Central nitrogen vacancies in polymeric carbon nitride for boosted photocatalytic H2O2 production

Feng Lin; Tong Wang; Zhujuan Ren; Xiaorong Cai; Yulin Wang; Jun Chen; Jianghao Wang; Shaohong Zang; Feifei Mao; Liang Lv

doi:10.1016/j.jcis.2023.01.036

Central nitrogen vacancies in polymeric carbon nitride for boosted photocatalytic H₂O₂ production

J Colloid Interface Sci. 2023 Apr 15:636:223-229. doi: 10.1016/j.jcis.2023.01.036. Epub 2023 Jan 7.

Authors

Feng Lin¹, Tong Wang², Zhujuan Ren³, Xiaorong Cai⁴, Yulin Wang², Jun Chen⁵, Jianghao Wang⁵, Shaohong Zang⁴, Feifei Mao⁶, Liang Lv⁷

Affiliations

¹ College of Chemical and Materials Engineering, Quzhou University, Quzhou 324000, China. Electronic address: linfeng@qzc.edu.cn.
² College of Chemical and Materials Engineering, Quzhou University, Quzhou 324000, China.
³ College of Science, Nanjing Agricultural University, Nanjing 210095, China.
⁴ Institute of Innovation & Application, National Engineering Research Central for Marine Aquaculture, Zhejiang Ocean University, Zhoushan 316022, China.
⁵ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China; Institute of Zhejiang University-Quzhou, Quzhou 324000, China.
⁶ College of Science, Nanjing Agricultural University, Nanjing 210095, China; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China. Electronic address: maofeifei@njau.edu.cn.
⁷ College of Chemical and Materials Engineering, Quzhou University, Quzhou 324000, China. Electronic address: lianglv_buct@126.com.

PMID: 36634392
DOI: 10.1016/j.jcis.2023.01.036

Abstract

Polymeric carbon nitride (PCN) with vacancies usually exhibits distinguished mass transfer efficiency, outstanding carrier kinetics and excellent photoactivity. Previous studies have revealed the effect of edge vacancies in heptazine units of PCN; however, the roles of central nitrogen vacancies are scarcely investigated. Herein, central nitrogen vacancies polymeric carbon nitride (PCN-NV_C) is rationally prepared for photocatalytic H₂O₂ production with a rate of 25.1 umol/h (λ > 420 nm), which is 3.5 times than that of pristine PCN. Photoelectronic measurements reveal that the central nitrogen vacancies optimize the kinetic process of electron-hole pairs. Density functional theory (DFT) calculations disclose that PCN-NV_C displays lower O₂ adsorption energy, thereby accelerating the OOH* formation and decreasing the H₂O₂ generation energy barrier. This work not only provides a strategy for constructing central nitrogen vacancies polymeric carbon nitrogen, but also affords a deep understanding of its roles in photocatalytic H₂O₂ production.

Keywords: Central nitrogen vacancies; H(2)O(2) production; Photocatalysis; Photogenerated carrier; Polymeric carbon nitride.