Engineering Z-Scheme FeOOH/PCN with Fast Photoelectron Transfer and Surface Redox Kinetics for Efficient Solar-Driven CO2 Reduction

Solar-driven conversion of carbon dioxide (CO2) without sacrificial agents offers an attractive alternative in sustainable energy research; nevertheless, it is often retarded by the sluggish water oxidation kinetics and severe charge recombination. To this end, a Z-scheme iron oxyhydroxide/polymeric carbon nitride (FeOOH/PCN) heterojunction, as identified by quasi in situ X-ray photoelectron spectroscopy, is constructed. In this heterostructure, the two-dimensional FeOOH nanorod provides rich coordinatively unsaturated sites and highly oxidative photoinduced holes to boost the sluggish water decomposition kinetics. Meanwhile, PCN acts as a robust agent for CO2 reduction. Consequently, FeOOH/PCN achieves efficient CO2 photoreduction with a superior selectivity of CH4 (>85%), together with an apparent quantum efficiency of 2.4% at 420 nm that outperforms most two-step photosystems to date. This work offers an innovative strategy for the construction of photocatalytic systems toward solar fuel production.