Modulating the local electron density at built-in interface iron single sites in Fe-CN/MoO3 heterostructure for enhanced CO2 reduction to CH4 and photo-Fenton reaction

Muhammad Arif; Ayaz Mahsud; Haoran Xing; Abdul Hannan Zahid; Qian Liang; Muhammad Amjad Majeed; Amjad Ali; Xiazhang Li; Zhansheng Lu; Francis Leonard Deepak; Tahir Muhmood; Yinjuan Chen

doi:10.1016/j.jcis.2024.11.038

Modulating the local electron density at built-in interface iron single sites in Fe-CN/MoO₃ heterostructure for enhanced CO₂ reduction to CH₄ and photo-Fenton reaction

J Colloid Interface Sci. 2024 Nov 9;680(Pt A):1053-1066. doi: 10.1016/j.jcis.2024.11.038. Online ahead of print.

Authors

Affiliations

¹ Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University, Changzhou 213164, China.
² School of Physics, Henan Key Laboratory of Advanced Semiconductor & Functional Device Integration, Henan Normal University, Xinxiang 453007, China.
³ State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Street, Nanjing 210023, China.
⁴ Department of Chemical Engineering, University of Gujrat, Gujrat 50700, Pakistan.
⁵ Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, Norrköping SE-60174, Sweden.
⁶ National-local Joint Engineering Research Center of Biomass Refining and High-quality Utilization, Changzhou University, Changzhou 213164, China.
⁷ School of Physics, Henan Key Laboratory of Advanced Semiconductor & Functional Device Integration, Henan Normal University, Xinxiang 453007, China; College of Mathematics and Physics, Beijing University of Chemical Technology, Beijing 100029, China. Electronic address: [email protected].
⁸ International Iberian Nanotechnology Laboratory, avenida mestre josé veiga, Braga 4715-310, Portugal.
⁹ International Iberian Nanotechnology Laboratory, avenida mestre josé veiga, Braga 4715-310, Portugal. Electronic address: [email protected].
¹⁰ Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University, Changzhou 213164, China. Electronic address: [email protected].

PMID: 39549349
DOI: 10.1016/j.jcis.2024.11.038

Abstract

The catalytic efficiency of heterogeneous photocatalytic CO₂ reduction and photo-Fenton H₂O₂ activationisclosely related to the local electron density of reaction center atoms. However, electron-hole recombination from random charge transfer significantly restricts the targeted electron delivery to the active center. Herein, Fe-C₃N₄/MoO₃ heterojunction with interfacial coordination of atomically dispersed Fe-N₄ sites with the O interface of MoO₃ was synthesized by simple hydrothermal method. Based on the experimental results and density functional theory calculation (DFT), the heterojunction structure fosters accelerated interfacial electron transfer due to directional interfacial electric field (IEF) between Fe-CN and MoO heterogeneous interfaces, and the interfacial bond between Fe-N₄ sites and O at the built-in interface regulates the local electron density of Fe-N₄ active center. DFT further reveals that the interfacial electron flow and concentrated electron density at Fe-N₄ sites result from the coordination between Fe-N₄ and MoO₃ interfaces. This directs electron flow towards the Fe center, significantly enhancing CO₂ adsorption and H₂O₂ conversion efficiency. PDOS analysis shows that the d_yz and d_z² orbitals of the isolated Fe atom in Fe-CN overlap with the p_z orbital of the O atom in MoO₃, playing a pivotal role in CO₂ adsorption. Consequently, the Fe-CN/MoO₃ heterojunction demonstrated highly efficient photocatalytic CO₂ reduction to CH₄, coupled with benzyl alcohol oxidation and photo-Fenton tetracycline degradation. These findings offer a promising multifunctional catalyst strategy for the development of energy conversion and environmental remediation.

Keywords: Built-in interface; Heterostructure; Iron single sites; Local electron density; Photocatalysis.