Narrow-Band-Gap Particulate Photocatalysts for One-Step-Excitation Overall Water Splitting

ConspectusSunlight-driven one-step-excitation overall water splitting (OWS) using a single particulate photocatalyst is a simple and cost-effective approach to producing sustainable hydrogen on a large scale, providing an important impetus to achieving a carbon-neutral society. Technoeconomic studies have determined that a minimum solar-to-hydrogen (STH) energy conversion efficiency of 5% must be achieved to allow this process to be economically competitive. Meeting this goal will require the fabrication of particulate photocatalysts comprising composites of semiconductors and cocatalysts that are sufficiently active under sunlight. A one-step-excitation OWS system based on a metal oxide semiconductor having a wide bandgap was first reported in 1980, and the performance of such systems has been improved significantly over the past decade. In particular, work by the authors' group increased the apparent quantum yield (AQY) obtainable for ultraviolet (UV)-active SrTiO₃ to more than 90% in 2020. However, the STH conversion efficiency of a photocatalyst that absorbs only UV light (that is, λ < 400 nm) is limited to 1.7% even at an AQY of unity. It is therefore highly important to develop one-step-excitation OWS processes utilizing narrow bandgap photocatalysts having absorption edge wavelengths equal to or longer than 500 nm. Such systems would be expected to meet the desired 5% STH energy conversion efficiency once a constant AQY of approximately 63% is obtained.This Account summarizes the development and application of narrow-band-gap (oxy)nitride and oxysulfide photocatalysts in the authors' laboratory that are able to split water in response to wavelengths as high as 500 to 650 nm via single-step photoexcitation. At first, the authors briefly recount the key steps required to progress from the initial utilization of a UV-active SrTiO₃ photocatalyst as an OWS-active material to the realization of an AQY of almost unity. Multiple design and refinement strategies applied to both the semiconductor and cocatalysts associated with this benchmark photocatalyst are summarized, providing insights into the rational design of narrow-band-gap OWS-active photocatalysts. Furthermore, the necessity, target, and current status of developing narrow-band-gap OWS-active photocatalysts are discussed, followed by a comprehensive discussion of progress in the fabrication of OWS-active (oxy)nitride and oxysulfide photocatalysts with absorption edge wavelengths at up to the range of 500-650 nm in our laboratory. Specific examples are used to show the importance of several factors. First, adjusting the properties of the semiconducting material based on designing appropriate precursors, optimizing the synthetic conditions and aliovalent doping is described. Second, loading of efficient dual cocatalysts is examined. Lastly, the effectiveness of coating the particulate photocatalysts with surface nanolayers is addressed. Deficits related to the performance of present-day photocatalysts are also evaluated. Expectations with regard to future improvements of (oxy)nitride- and oxysulfide-based photocatalysts as a means of increasing the AQY are considered. The strategies summarized in this Account are expected to promote the development of nonsacrificial long-wavelength-responsive photosynthesis systems using water as a hydrogen/oxygen source.