides (f) of MXenes. Reprinted with permission from Ref. [139]. Copyright 2018, Wiley-VCH.

Fig. 12. (a-e) HAADF-STEM images of defects in single-layer Ti3C2Tx. (f) VTi formation energies on bare Ti3C2 and terminated single-layer Ti3C2Tx; (g) Formation energy of VTiC clusters as a function of the VTi number. Reproduced with permission [140]. Copyright 2016 American Chemical Society.

Fig. 13. (a) AFM image of TBA-Ti3C2Tx. (b) Ar adsorption and desorption isotherms. Reprinted with permission from Ref. [111] Copyright 2019, American Chemical Society. (c) Depicting the merits of a 3D MXene. SEM images of 3D Ti3C2 (d), pristine Ti3C2 MXene after being compressed (e), and vacuum filtered Ti3C2 MXene (f). The insets show images of materials dispersed in water after ultrasonication. Reprinted with permission from Ref. [146]. Copyright 2018, American Chemical Society.

Fig. 14. (a) Degradation of Ti3C2Tx in various environments. (b) MXene oxidation mechanisms at various pH values. Three methods for improving the structure and activity of an MXene: (c) layer-spacing expansion; (d) stereo-model assembly; (e) active-phase decoration.

Fig. 15. Syntheses of SA-Cu-MXene (a), RuSA-N-S-Ti3C2Tx (b), and Cu-SA/Ti3C2Tx (c). (a) Reprinted with permission from Ref. [36]. Copyright 2021, American Chemical Society. (b) Reprinted with permission from Ref. [165]. Copyright 2019, Wiley-VCH. (c) Reprinted with permission from Ref. [167]. Copyright 2021, Macmillan Publishers Limited.

Fig. 16. (a) Four different oxygen vacancy sites and four different neighboring adsorption sites for the 4 × 4 supercell structure. (b) Theoretical calculational results for six pairs of metal atoms adsorbed onto the eight DAC sites in (a). (c,d) Calculated Gibbs free energy differences (ΔG) for the elem entary reaction steps along OER and ORR pathways. Reprinted with permission from Ref. [169]. Copyright 2021, Wiley-VCH GmbH.

Fig. 17. DFT calculational system. (a) Structure of an OBA and possible oxygen adsorption sites. (b) Promising OBA HER catalysts. Reprinted with permission from Ref. [176]. Copyright The Royal Society of Chemistry 2020.

Fig. 18. (a) Synthesis of a N-doped MXene. Reprinted with permission from Ref. [180]. Copyright 2019, American Chemical Society. (b,c) Deconvoluted XPS spectra of N-MXene-T; LSV traces (d) and Tafel slopes (e) of N-MXene-T. Reprinted with permission from Ref. [182]. Copyright 2020, Elsevier.

Fig. 19. (a) Synthesis of Nb1.33CTx; HRTEM image (b) and the top-view schematic (c) of Nb1.33CTx. Reprinted with permission from Ref. [191]. Copyright 2018, American Chemical Society. (d-f) Formation of defects in Ti3CNTx. (g) Three types of N active site; N 1s XPS spectra of Ti3AlCN (h) and Ti3CNTx (i). Reprinted with permission from Ref. [192]. Copyright 2021, Elsevier. (j,k) Modulating the HER performance of V2CO2 by introducing a transition metal onto the surface. Reprinted with permission from Ref. [194]. Copyright 2016, WILEY-VCH.

Fig. 20. Syntheses of VO-Nb2O5/Nb2C (a), VS-CdS/Ti3C2 (b), o-P-CoTe2/MXene (c), and MoxS@TiO2@Ti3C2 (d). (a) Reprinted with permission from Ref. [199]. Copyright 2020, Elsevier. (b) Reprinted with permission from Ref. [200]. Copyright 2021, Elsevier. (c) Reprinted with permission from Ref. [201]. Copyright 2021, Wiley-VCH. (d) Reprinted with permission from Ref. [203]. Copyright 2019, Elsevier.

Fig. 21. (a) Synthesis of Ti3C2 NFs; High-magnification SEM (b) and TEM (c) images of Ti3C2 NFs. Reprinted with permission from Ref. [207]. Copyright 2018, American Chemical Society. (d) Synthesis of a multilevel hollow MXene tailored low-Pt catalyst; SEM images (e,f), TEM image (g) and HRTEM image (h) of the mh-3D MXene with a honeycomb surface. Reprinted with permission from Ref. [209]. Copyright 2020, Wiley-VCH.

Table 1 MXenes modified using different strategies for use in the HER/OER.

Modification strategy	Catalyst	Electrolyte	Application		η₁₀ (mV)	Tafel slope (mV dec^-1)	Ref.
Surface modification	Mo₂CT_x	0.5 mol/L H₂SO₄	HER		189	75	[129]
	E-Ti₃C₂O_x	0.5 mol/L H₂SO₄		HER	190	60.7	[154]
	E-Ti₃C₂(OH)_x	0.5 mol/L H₂SO₄		HER	217	88.5
	E-Ti₃C₂T_x-450	0.5 mol/L H₂SO₄		HER	266	109.8
	Ti₂CT_x nanosheets	0.5 mol/L H₂SO₄	HER		170	100	[131]
	I-Na-Ti₃C₂T_x/MoS₂	0.5 mol/L H₂SO₄	HER		139	78	[211]
	P-Mo₂CT_x	0.5 mol/L H₂SO₄	HER		186	—	[157]
	Ti₃C₂T_x:Co-12h	1 mol/L KOH	HER		103.6	104.42	[58]
	Ru-SA/Ti₃C₂T_x	0.1 mol/L HClO₄	HER		70	27.7	[121]
		0.1 mol/L HClO₄	OER		290	37.9
		0.1 mol/L HClO₄	ORR		0.82 (E_1/2/V)	60.4
Lattice substitution	Mo₂TiC₂T_x	0.5 mol/L H₂SO₄	HER		248	74	[129]
	Mo₂Ti₂C₃T_x	0.5 mol/L H₂SO₄	HER		275	99	[129]
	Ru_SA-N-Ti₃C₂T_x	0.5 mol/L H₂SO₄	HER		23	42	[166]
	Ru_SA-N-Ti₃C₂T_x	1 mol/L KOH	HER		28	29	[166]
	Ru_SA-N-S-Ti₃C₂T_x	0.5 mol/L H₂SO₄	HER		76	90	[165]
	Mo₂CT_x:Co	1 mol/L H₂SO₄	HER		180	59	[137]
	Ni_0.9Co_0.1@NTM	1 mol/L KOH	HER		43.4	116	[173]
	N-Ti₃C₂T_x@600	0.5 mol/L H₂SO₄	HER		198	92	[180]
	N-MXene-35	0.5 mol/L H₂SO₄	HER		162	69	[182]
	P₃-V₂CT_x	0.5 mol/L H₂SO₄	HER		163	74	[189]
	Ti₃C_1.6N_0.4	1 mol/L KOH	OER		—	216.4	[190]
Defect engineering	Ti₃C₂T_x-N₆	1 mol/L KOH	HER		119.17	61.81	[27]
	Ti₃C₂T_x-N₆	1 mol/L KOH	OER		360	76.68	[27]
	D-Mo₂TiC₂/Ni	0.1 mol/L H₂SO₄	HER		780	56.7	[174]
	Mo₂TiC₂O₂-V_Mo	0.5 mol/L H₂SO₄	HER		—	44	[172]
	Mo₂TiC₂O₂-Pt_SA	0.5 mol/L H₂SO₄	HER		30	30	[172]
Morphology control	CoP@3D Ti₃C₂-MXene	1 mol/L KOH	HER		168	58	[146]
	3D MX (35%)/NG	0.5 mol/L H₂SO₄	OER		298	51	[212]
	Nb₄C₃T_x-180	1 mol/L KOH	HER		398	122.2	[213]
	Ti₃C₂ NFs	0.5 mol/L H₂SO₄	HER		169	97	[207]
	MoS₂/Ti₃C₂T_x	0.5 mol/L H₂SO₄	HER		152	70	[208]
	W₂C@WS₂ nanoflowers	0.5 mol/L H₂SO₄	HER		320	55.4	[210]
	Pt@mh-3D MXene	1 mol/L KOH	HER		27	42	[209]

Fig. 22. Different MXene-based heterojunction structures.

Fig. 23. (a) HAADF-STEM image of used Pt/Ti3C2Tx-550. (b) DFT calculations. (c) HER polarization curves and (d) a magnification of the 0?10 mA region. (e) Mass activity and (f) specific activity of catalysts. (g) Tafel curves. (h) Nyquist plots of Pt/Ti3C2Tx. Reprinted with permission from Ref. [85]. Copyright 2019, American Chemical Society.

Fig. 24. (a) Polarization curves. (b) A comparison of the catalysts in onset potential and overpotential at j = 10 mA cm-2. (c) Tafel plots. (d) time-dependent current density curves at η = 130 mV for MoS2/Ti3C2-MXene@C catalyst. (e) Polarization curves after continuous potential sweeps of 2000 cycles. (f) EIS spectra at η = 100 mV. Reprinted with permission from Ref. [236]. Copyright 2017, Wiley-VCH. (g) Schematic diagram of the MoS2-Ti3C2 compound. (h) Single-layer polymorph mode of MoS2. (i,k) HRTEM images of the top profile of MoS2-Ti3C2. (j,l) HRTEM images of epitaxial MoS2 flakes in MoS2-Ti3C2. Reprinted with permission from Ref. [115]. Copyright 2021, Elsevier.

Fig. 25. (a) Synthesis of NFPS@MXene. Reprinted with permission from Ref. [250]. Copyright 2018, WILEY-VCH. (b) Schematic depicting the oxidation of the metal center and the anionic components with subsequent deposition. (c) Dissolved concentrations of Co, P and Se in the electrolyte after the OER. (d) P and Se contents of catalysts before and after the OER. Reprinted with permission from Ref. [120]. Copyright 2019, The Royal Society of Chemistry.

Fig. 26. (a) Structural models of CoxMo2-xC/NG and Mo2C/NG. (C: silver, N: blue, Mo: green, and Co: purple). DFT-calculated HER free energies (b) and reaction energies (d) for water dissociation on CoxMo2-xC/NG and Mo2C/NG; UPS (c) and FTIR-ATR spectra (e) of CoxMo2-xC/MXene/NC and Mo2C/MXene/NC. Reprinted with permission from Ref. [263]. Copyright 2019, Wiley-VCH.

Fig. 27. (a) Synthesis of TiOF2@Ti3C2Tx. (b) Interfacial structure of TiOF2@Ti3C2Tx. Reprinted with permission from Ref. [273]. Copyright 2019, Elsevier. (c) Synthesis of PtOaPdObNPs@Ti3C2Tx. Reprinted with permission from Ref. [272]. Copyright 2018, American Chemical Society. (d) Synthesis of Mn3O4/MXene. Reprinted with permission from Ref. [274]. Copyright 2017, The Royal Society of Chemistry.

Fig. 28. Syntheses of CoFe-LDH/MXene (a), FeNi-LDH/Ti3C2-MXene (b), NiFeCe-LDH/MXene (c), and TTL (d). (a) Reprinted with permission from Ref. [280]. Copyright 2019, Elsevier. (b) Reprinted with permission from Ref. [127]. Copyright 2017, Elsevier. (c) Reprinted with permission from Ref. [279]. Copyright 2020, Science Press. (d) Reprinted with permission from Ref. [283]. Copyright 2018, The Royal Society of Chemistry.

Fig. 29. (a) Local densities of states of surface C atoms on freestanding N-doped graphene and that supported by a V2C monolayer. (b) The pz band center (top panel) and work function (bottom panel) as functions of the lowest binding energy of the OH* species for various graphene/MXene heterostructures (colored open circles) and for GN. (c) DOSs of the pz orbitals of O* species adsorbed on various graphene/MXene heterostructures and on GN. (d) Schematic diagram showing orbital hybridization between C and adsorbate atoms to form fully filled bonding (σ) and antibonding (σ*) orbitals. Reprinted with permission from Ref. [287]. Copyright 2018, The Royal Society of Chemistry. (e) Preparation of fabrication of MXene@Pt/SWCNTs. Reprinted with permission from Ref. [164]. Copyright 2020, WILEY-VCH.

Fig. 30. (a) Synthesis of BPQD/TNS. Reprinted with permission from Ref. [301]. Copyright 2018, WILEY-VCH. (b,c) HER and OER performance of BP QDs/MXene. (d) Computational models for BP, Ti3C2Tx and BP QDs/MXene. (e) Diagram showing calculated ΔG for the HER on various electrocatalysts. Sites 1 and 2 that correspond to the adsorption of H* above the BP QDs and near the interface are highlighted in red. Reprinted with permission from Ref. [235]. Copyright 2018, The Royal Society of Chemistry.

Table 2 HER performance data for MXene-based hybrids.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Ref.
Ru@B-Ti₃C₂T_x	0.5 mol/L H₂SO₄	62.9	100	[29]
Pt NCs-MXene	0.5 mol/L H₂SO₄	40	50.8	[59]
40Pt-TBA-Ti₃C₂T_x	0.5 mol/L H₂SO₄	67.8	69.8	[110]
TBA-Ti₃C₂T_x-Pt-20	0.5 mol/L H₂SO₄	55	65	[111]
Pt/Ti₃C₂T_x-550	1 mol/L KOH	32.7	32.3	[85]
Ti₃C₂T_x@0.1Pt	0.5 mol/L H₂SO₄	43	80	[89]
P-Mo₂C/Ti₃C₂@NC	0.5 mol/L H₂SO₄	177	57.3	[135]
MoS₂/Ti₃C₂-MXene@C	0.5 mol/L H₂SO₄	135	45	[236]
Mo₂CT_x/2H-MoS₂	0.5 mol/L H₂SO₄	119	60	[238]
MoS₂⊥Ti₃C₂@220	0.5 mol/L H₂SO₄	95	40	[239]
MD-Ti₃C₂/MoS_x-100	0.5 mol/L H₂SO₄	165	41	[244]
MoS₂-Ti₃C₂	0.5 mol/L H₂SO₄	98	45	[115]
CoS₂@MXene	0.1 mol/L KOH	175	97	[65]
TiOF₂@Ti₃C₂T_x	0.5 mol/L H₂SO₄	103	56.2	[273]
S-M-5Pt	0.5 mol/L H₂SO₄	62	78	[164]
PtO_aPdO_bNPs@Ti₃C₂T_x	0.5 mol/L H₂SO₄	26.5	39	[272]
CoP/MXene	1 mol/L KOH	113	57	[120]
CoP/Ti₃C₂ MXene	0.5 mol/L H₂SO₄	71	57.6	[258]
	1 mol/L PBS	124	96.8
	1 mol/L KOH	102	68.7
Ti₃C₂@mNiCoP	1 mol/L KOH	127	103	[260]
Ti₂NT_x@MOF-CoP	1 mol/L KOH	112	67.1	[66]
	1 mol/L PBS	131	125.6
	0.5 mol/L H₂SO₄	129	96.7
Co_0.31Mo_1.69C/MXene/NC	0.5 mol/L H₂SO₄	81	24	[263]
	0.1 mol/L PBS	126	46
	1 mol/L KOH	75	32
P-TiO₂@Ti₃C₂	1 mol/L KOH	97	48.4	[202]
MX@C	1 mol/L KOH	134	32	[206]
NiS₂/V-MXene	1 mol/L KOH	179	85	[245]
Co-MoS₂/Mo₂CT_x	1 mol/L KOH	112	82	[234]
Ag@N-Ti₃C₂T_x	1 mol/L KOH	153	137.9	[223]
Ni₂P/Ti₃C₂T_x/NF	1 mol/L KOH	135	86.6	[226]
3D CNTs@Ti₃C₂T_x	1 mol/L KOH	93	128	[294]
1T/2H MoSe₂/MXene	1 mol/L KOH	95	91	[248]
NiSe₂/Ti₃C₂T_x	2 mol/L KOH	200	37.7	[246]
Ni_0.7Fe_0.3PS₃@MXene	1 mol/L KOH	282	36.5	[250]
VOOH/Ti₃C₂T_x	1 mol/L KOH	100	81.8	[216]
NiFe-LDH/MXene/NF	1 mol/L KOH	132	70	[126]
NiFe₂O₄/Ti₃C₂	0.5 mol/L KOH	173	112.2	[31]
Co-CoO/Ti₃C₂-MXene	1 mol/L KOH	45	47	[220]
BP QDs/MXene	1 mol/L KOH	190	83	[235]

Table 3 OER performance data for MXene-based hybrids.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Ref.
CoNi-ZIF-67@Ti₃C₂T_x	0.1 mol/L KOH	323	65.1	[266]
Ti₃C₂T_x/TiO₂/NiFeCo-LDH	0.1 mol/L KOH	320	98.4	[283]
PtO_aPdO_bNPs@Ti₃C₂T_x	0.1 mol/L KOH	320	78	[272]
Co-CoO/Ti₃C₂-MXene	1 mol/L KOH	271	47	[220]
NiFe₂O₄/Ti₃C₂	0.5 mol/L KOH	266	73.6	[31]
FeOOH NSs/Ti₃C₂	1 mol/L KOH	400	95	[276]
M₃OOH@V₄C₃T_x	1 mol/L KOH	275.2	51.4	[277]
Ti₃C₂T_x-FeOOH	1 mol/L KOH	430	31.7	[278]
CoFe-LDH/MXene	1 mol/L KOH	319	50	[280]
FeCo-LDH/MXene	1 mol/L KOH	268	85	[281]
NiFeCe-LDH/MXene	1 mol/L KOH	260	42.8	[279]
FeNi-LDH/Ti₃C₂-MXene	1 mol/L KOH	298	43	[127]
Co-LDH@Ti₃C₂T_x	1 mol/L KOH	340	82	[282]
CoNi LDH/Ti₃C₂T_x	1 mol/L KOH	—	68	[119]
NiFe LDH/N₁₀TC/NF	1 mol/L KOH	196	68.4	[221]
NiCoFe-LDH/Ti₃C₂ MXene/ NCNT	0.1 mol/L KOH	332	60	[30]
VOOH/Ti₃C₂T_x	1 mol/L KOH	238	81.6	[216]
NiFe-LDH/MXene/NF	1 mol/L KOH	229	44	[126]
1T/2H MoSe₂/MXene	1 mol/L KOH	340	90	[248]
Ni_0.9Fe_0.1PS₃@MXene	1 mol/L KOH	196	114	[250]
CoS₂@MXene	0.1 mol/L KOH	270	92	[65]
CoP/MXene	1 mol/L KOH	230	50	[120]
CoP/Ti₃C₂ MXene	1 mol/L KOH	280	95.4	[258]
Ti₃C₂@mNiCoP	1 mol/L KOH	237	104	[260]
BP QDs/MXene	1 mol/L KOH	360	64.3	[235]

Table 4 ORR performance data for MXene-based hybrids.

Catalyst	Electrolyte	E_onset (V vs. RHE)	E_1/2 (V vs. RHE)	Ref.
Ru/Ti₃C₂T_x	0.1 mol/L HClO₄	0.92	0.80	[121]
Pt/Ti₃C₂T_x	0.1 mol/L HClO₄	—	0.847	[302]
Pt/Ti₃C₂T_x	1 mol/L KOH	0.95	—	[224]
MXene/NW-Ag_0.9Ti_0.1	1 mol/L KOH	0.921	0.782	[225]
Pt NWs/Ti₃C₂T_x-CNT	0.1 mol/L HClO₄	1.02	0.896	[303]
Pt/CNT-Ti₃C₂T_x	0.1 mol/L HClO₄	—	0.876	[304]
Pd/Ti₃C₂T_x-CNT	0.1 mol/L KOH	1.085	0.925	[293]
FeCo-N-d-Ti3C₂	0.1 mol/L KOH	0.96	0.80	[305]
Fe-N-C@Ti₃C₂T_x	0.1 mol/L HClO₄	—	0.777	[269]
Fe-N-C@Ti₃C₂T_x	0.1 mol/L KOH	—	0.887	[269]
Fe-N-C/Ti₃C₂T_x	0.1 mol/L KOH	1	0.814	[306]
Fe-N-C/Ti₃C₂T_x	0.1 mol/L KOH	0.92	0.84	[125]
FePc/Ti₃C₂T_x	0.1 mol/L KOH	0.97	0.89	[307]
g-C₃N₄/Ti₃C₂	0.1 mol/L KOH	0.92	0.79	[105]
MoS₂QDs@ Ti₃C₂T_xQDs@MWCNTs	1.0 mol/L KOH	0.87	0.75	[205]
MXene@PPy-800	0.1 mol/L KOH	0.85	0.710	[291]
Co-CNT/Ti₃C₂-60	0.1 mol/L KOH	—	0.820	[124]
Ti₃C₂/NSCD-600	0.1 mol/L KOH	0.98	0.81	[308]
Co₃O₄/NCNT/Ti₃C₂	0.1 mol/L KOH	—	0.79	[309]
CoS₂@MXene	0.1 mol/L KOH	0.87	0.80	[65]
NiFeMn-N/N-Ti₃C₂	0.1 mol/L KOH	0.95	0.84	[310]
N-CoSe₂/Ti₃C₂T_x	0.1 mol/L KOH	0.95	0.79	[311]
NiCo₂O₄/MXene	0.1 mol/L KOH	—	0.70	[118]
Mn₃O₄/MXene	0.1 mol/L KOH	0.89	—	[274]
NiCoFe-LDH/Ti₃C₂ MXene/NCNT	0.1 mol/L KOH	0.93	0.78	[30]

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