Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Graphical Abstract
Abstract
Keywords
Electronic Supplementary Material
References
Show full outline
Hide outline
Research Article

P-band center theory guided activation of MoS2 basal S sites for pH-universal hydrogen evolution

Chao Meng1,2, Yuanfeng Gao3, Yue Zhou3(), Kang Sun4, Yanmin Wang3, Ye Han5(), Qianqian Zhao2, Xuemin Chen6, Han Hu1 (), Mingbo Wu1
State Key Laboratory of Heavy Oil Processing, Institute of New Energy, China University of Petroleum (East China), Qingdao 266580, China
College of Electrical Engineering and Automation, Shandong University of Science and Technology, Qingdao 266590, China
College of Energy Storage Technology, Shandong University of Science and Technology, Qingdao 266590, China
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China
School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China
College of Science, Hebei University of Science and Technology, Shijiazhuang 050018, China
Show Author Information

Graphical Abstract

View original image Download original image
The rational combination of 1T and 2H phases raises the p-band center of the basal S sites while the intercalated NH4+ ions further optimize and stabilize the electronic band of these sites, thus contributing to efficient pH-universal hydrogen evolution.

Abstract

The edge S sites of thermodynamically stable 2H MoS2 are active for hydrogen evolution reaction (HER) but the active sites are scarce. Despite the dominance of the basal S sites, they are generally inert to HER because of the low p-band center. Herein, we reported a synergistic combination of phase engineering and NH4+ intercalation to promote the HER performance of MoS2. The rational combination of 1T and 2H phases raises the p-band center of the basal S sites while the intercalated NH4+ ions further optimize and stabilize the electronic band of these sites. The S sites with regulated band structures afford moderate hydrogen adsorption, thus contributing to excellent HER performance over a wide pH range. In an acid medium, this catalyst exhibits a low overpotential of 169 mV at 10 mA·cm−2 and Tafel slope of 39 mV·dec−1 with robust stability, superior to most of recently reported MoS2-based non-noble catalysts. The combined use of in/ex-situ characterizations ravels that the appearance of more unpaired electrons at the Mo 4d-orbital reduces the d-band center which upshifts the p-band center of the adjacent S for essentially improved HER performance. This work provides guidelines for the future development of layered transition-metal-dichalcogenide catalysts.

Keywords

molybdenum disulfidep-orbital electron structurebasal S siteshydrogen evolutionsynergistic mechanism

Electronic Supplementary Material

Download File(s)
12274_2022_5287_MOESM1_ESM.pdf (3.1 MB)

References

[1]

Han, A. L.; Zhou, X. F.; Wang, X. J.; Liu, S.; Xiong, Q. H.; Zhang, Q. H.; Gu, L.; Zhuang, Z. C.; Zhang, W. J.; Li, F. X. et al. One-step synthesis of single-site vanadium substitution in 1T-WS2 monolayers for enhanced hydrogen evolution catalysis. Nat. Commun. 2021, 12, 709.

Crossref Google Scholar
[2]

Cai, C.; Liu, K.; Zhu, Y. M.; Li, P. C.; Wang, Q. Y.; Liu, B.; Chen, S. Y.; Li, H. J. W.; Zhu, L.; Li, H. M. et al. Optimizing hydrogen binding on Ru sites with RuCo alloy nanosheets for efficient alkaline hydrogen evolution. Angew. Chem., Int. Ed. 2022, 61, 202113664.

Crossref Google Scholar
[3]

Li, Z. H.; Li, X. F.; Zhou, H.; Xu, Y.; Xu, S. M.; Ren, Y.; Yan, Y. F.; Yang, J. R.; Ji, K. Y.; Li, L. et al. Electrocatalytic synthesis of adipic acid coupled with H2 production enhanced by a ligand modification strategy. Nat. Commun. 2022, 13, 5009.

Crossref Google Scholar
[4]

Liu, H.; Zhang, Z.; Li, M. X.; Wang, Z. L.; Zhang, X. H.; Li, T. S.; Li, Y. P.; Tian, S. B.; Kuang, Y.; Sun, X. M. Iridium doped pyrochlore ruthenates for efficient and durable electrocatalytic oxygen evolution in acidic media. Small 2022, 18, 2202513.

Crossref Google Scholar
[5]

Zuo, S. W.; Wu, Z. P.; Zhang, H. B.; Lou, X. W. Operando monitoring and deciphering the structural evolution in oxygen evolution electrocatalysis. Adv. Energy Mater. 2022, 12, 2103383.

Crossref Google Scholar
[6]

Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, 15, 7806–7839.

Crossref Google Scholar
[7]

Li, P. S.; Duan, X. X.; Kuang, Y.; Sun, X. M. Iridium in tungsten trioxide matrix as an efficient Bi-functional electrocatalyst for overall water splitting in acidic media. Small 2021, 17, 2102078.

Crossref Google Scholar
[8]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.

Crossref Google Scholar
[9]

Qin, J. Y.; Xi, C.; Zhang, R.; Liu, T.; Zou, P. C.; Wu, D. Y.; Guo, Q. J.; Mao, J.; Xin, H. L.; Yang, J. Activating edge-Mo of 2H-MoS2 via coordination with pyridinic N-C for pH-universal hydrogen evolution electrocatalysis. ACS Catal. 2021, 11, 4486–4497.

Crossref Google Scholar
[10]

Meng, X. Y.; Ma, C.; Jiang, L. Z.; Si, R.; Meng, X. G.; Tu, Y. C.; Yu, L.; Bao, X. H.; Deng, D. H. Distance synergy of MoS2-confined rhodium atoms for highly efficient hydrogen evolution. Angew. Chem., Int. Ed. 2020, 59, 10502–10507.

Crossref Google Scholar
[11]

Huang, X. L.; Leng, M.; Xiao, W.; Li, M.; Ding, J.; Tan, T. L.; Lee, W. S. V.; Xue, J. M. Activating basal planes and S-terminated edges of MoS2 toward more efficient hydrogen evolution. Adv. Funct. Mater. 2017, 27, 1604943.

Crossref Google Scholar
[12]

Geng, S.; Tian, F. Y.; Li, M. G.; Liu, Y. Q.; Sheng, J.; Yang, W. W.; Yu, Y. S.; Hou, Y. L. Activating interfacial S sites of MoS2 boosts hydrogen evolution electrocatalysis. Nano Res. 2021, 15, 1809–1816.

Crossref Google Scholar
[13]

Niu, S. W.; Cai, J. Y.; Wang, G. M. Two-dimensional MoS2 for hydrogen evolution reaction catalysis: The electronic structure regulation. Nano Res. 2020, 14, 1985–2002.

Crossref Google Scholar
[14]

Meng, C.; Lin, M. C.; Du, X. W.; Zhou, Y. Molybdenum disulfide modified by laser irradiation for catalyzing hydrogen evolution. ACS Sustain. Chem. Eng. 2019, 7, 6999–7003.

Crossref Google Scholar
[15]

Tsai, C.; Li, H.; Park, S.; Park, J.; Han, H. S.; Nørskov, J. K.; Zheng, X. L.; Abild-Pedersen, F. Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution. Nat. Commun. 2017, 8, 15113.

Crossref Google Scholar
[16]

Wu, X.; Zhang, H. B.; Zuo, S. W.; Dong, J. C.; Li, Y.; Zhang, J.; Han, Y. Engineering the coordination sphere of isolated active sites to explore the intrinsic activity in single-atom catalysts. Nano-Micro Lett. 2021, 13, 136.

Crossref Google Scholar
[17]

Wang, Y. C.; Ren, B. Y.; Ou, J. Z.; Xu, K.; Yang, C. H.; Li, Y. X.; Zhang, H. J. Engineering two-dimensional metal oxides and chalcogenides for enhanced electro- and photocatalysis. Sci. Bull. 2021, 66, 1228–1252.

Crossref Google Scholar
[18]

Wang, J. S.; Zhang, Z. F.; Song, H. R.; Zhang, B.; Liu, J.; Shai, X. X.; Miao, L. Water dissociation kinetic-oriented design of nickel sulfides via tailored dual sites for efficient alkaline hydrogen evolution. Adv. Funct. Mater. 2021, 31, 2008578.

Crossref Google Scholar
[19]

Liu, X.; Ni, K.; Niu, C. J.; Guo, R. T.; Xi, W.; Wang, Z. Y.; Meng, J. S.; Li, J. T.; Zhu, Y. W.; Wu, P. J. et al. Upraising the O 2p orbital by integrating Ni with MoO2 for accelerating hydrogen evolution kinetics. ACS Catal. 2019, 9, 2275–2285.

Crossref Google Scholar
[20]

Sun, Q.; Dai, Z. Y.; Zhang, Z. B.; Chen, Z. L.; Lin, H. Q.; Gao, Y.; Chen, D. J. Double perovskite PrBaCo2O5.5: An efficient and stable electrocatalyst for hydrogen evolution reaction. J. Power Sources 2019, 427, 194–200.

Crossref Google Scholar
[21]

Xie, Z. J.; Huang, X.; Zhang, Z.; Xu, H. Identification of electronic descriptors for catalytic activity of transition-metal and non-metal doped MoS2. Phys. Chem. Chem. Phys. 2021, 23, 15101–15106.

Crossref Google Scholar
[22]

Liu, M. J.; Hybertsen, M. S.; Wu, Q. A physical model for understanding the activation of MoS2 basal-plane sulfur atoms for the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2020, 59, 14835–14841.

Crossref Google Scholar
[23]

Liu, P. T.; Zhu, J. Y.; Zhang, J. Y.; Tao, K.; Gao, D. Q.; Xi, P. X. Active basal plane catalytic activity and conductivity in Zn doped MoS2 nanosheets for efficient hydrogen evolution. Electrochim. Acta 2018, 260, 24–30.

Crossref Google Scholar
[24]

Xu, L. N.; Zhang, Y. H.; Feng, L. L.; Li, X.; Cui, Y. Y.; An, Q. Active basal plane catalytic activity via interfacial engineering for a finely tunable conducting polymer/MoS2 hydrogen evolution reaction multilayer structure. ACS Appl. Mater. Interfaces 2021, 13, 734–744.

Crossref Google Scholar
[25]

Maiti, P. S.; Ganai, A. K.; Bar-Ziv, R.; Enyashin, A. N.; Houben, L.; Bar Sadan, M. Cu2−xS-MoS2 nano-octahedra at the atomic scale: Using a template to activate the basal plane of MoS2 for hydrogen production. Chem. Mater. 2018, 30, 4489–4492.

Crossref Google Scholar
[26]

He, H. N.; Li, X. L.; Huang, D.; Luan, J. Y.; Liu, S. L.; Pang, W. K.; Sun, D.; Tang, Y. G.; Zhou, W. Z.; He, L. R. et al. Electron-injection-engineering induced phase transition toward stabilized 1T-MoS2 with extraordinary sodium storage performance. ACS Nano 2021, 15, 8896–8906.

Crossref Google Scholar
[27]

Tong, X.; Li, Y.; Ruan, Q. D.; Pang, N.; Zhou, Y.; Wu, D. J.; Xiong, D. Y.; Xu, S. H.; Wang, L. W.; Chu, P. K. Plasma engineering of basal sulfur sites on MoS2@Ni3S2 nanorods for the alkaline hydrogen evolution reaction. Adv. Sci. 2022, 9, 2104774.

Crossref Google Scholar
[28]

Li, G. W.; Huang, J.; Yang, Q.; Zhang, L. G.; Mu, Q. G.; Sun, Y.; Parkin, S.; Chang, K.; Felser, C. MoS2 on topological insulator Bi2Te3 thin films: Activation of the basal plane for hydrogen reduction. J. Energy Chem. 2021, 62, 516–522.

Crossref Google Scholar
[29]

Luo, Z. Y.; Li, J. J.; Li, Y. L.; Wu, D. J.; Zhang, L.; Ren, X. Z.; He, C. X.; Zhang, Q. L.; Gu, M.; Sun, X. L. Band engineering induced conducting 2H-phase MoS2 by Pd-S-Re sites modification for hydrogen evolution reaction. Adv. Energy Mater. 2022, 12, 2103823.

Crossref Google Scholar
[30]

Geng, X. M.; Sun, W. W.; Wu, W.; Chen, B.; Al-Hilo, A.; Benamara, M.; Zhu, H. L.; Watanabe, F.; Cui, J. B.; Chen, T. P. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. Nat. Commun. 2016, 7, 10672.

Crossref Google Scholar
[31]

Jiménez Sandoval, S.; Yang, D.; Frindt, R. F.; Irwin, J. C. Raman study and lattice dynamics of single molecular layers of MoS2. Phys. Rev. B 1991, 44, 3955–3962.

Crossref Google Scholar
[32]

Lu, J.; Wang, H.; Sun, Y. X.; Wang, X. Y.; Song, X. M.; Wang, R. F. Charge state manipulation induced through cation intercalation into MnO2 sheet arrays for efficient water splitting. Chem. Eng. J. 2021, 417, 127894.

Crossref Google Scholar
[33]

Al-Temimy, A.; Prenger, K.; Golnak, R.; Lounasvuori, M.; Naguib, M.; Petit, T. Impact of cation intercalation on the electronic structure of Ti3C2Tx MXenes in sulfuric acid. ACS Appl. Mater. Interfaces 2020, 12, 15087–15094.

Crossref Google Scholar
[34]

Chen, X.; Liu, Y. Q.; Gao, W. C.; Yang, G.; Qureshi, A. H.; Chen, M.; Yao, X. J.; Zhou, M.; Zhang, X. Y.; Liu, Y. J. High electrocatalytic activity of defected MX2/graphene heterostructures (M = Mo, W; X = S, Se) for hydrogen evolution reaction. J. Phys. Chem. C 2021, 125, 15292–15300.

Crossref Google Scholar
[35]

Wang, L. C.; Gao, W. C.; Chen, X.; Liu, Y. Q.; Qureshi, A. H.; Liu, Y. J.; Chen, M.; Zhang, X. Y.; Guo, Y. L.; Wang, J. L. Charge-modulated VS2 monolayer for effective hydrogen evolution reaction. J. Phys. Chem. C 2021, 125, 12004–12011.

Crossref Google Scholar
[36]

Ali, H.; Golnak, R.; Seidel, R.; Winter, B.; Xiao, J. In-situ X-ray spectroscopy of the electric double layer around TiO2 nanoparticles dispersed in aqueous solution: Implications for H2 generation. ACS Appl. Nano Mater. 2020, 3, 264–273.

Crossref Google Scholar
[37]

Singh, Y. D.; Mahanta, P.; Bora, U. Comprehensive characterization of lignocellulosic biomass through proximate, ultimate and compositional analysis for bioenergy production. Renew. Energy 2017, 103, 490–500.

Crossref Google Scholar
[38]

Tan, S.; Shi, J. J.; Yu, B. C.; Zhao, W. Y.; Li, Y. S.; Li, Y. M.; Wu, H. J.; Luo, Y. H.; Li, D. M.; Meng, Q. B. Inorganic ammonium halide additive strategy for highly efficient and stable CsPbI3 perovskite solar cells. Adv. Funct. Mater. 2021, 31, 2010813.

Crossref Google Scholar
[39]

Wang, D. Z.; Zhang, X. Y.; Bao, S. Y.; Zhang, Z. T.; Fei, H.; Wu, Z. Z. Phase engineering of a multiphasic 1T/2H MoS2 catalyst for highly efficient hydrogen evolution. J. Mater. Chem. A 2017, 5, 2681–2688.

Crossref Google Scholar
[40]

Gong, S.; Zhao, G. Y.; Lyu, P. B.; Sun, K. N. Insights into the intrinsic capacity of interlayer-expanded MoS2 as a Li-ion intercalation host. J. Mater. Chem. A 2019, 7, 1187–1195.

Crossref Google Scholar
[41]

Wu, C. Q.; Fang, Q.; Liu, Q.; Liu, D. B.; Wang, C. D.; Xiang, T.; Khalil, A.; Chen, S. M.; Song, L. Engineering interfacial charge-transfer by phase transition realizing enhanced photocatalytic hydrogen evolution activity. Inorg. Chem. Front. 2017, 4, 663–667.

Crossref Google Scholar
[42]

Zhu, J. Q.; Wang, Z. C.; Yu, H.; Li, N.; Zhang, J.; Meng, J. L.; Liao, M. Z.; Zhao, J.; Lu, X. B.; Du, L. J. et al. Argon plasma induced phase transition in monolayer MoS2. J. Am. Chem. Soc. 2017, 139, 10216–10219.

Crossref Google Scholar
[43]

Li, Y.; Zuo, S. W.; Li, Q. H.; Wu, X.; Zhang, J.; Zhang, H. B.; Zhang, J. Vertically aligned MoS2 with in-plane selectively cleaved Mo–S bond for hydrogen production. Nano Lett. 2021, 21, 1848–1855.

Crossref Google Scholar
[44]

Sun, B.; Shi, T. L.; Liu, Z. Y.; Wu, Y. N.; Zhou, J. X.; Liao, G. L. Large-area flexible photodetector based on atomically thin MoS2/graphene film. Mater. Des. 2018, 154, 1–7.

Crossref Google Scholar
[45]

Shang, B.; Cui, X. Q.; Jiao, L.; Qi, K.; Wang, Y. W.; Fan, J. C.; Yue, Y. Y.; Wang, H. Y.; Bao, Q. L.; Fan, X. F. et al. Lattice-mismatch-induced ultrastable 1T-Phase MoS2-Pd/Au for plasmon-enhanced hydrogen evolution. Nano Lett. 2019, 19, 2758–2764.

Crossref Google Scholar
[46]

Lin, X. Y.; Wang, J.; Chu, Z. Y.; Liu, D. Q.; Guo, T. T.; Yang, L. N.; Huang, Z. Y.; Mu, S. T.; Li, S. The optimization of hydrothermal process of MoS2 nanosheets and their good microwave absorption performances. Chin. Chem. Lett. 2020, 31, 1124–1128.

Crossref Google Scholar
[47]

Cheng, Z. H.; Xiao, Y. K.; Wu, W. P.; Zhang, X. Q.; Fu, Q.; Zhao, Y.; Qu, L. T. All-pH-tolerant in-plane heterostructures for efficient hydrogen evolution reaction. ACS Nano 2021, 15, 11417–11427.

Crossref Google Scholar
[48]

Zhang, G.; Liu, H. J.; Qu, J. H.; Li, J. H. Two-dimensional layered MoS2: Rational design, properties and electrochemical applications. Energy Environ. Sci. 2016, 9, 1190–1209.

Crossref Google Scholar
[49]

Liu, M. M.; Li, H. X.; Liu, S. J.; Wang, L. L.; Xie, L. B.; Zhuang, Z. C.; Sun, C.; Wang, J.; Tang, M.; Sun, S. J. et al. Tailoring activation sites of metastable distorted 1T'-phase MoS2 by Ni doping for enhanced hydrogen evolution. Nano Res. 2022, 15, 5946–5952.

Crossref Google Scholar
[50]

Wang, W.; Wu, Y. X.; Lin, Y. X.; Yao, J. X.; Wu, X. S.; Wu, C. Q.; Zuo, X. Q.; Yang, Q.; Ge, B. H.; Yang, L. et al. Confining zero-valent platinum single atoms in α-MoC1−x for pH-universal hydrogen evolution reaction. Adv. Funct. Mater. 2022, 32, 2108464.

Crossref Google Scholar
[51]

Attanayake, N. H.; Thenuwara, A. C.; Patra, A.; Aulin, Y. V.; Tran, T. M.; Chakraborty, H.; Borguet, E.; Klein, M. L.; Perdew, J. P.; Strongin, D. R. Effect of intercalated metals on the electrocatalytic activity of 1T-MoS2 for the hydrogen evolution reaction. ACS Energy Lett. 2018, 3, 7–13.

Crossref Google Scholar
[52]

Chen, Y.; Zhang, G.; Ji, Q. H.; Liu, H. J.; Qu, J. H. Triggering of low-valence molybdenum in multiphasic MoS2 for effective reactive oxygen species output in catalytic fenton-like reactions. ACS Appl. Mater. Interfaces 2019, 11, 26781–26788.

Crossref Google Scholar
[53]

Li, H. Y.; Jia, X. F.; Zhang, Q.; Wang, X. Metallic transition-metal dichalcogenide nanocatalysts for energy conversion. Chem 2018, 4, 1510–1537.

Crossref Google Scholar
[54]

Liu, L.; Yang, W. J.; Chen, H. D.; Chen, X. T.; Zhang, K. Q.; Zeng, Q.; Lei, S. L.; Huang, J. J.; Li, S. J.; Peng, S. L. High zinc-ion intercalation reaction activity of MoS2 cathode based on regulation of thermodynamic metastability and interlayer water. Electrochim. Acta 2022, 410, 140016.

Crossref Google Scholar
[55]

Sharma, S. K.; Porter, J. N.; Misra, A. K.; Acosta-Maeda, T. E.; Angel, S. M.; McKay, C. P. Standoff Raman spectroscopy for future Europa Lander missions. J. Raman Spectrosc. 2020, 51, 1782–1793.

Crossref Google Scholar
[56]

Chen, J. Z.; Liu, G. G.; Zhu, Y. Z.; Su, M.; Yin, P. F.; Wu, X. J.; Lu, Q. P.; Tan, C. L.; Zhao, M. T.; Liu, Z. Q. et al. Ag@MoS2 core–shell heterostructure as SERS platform to reveal the hydrogen evolution active sites of single-layer MoS2. J. Am. Chem. Soc. 2020, 142, 7161–7167.

Crossref Google Scholar
Nano Research
Volume 16 Issue 5,
May 2023
Pages 6228-6236
DOI: 10.1007/s12274-022-5287-1
Cite this article:
Meng C, Gao Y, Zhou Y, et al. P-band center theory guided activation of MoS2 basal S sites for pH-universal hydrogen evolution. Nano Research, 2023, 16(5): 6228-6236. https://doi.org/10.1007/s12274-022-5287-1
Topics:
Hydrogen evolution reaction
Part of a topical collection:
Key Nanomaterials for Industrial Chemical Process
Metrics & Citations  
Article History
Copyright
Return