Ni Foam Supported TiO2 Nanorod Arrays with CdS Branches: Type II and Z‐Scheme Mechanisms Coexisted Monolithic Catalyst Film for Improved Photocatalytic H2 Production

TiO 2 has garnered a flourish of interest in the field of energy storage and energy conversion. Herein, a new generation of 3D Ni foam supported in situ grown 1D TiO 2 nanoarray (Ni/TiO 2 ) is successfully prepared, through an easy solution‐phase hydrothermal process, and then CdS nanorods branched Ni/TiO 2 nanoarrays are fabricated (Ni/TiO 2 @CdS). Their formation parameters and growth mechanism are carefully studied. Both Ni/TiO 2 and Ni/TiO 2 @CdS monolithic catalysts exhibit advantaged photocatalytic (PC) and photoelectrocatalytic (PEC) water splitting properties compared with that of most previously reported TiO 2 ‐based film photocatalysts. Mechanism investigation reveals that both type II and Z‐scheme charge transport mechanisms coexist in Ni/TiO 2 @CdS sample, and an additional Z‐scheme charge transfer effect accelerates the photogenerated charge separation and transport efficiency. This study may open a new avenue for the utilization of TiO 2 ‐based film catalysts in a broader field of energy and environmental catalysis areas.