Uleashing efficient and CO-resilient alkaline hydrogen oxidation of Pd3P through phosphorus vacancy defect engineering

doi:10.1016/S1872-2067(23)64570-X

Abstract

Abstract:

A high-performance and highly CO-resilient hydrogen oxidation reaction (HOR) electrocatalyst is heralded as core material to solve the commercial deployment of hydrogen fuel cells. Phosphorus vacancies, as a type of delicate point defect, could effectively and flexibly modulate the catalytic performance. Therefore, based on the vacancy design philosophy of “less is more”, we synthesize a phosphorus-vacancy-rich Pd₃P@C (V_p-Pd₃P@C) catalyst with bowl-like hemisphere structure for alkaline HOR, for the first time. The V_p-Pd₃P@C catalyst exhibits remarkable mass activity and exchange current density of 1.66 mA μg_Pd^-1 and 3.2 mA cm^-2, respectively, surpassing those of Pd₃P@C (0.45 mA μg_Pd^-1, 1.78 mA cm^-2) and commercial Pt/C (0.3 mA μg_Pt^-1, 2.29 mA cm^-2). Intriguingly, the catalyst can tolerate 1000 ppm CO that Pt/C catalyst lacks. Density functional theory calculations uncover that the optimal local coordination environment and favorable electronic structure that rooted from phosphorus vacancy enable optimum adsorption kinetics of hydrogen and hydroxyl while concomitantly suppressing Pd 4d → CO 2π* back donation, contributing to the remarkable HOR reactivity and CO tolerance.

Key words: Hydrogen oxidation reaction, CO tolerance, Phosphorus vacancy, V_p-Pd₃P@C, Bowl-like hemisphere

Yuting Yang, Luyan Shi, Qinrui Liang, Yi Liu, Jiaxin Dong, Tayirjan Taylor Isimjan, Bao Wang, Xiulin Yang. Uleashing efficient and CO-resilient alkaline hydrogen oxidation of Pd₃P through phosphorus vacancy defect engineering[J]. Chinese Journal of Catalysis, 2024, 56: 176-187.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64570-X

https://www.cjcatal.com/EN/Y2024/V56/I1/176

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Fig. 1. (a) Schematic protocol of the synthesis strategy for Vp-Pd3P@C. SEM images of SiO2/SiO2@RF (b), bowl-like hemispheres (c) and Vp-Pd3P@C (d). TEM (e) and HRTEM (f) images of the Vp-Pd3P@C (inset: the corresponding FFT pattern). (g) HAADF-STEM image and corresponding elemental mappings of Vp-Pd3P@C.

Fig. 2. (a,b) Powder XRD patterns of synthesized palladium phosphides (PdxPy@C). (c) Crystal structures of various palladium phosphides spanning a range of temperature and Pd:P mass ratios. (d) EPR spectra of PdxPy@C.

Fig. 3. High-resolution XPS spectra of Pd 3d (a,b), and P 2p (c) spectra of regions in PdxPy@C. (d) Pdδ+ and Pδ- percentages in PdxPy@C.

Fig. 4. (a) HOR polarization curves of Vp-Pd3P@C, Pd3P@C, Pd@C, commercial Pd/C and commercial Pt/C, respectively. (b) HOR polarization curves for Vp-Pd3P@C at various rotation speeds. Inset in b shows corresponding Koutecky-Levich plots at an overpotential of 75 mV. (c) Tafel plots. (d) Linear current potential region around the equilibrium potential of studied catalysts. (e) Comparison of apparent exchange current density (j0), kinetic current density (jk) at 50 mV, mass activity (MA) at 50 mV, ECSA, and specific activity (SA) at 50 mV of the comparative catalysts. (f) Comparison of mass activity at 50 mV and j0 with other recently reported excellent HOR catalysts. (g) HOR polarization curves for Vp-Pd3P@C and Pt/C in H2-saturated 0.1 mol L?1 KOH with (dashed lines) and without (solid lines) the presence of 1000 ppm CO. (h) HOR polarization curves for Vp-Pd3P@C in H2-saturated 0.1 mol L?1 KOH before and after 1000 cycles, respectively. Inset shows chronoamperometry (j-t) responses recorded on Vp-Pd3P@C at 50 mV.

Fig. 5. (a) Schematic diagram of σ-type/π-type orbital interactions between metal catalysts and CO molecules. (b) UPS spectra. (c) Band structure alignment of the Vp-Pd3P@C, Pd3P@C, and Pd@C. (d) CO stripping curves in N2-statured 0.1 mol L?1 KOH of Vp-Pd3P@C, Pd3P@C, and Pd@C. (e) Zeta potential of Vp-Pd3P@C, Pd3P@C, and Pd@C. Error bars represent the standard deviation for triplicated experiments.

Fig. 6. (a) Charge-density distribution of the Vp-Pd3P@C model, yellow and cyan areas indicate electron accumulation and depletion. (b) 2D charge difference isosurface based on DFT analysis, red is the electron-rich area while blue is the deficient area. (c) The PDOS of Pd 4d in Vp-Pd3P@C, Pd3P@C and Pd@C (each d-band center is marked by a dashed line). (d) Hydrogen binding energy on Vp-Pd3P@C, Pd3P@C, and Pd@C models. (e) Hydroxyl binding energy on Vp-Pd3P@C, Pd3P@C, and Pd@C models. (f) The reaction pathways of Vp-Pd3P@C, Pd3P@C, and Pd@C for alkaline HOR. (g) Schematic illustration of HOR catalysis on the Vp-Pd3P@C.

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Uleashing efficient and CO-resilient alkaline hydrogen oxidation of Pd₃P through phosphorus vacancy defect engineering

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