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Catalysts
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Electron Paramagnetic Resonance in Photocatalysis
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Electron Paramagnetic Resonance in Photocatalysis

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Photocatalysis".

Deadline for manuscript submissions: closed (20 February 2022) | Viewed by 17324

Special Issue Editor

Dr. Andrea Folli

E-Mail Website1 Website2
Guest Editor
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
Interests: photo-redox and electro- catalysis; heterogeneous catalysis; electron paramagnetic resonance (EPR) spectroscopy; electrochemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Photocatalytic reactions mostly involve species carrying unpaired electrons. These include electron–hole pairs, trapped charge carriers, paramagnetic redox metal centres, surface defects, organic radicals, as well as reactive oxygen species. These systems can be systematically interrogated, probed, and studied using electron paramagnetic resonance (EPR) and hyperfine spectroscopies. These techniques are capable of providing information on the identity, chemical composition, and dynamics of the paramagnetic centres (and their surroundings) involved in the photocatalytic events. This Special Issue aims to showcase current scientific developments in the area of EPR spectroscopy applied to photocatalysts used for environmental remediation, clean energy production, and chemical synthesis/processing. The Special Issue is open to both original research articles as well as extended reviews.

Dr. Andrea Folli
Guest Editor

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Keywords

  • Electron paramagnetic resonance
  • Endor
  • Eseem
  • Hyscore
  • Photocatalysis
  • Transition metal oxides
  • Graphene
  • Doped semiconductors
  • Electron–hole pairs
  • Charge carrier
  • Paramagnetic metal centres
  • Electron transfer
  • Spin chemistry

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Published Papers (3 papers)

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Research

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21 pages, 2923 KiB  
Article
A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO2 Nanoparticle/Water Interfaces
by Sam Gorman, Kirstie Rickaby, Li Lu, Christopher J. Kiely, Donald E. Macphee and Andrea Folli
Catalysts 2021, 11(11), 1305; https://doi.org/10.3390/catal11111305 - 28 Oct 2021
Viewed by 2161
Abstract
The doping of TiO2-based nanomaterials for semiconductor-sensitised photoreactions has been a practice extensively studied and applied for many years. The main goal remains the improvement of light harvesting capabilities under passive solar irradiation, that in the case of undoped [...] Read more.
The doping of TiO2-based nanomaterials for semiconductor-sensitised photoreactions has been a practice extensively studied and applied for many years. The main goal remains the improvement of light harvesting capabilities under passive solar irradiation, that in the case of undoped TiO2 is limited and restricted to relatively low latitudes. The activity and selectivity of doped TiO2 photocatalysts are generally discussed on the basis of the modified band structure; energetics of intrinsic or extrinsic band gaps including trapping states; redox potentials of band edges, including band bending at solid/fluid interfaces; and charge carriers scavenging/transfer by/to adsorbed species. Electron (and hole) transfer to adsorbates is often invoked to justify the formation of highly reactive species (e.g., HO. from water); however, a complete description of the nanoparticle surface chemistry dictating adsorption/desorption events is often missing or overlooked. Here, we show that by employing a surface electrochemical triple-layer (TLM) approach for the nanoparticles/water interface, in combination with electron paramagnetic resonance spectroscopy (EPR), transmission electron microscopy and electrophoretic measurements, we can elucidate the surface chemistry of doped TiO2 nanoparticles and link it to the nature of the dopants. Exemplifying it for the cases of undoped, as well as W- and N-doped and codoped TiO2 nanoparticles, we show how surface charge density; surface, Stern and ζ potentials; surface acidity constants; and speciation of surface sites are influenced by the nature of the dopants and their loading. Full article
(This article belongs to the Special Issue Electron Paramagnetic Resonance in Photocatalysis)
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Review

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21 pages, 3057 KiB  
Review
Electron Paramagnetic Resonance Spin Trapping (EPR–ST) Technique in Photopolymerization Processes
by Fabienne Peyrot, Sonia Lajnef and Davy-Louis Versace
Catalysts 2022, 12(7), 772; https://doi.org/10.3390/catal12070772 - 12 Jul 2022
Cited by 13 | Viewed by 6033
Abstract
To face economic issues of the last ten years, free-radical photopolymerization (FRP) has known an impressive enlightenment. Multiple performing photoinitiating systems have been designed to perform photopolymerizations in the visible or near infrared (NIR) range. To fully understand the photochemical mechanisms involved upon [...] Read more.
To face economic issues of the last ten years, free-radical photopolymerization (FRP) has known an impressive enlightenment. Multiple performing photoinitiating systems have been designed to perform photopolymerizations in the visible or near infrared (NIR) range. To fully understand the photochemical mechanisms involved upon light activation and characterize the nature of radicals implied in FRP, electron paramagnetic resonance coupled to the spin trapping (EPR–ST) method represents one of the most valuable techniques. In this context, the principle of EPR–ST and its uses in free-radical photopolymerization are entirely described. Full article
(This article belongs to the Special Issue Electron Paramagnetic Resonance in Photocatalysis)
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37 pages, 10272 KiB  
Review
Application of EPR Spectroscopy in TiO2 and Nb2O5 Photocatalysis
by Osama Al-Madanat, Barbara Nascimento Nunes, Yamen AlSalka, Amer Hakki, Mariano Curti, Antonio Otavio T. Patrocinio and Detlef W. Bahnemann
Catalysts 2021, 11(12), 1514; https://doi.org/10.3390/catal11121514 - 13 Dec 2021
Cited by 38 | Viewed by 7903
Abstract
The interaction of light with semiconducting materials becomes the center of a wide range of technologies, such as photocatalysis. This technology has recently attracted increasing attention due to its prospective uses in green energy and environmental remediation. The characterization of the electronic structure [...] Read more.
The interaction of light with semiconducting materials becomes the center of a wide range of technologies, such as photocatalysis. This technology has recently attracted increasing attention due to its prospective uses in green energy and environmental remediation. The characterization of the electronic structure of the semiconductors is essential to a deep understanding of the photocatalytic process since they influence and govern the photocatalytic activity by the formation of reactive radical species. Electron paramagnetic resonance (EPR) spectroscopy is a unique analytical tool that can be employed to monitor the photoinduced phenomena occurring in the solid and liquid phases and provides precise insights into the dynamic and reactivity of the photocatalyst under different experimental conditions. This review focus on the application of EPR in the observation of paramagnetic centers formed upon irradiation of titanium dioxide and niobium oxide photocatalysts. TiO2 and Nb2O5 are very well-known semiconductors that have been widely used for photocatalytic applications. A large number of experimental results on both materials offer a reliable platform to illustrate the contribution of the EPR studies on heterogeneous photocatalysis, particularly in monitoring the photogenerated charge carriers, trap states, and surface charge transfer steps. A detailed overview of EPR-spin trapping techniques in mechanistic studies to follow the nature of the photogenerated species in suspension during the photocatalytic process is presented. The role of the electron donors or the electron acceptors and their effect on the photocatalytic process in the solid or the liquid phase are highlighted. Full article
(This article belongs to the Special Issue Electron Paramagnetic Resonance in Photocatalysis)
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