Sponge-shaped Au nanoparticles: a stand-alone metallic photocatalyst for driving the light-induced CO2reduction reaction.

Coinage metal nanoparticles (NPs) enable plasmonic catalysis by generating hot carriers that drive chemical reactions. Making NPs porous enhances the adsorption of reactant molecules. We present a dewetting and dealloying strategy to fabricate porous gold nanoparticles (Au-Sponge) and compare their CO₂photoreduction activity with respect to the conventional gold nanoisland (Au-Island) morphology. Porous gold nanoparticles exhibit an unusually broad and red-shifted plasmon resonance which is in agreement with the results of finite difference time domain (FDTD) simulations. The key insight of this work is that the multi-step reduction of CO₂driven by short-lived hot carriers generated by the d → s interband transition proceeds extremely quickly as evidenced by the generation of methane. A 3.8-fold enhancement in the photocatalytic performance is observed for the Au-Sponge in comparison to the Au-Island. Electrochemical cyclic voltammetry measurements confirm the 2.5-fold increase in the surface area and roughness factor of the Au-Sponge sample due to its porous nature. Our results indicate that the product yield is limited by the amount of surface adsorbates i.e. reactant-limited. Isotope-labeled mass spectrometry using¹³CO₂was used to confirm that the reaction product (¹³CH₄) originated from CO₂photoreduction. We also present the plasmon-mediated photocatalytic transformation of 4-aminothiophenol (PATP) into p,p'-dimercaptoazobenzene (DMAB) using Au-Sponge and Au-Island samples.