Interfacial charge transfer in carbon nitride heterojunctions monitored by optical methods

Solar energy conversion is inciting tremendous research efforts in many fields due to the vast potential of sunlight as a sustainable energy source. For solar energy to become widely used and become a major component of our energy mix, energy storage on large scales must be addressed and the components used must be abundant. Artificial photosynthesis to produce solar fuels holds promise as a way to convert solar energy into storable energy. Organic photocatalysts have rapidly established themselves as a viable alternative to inorganic systems. Organic photocatalyst can be prepared from inexpensive precursors and offer a synthetic versatility and tunability that can be exploited to improve efficiencies. Carbon nitride (CN_x) has emerged as a leading organic photocatalyst with advantageous chemical and photo stabilities. Recombination of photogenerated electrons and holes limit the efficiency of CN_x materials below levels necessary to become a viable energy production system. To improve the efficiency and key characteristics such as light harvesting, charge carrier lifetime, and interfacial rate of charge transfer, a second material is put in contact with CN_x to form a heterojunction. While there are many examples of heterojunctions improving the photocatalytic activity beyond that of the isolated CN_x, we are still lacking the deep understanding of charge carrier dynamics necessary to rationalize the improvements and design optimal junctions. This review covers the studies of CN_x heterojunctions that have used optical methods to monitor the charge carrier dynamics. Time-resolved photoluminescence (TRPL) is the most common technique used and there are many examples that have used transient absorption spectroscopy (TAS) to probe the charge carrier dynamics. However, attempting to link the lifetime change to the activity differences does not yield a clear trend. It is likely that the reactive charges are not consistently being monitored and is obscuring the expected correlations. Both shorter and longer charge carrier lifetimes can be observed with both TRPL and TAS techniques and can be interpreted as arising from interfacial charge separation. Even when the same materials are used in the junction there is no consistency in observing a shorter or longer lifetime. The holistic view of charge carrier dynamics in CN_x heterojunctions presented here intends to identify overarching themes from a wide range of CN_x-containing systems and help take stock of where our current understanding stands. More specific spectral assignments and linking the observed lifetimes to certain photophysical or photochemical processes are needed to build models to help us understand the links between the charge carrier dynamics and the activity. These are crucial to develop general strategies that will lead to optimal CN_x heterojunctions.