Photothermal Catalyst Engineering: Hydrogenation of Gaseous CO(2) with High Activity and Tailored Selectivity

This study has designed and implemented a library of hetero‐nanostructured catalysts, denoted as Pd@Nb(2)O(5), comprised of size‐controlled Pd nanocrystals interfaced with Nb(2)O(5) nanorods. This study also demonstrates that the catalytic activity and selectivity of CO(2) reduction to CO and CH(4) products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb(2)O(5) nanorods. Using large Pd nanocrystals, this study achieves CO and CH(4) production rates as high as 0.75 and 0.11 mol h(−1) g(Pd) (−1), respectively. By contrast, using small Pd nanocrystals, a CO production rate surpassing 18.8 mol h(−1) g(Pd) (−1) is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar‐powered gas‐phase heterogeneous CO(2) reduction. The remarkable control over the catalytic performance of Pd@Nb(2)O(5) is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry.