Preparation and gas sensing properties of a novel two-dimensional material Ti3C2Tx MXene

Han Dan; Liu Zhi-Hua; Liu Lu-Lu; Han Xiao-Mei; Liu Dong-Ming; Zhuo Kai; Sang Sheng-Bo

doi:10.7498/aps.71.20211048

Abstract

Since the discovery of graphene materials, two-dimensional materials have been widely recognized and gradually applied. Two-dimensional transition metal carbides (MXenes) have better mechanical, magnetic and electrical properties than traditional two-dimensional materials. In this work, Ti₃C₂T_x samples are prepared by etching Ti₃AlC₂ with different etching agents for the solutions of HF and LiF/HCl. The effects of etching agents on the structure and gas sensing properties of Ti₃C₂T_x materials are studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and gas sensing properties analysis. The material structure analysis shows that both HF and LiF/HCl etching agents have good etching effect on Ti₃C₂T_x material. The results of gas sensing properties show that the gas sensing properties of Ti₃C₂T_x prepared by LiF/HCl etching agent is better than by HF etching agent, and the wide range, high sensitivity and high stability of NH₃ detection can be achieved at room temperature. The analysis shows that the high sensing performance of Ti₃C₂T_x prepared by LiF/HCl solution etching is mainly due to the high proportion of —O and —OH functional groups on the surface of Ti₃C₂T_x. The experimental studies can lay a theoretical foundation for studying the gas sensing and practical application of Ti₃C₂T_x based sensor.

Keywords:

Authors and contacts

Taiyuan University of Technology, College of information and computer, MicroNano System Research Center, Taiyuan 030600, China

Corresponding author: Zhuo Kai, zhuokai@tyut.edu.cn ; Sang Sheng-Bo, sunboa-sang@tyut.edu.cn

Funds: Project supported by the Key Program of the National Natural Science Foundation of China(Grant No.62031022) and the National NaturalScience Foundationof China (Grant Nos. 51975400, 61971301).

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References

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Cited By

图 1 MAX相及其对应的MXene结构

Figure 1. MAX phase and its corresponding MXene structure.

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图 2 (a)和(b) HF溶液刻蚀制备Ti₃C₂T_x材料SEM图像; (c)和(d) LiF/HCl溶液刻蚀制备Ti₃C₂T_x材料SEM图像

Figure 2. (a) and (b) SEM images of Ti₃C₂T_x prepared by HF solution etching; (c) and (d) SEM image of Ti₃C₂T_x prepared by LiF/HCl solution etching.

DownLoad: Full-Size Img PowerPoint

图 3 HF溶液刻蚀制备Ti₃C₂T_x材料的　(a) XPS光谱图; (b) Ti 2p光谱; (c) C 1s光谱和(d) O 1s光谱; LiF/HCl溶液刻蚀制备Ti₃C₂T_x材料的(e) XPS光谱图; (f) Ti 2p光谱; (g) C 1s光谱和(h) O 1s光谱

Figure 3. (a) XPS spectra of Ti₃C₂T_x prepared by HF solution etching; (b) Ti 2p spectrum; (c) C 1s spectrum and (d) O 1s spectrum; (e) XPS spectra of Ti₃C₂T_x prepared by LiF/HCl solution etching; (f) Ti 2p spectrum; (g) C 1s spectrum; (h) O 1s spectrum.

DownLoad: Full-Size Img PowerPoint

图 4 室温下, (a) HF溶液, (b) LiF/HCl溶液刻蚀制备Ti₃C₂T_x基气体传感器对不同浓度NH₃的响应度; (c) HF溶液, (d) LiF/HCl溶液刻蚀制备的Ti₃C₂T_x基气体传感器的响应度随NH₃浓度变化的朗缪尔等温线

Figure 4. Response of Ti₃C₂T_x based gas sensor prepared by etching: (a) HF solution and (b) LiF/HCl solution to NH₃ with different concentrations at room temperature; Langmuir isotherm of the responsivity of Ti₃C₂T_x based gas sensor prepared by the etching of (c) HF solution and (d) LiF/HCl solution.

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图 5 室温下,　(a) HF溶液刻蚀制备和(b) LiF/HCl溶液刻蚀制备的Ti₃C₂T_x基气体传感器对10 ppm NH₃的重复性; (c)室温下, 两种刻蚀剂刻蚀制备的Ti₃C₂T_x基气体传感器对10 ppm NH₃ 的稳定性; (d)室温下, 两种刻蚀剂刻蚀制备的Ti₃C₂T_x基气体传感器对不同气体的响应度

Figure 5. At room temperature, (a) Ti₃C₂T_x based gas sensor prepared by etching HF solution and (b) Ti₃C₂T_x based gas sensor prepared by etching LiF/HCl solution was repeatable to 10 ppm NH₃. (c) at room temperature, the stability of Ti₃C₂T_x based gas sensor prepared by two etching agents for 10 ppm NH₃; (d) response of Ti₃C₂T_x based gas sensor etched by two etching agents to different gases at room temperature.

DownLoad: Full-Size Img PowerPoint

图 6 气体分子吸附在不同端接官能团Ti₃C₂T_x上的密度泛函理论模拟结果　(a) Ti₃C₂(OH)₂, (b) Ti₃C₂O₂和(c) Ti₃C₂F₂上NH₃最小能量配置的侧面和顶部视图(1 Å = 0.1 nm)

Figure 6. DFT simulation results of gas molecules adsorbed on different terminated functional groups Ti₃C₂T_x. Side and top views of the minimum energy configuration for NH₃ on (a) Ti₃C₂(OH)₂, (b) Ti₃C₂O₂ and (c) Ti₃C₂F₂ (1 Å = 0.1 nm).

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图 7 Ti₃C₂T_x基气体传感器对NH₃的传感机理

Figure 7. Sensing mechanism of NH₃ by Ti₃C₂T_x based gas sensor.

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表 1 两种不同刻蚀剂制备获得的Ti₃C₂T_x材料比表面积

Table 1. Specific surface area of Ti₃C₂T_x prepared by two different etchers.

样品刻蚀剂比表面积/(m²·g^–1)

Ti₃C₂T_x HF溶液 5.265
Ti₃C₂T_x LiF/HCl溶液 5.263

DownLoad: CSV

表 2 图4(c)和图4(d)朗缪尔等温线系数

Table 2. Figs. 4(c) and 4(d) Langmuir isotherm coefficients.

刻蚀剂 LiF/HCl HF

工作温度室温室温
a 38.94405 14.41327
b 0.06246 0.3099

DownLoad: CSV

map

[1]	Naguib M, Kurtoglu M, Presser V, Lu J, Niu J, Heon M, Hultman L, Gogotsi Y, Barsoum M W 2011 Adv. Mater. 23 4248 Google Scholar
[2]	Deysher G, Shuck C E, Hantanasirisakul K, Frey N C, Foucher A C, Maleski K, Sarycheva A, Shenoy V B, Stach E A, Anasori B, Gogotsi Y 2020 ACS Nano 14 204 Google Scholar
[3]	Sokol M, Natu V, Kota S, Barsoum M W 2019 Trends Environ. Anal. Chem. 1 210 Google Scholar
[4]	Tao Q, Lu J, Dahlqvist M, Mockute A, Calder S, Petruhins A, Meshkian R, Rivin O, Potashnikov D, Caspi E a N, Shaked H, Hoser A, Opagiste C, Galera R M, Salikhov R, Wiedwald U, Ritter C, Wildes A R, Johansson B, Hultman L, Farle M, Barsoum M W, Rosen J 2019 Chem. of Mater. 31 2476 Google Scholar
[5]	Shein I R, Ivanovskii A L 2013 Micro Nano Lett. 8 59 Google Scholar
[6]	Ding L, Wei Y, Li L, Zhang T, Wang H, Xue J, Ding L X, Wang S, Caro J, Gogotsi Y 2018 Nat. Commun. 9 155 Google Scholar
[7]	Anasori B, Lukatskaya M R, Gogotsi Y 2017 Nat. Rev. Mater. 2 16098 Google Scholar
[8]	Ding L, Wei Y, Wang Y, Chen H, Caro J, Wang H 2017 Angew. Chem. Int. Ed. Engl. 56 1825 Google Scholar
[9]	Khazaei M, Ranjbar A, Ghorbani Asl M, Arai M, Sasaki T, Liang Y, Yunoki S 2016 Phys. Rev. B 93 205125 Google Scholar
[10]	Yang Z, Jiang L, Wang J, Liu F, He J, Liu A, Lv S, You R, Yan X, Sun P, Wang C, Duan Y, Lu G 2021 Sens. Actuators B Chem. 326 128828 Google Scholar
[11]	Tai H, Duan Z, He Z, Li X, Xu J, Liu B, Jiang Y 2019 Sens. Actuators B Chem. 298 126874 Google Scholar
[12]	Wu M, He M, Hu Q, Wu Q, Sun G, Xie L, Zhang Z, Zhu Z, Zhou A 2019 ACS Sens. 4 2763 Google Scholar
[13]	Feng A, Yu Y, Wang Y, Jiang F, Yu Y, Mi L, Song L 2017 Mater. Des. 114 161 Google Scholar
[14]	Halim J, Lukatskaya M R, Cook K M, Lu J, Smith C R, Naslund L A, May S J, Hultman L, Gogotsi Y, Eklund P, Barsoum M W 2014 Chem. Mater. 26 2374 Google Scholar
[15]	Yang S, Zhang P, Wang F, Ricciardulli A G, Lohe M R, Blom P W M, Feng X 2018 Angew. Chem. Int. Ed. Engl. 57 15491 Google Scholar
[16]	黄大朋 2020 博士学位论文 (济南: 山东大学) Huang D P 2020 Ph. D. Dissertation(Jinan: Shandong University) (in Chinese)
[17]	Lee E, VahidMohammadi A, Prorok B C, Yoon Y S, Beidaghi M, Kim D J 2017 ACS Appl. Mater. Inter. 9 37184 Google Scholar
[18]	Alhabeb M, Maleski K, Anasori B, Lelyukh P, Clark L, Sin S, Gogotsi Y 2017 Chem. Mater. 29 7633 Google Scholar
[19]	Cheng Y, Ma Y, Li L, Zhu M, Yue Y, Liu W, Wang L, Jia S, Li C, Qi T, Wang J, Gao Y 2020 ACS Nano 14 2145 Google Scholar
[20]	Halim J, Cook K M, Naguib M, Eklund P, Gogotsi Y, Rosen J, Barsoum M W 2016 Appl. Surf. Sci. 362 406 Google Scholar
[21]	Wu Y, Nie P, Wang J, Dou H, Zhang X 2017 ACS Appl. Mater. Interfaces 9 39610 Google Scholar
[22]	Kim S J, Koh H J, Ren C E, Kwon O, Maleski K, Cho S Y, Anasori B, Kim C K, Choi Y K, Kim J, Gogotsi Y, Jung H T 2018 ACS Nano 12 986 Google Scholar
[23]	Ghidiu M, Halim J, Kota S, Bish D, Gogotsi Y, Barsoum M W 2016 Chem. Mater. 28 3507 Google Scholar
[24]	Choi Y R, Yoon Y G, Choi K S, Kang J H, Shim Y S, Kim Y H, Chang H J, Lee J H, Park C R, Kim S Y, Jang H W 2015 Carbon 91 178 Google Scholar
[25]	Geistlinger H 1993 Sens. Actuators B Chem. 17 47 Google Scholar
[26]	Lu G, Ocola L E, Chen J 2009 Nanotechnology 20 445502 Google Scholar
[27]	Yu X F, Li Y C, Cheng J B, Liu Z B, Li Q Z, Li W Z, Yang X, Xiao B 2015 ACS Appl. Mater. Inter. 7 13707 Google Scholar
[28]	Tang Q, Zhou Z, Shen P 2012 J. Am. Chem. Soc. 134 16909 Google Scholar
[29]	Anasori B, Lukatskaya M R, Gogotsi Y 2017 Nature Reviews Materials 2 16098
[30]	Xiao B, Li Y C, Yu X F, Cheng J B 2016 Sens. Actuators B Chem. 235 103 Google Scholar
[31]	Ghosh R, Singh A, Santra S, Ray S K, Chandra A, Guha P K 2014 Sens. Actuators B Chem. 205 67 Google Scholar

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Preparation and gas sensing properties of a novel two-dimensional material Ti₃C₂T_xMXene