Amino Pre-Coordination Confinement-Induced PtCo Ordered Intermetallics with Declined H₂O Dissociation Barrier for Boosted Ammonia Borane Hydrolysis

Abstract

Hydrolysis of ammonia borane is deemed as a promising technique for robust hydrogen production, yet its deployment is still restricted due to the sluggish kinetics of the water dissociation step. An appropriate catalyst that can effectively reduce the H₂O dissociation barrier is quite desirable for sustainable ammonia borane-to-hydrogen conversion. Herein, an amino pre-coordination confinement strategy is profiled to achieve sub-2 nm ordered PtCo intermetallics uniformly on N-doped hollow mesoporous carbon spheres (O-PtCo/NHMS) for ammonia borane catalytic hydrolysis. Such a confined approach showcases the capacity of preventing nanoparticles from agglomeration and growth for accurate size control and can be extended to other ordered intermetallic systems (e.g. PtFe and PtCu). As for the ammonia borane hydrolysis, the ordered PtCo intermetallics have delivered a five times higher turnover frequency activity of 1264.1 min⁻¹ than that of the disordered PtCo catalyst, together with excellent catalytic durability. Mechanism studies indicate that the ordered PtCo structure promotes the balanced adsorption of H₂O and ammonia borane molecules at Co and Pt sites and reduces the energy barrier for the rate-determining H₂O dissociation step to boost the ammonia borane hydrolysis. This work provides valuable insights into the rational design of efficient ordered PtM intermetallic catalysts and expands their application in hydrogen production via ammonia borane hydrolysis.

Keywords

ammonia borane / confined synthesis / hydrogen production / intermetallics / water dissociation

References

[1] V. Vallejo, Q. Nguyen, A. P. Ravikumar, Nat. Energy 2024, 9, 1571.

[2] Y. Xie, S. Xu, A. C. Meng, B. Zheng, Z. Chen, J. M. Tour, J. Lin, Energy Environ. Sci. 2024, 17, 8670.

[3] K. de Kleijne, M. A. J. Huijbregts, F. Knobloch, R. van Zelm, J. P. Hilbers, H. de Coninck, S. V. Hanssen, Nat. Energy 2024, 9, 1139.

[4] L. Zhang, Y. Lei, Y. Yang, D. Wang, Y. Zhao, X. Xiang, H. Shang, B. Zhang, Adv. Sci. 2024, 11, 2407475.

[5] Y. Chen, Z. Lang, K. Feng, K. Wang, Y. Li, Z. Kang, L. Guo, J. Zhong, J. Lu, Nat. Commun. 2024, 15, 9113.

[6] C. Wan, R. Li, J. Wang, D.-G. Cheng, F. Chen, L. Xu, M. Gao, Y. Kang, M. Eguchi, Y. Yamauchi, Angew. Chem. Int. Ed. 2024, 63, e202404505.

[7] S. Guan, Z. Yuan, S. Zhao, Z. Zhuang, H. Zhang, R. Shen, Y. Fan, B. Li, D. Wang, B. Liu, Angew. Chem. Int. Ed. 2024, 63, e202408193.

[8] Y. Li, J. Liao, Y. Feng, J. Li, Q. Liu, W. Zhou, M. He, H. Li, Adv. Funct. Mater. 2024, 34, 2405361.

[9] S. Guan, Y. Liu, H. Zhang, R. Shen, H. Wen, N. Kang, J. Zhou, B. Liu, Y. Fan, J. Jiang, B. Li, Adv. Sci. 2023, 10, 2300726.

[10] J. Liao, Y. Li, J. Tian, Y. Feng, Q. Liu, H. Li, J. Colloid Interface Sci. 2025, 680, 78.

[11] J. Li, Y. Feng, X. Li, T. Zhang, X. Liu, N. Wang, Q. Sun, ACS Catal. 2024, 14, 14665.

[12] J. Liao, Y. Shao, Y. Feng, J. Zhang, C. Song, W. Zeng, J. Tang, H. Dong, Q. Liu, H. Li, Appl. Catal. B 2023, 320, 121973.

[13] J. Li, Q. Guan, H. Wu, W. Liu, Y. Lin, Z. Sun, X. Ye, X. Zheng, H. Pan, J. Zhu, S. Chen, W. Zhang, S. Wei, J. Lu, J. Am. Chem. Soc. 2019, 141, 14515.

[14] S. Zhou, Y. Yang, P. Yin, Z. Ren, L. Wang, M. Wei, ACS Appl. Mater. Interfaces 2022, 14, 5275.

[15] A. Zhu, Y. Cao, N. Zhao, Y. Jin, Y. Li, L. Yang, C. Zhang, Y. Gao, Z. Zhang, Y. Zhang, W. Xie, J. Am. Chem. Soc. 2024, 146, 33002.

[16] S. Wang, S. Li, Y. Yu, T. Zhang, J. Qu, Q. Sun, Small Methods 2024, 8, 2400376.

[17] Y. Wang, L. Sun, H. Lv, C. Zheng, B. Liu, CCS Chem. 2022, 5, 1896.

[18] C. Wan, G. Li, J. Wang, L. Xu, D.-G. Cheng, F. Chen, Y. Asakura, Y. Kang, Y. Yamauchi, Angew. Chem. Int. Ed. 2023, 62, e202305371.

[19] Y. Meng, Q. Sun, T. Zhang, J. Zhang, Z. Dong, Y. Ma, Z. Wu, H. Wang, X. Bao, Q. Sun, J. Yu, J. Am. Chem. Soc. 2023, 145, 5486.

[20] R. Xu, H. Li, L. Xu, Y. Pan, M. Ge, C. Wang, Z. Sun, Chem. Eng. J. 2024, 479, 147773.

[21] Z. Zhong, Y. Tu, L. Zhang, J. Ke, C. Zhong, W. Tan, L. Wang, J. Zhang, H. Song, L. Du, Z. Cui, ACS Catal. 2024, 14, 2917.

[22] H. Lv, B. Liu, Chem. Soc. Rev. 2024, 53, 11321.

[23] Y. Yuan, E. Huang, S. Hwang, P. Liu, J. G. Chen, Nat. Commun. 2024, 15, 6529.

[24] Z. Shi, Z. Liu, W. Liu, P. Song, X. Liu, M. Wang, J. Electroanal. Chem. 2023, 950, 117900.

[25] P. Liu, A. Klyushin, P. Chandramathy Surendran, A. Fedorov, W. Xie, C. Zeng, X. Huang, ACS Nano 2023, 17, 24395.

[26] X. Wang, Y. Tong, W. Feng, P. Liu, X. Li, Y. Cui, T. Cai, L. Zhao, Q. Xue, Z. Yan, X. Yuan, W. Xing, Nat. Commun. 2023, 14, 3767.

[27] H. Lv, R. Wei, X. Guo, L. Sun, B. Liu, J. Phys. Chem. C 2021, 12, 696.

[28] X.-K. Wan, H. B. Wu, B. Y. Guan, D. Luan, X. W. Lou, Adv. Mater. 2020, 32, 1901349.

[29] K. Wan, C. Luo, J. Wang, H. Chen, J. Zhang, B. Li, M. Chai, P. Ming, C. Zhang, ACS Catal. 2024, 14, 10181.

[30] H. Huang, X. Guo, C. Zhang, L. Yang, Q. Jiang, H. He, M. A. Amin, W. A. Alshahrani, J. Zhang, X. Xu, Y. Yamauchi, ACS Nano 2024, 18, 10341.

[31] Q. Li, X. Wang, Z. Xie, X. Peng, L. Guo, X. Yu, X. Yang, Z. Lu, X. Zhang, L. Li, Appl. Catal. B 2022, 305, 121020.

[32] W. Yu, H. Huang, Y. Qin, D. Zhang, Y. Zhang, K. Liu, Y. Zhang, J. Lai, L. Wang, Adv. Energy Mater. 2022, 12, 2200110.

[33] X. Wang, N. Zhang, S. Guo, H. Shang, X. Luo, Z. Sun, Z. Wei, Y. Lei, L. Zhang, D. Wang, Y. Zhao, F. Zhang, L. Zhang, X. Xiang, W. Chen, B. Zhang, J. Am. Chem. Soc. 2024, 146, 21357.

[34] Z. Tian, W. Wang, C. Dong, X. Deng, G.-H. Wang, ACS Nano 2023, 17, 3889.

[35] X. Wang, N. Zhang, H. Shang, H. Duan, Z. Sun, L. Zhang, Y. Lei, X. Luo, L. Zhang, B. Zhang, W. Chen, Nat. Commun. 2025, 16, 470.

[36] S. Chen, B. Gong, J. Gu, Y. Lin, B. Yang, Q. Gu, R. Jin, Q. Liu, W. Ying, X. Shi, W. Xu, L. Cai, Y. Li, Z. Sun, S. Wei, W. Zhang, J. Lu, Angew. Chem. Int. Ed. 2022, 61, e202211919.

[37] L. Zhang, N. Zhang, H. Shang, Z. Sun, Z. Wei, J. Wang, Y. Lei, X. Wang, D. Wang, Y. Zhao, Z. Sun, F. Zhang, X. Xiang, B. Zhang, W. Chen, Nat. Commun. 2024, 15, 9440.

[38] Y. Cao, Y. Wang, J. Nie, C. Gao, W. Cao, W. Wang, H. Xi, W. Chen, P. Zhong, X. Ma, J. Colloid Interface Sci. 2024, 671, 553.

[39] W. R. Mason III, H. B. Gray, J. Am. Chem. Soc. 1968, 90, 5721.

[40] Z. Lionet, T.-H. Kim, Y. Horiuchi, S. W. Lee, M. Matsuoka, ChemNanoMat 2019, 5, 1467.

[41] W. Zhai, J. Li, Y. Tian, H. Liu, Y. Liu, Z. Guo, T. Sakthivel, L. Bai, X.-F. Yu, Z. Dai, Nano Lett. 2024, 24, 14632.

[42] Q. Liang, F. Meng, W. Li, X. Zou, K. Song, X. Ge, Z. Jiang, Y. Liu, M. Liu, Z. Li, T. Dong, Z. Chen, W. Zhang, W. Zheng, Sci. Bull. 2024, 69, 1091.

[43] X. Han, Y. Zhou, X. Tai, G. Wu, C. Chen, X. Hong, L. Tong, F. Xu, H.-W. Liang, Y. Lin, Nat. Commun. 2024, 15, 7200.

[44] L. Zhang, L. Tong, S. Li, C.-S. Ma, K.-Z. Xue, H.-W. Liang, J. Energy Chem. 2025,

[45] Y. Jiang, Q. Zhang, J. Qian, Y. Wang, Y. Mu, Z. Zhang, Z. Li, T. Zhao, B. Liu, L. Zeng, ACS Catal. 2024, 14, 6992.

[46] M. Xie, Z. Lyu, R. Chen, M. Shen, Z. Cao, Y. Xia, J. Am. Chem. Soc. 2021, 143, 8509.

[47] D. He, Y. Zhang, T. Li, D. Chen, H. Wang, L. Zhang, J. Liu, X. Cao, J. Lu, Y. Luo, Adv. Funct. Mater. 2025, 35, 2412895.

[48] Y. Zhang, Q. Zhao, B. Danil, W. Xiao, X. Yang, Adv. Mater. 2024, 36, 2400198.

[49] Z. Wang, W. Wu, H. Jiang, S. Chen, R. Chen, Y. Zhu, Y. Xiao, H. Lv, J. Zhong, N. Cheng, Adv. Funct. Mater. 2024, 34, 2406347.

[50] R. Wu, Q. Meng, J. Yan, Z. Zhang, B. Chen, H. Liu, J. Tai, G. Zhang, L. Zheng, J. Zhang, B. Han, Nat. Catal. 2024, 7, 702.

[51] T. Chen, C. Qiu, X. Zhang, H. Wang, J. Song, K. Zhang, T. Yang, Y. Zuo, Y. Yang, C. Gao, W. Xiao, Z. Jiang, Y. Wang, Y. Xiang, D. Xia, J. Am. Chem. Soc. 2024, 146, 1174.

[52] X. Zhang, Z. Li, H. Li, D. Yang, Z. Ren, Y. Zhang, J. Zhang, X.-H. Bu, Angew. Chem. Int. Ed. 2024, 63, e202404386.

[53] F. Kong, Y. Huang, X. Yu, M. Li, K. Song, Q. Guo, X. Cui, J. Shi, J. Am. Chem. Soc. 2024, 146, 30078.

[54] Q. Cheng, S. Yang, C. Fu, L. Zou, Z. Zou, Z. Jiang, J. Zhang, H. Yang, Energ. Environ. Sci. 2022, 15, 278.

[55] J. Zhang, X. Zheng, W. Yu, X. Feng, Y. Qin, Appl. Catal. B 2022, 306, 121116.

[56] Y. Huang, Z. Zeng, T. Wang, Z. Che, Chem. Eng. J. 2025, 504, 158543.

[57] Y. Yang, L. Zhao, X. Gao, Y. Zhao, Nano Res 2023, 16, 6687.

[58] Z. Gao, G. Wang, T. Lei, Z. Lv, M. Xiong, L. Wang, S. Xing, J. Ma, Z. Jiang, Y. Qin, Nat. Commun. 2022, 13, 118.

[59] M. Li, S. Zhang, J. Zhao, H. Wang, ACS Appl. Mater. Interfaces 2021, 13, 57362.

[60] M. Huang, Q. He, J. Wang, X. Liu, F. Xiong, Y. Liu, R. Guo, Y. Zhao, J. Yang, L. Mai, Angew. Chem. Int. Ed. 2023, 62, e202218922.

[61] Y. Guo, C. Luo, M. Yang, H. Wang, W. Ma, K. Hu, L. Li, F. Wu, R. Chen, Angew. Chem. Int. Ed. 2024, 63, e202406597.

[62] Y. Liu, L. Li, X. Li, Y. Xu, D. Wu, T. Sakthivel, Z. Guo, X. Zhao, Z. Dai, Sci. Adv. 2025, 11, eads0861.

[63] L. Zhang, H. Hu, C. Sun, D. Xiao, H.-T. Wang, Y. Xiao, S. Zhao, K. H. Chen, W.-X. Lin, Y.-C. Shao, X. Wang, C.-W. Pao, L. Han, Nat. Commun. 2024, 15, 7179.

[64] S. Wang, Y. Shi, T. Shen, G. Wang, Y. Sun, G. Wang, L. Xiao, C. Yan, C. Wang, H. Liu, Y. Wang, H. Liao, L. Zhuang, D. Wang, Angew. Chem. Int. Ed. 2025, 64, e202420470.

[65] A. Zunger, S. H. Wei, L. G. Ferreira, J. E. Bernard, Phys. Rev. Lett. 1990, 65, 353.

[66] A. van de Walle, Calphad 2009, 33, 266.

[67] A. van de Walle, G. Ceder, J. Phase Equilib. 2002, 23, 348.

[68] A. van de Walle, M. Asta, G. Ceder, Calphad 2002, 26, 539.

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