Engineered disorder in CO<sub>2</sub> photocatalysis.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 36418855.
- Also identified by DOI 10.1038/s41467-022-34798-1 and PMC identifier 9684568.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO2 can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO2 forms a core-shell c-TiO2@a-TiO2-x(OH)y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO2 reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO2 photocatalysts.