Symmetry-breaking synthesis of Janus Au/CeO2 nanostructures for visible-light nitrogen photofixation.

Precise manipulation of the reactive site spatial distribution in plasmonic metal/semiconductor photocatalysts is crucial to their photocatalytic performance, but the construction of Janus nanostructures through symmetry-breaking synthesis remains a significant challenge. Here we demonstrate a synthetic strategy for the selective growth of a CeO2 semi-shell on Au nanospheres (NSs) to fabricate Janus Au NS/CeO2 nanostructures with the assistance of a SiO2 hard template and autoredox reaction between Ag+ ions and a ceria precursor. The obtained Janus nanostructures possess a spatially separated architecture and exhibit excellent photocatalytic performance toward N2 photofixation under visible-light illumination. In this scenario, N2 molecules are reduced by hot electrons on the CeO2 semi-shell, while hole scavengers are consumed by hot holes on the exposed Au NS surface, greatly promoting the charge carrier separation. Moreover, the exposed Au NS surface in the Janus structures offers an additional opportunity for the fabrication of ternary Janus noble metal/Au NS/CeO2 nanostructures. This work highlights the genuine superiority of the spatially separated nanoarchitectures in the photocatalytic reaction, offering instructive guidance for the design and construction of novel plasmonic photocatalysts.

(Plasmonic gold core)@(ultrathin ruthenium shell) nanostructures as antenna-reactor photocatalysts toward nitrogen photofixation.

Ruthenium (Ru) is known as the optimal metal catalyst for ammonia (NH3) synthesis, but the poor light-harvesting capability restricts its application in photocatalysis. Herein, we construct an antenna-reactor nanostructure through the controllable growth of an ultrathin Ru nanocluster shell with desired catalytic activity on the plasmonic gold (Au) nanoantennas. In this nanostructure, Au nanoantennas interact strongly with light to generate hot carriers, meanwhile Ru nanoclusters adsorb and activate N2, leading to the reduction of N2 to NH3 by the generated hot electrons. This antenna-reactor plasmonic photocatalyst exhibits shell-thickness-dependent photocatalytic activity toward nitrogen (N2) photofixation under visible and near-infrared light illumination.

Janus silver/ternary silver halide nanostructures as plasmonic photocatalysts boost the conversion of CO2 to acetaldehyde.

Photocatalytic conversion of carbon dioxide (CO2) to liquid product acetaldehyde (CH3CHO) remains a great challenge due to the involvement of a complex 10-electron reduction process and a sluggish C-C coupling reaction. Herein, we report the synthesis of Janus silver/ternary silver halide (Ag/AgClBr) nanostructures through precisely manipulating the growth kinetics and its function as a plasmonic photocatalyst to boost the conversion of CO2 to CH3CHO. The obtained Janus nanostructures featuring both spatially separated architecture and broad light-harvesting capability facilitate the photocatalytic reduction of CO2 under solar illumination. The photocatalytic CO2 reduction with the characteristics of high activity and good selectivity can generate a 10-electron reduction product CH3CHO with a generation rate of 209.3 ± 9.5 µmol h-1 g-1 and a selectivity of 96.9%, which are rarely achieved in previously reported photocatalytic CO2 reduction systems. The excellent photocatalytic performance can be ascribed to the plasmonic effect of Ag nanocrystals and the favorable active sites on the catalyst surface. This research demonstrates for the first time the utilization of the Janus Ag/AgClBr nanostructures to generate the value-added C2 liquid product through photocatalytic CO2 reduction, paving the way for the design and construction of novel plasmonic photocatalysts.