Spatially separated oxygen vacancies and nickel sites for ensemble promotion of selective CO2 photoreduction to CO

Trade-Off of Metal Sites in Fe–Ni Bimetal Metal–Organic Frameworks for Efficient CO2 Photoreduction with Nearly 100% CO Selectivity

“…Among all FeNi x PBAs, the strongest photocurrent response (Figure c) and the smallest electrochemical impedance (Figure d) were observed from FeNi 0.50 PBA, which has the highest Fe content. It demonstrates the efficient charge transfer in Fe-rich PBAs, which supports the fast transport of electrons of catalysts to the active sites where the CO 2 reduction will occur . To verity this, the electronic structure of FeNi x PBA was further investigated by running DFT calculations of Fe–Ni PBA models with arbitrarily high and low Ni/Fe ratios (Figure S13).…”

“…Using the solar-driven CO 2 reduction reaction (CRR) to synthesize value-added chemicals is a promising approach to alleviate the current energy and environmental crisis. − The performance of CRR catalysts strongly relies on their active metal centers as the photogenerated charge carriers must be efficiently separated and sent to the active sites where the redox reaction is to occur. − In biogeochemical cycles, various pathways exist in nature for the reduction of CO 2 , and many of them involve complex metal clusters as the catalytically active sites . For instance, the Ni,Fe-containing carbon monoxide dehydrogenase (Ni-CODH) selectively reduces CO 2 to CO with high efficiency. , It is thus inspiring and potentially rewarding to design biomimetic CRR catalysts through a judicious installation of multiple metal centers in close spatial proximity. , …”

Sponge‐Like Nickel Carbonate of High Porosity and Carbonate Vacancy for High‐Performance CO2 Photoreduction

“…The DFT calculations manifest both carbonate vacancy and oxygen vacancy benefits the CO 2 adsorption . [26] However, the carbonate vacancy (V CO3 ) decreases ΔE ad-CO2 (from −0.541 to −1.292 eV) more significantly than the oxygen vacancy (V O ) (from −0.254 to −0.614 eV, Figure 4d), thus giving the V CO3 -NiCO 3 surface the strongest CO 2 adsorption ability. The calculation results here are in agreement with the findings of the preceding CO 2 adsorption and CO 2 -TPD measurements.…”

Atomically dispersed and oxygen deficient CuO clusters as an extremely efficient heterogeneous catalyst

“…Atomically dispersed clusters (<2 nm) are one of the most intriguing categories of heterogeneous catalysts in modern industry as well as biological systems to alleviate the energy and environmental crises. 1,2 Clusters consist of a finite number of atoms (up to only several thousands), and catalysts made of clusters are rich in active sites, have appealing activities, and perform exquisitely in various reactions, spanning H 2 O splitting, 3 CO 2 reduction, 4,5 pollutant oxidation, 6 and chemical synthesis. 7 Despite their structural appeal, the rational design of high-performance clusters remains a formidable challenge.…”