Pulsed‐Laser‐Driven CO₂ Reduction Reaction for the Control of the Photoluminescence Quantum Yield of Organometallic Gold Nanocomposites

Abstract

Over the last decade, the CO2 reduction reaction (CO2RR) has been increasingly exploited for the synthesis of high‐value raw materials in gaseous or liquid form, although no examples of CO2 fixation in nanoparticle systems have been demonstrated. Herein, CO2 fixation into solid nanomaterials by laser synthesis and processing of gold colloids in water, traditionally considered a green approach leading to ligand‐free nanoparticles without the formation of by‐products, is reported. If carbon monoxide‐rich gold nanoparticles are observable even after synthesis in deionized water, the presence of CO2 derivatives in alkaline water environment leads to C2 and C3 coupling with the production of carboxylic acids as a typical CO2RR fingerprint. While laser processing of preformed gold colloids is selective for C2 coupling, both C2 and C3 coupling to lactic acid are observed during pulsed laser ablation of a gold target. In the latter case, it is demonstrated that it is possible to synthesize photoluminescent organometallic nanocomposites in the blue spectral region with a quantum yield of about 20% under adequate experimental conditions. In this research, new pathways are offered to be explored in energetics, photonics, catalysis, and synthesis at the nanoscale.

Laser synthesis of nanoparticles in organic solvents – products, reactions, and perspectives

“…It indicates a certain controllability of the redox reactions occurring during reductive or oxidative laser processing in aqueous media at constant particle size. Furthermore, focusing laser pulses in CO 2 -saturated water leads to the reduction of CO 2 , which selectively yields CO [ 74 ] or oxocarbon-encapsulated nanoparticles [ 75 – 76 ]. Beyond the formation of carbon monoxide, the direct reduction of permanent solutes in liquids via LRL, sometimes termed laser bubbling in liquid (LBL), has been demonstrated recently for alternative reactants, such as hydrogen extraction from ammonia [ 77 ] or methanol [ 78 ], and direct synthesis of HCN [ 79 ].…”