新型二维材料MXene的研究进展

doi:10.15541/jim20160479

摘要/Abstract

摘要：

MXene是一种新型的二维过渡金属碳化物或碳氮化物, 具有类似石墨烯的二维结构, 其化学通式是M_n₊₁X_nT_z, n = 1, 2, 3, 其中M为早期过渡金属元素, X为碳或氮元素, T为表面链接的F^-、OH^-、O^2-等活性官能团。通过化学液相法可以选择性蚀刻掉MAX相中的A元素得到相应的MXene相。现今较为成熟的制备方法是HF蚀刻法。对MXene的结构与性能进行的第一性原理计算表明, 其具有独特的二维层状结构、较大的比表面积及良好的导电性、稳定性、磁性能和力学性能, 已广泛应用于储能、催化、吸附等多处领域。本文综述了类石墨烯二维材料MXene的理论、制备和应用方面的研究进展, 并对现有挑战和未来发展提出了建议。随着研究的进一步深入, MXene将被应用于更广泛的领域。

关键词: MXene, 化学液相蚀刻法, 第一性原理计算, 应用

Abstract:

MXene is a new family of two-dimensional transition metal carbides or carbonitrides with graphene-like 2D morphology. The chemical formula of MXene is M_n₊₁X_nT_z, where M is an early transition metal, X is C and/or N, T stands for surface-terminating functional groups like F^-, OH^-, O^2-, etc., and n = 1, 2, or 3. It can be achieved by selective etching of the A element from the MAX phases, and HF is an etchant mostly used. First-principles calculations about MXene have been performed to reveal the structure and properties. MXene has also been found to have a unique two-dimensional layered structure, large specific surface area and good electrical conductivity, stability, magnetic and mechanical properties, and thus it is promising in many fields, including energy storage, catalysis and adsorption. This article reviews the quite recent progress of MXene based on theoretical and experimental considerations, especially its structure, synthesis, and applications. Finally, the suggestions about existing challenges and future developments are proposed. MXene is expected to be used for more various applications with further extensive research.

Key words: MXene, chemical liquid phase etching method, the first-principles calculation, application

中图分类号:

TQ174

张建峰, 曹惠杨, 王红兵. 新型二维材料MXene的研究进展[J]. 无机材料学报, 2017, 32(6): 561-570.

ZHANG Jian-Feng, CAO Hui-Yang, WANG Hong-Bing. Research Progress of Novel Two-dimensional Material MXene[J]. Journal of Inorganic Materials, 2017, 32(6): 561-570.

图/表 10

图1 MAX相元素在元素周期表上的位置, 插图为MAX相的原子簇示意图[11]

Fig. 1 Fragment of the periodic table, showing elements forming MAX phases with general composition Mn+1AXn. Inset is an example of packing motif for the MAX phases[11]

图2 三种MAX相的结构示意图

Fig. 2 Structure diagrams of three typical MAX phases

图3 MXene的引文报告数据分析图

Fig. 3 Citation reports analysis of Mxene(a) The number of MXene papers published recently; (b) The number of citations about MXene published recently; (c) The contribution rate of ten main organizations in the 306 papers about MXene; (d) The contribution rate of ten main authors in the 306 papers about MXene

表1 Tin+1AlCn、NB-Tin+1Al0.5Cn、NB-Tin+1Cn、B1-TiC的结合能Ecoh及结合能差ΔEcoh[37]

Table1 Cohesive energies ( Ecoh, ) and differences in Ecoh ( ΔE ) for MAX Tin+1AlCn phases, Tin+1Al0.5Cn and Tin+1Cn free-standing NBs uersus B1-TiC[37]

System	^*E_coh/ eV	^*ΔE_coh/ eV
^*TiC	7.49(7.16^a; 9.14^b; 9.28^c; 7.20^d; 7.30^e; 7.31^f; 7.45ⁱ)	-
^*Ti₂AlC	6.29(7.79^c)	1.20(1.49^c)
Ti₂Al_0.5C	6.28	1.21
Ti₂C	6.28	1.21
Ti₃AlC₂	6.71(8.32^c; 6.93^g; 7.70^h; 8.499^j)	0.78(0.96^c)
Ti₃Al_0.5C₂	6.76	0.73
Ti₃C₂	6.82	0.67

图4 官能团化MXenes、石墨烯、烷、BN、MoS2的最低近自由电子态和费米能级(Ef)的相对能量与功函数的关系图[47]

Fig. 4 The relative energy position of the lowest NFE state for functionalized MXenes, as well as for graphene, graphane, BN, and MoS2 layers with respect to the Fermi level (Ef) as a function of the work function[47]

表2 Ti3C2Tx、Ti3C2Tx/PVA和PVA薄膜物理性质[53]

Table2 Physical properties of Ti3C2Tx, Ti3C2Tx/PVA and PVA films[53]

MXene content/wt%	Thickness/μm	Conductivity/(S·m^-1)	Tensile strength/MPa	Young’s modulus/GPa	Strain to failure/%
100	3.3	240238±3500	22±2	3.52±0.01	1.0±0.2
90	3.9	22433±1400	30±3	3.00±0.01	1.8±0.3
80	6.1	137±3	25±4	1.7±0.2	2.0±0.4
60	7.2	1.30±0.08	43±8	1.8±0.6	3.0±0.5
40	12.0	0.040±0.003	91±10	3.70±0.02	4.0±0.5
0	13.0	-	30±5	1.0±0.3	15.0±6.5

图5 HF剥离Ti3AlC2的过程示意图

Fig. 5 Schematic of the exfoliation process for Ti3AlC2(a) Ti3AlC2 structure; (b) Selective etching of the A element from the MAX phases after reaction with HF; (c) surface-terminating functional groups

表3 不同工艺条件下HF剥离MAX制备MXene的晶格参数c值

Table3 Process conditions and c-lattice parameters for MXene synthesis from MAX phases

MAX structure	MAX	MXene	Etching conduction			Particle size /μm	c-lattice parameter/nm		Ref.
MAX structure	MAX	MXene	HF/%	Time/h	Temp. /℃	Particle size /μm	MAX	MXene	Ref.
211	Ti₂AlC	Ti₂CT_x	10	10	25	<35	1.360	1.504	[10]
	Nb₂AlC	Nb₂CT_x	50	90	25	<38	1.388	2.234	[58]
	V₂AlC	V₂CT_x	40	168	25	<74	1.315	2.370	[59]
	TiNbAlC	TiNbCT_x	50	28	25	<35	1.379	1.488	[10]
312	Ti₃AlC₂	Ti₃C₂T_x	50	2	25	<35	1.842	2.051	[10-11]
	Ti₃AlC₂	Ti₃C₂T_x	40	20	25	-	1.862	2.089	[60]
	Ti₃AlC₂	Ti₃C₂T_x	49	24	60	-	1.830	1.990	[61]
	Ti₃AlCN	Ti₃CNT_x	30	18	25	<35	1.841	2.228	[10]
	(V_0.5Cr_0.5)₂AlC₂	(V_0.5Cr_0.5)₂C₂T_x	50	69	25	<35	1.773	2.426	[10]
413	Ta₄AlC₃	Ta₄C₃T_x	50	72	25	<35	2.408	3.034	[10]
	Nb₄AlC₃	Nb₄C₃T_x	48-51	96	25	<38	2.242	3.059	[21]

图6 通过芳基重氮盐表面改性分离多层MXene的示意图[31]

Fig. 6 Schematic illustration for delamination process of surface modified MXene multilayers by aryl diazonium salts[31]

图7 重氮盐表面改性MXene Ti3C2前后的红外光谱图[31]

Fig. 7 FTIR spectra of MXene Ti3C2 before and after surface modification with diazonium salts[31]

参考文献 86

[1]	NOVOSELOV K S, GEIM A K, MOROZOV S V, et al.Electric field effect in atomically thin carbon films.Science, 2004, 306(5696): 666-669.
[2]	KUANG DA, HU WEN-BIN.Research progress of grapheme composites.Journal of Inorganic Materials, 2013, 28(3): 235-246.
[3]	ZHU Y, MURALI S, CAI W, et al.Graphene and graphene oxide: synthesis, properties, and applications.Adv. Mater., 2010, 22(46): 5226.
[4]	HUANG X, YIN Z, WU S, et al.Graphene-based materials: synthesis, characterization, properties, and applications.Small, 2011, 7(14): 1876-1902.
[5]	HUANG H, YANG S, ROBERT V, et al.Pt-Decorated 3D architectures built from graphene and graphitic carbon nitride nanosheets as efficient methanol oxidation catalysts.Adv. Mater., 2014, 26(30): 5160-5165.
[6]	HUANG H, CHEN Q, HE M, et al.A ternary Pt/MnO2/graphene nanohybrid with an ultrahigh electrocatalytic activity toward methanol oxidation.J. Power Sources, 2013, 239(10): 189-195.
[7]	HUANG H, CHEN H, SUN D, et al.Graphene nanoplate-Pt composite as a high performance electrocatalyst for direct methanol fuel cells.J. Power Sources, 2012, 204(1): 46-52.
[8]	JIANG Q G, ZHANG J F, AO Z M, et al.Density functional theory study on the electronic properties and stability of silicene/silicane nanoribbons.J. Mater. Chem., 2015, 3(16): 3954-3959.
[9]	MICHAEL N, MURAT K, VOLKER P, et al.Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2.Adv. Mater., 2011, 21(1): 17-35.
[10]	NAGUIB M, MASHTALIR O, CARLE J, et al.Two-dimensional transition metal carbides.ACS Nano, 2012, 6(2): 1322-1331.
[11]	IVANOVSKII A L, ENYASHIN A N.Graphene-like transition- metal nanocarbides and nanonitrides.Russ. Chem. Rev., 2013, 82(8): 735-746.
[12]	NOWOTNY V H.Strukturchemie einiger Verbindungen der Übergangsmetalle mit den elementen C, Si, Ge, Sn.Prog. Solid State Chem., 1971, 5(71): 27-70.
[13]	BARSOUM M W.The Mn+1AXn phases: a new class of solids: Thermodynamically stable nanolaminates.Prog. Solid State Chem., 2000, 28(1-4): 201-281.
[14]	ZHOU AI-GUO, LI ZHENG-YANG, LI LIANG, et al.Preparation and microstructure of Ti3SiC2 bonded cubic boron nitride superhard composites.Journal of the Chinese Ceramic Society, 2014, 42(2): 220-224.
[15]	LV TIAN-BAO.Transformation of WPA process from dehydrated into dehydrated-hemihydrates method.Phosphate Compound Fertilizer, 2010, 25(2): 31-32.
[16]	BARSOUM M W, EL-RAGHY T.The MAX phases: unique new carbide and nitride materials: ternary ceramics turn out to be surprisingly soft and machinable, yet also heat-tolerant, strong and lightweight.Americanentist, 2001, 89(4): 334-343.
[17]	EKLUND P, BECKERS M, JANSSON U, et al.The Mn+1AXn phases: materials science and thin-film processing.Thin Solid Films, 2010, 518(8): 1851-1878.
[18]	ZHANG X, XUE M, YANG X, et al.Preparation and tribological properties of Ti3C2(OH)2 nanosheets as additives in base oil.RSC Adv., 2014, 5(4): 56-63.
[19]	QING T, ZHEN Z, PANWEN S.Are MXenes promising anode materials for Li ion batteries? Computational studies on electronic properties and Li storage capability of Ti3C2 and Ti3C2X2 (X = F, OH) monolayer.J. Am. Chem. Soc., 2012, 134(40): 16909-16916.
[20]	SHEIN I R, IVANOVSKII A L.Graphene-like nanocarbides and nanonitrides of d metals (MXenes): synthesis, properties and simulation.Micro Nano Lett., 2013, 8(2): 59-62.
[21]	GHIDIU M, NAGUIB M, SHI C, et al.Synthesis and characterization of two-dimensional Nb4C3 (MXene).Chem. Commun., 2014, 50(67): 9517-9520.
[22]	MASHTALIR O, LUKATSKAYA M R, ZHAO M Q, et al.Amine-assisted delamination of Nb2C MXene for Li-ion energy storage devices.Adv. Mater., 2015, 27(23): 3501-3506.
[23]	MICHAEL G, LUKATSKAYA M R, ZHAO MENG-QIANG, et al.Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance.Nature, 2014, 516(7529): 78-81.
[24]	SUN Z M.Progress in research and development on MAX phases: a family of layered ternary compounds.Int. Mater. Rev., 2011, 56(3): 143-166.
[25]	NAGUIB M, MOCHALIN V N, BARSOUM M W, et al.25th anniversary article: MXenes: a new family of two-dimensional materials.Adv. Mater., 2014, 26(7): 992-1005.
[26]	ZHANG H, WANG L, CHEN Q, et al.Preparation, mechanical and anti-friction performance of MXene/polymer composites.Mater. Design, 2016, 92(11): 682-689.
[27]	MA T Y, CAO J L, JARONIEC M, et al.Interacting carbon nitride and titanium carbide nanosheets for high-performance oxygen evolution.Angew. Chem., Int. Ed., 2016, 55(3): 1138-1142.
[28]	ZHANG X, LEI J C, WU D H, et al.A Ti-anchored Ti2CO2 monolayer (MXene) as a single-atom catalyst for CO oxidation.J. Mater. Chem. A, 2016, 4(13): 4871-4876.
[29]	SUN D D, HU Q K, CHEN J F, et al.Structural transformation of MXene (V2C, Cr2C, and Ta2C) with O groups during lithiation: A first-principles investigation.ACS Appl. Mater. Inter., 2016, 8(1): 74-81.
[30]	GUO X, ZHANG X T, ZHAO S J, et al.High adsorption capacity of heavy metals on two-dimensional MXenes: an ab initio study with molecular dynamics simulation.Phys. Chem. Chem. Phys., 2016, 18(1): 228-233.
[31]	WANG H, ZHANG J, WU Y, et al.Surface modified MXene Ti3C2 multilayers by aryl diazonium salts leading to large-scale delamination.Appl. Surf. Sci., 2016, 384: 287-293.
[32]	WANG H, WU Y, ZHANG J, et al.Enhancement of the electrical properties of MXene Ti3C2 nanosheets by post-treatments of alkalization and calcination.Materials Letters, 2015, 160: 537-540.
[33]	WANG K, ZHOU Y, XU W, et al.Fabrication and thermal stability of two-dimensional carbide Ti3C2 nanosheets.Ceram. Int., 2016, 42(7): 8419-8424.
[34]	YANG J, LUO X, ZHANG S, et al.Magnetic and electronic properties of transition metal doped Sc2CT2 (T = O, OH or F) by a first principles study.Phys. Chem. Chem. Phys., 2016, 18(18): 12914-12919.
[35]	PENG QIUMING, GUO JIANXIN, ZHANG QINGRUI, et al.Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide.J. Am. Chem. Soc., 2014, 136(11): 4113-4116.
[36]	SHEIN I R, IVANOVSKII A L.Graphene-like titanium carbides and nitrides Tin+1Cn, Tin+1Nn(n= 1, 2, and 3) from de-intercalated MAX phases: First-principles probing of their structural, electronic properties and relative stability.Comp. Mater. Sci., 2012, 65: 104-114.
[37]	SHEIN I R, IVANOVSKII A L.Planar nano-block structures Tin+1Al0.5Cn and Tin+1Cn(n = 1, and 2) from MAX phases: structural, electronic properties and relative stability from first principles calculations.Superlattices Microstruct., 2012, 52(2): 147-157.
[38]	ENYASHIN A N, IVANOVSKII A L.Atomic structure, comparative stability and electronic properties of hydroxylated Ti2C and Ti3C2 nanotubes.Comput. Theor. Chem., 2012, 989(6): 27-32.
[39]	TAO H, JIEMIN W, HUI Z, et al.Vibrational properties of Ti3C2 and Ti3C2T2 (T = O, F, OH) monosheets by first-principles calculations: a comparative study.Phys. Chem. Chem. Phys., 2015, 17(15): 9997-10003.
[40]	ENYASHIN A N, IVANOVSKII A L.Two-dimensional titanium carbonitrides and their hydroxylated derivatives: structural, electronic properties and stability of MXenes Ti3C2-xNx(OH)2 from DFTB calculations.J. Solid State Chem., 2013, 207: 42-48.
[41]	MAUCHAMP V, BUGNET M, BELLIDO E P, et al.Enhanced and tunable surface plasmons in two-dimensional Ti3C2 stacks: Electronic structure versus boundary effects.Phys. Rev. B, 2014, 89(23): 2495-2502.
[42]	XIE Y, KENT P R C. Hybrid density functional study of structural and electronic properties of functionalized Tin+1Xn(X=C, N) monolayers.Phys. Rev. B, 2013, 87(23): 939-949.
[43]	ZHAO S, KANG W, XUE J.Manipulation of electronic and magnetic properties of M2C (M=Hf, Nb, Sc, Ta, Ti, V, Zr) monolayer by applying mechanical strains.Appl. Phys. Lett., 2014, 104(13): 133106-133109.
[44]	WANG S, LI J X, DU Y L, et al.First-principles study on structural, electronic and elastic properties of graphene-like hexagonal Ti2C monolayer.Computational Materials Science, 2014, 83: 290-293.
[45]	LASHGARI H, ABOLHASSANI M R, BOOCHANI A, et al.Electronic and optical properties of 2D graphene-like compounds titanium carbides and nitrides: DFT calculations.Solid State Commun., 2014, 195(10): 61-69.
[46]	LANE N J, BARSOUM M W, RONDINELLI J M.Correlation effects and spin-orbit interactions in two-dimensional hexagonal 5d transition metal carbides, Tan+1Cn (n = 1, 2, 3).EPL, 2013, 101(5): 57004-57008.
[47]	KHAZAEI M, RANJBAR A, GHORBANIASL M, et al.Nearly free electron states in MXenes.Phys. Rev. B, 2016, 93(20): 205125-205135.
[48]	SHAO JIAO-JING, ZHENG DE-YI, LI ZHENG-JIE, et al.Top-down fabrication of two-dimensional nanomaterials: controllable liquid phase exfoliation.New Carbon Materials, 2016, 31(2): 97-114.
[49]	KHAZAEI M, ARAI M, SASAKI T, et al.Novel electronic and magnetic properties of two-dimensional transition metal carbides and Nitrides.Adv. Funct. Mater., 2013, 23(17): 2185-2192.
[50]	WU F, LUO K, HUANG C, et al.Theoretical understanding of magnetic and electronic structures of Ti3C2 monolayer and its derivatives.Solid State Commun., 2015, 222: 9-13.
[51]	LANE N J, BARSOUM M W, RONDINELLI J M.Electronic structure and magnetism in two-dimensional hexagonal 5d transition metal carbides, Tan+1Cn (n=1, 2, 3).Europhys. Lett., 2013, 101(5): 1-5.
[52]	KURTOGLU M, NAGUIB M, GOGOTSI Y, et al.First principles study of two-dimensional early transition metal carbides.Mrs Communications, 2012, 2(4): 133-137.
[53]	LING Z, REN C E, ZHAO M Q, et al.Flexible and conductive MXene films and nanocomposites with high capacitance.Proc. Natl. Acad. Sci. U. S. A., 2014, 111(47): 16676-16681.
[54]	DIKIN D A, STANKOVICH S, ZIMNEY E J, et al.Preparation and characterization of graphene oxide paper.Nature, 2007, 448(7152): 457-460.
[55]	LI Z, XU J, O'BYRNE J P, et al. Freestanding bucky paper with high strength from multi-wall carbon nanotubes.Mater. Chem. Phys., 2012, 135(2/3): 921-927.
[56]	SUN D D, HU Q K, CHEN J F, et al. First principles calculations of the relative stability, structure and electronic properties of two dimensional metal carbides and nitrides. Key Eng. Mater., 2014, 602-603: 527-531.
[57]	KHAZAEI M, ARAI M, SASAKI T, et al.The effect of the interlayer element on the exfoliation of layered MoAC (A = Al, Si, P, Ga, Ge, As or In) MAX phases into two-dimensional MoC nanosheets.Sci. Technol. Adv. Mat., 2014, 15(1): 1-7.
[58]	NAGUIB M, HALIM J, LU J, et al.New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries.ChemInform, 2013, 135(43): 15966-15969.
[59]	WANG L, YUAN L, CHEN K, et al.Loading actinides in multilayered structures for nuclear waste treatment: the first case study of uranium capture with vanadium carbide MXene.ACS Appl. Mater. Inter., 2016, 8(25): 16396-16403.
[60]	CHANG F, LI C, YANG J, et al.Synthesis of a new graphene-like transition metal carbide by de-intercalating Ti3AlC2.Mater. Lett., 2013, 109(10): 295-298.
[61]	SUN D, WANG M, LI Z, et al.Two-dimensional Ti3C2 as anode material for Li-ion batteries.Electrochem. Commun., 2014, 47(10): 80-83.
[62]	MASHTALIR O, NAGUIB M, DYATKIN B, et al.Kinetics of aluminum extraction from Ti3AlC2 in hydrofluoric acid.Mater. Chem. Phys., 2013, 139(1): 147-152.
[63]	HALIM J, LUKATSKAYA M R, COOK K M, et al.Transparent conductive two-dimensional titanium carbide epitaxial thin films.Chem. Mater., 2014, 26(7): 2374-2381.
[64]	MASHTALIR O, NAGUIB M, MOCHALIN V N, et al.Intercalation and delamination of layered carbides and carbonitrides.Nat. Commun., 2013, 4(2): 216-219.
[65]	NAGUIB M, UNOCIC R R, ARMSTRONG B L, et al.Large-scale delamination of multi-layers transition metal carbides and carbonitrides “Mxenes”.Dalton Trans., 2015, 44(20): 9353-9358.
[66]	SI Y, SAMULSKI E T.Synthesis of water soluble graphene.Nano Lett., 2008, 8(6): 1679-1682.
[67]	ORLER E B, YONTZ D J, MOORE R B.Sulfonation of syndiotactic polystyrene for model semicrystalline ionomer investigations.Macromolecules, 2002, 21(2): 73-82.
[68]	LIU F, SUN J, ZHU L, et al.Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions.J. Mater. Chem., 2012, 22(12): 5495-5502.
[69]	NAGUIB M, COME J, DYATKIN B, et al.MXene: a promising transition metal carbide anode for lithium-ion batteries.Electrochem. Commun., 2012, 16(1): 61-64.
[70]	KIM S J, NAGUIB M, ZHAO M, et al.High mass loading, binder-free MXene anodes for high areal capacity Li-ion batteries.Electrochim. Acta, 2015, 163: 246-251.
[71]	LUKATSKAYA M R, OLHA M, REN C E, et al.Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide.Science, 2013, 341(6153): 1502-1505.
[72]	YOON Y, LEE K, LEE H.Low-dimensional carbon and MXene-based electrochemical capacitor electrodes.Nanotechnology, 2016, 27(17): 172001-172021.
[73]	DING B, WANG J, WANG Y, et al.A two-step etching route to ultrathin carbon nanosheets for high performance electrical double layer capacitors.Nanoscale, 2016, 8(21): 11136-11142.
[74]	DALL'AGNESE Y, LUKATSKAYA M R, COOK K M, et al. High capacitance of surface-modified 2D titanium carbide in acidic electrolyte.Electrochem. Commun., 2014, 48(48): 118-122.
[75]	XIAOHONG X, SIGUO C, WEI D, et al.An extraordinarily stable catalyst: Pt NPs supported on two-dimensional Ti3C2X2 (X = OH, F) nanosheets for oxygen reduction reaction.Chem. Commun., 2013, 49(86): 10112-10114.
[76]	LI X, FAN G, ZENG C.Synthesis of ruthenium nanoparticles deposited on graphene-like transition metal carbide as an effective catalyst for the hydrolysis of sodium borohydride.Int. J. Hydrogen Energy, 2014, 39(27): 14927-14934.
[77]	GAO Y, WANG L, LI Z, et al.Preparation of MXene-Cu2O nanocomposite and effect on thermal decomposition of ammonium perchlorate.Solid State Sci., 2014, 35(9): 62-65.
[78]	ENYASHIN A N, IVANOVSKII A L.Structural and electronic properties and stability of MXenes Ti2C and Ti3C2 functionalized by methoxy groups.J. Phys. Chem. C, 2013, 117(26): 13637-13643.
[79]	MASHTALIR O, COOK K M, MOCHALIN V N, et al.Dye adsorption and decomposition on two-dimensional titanium carbide in aqueous media.J. Mater. Chem., 2014, 2(35): 14334-14338.
[80]	GAO Y, WANG L, ZHOU A, et al.Hydrothermal synthesis of TiO2/Ti3C2 nanocomposites with enhanced photocatalytic activity.Mater. Lett., 2015, 150: 62-64.
[81]	HU QIANKU, SUN DANDAN, WU QINGHUA, et al.MXene: a new family of promising hydrogen storage medium.J. Phys. Chem. A, 2013, 117(51): 14253-14260.
[82]	SUN DAN-DAN, HU QIAN-KU, LI ZHENG-YANG, et al.Research progress of new two-dimensional MXene crystals.Journal of Synthetic Crystals, 2014, 43(11): 2950-2956.
[83]	霍苗. 二维MXene衍生物对NaAlH4体系吸/放氢性能的影响. 河北: 河北师范大学硕士学位论文, 2016.
[84]	YANG J, CHEN B, SONG H, et al.ChemInform abstract: Synthesis, characterization, and tribological properties of two-dimensional Ti3C2.Cryst. Res. Technol., 2014, 49(11): 926-932.
[85]	WANG F, YANG C H, DUAN C Y, et al.An organ-like titanium carbide material (MXene) with multilayer structure encapsulating hemoglobin for a mediator-free biosensor.J. Electrochem. Soc., 2015, 162(1): 16-21.
[86]	LIU H, DUAN C, YANG C, et al.A novel nitrite biosensor based on the direct electrochemistry of hemoglobin immobilized on MXene-Ti3C2.Sens. Actuators, B, 2015, 218: 60-66.