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The energy sector has demonstrated significant enthusiasm for investigating post‐combustion CO2 capture, storage, and separation. However, the practical application of current porous adsorbents is impeded by challenges related to cost competitiveness, stability, and scalability. Intregation of heteroatoms in the porous organic polymers (POPs) dispense it more susceptible for CO2 adsorption to attenuate green house gases. In this regard, two hydroxy rich hypercrosslinked POPs, namely Ph/Tt‐POP have been developed by one‐pot condensation polymerization using a facile synthetic strategy. The high surface areas of both the Ph/Tt‐POP (1057 and 893 m2g−1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt‐POP are found to be 2.45 and 2.2 mmol g−1, at 273 K respectively. Further, in‐situ static 13C NMR experiment shows that CO2 molecules in Tt‐POP appear to be less mobile than those in Ph‐POP which probably due to the presence of triazine functional groups along with high abundant −OH groups in the Tt‐POP framework. An in‐depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph‐POP with the more negative interaction energies values compared to that of Tt‐POP. Further, Non‐covalent interaction (NCI) plot reveals that CO2 molecules adsorb more on the Ph‐POP than Tt‐POP, which can be explain by hydrogen bond formation in case of Tt‐POP repeating units turning aside CO2 molecule to interact with the Ph component. Overall, our present study reflects the comprising effects of surface area of the solid adsorbents as well as their functionality can be beneficial for developing efficient hypercrosslinked porous polymers as solid CO2 adsorbent. [ABSTRACT FROM AUTHOR]

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 CO 2 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 CO 2 fixation reactions., (© 2023 Wiley-VCH GmbH.)