Solar-Driven Conversion of CO 2 to C 2 Products by the 3d Transition Metal Intercalates of Layered Lead Iodides.
Jinlin YinDongyang LiChen SunYilin JiangYukong LiHonghan FeiPublished in: Advanced materials (Deerfield Beach, Fla.) (2024)
Photocatalytic CO 2 reduction to high-value-added C 2+ products presents significant challenges, which is attributed to the slow kinetics of multi-e - CO 2 photoreduction and the high thermodynamic barrier for C-C coupling. Incorporating redox-active Co 2+ /Ni 2+ cations into lead halide photocatalysts has high potentials to improve carrier transport and introduce charge polarized bimetallic sites, addressing the kinetic and thermodynamic issues, respectively. In this study, we have developed a coordination-driven synthetic strategy to introduce 3d transition metals into the interlamellar region of layered organolead iodides with atomic precision. The resultant bimetallic halide hybrids exhibit selective photoreduction of CO 2 to C 2 H 5 OH using H 2 O vapor at the evolution rates of 24.9∼31.4 μmol g -1 h -1 and high selectivity of 89.5∼93.6%, while pristine layered lead iodide yields only C 1 products. Band structure calculations and photoluminescence studies indicate that the interlayer Co 2+ /Ni 2+ species greatly contribute to the frontier orbitals and enhance exciton dissociation into free carriers, facilitating carrier transport between adjacent lead iodide layers. In addition, Bader charge distribution calculations and in situ experimental spectroscopic studies reveal that the asymmetric Ni-O-Pb bimetallic catalytic sites exhibit intrinsic charge polarization, promoting C-C coupling and leading to the formation of the key *OC-CHO intermediate. This article is protected by copyright. All rights reserved.
Keyphrases
- transition metal
- solar cells
- density functional theory
- metal organic framework
- reduced graphene oxide
- molecular dynamics
- highly efficient
- aqueous solution
- gene expression
- heavy metals
- quantum dots
- molecular docking
- risk assessment
- room temperature
- dna methylation
- gold nanoparticles
- energy transfer
- health risk
- drinking water
- human health
- genome wide