Enhanced Hydrogen Evolution Reaction Performance of Ni-Doped MoS₂ with 1T Structure for Alkaline Water Electrolyzer: Introduction of 1T Phase and Morphological Optimization Through Co-Sputtering Technique

Abstract

Molybdenum disulfide holds promise as a low cost and abundant catalyst for the hydrogen evolution reaction in an alkaline environment. However, its hydrogen evolution reaction activity is not sufficient for practical application because of its semiconducting properties in the 2H phase, presence of an electrochemically inert basal plane, and suboptimal hydrogen adsorption energy for hydrogen evolution reaction. In this article, we present a facile synthesis method for fabricating a Ni-doped molybdenum disulfide hydrogen evolution reaction electrode with a 1T structure through co-sputtering of molybdenum disulfide and Ni. Our results demonstrate that Ni doping not only promotes the 1T-phase yield in molybdenum disulfide structure but also activates the basal plane and improves the hydrogen adsorption energy of the edge plane. Also, the surface morphologies and 1T-phase yield, which are influenced by sputtering power and deposition time, are critical factors for the variation of hydrogen evolution reaction performance. Our Ni-doped molybdenum disulfide electrode, which exhibits high 1T yield and increased electrochemical surface area by tuning the morphology, shows an overpotential of ~91 mV at 10 mA cm⁻², nearly 2.5 times lower than that of ~227 mV observed for molybdenum disulfide. Also, the single-cell test exhibits enhanced cell performance with improved durability in the repetitive on/off evaluation for the potential application of renewable energy integration.

Keywords

alkaline water electrolysis / electrode / hydrogen evolution reaction / molybdenum disulfide / nickel / sputtering

References

[1] I. Roger, M. A. Shipman, M. D. Symes, Nat. Rev. Chem. 2017, 1, 0003.

[2] C. Lei, Y. Wang, Y. Hou, P. Liu, J. Yang, T. Zhang, X. Zhuang, M. Chen, B. Yang, L. Lei, C. Yuan, M. Qiu, X. Feng, Energy Environ. Sci. 2019, 12, 149.

[3] Z. P. Ifkovits, J. M. Evans, M. C. Meier, K. M. Papadantonakis, N. S. Lewis, Energy Environ. Sci. 2021, 14, 4740.

[4] J. M. Serra, J. F. Borrás-Morell, B. García-Baños, M. Balaguer, P. Plaza-González, J. Santos-Blasco, D. Catalán-Martínez, L. Navarrete, J. M. Catalá-Civera, Nat. Energy 2020, 5, 910.

[5] T. Wang, M. Wang, H. Yang, M. Xu, C. Zuo, K. Feng, M. Xie, J. Deng, J. Zhong, W. Zhou, T. Cheng, Y. Li, Energy Environ. Sci. 2019, 12, 3522.

[6] C. Hu, L. Zhang, J. Gong, Energy Environ. Sci. 2019, 12, 2620.

[7] G. Zhao, K. Rui, S. X. Dou, W. Sun, Adv. Funct. Mater. 2018, 28, 1803291.

[8] N. Wang, S. Song, W. Wu, Z. Deng, C. Tang, Adv. Energy Mater. 2024, 14, 2303451.

[9] M. Ďurovič, J. Hnát, K. Bouzek, J. Power Sources 2021, 493, 229708.

[10] H. G. Xu, X. Y. Zhang, Y. Ding, H. Q. Fu, R. Wang, F. Mao, P. F. Liu, H. G. Yang, Small Struct. 2023, 4, 2200404.

[11] N. Mahmood, Y. Yao, J.-W. Zhang, L. Pan, X. Zhang, J.-J. Zou, Adv. Sci. 2018, 5, 1700464.

[12] H. Li, C. Cai, Q. Wang, S. Chen, J. Fu, B. Liu, Q. Hu, K. Hu, H. Li, J. Hu, Q. Liu, S. Chen, M. Liu, Chem. Eng. J. 2022, 435, 134860.

[13] J. R. McKone, B. F. Sadtler, C. A. Werlang, N. S. Lewis, H. B. Gray, ACS Catal. 2013, 3, 166.

[14] Y. Wang, G. Zhang, W. Xu, P. Wan, Z. Lu, Y. Li, X. Sun, ChemElectroChem 2014, 1, 1138.

[15] J. Zhu, Z.-C. Wang, H. Dai, Q. Wang, R. Yang, H. Yu, M. Liao, J. Zhang, W. Chen, Z. Wei, N. Li, L. Du, D. Shi, W. Wang, L. Zhang, Y. Jiang, G. Zhang, Nat. Commun. 2019, 10, 1348.

[16] N. Jiang, Q. Tang, M. Sheng, B. You, D. Jiang, Y. Sun, Cat. Sci. Technol. 2016, 6, 1077.

[17] X. Wu, B. Yang, Z. Li, L. Lei, X. Zhang, RSC Adv. 2015, 5, 32976.

[18] M. Pi, T. Wu, W. Guo, X. Wang, D. Zhang, S. Wang, S. Chen, J. Power Sources 2017, 349, 138.

[19] J. Tian, Q. Liu, A. M. Asiri, X. Sun, J. Am. Chem. Soc. 2014, 136, 7587.

[20] Z. Shi, Y. Wang, H. Lin, H. Zhang, M. Shen, S. Xie, Y. Zhang, Q. Gao, Y. Tang, J. Mater. Chem. A 2016, 4, 6006.

[21] Z. Chen, W. Gong, S. Cong, Z. Wang, G. Song, T. Pan, X. Tang, J. Chen, W. Lu, Z. Zhao, Nano Energy 2020, 68, 104335.

[22] H. Liu, S. Hu, B. Long, H. Dai, Y. Yang, M. Yang, Q. Zhang, Z. Ke, W. Li, D. He, Z. Wang, X. Xiao, Energy Environ. Mater. 2025, 8, e12834.

[23] J. Yao, Y. Zhang, F. Gao, Q. Jin, L. Zhang, L. Xu, M. Zhang, H. Gao, P. Yu, Energy Environ. Mater. 2025, 8, e70013.

[24] Q. Li, C. Chen, W. Luo, X. Yu, Z. Chang, F. Kong, L. Zhu, Y. Huang, H. Tian, X. Cui, J. Shi, Adv. Energy Mater. 2024, 14, 2304099.

[25] L. Wu, F. Zhang, S. Song, M. Ning, Q. Zhu, J. Zhou, G. Gao, Z. Chen, Q. Zhou, X. Xing, T. Tong, Y. Yao, J. Bao, L. Yu, S. Chen, Z. Ren, Adv. Mater. 2022, 34, 2201774.

[26] J. Wang, J. Hu, S. Niu, S. Li, Y. Du, P. Xu, Small 2022, 18, 2105972.

[27] K. Zhang, J. Jia, E. Yang, S. Qi, H. Tian, J. Chen, J. Li, Y. Lou, Y. Guo, Nano Energy 2023, 114, 108601.

[28] K. Zhang, Y. Duan, N. Graham, W. Yu, Appl. Catal. Environ. 2023, 323, 122144.

[29] P. Xiao, W. Chen, X. Wang, Adv. Energy Mater. 2015, 5, 1500985.

[30] Y. Zheng, Y. Jiao, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed. 2015, 54, 52.

[31] C. Meng, X. Chen, Y. Gao, Q. Zhao, D. Kong, M. Lin, X. Chen, Y. Li, Y. Zhou, Molecules 2020, 25, 1136.

[32] G. Li, D. Zhang, Q. Qiao, Y. Yu, D. Peterson, A. Zafar, R. Kumar, S. Curtarolo, F. Hunte, S. Shannon, Y. Zhu, W. Yang, L. Cao, J. Am. Chem. Soc. 2016, 138, 16632.

[33] B. Pattengale, Y. Huang, X. Yan, S. Yang, S. Younan, W. Hu, Z. Li, S. Lee, X. Pan, J. Gu, J. Huang, Nat. Commun. 2020, 11, 4114.

[34] T. F. Jaramillo, K. P. Jørgensen, J. Bonde, J. H. Nielsen, S. Horch, I. Chorkendorff, Science 2007, 317, 100.

[35] H. Li, C. Tsai, A. L. Koh, L. Cai, A. W. Contryman, A. H. Fragapane, J. Zhao, H. S. Han, H. C. Manoharan, F. Abild-Pedersen, J. K. Nørskov, X. Zheng, Nat. Mater. 2016, 15, 48.

[36] B. Hinnemann, P. G. Moses, J. Bonde, K. P. Jørgensen, J. H. Nielsen, S. Horch, I. Chorkendorff, J. K. Nørskov, J. Am. Chem. Soc. 2005, 127, 5308.

[37] D. Voiry, M. Salehi, R. Silva, T. Fujita, M. Chen, T. Asefa, V. B. Shenoy, G. Eda, M. Chhowalla, Nano Lett. 2013, 13, 6222.

[38] J. Kibsgaard, Z. Chen, B. N. Reinecke, T. F. Jaramillo, Nat. Mater. 2012, 11, 963.

[39] Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong, H. Dai, J. Am. Chem. Soc. 2011, 133, 7296.

[40] B. Seo, G. Y. Jung, Y. J. Sa, H. Y. Jeong, J. Y. Cheon, J. H. Lee, H. Y. Kim, J. C. Kim, H. S. Shin, S. K. Kwak, S. H. Joo, ACS Nano 2015, 9, 3728.

[41] B. Gao, Y. Zhao, X. Du, Y. Chen, B. Guan, Y. Li, Y. Li, S. Ding, H. Zhao, C. Xiao, Z. Song, J Mater Chem A 2021, 9, 8394.

[42] K. M. M. D. K. Kimbulapitiya, B. Rehman, S. S. Wani, C.-T. Chen, R.-H. Cyu, A. Manikandan, M. K. Date, Y.-R. Peng, R. J. G. L. R. Kumara, F.-C. Chuang, Y.-L. Chueh, Nano Energy 2024, 122, 109235.

[43] H. Liu, S. Zhang, Y. Chai, B. Dong, Angew. Chem. 2023, 135, e202313845.

[44] M. Liu, H. Li, S. Liu, L. Wang, L. Xie, Z. Zhuang, C. Sun, J. Wang, M. Tang, S. Sun, S. Liu, Q. Zhao, Nano Res. 2022, 15, 5946.

[45] J. Deng, H. Li, J. Xiao, Y. Tu, D. Deng, H. Yang, H. Tian, J. Li, P. Ren, X. Bao, Energy Environ. Sci. 2015, 8, 1594.

[46] G. Gao, Q. Sun, A. Du, J. Phys. Chem. C 2016, 120, 16761.

[47] M. Kumar, B. Ramulu, J. S. Yu, J. Clean. Prod. 2023, 414, 137589.

[48] J. Xie, H. Zhang, S. Li, R. Wang, X. Sun, M. Zhou, J. Zhou, X. W. D. Lou, Y. Xie, Adv. Mater. 2013, 25, 5807.

[49] G. Ye, Y. Gong, J. Lin, B. Li, Y. He, S. T. Pantelides, W. Zhou, R. Vajtai, P. M. Ajayan, Nano Lett. 2016, 16, 1097.

[50] Z. Wang, Y. Zhang, E. C. Neyts, X. Cao, X. Zhang, B. W.-L. Jang, C. Liu, ACS Catal. 2018, 8, 2093.

[51] Y. Kim, D. H. K. Jackson, D. Lee, M. Choi, T.-W. Kim, S.-Y. Jeong, H.-J. Chae, H. W. Kim, N. Park, H. Chang, T. F. Kuech, H. J. Kim, Adv. Funct. Mater. 2017, 27, 1701825.

[52] Q. Tang, D. Jiang, ACS Catal. 2016, 6, 4953.

[53] D. Liang, Y.-W. Zhang, P. Lu, Z. G. Yu, Nanoscale 2019, 11, 18329.

[54] B. Gao, X. Du, Y. Li, S. Ding, C. Xiao, Z. Song, ACS Appl. Mater. Interfaces 2020, 12, 877.

[55] C. Tan, W. Zhao, A. Chaturvedi, Z. Fei, Z. Zeng, J. Chen, Y. Huang, P. Ercius, Z. Luo, X. Qi, B. Chen, Z. Lai, B. Li, X. Zhang, J. Yang, Y. Zong, C. Jin, H. Zheng, C. Kloc, H. Zhang, Small 2016, 12, 1866.

[56] M. Acerce, D. Voiry, M. Chhowalla, Nat. Nanotech 2015, 10, 313.

[57] W. Chen, J. Gu, Q. Liu, R. Luo, L. Yao, B. Sun, W. Zhang, H. Su, B. Chen, P. Liu, D. Zhang, ACS Nano 2018, 12, 308.

[58] C. Tan, Z. Luo, A. Chaturvedi, Y. Cai, Y. Du, Y. Gong, Y. Huang, Z. Lai, X. Zhang, L. Zheng, X. Qi, M. H. Goh, J. Wang, S. Han, X.-J. Wu, L. Gu, C. Kloc, H. Zhang, Adv. Mater. 2018, 30, 1705509.

[59] Y. Sun, Y. Zang, W. Tian, X. Yu, J. Qi, L. Chen, X. Liu, H. Qiu, Energy Environ. Sci. 2022, 15, 1201.

[60] J. Zhu, Z. Wang, H. Yu, N. Li, J. Zhang, J. Meng, M. Liao, J. Zhao, X. Lu, L. Du, R. Yang, D. Shi, Y. Jiang, G. Zhang, J. Am. Chem. Soc. 2017, 139, 10216.

[61] Y.-C. Lin, D. O. Dumcenco, Y.-S. Huang, K. Suenaga, Nat. Nanotech 2014, 9, 391.

[62] A. L. Friedman, A. T. Hanbicki, F. K. Perkins, G. G. Jernigan, J. C. Culbertson, P. M. Campbell, Sci. Rep. 2017, 7, 3836.

[63] M. Wu, J. Zhan, K. Wu, Z. Li, L. Wang, B. Geng, L. Wang, D. Pan, J. Mater. Chem. A 2017, 5, 14061.

[64] S. Shi, Z. Sun, Y. H. Hu, J. Mater. Chem. A 2018, 6, 23932.

[65] C. Gómez-Sacedón, A. R. González-Elipe, V. Rodríguez-Pintor, J. M. Luque-Centeno, F. Yubero, J. Gil-Rostra, A. De Lucas-Consuegra, Curr. Opin. Electrochem. 2025, 49, 101622.

[66] Q.-N. Ha, C.-H. Yeh, N. S. Gultom, D.-H. Kuo, J. Mater. Chem. A 2024, 12, 460.

[67] H.-S. Kim, M. D. Kumar, J. Kim, D. Lim, Sensors Actuators A Phys. 2018, 269, 355.

[68] D.-S. Um, M.-J. Jin, J.-C. Woo, D.-P. Kim, J. Park, Y. Jo, G.-H. Kim, Crystals 2021, 11, 351.

[69] Y. Lee, X. Zhang, W. Zhang, M. Chang, C. Lin, K. Chang, Y. Yu, J. T. Wang, C. Chang, L. Li, T. Lin, Adv. Mater. 2012, 24, 2320.

[70] W. Li, G. Liu, J. Li, Y. Wang, L. Ricardez-Sandoval, Y. Zhang, Z. Zhang, Appl. Surf. Sci. 2019, 498, 143869.

[71] Y. Li, L. Wang, S. Zhang, X. Dong, Y. Song, T. Cai, Y. Liu, Cat. Sci. Technol. 2017, 7, 718.

[72] S.-F. Chen, T. Wu, Y. Soo, Sci. Rep. 2023, 13, 15184.

[73] X. Fan, P. Xu, D. Zhou, Y. Sun, Y. C. Li, M. A. T. Nguyen, M. Terrones, T. E. Mallouk, Nano Lett. 2015, 15, 5956.

[74] J. Bai, B. Zhao, J. Zhou, J. Si, Z. Fang, K. Li, H. Ma, J. Dai, X. Zhu, Y. Sun, Small 2019, 15, 1805420.

[75] D. Kong, H. Wang, J. J. Cha, M. Pasta, K. J. Koski, J. Yao, Y. Cui, Nano Lett. 2013, 13, 1341.

[76] L. Cai, W. Cheng, T. Yao, Y. Huang, F. Tang, Q. Liu, W. Liu, Z. Sun, F. Hu, Y. Jiang, W. Yan, S. Wei, J. Phys. Chem. C 2017, 121, 15071.

[77] X. Chen, Z. Wang, Y. Wei, X. Zhang, Q. Zhang, L. Gu, L. Zhang, N. Yang, R. Yu, Angew. Chem. Int. Ed. 2019, 58, 17621.

[78] X. Gan, L. Y. S. Lee, K. Wong, T. W. Lo, K. H. Ho, D. Y. Lei, H. Zhao, ACS Appl. Energy Mater. 2018, 1, 4754.

[79] A. Manikandan, P. R. Ilango, C.-W. Chen, Y.-C. Wang, Y.-C. Shih, L. Lee, Z. M. Wang, H. Ko, Y.-L. Chueh, J. Mater. Chem. A 2018, 6, 15320.

[80] U. Maitra, U. Gupta, M. De, R. Datta, A. Govindaraj, C. N. R. Rao, Angew. Chem. Int. Ed. 2013, 52, 13057.

[81] J. Zhang, T. Wang, P. Liu, S. Liu, R. Dong, X. Zhuang, M. Chen, X. Feng, Energy Environ. Sci. 2016, 9, 2789.

[82] T. Shinagawa, A. T. Garcia-Esparza, K. Takanabe, Sci. Rep. 2015, 5, 13801.

[83] Q. Qin, L. Chen, T. Wei, X. Liu, Small 2019, 15, 1803639.

[84] M. Yang, Y.-X. Guo, Z. Liu, X.-Y. Li, Q. Huang, X.-Y. Yang, C.-F. Ye, Y. Li, J.-P. Liu, L.-H. Chen, B.-L. Su, Y.-L. Wang, Langmuir 2023, 39, 236.

[85] J. Hafner, G. Kresse, in Properties of Complex Inorganic Solids (Eds: A. Gonis, A. Meike, P. E. A. Turchi), Springer US, Boston, MA 1997, pp. 69–82.

[86] G. Kresse, J. Furthmüller, Phys. Rev. B 1996, 54, 11169.

[87] G. Kresse, D. Joubert, Phys. Rev. B 1999, 59, 1758.

[88] P. E. Blöchl, Phys. Rev. B 1994, 50, 17953.

[89] J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, C. Fiolhais, Phys. Rev. B 1992, 46, 6671.

[90] S. N. Maximoff, M. Ernzerhof, G. E. Scuseria, J. Chem. Phys. 2004, 120, 2105.

[91] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

[92] Y. Inada, H. Orita, J. Comput. Chem. 2008, 29, 225.

[93] J. W. Lee, J. H. Lee, C. Lee, H.-S. Cho, M. Kim, S.-K. Kim, J. H. Joo, W.-C. Cho, C.-H. Kim, Chem. Eng. J. 2022, 428, 131149.

RIGHTS & PERMISSIONS

2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.