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Exciting progress has been made in the area of solar fuel generation by CO 2 reduction. New photocatalytic materials containing well-defined surface catalytic sites have emerged in recent years, including heterogenized molecular catalysts and single atom catalysts. This Feature Article summarizes our recent research in this area, together with brief discussions of relevant literature. In our effort to obtain heterogenized molecular catalysts, a diimine-tricarbonyl Re( i ) complex and a tetraaza macrocyclic Co( iii ) compound were covalently attached to different surfaces, and the effects of ligand derivatization and surface characteristics on their structures and photocatalytic activities were investigated. Single atom catalysts combine the advantages of homogeneous and heterogeneous catalysis. A single-site cobalt catalyst was prepared on graphitic carbon nitride, which demonstrated excellent activity in selective CO 2 reduction under visible-light irradiation. Doping carbon nitride with carbon was found to have profound effects on the structure and activity of the single-site cobalt catalyst. Our research achievements are presented to emphasize how spectroscopic techniques, including infrared, UV-visible, electron paramagnetic resonance, and X-ray absorption spectroscopies, could be combined with catalyst synthesis and computation modeling to understand the structures and properties of well-defined surface catalytic sites at the molecular level. This article also highlights challenges and opportunities in the broad context of solar CO 2 reduction.
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Solar CO2 reduction using a molecular Re(I) catalyst grafted on SiO2 via amide and alkyl amine linkages
Heterogenized molecular catalysts have shown interesting activities in different chemical transformations. In our previous studies, a molecular catalyst, Re(bpy)(CO)3Cl where bpy is 2,2’-bipyridine, was covalently attached to silica surfaces via an amide linkage for use in photocatalytic CO2 reduction. Derivatizing the bpy ligand with electron-withdrawing amide groups led to detrimental effects on the catalytic activity of Re(bpy)(CO)3Cl. In this study, an alkyl amine linkage is utilized to attach Re(bpy)(CO)3Cl onto SiO2 in order to eliminate the detrimental effects of the amide linkage by breaking the conjugation between the bpy ligand and the amide group. However, the heterogenized Re(I) catalyst containing the alkyl amine linkage demonstrates even lower activity than the one containing the amide linkage in photocatalytic CO2 reduction. Infrared studies suggest that the presence of the basic amine group led to the formation of a photocatalytically inactive Re(I)-OH species on SiO2. Furthermore, the amine group likely contributes to the stabilization of a surface Re(I)-carboxylato species formed upon light irradiation, resulting in the low activity of the heterogenized Re(I) catalyst containing the alkyl amine linkage.
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- PAR ID:
- 10616016
- Publisher / Repository:
- The Royal Society of Chemistry
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 53
- Issue:
- 6
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 2645 to 2652
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d3dt03623e
