High-entropy alloy FeCoNiCuPt with donor-bridge effect for enhancing urea electrosynthesis from CO2 and nitrate

doi:10.1016/S1872-2067(26)64981-9

Abstract

Abstract:

Electrocatalytic co-reduction of nitrate (NO₃^-) and carbon dioxide (CO₂) offers a promising route for sustainable urea synthesis, yet the process remains limited by the complexity of intermediate species and poorly understood C-N coupling mechanisms. Herein, we report a high-entropy alloy (HEA) FeCoNiCuPt catalyst that enables efficient and selective urea production through donor-bridge-acceptor interactions. Benefiting from the atomic-level disorder of the HEA, the catalyst provides a diverse array of active sites capable of accommodating the distinct adsorption and activation pathways of NO₃^- and CO₂ intermediates. At -0.7 V vs. RHE, the FeCoNiCuPt catalyst achieves a urea yield of 49.26 mmol h^-1 g_cat^-1 and a Faradaic efficiency of 25.51%, outperforming most reported systems. Mechanistic studies show that Pt sites act as electron donors, while neighboring transition metal atoms serve as electron bridges, enhancing electron transfer toward critical *NO₂ and *CO₂ species. This donor-bridge facilitates C-N coupling and promotes efficient urea formation, offering new insights into catalyst design for tandem small-molecule electrosynthesis.

Key words: Electron donor-bridge effect, High-entropy alloy, Urea electrosynthesis, D-band center, CO₂ reduction

Wei Guo, Zhenlin Mo, Laiji Xu, Yu Zhang, Minghui Yang, Baojun Liu. High-entropy alloy FeCoNiCuPt with donor-bridge effect for enhancing urea electrosynthesis from CO₂ and nitrate[J]. Chinese Journal of Catalysis, 2026, 84: 159-174.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64981-9

https://www.cjcatal.com/EN/Y2026/V84/I5/159

Figures/Tables 6

Fig. 1. (a) Diagram of the preparation process of the FeCoNiCuPt. (b) XRD pattern of the FeCoNiCuPt. (c) AC-STEM image with the fast Fourier transform (FFT) pattern. (d) HAADF-HRTEM image and corresponding elemental maps (Fe, Ni, Co, Cu, Pt. Scale Bar: 10 nm) of the HEA. (e) 3D surface intensity profile of atoms in the selection of Fig. (d). (f) AC-STEM-EDX mapping images and ratio of the elements (inset). (g) The elemental proportions of the FeCoNiCuPt alloy obtained by electron microscopy at different scales, ICP, and XPS test.

Fig. 2. (a-e) The high-resolution XPS spectra of Fe 2p, Co 2p, Ni 2p, Cu 2p, and Pt 4f. (f) XANES spectra of Pt atomic and its corresponding metallic foil at the Pt L3-edge. (g) FT-EXAFS spectra of Pt L3-edge. (h) WTs of EXAFS spectra of metallic foil, HEA-Pt and PtO. (i) Fitting results of the magnitude of the Fourier transform of the k3-weighted EXAFS spectra for HEA-Pt. (j) The electrostatic potential (ESP) and electron localization function (ELF) surrounding the Pt metal atom. (k) The PDOS of the 3d orbitals of Fe, Co, Ni, Cu atoms coordinated with Pt atoms.

Fig. 3. Electrochemical performance for urea synthesis. (a) Yield rate of urea. (b)Faraday efficiency (FE). (c) Comparison of properties between FeCoNiCuPt alloy with monometal Fe, Ni, Co, Cu. (d) LSV curves of FeCoNiCuPt alloy and monometal Fe, Ni, Co, Cu. (e) Cdl plots obtained from CV curves (Inset Fig. S9). (f) 1H NMR spectra of urea obtained by using K15NO3 and K14NO3 as the reactants. Electrocatalytic stability test of the FeCoNiCuPt alloy by intermittent (g) and non-intermittent (h) electrolyte replacement testing.

Fig. 4. (a) Variation trend of CO2 adsorption energy on the FeCoNiCuPt alloy and monometal Fe, Ni, Co, Cu, and Pt. (b) The adsorption energy of CO2 at different adsorption sites on the surface of the FeCoNiCu alloy. (c) CO2-TPD profiles of the FeCoNiCuPt and the FeCoNiCu alloy. (d) Differential charge distribution and profile of the Pt-M (M = Fe, Ni, Co, or Cu) bridge adsorption sites of CO2. (e) The gain or loss charge distribution diagram along the Z direction. (f) Schematic diagram of the electron donor-bridge effect for enhanced CO2 adsorption. (g) Variation trend of NO3- adsorption energy on the FeCoNiCuPt, the FeCoNiCu alloy and monometal Fe, Ni, Co, Cu, and Pt. (h) Comparison of the average d-band centers of metal atom. (i) The charge difference and transfer amount of FeCoNiCuPt and FeCoNiCu alloys when adsorbing NO3-. (j) Dynamic process snapshots of electrolyte solutions on the FeCoNiCuPt alloy surface at different simulation times.

Fig. 5. Comparison of yield (a) and Faraday efficiency (b) of the alloys with different Pt contents (FeCoNiCuPtn: n represents the theoretical proportion of metal Pt content) in electrocatalytic urea synthesis. (c) The urea synthesis performance of catalysts with different alloys of Pt. The change of in-situ FTIR spectra with time using the FeCoNiCu (d) and the FeCoNiCuPt (e) alloys as catalysts. The change of in-situ FTIR spectra with applied voltage (FeCoNiCu (f), FeCoNiCuPt (g)). (h) Variation of NO2- concentration with applied voltage during electrocatalytic urea synthesis using the FeCoNiCu alloy and the FeCoNiCuPt alloy, respectively. (i) The adverse effect of easily desorbed NO2- on C-N coupling.

Fig. 6. (a) Free energy change of co-reduction of NO3- and CO2 to urea by the FeCoNiCu and the FeCoNiCuPt alloys catalyst. (b) Comparison of overcoming energy barriers for first C-N coupling at different CO2 adsorption sites on the FeCoNiCu alloy and the FeCoNiCuPt alloy. (c) The differential charge during the first C-N coupling reaction. (d) Schematic diagram of electron donor-bridge transfer during the first coupling reaction of C-N. (e) Diagram of the reaction path of urea synthesis.

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High-entropy alloy FeCoNiCuPt with donor-bridge effect for enhancing urea electrosynthesis from CO₂ and nitrate

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