A monolithically integrated device, protected by a TiO2 stabilization layer, splits water using sunlight.

Films of CoP have been electrochemically synthesized, characterized, and evaluated for performance as a catalyst for the hydrogen-evolution reaction (HER). The film was synthesized by cathodic deposition from a boric acid solution of Co2+ and H2PO2 – on copper substrates followed by operando remediation of exogenous contaminants. The films were characterized structurally and compositionally by scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectrophotometry. The catalytic activity was evaluated by cyclic voltammetry and chronopotentiometry. Surface characterization prior to electrocatalysis indicated that the film consisted of micrometer-sized spherical clusters located randomly and loosely on a slightly roughened surface. The composition of both the clusters and surface consisted of cobalt in the metallic, phosphide, and amorphous-oxide forms (CoO·Co2O3) and of phosphorus as phosphide and orthophosphate. The orthophosphate species, produced by air-oxidation, were eliminated upon HER electrocatalysis in sulfuric acid. The operando film purification yielded a functional electrocatalyst with a Co:P stoichiometric ratio of 1:1. After the HER, the surface was densely packed with micrometer-sized, mesa-like particles whose tops were flat and smooth. The CoP eletrodeposit exhibited an 85 mV overvoltage (η) for the HER at a current density of 10 mA cm–2 and was stable under operation in highly acidic solution, with an increase in η of 18 mV after 24 h of continuous operation. The comparative HER catalytic performance of CoP, film or nanoparticles, is as follows: ηPt < ηCoP film = ηCoP NP, ηNi2P < ηCoSe2 < ηMoS2 < ηMoSe2 .

A solar-driven CO2 reduction (CO2R) cell was constructed, consisting of a tandem GaAs/InGaP/TiO2/Ni photoanode in 1.0 M KOH­(aq) (pH = 13.7) to facilitate the oxygen-evolution reaction (OER), a Pd/C nanoparticle-coated Ti mesh cathode in 2.8 M KHCO3(aq) (pH = 8.0) to perform the CO2R reaction, and a bipolar membrane to allow for steady-state operation of the catholyte and anolyte at different bulk pH values. At the operational current density of 8.5 mA cm–2, in 2.8 M KHCO3(aq), the cathode exhibited <100 mV overpotential and >94% Faradaic efficiency for the reduction of 1 atm of CO2(g) to formate. The anode exhibited a 320 ± 7 mV overpotential for the OER in 1.0 M KOH­(aq), and the bipolar membrane exhibited ∼480 mV voltage loss with minimal product crossovers and >90 and >95% selectivity for protons and hydroxide ions, respectively. The bipolar membrane facilitated coupling between two electrodes and electrolytes, one for the CO2R reaction and one for the OER, that typically operate at mutually different pH values and produced a lower total cell overvoltage than known single-electrolyte CO2R systems while exhibiting ∼10% solar-to-fuels energy-conversion efficiency.