Amorphous-crystalline heterostructured RuMoNiN/Ni-MoO2 for highly efficient and stable alkaline hydrogen evolution reaction

doi:10.1016/S1872-2067(26)65011-5

Abstract

Abstract:

The amorphization and heterostructuralization of noble metal-based materials are effective approaches to enhance the electrocatalytic performance towards the hydrogen evolution reaction (HER) in water splitting. Herein, (NH₄)₄[NiH₆Mo₆O₂₄]·5H₂O (NiMo₆) polyoxometalate was employed for the Ru combination to fabricate a heterostructured catalyst consisting of amorphous Ru_MoNiN and crystalline Ni-MoO₂ (Ru_MoNiN/Ni-MoO₂) via a simple annealing process under Ar/NH₃ atmosphere. Comprehensive structural characterizations and theoretical investigations suggest that the formation of such unique amorphous-crystalline heterostructures is governed by the application of NiMo₆ precursor and Ar/NH₃ atmosphere, which leads to the joint regulation on the electronic structure of Ru sites through -NH₂ coordination and heterostructured interaction, and thus facilitating the water dissociation and H intermediates sorption steps in the alkaline HER process. Accordingly, the as-fabricated Ru_MoNiN/Ni-MoO₂ manifests excellent HER performance demanding an overpotential of only 18.3 mV at the current density of 10 mA cm^‒2 with a minimal overpotential decay rate of 0.62 mV h^‒1 during continuous operation at 1 A cm^‒2. This work offers constructive suggestions for the facile construction and structural regulation of amorphous-crystalline heterostructured noble metal-based electrocatalysts for various promising energy applications.

Key words: Noble metal, Amorphous, Heterostructured, Hydrogen evolution reaction, Electrocatalysis

Mingtao Chu, Huimin Zhang, Bianqing Ren, Jing Cao, Teng Zhang, Ping Song, Zizhun Wang, Ce Han, Weilin Xu. Amorphous-crystalline heterostructured Ru_MoNiN/Ni-MoO₂ for highly efficient and stable alkaline hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2026, 84: 96-105.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65011-5

https://www.cjcatal.com/EN/Y2026/V84/I5/96

Figures/Tables 4

Fig. 1. (a) Schematic illustration for the fabrication process of RuMoNiN/Ni-MoO2. (b) XRD patterns of RuMoNiN/Ni-MoO2, POM-pre-sample and Salt-pre-sample. TEM image (c), HRTEM image (d) and corresponding magnified lattice fringes (e) of RuMoNiN/Ni-MoO2. (f) HAADF-STEM image of the amorphous phase in RuMoNiN/Ni-MoO2. Inset: corresponding Fourier transform pattern. Elemental mappings (g) and line scanning analysis (h) of O, Mo, Ni, Ru, and N for RuMoNiN/Ni-MoO2. TEM (i), HRTEM (j) images and elemental mappings (k) of Ar-sample. (l) TEM images of POM-pre-sample.

Fig. 2. (a) XPS survey spectrum of RuMoNiN/Ni-MoO2. XPS spectra of Mo 3d (b), Ni 2p (c), and N 1s (d) for RuMoNiN/Ni-MoO2 and the POM-pre-sample. (e) XPS spectrum of Ru 3d for RuMoNiN/Ni-MoO2. (f) EPR spectra of RuMoNiN/Ni-MoO2 and POM-pre-sample.

Fig. 3. (a) LSV curves with 85% iR compensation for RuMoNiN/Ni-MoO2, POM-pre-sample, Salt-pre-sample, Ru-pre-sample, and Pt/C. Corresponding Tafel plots (b) and EIS spectra (c). (d) Electrochemical double-layer capacitances of RuMoNiN/Ni-MoO2, POM-pre-sample, Salt-pre-sample, and Ru-pre-sample. (e) Chronopotentiometry measurements of RuMoNiN/Ni-MoO2 at the current densities of 10 and 1000 mA cm?2.

Fig. 4. (a) Theoretical model of the amorphous-crystalline heterostructured RuMoNiN/Ni-MoO2 with diverse Ru sites from the top view. Bader charge analysis (b), and calculated free-energy profiles for water dissociation (c) and hydrogen sorption (d) at diverse Ru sites within RuMoNiN/Ni-MoO2.

References

[1]	B. Azizimehr, T. Armaghani, R. Ghasemiasl, A. Kaabi Nejadian, M. A. Javadi, Int. J. Hydrogen Energy, 2024, 72, 716-729.
[2]	B. S. Zainal, P. J. Ker, H. Mohamed, H. C. Ong, I. M. R. Fattah, S. M. A. Rahman, L. D. Nghiem, T. M. Indra Mahlia, Renew. Sustain. Energy Rev., 2024, 189, 113941.
[3]	T. Terlouw, C. Bauer, R. McKenna, M. Mazzotti, Energy Environ. Sci., 2022, 15, 3583-3602.
[4]	T. J. Wallington, M. Woody, G. M. Lewis, G. A. Keoleian, E. J. Adler, J. R. R. A. Martins, M. D. Collette, Joule, 2024, 8, 2190-2207.
[5]	G. Yang, Y. Guo, X. Bo, J. Colloid Interface Sci., 2022, 608, 1696-1706.
[6]	H. Wang, M. Zhou, X. Bo, L. Guo, Electrochim. Acta, 2021, 382, 138337.
[7]	N. Wang, X. Bo, M. Zhou, J. Colloid Interface Sci., 2021, 604, 885-893.
[8]	A. L. Hoang, S. Balakrishnan, A. Hodges, G. Tsekouras, A. Al-Musawi, K. Wagner, C.-Y. Lee, G. F. Swiegers, G. G. Wallace, Sustain. Energy Fuels, 2022, 7, 31-60.
[9]	H. Yoon, B. Ju, D.-W. Kim, Battery Energy, 2023, 2, 20230017.
[10]	X. Chen, X.-T. Wang, J.-B. Le, S.-M. Li, X. Wang, Y.-J. Zhang, P. Radjenovic, Y. Zhao, Y.-H. Wang, X.-M. Lin, J.-C. Dong, J.-F. Li, Nat. Commun., 2023, 14, 5289.
[11]	Y. Zhu, M. Klingenhof, C. Gao, T. Koketsu, G. Weiser, Y. Pi, S. Liu, L. Sui, J. Hou, J. Li, H. Jiang, L. Xu, W.-H. Huang, C.-W. Pao, M. Yang, Z. Hu, P. Strasser, J. Ma, Nat. Commun., 2024, 15, 1447.
[12]	Y. Zhu, K. Fan, C.-S. Hsu, G. Chen, C. Chen, T. Liu, Z. Lin, S. She, L. Li, H. Zhou, Y. Zhu, H.-M. Chen, H. Huang, Adv. Mater., 2023, 35, 2301133.
[13]	J. Xu, X. Kong, Small Methods, 2022, 6, 2101432.
[14]	F. Tian, S. Geng, M. Li, L. Qiu, F. Wu, L. He, J. Sheng, X. Zhou, Z. Chen, M. Luo, H. Liu, Y. Yu, W. Yang, S. Guo, Adv. Mater., 2025, 37, 2501230.
[15]	Q. Fu, L. W. Wong, F. Zheng, X. Zheng, C. S. Tsang, K.-H. Lai, W. Shen, T. H. Ly, Q. Deng, J. Zhao, Nat. Commun., 2023, 14, 6462.
[16]	H. Meng, Z. Chen, J. Zhu, B. You, T. Ma, W. Wei, S. Vernuccio, J. Xu, B.-J. Ni, Adv. Funct. Mater., 2024, 34, 2405270.
[17]	C. Liang, R. R. Rao, K. L. Svane, J. H. L. Hadden, B. Moss, S. B. Scott, M. Sachs, J. Murawski, A. M. Frandsen, D. J. Riley, M. P. Ryan, J. Rossmeisl, J. R. Durrant, I. E. L. Stephens, Nat. Catal., 2024, 7, 763-775.
[18]	J. Kang, F. Li, Z. Xu, X. Chen, M. Sun, Y. Li, X. Yang, L. Guo, JACS Au, 2023, 3, 2660-2676.
[19]	A. Salah, H.-D. Ren, N. Al-Ansi, A. Al-Salihy, F. A. Qaraah, S. A. Mahyoub, A. A. Ahmed, Q. A. Drmosh, ACS Appl. Mater. Interfaces, 2024, 16, 60310-60320.
[20]	S. Wang, Z. Li, T. Shen, D. Wang, ChemSusChem, 2023, 16, e202202128.
[21]	G. Lee, S. E. Jun, J. Lim, J. Kim, H. Lee, W. S. Cheon, G. W. Ryoo, B.-G. Cho, S. Lee, M. S. Kwon, I.-H. Park, H. W. Jang, S. H. Park, K. C. Kwon, Adv. Sci., 2025, 12, 2414622.
[22]	K. Wang, J. Zhou, M. Sun, F. Lin, B. Huang, F. Lv, L. Zeng, Q. Zhang, L. Gu, M. Luo, S. Guo, Adv. Mater., 2023, 35, 2300980.
[23]	H. Zhang, P. Song, X. Mei, D. Zhang, C. Liu, M. Chu, T. Zhang, C. Han, W. Xu, ACS Catal., 2025, 15, 12395-12406.
[24]	Y. Liu, X. Liu, A. R. Jadhav, T. Yang, Y. Hwang, H. Wang, L. Wang, Y. Luo, A. Kumar, J. Lee, H. T. D. Bui, M. Gyu Kim, H. Lee, Angew. Chem. Int. Ed., 2022, 61, e202114160.
[25]	W. Yu, Z. Chen, Y. Fu, W. Xiao, B. Dong, Y. Chai, Z. Wu, L. Wang, Adv. Funct. Mater., 2023, 33, 2210855.
[26]	J. Xu, S. Chen, J. Chen, J. Li, Y. Yao, Z. Wang, J. Xiong, Y. Li, Fuel, 2025, 396, 135379.
[27]	M. Zhou, Y. Zeng, Y. Liu, Y. Sun, F. Lu, X. Zhang, R. Cao, Y. Xue, X. Zeng, Y. Wu, Appl. Surf. Sci., 2022, 597, 153597.
[28]	B. Ren, X. Gong, J. Cao, D. Zhang, Z. Wang, P. Song, C. Han, W. Xu, J. Energy Chem., 2024, 92, 698-704.
[29]	K. Nomiya, T. Takahashi, T. Shirai, M. Miwa, Polyhedron, 1987, 6, 213-218.
[30]	F. Yang, R. Yao, Z. Lang, F. Yu, H. Dong, Y. Wang, Y. Li, H. Tan, ACS Energy Lett., 2023, 8, 5175-5183.
[31]	L. Kaluža, K. Jirátová, A. A. Spojakina, J. Balabánová, D. Gulková, M. Koštejn, R. Palcheva, G. Tyuliev, R. Fajgar, Catal. Lett., 2024, 154, 430-447.
[32]	J. Zhang, K. Feng, Z. Li, B. Yang, B. Yan, K.-H. Luo, JACS Au, 2023, 3, 2736-2748.
[33]	T. Yang, Y. Xu, H. Lv, M. Wang, X. Cui, G. Liu, L. Jiang, ACS Sustainable Chem. Eng., 2021, 9, 13106-13113.
[34]	J. Chen, Y. Ma, C. Cheng, T. Huang, R. Luo, J. Xu, X. Wang, T. Jiang, H. Liu, S. Liu, T. Huang, L. Zhang, W. Chen, J. Am. Chem. Soc., 2025, 147, 8720-8731.
[35]	Y. An, W. Gong, J. Wang, J. Liu, L. Zhou, Y. Xia, C. Pan, M. Wang, D. Fang, Sustainability, 2022, 14, 4880.
[36]	M. Aftabuzzaman, C. K. Kim, H. Zhou, H. K. Kim, Nanoscale, 2020, 12, 1602-1616.
[37]	S. Zhong, Z. Zhang, Q. Zhao, Z. Yue, C. Xiong, G. Chen, J. Wang, L. Li, Nat. Commun., 2024, 15, 8097.
[38]	Y. Yun, J. Shao, Y. Chen, Z. Cao, Q. Qu, H. Zheng, ACS Appl. Nano Mater., 2019, 2, 1883-1889.
[39]	J. Huang, Y. Sun, X. Du, Y. Zhang, C. Wu, C. Yan, Y. Yan, G. Zou, W. Wu, R. Lu, Y. Li, J. Xiong, Adv. Mater., 2018, 30, 1803367.
[40]	X. Gao, X. Liu, W. Zang, H. Dong, Y. Pang, Z. Kou, P. Wang, Z. Pan, S. Wei, S. Mu, J. Wang, Nano Energy, 2020, 78, 105355.
[41]	T. Liu, M. Li, P. Dong, Y. Zhang, M. Zhou, Sens. Actuat. B, 2018, 260, 962-975.
[42]	Y. Du, C. Jiang, L. Song, B. Gao, H. Gong, W. Xia, L. Sheng, T. Wang, J. He, Nano Res., 2020, 13, 2784-2790.
[43]	H. Hu, Z. Zhang, Y. Zhang, T. Thomas, H. Du, K. Huang, J. P. Attfield, M. Yang, Energy Environ. Sci., 2023, 16, 4584-4592.
[44]	A. Wu, Y. Xie, H. Ma, C. Tian, Y. Gu, H. Yan, X. Zhang, G. Yang, H. Fu, Nano Energy, 2018, 44, 353-363.
[45]	S. Guan, Z. Yuan, Z. Zhuang, H. Zhang, H. Wen, Y. Fan, B. Li, D. Wang, B. Liu, Angew. Chem. Int. Ed., 2024, 63, e202316550.
[46]	T. Gong, L. Qin, Y. Hu, J. Li, W. Zhang, L. Hui, H. Feng, Appl. Surf. Sci., 2023, 608, 155200.
[47]	J. Schuch, S. Klemenz, P. Schuldt, A.-M. Zieschang, S. Dolique, P. Connor, B. Kaiser, U. I. Kramm, B. Albert, W. Jaegermann, ChemCatChem, 2021, 13, 1772-1780.
[48]	Z. Xiao, J. Wang, C. Liu, B. Wang, Q. Zhang, Z. Xu, M. T. Sarwar, A. Tang, H. Yang, Appl. Surf. Sci., 2022, 602, 154314.
[49]	J. Luo, Y. Tuo, J. Zhang, W. Li, S. Wang, Y. Li, Y. Pan, Y. Zhou, J. Zhang, Chem. Eng. J., 2025, 510, 161519.
[50]	D. Chen, J. Liu, B. Liu, Y. Qin, X. Lin, X. Qiu, Adv. Mater., 2025, 37, 2501113.
[51]	P. Lu, J. Huo, M. Cui, Y. Dou, W. Li, H.-K. Liu, Z. Bai, S.-X. Dou, R. Ge, Adv. Funct. Mater., 2025, e16798.
[52]	K. Zhang, T. Zou, J. Zhang, S. Wang, X. Liu, H. Yang, J. Li, X. Han, Y. Han, Chem. Eng. J., 2025, 511, 162097.
[53]	R. Andaveh, A. Sabour Rouhaghdam, J. Ai, M. Maleki, K. Wang, A. Seif, G. Barati Darband, J. Li, Appl. Catal. B, 2023, 325, 122355.
[54]	S. Sidra, V. H. Hoa, D. H. Kim, J. Energy Chem., 2025, 103, 264-273.
[55]	C. Han, B. Mei, Q. Zhang, H. Zhang, P. Yao, P. Song, X. Gong, P. Cui, Z. Jiang, L. Gu, W. Xu, Chin. J. Catal., 2023, 51, 80-89.
[56]	F. Sun, Q. Tang, D.-E. Jiang, ACS Catal., 2022, 12, 8404-8433.

Amorphous-crystalline heterostructured Ru_MoNiN/Ni-MoO₂ for highly efficient and stable alkaline hydrogen evolution reaction

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 4

References

Related Articles 15

Recommended Articles

Metrics

[1]	Zijie Wan, Yuqi Yang, Zhenquan Wang, Linrui Wu, Haipeng Zhang, Qingfang Shi, Xiang Liu, Hanlin Yang, Bohan Kang, Quan Xu, Jiaqing Luo, Jian Liu. Spatial confinement and nitrogenous defect anchoring synergistically enhance Ru nanoparticles catalyst performance for industrial current densities hydrogen evolution [J]. Chinese Journal of Catalysis, 2026, 84(5): 130-143.
[2]	Peilin Liu, Xiaqing Zhuang, Tianze Cui, Zisen Wei, Hua Xu, Ruolin Zhang, Yuqi Yang, Jiaqing Luo, Weiyu Song, Yunpeng Liu, Yu Kong, Zhenxing Li, Zhen Zhao, Jian Liu, Yuanqing Sun. Dual-engine active centers of Ru single atoms and nanoclusters synergistically enhancing hydrogen evolution reaction [J]. Chinese Journal of Catalysis, 2026, 84(5): 80-95.
[3]	Tao Wei, Zhanpeng Liang, Boxin Zhang, Yunhao Xu, Zhaoxue Sun, Minghao Duo, Minghui Chen, Sheng Zhang, Bao Zhang. Efficient electrocatalytic CO₂ reduction by crystalline polymetallophthalocyanine covalent organic frameworks unprecedentedly constructed involving 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst [J]. Chinese Journal of Catalysis, 2026, 83(4): 319-329.
[4]	Jegon Lee, Do-Hyun Kim, Seulgi Ji, Sangmoon Yoon, Seung Hyun Nam, Jucheol Park, Jin Young Oh, Seung Gyo Jeong, Jong-Seong Bae, Sang A. Lee, Heechae Choi, Woo Seok Choi. Awakening catalytically active surface of BaRuO₃ thin film for alkaline hydrogen evolution [J]. Chinese Journal of Catalysis, 2026, 83(4): 341-350.
[5]	Hongwen Zhang, Yinghui Cai, Bingyue Li, Wei Shan, Hua Tang. Isolated Cu atoms and CuO nanoclusters synergistically boost hydrogen evolution over TiO₂ [J]. Chinese Journal of Catalysis, 2026, 83(4): 162-171.
[6]	Runlin Ma, Xiandi Ma, Hejing Wang, Xu Zhang, Yongzheng Fang, Menggai Jiao, Zhen Zhou. Bifunctional electrocatalysis of hydrazine oxidation and hydrogen evolution reactions on 2D CoX (X = P, S, As, Se): Insights from DFT calculations [J]. Chinese Journal of Catalysis, 2026, 82(3): 115-124.
[7]	Lin Liu, Jun Chen, Ailong Li, Shuang Kong, Ying Zhang, Yafei Qiao, Pengfei Zhang, Can Li, Hongxian Han. Harmonization of acidic OER activity and stability of ruthenium-manganese oxide by optimization of amorphous-crystalline heterostructure [J]. Chinese Journal of Catalysis, 2026, 82(3): 61-73.
[8]	Miao-Miao Shi, Yue-Xuan He, Ning Zhang, Di Bao, Da-Ming Zhao, Hai-Xia Zhong, Jun-Min Yan, Qing Jiang. Direct electrochemical liquid ammonia splitting for onsite hydrogen generation under room temperature [J]. Chinese Journal of Catalysis, 2026, 81(2): 310-318.
[9]	Jiaqi Xiang, Limiao Chen, Shanyong Chen, You-Nian Liu. Alkali cation effects in electrochemical carbon dioxide reduction [J]. Chinese Journal of Catalysis, 2026, 80(1): 38-58.
[10]	Xin Song, Zhonghua Li, Li Sheng, Yang Liu. Spin density symmetry breaking-mediated hydrogen evolution in single-atom catalysts [J]. Chinese Journal of Catalysis, 2026, 80(1): 213-226.
[11]	Binjie Du, Yuhang Xiao, Xiaohong Tan, Weidong He, Yingying Guo, Hao Cui, Chengxin Wang. Dual-phase Cu-Co/CoO heterojunctions for efficient tandem nitrate electroreduction via smooth intermediate handover [J]. Chinese Journal of Catalysis, 2026, 80(1): 270-281.
[12]	Wenbo Shi, Kai Zhu, Xiaogang Fu, Chenhong Liu, Yang Yuan, Jialiang Pan, Qing Zhang, Zhengyu Ba. Dual-site confinement strategy tuning Fe-N-C electronic structure to enhance oxygen reduction performance in PEM fuel cells [J]. Chinese Journal of Catalysis, 2026, 80(1): 293-303.
[13]	Juxia Xiong, Hao Ma, Yingjun Dong, Benjamin Liu, Xiangji Zhou, Linbo Li, Yuanmiao Sun, Xiaolong Zhang, Hui-Ming Cheng. Improving the electrocatalytic CO₂ to formate conversion on bismuth using polyaniline as an electron pump [J]. Chinese Journal of Catalysis, 2026, 80(1): 237-247.
[14]	Hong-Rui Zhu, Xi-Lun Wang, Juan-Juan Zhao, Meng-Han Yin, Hui-Min Xu, Gao-Ren Li. Efficient photoelectrochemical cell composed of Ni single atoms/P, N-doped amorphous NiFe₂O₄ as anode catalyst and Ag NPs@CuO/Cu₂O nanocubes as cathode catalyst for microplastic oxidation and CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 76(9): 159-172.
[15]	Dan Yang, Xiang Cui, Zhou Xu, Qian Yan, Yating Wu, Chunmei Zhou, Yihu Dai, Xiaoyue Wan, Yuguang Jin, Leonid M. Kustov, Yanhui Yang. Efficient electrocatalytic oxidation of glycerol toward formic acid over well-defined nickel nanoclusters capped by ligands [J]. Chinese Journal of Catalysis, 2025, 76(9): 185-197.