1T′-MoTe2单层: 一种有前景的电催化合成双氧水的催化剂

doi:10.1016/S1872-2067(21)64007-X

摘要/Abstract

摘要：

在酸性介质中, 氧气(O₂)的电化学两电子氧还原反应(2e-ORR)是一种新兴的合成双氧水(H₂O₂)的绿色方法. 然而, 目前该方法普遍依赖贵金属电催化剂, 严重影响了其在工业上的大规模应用. 与传统材料相比, 二维材料具有超高比表面积和表面原子比率, 这非常有利于其在催化领域的应用. 实验和理论研究结果表明, 以2H-MoS₂为代表的过渡金属二硫属化合物(TMDs)具有较强的电化学析氢性能. 最近, 有研究团队发现2H-MoTe₂在酸性介质中对O₂的电化学还原制H₂O₂具有较高的催化活性(Natl. Sci. Rev., 2020, 7, 1360‒1366), 这也为2e-ORR催化剂的开发带来了新的机遇. 然而与其他TMDs材料类似, 2H-MoTe₂只有边缘原子具有催化活性, 暴露最多的表面原子是催化惰性的, 导致其催化效率受限.
除常规2H相外, 二维MoTe₂还有稳定的1T′相. 由于1T′-MoTe₂单层是半金属特性的, 因此它的电催化性能要优于半导体性质的2H-MoTe₂. 本文通过理论计算发现, 1T′-MoTe₂的剥离能为0.45 J/m², 与2H-MoS₂的解离能相近, 表明通过机械剥离或者液相剥离来制备1T′-MoTe₂单层结构是可行的. 进一步计算了1T′-MoTe₂单层的声子谱, 并对其进行了第一性原理分子动力学(FPMD)模拟. 结果表明, 1T′-MoTe₂单层的声子谱中没有虚频, 并且其在整个FPMD模拟过程中都能保持良好的晶体结构, 表明1T′-MoTe₂单层具有良好的动力学和热力学稳定性.
中间体OOH*的吸附自由能(ΔG_OOH*)是2e-ORR催化剂的活性描述符, 本文发现1T′-MoTe₂单层的ΔG_OOH*为4.24 eV, 非常接近其催化活性理论最佳值(4.22 eV), 优于PtHg₄催化剂(4.28 eV). 此外, 采用微观动力学模拟的方法, 对1T′-MoTe₂单层的2e-ORR催化性能进行了定性分析; 通过求解反应物种的速率方程, 得到了其2e-ORR极化曲线. 根据模拟结果, 1T′-MoTe₂单层的起始电压约为0.62 V, 相当于80 mV的过电势. 这个结果略优于最先进的PtHg₄催化剂. 进一步通过动力学分析研究了1T′-MoTe₂单层催化剂对2e-ORR的选择性, 发现其生成H₂O₂步骤的动力学势垒远低于4e路径中生成O*和H₂O的动力学势垒. 从动力学角度看, 2e路径比4e路径更有利, 因此1T′-MoTe₂单层对2e-ORR具有高的选择性. 本研究为高效2e-ORR催化剂的设计提供了新思路.

关键词: 1T′-MoTe₂, 二维材料, 电催化合成双氧水, DFT计算, 微动力学模拟

Abstract:

The direct synthesis of hydrogen peroxide (H₂O₂) via a two-electron oxygen reduction reaction (2e-ORR) in acidic media has emerged as a green process for the production of this valuable chemical. However, such an approach employs expensive noble-metal-based electrocatalysts, which severely undermines its feasibility when implemented on an industrial scale. Herein, based on density functional theory computations and microkinetic modeling, we demonstrate that a novel two-dimensional (2D) material, namely a 1T′-MoTe₂ monolayer, can serve as an efficient non-precious electrocatalyst to facilitate the 2e-ORR. The 1T′-MoTe₂ monolayer is a stable 2D crystal that can be easily produced through exfoliation techniques. The surface-exposed Te sites of the 1T′-MoTe₂ monolayer exhibit a favorable OOH* binding energy of 4.24 eV, resulting in a rather high basal plane activity toward the 2e-ORR. Importantly, kinetic computations indicate that the 1T'-MoTe₂ monolayer preferentially promotes the formation of H₂O₂ over the competing four-electron ORR step. These desirable characteristics render 1T′-MoTe₂ a promising candidate for catalyzing the electrochemical reduction of O₂ to H₂O₂.

Key words: 1T′-MoTe₂, Two-dimensional catalyst, Electrochemical H₂O₂ production, Density functional theory computations, Microkinetic modeling

孙晓旭, 朱晓蓉, 王彧, 李亚飞. 1T′-MoTe₂单层: 一种有前景的电催化合成双氧水的催化剂[J]. 催化学报, 2022, 43(6): 1520-1526.

Xiaoxu Sun, Xiaorong Zhu, Yu Wang, Yafei Li. 1T′-MoTe₂ monolayer: A promising two-dimensional catalyst for the electrochemical production of hydrogen peroxide[J]. Chinese Journal of Catalysis, 2022, 43(6): 1520-1526.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64007-X

https://www.cjcatal.com/CN/Y2022/V43/I6/1520

图/表 5

Fig. 1. (a) Top and side views of the optimized structure of 1T′-MoTe2 monolayer within a 2 × 3 supercell. The brown and green balls represent Te and Mo atoms, respectively. (b) Cleavage energy as a function of the separation distance for a fracture in 1T′-MoTe2. The inset is a schematic of monolayer separation from its neighboring four-layer configuration.

Fig. 2. Top and side views of the optimized structure of OOH* (a) and H2O2 (c) adsorbed on the 1T'-MoTe2 monolayer. The red and white balls represent O and H atoms, respectively. (b) Free energy profile for the reduction of O2 to H2O2 on Pt, Pd, PtHg4, and 1T'-MoTe2 monolayer at the equilibrium potential of 2e-ORR (0.70 V). The data of Pt, Pd, and PtHg4 are taken from ref 15. (d) Computed p-band center εp for the TeI and TeII sites of 1T'-MoTe2 monolayer.

Fig. 3. Simulated polarization curves of 1T′-MoTe2 and 2H-MoTe2.

Fig. 4. (a) Schematic of a H3O+ ion attached to different O in the intermediate OOH* species (-O-OH) on the 1T'-MoTe2 monolayer; Top and side views of the optimized structures of the former O (b) and the latter O (c) configurations. The numbers represent the relative adsorption energy.

Fig. 5. Representative configurations (IS: initial state; TS: transition state; FS: final state) and the corresponding energy barriers along the kinetic pathways of OOH* protonation to H2O2 (a) and *O + H2O (b) on the 1T′-MoTe2 monolayer.

参考文献

[1]	J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, Angew. Chem. Int. Ed., 2006, 45, 6962-6984.
[2]	S. C. Perry, D. Pangotra, L. Vieira, L. I. Csepei, V. Sieber, L. Wang, C. P. de León, F. C. Walsh, Nat. Rev. Chem., 2019, 3, 442-458.
[3]	C. Samanta, Appl. Catal. A, 2008, 350, 133-149.
[4]	J. K. Edwards, S. J. Freakley, R. J. Lewis, J. C. Pritchard, G. J. Hutchings, Catal. Today, 2015, 248, 3-9.
[5]	S. J. Freakley, Q. He, J. H. Harrhy, L. Lu, D. A. Crole, D. J. Morgan, E. N. Ntainjua, J. K. Edwards, A. F. Carley, A. Y. Borisevich, C. J. Kiely, G. J. Hutchings, Science, 2016, 351, 965-968.
[6]	C. Xia, Y. Xia, P. Zhu, L. Fan, H. Wang, Science, 2019, 366, 226-231.
[7]	Z. Lu, G. Chen, S. Siahrostami, Z. Chen, K. Liu, J. Xie, L. Liao, T. Wu, D. Lin, Y. Liu, T. F. Jaramillo, J. K. Nørskov, Y. Cui, Nat. Catal., 2018, 1, 156-162.
[8]	S. Siahrostami, S. J. Villegas, A. H. B. Mostaghimi, S. Back, A. B. Farimani, H. Wang, K. A. Persson, J. Montoya, ACS Catal., 2020, 10, 7495-7511.
[9]	M. K. Debe, Nature, 2012, 486, 43-51.
[10]	S. Tian, C. Deng, Y. Tang, Q. Tang, J. Phys. Chem. C, 2020, 124, 24899-24907.
[11]	H. Zhang, Y. Tian, J. Zhao, Q. Cai, Z. Chen, Electrochim. Acta, 2017, 225, 543-550.
[12]	X. Sun, K. Li, C. Yin, Y. Wang, F. He, H. Tang, Z. Wu, Phys. Chem. Chem. Phys., 2017, 19, 17670-17676.
[13]	Y. Wang, Y. Tang, K. Zhou, J. Am. Chem. Soc., 2019, 141, 14115-14119.
[14]	A. Verdaguer-Casadevall, D. Deiana, M. Karamad, S. Siahrostami, P. Malacrida, T. W. Hansen, J. Rossmeisl, I. Chorkendorff, I. E. L. Stephens, Nano Lett., 2014, 14, 1603-1608.
[15]	S. Siahrostami, A. Verdaguer-Casadevall, M. Karamad, D. Deiana, P. Malacrida, B. Wickman, M. Escudero-Escribano, E. A. Paoli, R. Frydendal, T. W. Hansen, I. Chorkendorff, I. E. L. Stephens, J. Rossmeisl, Nat. Mater., 2013, 12, 1137-1143.
[16]	Z. Zheng, Y. H. Ng, D. Wang, R. Amal, Adv. Mater., 2016, 28, 9949-9955.
[17]	E. Pizzutilo, S. J. Freakley, S. Cherevko, S. Venkatesan, G. J. Hutchings, C. H. Liebscher, G. Dehm, K. J. J. Mayrhofer, ACS Catal., 2017, 7, 5699-5705.
[18]	H. W. Kim, M. B. Ross, N. Kornienko, L. Zhang, J. Guo, P. Yang, B. D. Mccloskey, Nat. Catal., 2018, 1, 282-290.
[19]	Y. Liu, X. Quan, X. Fan, H. Wang, S. Chen, Angew. Chem. Int. Ed., 2015, 54, 6837-6841.
[20]	F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A. C. Ferrari, R. S. Ruoff, V. Pellegrini, Science, 2015, 347, 1246501.
[21]	X. Chia, M. Pumera, Nat. Catal. 2018, 1, 909-921.
[22]	X. Zhang, A. Chen, L. Chen, Z. Zhou, Adv. Energy Mater., 2021, 11, 2003841.
[23]	S. Li, J. Sun, J. Guan, Chin. J. Catal., 2021, 42, 511-556.
[24]	T. F. Jaramillo, K. P. Jørgensen, J. Bonde, J. H. Nielsen, S. Horch, I. Chorkendorff, Science, 2007, 317, 100-102.
[25]	P. V. Sarma, A. Kayal, C. H. Sharma, M. Thalakulam, J. Mitra, M. M. Shaijumon, ACS Nano, 2019, 13, 10448-10455.
[26]	Y. Tang, Y. Wang, X. Wang, S. Li, W. Huang, L. Dong, C. Liu, Y. Li, Y. Lan, Adv. Energy Mater., 2016, 6, 1600116.
[27]	Y. Ouyang, C. Ling, Q. Chen, Z. Wang, L. Shi, J. Wang, Chem. Mater., 2016, 28, 4390-4396.
[28]	N. Ran, B. Sun, W. Qiu, E. Song, T. Chen, J. Liu, J. Phys. Chem. Lett., 2021, 12, 2102-2111.
[29]	X. Zhao, Y. Wang, Y. Da, X. Wang, T. Wang, M. Xu, X. He, W. Zhou, Y. Li, J. N. Coleman, Y. Li,, Natl. Sci. Rev., 2020, 7, 1360-1366.
[30]	K. A. N. Duerloo, Y. Li, E. J. Reed, Nat. Commun., 2014, 5, 4214.
[31]	G. Kresse, J. Hafner, Phys. Rev. B, 1993, 47, 558-561.
[32]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[33]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[34]	J. P. Perdew, L. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[35]	S. Grimme, J. Antony, S. Ehrlich, S. Krieg, J. Chem. Phys., 2010, 132, 154104.
[36]	S. Grimme, S. Ehrlich, L. Goerigk, J. Comp. Chem., 2011, 32, 1456-1465.
[37]	K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys., 2014, 140, 084106.
[38]	G. Henkelman, B. P. Uberuaga, H. Jonsson, J. Chem. Phys., 2000, 113, 9901-9904.
[39]	A. Togo, I. Tanaka, Scr. Mater., 2015, 108, 1-5.
[40]	G. J. Martyna, M. L. Klein, M. Tuckerman, J. Chem. Phys., 1992, 97, 2635-2643.
[41]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[42]	H. A. Hansen, V. Viswanathan, J. K. Nørskov, J. Phys. Chem. C, 2014, 118, 6706-6718.
[43]	Y. Li, S. Zhang, J. Yu, Q. Wang, Q, Sun, P. Jena, Nano Res., 2015, 8, 2901-2912.
[44]	Y. Wang, Y. Li, T. Heine, J. Am. Chem. Soc., 2018, 140, 12732-12735.
[45]	D. H. Keum, S. Cho, J. H. Kim, D. H. Choe, H. J. Sung, M. Kan, H. Kang, J. Y. Hwang, S. W. Kim, H. Yang, K. J. Chang, Y. H. Lee, Nat. Phys., 2015, 11, 482-486.
[46]	T. Bjorkman, A. Gulans, A. V. Krasheninnikov, R. M. Nieminen, Phys. Rev. Lett., 2012, 108, 235502.
[47]	L. Huang, T. M. McCormick, M. Ochi, Z. Zhao, M. T. Suzuki, R. Arita, Y. Wu, D. Mou, H. Cao, J. Yan, N. Trivedi, A. Kaminski, Nat. Mater., 2016, 15, 1155-1160.
[48]	X. Zhao, Y. Liu, J. Am. Chem. Soc., 2021, 143, 9423-9428.

1T′-MoTe₂单层: 一种有前景的电催化合成双氧水的催化剂

1T′-MoTe₂ monolayer: A promising two-dimensional catalyst for the electrochemical production of hydrogen peroxide

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