We report on the first demonstration of stable photoelectrochemical water splitting and hydrogen generation on a double-band photoanode in acidic solution (hydrogen bromide), which is achieved by InGaN/GaN core/shell nanowire arrays grown on Si substrate using catalyst-free molecular beam epitaxy. The nanowires are doped n-type using Si to reduce the surface depletion region and increase current conduction. Relatively high incident-photon-to-current-conversion efficiency (up to ~27%) is measured under ultraviolet and visible light irradiation. Under simulated sunlight illumination, steady evolution of molecular hydrogen is further demonstrated.

As a class of key building blocks in the chemical industry, aromatic compounds are mainly derived from the catalytic reforming of petroleum-based long chain hydrocarbons. The dehydroaromatization of methane can also be achieved by using zeolitic catalysts under relatively high temperature. Herein we demonstrate that Si-doped GaN nanowires (NWs) with a 97% rationally constructed m-plane can directly convert methane into benzene and molecular hydrogen under ultraviolet (UV) illumination at rt. Mechanistic studies suggest that the exposed m-plane of GaN exhibited particularly high activity toward methane C-H bond activation and the quantum efficiency increased linearly as a function of light intensity. The incorporation of a Si-donor or Mg-acceptor dopants into GaN also has a large influence on the photocatalytic performance.

We report on the first demonstration of high-conversion-rate photochemical reduction of carbon dioxide (CO2) on gallium nitride (GaN) nanowire arrays into methane (CH4) and carbon monoxide (CO). It was observed that the reduction of CO2 to CO dominates on as-grown GaN nanowires under ultraviolet light irradiation. However, the production of CH4 is significantly increased by using the Rh/Cr2O3 core/shell cocatalyst, with an average rate of ∼3.5 μmol gcat –1 h–1 in 24 h. In this process, the rate of CO2 to CO conversion is suppressed by nearly an order of magnitude. The rate of photoreduction of CO2 to CH4 can be further enhanced and can reach ∼14.8 μmol gcat –1 h–1 by promoting Pt nanoparticles on the lateral m-plane surfaces of GaN nanowires, which is nearly an order of magnitude higher than that measured on as-grown GaN nanowire arrays. This work establishes the potential use of metal-nitride nanowire arrays as a highly efficient photocatalyst for the direct photoreduction of CO2 into chemical fuels. It also reveals the potential of engineered core/shell cocatalysts in improving the selectivity toward more valuable fuels.

Syngas, the mixture of CO and H , is a key feedstock to produce methanol and liquid fuels in industry, yet limited success has been made to develop clean syngas production using renewable solar energy. We demonstrated that syngas with a benchmark turnover number of 1330 and a desirable CO/H ratio of 1:2 could be attained from photoelectrochemical CO and H O reduction in an aqueous medium by exploiting the synergistic co-catalytic effect between Cu and ZnO. The CO/H ratio in the syngas products was tuned in a large range between 2:1 and 1:4 with a total unity Faradaic efficiency. Moreover, a high Faradaic efficiency of 70 % for CO was acheived at underpotential of 180 mV, which is the lowest potential ever reported in an aqueous photoelectrochemical cell. It was found that the combination of Cu and ZnO offered complementary chemical properties that lead to special reaction channels not seen in Cu, or ZnO alone.

We have studied the photoelectrochemical properties of both undoped and Si-doped GaN nanowire arrays in 1 mol l(-1) solutions of hydrogen bromide and potassium bromide, which were used separately as electrolytes. It is observed that variations of the photocurrent with bias voltage depend strongly on the n-type doping in GaN nanowires in both electrolytes, which are analyzed in the context of GaN surface band bending and its variation with the incorporation of Si-doping. Maximum incident-photon-to-current-conversion efficiencies of ~15% and 18% are measured for undoped and Si-doped GaN nanowires under ~350 nm light illumination, respectively. Stable hydrogen generation is also observed at a zero bias potential versus the counter-electrode.