Photocatalytic reduction of CO2 into energy-rich carbon compounds has attracted increasing attention. However, it is still a challenge to selectively and effectively convert CO2 to a desirable reaction product. Herein, we report a design of a synergistic photocatalyst for selective reduction of CO2 to CO by using a covalent organic framework bearing single Ni sites (Ni-TpBpy), in which electrons transfer from photosensitizer to Ni sites for CO production by the activated CO2 reduction under visible-light irradiation. Ni-TpBpy exhibits an excellent activity, giving a 4057 μmol g–1 of CO in a 5 h reaction with a 96% selectivity over H2 evolution. More importantly, when the CO2 partial pressure was reduced to 0.1 atm, 76% selectivity for CO production is still obtained. Theoretical calculations and experimental results suggest that the promising catalytic activity and selectivity are ascribed to synergistic effects of single Ni catalytic sites and TpBpy, in which the TpBpy not only serves as a host for CO2 molecules and Ni catalytic sites but also facilitates the activation of CO2 and inhibits the competitive H2 evolution.

No abstract

Covalent triazine-based frameworks (CTFs) with a graphene-like layered morphology have been controllably synthesized by the trifluoromethanesulfonic acid-catalyzed nitrile trimerization reactions at room temperature via selecting different monomers. Platinum nanoparticles are well dispersed in CTF-T1, which is ascribed to the synergistic effects of the coordination of triazine moieties and the nanoscale confinement effect of CTFs. CTF-T1 exhibits excellent photocatalytic activity and stability for H2 evolution in the presence of platinum under visible light irradiation (λ ≥ 420 nm). The activity and stability of CTF-T1 are comparable to those of g-C3 N4 . Importantly, as a result of the tailorable electronic and spatial structures of CTFs that can be achieved through the judicial selection of monomers, CTFs not only show great potential as organic semiconductor for photocatalysis but also may provide a molecular-level understanding of the inherent heterogeneous photocatalysis.

Sulfur-doped covalent organic frameworks were synthesized via a simple approach for enhanced photocatalytic hydrogen evolution from water under visible light.

Monolayer HNb3O8 2D nanosheets have been used as highly chemoselective and active photocatalysts for the selective oxidation of alcohols. The nanosheets exhibit improved photocatalytic activity over their layered counterparts. Results of in situ FTIR, DRS, ESR, and DFT calculations show the formation of surface complexes between the Lewis acid sites on HNb3O8 2D nanosheets and alcohols. These complexes play a key role in the photocatalytic activity of the material. Furthermore, the unique structural features of the nanosheets contributed to their high photocatalytic activity. An electron transition from the coordinated alcohol species to surface Nb atoms takes place and initiates the aerobic oxidation of alcohols with high product selectivity under visible light irradiation. This reaction process is distinct from that of classic semiconductor photocatalysis.