Reducing CO2 into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and efficient photocatalytic system for CO2 reduction. Driven by electrostatic attraction, an anionic metal–organic framework Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host and a cationic photosensitizer [Ru­(phen)3]2+ (phen = 1,10-phenanthroline) as guest were self-assembled into a photocatalytic system Ru@Cu-HHTP, which showed high activity for photocatalytic CO2 reduction under laboratory light source (CO production rate of 130(5) mmol g–1 h–1, selectivity of 92.9%) or natural sunlight (CO production rate of 69.5 mmol g–1 h–1, selectivity of 91.3%), representing the remarkable photocatalytic CO2 reduction performance. More importantly, the photosensitizer [Ru­(phen)3]2+ in Ru@Cu-HHTP is only about 1/500 in quantity reported in the literature. Theoretical calculations and control experiments suggested that the assembly of the catalysts and photosensitizers via electrostatic attraction interactions can provide a better charge transfer efficiency, resulting in high performance for photocatalytic CO2 reduction.

Electrocatalytic reduction of CO2 into multicarbon (C2+) products powered by renewable electricity offers one promising way for CO2 utilization and promotes the storage of renewable energy under the ambient environment....

Photocatalytic CO2 conversion into a high-value-added C2 product is a highly challenging task because of insufficient electron deliverability and sluggish C–C coupling kinetics. Engineering catalytic interfaces in photocatalysts provides a promising approach to manipulate photoinduced charge carriers and create multiple catalytic sites for boosting the generation of C2 product from CO2 reduction. Herein, a Cuδ+/CeO2-TiO2 photocatalyst that contains atomically dispersed Cuδ+ sites anchored on the CeO2-TiO2 heterostructures consisting of highly dispersed CeO2 nanoparticles on porous TiO2 is designedly constructed by the pyrolytic transformation of a Cu2+-Ce3+/MIL-125-NH2 precursor. In the designed photocatalyst, TiO2 acts as a light-harvesting material for generating electron–hole pairs that are efficiently separated by CeO2-TiO2 interfaces, and the Cu–Ce dual active sites synergistically facilitate the generation and dimerization of *CO intermediates, thus lowering the energy barrier of C–C coupling. As a consequence, the Cuδ+/CeO2-TiO2 photocatalyst exhibits a production rate of 4.51 μmol–1·gcat –1·h–1 and 73.9% selectivity in terms of electron utilization for CO2 to C2H4 conversion under simulated sunlight, with H2O as hydrogen source and hole scavenger. The photocatalytic mechanism is revealed by operando spectroscopic methods as well as theoretical calculations. This study displays the rational construction of heterogeneous photocatalysts for boosting CO2 conversion and emphasizes the synergistic effect of multiple active sites in enhancing the selectivity of C2 product.

Hydrogen evolution reaction (HER) in neutral media is of great practical importance for sustainable hydrogen production, but generally suffers from low activities, the cause of which has been a puzzle yet to be solved. Herein, by investigating the synergy between Ru single atoms (RuNC) and RuSex cluster compounds (RuSex) for HER using ab initio molecular dynamics, operando X-ray absorption spectroscopy, and operando surface-enhanced infrared absorption spectroscopy, we establish that the interfacial water governs neutral HER. The rigid interfacial water layer in neutral media would inhibit the transport of H2O*/OH* at the electrode/electrolyte interface of RuNC, but the RuSex can promote H2O*/OH* transport to increase the number of available H2O* on RuNC by disordering the interfacial water network. With the synergy of RuSex and RuNC, the resulting neutral HER performance in terms of mass-specific activity is 6.7 times higher than that of 20 wt.% Pt/C at overpotential of 100 mV.