Efficient structure tuning over the defective modulated zirconium metal organic framework with active coordinate surface for photocatalyst CO2 reduction

Maria Yaseen; Jinhe Li; Haopeng Jiang; M Ashfaq Ahmad; Iltaf Khan; Liyong Tang; Chunxia Wu; Amjid Ali; Qinqin Liu

doi:10.1016/j.jcis.2023.09.053

Efficient structure tuning over the defective modulated zirconium metal organic framework with active coordinate surface for photocatalyst CO₂ reduction

J Colloid Interface Sci. 2024 Jan;653(Pt A):370-379. doi: 10.1016/j.jcis.2023.09.053. Epub 2023 Sep 9.

Authors

Maria Yaseen¹, Jinhe Li², Haopeng Jiang², M Ashfaq Ahmad³, Iltaf Khan⁴, Liyong Tang², Chunxia Wu², Amjid Ali⁵, Qinqin Liu⁶

Affiliations

¹ School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China. Electronic address: mariayaseen1058@gmail.com.
² School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China.
³ Department of Physics, COMSATS University Islamabad, Lahore Campus, Lahore Pakistan.
⁴ School of Environmental & Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, China.
⁵ Research School of Polymeric Materials Science & Engineering, Jiangsu University, Zhenjiang 212013, China; Institute of Chemistry, University of Silesia, Szkolan 9, Katowice 40-600, Poland.
⁶ School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China. Electronic address: qqliu@ujs.edu.cn.

PMID: 37717437
DOI: 10.1016/j.jcis.2023.09.053

Abstract

Structure engineering of zirconium-based metal organic frameworks (MOFs) aims to develop efficient catalysts for transforming intermittent renewable energy into value-added chemical fuels. In order to have a deeper understanding of industrial scaling, it is vital to ascertain the favourable operational parameters that are necessary for projecting at the atomic level. The proposed paradigm provides a robust basis for the efficient design of MOFs based heterogeneous photocatalysts. In this study, set of defective MOF (D-NUiO66) was effectively produced using a modular acidic method. Afterwards, the D-NUiO66 was combined with CeO₂ to form the D-CeNUiO66 heterojunction for the purpose of carbon dioxide reduction. The morphological aspect of the composite investigation suggested that D-CeNUiO66 had a mesoporous structure with favourable adsorption properties. The optimized D-CeNUiO66 photocatalyst showed the high activity for the reduction of CO₂ to CO, with a rate of 38.6 µmolg^-1h^-1 and demonstrated remarkable repeatability in terms of CO production. The incorporation of defect sites in the D-NUiO66 enhanced the light response to visible light, resulting in reduced band gap of 2.9 eV. The photoelectrochemical tests indicated that the introduction of defects in the UiO66 and coupling CeO₂ in the D-CeNUiO66 composite induced fast charge transfer, therefore suppressing the charge recombination rate. This study provides valuable insights into the use of defective engineering and heterojunction approaches to metal-organic frameworks for photocatalytic applications.

Keywords: CO(2) reduction; Cerium oxide; Defective metal–organic frameworks; Photocatalyst; Zr-UiO66-NH(2).