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      Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles†

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          Abstract

          Nonadiabatic molecular dynamics simulations suggest an excited state electron proton transfer mechanism and explain the observation of mobile hydroxyl radicals.

          Abstract

          We present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO 2 nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron–proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S 1 potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron–hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances in NAMD methods and emphasize the importance of explicit simulation of electronic excitations.

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          Electronic structure of defect states in hydroxylated and reduced rutile TiO2(110) surfaces.

          Cristiana Di Bello, Annabella Selloni, Ralfo G Pacchioni (2006)
          It has been experimentally observed that a bridging oxygen vacancy on the rutile TiO2(110) surface introduces localized Ti3+ 3d1 states about 1 eV below the conduction band which are not removed upon dissociation of a water molecule and formation of a pair of hydroxyl groups. Density functional calculations based on pure exchange-correlation functionals have not been able to satisfactorily reproduce and analyze these findings. Here we show that a correct description of the localized defect states on reduced and hydroxylated TiO2(110) is achieved only if proper geometry relaxation is accounted for using hybrid exchange functionals. We confirm the electron trapping nature of Ti(OH) groups but find no evidence that these defects should also act as hole traps by formation of Ti4+(OH)* radicals.
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            Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces.

            Sencer Selcuk, Annabella Selloni (2016)
            Excess electrons from intrinsic defects, dopants and photoexcitation play a key role in many of the properties of TiO2. Understanding their behaviour is important for improving the performance of TiO2 in energy-related applications. We focus on anatase, the TiO2 polymorph most relevant in photocatalysis and solar energy conversion. Using first-principles simulations, we investigate the states and dynamics of excess electrons from different donors near the most common anatase (101) and (001) surfaces and aqueous interfaces. We find that the behaviour of excess electrons depends strongly on the exposed anatase surface, the environment and the character of the electron donor. Whereas no electron trapping is observed on the (101) surface in vacuo, an excess electron at the aqueous (101) interface can trigger water dissociation and become trapped into a stable surface Ti(3+)-bridging OH complex. By contrast, electrons avoid the (001) surface, indicating that oxidation reactions are favoured on this surface. Our results provide a bridge between surface science experiments and observations of crystal-face-dependent photocatalysis on anatase, and support the idea that optimization of the ratio between {101} and {001} facets could provide a way to enhance the photocatalytic activity of this material.
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              Quantum coherence in a processable vanadyl complex: new tools for the search of molecular spin qubits † †Electronic supplementary information (ESI) available: Full experimental section and methods. Additional characterization including: AC susceptibility data (Fig. S1–S5); CW- and pulsed EPR results (Fig. S6–S11); STM and XPS of the UHV deposition (Fig. S12–S14); calculated field dependence of the eigenvectors composition (Fig. S15). See DOI: 10.1039/c5sc04295j

              Lorenzo Tesi, Eva Lucaccini, Irene Cimatti … (2015)
              A multitechnique investigation of an evaporable vanadyl spin system with long-lived quantum coherence that self-assembles on gold.
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                Author and article information

                Journal
                Journal ID (nlm-ta): Chem Sci
                Journal ID (iso-abbrev): Chem Sci
                Title: Chemical Science
                Publisher: Royal Society of Chemistry
                ISSN (Print): 2041-6520
                ISSN (Electronic): 2041-6539
                Publication date (Print): 01 March 2017
                Publication date (Electronic): 07 December 2016
                Volume: 8
                Issue: 3
                Pages: 2179-2183
                Affiliations
                [a ] Department of Chemistry , University of California , 1102 Natural Sciences II , Irvine , CA 92697-2025 , USA . Email: mmuurone@ 123456uci.edu ; Email: filipp.furche@ 123456uci.edu ; Fax: +1 949 824 8571 ; Tel: +1 949 824-5051
                [b ] Department of Chemistry , Imperial College London , South Kensington , London , SW7 2AZ , UK
                [c ] Department of Chemistry , University College London , 20 Gordon Street , London WC1H 0AJ , UK
                Author information
                http://orcid.org/0000-0001-9647-7070
                http://orcid.org/0000-0002-1110-3393
                http://orcid.org/0000-0003-3979-2247
                http://orcid.org/0000-0001-5291-2130
                http://orcid.org/0000-0001-8520-3971
                Article
                Publisher ID: c6sc04378j
                DOI: 10.1039/c6sc04378j
                PMC ID: 5407260
                SO-VID: 16eab68d-4530-48fe-805e-44367a9e0297
                Copyright © This journal is © The Royal Society of Chemistry 2016
                License:

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                Date received : 1 October 2016
                Date accepted : 5 December 2016
                Categories
                Subject: Chemistry

                Notes

                †Electronic supplementary information (ESI) available: Full details on computational methodology, analysis of reactive trajectory for (TiO 2) 4(OH) 4(H 2O) 4 and of non-adiabatic transitions. See DOI: 10.1039/c6sc04378j


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