No abstract

An all-inorganic perovskite (CsPbBr3) was introduced into g-C3N4 to fabricate the CsPbBr3@g-C3N4 photocatalyst for photochemical reduction in diluted CO2.

CO2 photoreduction is a promising avenue to alleviate climate change and energy shortage, and highly active and selective photocatalysts have been pursued. Discrete metal–organic cages (MOCs) with tunable structures and dispersion not only render integration of multiple functional moieties but also facilitate the accessibility of catalytic sites, yet the studies of MOCs on CO2 reduction are still underexplored. Herein, a single molecular cage of the Ir­(III) complex-decorated Zr-MOC (IrIII-MOC-NH2) is proposed for CO2 photoreduction. IrIII-MOC-NH2 shows high reactivity and selectivity in converting CO2 into CO under visible light. The selectivity is of 99.5% and the turnover frequency reaches ∼120 h–1 which is 3.4-fold higher than that of bulk IrIII-MOC-NH2 and two orders of magnitude higher than that of the classical metal–organic framework counterpart (IrIII-Uio-67-NH2). The apparent quantum yield is up to 6.71% that ranks the highest among the values reported for crystalline porous materials. Moreover, aggregation-induced deactivation of the Ir­(III) complex is restrained after incorporating into MOC-NH2. The density functional theory calculations and dedicated experiments including cyclic voltammetry, mass spectrometry and in situ IR show that the Ir­(III) complex is the catalytic center, and −NH2 in the framework plays the synergetic role in the stabilization of the transition state and CO2 adducts.

At present, the fixation of CO2 always requires it to be extracted from the atmosphere first, which leads to more energy consumption. Thus, direct photoreduction of low‐concentration CO2 to useful chemicals (e.g., syngas) under sunlight is significant from an energy‐saving and environmentally friendly perspective. Here, the design and fabrication of a [Ru(bpy)3]/[Co20Mo16P24] composite is demonstrated for visible‐light‐driven syngas production from diluted CO2 (3–20 %) gas with a high yield of approximately 1000 TONs (turnover number of syngas). This activity is an order of magnitude higher than the reported system with [Ru(bpy)3]2+ participation. With evidence from ultrafast transient absorption, GC‐MS, 1H NMR spectroscopy and in situ transient photovoltage tests, a clear and fundamental understanding of the highly efficient photoreduction of CO2 by the [Ru(bpy)3]/[Co20Mo16P24] composite is achieved. Making use of the structure and property designable polyoxometalates towards the photo‐fixation of CO2 is a conceptually distinct and commercially interesting strategy for making useful chemicals and environmental protection.