Incorporation of Metal Active Sites on Porous Polycarbazoles for Photocatalytic CO₂ Reduction

Abstract

Photocatalytic conversion of carbon dioxide (CO 2 ) to valuable products is one of the promising approaches to mitigate climate change and provide chemical fuels. The structural design of photocatalysts has been therefore directed to enhancing the CO 2 conversion efficiency and selectivity. Herein, we report that the metalated porous polycarbazoles, made by facile one-pot oxidative polymerization and successive transition metal impregnation, can effectively convert CO 2 into carbon monoxide (CO) with high selectivity under visible light irradiation. The high porosity of the porous polycarbazoles provides enhanced CO 2 adsorption and the incorporated metals facilitate the CO 2 activation. The type of metal ions influences the CO selectivity by altering surface reaction kinetics for CO 2 reduction. Our approach proves that the photocatalytic CO 2 reduction ability and selectivity of porous conjugated polymers can be improved by decorating functional metal species to modulate the adsorption and activation behavior of CO 2 molecules.[a] W.

Ni–Co Bimetallic Hydroxide Nanosheet Arrays Anchored on Graphene for Adsorption‐Induced Enhanced Photocatalytic CO2 Reduction

“…Environmental pollution and energy-resource depletion arising from rapid industrialization have attracted widespread attention, especially the massive emission of CO 2 , a greenhouse gas that contributes to global warming. [1][2][3] Therefore, efforts have been focused on developing efficient and low-cost methods based on electrochemistry, thermochemistry, bioelectrochemistry, and photocatalysis to convert CO 2 into fuels and related chemicals. Photocatalytic methods, using solar energy to reduce CO 2 and store the products in fuel cells, have been extensively composite components, and enhanced activity of metal centers from electrostatic charge transfer on rGO.…”

Surface Engineering of Conjugated Polybenzothiadiazoles and Integration with Cobalt Oxides for Photocatalytic Water Oxidation

“…As shown in Figure 2a, the bandgaps of the polymers decreased from 2.30 eV to 2.17 eV as the temperature increased. Based on the band gaps and the results of UPS measurement (Figure S8), [3g] the HOMO (VB) and LUMO (CB) levels of polymers were then calculated as shown in Figure 2b. Almost the same results could be obtained by cyclic voltammetry (CV) measurements (Figure S9), [3c] further proving the HOMO and LOMO levels of B‐BT catalysts.…”

Recent Research Progress and Perspectives on Porphyrin-Based Porous Photocatalysts in the Field of CO2 Reduction

“…A reasonable structural design and sufficient active sites are beneficial to promote CO 2 adsorption/activation . The pores and catalytic sites of photocatalysts always act as the carrier and donor of catalytic sites . Thus, the in-depth study on the regulation of the pore structure with matched construction of catalytic activity sites will further improve the CO 2 adsorption/activation ability for porphyrin-based porous photocatalysts.…”