The photocatalytic transformation of carbon dioxide (CO) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA). The resultant PAOs show tunable D-A structures and electronic band positions depending on the degree of oxidation, which can catalyze the photoreduction of CO with water under visible light irradiation, generating CO as the sole carbonaceous product without H generation. Especially, the PAO with an oxygen content of 17.6% afforded the highest CO production rate of 161.9 μmol g h. It is verified that the redox transformation between quinone and phenolic hydroxyl in PAOs achieves CO photoreduction coupled with water oxidation. This study provides a facile way to access conjugated polymers with a tunable D-A structure and demonstrates that the resultant PAOs are promising photocatalysts for CO reduction.
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http://dx.doi.org/10.1021/acs.langmuir.4c00210 | DOI Listing |
Langmuir
March 2024
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Chinese Academy of Sciences (CAS), Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, CAS, Beijing 100190, P. R. China.
The photocatalytic transformation of carbon dioxide (CO) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA).
View Article and Find Full Text PDFChem Rev
February 2024
University of Regensburg, Institute of Inorganic Chemistry, 93040 Regensburg, Germany.
This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident.
View Article and Find Full Text PDFJ Am Chem Soc
November 2023
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
We herein report the iridium-catalyzed enantioselective C-H borylation of aryl chlorides. A variety of prochiral biaryl compounds could be well-tolerated, affording a vast array of axially chiral biaryls with high enantioselectivities. The current method exhibits a high turnover number (TON) of 7000, which represents the highest in functional-group-directed asymmetric C-H activation.
View Article and Find Full Text PDFJ Am Chem Soc
July 2022
Massachusetts Institute of Technology, Department of Chemistry, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Catalyst transfer polymerization (CTP) is widely applied to the synthesis of well-defined π-conjugated polymers. Unlike other polymerization reactions that can be performed in water (e.g.
View Article and Find Full Text PDFMaterials (Basel)
December 2021
Institute of Chemistry, Faculty of Science and Technology, University of Silesia, Bankowa 14, 40-007 Katowice, Poland.
Phenyl, naphthyl, polyarylphenyl, coronene, and other aromatic and polyaromatic moieties primarily influence the final materials' properties. One of the synthetic tools used to implement (hetero)aromatic moieties into final structures is Diels-Alder cycloaddition (DAC), typically combined with Scholl dehydrocondensation. Substituted 2-pyranones, 1,1-dioxothiophenes, and, especially, 1,3-cyclopentadienones are valuable substrates for [4 + 2] cycloaddition, leading to multisubstituted derivatives of benzene, naphthalene, and other aromatics.
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