Today`s industrial production of chemicals is still heavily reliant on noble metal catalysts. In search of more sustainable alternatives, recent research suggests that transition metal phosphides (TMPs) can efficiently catalyze reactions such as hydrogenations or water splitting.^[1-2] However, catalytic activity and stability still need to be further improved. This may be possible by doping TMPs with heteroatoms.^[3-4] In particular, doping with multiple elements can provide synergistic effects in catalysis.^[5-6] To implement such doping strategies effectively for TMP catalysis, more insight into the nature of different doping sites and what controls doping of these sites is needed. However, this knowledge is challenging to obtain with current doping methods that offer little control over the doping process. Herein, we show that our recently reported method for sulfur-doping of cobalt phosphide (CoP)^[7] can be further developed to allow dual-doping of a CoP surface with multiple different chalcogenide heteroatoms. Our approach allowed us to gain more insight into the nature of the different doping-sites available on amorphous CoP material. Furthermore, our results provide a better understanding of the factors that govern the dual-doping outcome. Our work therefore shows the road for a more systematic development of new multi-doped TMP catalysts.

[1]    S. T. Oyama, T. Gott, H. Zhao, Y.-K. Lee, Catalysis Today, 2009, 143, 94-107.
[2]    Y. Shi, B. Zhang, Chem. Soc. Rev., 2016, 45, 1529-1541.
[3]    S. M. El-Refaei, P. A. Russo, N. Pinna, ACS Appl. Mater. Interfaces, 2021, 13, 22077-22097.
[4]    Y. Sun, T. Zhang, C. Li, K. Xu, Y. Li, J. Mater. Chem. A, 2020, 8, 13415-13436.
[5]    H. Bai, D. Chen, Q. Ma, R. Qin, H. Xu, Y. Zhao, J. Chen, S. Mu, Electrochem. Energy Rev., 2022, 5:24
[6]    Y. Lin, Y. Pan, J. Zhang, Y. Chen, K. Sun, Y. Liu, C. Liu, Electrochim. Acta, 2016, 222, 246-256
[7]    N. A. Arnosti, V. Wyss, M. F. Delley, J. Am. Chem. Soc., 2023, 145, 23556-23567.