Chemically controlled interfacial nanoparticle assembly into nanoporous gold films for electrochemical applications

Nanoporous gold (NPG) is an effective material for electrocatalysis and can be made via a dealloy method such as etching of silver–gold alloys. Dealloyed NPG may contain residual silver that affects its catalytic performance. Herein, a different approach has been reported for the formation of NPG at the liquid/air interface starting from gold nanoparticles (AuNPs) in an aqueous solution, providing silver-free gold films. Chloroauric acid is reduced to AuNP building blocks by 2-(N-morpholino)ethanesulfonic acid, which also acts as a protecting agent and pH buffer. By adding potassium chloride before AuNP synthesis and hydrochloric acid to the resultant AuNP solutions, we can reproducibly obtain continuous gold networks. The sintered AuNPs produced by this method result in chemically synthesized nanoporous gold films (cNPGFs) that resemble dealloyed NPG in terms of morphology and porosity; additionally, they can be controlled by varying the temperature, chloride concentration, ionic strength, and protonation of the buffer. cNPGF formation is attributed to the destabilization of AuNPs at the air–liquid interface. The developed method generates electrochemically stable cNPGFs up to 20 cm² in size with an average thickness of 500 ± 200 nm, areal density of 50–150 μg cm⁻², and porosity as high as 85%. Importantly, cNPGFs can effectively catalyze both CO₂ reduction and CO oxidation electrochemically. Thus, the developed synthetic method offers large-scale production of pure bottom-up NPGFs for multifarious electrocatalytic applications