超声辅助刻蚀对Ti_3C_2T_x微观结构的影响
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摘要
二维层状材料MXene由于其独特的物理化学性质,受到了广泛关注。本文通过超声辅助刻蚀Ti_3AlC_2的方法制备了多层的Ti_3C_2T_x,利用X射线衍射仪、N_2吸脱附测试、扫描电子显微镜和透射电子显微镜对其微观结构的变化特征进行了详细的表征和分析,并与磁力搅拌刻蚀制备的Ti_3C_2T_x样品相对比。结果表明,与磁力搅拌刻蚀相比,超声辅助刻蚀可以进一步减小Ti_3C_2T_x平均薄层厚度和增加原子层间距,主要原因是超声处理能够促进未发生反应的薄片层中Al原子层的刻蚀。刻蚀过程中同一Al原子层有些区域先发生刻蚀,而一些区域依然存在Al原子。探明了附着在Ti_3C_2T_x表面几十纳米的颗粒是空间群为■的六方结构AlF_3,并且随着刻蚀时间的增加,其逐渐向非晶体转变。
Two-dimensional MXenes attract great interest due to their unique physical and chemical properties.Ti_3C_2T_x MXene is synthesized by ultrasonic assisted etching.The resulted microstructures are characterized and compared with those Ti_3C_2T_x samples synthesized via magnetically stirring etching,by X-ray diffractometer,N_2 adsorption and desorption,scanning electron microscope(SEM) and transmission electron microscope(TEM).The results demonstrate that ultrasonic assisted etching can further reduce the lamellar thickness of Ti_3C_2T_x and increase the atomic layer spacing,comparing with the method of magnetically stirring etching.A gradual dissolution is observed in the same Al atomic layers during etching.The particles with several tens of nanometers in size are frequently formed in contact with the surface of Ti_3C_2T_x.These nano-particles are determined to be hexagonal AlF_3 with space group of ■.A gradual change from crystalline form to amorphous structure is also detected for hexagonal AlF_3 with prolonged etching time.
Two-dimensional MXenes attract great interest due to their unique physical and chemical properties.Ti_3C_2T_x MXene is synthesized by ultrasonic assisted etching.The resulted microstructures are characterized and compared with those Ti_3C_2T_x samples synthesized via magnetically stirring etching,by X-ray diffractometer,N_2 adsorption and desorption,scanning electron microscope(SEM) and transmission electron microscope(TEM).The results demonstrate that ultrasonic assisted etching can further reduce the lamellar thickness of Ti_3C_2T_x and increase the atomic layer spacing,comparing with the method of magnetically stirring etching.A gradual dissolution is observed in the same Al atomic layers during etching.The particles with several tens of nanometers in size are frequently formed in contact with the surface of Ti_3C_2T_x.These nano-particles are determined to be hexagonal AlF_3 with space group of ■.A gradual change from crystalline form to amorphous structure is also detected for hexagonal AlF_3 with prolonged etching time.
引文
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[2] ANASORI B,LUKATSKAYA M R,GOGOTSI Y. 2D metal carbides and nitrides(MXenes)for energy storage[J]. Nature Reviews Materials,2017,2(2):16098.
[3] PENG Q,GUO J,ZHANG Q,et al. Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide[J]. Journal of the American Chemical Society,2014,136(11):4113-4118.
[4] LUKATSKAYA M R,KOTA S,LIN Z,et al.Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides[J]. Nature Energy,2017,2(8):17105.
[5] DALL'AGNESE Y,LUKATSKAYA M R,COOK K M,et al. High capacitance of surface-modified 2D titanium carbide in acidic electrolyte[J]. Electroche-mistry Communications,2014,48:118-122.
[6] HU M,HU T,LI Z,et al. Surface functional groups and interlayer water determine the electrochemical capacitance of Ti_3C_2T_x MXene[J].American Chemical Society Nano,2018,12(4):3578-3586.
[7] GHIDIU M,LUKATSKAYA M R,ZHAO M Q,et al.Conductive two-dimensional titanium carbide “clay” with high volumetric capacitance[J].Nature,2014,516(7529):78-81.
[8] MASHTALIR O,NAGUIB M,MOCHALIN V N,et al.Intercalation and delamination of layered carbides and carbonitrides[J].Nature Communication,2013,4:1716.
[9] LING Z,REN C E,ZHAO M Q,et al. Flexible and conductive MXene films and nanocomposites with high capacitance[J]. Proceedings of the National Aca demy of Sciences,2014,111(47):16676-16681.
[10] NAGUIB M,MOCHALIN V N,BARSOUM M W,et al. MXenes:A new family of two-dimensional materials[J]. Advanced Materials,2014,26(7):992-1005.
[11] ZHANG X,XUE M,YANG X,et al.Preparation and tribological properties of Ti3C2(OH)2nanosheets as additives in base oil[J]. Royal Society of Chemistry Advances,2015,5(4):2762-2767.
[12] WANG L,ZHANG H,WANG B,et al.Synthesis and electrochemical performance of Ti_3C_2T_x with hydrothe-rmal process[J].Electronic Materials Letters,2016,12(5):702-710.
[13] NAGUIB M,PRESSER V,LANE N,et al.Synthesis of a new nanocrystalline titanium aluminum fluoride phase by reaction of Ti2AlC with hydrofluoric acid[J].Royal Society of Chemistry Advances,2011,1(8):1493-1499.
[14] LIU Y,ZHANG X,DONG S,et al. Synthesis and tribological property of Ti_3C_2T_x nanosheets[J].Journal of Materials Science,2017,52(4):2200-2209.
[15] FENG W,LUO H,WANG Y,et al.Ultrasonic assis-ted etching and delaminating of Ti3C2Mxene[J].Ceramics International,2018,44(6):7084-7087.
[16] CHANG F,LI C,YANG J,et al.Synthesis of a new graphene-like transition metal carbide by deintercala-ting Ti3AlC2[J].Materials Letters,2013,109:295-298.
[17] WANG X,SHEN X,GAO Y,et al.Atomic-scale rec-ognition of surface structure and intercalation mecha-nism of Ti_3C_2T_x[J].Journal of the American Chemical Society,2015,137(7):2715-2721.