Plasmon-induced photocatalytic reactions are important in the process of conversion of solar energy into fuels. To efficiently harvest energetic charge carriers from light-excited plasmonic materials, contact of the metallic nanostructures with semiconductors is necessary. Herein, we report that, even on single Au nanowires that are not in contact with any semiconductors, prominent photocatalytic water oxidation reactions could be still observed. The involved Au nanowires have dimensions of 300 nm in diameter, and the fabricated nanoelectrode presents an obvious photocurrent of 0.4 mA/cm2 at the potential of 1.2 V vs Ag/AgCl. The corresponding incident photon-to-electron conversion efficiency is realized as 0.24% at the wavelength of 520 nm. Detailed investigations reveal that the hot holes around the d-band of the plasmonic nanomaterials are responsible for such photocatalytic behaviors. Our results provide a special perspective to the plasmon-related reactions.
Water splitting for the oxygen evolution reaction (OER) through electrocatalysis holds significant promise for energy conversion. However, its real application is yet hindered owing to the lack of efficient electrocatalysts. Herein, we propose a plasmon activation approach for the acceleration of the OER on a Au nanorod–2D ultrathin metal–organic framework (NiCo-MOF) hybrid. The plasmon-generated hot holes of Au nanorods (AuNRs) can be injected into the nickel active sites of the OER catalyst, significantly increasing the generation of high valence Ni* active species in NiCo-MOFs with better matched energy levels for the OER, in turn decreasing the OER activation energy. Thus, excellent OER performance of the NiCo-MOFs under surface plasmon resonance of AuNRs is achieved with an overpotential of 240 mV at a current density of 10 mA cm−2 and a Tafel slope of 69 mV dec−1, which is much better than that of the reported catalysts. This finding highlights the importance of noble metal LSPR in facilitating the OER performance of MOFs and opens up a new avenue for improving the intrinsic electrocatalytic activity of pristine MOFs.
Shouren Zhang,Wenjing Yi,Yanzhen Guo,Ruibin Jiang,Xiao-Lan Chen,Baocheng Yang,Jianfang Wang
Driving organic reactions by heterogeneous photocatalysts is highly desired in green chemistry. (Plasmonic metal)/semiconductor heterostructures can greatly increase the photocatalytic activity by virtue of effective plasmonic harvesting of sunlight. Herein, we report on the driving of click reactions using (plasmonic Au nanosphere core)@(Cu2O shell) nanostructures under near-infrared light illumination. Upon plasmon excitation, the hybrid nanostructures exhibit excellent catalytic performance for the regioselective production of 1,2,3-triazoles. The yields of the click reactions under light illumination are about two times those of the reactions under sole thermal heating at the same temperatures. The reduced reaction yields in the presence of methanol, a hole scavenging agent, suggest that the plasmonic hot holes play a crucial role in the click reactions. Our results and the gained understanding will be valuable for the design of high-performance plasmonic photocatalysts for different regioselective organic reactions.
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