Role of Short-Range Chemical Ordering in (GaN)<sub>1–<i>x</i></sub>(ZnO)<sub><i>x</i></sub> for Photodriven Oxygen Evolution

(GaN)<sub>1–<i>x</i></sub>(ZnO)<sub><i>x</i></sub> (GZNO) is capable of visible-light driven water splitting, but its bandgap at <i>x</i> ≤ 0.15 (>2.7 eV) results in poor visible-light absorption. Unfortunately, methods to narrow its bandgap by incorporating higher ZnO concentrations are accompanied by extensive Urbach tailing near the absorption-edge, which is indicative of structural disorder or chemical inhomogeneities. We evaluated whether this disorder is intrinsic to the bond-length distribution in GZNO or is a result of defects introduced from the loss of Zn during nitridation. Here, the synthesis of GZNO derived from layered double hydroxide (LDH) precursors is described which minimizes Zn loss and chemical inhomogeneities and enhances visible-light absorption. The average and local atomic structures of LDH-derived GZNO were investigated using X-ray and neutron scattering and are correlated with their oxygen evolution rates. An isotope-contrasted neutron-scattering experiment was conducted in conjunction with reverse Monte Carlo (RMC) simulations. We showed that a bond-valence bias in the RMC refinements reproduces the short-range ordering (SRO) observed in structure refinements using isotope-contrasted neutron data. The findings suggest that positional disorder of cation–anion pairs in GZNO partially arises from SRO and influences local bond relaxations. Furthermore, particle-based oxygen evolution reactions (OERs) in AgNO<sub>3</sub> solution reveal that the crystallite size of GZNO correlates more than positional disorder with oxygen evolution rate. These findings illustrate the importance of examining the local structure of multinary photocatalysts to identify dominant factors in particulate-based photodriven oxygen evolution.