Harnessing biomass: High-entropy phosphide nanosheets-carbon hybrid electrocatalysts for efficient hydrogen production

doi:10.1016/j.jmst.2025.07.059

Abstract

Abstract: The economically viable water electrolysis technology offers great potential for the rapid development of sustainable and clean hydrogen fuel. The multiple proton-coupled electron transfer processes lead to the sluggish kinetics of the oxygen evolution reaction at the anode, which becomes the key rate-controlling step in hydrogen production by water electrolysis. Development of electrocatalysts with superior performance for biomass electrocatalytic conversion-coupled H₂ generation has emerged as an attractive strategy to mitigate the OER hurdle. Herein, high-entropy phosphide nanosheets (NiFeCoWMoP) are grown on low-curvature hierarchically porous carbonized wood (CW) (NiFeCoWMoP/CW) via solvothermal and phosphide topological methods. The produced NiFeCoWMoP/CW is used as an integrated carbon electrode and presents a remarkable bifunctional properties towards both the hydrogen evolution reaction (HER) and glucose electrocatalytic conversion (GCR), delivering a high current density of 100 mA cm^-2 at potentials of only -0.151 V and +1.343 V in 1 M KOH, respectively. Furthermore, the NiFeCoWMoP/CW-based electrolysis system can achieve a reaction current of 100 mA cm^-2 at a low voltage of only 1.534 V for GCR coupled with H₂ production. Results from this study underscore the significance of high-entropy phosphide nanosheets as multifunctional electrocatalysts for biomass electrocatalytic conversion and hydrogen production.

Key words: High-entropy phosphide, Carbonized wood, Bifunctional electrocatalyst, Glucose electrocatalytic conversion, Hydrogen production

Ning Wei, Sufeng Zhang, Xue Yao, Yao Feng, Tianchen Cui, Scott Renneckar, Andreea Laura Chibac-Scutaru, Shaowei Chen. Harnessing biomass: High-entropy phosphide nanosheets-carbon hybrid electrocatalysts for efficient hydrogen production[J]. J. Mater. Sci. Technol., 2026, 254: 156-167.

References

[1] J.N. Tiwari, S. Sultan, C.W. Myung, T. Yoon, N. Li, M. Ha, A.M. Harzandi, H.J. Park, D.Y. Kim, S.S. Chandrasekaran, W.G. Lee, V. Vij, H. Kang, T.J. Shin, H.S. Shin, G. Lee, Z. Lee, K.S. Kim, Nat. Energy 3 (2018) 773-782.
[2] Y. He, L. Liu, C. Zhu, S. Guo, P. Golani, B. Koo, P. Tang, Z. Zhao, M. Xu, C. Zhu, P. Yu, X. Zhou, C. Gao, X. Wang, Z. Shi, L. Zheng, J. Yang, B. Shin, J. Arbiol, H. Duan, Y. Du, M. Heggen, R.E.Dunin-Borkowski, W.Guo, Q.J. Wang, Z. Zhang, Z. Liu, Nat. Catal. 5 (2022) 212-221.
[3] H. Xie, Z. Zhao, T. Liu, Y. Wu, C. Lan, W. Jiang, L. Zhu, Y. Wang, D. Yang, Z. Shao, Nature 612 (2022) 673-678.
[4] D. Voiry, R. Fullon, J. Yang, E.S.C. de Carvalho Castro, R.Kappera, I. Bozkurt, D. Kaplan, M.J. Lagos, P.E. Batson, G. Gupta, A.D. Mohite, L. Dong, D. Er, V.B. Shenoy, T. Asefa, M. Chhowalla, Nat. Mater. 15 (2016) 10 03-10 09.
[5] H.J. Niu, C. Huang, T. Sun, Z. Fang, X. Ke, R. Zhang, N. Ran, J. Wu, J. Liu, W. Zhou, Angew. Chem. Int. Ed. 63 (2024) 202401819.
[6] F. Qian, L. Peng, D. Cao, W. Jiang, C. Hu, J. Huang, X. Zhang, J. Luo, S. Chen, X. Wu, L. Song, Q. Chen, Joule 8 (2024) 2342-2356.
[7] Y. Zhai, X. Ren, Y. Sun, D. Li, B. Wang, S. Liu, Appl. Catal. B-Environ. 323 (2023) 122091.
[8] L. Huang, R. Yao, X. Wang, S. Sun, X. Zhu, X. Liu, M.G. Kim, J. Lian, F. Liu, Y. Li, H. Zong, S. Han, X. Ding, Energy Environ. Sci. 15 (2022) 2425-2434.
[9] P. Zhai, C. Wang, Y. Zhao, Y. Zhang, J. Gao, L. Sun, J. Hou, Nat. Commun. 14 (2023) 1873.
[10] L. Wu, Q. Wu, Y. Han, D. Zhang, R. Zhang, N. Song, X. Wu, J. Zeng, P. Yuan, J. Chen, A. Du, K. Huang, X. Yao, Adv. Mater. 36 (2024) 2401857.
[11] T. Wang, L. Miao, S. Zheng, H. Qin, X. Cao, L. Yang, L. Jiao, ACS Catal. 13 (2023) 4091-4100.
[12] G. Feng, Y. Pan, D. Su, D. Xia, Adv. Mater. 36 (2024) 2309715.
[13] L. Chen, Z.-H. Yin, J.-Y. Cui, C.-Q. Li, K. Song, H. Liu, J.-J. Wang, J. Am. Chem. Soc. 146 (2024) 27090-27099.
[14] S. Li, S. Wang, Y. Wang, J. He, K. Li, Y. Xu, M. Wang, S. Zhao, X. Li, X. Zhong, J. Wang, Adv. Funct. Mater. 33 (2023) 2214488.
[15] J. Wu, J. Chen, T. Yu, Z. Zhai, Y. Zhu, X. Wu, S. Yin, ACS Catal. 13 (2023) 13257-13266.
[16] X. Wu, Z.-J. Zhao, X.Shi, L. Kang, P. Das, S. Wang, S. Chu, H. Wang, K. Davey, B. Zhang, S.-Z. Qiao, J. Gong, Z.-S. Wu, Energy Environ. Sci. 17 (2024) 3042-3051.
[17] Y. Zhang, B. Zhou, Z. Wei, W. Zhou, D. Wang, J. Tian, T. Wang, S. Zhao, J. Liu, L. Tao, S. Wang, Adv. Mater. 33 (2021) 2104791.
[18] N. Wei, S. Zhang, X. Yao, Q. Li, N. Li, J. Li, D. Pan, Q. Liu, S. Chen, S. Renneckar, Adv. Sci. 12 (2024) 2412872.
[19] M. van der Ham, J.Creus, J.H. Bitter, M.T.M. Koper, P.P. Pescarmona, Chem. Rev. 124 (2024) 11915-11961.
[20] N. Wei, S. Zhang, X. Yao, Y. Feng, V. Nica, J. Yang, Q. Zhou, Sep. Purif. Technol. 343 (2024) 127178.
[21] Y. Zhang, Y. Qiu, Z. Ma, Y. Wang, Y. Zhang, Y. Ying, Y. Jiang, Y. Zhu, S. Liu, J. Mater. Chem. A 9 (2021) 10893-10908.
[22] Y. Wang, Y. Zhang, P. Xing, X. Li, Q. Du, X. Fan, Z. Cai, R. Yin, Y. Yao, W. Gan, Adv. Mater. 36 (2024) 2402391.
[23] Z. Shi, C. Mao, L. Zhong, J. Peng, M. Liu, H. Li, J. Huang, Appl. Catal. B-Environ. 339 (2023) 123123.
[24] X. Ding, H. Li, M. Su, C. Zhang, J. Shi, F. Gao, Q. Lu, ACS Appl. Mater. Interfaces 15 (2023) 52843-52852.
[25] X. Lei, Q. Tang, Y. Zheng, P. Kidkhunthod, X. Zhou, B. Ji, Y. Tang, Nat. Sustain. 6 (2023) 816-826.
[26] L. Fan, Y. Ji, G. Wang, J. Chen, K. Chen, X. Liu, Z. Wen, J. Am. Chem.Soc. 144 (2022) 7224-7235.
[27] G. Cao, J. Liang, Z. Guo, K. Yang, G. Wang, H. Wang, X. Wan, Z. Li, Y. Bai, Y. Zhang, J. Liu, Y. Feng, Z. Zheng, C. Lu, G. He, Z. Xiong, Z. Liu, S. Chen, Y. Guo, M. Zeng, J. Lin, L. Fu, Nature 619 (2023) 73-77.
[28] K. Miao, W. Jiang, Z. Chen, Y. Luo, D. Xiang, C. Wang, X. Kang, Adv. Mater. 36 (2023) 2308490.
[29] F. Wang, P. Zou, Y. Zhang, W. Pan, Y. Li, L. Liang, C. Chen, H. Liu, S. Zheng, Nat. Commun. 14 (2023) 6019.
[30] Y. Zhou, L. Gao, H. Chen, H. Wang, J. Zhang, X. Li, F. Duo, G. Guan, J. Mater. Sci.Technol. 168 (2024) 62-70.
[31] M. Cui, C. Yang, B. Li, Q. Dong, M. Wu, S. Hwang, H. Xie, X. Wang, G. Wang, L. Hu, Adv. Energy Mater. 11 (2020) 2002887.
[32] J. Wang, J. Zhang, L. Zhang, L. Chen, G. He, H. Jiang, Appl. Catal. B-Environ. 342 (2024) 123382.
[33] Y. Mei, Y. Feng, C. Zhang, Y. Zhang, Q. Qi, J. Hu, ACS Catal. 12 (2022) 10808-10817.
[34] X. Zou, J. Xie, Z. Mei, Q. Jing, X. Sheng, C. Zhang, Y. Yang, M. Sun, F. Ren, L. Wang, T. He, Y. Kong, H. Guo, Proc. Natl. Acad. Sci. U. S. A. 121 (2024) 2313239121.
[35] D. Lai, Q. Kang, F. Gao, Q. Lu, J. Mater. Chem. A 9 (2021) 17913-17922.
[36] Z. Wang, J. Li, S. Yuan, J. Yang, Z. Jin, X. Tan, J. Dang, W. Mu, G. Li, Q. Wang, Chem. Eng. J. 497 (2024) 154650.
[37] D. Li, Z. Li, Z. Chen, G. Shi, L. Wang, Z. Chen, W. Tu, R. Xia, E.I. Iwuoha, C. Liu, X. Peng, Adv. Energy Mater. 13 (2023) 2300427.
[38] G. Meng, Z. Chang, L. Zhu, C. Chen, Y. Chen, H. Tian, W. Luo, W. Sun, X. Cui, J. Shi, Nano-Micro Lett. 15 (2023) 212.
[39] E. Vijayakumar, S. Ramakrishnan, C. Sathiskumar, D.J. Yoo, J. Balamurugan, H.S. Noh, D. Kwon, Y.H. Kim, H. Lee, Chem. Eng. J. 428 (2022) 131115.
[40] H. Liu, Q. Jia, S. Huang, L. Yang, S. Wang, L. Zheng, D. Cao, J. Mater. Chem. A 10 (2022) 4 817-4 824.
[41] B. Wu, S. Gong, Y. Lin, T. Li, A. Chen, M. Zhao, Q. Zhang, L. Chen, Adv. Mater. 34 (2022) 2108619.
[42] D. Li, Z. Li, R. Zou, G. Shi, Y. Huang, W. Yang, W. Yang, C. Liu, X. Peng, Appl. Catal. B-Environ. 307 (2022) 121170.
[43] P. Zhang, Y. Liu, S. Wang, L. Zhou, T. Liu, K. Sun, H. Cao, J. Jiang, X. Wu, B. Li, Small 18 (2022) 2202725.
[44] L. He, N. Wang, B. Sun, L. Zhong, M. Yao, W. Hu, S. Komarneni, J. Cleaner Prod. 356 (2022) 131680.
[45] A. Wang, S. Gao, J. Yan, C. Zhao, M. Yu, W. Wang, J. Energy Chem. 81 (2023) 533-542.
[46] Y. Wang, Y. Zhuang, Y. Hu, F. Kong, G. Yang, O.J. Rojas, M. He, Nanoscale 15 (2023) 18033-18043.
[47] Y. Wang, M. Ni, W. Yan, C. Zhu, D. Jiang, Y. Yuan, H. Du, Adv. Funct. Mater. 34 (2023) 2311611.
[48] R. Luo, Y. Li, L. Xing, N. Wang, R. Zhong, Z. Qian, C. Du, G. Yin, Y. Wang, L. Du, Appl. Catal. B-Environ. 311 (2022) 121357.
[49] J. Jiang, H. Su, S. Song, W. Liu, N. Li, Y. Gao, L. Ge, Nano Res. 16 (2023) 12116-12125.
[50] M. Bi, Y. Zhang, X. Jiang, J. Sun, X. Wang, J. Zhu, Y. Fu, Adv. Funct. Mater. 34 (2023) 2309330.
[51] Y. Gao, Z. Chen, Y. Zhao, W. Yu, X. Jiang, M. He, Z. Li, T. Ma, Z. Wu, L. Wang, Appl. Catal. B-Environ. 303 (2022) 120879.
[52] L.A. Zavala, K. Kumar, V. Martin, F. Maillard, F. Maugé, X. Portier, L. Oliviero, L. Dubau, ACS Catal. 13 (2023) 1221-1229.
[53] L. Li, X. Cao, J. Huo, J. Qu, W. Chen, C. Liu, Y. Zhao, H. Liu, G. Wang, J. Energy Chem. 76 (2023) 195-213.
[54] Z. Xia, C. Ma, Y. Fan, Y. Lu, Y.-C. Huang, Y.Pan, Y. Wu, Q. Luo, Y. He, C.-L. Dong, S. Wang, Y. Zou, ACS Catal. 14 (2024) 1930-1938.
[55] W. Luo, H. Tian, Q. Li, G. Meng, Z. Chang, C. Chen, R. Shen, X. Yu, L. Zhu, F. Kong, X. Cui, J. Shi, Adv. Funct. Mater. 34 (2023) 2306995.
[56] N. Wei, S. Zhang, X. Yao, J. Yang, V. Nica, Q. Zhou, Sci. China Mater. 66 (2023) 4650-4662.
[57] Y. Wang, W. Yan, M. Ni, C. Zhu, H. Du, Chem. Commun. 59 (2023) 2485-2488.
[58] J. Wu, Z. Zhai, S. Yin, S. Wang, Adv. Funct. Mater. 34 (2023) 2308198.
[59] J. Li, Y. Zhang, L. Zhang, Q. Zhou, J. Yang, Y. Fu, L. Yu, Y. Sun, Z. Li, Y. Qin, D. Yi, H. Zhang, D. Wang, Z. Zhang, Angew. Chem. Int. Ed. 64 (2025) 202425006.
[60] E. Wiercigroch, E. Szafraniec, K. Czamara, M.Z. Pacia, K. Majzner, K. Kochan, A. Kaczor, M. Baranska, K. Malek, Spectroch. Acta A 185 (2017) 317-335.
[61] G. Montana-Mora, K.V. Mejia-Centeno, X. Qi, Q. Xue, J. Chacon-Borrero, F. Salu- tari, M.C. Spadaro, T. Andreu, G. Salazar-Alvarez, F. Guell, J. Llorca, J. Arbiol, P.R. Martinez-Alanis, A. Cabot, ChemSusChem 18 (2024) 202401256.
[62] H. Zhou, Y. Ren, B. Yao, Z. Li, M. Xu, L. Ma, X. Kong, L. Zheng, M. Shao, H. Duan, Nat. Commun. 14 (2023) 5621.
[63] M. Li, F. Lin, S. Zhang, R. Zhao, L. Tao, L. Li, J. Li, L. Zeng, M. Luo, S. Guo, Sci. Adv. 10 (2024) eadn2877.
[64] J. Hu, T. Guo, X. Zhong, J. Li, Y. Mei, C. Zhang, Y. Feng, M. Sun, L. Meng, Z. Wang, B. Huang, L. Zhang, Z. Wang, Adv. Mater. 36 (2024) 2310918.
[65] J. Zhou, P. Li, X. Xia, Y. Zhao, Z. Hu, Y. Xie, L. Yang, Y. Liu, Y. Du, Q. Zhou, L. Yu, Y. Yu, Appl. Catal. B-Environ. 359 (2024) 124461.