TiO<sub>2</sub> photoanodes with exposed {0 1 0} facets grown by aerosol-assisted chemical vapor deposition of a titanium oxo/alkoxy cluster

Regue, Miriam; Sibby, Sandra; Ahmet, Ibbi Y.; Friedrich, Dennis; Abdi, Fatwa F.; Johnson, Andrew L.; Eslava, Salvador

doi:10.1039/c9ta04482e

Cited by 18 publications

(15 citation statements)

References 80 publications

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“…All photoanodes were prepared using AACVD on FTO-coated glass and named after their constituent elements (e.g., Fe–Ti–O–Zn and Fe–Ti–O). The aerosol droplets were generated using a TSI Model 3076 Constant Output atomizer using argon as a carrier gas (Figure ) with the following precursor solutions. , For Fe–Ti–O films, titanium(IV) isopropoxide (1.478 mL, 5.0 mmol) was dissolved in 10 mL of methanol and mixed together with a solution of iron(III) acetylacetonate (3.531 g, 10 mmol) in 100 mL of ethyl acetate. For Fe–Ti–O–Zn films, zinc acetate dihydrate (0.0549 g, 0.25 mmol) was added to the previous iron and titanium solution, corresponding to a molar percentage of 2.5% compared to Fe.…”

Section: Methodsmentioning

confidence: 99%

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Regue

Ahmet

Bassi

et al. 2020

ACS Appl. Energy Mater.

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Water splitting in photoelectrochemical cells is a promising technology to produce solar hydrogen. Fe2TiO5 pseudobrookite with a bandgap of around 2 eV absorbs the predominant visible range of the solar spectrum and is emerging as a promising photoanode for such cells. Herein, we present Fe2TiO5 pseudobrookite-based films prepared by aerosol-assisted chemical vapor deposition and the positive impact of Zn 2+ doping in their formation and performance. Undoped and Zn 2+doped Fe2TiO5 pseudobrookite-based photoanodes were characterized by techniques such as XRD, XPS, UPS and Mott-Schottky analysis. We find that the Zn 2+ ions are preferentially incorporated in the pseudobrookite phase over a present secondary hematite (α-Fe2O3) phase. The Zn 2+ doping modifies the electronic properties of the films, increases their charge carrier concentration and upshifts their Fermi level, significantly improving their anodic photocurrent response by a factor of three. In addition, charge transfer efficiency calculations reveal that Zn 2+ doping improves both charge separation and injection efficiencies, overall demonstrating a promising approach for the design of enhanced pseudobrookite-based photoanodes.

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Section: Methodsmentioning

confidence: 99%

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Regue

Ahmet

Bassi

et al. 2020

ACS Appl. Energy Mater.

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“…Recently, significant attention has been paid to develop titanium-oxo clusters (TOCs) due to their precise cluster structures and because their photocatalytic properties are similar to those of nano TiO 2 . − During the past decade, TOCs with various modifications have been synthesized, such as heterometallically doped TOCs and functional ligand-modified TOCs . Applications of heterometallic and functional TOCs in photocatalysis and photoelectrochemistry have been the main concerns of TOC research. − In addition to the abundant neutral TOCs, some ionic TOCs with different counterions were reported. − One of the examples is the process by which the TOC cations co-crystallized with copper halide anion clusters to form supersalt-type cluster-based materials . Although assembly of nano TiO 2 with heterosemiconductors is well-known, there have been relatively few studies of the assembly of the TOCs with other semiconductor clusters.…”

Section: Introductionmentioning

confidence: 99%

Assembly of a Titanium-Oxo Cluster and a Bismuth Iodide Cluster, a Single-Source Precursor of a p–n-Type Photocatalyst

Wang

Zhai

et al. 2021

Inorg. Chem.

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Titanium oxides and bismuth halides or oxyhalides have been known to be excellent semiconductors with both excellent photocatalytic and photoelectric properties. The design of supersalts assembled by titanium-oxo clusters (TOCs) and bismuth iodide clusters is a hopeful strategy for exploring the chemistry and application of new titanium-oxo clusters. We report herein a series of unusual ionic TOCs with Ti12 oxo cluster cations and bismuth iodide anions, [Ti12O15(O i Pr)17]3[Bi3I12] (Bi3), [Ti12O14(O i Pr)18][Bi4I14(THF)2] (Bi4), and [Ti12O14(O i Pr)18][Ti11BiO14(O i Pr)17][Bi6I22] (Bi6). Single-crystal X-ray analysis revealed that the type and charge of the Ti12 clusters varied with the charges of different bismuth iodide clusters. Taking advantage of the easy hydrolysis of the TOCs and BiI clusters in water, we used these supersalt crystals as single-source precursors to prepare a p–n-type BiOI-TiO photocatalyst. The heterojunction materials were carefully characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, etc. The synergistic effect of the two components of BiOI and TiO on the photocatalytic degradation of RhB in water is demonstrated. This is a very convenient method for obtaining a p–n-type BiOI-TiO heterojuction photocatalyst by just placing the ground TOC crystals into water.

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“…Titanium-oxo clusters (TOCs) recently have received great interest − and are emerging as a class of very promising crystalline materials, promoted by their applications as well-defined and soluble molecular TiO materials, − single-source precursors of TiO oxides, − and the structural and electronic models of nanosized TiO 2 . − Despite the fact that numerous TOCs with or without modified metals or functional ligands have been reported and studied experimentally and theoretically, the calculated electronic state of small clusters (nuclearity <10) showed large variations with varied cluster nuclearity, which is not typical for nanoscale TiO materials. Therefore, synthesis of high nuclearity TOCs and theoretical study based on these large TOCs merit more attention.…”

Section: Introductionmentioning

confidence: 99%

Mono- and Bismetalphenanthroline-Substituted Ti₁₂ Clusters: Structural Variance and the Effect on Electronic State and Photocurrent Property

Wang

Zhai

et al. 2021

Inorg. Chem.

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Despite the numerous titanium-oxo clusters (TOCs) which have been reported, the nature of small clusters (nuclearity < 10) as model compounds showed large deviation from that of nanoscale TiO materials. Therefore, theoretical and experimental studies for large TOCs merit more attention. We recently prepared and crystallographically characterized a series of l a r g e T O C s : 3), and Ti 10 O 14 (OEt) 16 (Mnphphen) 2 (4) (phen = 1,10-phenanthroline, phphen = 4,7-biphenyl-phen). These compounds are derivatives of a Ti 12 parent cluster by replacing one or two of the five-coordinated titanium atoms of the Ti 12 cluster with a transition metal M, Co(II) and Mn(II), that is chelated by a phen group. The effects of mono-and bis-substituted Mphen on the charge and structure of the clusters are discussed. Theoretical evaluation of the frontier orbitals of the clusters is carried out on the basis of the precisely defined crystal structures. Different from the dye molecule to TiO core charge transfer for the dye-modified TOCs, charge transfer in these clusters is from TiO/TiOM to phen/Mphen. The effects of different metal ions and the number of substituted Mphen moieties on the photocurrent properties are evaluated. The results will be of interest to research on cluster chemistry, especially on the TOC chemistry.

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TiO₂ photoanodes with exposed {0 1 0} facets grown by aerosol-assisted chemical vapor deposition of a titanium oxo/alkoxy cluster

Abstract: TiO2 photoanodes with {0 1 0} facets exposed show high photoelectrochemical performance and IPCE of 100% at 350 nm.

Cited by 18 publications

References 80 publications

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Assembly of a Titanium-Oxo Cluster and a Bismuth Iodide Cluster, a Single-Source Precursor of a p–n-Type Photocatalyst

Mono- and Bismetalphenanthroline-Substituted Ti₁₂ Clusters: Structural Variance and the Effect on Electronic State and Photocurrent Property

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TiO2 photoanodes with exposed {0 1 0} facets grown by aerosol-assisted chemical vapor deposition of a titanium oxo/alkoxy cluster

Abstract: TiO2 photoanodes with {0 1 0} facets exposed show high photoelectrochemical performance and IPCE of 100% at 350 nm.

Cited by 18 publications

References 80 publications

Zn-Doped Fe2TiO5 Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Zn-Doped Fe2TiO5 Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Assembly of a Titanium-Oxo Cluster and a Bismuth Iodide Cluster, a Single-Source Precursor of a p–n-Type Photocatalyst

Mono- and Bismetalphenanthroline-Substituted Ti12 Clusters: Structural Variance and the Effect on Electronic State and Photocurrent Property

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TiO₂ photoanodes with exposed {0 1 0} facets grown by aerosol-assisted chemical vapor deposition of a titanium oxo/alkoxy cluster

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Zn-Doped Fe₂TiO₅ Pseudobrookite-Based Photoanodes Grown by Aerosol-Assisted Chemical Vapor Deposition

Mono- and Bismetalphenanthroline-Substituted Ti₁₂ Clusters: Structural Variance and the Effect on Electronic State and Photocurrent Property