Boosting the Volmer step by synergistic coupling of dilute CuRu nanoalloy with Cu/Ru dual single atoms for efficient and CO-tolerant alkaline hydrogen oxidation

doi:10.1016/S1872-2067(25)64670-5

Abstract

Abstract:

Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction (HOR) are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles (N-(CuRu)_NP+SA@NC) through a strategy involving weak chemical reduction and ammonia-assisted gas-phase nitridation. The resultant N-(CuRu)_NP+SA@NC electrocatalysts feature nitrogen atoms coordinated to both Cu and Ru metal atoms via strong N-metal interactions. Density functional theory calculations revealed that alloyed CuRu nanoparticles and monodispersed Cu atoms are vital for altering the electronic configuration of the host Ru elements. This finely tuned structure enhanced the adsorption of H and OH and promoted CO oxidation over the N-(CuRu)_NP+SA@NC electrocatalyst, resulting in high alkaline HOR activity, as evidenced by the higher exchange current density of 3.74 mA cm^-2 and high mass activity of 3.28 mA μg_Ru^-1, which are far superior to those of most Ru-based catalysts reported to date. Moreover, the N-(CuRu)_NP+SA@NC electrocatalysts are resistant to CO poisoning and can be used at a high concentration of 1000 ppm CO with no distinct decay in the activity, in stark contrast to the commercial Pt/C catalyst under the same conditions.

Key words: Dilute CuRu nanoalloy, N incorporation, Hydrogen oxidation reaction, Synergistic effect, CO-tolerant

Yi Liu, Shuqing Zhou, Chenggong Niu, Tayirjan Taylor Isimjan, Yongfa Zhu, Dingsheng Wang, Xiulin Yang, Jieshan Qiu, Bin Wu. Boosting the Volmer step by synergistic coupling of dilute CuRu nanoalloy with Cu/Ru dual single atoms for efficient and CO-tolerant alkaline hydrogen oxidation[J]. Chinese Journal of Catalysis, 2025, 72: 266-276.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64670-5

https://www.cjcatal.com/EN/Y2025/V72/I5/266

Figures/Tables 5

Fig. 1. Key characteristics of N-(CuRu)NP+SA@NC. (a) Schematic illustrations of the preparation of N-(CuRu)NP+SA@NC. (b) XRD patterns of N-(CuRu)NP+SA@NC and N-RuNP+SA@NC. (c) SEM, (d) TEM and (e) high-resolution TEM images. (f) AC HAADF-STEM image of N-(CuRu)NP+SA@NC (The spots in the red dashed circle are attributed to Ru/Cu single atoms). (g) N2 adsorption-desorption isotherms and pore size distribution (inset). (h) HAADF-STEM and corresponding elemental mappings images of N-(CuRu)NP+SA@NC.

Fig. 2. Physicochemical characterization analysis. (a) Ru K-edge XANES spectra of N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, Ru foil, RuCl3 and RuO2. (b) Ru K-edge FT-EXAFS spectra. (c) Cu K-edge XANES of N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, Cu foil, Cu2O and CuO. (d) Cu K-edge FT-EXAFS spectra. (e) Ru K-edge EXAFS WT analysis. (f) Cu K-edge EXAFS WT analysis. High-resolution XPS spectra of (g) Ru 3p, (h) Cu 2p in N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, and N-RuNP+SA@NC.

Fig. 3. Electrocatalytic HOR activity. (a) HOR polarization curves of different samples. (b) HOR polarization curves of N-(CuRu)NP+SA@NC at different rotation speeds. Inset shows corresponding Koutecky-Levich plot. (c) Tafel plots. (d) Linear fitting curves in micropolarization region. (e) Comparison of various performance parameters of comparative electrocatalysts. (f) Comparison of the obtained MA and j0 with those of recently reported alkaline HOR electrocatalysts. (g) HOR polarization curves for N-(CuRu)NP+SA@NC and comm. Pt/C before and after 1000 cycles. (h) Relative current-time chronoamperometry responses of different catalysts in pure H2-saturated 0.1 mol L?1 KOH.

Fig. 4. CV curves (a) and CO-stripping voltammetry curves (b) of N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, N-RuNP+SA@NC and Pt/C. (c) Zeta potential of N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, N-RuNP+SA@NC. HOR polarization curves of N-(CuRu)NP+SA@NC (d) and Pt/C (e) in 1000 ppm CO/H2-saturated 0.1 mol L-1 KOH. (f) Chronoamperometry (j-t) response at 50 mV in H2/1000 ppm CO-saturated 0.1 mol L-1 KOH.

Fig. 5. (a) Differential charge density distributions of N-(CuRu)NP+SA@NC. The blue, green and pink spheres represented Ru, N and Cu atoms, respectively. (b) Density of state (DOS) plots. (c) The pDOS diagram for the d orbitals of metals in N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC, N-RuNP+SA@NC. (d) Calculated HBE and OHBE values. (e) CO absorption energies on N-(CuRu)NP+SA@NC, (CuRu)NP+SA@NC and N-RuNP+SA@NC models. (f) Calculated energy profile for hydrogen oxidation into H2O. (g) Schematic illustration of HOR catalysis on N-(CuRu)NP+SA@NC.

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