Engineering 0D/2D Architecture of Ni(OH)2 Nanoparticles on Covalent Organic Framework Nanosheets for Selective Visible-Light-Driven CO2 Reduction.

Low-dimensional materials serving as photocatalysts favor providing abundant unsaturated active sites and shortening the charge transport distance, but the high surface energy readily causes the aggregation that limits their application. Herein, it is demonstrated that 2D covalent organic framework (COF) TpBD nanosheets are effective in the dispersion and stabilization of 0D Ni(OH)2 . The COF precursor TpBD is synthesized from the Schiff base condensation of 1,3,5-triformylphloroglucinol (Tp) and benzidine (BD) and exfoliated into 2D nanosheets named BDNs via ultrasonication. The formation of highly dispersive 0D Ni(OH)2 on BDNs is reached under a mild weak basic condition, enabling robust active sites for CO2 adsorption/activation and rapid interface cascaded electron transport channels for the accumulation of long-lived photo-generated charges. The champion catalyst 30%Ni-BDNs effectively catalyze the CO2 to CO conversion under visible-light irradiation, offering a high CO evolution rate of 158.4 mmol g-1 h-1 and turnover frequency of 51 h-1 . By contrast, the counterpart photocatalyst, the bulk TpBD stabilized Ni(OH)2 , affords a much lower CO evolution rate and selectivity. This work demonstrates a new avenue to simultaneously construct efficient active sites and electron transport channels by coupling 0D metal hydroxides and 2D COF nanosheets for CO2 photoreduction.

Imidazolium-Functionalized Ionic Hypercrosslinked Porous Polymers for Efficient Synthesis of Cyclic Carbonates from Simulated Flue Gas.

The rapid growth of CO2 emissions, especially from power plants, has led to the urgent need to directly capture and fix CO2 in the flue gas after simple purification rather than energy-intensive gas separation. Herein, imidazolium-functionalized ionic hypercrosslinked porous polymers (HCPs) bearing adjustable surface groups were straightforwardly synthesized through co-hypercrosslinking of benzylimidazole salts and crosslinker through Friedel-Crafts alkylation. Abundant microporosity and relatively high ionic moieties were obtainable in the ethyl-group-tethered ionic HCP, giving a remarkably selective CO2 capture performance with a CO2 uptake of 3.05 mmol g-1 and an ideal adsorbed solution theory (IAST) CO2 /N2 selectivity as high as 363 (273 K, 1 bar). This ionic polymer demonstrated high efficiency in the synthesis of cyclic carbonates from the coupling of various epoxides with the simulated flue gas (15 % CO2 and 85 % N2 ), giving high yields, large turnover numbers (up to 4800), and stable reusability under additive- and solvent-free conditions.