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Special Issue "Current Advances in Photochemistry"

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Photochemistry".

Deadline for manuscript submissions: 15 January 2024 | Viewed by 2789

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Special Issue Editors

Dr. Giuseppina La Ganga

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Guest Editor

Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, and Interuniversitary Research Center for Artificial Photosynthesis (SOLAR-CHEM), Università degli Studi di Messina, Via F. Stagno d’Alcontres 31, 98166 Messina, Italy
Interests: artificial photosynthesis; supramolecular photochemistry; photophysics and photochemistry of coordination compounds/photocatalysis; photoinduced electron and energy transfer

Dr. Serena Berardi

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Guest Editor

Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, Ferrara, Italy
Interests: photoelectrochemistry; semiconductor; catalysis

Special Issue Information

Dear Colleagues,

In recent years, photochemistry has undergone considerable development in various fields of science, as well as influenced several aspects of our life. The study of photochemical systems can exploit sunlight in order to drive chemical reactions or to generate electricity, which is of great practical significance for the production of sustainable energy vectors.

This Special Issue aims to provide an overview on the latest achievements in photochemistry, highlighting new molecular, supramolecular, and/or material-based systems, as well as their use in applications such as (but not limited to) bioimaging, functional devices, and catalysis. Particular attention can be given to the artificial photosynthesis approach, i.e., to the design of new molecular chromophores, redox catalysts, and electron donors/acceptors for solar energy conversion into value-added products or fuels. Studies of the dynamics of energy/charge transfer processes, also by means of ultrafast techniques, will also be welcomed.

Dr. Giuseppina La Ganga
Dr. Serena Berardi
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

supramolecular photochemistry
photocatalysis
new luminescent material
artificial photosynthesis
photochemistry and photophysics of coordination compounds
environmental photocatalysis
photoinduced electron and energy transfer
photoelectrocatalysis

Published Papers (4 papers)

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Research

14 pages, 2295 KiB

Open AccessArticle

Possible Effects of Changes in Carbonate Concentration and River Flow Rate on Photochemical Reactions in Temperate Aquatic Environments

Davide Vione

Federica Saglia

and

Carola Pelazza

Molecules 2023, 28(20), 7072; https://doi.org/10.3390/molecules28207072 - 13 Oct 2023

Viewed by 351

Abstract

In temperate environments, climate change could affect water pH by inducing enhanced dissolution of CaSO₄ followed by biological sulphate reduction, with the potential to basify water due to H⁺ consumption. At the same time, increased atmospheric CO₂ could enhance weathering of carbonate rocks (e.g., dolomite) and increase the total concentration of dissolved carbonate species. Both processes enhance phototransformation by the carbonate radical (CO₃^•−), as shown for the non-steroidal anti-inflammatory drug paracetamol, provided that the dissolved organic carbon of water does not undergo important fluctuations. Climate change could also affect hydrology, and prolonged drought periods might considerably decrease flow rates in rivers. This is a substantial problem because wastewater pollutants become less diluted and, as a result, can exert more harmful effects due to increased concentrations. At the same time, in low-flow conditions, water is also shallower and its flow velocity is decreased. Photochemical reactions become faster because shallow water is efficiently illuminated by sunlight, and they also have more time to occur because water takes longer to cover the same river stretch. As a result, photodegradation of contaminants is enhanced, which offsets lower dilution but only at a sufficient distance from the wastewater outlet; this is because photoreactions need time (which translates into space for a flowing river) to attenuate pollution. Full article

(This article belongs to the Special Issue Current Advances in Photochemistry)

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18 pages, 4098 KiB

Open AccessArticle

Excited-State Dynamics Leading Either to Triplet Formation or Coordinative Expansion following Photolysis of Cu(II)-Porphyrins: A DFT, TD-DFT, Luminescence and Femtosecond Time-Resolved Absorbance Study

and

Molecules 2023, 28(17), 6310; https://doi.org/10.3390/molecules28176310 - 29 Aug 2023

Viewed by 560

Abstract

The photophysical properties of Cu(II) complexes with 5,10,15,20-meso-tetrakis(phenyl)porphyrin and 5,10,15,20-meso-tetrakis(N-methylpyridium-4-yl)porphyrin are examined via the luminescence and femtosecond time-resolved absorbance methods, respectively. These studies are supported by DFT and TD-DFT calculations, which highlight the important role played by ligand-to-metal charge-transfer states in directing the system toward either intersystem crossing to the triplet hypersurface or coordinative expansion to a five-coordinate quasi-stable intermediate. The latter processes occur when the porphyrin is photolyzed in the presence of suitably located Lewis bases. Femtosecond time-resolved absorbance measurements of Cu(II)-5,10,15,20-meso-tetrakis(N-methylpyridium-4-yl)porphyrin confirm that the coordinative expansion in water occurs in approximately 700 fs, while crossing to the triplet hypersurface takes approximately 140 fs in the same solvent. These processes are mutually exclusive, although both can occur simultaneously depending on the environment of the porphyrin. The ratio of the two processes depends on the relative orientation of the Lewis base with respect to the copper atom at the time of excitation. As a consequence, copper porphyrins such as these are excellent probes in the environment of the porphyrin and can be used to identify the location of the porphyrin when interacting with DNA fragments. Full article

(This article belongs to the Special Issue Current Advances in Photochemistry)

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16 pages, 5261 KiB

Open AccessArticle

Effect of the Synthetic Parameters over ZnO in the CO₂ Photoreduction

Alessandro Di Michele

Giuseppe Cruciani

and

Michela Signoretto

Molecules 2023, 28(12), 4798; https://doi.org/10.3390/molecules28124798 - 16 Jun 2023

Viewed by 634

Abstract

Zinc oxide (ZnO) is an attractive semiconductor material for photocatalytic applications, owing to its opto-electronic properties. Its performances are, however, strongly affected by the surface and opto-electronic properties (i.e., surface composition, facets and defects), in turn related to the synthesis conditions. The knowledge on how these properties can be tuned and how they are reflected on the photocatalytic performances (activity and stability) is thus essential to achieve an active and stable material. In this work, we studied how the annealing temperature (400 °C vs. 600 °C) and the addition of a promoter (titanium dioxide, TiO₂) can affect the physico-chemical properties of ZnO materials, in particular surface and opto-electronic ones, prepared through a wet-chemistry method. Then, we explored the application of ZnO as a photocatalyst in CO₂ photoreduction, an appealing light-to-fuel conversion process, with the aim to understand how the above-mentioned properties can affect the photocatalytic activity and selectivity. We eventually assessed the capability of ZnO to act as both photocatalyst and CO₂ adsorber, thus allowing the exploitation of diluted CO₂ sources as a carbon source. Full article

(This article belongs to the Special Issue Current Advances in Photochemistry)

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11 pages, 1805 KiB

Open AccessArticle

Photochemical Implications of Changes in the Spectral Properties of Chromophoric Dissolved Organic Matter: A Model Assessment for Surface Waters

Nicole Altare

and

Davide Vione

Molecules 2023, 28(6), 2664; https://doi.org/10.3390/molecules28062664 - 15 Mar 2023

Viewed by 746

Abstract

Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (A_CDOM(λ), unitless) can be described by an exponential function that decays with increasing wavelength: A_CDOM(λ) = 100 d DOC A_o e⁻ ^S^λ, where d [m] is water depth, DOC [mg_C L⁻¹] is dissolved organic carbon, A_o [L mg_C⁻¹ cm⁻¹] is a pre-exponential factor, and S [nm⁻¹] is the spectral slope. Sunlight absorption by CDOM is higher when A_o and DOC are higher and S is lower, and vice versa. By the use of models, here we investigate the impact of changes in CDOM spectral parameters (A_o and S) on the steady-state concentrations of three PPRIs: the hydroxyl radical (^•OH), the carbonate radical (CO₃^•−), and CDOM excited triplet states (³CDOM*). A first finding is that variations in both A_o and S have impacts comparable to DOC variations on the photochemistry of CDOM, when reasonable parameter values are considered. Therefore, natural variability of the spectral parameters or their modifications cannot be neglected. In the natural environment, spectral parameters could, for instance, change because of photobleaching (prolonged exposure of CDOM to sunlight, which decreases A_o and increases S) or of the complex and still poorly predictable effects of climate change. A second finding is that, while the steady-state [³CDOM*] would increase with increasing A_CDOM (increasing A_o, decreasing S), the effect of spectral parameters on [^•OH] and [CO₃^•−] depends on the relative roles of CDOM vs. NO₃⁻ and NO₂⁻ as photochemical ^•OH sources. Full article

(This article belongs to the Special Issue Current Advances in Photochemistry)

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