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.

Deposition of a 50 nm thick CoOx layer on planar n-Si yields stable, high-performance photoanodes for water oxidation.

Introduction of an ultrathin (2 nm) film of cobalt oxide (CoOx) onto n-Si photoanodes

Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g).

Reduction of carbon dioxide in aqueous electrolytes at single-crystal MoS 2 or thin-film MoS 2 electrodes yields 1-propanol as the major CO 2 reduction product, along with hydrogen from water reduction as the predominant reduction process. Lower levels of formate, ethylene glycol, and t-butanol were also produced. At an applied potential of -0.59 V versus a reversible hydrogen electrode, the Faradaic efficiencies for reduction of CO 2 to 1-propanol were ~3.5% for MoS 2 single crystals and ~1% for thin films with low edge-site densities. Reduction of CO 2 to 1-propanol is a kinetically challenging reaction that requires the overall transfer of 18 e -and 18 H + in a process that involves the formation of 2 C-C bonds. NMR analyses using 13 CO 2 showed the production of 13 C-labelled 1-propanol. In all cases, the vast majority of the Faradaic current resulted in hydrogen evolution via water reduction. H 2 S was detected qualitatively when single-crystal MoS 2 electrodes were used, indicating that some desulfidization of single crystals occurred under these conditions.

The spatial variation in the photoelectrochemical performance for the reduction of an aqueous one-electron redox couple, Ru(NH 3 ) 6 3+/2+ , and for the evolution of H 2 (g) from 0.5 M H 2 SO 4 (aq) at the surface of bare and Pt-decorated p-type WSe 2 photocathodes has been investigated in situ using scanning photocurrent microscopy (SPCM). The measurements revealed significant differences in the charge-collection performance (quantified by the values of external quantum yields, Φ ext ) on various macroscopic terraces. Local spectral response measurements indicated a variation in the local electronic structure among the terraces which was consistent with a non-uniform spatial distribution of sub-band-gap states within the crystals. The photoconversion

Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. However, under water-oxidation conditions, the smallband-gap semiconductors required for efficient cell operation are unstable, either dissolving or forming insulating surface oxides. We describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for >100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). The 2 stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.

The in situ optical properties and electrocatalytic performance of representative water-oxidation catalyst have been considered.