Autogenous force-mediated assembly: A general strategy for constructing single-atom architectures in hierarchical hybrid electrocatalysts

doi:10.1016/S1872-2067(26)65155-8

Abstract

Abstract:

The design of efficient and pH-universal ruthenium (Ru) single-atom catalysts (SACs) remains a pivotal challenge for hydrogen economy systems. Here, inspired by tubular capillary phenomena, a novel approach is introduced—autogenous force-mediated assembly—enabled by a unique asymmetric N-doped carbon nanotubes (NCNTs) scaffold with a Co-embedded sealed end. The confined geometry drives a spontaneous, directional outward migration of Co²⁺ species at room temperature, which deposit as amorphous or poorly crystalline cobalt-based compounds at the outer surface while concurrently capturing and stabilizing Ru species in single-atom configurations. And these precursors transform into well-crystallized Co₃O₄ anchored with Ru single-atom upon calcination. This process yields a precisely organized three-dimensional architecture where metallic Co nanoparticles remain confined within the NCNTs, while atomically dispersed Ru sites are firmly anchored on the exterior Co₃O₄ lattice. The gradual migration-deposition process is inherently self-limiting, ensuring uniform dispersion of Ru single-atoms (SAs). The resulting lattice confinement induces a strong electronic metal-support interaction (EMSI), which effectively suppresses atomic aggregation and optimizes the electronic structure of the active sites. The integrated system—coupling the conductive Co@NCNT with the EMSI-enhanced Ru-Co₃O₄ interface—delivers outstanding hydrogen evolution reaction performance. This work establishes a generalizable synthesis paradigm that leverages internally generated forces for the precise spatial organization of active components, presenting a versatile route toward high-performance SACs for sustainable energy conversion.

Key words: Single-atom catalysts, Hydrogen evolution reaction, Metal-support interaction, Carbon nanotubes, Three-dimensional hierarchical, material

Ting Li, Xiaohui Chen, Xiaolin Li, Qi Xiao, Hongqun Luo, Nianbing Li. Autogenous force-mediated assembly: A general strategy for constructing single-atom architectures in hierarchical hybrid electrocatalysts[J]. Chinese Journal of Catalysis, 2026, 89: 232-245.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65155-8

https://www.cjcatal.com/EN/Y2026/V89/I10/232

Figures/Tables 5

Fig. 1. The synthetic process of Co@NCNTs/Ru-Co3O4.

Fig. 2. TEM image (a), elemental mapping images (b), and HRTEM image (c) of Co@NCNTs. TEM image (d), elemental mapping images (e), EDS mapping (f), HRTEM image (g), AC HAADF-STEM image (h), 3D atom-overlapping Gaussian function fitting mapping (i) of the dashed square in (i), and the intensity profiles along the dashed rectangles in AC HAADF-STEM image (j) of Co@NCNTs/Ru-Co3O4.

Fig. 3. (a) XRD patterns of Co@NCNTs/Ru-Co3O4, Co@NCNTs/Co3O4, and Co@NCNTs. High resolution XPS spectra of Co 2p (b) and C 1s + Ru 3d (c) for Co@NCNTs/Ru-Co3O4 and Co@NCNTs/Co3O4. (d) High resolution XPS spectra of Ru 3p for Co@NCNTs/Ru-Co3O4. (e) Ru L3-edge XANES spectra of Co@NCNTs/Ru-Co3O4, Ru foil, and RuO2. (f) Calculation of oxidation state of Ru in Co@NCNTs/Ru-Co3O4 from Fig. 3(e). (g) EXAFS spectra of Co@NCNTs/Ru-Co3O4, Ru foil, and RuO2. (h) FT-EXAFS fitting curves of Co@NCNTs/Ru-Co3O4 at the R space. WT-EXAFS of RuO2 (i), Ru foil (j), and Co@NCNTs/Ru-Co3O4 (k). (l) Tauc plots of Co@NCNTs/Ru-Co3O4 and Co@NCNTs/Co3O4 obtained from UV-vis spectroscopy.

Fig. 4. HER performance evaluation. LSV curves (a,b), Tafel slopes (c,d), Nyquist plots (e,f), and Cdl curves (g,h) of Co@NCNTs/Ru-Co3O4, Co@NCNTs/Co3O4, and Co@NCNTs in 1.0 mol L-1 KOH and in 0.5 mol L-1 H2SO4, respectively. Comparison of overpotentials at 10 mA cm-2 in 1.0 mol L-1 KOH (i) and 0.5 mol L-1 H2SO4 (j) [50,55-68].

Fig. 5. (a) Charge density difference of Co@NCNTs/Ru-Co3O4 with a side view and a top view. The Co, Ru, O, C, and N atoms are represented by light blue, light green, pink, black, and blue spheres, respectively. Yellow and cyan regions represent electron accumulation and depletion, respectively. (b) PDOS of Co@NCNTs/Ru-Co3O4 and Co@NCNTs/Co3O4 with aligned Fermi level. The vertical lines mark the positions of d-band center. (c) The Gibbs free energy diagrams for complete alkaline HER over Co@NCNTs/Ru-Co3O4 and Co@NCNTs/Co3O4. (d) The schematic illustrations for each step of the alkaline HER process over the Co@NCNTs/Ru-Co3O4. The *H2O, *H + *OH, *H + OH- indicate the adsorbed H2O on the catalyst, the adsorbed H and the adsorbed OH on the catalyst, the adsorbed H is still on the catalyst while the OH is undergoing the process of desorption, respectively. (e) The H adsorption energies on the Co@NCNTs/Ru-Co3O4 and Co@NCNTs/Co3O4, respectively.

References

[1]	P. Zhou, G. Hai, G. Zhao, R. Li, X. Huang, Y. Lu, G. Wang, Appl. Catal. B, 2023, 325, 122364.
[2]	Q. Yu, Z. Zhang, S. Qiu, Y. Luo, Z. Liu, F. Yang, H. Liu, S. Ge, X. Zou, B. Ding, W. Ren, H.-M. Cheng, C. Sun, B. Liu, Nat. Commun., 2021, 12, 6051.
[3]	C. Li, B. Kim, Z. Li, R. Thapa, Y. Zhang, J.-M. Seo, R. Guan, F. Tang, J.-H. Baek, Y. H. Kim, J.-P. Jeon, N. Park, J.-B. Baek, Adv. Mater., 2024, 36, 2403151.
[4]	Y. Li, A. Feng, L. Dai, B. Xi, X. An, S. Xiong, C. An, Adv. Funct. Mater., 2024, 34, 2316296.
[5]	M. Peng, Y. Ge, R. Gao, J. Yang, A. Li, Z. Xie, Q. Yu, J. Zhang, H. Asakura, H. Zhang, Z. Liu, Q. Zhang, J. Deng, J. Zhou, W. Zhou, G. J. Hutchings, D. Ma, Science, 2025, 387, 769-775.
[6]	S. Liu, Y. Wei, M. Wang, Y. Shen, Coord. Chem. Rev., 2025, 522, 216190.
[7]	Z. Xu, Z.-S. Wu, eScience, 2025, 5, 100334.
[8]	C. Xu, Y. Hong, Z. Li, X. Di, W. Wang, X. Dong, X. Mou, Coord. Chem. Rev., 2025, 523, 216287.
[9]	Z. Huang, T. Cheng, A. H. Shah, G. Zhong, C. Wan, P. Wang, M. Ding, J. Huang, Z. Wan, S. Wang, J. Cai, B. Peng, H. Liu, Y. Huang, W. A. Goddard III, X. Duan, Nat. Catal., 2024, 7, 678-688.
[10]	J. Kim, J. Oh, S. Baskaran, T. G. Kim, S. Kim, J. Yang, J. Jung, S. M. Yoon, Appl. Catal. B, 2024, 347, 123791.
[11]	C. Li, S. H. Kim, H. Y. Lim, Q. Sun, Y. Jiang, H.-J. Noh, S.-J. Kim, J. Baek, S. K. Kwak, J.-B. Baek, Adv. Mater., 2023, 35, 2301369.
[12]	Q. Zhang, M. Lao, Y. Yu, X. Ma, M. Li, Z. Fei, P. J. Dyson, S. Wang, D. Min, Adv. Funct. Mater., 2025, 35, 2416071.
[13]	Y. Li, S. Niu, P. Liu, R. Pan, H. Zhang, N. Ahmad, Y. Shi, X. Liang, M. Cheng, S. Chen, J. Du, M. Hu, D. Wang, W. Chen, Y. Li, Angew. Chem. Int. Ed., 2024, 63, e202316755.
[14]	T. Chao, W. Xie, Y. Hu, G. Yu, T. Zhao, C. Chen, Z. Zhang, X. Hong, H. Jin, D. Wang, W. Chen, X. Li, P. Hu, Y. Li, Energy Environ. Sci., 2024, 17, 1397-1406.
[15]	Y. Liu, G. Liu, X. Chen, C. Xue, M. Sun, Y. Liu, J. Kang, X. Sun, L. Guo, Nano-Micro Lett., 2024, 16, 202.
[16]	X. Wang, Y. Zhang, H. Si, Q. Zhang, J. Wu, L. Gao, X. Wei, Y. Sun, Q. Liao, Z. Zhang, K. Ammarah, L. Gu, Z. Kang, Y. Zhang, J. Am. Chem. Soc., 2020, 142, 4298-4308.
[17]	J. Xi, H. S. Jung, Y. Xu, F. Xiao, J. W. Bae, S. Wang, Adv. Funct. Mater., 2021, 31, 2170081.
[18]	X. Chen, D. Yuan, C. Rong, C. Wu, P. Liu, H.-K. Liu, D. Wang, S.-X. Dou, Y. Dou, Adv. Powder Mater., 2025, 4, 100330.
[19]	D. Leybo, U. J. Etim, M. Monai, S. R. Bare, Z. Zhong, C. Vogt, Chem. Soc. Rev., 2024, 53, 10450-10490.
[20]	X. Wang, Y. Zhang, J. Wu, Z. Zhang, Q. Liao, Z. Kang, Y. Zhang, Chem. Rev., 2022, 122, 1273-1348.
[21]	F. Zhang, S. Hong, R. Qiao, W.-H. Huang, Z. Tang, J. Tang, C.-W. Pao, M.-H. Yeh, J. Dai, Y. Chen, J. Lu, Z. Hu, Y. Zhu, H. Wang, ACS Nano, 2025, 19, 11176-11186.
[22]	J. Wu, X. Wang, W. Zheng, Y. Sun, Y. Xie, K. Ma, Z. Zhang, Q. Liao, Z. Tian, Z. Kang, Y. Zhang, J. Am. Chem. Soc., 2022, 144, 19163-19172.
[23]	C. Liao, B. Yang, N. Zhang, M. Liu, G. Chen, X. Jiang, G. Chen, J. Yang, X. Liu, T.-S. Chan, Y.-J. Lu, R. Ma, W. Zhou, Adv. Funct. Mater., 2019, 29, 1904020.
[24]	C. Zhong, J. Zhang, L. Zhang, Y. Tu, H. Song, L. Du, Z. Cui, ACS Energy Lett., 2023, 8, 1455-1462.
[25]	J. Chen, Y. Ha, R. Wang, Y. Liu, H. Xu, B. Shang, R. Wu, H. Pan, Nano-Micro Lett., 2022, 14, 186.
[26]	F. Dong, M. Wu, Z. Chen, N. Chen, M. Bakhtbidar, A. Ruediger, G. Zhang, S. Sun, Nano Energy, 2025, 133, 110497.
[27]	J. Liu, T. Wang, Z. Lin, M. Liao, S. Liu, S. Wang, Z. Cai, H. Sun, Y. Shen, Y. Huang, Q. Li, Energy Environ. Sci., 2024, 17, 3088-3098.
[28]	R. Zhang, Y. Zhang, F. Wei, Chem. Soc. Rev., 2017, 46, 3661-3715.
[29]	M. Varón, I. Ojea-Jimenez, J. Arbiol, L. Balcells, B. Martínez, V. F. Puntes, Nanoscale, 2013, 5, 2429-2436.
[30]	L. Wang, J. Nan, J. Zhang, C. Du, H. Xiang, Y. Chen, J. Zhang, Adv. Funct. Mater., 2025, 35, 2423783.
[31]	S.-N. Zhang, Q.-Y. Liu, B.-L. Leng, Z.-Q. Wang, Z.-H. Zhang, Z.-Z. Zhong, X. Liu, J.-S. Chen, X.-H. Li, Angew. Chem. Int. Ed., 2025, 64, e202512299.
[32]	Z. Zhou, G. Ye, C. Hou, Y. Wang, Y. Zong, L. Xu, Z. Lei, D. Wu, Environ. Sci. Technol., 2025, 59, 22273-22284.
[33]	H. Liu, G. Tan, M. Li, Z. Zhang, M. Getaye Sendeku, Y. Li, Y. Kuang, X. Sun, Chem. Eng. J., 2023, 458, 141414.
[34]	Z. Wang, J. Huang, L. Wang, Y. Liu, W. Liu, S. Zhao, Z.-Q. Liu, Angew. Chem. Int. Ed., 2022, 61, e202114696.
[35]	S. Pan, H. Li, T. Wang, Y. Fu, S. Wang, Z. Xie, L. Wei, H. Li, N. Li, ACS Catal., 2024, 14, 13814-13824.
[36]	Y. Zhai, C. Jin, Q. Xia, W. Han, J. Wu, X. Zhao, X. Zhang, Adv. Funct. Mater., 2024, 34, 2311063.
[37]	D. Cao, P. Gao, Y. Shen, L. Qiao, M. Ma, X. Guo, D. Cheng, Adv. Mater., 2025, 37, 2414138.
[38]	L. Zhang, H. Jang, Y. Wang, Z. Li, W. Zhang, M. G. Kim, D. Yang, S. Liu, X. Liu, J. Cho, Adv. Sci., 2021, 8, 2004516.
[39]	Y. Zhu, S. Zhang, R. Chen, Z. Wang, W. Wu, H. Jiang, H. Chen, N. Cheng, Small, 2024, 20, 2310611.
[40]	X. Zhao, Z. Li, H. Jang, X. Wei, L. Wang, M. G. Kim, J. Cho, X. Liu, Q. Qin, Small, 2024, 20, 2311172.
[41]	H. Liu, Z. Zhang, J. Fang, M. Li, M. G. Sendeku, X. Wang, H. Wu, Y. Li, J. Ge, Z. Zhuang, D. Zhou, Y. Kuang, X. Sun, Joule, 2023, 7, 558-573.
[42]	S. Laha, Y. Lee, F. Podjaski, D. Weber, V. Duppel, L. M. Schoop, F. Pielnhofer, C. Scheurer, K. Müller, U. Starke, K. Reuter, B. V. Lotsch, Adv. Energy Mater., 2019, 9, 1803795.
[43]	S. Zhu, R. Yang, Y. Xu, X. Li, Z. Shi, L. Yu, Y. Liu, H. Li, T. Zhai, J. Am. Chem. Soc., 2025, 147, 39494-39504.
[44]	X. Chen, W. Li, C. Wang, X. Lu, J. Colloid Interface Sci., 2023, 650, 304-312.
[45]	B. Qiu, Y. Zhang, X. Guo, Y. Ma, M. Du, J. Fan, Y. Zhu, Z. Zeng, Y. Chai, J. Mater. Chem. A, 2022, 10, 719-725.
[46]	Y. Wang, Q. Lu, F. Li, D. Guan, Y. Bu, Adv. Funct. Mater., 2023, 33, 2213523.
[47]	X. Gao, Y. Chen, Y. Wang, L. Zhao, X. Zhao, J. Du, H. Wu, A. Chen, Nano-Micro Lett., 2024, 16, 237.
[48]	A. Goyal, M. T. M. Koper, Angew. Chem. Int. Ed., 2021, 60, 13452-13462.
[49]	B. Zhang, J. Wang, G. Liu, C. M. Weiss, D. Liu, Y. Chen, L. Xia, P. Zhou, M. Gao, Y. Liu, J. Chen, Y. Yan, M. Shao, H. Pan, W. Sun, Nat. Catal., 2024, 7, 441-451.
[50]	K. Kim, C. Kim, S.-M. Bak, C.-Y. Nam, J. H. Moon, Chem. Eng. J., 2024, 488, 150976.
[51]	M. Cai, Q. Zhu, X. Hou, L. Yao, Y. Zhang, X. Wu, X. Yao, H. Chen, Y. Jia, S. Feng, K. Huang, ACS Energy Lett., 2024, 9, 5587-5595.
[52]	L. Yu, Z. Ren, Mater. Today Phys., 2020, 14, 100253.
[53]	A. Dong, G. Lin, Z. Li, W. Wu, X. Cao, W. Li, L. Wang, Y. Zhao, D. Chen, L. Sun, Nat. Commun., 2025, 16, 4955.
[54]	B. Guo, W. Li, H. Chen, H. Zhang, H. Li, X. Feng, B. Li, L. Wang, Z. Wang, Z. Kou, Nano Energy, 2025, 138, 110881.
[55]	D. Liu, Z. Wang, Y. Zhang, H. Zhou, Y. Zhang, D. Li, F. Yu, Nano Res., 2024, 17, 6977-6983.
[56]	S. Zhang, F. Le, W. Jia, X. Yang, P. Hu, X. Wu, W. Shu, Y. Xie, W. Xiao, D. Jia, Small Meth., 2025, 9, 2401103.
[57]	D. Jiao, W. Lu, X. Cai, Q. Song, W. Xu, R. Wang, Y. Wang, L. Xu, Q. Wang, Int. J. Hydrogen Energy, 2024, 74, 112-120.
[58]	Z. Chen, S. Mebs, I. Mondal, H. Yang, H. Dau, Z. Kang, M. Haumann, S. Ghosh, W. Cen, M. Driess, P. W. Menezes, Adv. Funct. Mater., 2024, 34, 2402699.
[59]	H. Zhang, W. Liu, Z. Li, L. Qiao, K. Chi, X. Guo, D. Cao, D. Cheng, Adv. Sci., 2024, 11, 2401398.
[60]	X. Li, Y. Yan, Y. Yao, Y. Liu, Chem. Eng. J., 2024, 489, 151237.
[61]	X. Tao, Y. Liu, R. Lu, J. Liu, H. I. Wang, J. Yang, M. Bonn, K. Müllen, Y. Zhou, Adv. Energy Mater., 2025, 15, 2404167.
[62]	Y. Wei, J. Wang, Y. Shang, C. Lv, X. He, T. Wang, Z. Chen, L. Ji, S. Wang, J. Mater. Chem. A, 2024, 12, 5294-5306.
[63]	Z.-J. Zhang, N. Yu, H.-Y. Sun, J.-Y. Lv, Y.-S. Zhang, X. Li, C.-Y. Liu, Y.-M. Chai, B. Dong, Int. J. Hydrogen Energy, 2024, 68, 722-730.
[64]	J. Li, Q. Wang, W. Zhang, K. Zhang, D. Shen, Int. J. Hydrogen Energy, 2024, 60, 909-916.
[65]	D. Gao, J. Guo, H. He, P. Xiao, Y. Zhang, Chem. Eng. J., 2022, 430, 133110.
[66]	H. Liu, Q. Liu, Y. Shao, R. Wang, M. Cheng, J. Hu, T. Wei, B. Liu, H. Jiang, L. Qi, M. Chen, W. Lu, W. Li, X. Li, Adv. Funct. Mater., 2025, 35, 2425826.
[67]	M. Liu, H. Chen, X. Tang, H. Liu, B. Tu, W. Guo, Y. Zheng, Y. Liu, Y. Tang, R. He, W. Zhu, Small, 2022, 18, 2107444.
[68]	J. Yu, Y. Wang, Y. Jing, M. Imran Asghar, Y. Li, Y. Zhang, Q. Liu, R. Li, J. Wang, P. D. Lund, Chem. Eng. J., 2024, 484, 149406.
[69]	B. Geng, R. Chen, G. Li, K. Liu, Y. Chen, Chem. Eng. J., 2025, 521, 166626.
[70]	X. Wang, Z. Qin, J. Qian, L. Chen, K. Shen, ACS Catal., 2023, 13, 10672-10682.
[71]	C. Yue, C. Feng, G. Sun, N. Liu, H. Hao, W. Bao, X. Zhang, F. Sun, C. Zhang, J. Bi, Y. Zhou, H.-C. Chen, Y. Pan, D. Sun, Y. Lu, Energy Environ. Sci., 2024, 17, 5227-5240.
[72]	Y. Liu, X. Liu, X. Wang, H. Ning, T. Yang, J. Yu, A. Kumar, Y. Luo, H. Wang, L. Wang, J. Lee, A. R. Jadhav, H. Hu, M. Wu, M. G. Kim, H. Lee, ACS Nano, 2021, 15, 15017-15026.
[73]	B. Zhou, J. Wang, L. Guo, H. Li, W. Xiao, G. Xu, D. Chen, C. Li, Y. Du, H. Ding, Y. Zhang, Z. Wu, L. Wang, Adv. Energy Mater., 2024, 14, 2402372.
[74]	F. Shen, Z. Zhang, Z. Wang, H. Ren, X. Liang, Z. Cai, S. Yang, G. Sun, Y. Cao, X. Yang, M. Hu, Z. Hao, K. Zhou, Nat. Commun., 2024, 15, 448.
[75]	W. Shao, Z. Xing, X. Xu, D. Ye, R. Yan, T. Ma, Y. Wang, Z. Zeng, B. Yin, C. Cheng, S. Li, J. Am. Chem. Soc., 2024, 146, 27486-27498.