This report builds on our recent disclosure of a fully-integrated, photoelectrochemical (PEC) device for hydrogen evolution using a structure incorporating a III-V triple-junction photovoltaic (PV) embedded in a Nafion membrane. Catalyst integration is realized by compression of catalyst-modified, carbon electrodes against the front and back PV contacts, resulting in a wireless, monolithic PEC assembly. Using this device architecture, we demonstrate significant enhancements in device stability and longevity, by transitioning from a liquid-water to water-vapor anode. Our use of a gas-fed anode enables 1000 h of cumulative device operation at a peak solar-to-hydrogen efficiency of 14%, during simulated, solar illumination at 1 sun and outdoor, diurnal cycling. Vapor-fed water oxidation is shown to reduce drops in device performance by mitigating the corrosion effects that are commonly associated with full-aqueous immersion of the electrochemical and photovoltaic elements in PEC devices.

Photoelectrochemical (PEC) conversion of carbon dioxide into valuable chemicals and fuels represents a promising path towards combating anthropogenic CO2 emissions. However, the limited conversion efficiencies, operation lifetimes and CO2 utilization efficiencies of PEC devices currently prohibit their application beyond the laboratory scale. Here, a wireless device converting CO2 and water into carbon monoxide and hydrogen at a peak solar conversion efficiency exceeding 16% under an illumination intensity of 5 suns is demonstrated. A CO/H2 product ratio between 10-20 is measured during a 17 h stability test. Fluctuations in device performance are rigorously analyzed via deconvolution of electrochemical and photoabsorber contributions. It is demonstrated that beneficial heat dissipation is enabled by wireless integration of the photoabsorber and electrocatalyst components, accounting for roughly 10% of the achieved conversion efficiency, an achievement unattainable with physically separated photoabsorber and electrolyzer components.

Increasing anthropogenic carbon dioxide emissions have prompted the search for photoelectrochemical (PEC) methods of converting CO2 to useful commodity products, including fuels. Ideally, such PEC approaches will be sustained using only sunlight, water, and CO2 as energetic and reactant inputs. However, low peak conversion efficiencies (<5%) have made commercialization of fully-integrated PEC devices prohibitive. Here, a 4 cm2 monolithic PEC device exceeding 10% solar-to-fuel efficiency with principal fuel products of carbon monoxide and hydrogen is reported. The corresponding solar-to-CO and solar-to-H2 efficiencies are 7% and 3.5%, respectively. Screening of a range of operating conditions reveals a tunable product mixture of H2 and CO using a gold electrocatalyst. Accordingly, it is shown that device optimization yields a H2-to-CO ratio of 1:2 commonly present in synthesis gas (syngas). Notably, the modularity and facile fabrication of this device permit the incorporation of a broad array of materials for various applications. For example, the electrocatalyst may easily be swapped to target a different set of products.