Triptycene incorporated carbon nitride based donor-acceptor conjugated polymers with superior visible-light photocatalytic activities

Yun Zheng; Lili Zhang; Yuke Li; Yayun Wang; Jingling Chen; Bizhou Lin; Yanzhen Zheng; Lin Cheng; Sibo Wang; Yilin Chen

doi:10.1016/j.jcis.2022.04.138

Triptycene incorporated carbon nitride based donor-acceptor conjugated polymers with superior visible-light photocatalytic activities

J Colloid Interface Sci. 2022 Sep 15:622:675-689. doi: 10.1016/j.jcis.2022.04.138. Epub 2022 Apr 29.

Authors

Yun Zheng¹, Lili Zhang¹, Yuke Li², Yayun Wang¹, Jingling Chen¹, Bizhou Lin¹, Yanzhen Zheng³, Lin Cheng¹, Sibo Wang⁴, Yilin Chen⁵

Affiliations

¹ Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, Fujian, China.
² Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Shatin, Hong Kong, China.
³ College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China. Electronic address: yanzhenzheng@jmu.edu.cn.
⁴ State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, China.
⁵ Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, Fujian, China. Electronic address: ylchen@hqu.edu.cn.

PMID: 35533482
DOI: 10.1016/j.jcis.2022.04.138

Abstract

Polymeric carbon nitride (CN) has evoked considerable attention in photocatalysis, however, its π-deficiency conjugated frameworks engendering weak visible-light absorption and rapid charge recombination hinder the practical utilizations. Herein, a novel donor-acceptor (D-A) conjugated polymer based on triptycene incorporated carbon nitride (T-CN) has been facilely prepared by thermal copolymerization of melamine and 2,6,14-triaminotriptycene. Combined with the density functional theory (DFT) calculations, it is found that the formation of intramolecular charge transfer and the extended π-conjugative effect in the D-A structure contribute to a broadened light-harvesting spectral range, a higher charge separation/transfer efficiency and more active sites of T-CN for photoredox reactions. The T-CN catalyst accomplished superior visible-light photocatalytic performance in both hydrogen evolving and carbon dioxide reduction. The optimal T-CN catalyst exhibited the highest hydrogen evolution rate of 80.9 ± 1.3 μmol·h^-1 and carbon monoxide production rate of 8.1 ± 0.2 μmol·h^-1, which are ca. 8-fold and 20-fold of bulk CN, respectively. The convenient strategy of constructing D-A conjugated structure opens up a new intriguing avenue toward the rational creation of efficient polymeric nanomaterials for versatile applications of solar fuel production.

Keywords: Carbon dioxide reduction; Carbon nitride; Hydrogen evolution; Photocatalysis; Triptycene.