Photoenzymatic Catalytic Cascade System of a Pyromellitic Diimide/g-C3N4 Heterojunction to Efficiently Regenerate NADH for Highly Selective CO2 Reduction toward Formic Acid

Pengye Zhang; Jundie Hu; Yangbin Shen; Xiaogang Yang; Jiafu Qu; Feng Du; Wei Sun; Chang Ming Li

doi:10.1021/acsami.1c13167

Photoenzymatic Catalytic Cascade System of a Pyromellitic Diimide/g-C₃N₄ Heterojunction to Efficiently Regenerate NADH for Highly Selective CO₂ Reduction toward Formic Acid

ACS Appl Mater Interfaces. 2021 Oct 6;13(39):46650-46658. doi: 10.1021/acsami.1c13167. Epub 2021 Sep 23.

Authors

Pengye Zhang¹, Jundie Hu², Yangbin Shen², Xiaogang Yang², Jiafu Qu², Feng Du², Wei Sun³, Chang Ming Li^{1

2

3

4}

Affiliations

¹ Institute of Advanced Cross-Field Science, College of Life Science, Qingdao University, Qingdao 266071, China.
² School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China.
³ Key Laboratory of Laser Technology and Optoelectronic Functional Materials of Hainan Province, Key Laboratory of Functional Materials and Photoelectrochemistry of Haikou, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, China.
⁴ Institute of Clean Energy & Advanced Materials, Southwest University, Chongqing 400715, China.

PMID: 34553901
DOI: 10.1021/acsami.1c13167

Abstract

Photocatalytic reduction of carbon dioxide (CO₂) holds great promise for both clean energy and environment protection. However, the low activity and poor selectivity of photocatalysts are the main bottlenecks. Herein, inspired by artificial photosynthesis and taking advantages of high efficiency and specificity of bioenzymes, we marry photo with enzyme to synergistically solve the above problems. A metal-free heterojunction of pyromellitic diimide/g-C₃N₄ (PDI/CN) with an excellent visible light response (λ < 660 nm) is fabricated for achieving a photoenzymatic catalytic cascade system, which efficiently regenerates nicotinamide adenine dinucleotide (NADH) and selectively reduces CO₂ to formic acid (HCOOH). The highest NADH yield of the PDI/CN hybrid achieved is 75%, and the HCOOH generation rate achieved is 1.269 mmol g^-1 h^-1 with nearly 100% selectivity, which is much higher than those of the reported materials. The excellent photocatalytic performance is attributed to the unique photoenzymatic catalytic cascade system, heterointerface effect, good conductivity, and a wide sunlight response range of the PDI/CN heterojunction. This work provides an efficient strategy and a corresponding photocatalyst for the directional conversion of CO₂ to HCOOH.

Keywords: CO2 reduction; NADH regeneration; formic acid; high selectivity; photoenzymatic catalysis.