ABSTRACT
Harvesting solar energy to produce value-added chemicals from carbon dioxide (CO2) presents a promising route for addressing the complexities of sustainable energy systems and environmental issues. In this context, the development of metal-coordinated porous organic polymers (POPs) offers a vital avenue for improving the photocatalytic performance of organic motifs. The current study presents a metal-integrated photocatalytic system (namely, Zn@BP-POP) developed via a one-pot Friedel-Crafts (F.C.) acylation strategy, for solid-gas phase photochemical CO2 reduction to CO (CO2RR). The postsynthetic incorporation of metal (Zn) active sites on the host polymeric backbone of BP-POP significantly influences the catalytic activity. Notably, Zn@BP-POP demonstrates good photocatalytic performance in the absence of any cocatalyst and photosensitizer yielding CO while impeding the competitive hydrogen evolution reaction (HER) from water. The experimental findings collectively propose that the observed catalytic activity and selectivity arise from the synergistic interplay between the singular zinc catalytic centers and the light-harvesting capacity of the highly conjugated polymeric backbone. Further, X-ray absorption spectroscopy (XAS) analysis has significantly highlighted the prominent role played by the ZnN2O4 single sites in the polymeric framework for activating the gaseous CO2 molecules. Further, time-dependent density functional theory (DFT) analysis also reveals the thermodynamic feasibility of CO2RR over HER under optimized reaction conditions. This work cumulatively presents an effective strategy to demonstrate the importance of metal-active sites and effectively establish their structure-activity relationship during photocatalysis.
ABSTRACT
Herein, a facile strategy is illustrated to develop pyrolysis-free out-of-plane coordinated single atomic sites-based M-POP via a one-pot Friedel Craft acylation route followed by a post-synthetic metalation. The optimized geometry of the Co@BiPy-POP clearly reveals the presence of out-of-plane Co-single atomic sites in the porous backbone. This novel photopolymer Co@BiPy-POP shows extensive π-conjugations followed by impressive light harvesting ability and is utilized for photochemical CO2 fixation to value-added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert-butyl ammonium bromide (TBAB). Synchrotron-based X-ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis-free out-of-plane-coordination strategy and further explores the role of single atomic sites in carrying out feasible CO2 fixation reactions.
