WO2.72-modulated Ru cluster boosting dual-site adsorption for efficient and CO-resistant anion exchange membrane fuel cells

doi:10.1016/S1872-2067(26)65066-8

Abstract

Abstract:

A dual-site synergistic catalytic mechanism is proposed to optimize the OHad binding energy (OHBE) by constructing ultrafine Ru nanoclusters modified with highly oxygenophilic WO_2.72 clusters in nitrogen-doped carbon carriers, which can optimize the adsorptions of OH_ad and active hydrogen species, respectively, resulting in a marked increase in hydrogen oxidation reaction (HOR) activity. The constructed Ru-WO_2.72-NC shows a HOR mass activity about 8 times that of Pt-C, and the corresponding alkaline exchange membrane fuel cells demonstrate rather higher peak power densities than Ru-NC with 1.193 W cm^-2 and more than 1 W cm^-2 in H₂ fuel and CO/H₂ mixtures, respectively. The excellent alkaline HOR performance of Ru-WO_2.72-NC is attributed to the adsorption of OH_ad species by WO_2.72 clusters, which synergizes with the adsorption and dissociation of hydrogen on Ru to facilitate the Volmer step. The success in constructing dual-site synergistic catalysis of Ru-WO_2.72-NC anode provides valuable insight and new guidelines for designing and studying high-activity alkaline HOR catalysts.

Key words: Anion exchange membrane fuel cells, Alkaline hydrogen oxidation reaction, CO resistance, Tungsten oxide, Synergistic catalysis

Xu Yu, Han Tian, Ziyi Yu, Fantao Kong, Min Wang, Ruxiang Shen, Xiangzhi Cui, Jianlin Shi. WO_2.72-modulated Ru cluster boosting dual-site adsorption for efficient and CO-resistant anion exchange membrane fuel cells[J]. Chinese Journal of Catalysis, 2026, 86: 302-314.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65066-8

https://www.cjcatal.com/EN/Y2026/V86/I7/302

Figures/Tables 6

Scheme 1. Scheme of the Ru-WO2.72-NC design strategy for efficient HOR and high CO-tolerance.

Fig. 1. Synthetic schematic (a), TEM (b), HRTEM (c), SAED (d), HAADF-STEM (e), andTEM-EDS elemental mappings (f) images of Ru-WO2.72-NC.

Fig. 2. XRD (a), Raman (b), and UV-vis-NIR (c) spectra of Ru-WO2.72-NC. High-resolution XPS spectra of Ru 3p (d), W 4f (e), and O 1s (f) of Ru-NC, WO2.72-NC and Ru-WO2.72-NC. (g) EPR spectra of the as-prepared samples. Ru K-edge XANES (h), EXAFS (i), and WT-EXAFS (j) spectra of the samples.

Fig. 3. HOR polarization curves (a), Tafel plots (b), and LSV curves (c) at varying rotating speeds (inset: K-L plots) for as-prepared catalysts and Pt-C. (d) Comparisons of E1/2, current densities and mass-normalized performance of Ru-WO2.72-NC (red), Ru-NC (blue) and Pt-C (green). (e) Relative current-time chronoamperometry curves of different catalysts at 0.1 V. (f) LSV curves of Ru-WO2.72-NC and Pt-C before and after ADT. (g) Polarization and power density curves of AEMFCs. (h) Mass current density and cost accounting of the catalysts in AEMFCs.

Fig. 4. LSV curves in pure H2, CO/H2 and after ADT in CO/H2 of Ru-WO2.72-NC (a) and Pt-C (b). (c) i-t curves of different catalysts in CO/H2 atmosphere. Polarization and power density curves of AEMFCs in 50 ppm CO/H2 anodic atmosphere (d) and corresponding PPD decay histograms (e). (g) CO-TPD of the samples. (h)Background-corrected VB spectra of Ru-WO2.72-NC and Pt-C. (i) CO-stripping voltammograms of Ru-WO2.72-NC and Pt-C.

Fig. 5. H2-TPD spectra (a) and zeta potential (b) of as-prepared catalysts. In-situ electrochemical Raman spectra on Ru-WO2.72-NC surfaces during HOR in the range of 1000-1800 cm-1 (c) and 3000-3800 cm-1 (d). (e) The reaction pathways of Ru-WO2.72-NC and Ru for alkaline HOR. (f) Schematic representation of the alkaline HOR mechanism for the proposed Ru-WO2.72-NC catalyst.

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