Recovering solar fuels from photocatalytic CO2 reduction over W6+-incorporated crystalline g-C3N4 nanorods by synergetic modulation of active centers

Graphitic carbon nitride (g-C 3 N 4 ) is promising for photocatalytic conversion of greenhouse gas CO 2 into valuable solar fuels. Crystalline g-C 3 N 4 (CCN) attracts great attention, nevertheless, the CO 2 reduction efficiency and selectivity are still dissatisfying, due to the lack of suitable active sites. In this study, tungsten doped CCN (CCN-W) is constructed by forming W-N 6 bonding at the cavity sites of adjacent heptazine units. Significantly, relative to CCN, the full-spectrum CO 2 reduction rate (11.91 μmol g −1 h −1 ) on CCN-W is increased by > 5 times, meanwhile, the photoelectron selectivity to hydrocarbons (CH 4 and C 2 H 4 ) approaching 83% is increased by > 2 times. The W 6+ -doping introduced W-N 6 as multifunctional active sites enrich both the photoelectrons and CO 2 molecules, and catalyze their selective conversion into hydrocarbons by reducing reaction barrier and moderately stabilizing CO intermediates. This study will offer new insight into modulating the CCN photocatalysts with multifunctional active sites for efficient and selective photocatalytic CO 2 reduction. • CCN-W photocatalysts with W-N 6 active sites are prepared and characterized. • The CCN-W exhibits excellent CO 2 RR performance with CO, CH 4 and C 2 H 4 yields of 5.75, 4.45, 1.71 μmol g −1 h −1 , respectively. • The W-N 6 active sites favor the accumulation and utilization of photoelectrons. • The W-N 6 modulate CO 2 RR efficiently and selectively by reducing the reaction barrier and stabilizing CO intermediate.