Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis

doi:10.1016/S1872-2067(25)64917-5

Abstract

Abstract:

The rational design of high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is significant to the widespread commercialization of alkaline exchange membrane fuel cells. However, precise regulation of proton adsorption states and interfacial transfer kinetics at the catalytic interface remains a significant challenge in advancing HOR under alkaline conditions. Herein, we demonstrate that construction of phosphorus-doped carbon-coated nickel (Ni) catalyst (Ni@PC) featuring the bridging oxygen structures (Ni-O-C/P) enables rapid desorption of adsorbed hydrogen species and dynamic reconstruction of interfacial hydrogen-bond network. Density functional theory calculations reveal that the Ni-O-P configuration induces a downward shift in the d-band center of Ni, thereby weakening hydrogen binding energy (HBE). Furthermore, the bridging oxygen atoms facilitate the formation of hydrogen bonds with interfacial water molecules, optimizing the proton transfer pathway. In-situ surface-enhanced infrared absorption spectroscopy confirms that the Ni-O-P structure effectively converts weakly hydrogen-bonded water into strongly hydrogen-bonded water, enhancing the connectivity of hydrogen-bond network and facilitating efficient proton transfer. This work successfully achieves optimization of proton dynamics during the alkaline HOR progress, while also providing a strategic framework for the rational design of advanced carbon-coated electrocatalysts.

Key words: Hydrogen oxidation reaction, Nickel, Interfacial water, Hydrogen-bond network, Mass transfer process

Jianchao Yue, Yu Zhang, Qianqian Xiong, Wei Luo. Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis[J]. Chinese Journal of Catalysis, 2026, 82: 144-152.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64917-5

https://www.cjcatal.com/EN/Y2026/V82/I3/144

Figures/Tables 5

Fig. 1. (a) The structural schematic diagram of Ni@PC. Ni, P, O, and C atoms are denoted by blue, pink, red, and gray spheres, respectively. (b) XRD patterns of the Ni@PC and Ni@C. (c-f) HRTEM images of the Ni@PC. (g) Elemental mappings of Ni, O, C, P and mix image.

Fig. 2. XPS Ni 2p3/2 (a), O 1s (b) and C 1s (c) spectra of Ni@PC and Ni@C. (d) XPS P 2p spectra in Ni@PC. (e) XANES spectra at the Ni K-edge of the Ni foil, NiO, Ni@C and Ni@PC. (f) Fourier transformed EXAFS spectra of the Ni foil, NiO, Ni@C and Ni@PC. (g)-(j) Corresponding wavelet transformation of Ni for Ni foil, Ni@C, Ni@PC and NiO.

Fig. 3. (a) HOR polarization curves with a scan rate of 5 mV s-1 in H2-saturated 0.1 mol L-1 KOH. (b) Tafel plots with the Butler-Volmer fitting lines. (c) Linear fitting curves in the micro-polarization region (-5 to 5 mV). (d) Comparison ECSA-normalized exchange current densities (j0,s) and exchange current densities normalized by metal mass (jk,m) of Ni, Ni@C and Ni@PC. (e) Comparisons of jk,m and j0,s of the Ni@PC with those of recently reported Ni-based HOR catalysts. (f) HOR polarization curves for Ni@PC in H2-saturated 0.1 mol L-1 KOH before and after 1000 CVs.

Fig. 4. Deconvolution of the O-H stretching vibration peaks (around 3000 to 3800 cm-1) of Ni@PC (a) and Ni (b). (c) Comparison of the O-H stretching vibration frequencies of all the samples. (d) Potential-dependent proportion of interfacial water with different structures from 0 to 0.25 V.

Fig. 5. The electron density difference after the existence of Ni-O-C/P structure for (a) Ni@PC and (b) Ni@C. (c) The relationship between j0,s (pink dots) and HBE (blue rhombus). ELF evaluation for H2O adsorption on Ni (d) and Ni@PC (e). (f) Schematic of the reaction mechanism on Ni (left) and Ni@PC (right). Ni, P, O, C, and K+ atoms are denoted by blue, pink, red, gray, and yellow spheres, respectively.

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