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Photocatalytic $H_2$ evolution reactions on pristine TiO$_2$ is characterizedby low efficiencies due to trapping and recombination of charge carriers, anddue to a sluggish kinetics of electron transfer. Noble metal (mainly Pt, Pd,Au) nanoparticles are typically decorated as cocatalyst on the TiO$_2$ surfaceto reach reasonable photocatalytic yields. However, owing to the high cost ofnoble metals, alternative metal cocatalysts are being developed. Here weintroduce an approach to fabricate an efficient noble metal free photocatalyticplatform for $H_2$ evolution based on alloyed NiCu cocatalytic nanoparticles atthe surface of anodic TiO$_2$ nanotube arrays. NiCu bilayers are deposited ontothe TiO$_2$ nanotubes by plasma sputtering. A subsequent thermal treatment iscarried out that leads to dewetting, that is, owing to surface diffusion the Niand Cu sputtered layers simultaneously mix with each other and split into NiCunanoparticles at the nanotube surface. The approach allows for a full controlover key features of the alloyed nanoparticles such as their composition, workfunction and cocatalytic ability towards $H_2$ generation. Dewetted-alloyedcocatalytic nanoparticles composed of equal Ni and Cu amounts not only aresignificantly more reactive than pure Ni or Cu nanoparticles, but also lead to$H_2$ generation rates that can be comparable to those obtained by conventionalnoble metal (Pt) decoration of TiO$_2$ nanotube arrays.

Templated Dewetting-Alloying of NiCu Bilayers on TiO$_2$ Nanotubes Enables Efficient Noble Metal-Free Photocatalytic $H_2$ Evolution