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.