Synergistic Regulation of Pt Dispersion and Electronic Structure by Defect Sites in Carbon Nanotubes for Efficient Alkaline Hydrogen Evolution

doi:10.1007/s40242-026-6053-9

Abstract

Abstract: Improving the performance of Pt-based catalysts in the alkaline hydrogen evolution reaction (HER) still represents a key challenge in this research area. To construct strong metal-support interaction (MSI) is conducive to boosting the performance of Pt catalysts. Herein, the N-doped carbon nanotubes (NCNTs) and defective carbon nanotubes (DCNTs) were synthesized via thermal annealing at two calcination temperatures, and then served as the supports. Compared with the N groups, the defective sites more effectively trapped Pt nanoparticles (NPs) uniformly and firmly due to the stronger MSI. Moreover, Pt dispersion and coordination were regulated by varying the density of defective sites in CNTs. The as-synthesized Pt/DCNT-4.5 showed excellent activity for HER in alkaline media with an overpotential of 17 mV at 10 mA/cm², presenting a greatly enhanced mass activity, intrinsic activity and stability than the Pt/NCNT, and even the commercial Pt/C catalyst. The highly defective nature of the DCNT support endowed the Pt/DCNT-4.5 catalyst with strong metal-support connection that effectively hindered the agglomeration and detachment of Pt NPs, while optimizing its electronic structure. This work provides a novel approach for designing low-Pt, high-performance HER electrocatalysts.

Key words: Defect engineering, C vacancy, Hydrogen evolution reaction (HER), Metal-support interaction, Microenvironment regulation

LUO Huihui, WEI Jiaao, PENG Wenwen, XU Shiyu, LI Yuting, KE Huijie, ZHONG Sihui, CHEN Tong, CHEN Guanglan, ZHANG Youlin, LI Xiaokun, CHEN Wei. Synergistic Regulation of Pt Dispersion and Electronic Structure by Defect Sites in Carbon Nanotubes for Efficient Alkaline Hydrogen Evolution[J]. Chemical Research in Chinese Universities, 2026, 42(3): 789-797.

References

[1] Zhou Y., Wang W., Li J., Ren W., Wang L., Liu Q., Chem. Res. Chinese Universities, 2025, 41, 687.
[2] Zhang H., Wan F., Li X., Chen X., Xiong S., Xi B., Adv. Funct. Mater., 2023, 33, 2306340.
[3] Zhu J., Hu L., Zhao P., Lee L. Y. S., Wong K.-Y., Chem. Rev., 2020, 120, 851.
[4] Xia Z., Guo S., Chem. Soc. Rev., 2019, 48, 3265.
[5] Jiang B., Tang Z., Liao F., Lin H., Lu S., Li Y., Shao M., J. Mater. Chem. A., 2017, 5, 21903.
[6] Guo Q., Zhang W., Zhang S., Su Z., Gao X., Yu B., Wang D., Fan Y., Hoseini S., Zheng F., Chen W., Rare. Met., 2025, 44, 4294.
[7] Xu W., Mo X., Zhou Y., Weng Z., Mo K., Wu Y., Jiang X., Li D., Lan T., Wen H., Zheng F., Fan Y., Chen W., Acta Phys.-Chim. Sin., 2024, 40, 2308003.
[8] Zhu S., Li Z., Hou L., Kim M. G., Jang H., Liu S., Liu X., Adv. Funct. Mater., 2024, 34, 2314899.
[9] Xu C., Yu H., Huang H., Li S., Cao Y., Peng W., Li Y., Ke H., Xu S., Mo H., Wu C., Wang H., Zhang Y., Li X., Chen W., Angew. Chem. Int. Ed., 2025, 64, e202504667.
[10] Chakraborty S., Servottam S., Samal P. K., Kalita D., Rao A., Bagchi D., Peter S. C., Eswaramoorthy M., Small, 2023, 19, 2303495.
[11] Muchharla B., Sushko P. V., Sadasivuni K. K., Cao W., Tomar A., Elsayed-Ali H., Adedeji A., Karoui A., Spurgeon J. M., Kumar B., Small Struct., 2023, 5, 2300265.
[12] Dong Y., Chen J., Ying J., Xiao Y., Tian G., Symes M., Yang X., Chem. Mater., 2022, 34, 8271.
[13] Ding L., Xie Z., Yu S., Wang W., Terekhov A. Y., Canfield B. K., Capuano C. B., Keane A., Ayers K., Cullen D. A., Zhang F.-Y., Nano-Micro Letters, 2023, 15, 144.
[14] Guo F., Macdonald T. J., Sobrido A. J., Liu L., Feng J., He G., Adv. Sci., 2023, 10, 2301098.
[15] Chen Q., Wei B., Wei Y., Zhai P., Liu W., Gu X., Yang Z., Zuo J., Zhang R., Gong Y., Appl. Catal. B: Environ. Energy, 2021, 301, 120754.
[16] Shao G., Xu J., Gao S., Zhang Z., Liu S., Zhang X., Zhou Z., Carbon Energy, 2023, 6, e417.
[17] Xu C., Yu H., Huang H., Huang W., Li S., Cao Y., Lu H., Li G., Li Y., Li X., Zhang Y., Chen W., Chem. Eng. J., 2024, 489, 151295.
[18] Zhang W., Liao X., Pan X., Yan M., Li Y., Tian X., Zha, Y., Xu L., Mai L., Small, 2019, 15, 1900964.
[19] Zhou C.-A., Ma K., Zhuang Z., Ran M., Shu G., Wang C., Song L., Zheng L., Yue H., Wang D., J. Am. Chem. Soc., 2024, 146, 21453.
[20] Li D., Xu D., Pei Y., Zhang Q., Lu Y., Zhang B., J. Am. Chem. Soc., 2024, 146, 28728.
[21] Li W., Wang D., Zhang Y., Tao L., Wang T., Zou Y., Wang Y., Chen R., Wang S., Adv. Mater., 2020, 32, 1907879.
[22] Neeraj K., Han T., Vesselin N. S., No T. A., Chem. Eng. J., 2024, 499, 156550.
[23] Tao L., Qiao M., Jin R., Li Y., Xiao Z., Wang Y., Zhang N., Xie C., He Q., Jiang D., Yu G., Li Y., Wang S., Angew. Chem. Int. Ed., 2019, 58, 1019.
[24] Sheng J., Li Y., ACS Appl. Mater. & Interf., 2021, 14, 20455.
[25] Feng K., Zheng H., Zhang D., Yua G., Chang L.-Y., Chen Y., Zhong J., J. Energy Chem., 2020, 58, 364.
[26] Jang D., Lee S., Kwon N. H., Kim T., Park S., Jang K. Y., Yoon E., Choi S., Han J., Lee T.-W., Kim J., Hwang S.-J., Park S., Carbon, 2023, 208, 290.
[27] Zhao K., Zhang J., Li H., Zhang X., Hua Y., Di L., Int. J. Hydrogen Energy, 2024, 90, 1271
[28] Zhang J., Zhao Y., Chen C., Huang Y.-C., Dong C.-L., Chen C.-J., Liu R.-S., Wang C., Yan K., Li Y., Wang G., J. Am. Chem. Soc., 2019, 141, 20118.
[29] Hong Z., Shen B., Chen Y., Lin B., Gao B., J. Mater. Chem. A, 2013, 1, 11754.
[30] Lv C., Qian Y., Yan C., Ding Y., Liu Y., Chen G., Yu G., Angew. Chem. Int. Ed., 2018, 57, 10246.
[31] Xiao Z., Xie C., Wang Y., Chen R., Wang S., J. Energy Chem., 2020, 53, 208.
[32] Cheng X., Mao C., Tian J., Xia M., Yang L., Wang X., Wu Q., Hu Z., Angew. Chem. Int. Ed., 2024, 63, 2401304.
[33] Cheng Q., Hu C., Wang G., Zou Z., Yang H., Dai L., J. Am. Chem. Soc., 2020, 142, 5594.
[34] Kuang P., Wang Y., Zhu B., Xia F., Tung C. W., Wu J., Chen H. M., Yu J., Adv. Mater., 2021, 33, 2008599.
[35] Zhang J., Zhao Y., Guo X., Chen C., Dong C.-L., Liu R.-S., Han C.-P., Li Y., Gogotsi Y., Wang G., Nat. Catal., 2018, 1, 985.
[36] Guo N., Xue H., Bao A., Wang Z., Sun J., Song T., Ge X., Zhang W., Huang K., He F., Wang Q., Angew. Chem. Int. Ed., 2020, 59, 13778.
[37] Han W., Chen L., Ma B., Wang J., Song W., Fan X., Li Y., Zhang F., Peng W., J. Mater. Chem. A, 2019, 7, 4734.
[38] Tian J., Xia M., Cheng X., Mao C., Chen Y., Zhang Y., Zhou C., Xu F., Yang L., Wang X., Wu Q., Hu Z., J. Am. Chem. Soc., 2024, 146, 33640.
[39] Zeng L., Zhao Z., Lv F., Xia Z., Lu S.-Y., Li J., Sun K., Wang K., Sun Y., Huang Q., Chen Y., Zhang Q., Gu L., Lu G., Guo S., Nat. Commun., 2022, 13, 3822.
[40] Xue Q., Bai J., Han C., Chen P., Jiang J.-X., Chen Y., ACS Catal., 2018, 8, 11287.
[41] Tian X., Zhao X., Su Y.-Q., Wang L., Wang H., Dang D., Chi B., Liu H., Hensen E. J. M., Lou X. W. D., Xia B. Y., Science., 2019, 366, 850.
[42] Yang Q., Liu H., Yuan P., Jia Y., Zhuang L., Zhang H., Yan X., Liu G., Zhao Y., Liu J., J. Am. Chem. Soc., 2022, 144, 2171.
[43] Lv Y., Wang K., Du C., Huang R., Zang S., Peng P., Adv. Mater., 2026, 38, e16082.
[44] Zhao W., Xu F., Liu L., Liu M., Weng B., Adv. Mater., 2023, 35, 2308060.
[45] Li J., Zhang Q., Liu H., Appl. Phys. Lett., 2025, 127, 203903.
[46] Zhang C., Liang X., Xu R., Adv. Funct. Mater., 2021, 31, 2008298.