Abstract
Conspectus Photocatalytic solar fuel production, for example, production of hydrogen via water-splitting, is an effective means of chemical storage of solar energy and provides a potential option for achieving a zero-emissions energy system. Conveniently, hydrogen can be converted back to electricity either via fuel cells or through combustion in gas turbines, or it can be mixed in low concentrations with natural gas or biogas for combustion in existing power plants. The cornerstone of a practical solar fuel production process is a stable, efficient, and scalable photocatalyst (a semiconductor material that accommodates photon absorption, charge carrier generation and transport, and catalytic reactions). Therefore, the quest for suitable photocatalyst materials is an ongoing process. Recently, carbon nitride (CN) has attracted widespread interest as a metal-free, earth-abundant, and highly stable photocatalyst. However, the catalytic efficiency of CN is not satisfactory because of its poor charge transport attributes. There is a direct relation between the photocatalytic efficiency and charge transport because the basic principle of light-promoted overall photodecomposition of water into H2 and O2 molecules (or, generally speaking, photoredox reactions) relies on separation and subsequent transfer of excited-state electron–hole pairs to relative redox couples. However, the excited states last for a very short time, typically nanoseconds to microseconds in liquids, and unless they are separated within this time frame, the excited-state electron–hole pairs undergo recombination with release of the captured light energy as heat or photon emission. To utilize light in a form other than heat or emitted photons by avoiding the recombination of excited-state electron–hole pairs, charged excitons must be scavenged before the absorption of subsequent photons to sustain a multielectron photoredox reaction. Otherwise, the extraction of charges becomes more difficult. This imposes a potential efficiency-limiting factor. An enhancement in water to hydrogen conversion efficiency in CN therefore requires the use of precious-metal cocatalysts (e.g., Pt) and sacrificial electron donor/acceptors to facilitate multielectron/multiproton transfers to overcome the high kinetic barriers. The use of Pt and sacrificial agents is not consistent with the notion of low-cost and sustainable hydrogen production from water. CN must overcome this dependence to stand out as a truly scalable photocatalyst. To make progress, the foremost requirement is to attain an in-depth understanding of the fundamental charge transport phenomena needed for the rational design of CN-based photocatalysts. In this Account, therefore, our aim is to provide a synopsis of current understanding and progress regarding charge-transport-related phenomena (e.g., recombination, trapping, transfer of charge carriers, etc.) and to discuss the effects of charge transport in enhancing the apparent quantum yield of hydrogen production in CN. This understanding is necessary to broaden the scope of CN for other catalytic applications, for example, efficient CO2 reduction to methanol or methane, fixation of nitrogen to ammonia, and use as an active material in solar cells. We also identify research gaps and issues to be addressed for a more clear elucidation of charge-transport-related phenomena in CN. Thus, this Account may inspire new research opportunities for tuning the extrinsic/intrinsic photophysicochemical properties of CN by rational design to attain the most favorable properties for improved catalytic efficiency.