Nanowire hydrogen bronzes of WO 3 nanowires decorated with Pd (Pd/H y WO 3−x ) were previously demonstrated to effectively capture broadband radiation across the ultraviolet to near-infrared wavelength range and catalyze the reverse water gas shift reaction (RWGS). Herein, we report a synthetic strategy to enhance the performance of this class of photocatalysts by conformally coating Cu atoms onto the surface of Pd/ H y WO 3−x by anchoring Cu(I)O t Bu to the Brønsted acidic protons of the bronze. The resulting materials are characterized by a suite of analytical methods, including electron microscopy and X-ray absorption spectroscopy. In addition, in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrated that for the lightdriven RWGS reaction, as little as 0.2 at. % Cu facilitates the formation of surface carboxylate species from CO 2 , resulting in a 300−500% enhancement in the rate of CO production. This metal anchoring method enables atom precise modification of the surfaces of metal oxide nanomaterials for catalytic applications, circumventing the need for complex and expensive atomic layer deposition processes.

Surface deposition of Ba II on Pd/H y WO 3Àx nanowires was developed by using as olution-phase atomic layer deposition process. The procedure involves the generation of Brønsted surfaceO Hs ites by H 2 spillovero nP d/ WO 3 ,w hich can then hydrolytically condense with Ba(OEt) 2 to produce surfaceB a II .A tj ust 0.2 at %B a, CO productionb yt he light-assisted activity of the reverse water-gas shift(RWGS) reactionw as observed to increase by about 300 %. In situ DRIFTS studies suggested enhanced CO 2 capturing capabilitieso faBa-decorated surface. This study further exemplifies the importance of surface chemistry in optimizing materials for catalysis.