Sub-Millisecond Laser-Irradiation-Mediated Surface Restructure Boosts the CO Production Yield of Cobalt Oxide...

The catalytic conversion of CO₂ into valuable commodities has the potential to balance ongoing energy and environmental issues. To this end, the reverse water-gas shift (RWGS) reaction is a key process that converts CO₂ into CO for various industrial processes. However, the competitive CO₂ methanation reaction severely limits the CO production yield; therefore, a highly CO-selective catalyst is needed. To address this issue, we have developed a bimetallic nanocatalyst comprising Pd nanoparticles on the cobalt oxide support (denoted as CoPd) via a wet chemical reduction method. Furthermore, the as-prepared CoPd nanocatalyst was exposed to sub-millisecond laser irradiation with per-pulse energies of 1 mJ (denoted as CoPd-1) and 10 mJ (denoted as CoPd-10) for a fixed duration of 10 s to optimize the catalytic activity and selectivity. For the optimum case, the CoPd-10 nanocatalyst exhibited the highest CO production yield of ∼1667 μmol g^-1_catalyst, with a CO selectivity of ∼88% at a temperature of 573 K, which is a 41% improvement over pristine CoPd (~976 μmol g^-1_catalyst). The in-depth analysis of structural characterizations along with gas chromatography (GC) and electrochemical analysis suggested that such a high catalytic activity and selectivity of the CoPd-10 nanocatalyst originated from the sub-millisecond laser-irradiation-assisted facile surface restructure of cobalt oxide supported Pd nanoparticles, where atomic CoOx species were observed in the defect sites of the Pd nanoparticles. Such an atomic manipulation led to the formation of heteroatomic reaction sites, where atomic CoOx species and adjacent Pd domains, respectively, promoted the CO₂ activation and H₂ splitting steps. In addition, the cobalt oxide support helped to donate electrons to Pd, thereby enhancing its ability of H₂ splitting. These results provide a strong foundation to use sub-millisecond laser irradiation for catalytic applications.