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Bi-functional Cu-TiO2/CuO photocatalyst for large-scale synergistic treatment of waste sewage containing organics and heavy metal ions

双功能Cu-TiO2/CuO光催化剂用于大规模协同处理含有机污染物和重金属离子的废水

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Abstract

Numerous photocatalysts have been prepared for the photocatalysis of either organic pollutant degradation or Cr(VI) reduction. However, most of the inorganic and organic pollutants usually co-exist in industrial sewage. Simultaneous elimination of mixed inorganic and organic pollutants remains highly challenging. Herein, we report bi-functional Cu-TiO2/CuO photocatalysts by the in-situ doping and heterostructure engineering strategies for large-scale and highly enhanced synergistic photocatalytic elimination of organic pollutants and transitional metallic ions from waste sewage in one shot. Specifically, this bi-functional photocatalyst displays about 2.35 and 3.84 times higher photocatalytic Rhodamine B (RhB) degradation and Cr(VI) reduction rates in the solution with co-existing RhB and Cr(VI) than that in the single RhB or Cr(VI) pollutant solution, respectively. A highly boosted synergetic effect between photocatalytic dye molecule degradation and Cr(VI) reduction is revealed. The bi-functional photocatalyst also displays extraordinary activity and stability in large-scale photocatalytic elimination of mixed pollutants. Moreover, theoretical calculations demonstrate that Cu doping and heterostructure engineering give rise to the narrowed bandgap for enhanced light harvesting, the increased density of states for high charge carrier density, the delocalized electron for fast photoinduced charge carrier separation, and the profitable charge transfer between TiO2 and CuO, thus bringing about the efficient synergetic photocatalysis. The bi-functional photocatalyst concept reported in this study opens a new avenue to construct bi-functional photocatalysts for solar-to-fuel conversion and large-scale industrial waste water treatment and river purification.

摘要

大多数所制备的光催化剂通常只用于单一地降解有机污染物或还原Cr(VI)的光催化. 然而, 无机和有机污染物通常共存于工业污水中.同时消除混合的无机和有机污染物仍然存在着巨大的挑战. 在本文中,我们通过原位掺杂和异质结工程策略, 制备出了新型的双功能Cu-TiO2/CuO光催化剂用于大规模高效协同光催化消除废水中的有机污染物和过渡金属离子. 具体而言, 这种双功能光催化剂在RhB和Cr(VI)共存溶液中的光催化RhB降解率和Cr(VI)还原率分别是在单一RhB或Cr(VI)污染物溶液中对应值的2.35和3.84倍. 光催化染料分子降解和Cr(VI)还原之间存在显著增强的协同效应. 此外, 该双功能光催化剂在大规模光催化消除混合污染物方面也表现出较好的活性和稳定性. 理论计算表明, 铜掺杂和异质结工程促进了高效的光吸收、增高的载流子密度以及快速的光生载流子转移, 从而产生高效的协同光催化作用.这种双功能光催化剂的概念为大规模工业废水处理和净化开辟了新途径.

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Acknowledgements

Ding Y thanks the financial support from the China Scholarship Council (201808310127). Chen LH acknowledges Hubei Provincial Department of Education for the “Chutian Scholar” program. This work was financially supported by the Foundation of Natural Science (61905159), the National Natural Science Foundation of China (U1663225) Program for Changjiang Scholars and Innovative Research Team (IRT_15R22), and the project “DepollutAir” of Interreg V France-Wallonie-Vlaanderen.

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Authors and Affiliations

  1. Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, 61 rue de Bruxelles, B-5000, Namur, Belgium

    Yang Ding  (丁杨), Runtian Zheng  (郑润田), Tarek Barakat & Bao-Lian Su  (苏宝连)

  2. Namur Institute of Structured Matter (NISM), University of Namur, 61 rue de Bruxelles, B-5000, Namur, Belgium

    Yang Ding  (丁杨), Runtian Zheng  (郑润田), Tarek Barakat & Bao-Lian Su  (苏宝连)

  3. Department of Chemical Engineering, University of Calcutta, 92, APC Road, Kolkata, West Bengal, 700009, India

    Soumyajit Maitra & Subhasis Roy

  4. Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium

    Chunhua Wang  (王春花)

  5. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Li-Hua Chen  (陈丽华) & Bao-Lian Su  (苏宝连)

  6. Clare Hall, University of Cambridge United Kingdom, Cambridge, CB2 1EW, UK

    Bao-Lian Su  (苏宝连)

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  1. Yang Ding  (丁杨)
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  2. Soumyajit Maitra
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  3. Chunhua Wang  (王春花)
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  5. Tarek Barakat
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  6. Subhasis Roy
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  7. Li-Hua Chen  (陈丽华)
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  8. Bao-Lian Su  (苏宝连)
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Contributions

Ding Y carried out all experiments and wrote the paper; Maitra S and Roy S conducted the DFT calculations; Wang C and Zheng R helped with the characterizations of photoluminescence, photoluminescence lifetime and EPR spectra; Chen LH and Barakat T guided the experiments, discussed the results and revised the paper; Su BL established the research direction, conceived the project, provided the scientific guidance and project realization ideas, revised and finalized the paper.

Corresponding authors

Correspondence to Li-Hua Chen  (陈丽华) or Bao-Lian Su  (苏宝连).

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Conflict of interest

The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Yang Ding received his MSc degree from the College of Chemistry and Materials Science, Shanghai Normal University in 2018. He is currently a PhD student in the Laboratory of Inorganic Materials Chemistry (CMI) of the University of Namur under the supervision of Prof. Bao-Lian Su. His research interests include the synthesis and characterization of porous materials, photocatalytic pollutant elimination and sustainable energy production.

Li-Hua Chen obtained his PhD degrees, one in inorganic chemistry from Jilin University, China (2009), and another in inorganic materials chemistry from the University of Namur, FUNDP, Belgium (2011). In 2011–2012, he held a project-researcher position at the University of Namur with Professor Bao-Lian Su, working on hierarchically porous zeolites. He is currently a full professor at Wuhan University of Technology, China. His research is aimed at new porous materials with designed hierarchically porosity.

Bao-Lian Su founded the CMI at the University of Namur, Belgium in 1995. He is full professor, Member of the European Academy of Sciences, Member of the Royal Academy of Belgium, Fellow of the Royal of Society of Chemistry, UK and Life Member of Clare Hall College, University of Cambridge. He is also a strategy scientist at Wuhan University of Technology, China. His research fields include the synthesis, the property study and the molecular engineering of organized, hierarchically porous materials and bio-organisms for artificial photosynthesis, (photo)catalysis, energy conversion and storage, biotechnology, cell therapy and biomedical applications.

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Bi-functional Cu-TiO2/CuO photocatalyst for large-scale synergistic treatment of waste sewage containing organics and heavy metal ions

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Ding, Y., Maitra, S., Wang, C. et al. Bi-functional Cu-TiO2/CuO photocatalyst for large-scale synergistic treatment of waste sewage containing organics and heavy metal ions. Sci. China Mater. 66, 179–192 (2023). https://doi.org/10.1007/s40843-022-2148-4

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