ABSTRACT
Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and inâ situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.
ABSTRACT
We report a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary and ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. The highest HER mass-activity was observed for Ni-Cr materials which exhibit metallic Ni as well as NiO x and Cr2O3 phases as determined by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. The onset of the HER is significantly improved compared to numerous binary and ternary Ni-alloys, including Ni-Mo materials. It is likely that at adjacent Ni/NiO x sites, the oxide acts as a sink for OHads, while the metallic Ni acts as a sink for the Hads intermediate of the HER, thus minimizing the high activation energy of hydrogen evolution via water reduction. This is confirmed by in situ XAS studies that show that the synergistic HER enhancement is due to NiO x content and that the Cr2O3 appears to stabilize the composite NiO x component under HER conditions (where NiO x would typically be reduced to metallic Ni0). Furthermore, in contrast to Pt, the Ni(O x )/Cr2O3 catalyst appears resistant to poisoning by the anion exchange ionomer (AEI), a serious consideration when applied to an anionic polymer electrolyte interface. Furthermore, we report a detailed model of the double layer interface which helps explain the observed ensemble effect in the presence of AEI.
ABSTRACT
Despite recent progress in developing active and durable oxygen reduction catalysts with reduced Pt content, lack of elegant bottom-up synthesis procedures with knowledge over the control of atomic arrangement and morphology of the Pt-alloy catalysts still hinders fuel cell commercialization. To follow a less empirical synthesis path for improved Pt-based catalysts, it is essential to correlate catalytic performance to properties that can be easily controlled and measured experimentally. Herein, using Pt-Co alloy nanoparticles (NPs) with varying atomic composition as an example, we show that the atomic distribution of Pt-based bimetallic NPs under operating conditions is strongly dependent on the initial atomic ratio by employing microscopic and in situ spectroscopic techniques. The PtxCo/C NPs with high Co content possess a Co concentration gradient such that Co is concentrated in the core and gradually depletes in the near-surface region, whereas the PtxCo/C NPs with low Co content possess a relatively uniform distribution of Co with low Co population in the near-surface region. Despite their different atomic structure, the oxygen reduction reaction (ORR) activity of PtxCo/C and Pt/C NPs is linearly related to the bulk average Pt-Pt bond length (RPt-Pt). The RPt-Pt is further shown to contract linearly with the increase in Co/Pt composition. These linear correlations together demonstrate that (i) the improved ORR activity of PtxCo/C NPs over pure Pt NPs originates predominantly from the compressive strain and (ii) the RPt-Pt is a valid strain descriptor that bridges the activity and atomic composition of Pt-based bimetallic NPs.
