Enhanced hybrid photocatalytic dry reforming using a phosphated Ni-CeO₂ nanorod heterostructure

Operating the dry reforming reaction photocatalytically presents an opportunity to produce commodity chemicals from two greenhouse gases, carbon dioxide and methane, however, the top-performing photocatalysts presented in the academic literature invariably rely on the use of precious metals. In this work, we demonstrate enhanced photocatalytic dry reforming performance through surface basicity modulation of a Ni-CeO₂ photocatalyst by selectively phosphating the surface of the CeO₂ nanorod support. An optimum phosphate content is observed, which leads to little photoactivity loss and carbon deposition over a 50-hour reaction period. The enhanced activity is attributed to the Lewis basic properties of the PO₄^3- groups which improve CO₂ adsorption and facilitate the formation of small nickel metal clusters on the support surface, as well as the mechanical stability of CePO₄. A hybrid photochemical-photothermal reaction mechanism is demonstrated by analyzing the wavelength-dependent photocatalytic activities. The activities, turnover numbers, quantum efficiencies, and energy efficiencies are shown to be on par with other dry-reforming photocatalysts that use noble metals, representing a step forward in understanding how to stabilize ignoble nickel-based dry reforming photocatalysts. The challenges associated with comparing the performance of photocatalysts reported in the academic literature are also commented on.