In situ turning defects of exfoliated Ti3C2 MXene into Fenton-like catalytic active sites

Yue Jiang; Didar Baimanov; Shan Jin; Japhet Cheuk-Fung Law; Pengcheng Zhao; Juanjuan Tang; Jian Peng; Liming Wang; Kelvin Sze-Yin Leung; Wenchao Sheng; Sijie Lin

doi:10.1073/pnas.2210211120

In situ turning defects of exfoliated Ti₃C₂ MXene into Fenton-like catalytic active sites

Proc Natl Acad Sci U S A. 2023 Jan 3;120(1):e2210211120. doi: 10.1073/pnas.2210211120. Epub 2022 Dec 27.

Authors

Yue Jiang^{1

2}, Didar Baimanov^{3

4}, Shan Jin⁵, Japhet Cheuk-Fung Law⁶, Pengcheng Zhao^{1

7}, Juanjuan Tang^{1

2}, Jian Peng^{1

2}, Liming Wang³, Kelvin Sze-Yin Leung⁶, Wenchao Sheng^{1

7}, Sijie Lin^{1

2}

Affiliations

¹ College of Environmental Science and Engineering, Biomedical Multidisciplinary Innovation Research Institute, Shanghai East Hospital, Tongji University, Shanghai 200092, China.
² Key Laboratory of Yangtze River Water Environment, Shanghai Institute of Pollution Control and Ecological Security, Tongji University, Shanghai 200092, China.
³ Chinese Academy of Sciences (CAS) Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety & Chinese Academy of Sciences and The University of Hong Kong (CAS-HKU) Joint Laboratory of Metallomics on Health and Environment, Institute of High Energy Physics, Beijing 100049, China.
⁴ University of Chinese Academy of Sciences, Beijing 100049, China.
⁵ Key Laboratory of Nanodevices and Applications, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China.
⁶ Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region 000000, China.
⁷ State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China.

Abstract

Controllable in situ formation of nanoclusters with discrete active sites is highly desirable in heterogeneous catalysis. Herein, a titanium oxide-based Fenton-like catalyst is constructed using exfoliated Ti₃C₂ MXene as a template. Theoretical calculations reveal that a redox reaction between the surface Ti-deficit vacancies of the exfoliated Ti₃C₂ MXene and H₂O₂ molecules facilitates the in situ conversion of surface defects into titanium oxide nanoclusters anchoring on amorphous carbon (TiO_x@C). The presence of mixed-valence Ti^δ+ (δ = 0, 2, 3, and 4) within TiO_x@C is confirmed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) characterizations. The abundant surface defects within TiO_x@C effectively promote the generation of reactive oxygen species (ROS) leading to superior and stable Fenton-like catalytic degradation of atrazine, a typical agricultural herbicide. Such an in situ construction of Fenton-like catalysts through defect engineering also applies to other MXene family materials, such as V₂C and Nb₂C.

Keywords: MXene; heterogeneous catalysis; in situ; multivalence; template synthesis.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Catalytic Domain
Hydrogen Peroxide* / chemistry
Titanium* / chemistry

Substances

Hydrogen Peroxide
titanium dioxide
Titanium
MXene