RESUMO
Manganese antimonate (MnySb1-yOx) electrocatalysts for the oxygen-evolution reaction (OER) were synthesized via chemical vapor deposition. Mn-rich rutile Mn0.63Sb0.37Ox catalysts on fluorine-doped tin oxide (FTO) supports drove the OER for 168 h (7 days) at 10 mA cm-2 with a time-averaged overpotential of 687 ± 9 mV and with >97% Faradaic efficiency. Time-dependent anolyte composition analysis revealed the steady dissolution of Mn and Sb. Extended durability analysis confirmed that Mn-rich MnySb1-yOx materials are more active but dissolve at a faster rate than previously reported Sb-rich MnySb1-yOx alloys.
RESUMO
The long-term stability for the hydrogen-evolution reaction (HER) of homojunction pn+-Ga0.52In0.48P photocathodes (band gap = 1.8 eV) with an electrodeposited Pt catalyst (pn+-GaInP/Pt) has been systematically evaluated in both acidic and alkaline electrolytes. Electrode dissolution during chronoamperometry was correlated with changes over time in the current density-potential (J-E) behavior to reveal the underlying failure mechanism. Pristine pn+-GaInP/Pt photocathodes yielded an open-circuit photopotential (Eoc) as positive as >1.0 V vs the potential of the reversible hydrogen electrode (RHE) and a light-limited current density (Jph) of >12 mA cm-2 (1-sun illumination). However, Eoc and Jph gradually degraded at either pH 0 or pH 14. The performance degradation was attributed to three different failure modes: (1) gradual thinning of the n+-emitter layer due to GaInP dissolution in acid; (2) active corrosion of the underlying GaAs substrate at positive potentials causing delamination of the upper GaInP epilayers; and (3) direct GaAs/electrolyte contact compromising the operational stability of the device. This work reveals the importance of both substrate stability and structural integrity of integrated photoelectrodes toward stable solar fuel generation.
RESUMO
Passivating defective regions on monolayer graphene with metal oxides remains an active area of research for graphene device integration. To effectively passivate these regions, a water-free atomic layer deposition (ALD) recipe was developed and yielded selective-area ALD (sa-ALD) of mixed-metal oxides onto line defects in monolayer graphene. The anisotropically deposited film targeted high-energy defect sites that were formed during synthesis or transfer of the graphene layer. The passivating layer exceeded 10 nm thickness with minimal deposition onto the basal plane of graphene. The mixed-metal oxide film was of comparable quality to films deposited using nonselective water-based ALD methods, as shown by X-ray photoelectron spectroscopy. The development of sa-ALD techniques to target defect regions on the graphene sheet, while keeping the basal plane intact, will provide a new mechanism to passivate graphene defects and modify the electronic and physical properties of graphene.
RESUMO
Earth-abundant catalysts for the hydrogen-evolution reaction require increased mass loadings, relative to Pt films, to achieve comparable activity and stability in acidic electrolytes. We report herein that spontaneous nanostructuring of opaque, electrodeposited CoP films, 40-120 nm in thickness, leads to transparent electrocatalyst films that exhibit up to 90% optical transmission in the visible spectrum. The photocurrent density under simulated sunlight at a representative n+p-Si(100)/CoP photocathode increases by 200% after exposure to 0.50 M H2SO4(aq) and remains stable for 12 h of continuous operation. Atomic force microscopy and scanning electron microscopy of the film before and after exposure to 0.50 M H2SO4(aq) validate an optical model for transparent CoP films as probed with spectroscopic ellipsometry.
