Toward a Comprehensive Understanding of Amorphous Photocatalysts: Fundamental Hypotheses and Applications in CO2 Photoreduction.

In principle, photocatalytic activity can be precisely controlled with crystalline catalysts. However, an amorphous photocatalyst could be a viable candidate for CO2 photoreduction to form value-added products. The amorphous phase is currently part of the crystalline material in several ongoing CO2 photoreduction studies. Additionally, no study indicates the amorphous material required for overall CO2 photoreduction. This perspective review article highlights fundamental assumptions that are necessary to gain insights and understand the effectiveness of amorphous photocatalysts for CO2 photoreduction. We start with basic ideas and theories about these materials, including light harvesting, variable coordination number, and the interaction of CO2 molecules with the amorphous catalytic surface. To understand the prospects of the amorphous photocatalyst, we explore machine learning with EXAFS. Furthermore, we discuss product selectivity and regeneration of photocatalysts in detail. Finally, we briefly review the work in progress on amorphous materials and compare it to that on crystalline ones.

Selective photocatalytic CO2 reduction to CH4 over metal-free porous polyimide in the solid-gas mode.

Using a catalyst-free one-pot polycondensation approach, a new donor-acceptor (D-A) based porous polyimide (PeTt-POP) photocatalyst was developed. PeTt-POP produced CH4 (125.63 ppm g-1 in 6 h) from CO2 under visible light irradiation in the gas-solid mode without the use of co-catalysts or sacrificial agents. The progress of the reaction and the corresponding intermediate species involved in the CO2 reduction were identified by operando DRIFTS experiments, from which a plausible reaction mechanism was proposed.

Single-Atom Catalysts (SACs) for Photocatalytic CO2 Reduction with H2 O: Activity, Product Selectivity, Stability, and Surface Chemistry.

In recent years, single-atom catalysts (SACs) have attracted the interest of researchers owing to their suitability for various catalytic applications. For instance, their optoelectronic features, site-specific activity, and cost-effectiveness make SACs ideal for photocatalytic CO2 reduction. The activity, product selectivity, and photostability of SACs depend on various factors such as the nature of the metal/support material, the interaction between the metal atoms and support, light-harvesting ability, charge separation behavior, CO2 adsorption ability, active sites, and defects. Consequently, it is necessary to investigate these factors in depth to elucidate the working principle(s) of SACs for catalytic applications. Herein, the recent progress in the development of SACs for photocatalytic CO2 reduction with H2 O is reviewed. First, a brief overview of CO2 photoreduction and SACs for CO2 conversion is provided. Several synthesis strategies and useful techniques for characterizing SACs employed in heterogeneous catalysis are then described. Next, the challenges of SACs for photocatalytic CO2 reduction and related optimization strategies, in terms of activity, product selectivity, and stability, are explored. The progress in the development of noble metal- and transition metal-based SACs and dual-SACs for photocatalytic CO2 reduction is discussed. Finally, the prospects of SACs for CO2 reduction are considered.

Nanoarchitectonics of Metal-Free Porous Polyketone as Photocatalytic Assemblies for Artificial Photosynthesis.

The main component of natural gas is methane, whose combustion contributes to global warming. As such, sustainable, energy-efficient, nonfossil-based methane production is needed to satisfy current energy demands and chemical feedstocks. In this article, we have constructed a metal-free porous polyketone (TPA-DPA PPK) with donor-acceptor (D-A) groups with an extensive π-conjugation by facile Friedel-Crafts acylation reaction between triphenylamine (TPA) and pyridine-2,6-dicarbonyl dichloride (DPA). TPA-DPA PPK is a metal-free catalyst for visible-light-driven CO2 photoreduction to CH4, which can be used as a solar fuel in the absence of any cocatalyst and sacrificial agent. CH4 production (152.65 ppm g-1) is ∼5 times greater than that of g-C3N4 under the same test conditions. Charge-density difference plots from excited-state time-dependent density functional theory (TD-DFT) calculations indicate a depletion and accumulation of charge density among the donor/acceptor functional groups upon photoexcitation. Most notably, binding energies from DFT demonstrate that H2O is more strongly bound with the pyridinic nitrogen group than CO2, which shed insight into mechanistic pathways for photocatalytic CO2 reduction.

Recent Developments in Lead and Lead-Free Halide Perovskite Nanostructures towards Photocatalytic CO2 Reduction.

Perovskite materials have been widely considered as emerging photocatalysts for CO2 reduction due to their extraordinary physicochemical and optical properties. Perovskites offer a wide range of benefits compared to conventional semiconductors, including tunable bandgap, high surface energy, high charge carrier lifetime, and flexible crystal structure, making them ideal for high-performance photocatalytic CO2 reduction. Notably, defect-induced perovskites, for example, crystallographic defects in perovskites, have given excellent opportunities to tune perovskites' catalytic properties. Recently, lead (Pb) halide perovskite and their composites or heterojunction with other semiconductors, metal nanoparticles (NPs), metal complexes, graphene, and metal-organic frameworks (MOFs) have been well established for CO2 conversion. Besides, various halide perovskites have come under focus to avoid the toxicity of lead-based materials. Therefore, we reviewed the recent progress made by Pb and Pb-free halide perovskites in photo-assisted CO2 reduction into useful chemicals. We also discussed the importance of various factors like change in solvent, structure defects, and compositions in the fabrication of halide perovskites to efficiently convert CO2 into value-added products.