Ultrathin Layered Catalyst for Photocatalytic Reduction of CO2

The acceleration of industrialization and the continuous upgradation of consumption structure has increased the atmospheric content of CO2 far beyond the past levels, leading to a serious global environmental problem. Photocatalytic reduction of CO2 is one of the most promising methods to solve the problem of rising atmospheric CO2 content. The core of this technology is to develop efficient, environment-friendly, and affordable photocatalysts. A photocatalyst is a semiconductor that can absorb photons from sunlight and produce electron-hole pairs to initiate a redox reaction. Owing to their low specific surface areas, significant electron-hole recombination, and less surface-active sites, bulk photocatalysts are not satisfactory. Ultrathin layered materials have shown great potential for photocatalytic CO2 reduction owing to their characteristics of large specific surface area, a large number of low-coordination surface atoms, short transfer distance from the inside to the catalyst surface, along with other advantages. Photoexcited electrons only need to cover a short distance to transfer to the nanowafer surface, and the speed of migrating electrons on the nanowafer surface is much higher than that in the layers or in the bulk catalyst. The ultrathin structure leads to significant coordinative unsaturation and even vacancy defects in the lattice structure of the atoms; while the former can be used as active sites for CO2 adsorption and reaction, the latter can improve the separation of the electron-hole pair. This review summarizes the latest developments in ultrathin layered photocatalysts for CO2 reduction. First, the photocatalytic reduction mechanism of CO2 is introduced briefly, and the factors governing product selectivity are explained. Second, the existing catalysts, such as g-C3N4, black phosphorus (BP), graphene oxide (GO), metal oxide, transition metal dichalcogenides (TMDCs), perovskite, BiOX (X = Cl, Br, I), layered double hydroxide (LDH), 2D-MOF, MXene, and two-dimensional honeycomb-like Ge-Si alloy compounds (gersiloxenes), are classified. In addition, the prevalent preparation methods are summarized, including mechanical stripping, gas stripping, liquid stripping, chemical etching, chemical vapor deposition (CVD), template method, self-assembly of surfactant, and the intermediate precursor method of lamellar Bi-oleate complex. Finally, we introduced the strategy of improving photocatalyst performance on the premise of maintaining its layered structure, including the factors of thickness adjustment, doping, structural defects, composite, etc. The future opportunities and challenges of ultrathin layered photocatalysts for the reduction of carbon dioxide have also been proposed.