Abstract:
Development of robust and efficient photocatalytic constructs for boosting the water oxidation reaction (WOR) is needed for establishing a sunlight-driven renewable energy infrastructure. Here we synthesized plasmonic core-shell nanoconstructs consisting of triangular gold nanoprism (Au-TNP) core with mixed manganese oxide (MnOx) shell for photoelectrocatalytic WOR. These constructs show electrocatalytic WOR with low onset overpotential requirement of 270 mV at pH 10.5. Photoexcitation showed further enhancement of their catalytic activity resulting in ~15% decrease of the onset overpotential requirement along with the generation of photocurrent density of up to 300 µA/cm2. We showed that such light-driven enhancement of AuTNP@MnOx dyad's catalytic activity includes contributions from both photocatalytic (hot carriers driven) and photothermal effects with photothermal effect playing the major role for wavelength between 532 nm and 808 nm. The contribution from the photocatalytic effect is appreciable only for high-energy excitations near the interband region, while the photothermal effect largely dominates for lower energy excitations near the LSPR wavelengths of the dyad.