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Surfaces
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Surface Aspects of Semiconductor Photochemistry
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Surface Aspects of Semiconductor Photochemistry

A special issue of Surfaces (ISSN 2571-9637).

Deadline for manuscript submissions: closed (15 February 2020) | Viewed by 29138

Special Issue Editors

Prof. Elena Selli

E-Mail Website
Guest Editor
Department of Chemistry, University of Milano, 20133 Milano, Italy
Interests: photocatalysis; photochemistry; photoactive materials; photocatalytic hydrogen and solar fuels production
Dr. Maria Vittoria Dozzi

E-Mail Website
Guest Editor
Department of Chemistry, Università degli Studi di Milano, 20133 Milano, Italy
Interests: TiO2 photocatalysis; semiconductor photochemistry and surface/bulk modification; solar energy conversion; environmental and energy applications; hydrogen production

Special Issue Information

Dear Colleagues,

The study of photochemical systems that use sunlight to catalyze chemical reactions of relevance for the environment remediation or for concentrating solar energy into renewable fuels (the well-known solar fuels) is a key topic for granting sustainability. While photon absorption and hole/electron separation and diffusion are not surface phenomena, the final steps of the complete process (i.e., the reactive events) are played at surfaces and ruled by them. 

So, an approach to a rational design of semiconductor photocatalysts cannot give up the assistance of surface science based tools and methods. They can provide both a deep and direct probing of the reaction sites, and, adopting time-resolved tools, provide dynamical details of reactions at the surfaces.  Such information is of value for the optimization of several strategic processes, e.g., water splitting, CO2 reduction and artificial photosynthesis.

This Special Issue is dedicated to the 7th International Conference on Semiconductor Photochemistry (SP7), https://www.sp7.unimi.it/. The aim of this Special Issue is to offer an open-access forum where researchers in the field of surface science, photochemistry, photophysics, photocatalysis, materials science can highlight significant advances made possible by the application of the surface science approach to heterogeneous photochemistry. In this Special Issue, papers addressing both basic science and more applied topics in the fields of photochemistry, photocatalysis, energy conversion, laser/surface interactions and laser ablation are welcome.

Prof. Elena Selli
Dr. Maria Vittoria Dozzi
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Surfaces is an international peer-reviewed open access quarterly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1600 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

  • photocatalysis, photophysics, photochemistry
  • in-situ and operando techniques for the study of surface reactions stimulated by sunlight
  • structural and chemical characterization of semiconductor materials surfaces
  • materials for photoelectrochemical energy conversion
  • model and real world photo- and photoelectro-catalysts
  • computational studies and modeling

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Published Papers (8 papers)

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Editorial

Jump to: Research, Review

6 pages, 242 KiB  
Editorial
Surface Aspects of Semiconductor Photochemistry
by Maria Vittoria Dozzi and Elena Selli
Surfaces 2020, 3(3), 467-472; https://doi.org/10.3390/surfaces3030033 - 2 Sep 2020
Cited by 1 | Viewed by 2415
Abstract
The Surfaces Special Issue entitled “Surface Aspects of Semiconductor Photochemistry” is mainly devoted to the 7th International Conference on Semiconductor Photochemistry (SP7), which was held on 11–14 September 2019 in Milano, Italy, in the beautiful Renaissance “Ca’ Granda” main building of [...] Read more.
The Surfaces Special Issue entitled “Surface Aspects of Semiconductor Photochemistry” is mainly devoted to the 7th International Conference on Semiconductor Photochemistry (SP7), which was held on 11–14 September 2019 in Milano, Italy, in the beautiful Renaissance “Ca’ Granda” main building of the University Milan [...] Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)

Research

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14 pages, 3154 KiB  
Article
Ni-Doped Titanium Dioxide Films Obtained by Plasma Electrolytic Oxidation in Refrigerated Electrolytes
by Hamed Arab, Gian Luca Chiarello, Elena Selli, Giacomo Bomboi, Alberto Calloni, Gianlorenzo Bussetti, Guglielmo Albani, Massimiliano Bestetti and Silvia Franz
Surfaces 2020, 3(2), 168-181; https://doi.org/10.3390/surfaces3020013 - 17 Apr 2020
Cited by 8 | Viewed by 3488
Abstract
Porous crystalline Ni-doped TiO2 films were produced using DC plasma electrolytic oxidation in refrigerated H2SO4 aqueous solutions containing NiSO4. The crystalline phase structure consisted of a mixture of anatase and rutile, ranging from ~30 to ~80 wt [...] Read more.
Porous crystalline Ni-doped TiO2 films were produced using DC plasma electrolytic oxidation in refrigerated H2SO4 aqueous solutions containing NiSO4. The crystalline phase structure consisted of a mixture of anatase and rutile, ranging from ~30 to ~80 wt % rutile. The oxide films obtained at low NiSO4 concentration showed the highest photocurrent values under monochromatic irradiation in the UV-vis range, outperforming pure TiO2. By increasing NiSO4 concentration above a threshold value, the photoelectrochemical activity of the films decreased below that of undoped TiO2. Similar results were obtained using cyclic voltammetry upon polychromatic UV-vis irradiation. Glow discharge optical emission spectrometry (GD-OES) analysis evidenced a sulfur signal peaking at the TiO2/Ti interface. XPS spectra revealed that oxidized Ni2+, S4+ and S6+ ions were included in the oxide films. In agreement with photocurrent measurements, photoluminescence (PL) spectra confirmed that less intense PL emission, i.e., a lower electron-hole recombination rate, was observed for Ni-doped samples, though overdoping was detrimental. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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11 pages, 3477 KiB  
Article
Multilayer WO3/BiVO4 Photoanodes for Solar-Driven Water Splitting Prepared by RF-Plasma Sputtering
by Matteo Pedroni, Gian Luca Chiarello, Espedito Vassallo and Elena Selli
Surfaces 2020, 3(1), 105-115; https://doi.org/10.3390/surfaces3010010 - 13 Mar 2020
Cited by 9 | Viewed by 3832
Abstract
A series of WO3, BiVO4 and WO3/BiVO4 heterojunction coatings were deposited on fluorine-doped tin oxide (FTO), by means of reactive radio frequency (RF) plasma (co)sputtering, and tested as photoanodes for water splitting under simulated AM 1.5 G [...] Read more.
A series of WO3, BiVO4 and WO3/BiVO4 heterojunction coatings were deposited on fluorine-doped tin oxide (FTO), by means of reactive radio frequency (RF) plasma (co)sputtering, and tested as photoanodes for water splitting under simulated AM 1.5 G solar light in a three-electrode photoelectrochemical (PEC) cell in a 0.5 M NaSO4 electrolyte solution. The PEC performance and time stability of the heterojunction increases with an increase of the WO3 innermost layer up to 1000 nm. A two-step calcination treatment (600 °C after WO3 deposition followed by 400 °C after BiVO4 deposition) led to a most performing photoanode under back-side irradiation, generating a photocurrent density of 1.7 mA cm−2 at 1.4 V vs. SCE (i.e., two-fold and five-fold higher than that generated by individual WO3 and BiVO4 photoanodes, respectively). The incident photon to current efficiency (IPCE) measurements reveal the presence of two activity regions over the heterojunction with respect to WO3 alone: The PEC efficiency increases due to improved charge carrier separation above 450 nm (i.e., below the WO3 excitation energy), while it decreases below 450 nm (i.e., when both semiconductors are excited) due to electron–hole recombination at the interface of the two semiconductors. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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12 pages, 3427 KiB  
Article
Hydrogenation of ZnFe2O4 Flat Films: Effects of the Pre-Annealing Temperature on the Photoanodes Efficiency for Water Oxidation
by Annalisa Polo, Charles R. Lhermitte, Maria Vittoria Dozzi, Elena Selli and Kevin Sivula
Surfaces 2020, 3(1), 93-104; https://doi.org/10.3390/surfaces3010009 - 12 Mar 2020
Cited by 12 | Viewed by 3135
Abstract
The effects induced by post-synthesis hydrogenation on ZnFe2O4 flat films in terms of photoelectrochemical (PEC) performance of photoanodes for water oxidation have been deeply investigated as a function of the pre-annealing temperature of the materials. The structure and morphology of [...] Read more.
The effects induced by post-synthesis hydrogenation on ZnFe2O4 flat films in terms of photoelectrochemical (PEC) performance of photoanodes for water oxidation have been deeply investigated as a function of the pre-annealing temperature of the materials. The structure and morphology of the films greatly affect the efficacy of the post synthesis treatment. In fact, highly compact films are obtained upon pre-annealing at high temperatures, and this limits the exposure of the material bulk to the reductive H2 atmosphere, making the treatment largely ineffective. On the other hand, a mild hydrogen treatment greatly enhances the separation of photoproduced charges in films pre-annealed at lower temperatures, as a result of the introduction of oxygen vacancies with n-type character. A comparison between present results and those obtained with ZnFe2O4 nanorods clearly demonstrates that specific structural and/or surface properties, together with the initial film morphology, differently affect the overall contribution of post-synthesis hydrogenation on the efficiency of zinc ferrite-based photoanodes. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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11 pages, 5701 KiB  
Article
Citric Acid Regulated Fabrication of Macroporous TiO2
by Rui Chen, Ningning Shao, Xiaoquan Zhou and Tiehong Chen
Surfaces 2020, 3(1), 50-60; https://doi.org/10.3390/surfaces3010006 - 3 Feb 2020
Cited by 4 | Viewed by 3342
Abstract
Macroporous TiO2 monolith was prepared by a microphase separation method. After citric acid was added to the synthesis procedure, the yield of the titanium precursor has been significantly increased, and the stability of macroporous structure can be obviously enhanced. Anatase and rutile [...] Read more.
Macroporous TiO2 monolith was prepared by a microphase separation method. After citric acid was added to the synthesis procedure, the yield of the titanium precursor has been significantly increased, and the stability of macroporous structure can be obviously enhanced. Anatase and rutile phase of TiO2 were obtained after a 550 °C and 800 °C calcination, respectively. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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15 pages, 5880 KiB  
Article
Digitally Printed AgNPs Doped TiO2 on Commercial Porcelain-Grès Tiles: Synergistic Effects and Continuous Photocatalytic Antibacterial Activity
by Claudia Letizia Bianchi, Giuseppina Cerrato, Bianca Maria Bresolin, Ridha Djellabi and Sami Rtimi
Surfaces 2020, 3(1), 11-25; https://doi.org/10.3390/surfaces3010002 - 14 Jan 2020
Cited by 19 | Viewed by 4225
Abstract
In the present study, we use commercial digitally printed ceramic tiles, functionnalized by AgNPs doped micro–TiO2, to investigate the mechanism of Ag in the continouos photocatalytic antibacterial activity. The novelty of the research lies in the attempt to understand the mechanism [...] Read more.
In the present study, we use commercial digitally printed ceramic tiles, functionnalized by AgNPs doped micro–TiO2, to investigate the mechanism of Ag in the continouos photocatalytic antibacterial activity. The novelty of the research lies in the attempt to understand the mechanism of Ag, supported on TiO2, able to exhibit the same antibacterial activity of a standard system containing Ag species, but here, totally embedded on the tile surface, and thus not free to move and damage the bacteria cell. UV/vis diffuse reflectance spectroscopy (DRS) of AgNPs–TiO2 tiles indicated an enhanced visible light response, wherein a new absorption band was produced around 18,000–20,000 cm−1 (i.e., in the 400–600 nm range) owing to the surface plasmon resonance (SPR) of AgNPs. The antibacterial photocatalytic experiments were conducted towards the inactivation of E. coli under solar light and indoor light. It was found that the degradation speed of E. coli in the presence of AgNPs–TiO2 tiles is solar light-intensity depending. This justifies the semiconductor behavior of the material. Furthermore, the AgNPs–TiO2 tiles exhibit a high ability for the inactivation of E. coli at a high load (104–107 colony-forming unit (CFU)/mL). Additionally, AgNPs–TiO2 tiles showed a remarkable antibacterial activity under indoor light, which confirms the good photocatalytic ability of such tiles. On the basis of the reactive oxygen species (ROS) quenching experiments, O2•− species and h+ were more reactive for the inactivation of E. coli rather than •OH species. This is because of the different lifetime (bacteria are more likely oxidized by ROS with longer lifetime); in fact, O2•− and h+ exhibit a longer lifetime compared with •OH species. The generation of H2O2 as the most stable ROS molecule was also suggested. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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Graphical abstract

14 pages, 4357 KiB  
Article
UV Light Driven Selective Oxidation of Cyclohexane in Gaseous Phase Using Mo-Functionalized Zeolites
by Vincenzo Vaiano and Diana Sannino
Surfaces 2019, 2(4), 546-559; https://doi.org/10.3390/surfaces2040040 - 9 Dec 2019
Cited by 2 | Viewed by 2984
Abstract
Heterogeneous photocatalysis in the gas phase has been applied as a promising technique for organic syntheses in mild conditions. Modified zeolites have been used under UV irradiation as novel photocatalysts. In this study, we preliminarily investigated the photoxidation of cyclohexane on ferrierite and [...] Read more.
Heterogeneous photocatalysis in the gas phase has been applied as a promising technique for organic syntheses in mild conditions. Modified zeolites have been used under UV irradiation as novel photocatalysts. In this study, we preliminarily investigated the photoxidation of cyclohexane on ferrierite and MoOx-functionalized ferrierite in a gas–solid continuous flow reactor. In the presence of UV light, MoOx-functionalized ferrierite showed the formation of benzene and cyclohexene as reaction products, indicating the occurrence of photocatalysed cyclohexane oxydehydrogenation. By contrast, unmodified ammonium ferrierite exhibited relevant activity for total oxidation of cyclohexane to carbon dioxide and water. The influence of Mo loading on cyclohexane conversion and products selectivity was evaluated. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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Review

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21 pages, 3999 KiB  
Review
Recent Advancements in the Understanding of the Surface Chemistry in TiO2 Photocatalysis
by Alexander V. Vorontsov, Héctor Valdés, Panagiotis G. Smirniotis and Yaron Paz
Surfaces 2020, 3(1), 72-92; https://doi.org/10.3390/surfaces3010008 - 18 Feb 2020
Cited by 21 | Viewed by 5011
Abstract
Surface chemistry plays a major role in photocatalytic and photoelectrochemical processes taking place with the participation of TiO2. The synthesis methods, surface characterizations, theoretical research methods, and hardware over the last decade generated opportunities for progress in the surface science of [...] Read more.
Surface chemistry plays a major role in photocatalytic and photoelectrochemical processes taking place with the participation of TiO2. The synthesis methods, surface characterizations, theoretical research methods, and hardware over the last decade generated opportunities for progress in the surface science of this photocatalyst. Very recently, attention was paid to the design of photocatalysts at the nanoscale level by adjusting the types of exposed surfaces and their ratio, the composition and the surface structure of nanoparticles, and that of individual surfaces. The current theoretical methods provide highly detailed designs that can be embodied experimentally. The present review article describes the progress in the surface science of TiO2 and TiO2-based photocatalysts obtained over the last three years. Such aspects including the properties of macro- and nano-scale surfaces, noble-metal-loaded surfaces, doping with Mg and S, intrinsic defects (oxygen vacancies), adsorption, and photoreactions are considered. The main focus of the article is on the anatase phase of TiO2. Full article
(This article belongs to the Special Issue Surface Aspects of Semiconductor Photochemistry)
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