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Functional Titanium-Based Materials: Complexes, Composites and Coatings

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (15 May 2020) | Viewed by 18392

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Assoc. Prof. Piotr Piszczek

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Department of Chemistry, Nicolaus Copernicus University in Toruń, 87-100 Toruń, Poland
Interests: titanium and titania-based biomaterial; titanium(IV) oxo-complexes; structural studies and spectral characterization; physicochemical properties; bioactivity; medical applications
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Special Issue Information

Dear Colleagues,

Titanium and titanium-based materials are widely applied in variety of fields, ranging from the aviation and automotive industries to biomedical technologies. This is due to the high mechanical strength of titanium in relation to its low weight, adequate linear elasticity, and good corrosion resistance in most aggressive environments. Simultaneously, the photocatalytic activity, semiconducting properties, and bioactivity of materials such as titania nanocoatings of different structure and surface architecture, as well as titania-based nanocomposites, contribute to the great interest in studies on the possibility of their application as biomedical and self-cleaning coatings. The works on new materials exhibiting appropriate biointegral properties and adequate antimicrobial activity, which may be applied in the design and the construction of modern medical devices (e.g., implants) are especially important. Moreover, the composites containing titanium(IV) oxo-complexes as inorganic blocks arouse interest lately due to the possibility of their use as systems for disinfection, sterilization, and deodorization.

In spite of many published publications, titanium complexes and titania-based materials are still attractive topics in many research studies on their production, structural, and spectral characterization, estimation of their physicochemical and mechanical properties, and of their photocatalytic activity and bioactivity. Knowledge of these properties and their synergistic effects is very important for optimal applications of these materials in various fields.

The purpose of this Special Issue is to present the results of the latest works about titanium-based materials, especially titania nanocoatings of different architectures, titanium complexes/oxo-complexes, and also titanium-based nanocomposites. This Special Issue should be a place for both exchanging experiences as well as for further cooperation.

Your contributions are welcome.

Prof. Piotr Piszczek
Guest Editor

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Keywords

titanium-based materials
titanium complexes and oxo-complexes
titania nanocoatings
nanocomposites
physicochemical, mechanical properties
photocatalytic activity
bioactivity of titanium-based materials
titanium medical devices.

Published Papers (7 papers)

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Research

11 pages, 2208 KiB

Open AccessArticle

Synthesis of Ti₄O₇/Ti₃O₅ Dual-Phase Nanofibers with Coherent Interface for Oxygen Reduction Reaction Electrocatalysts

by Ruyue Shi, Ying Huang, Miaoran Li, Ying Zhu, Xuexia He, Ruibin Jiang, Zhibin Lei, Zonghuai Liu and Jie Sun

Materials 2020, 13(14), 3142; https://doi.org/10.3390/ma13143142 - 14 Jul 2020

Cited by 11 | Viewed by 2282

Abstract

Electrocatalysts play an important role in oxygen reduction reaction (ORR) in promoting the reaction process. Although commercial Pt/C exhibits excellent performance in ORR, the low duration, high cost, and poor methanol tolerance seriously restrict its sustainable development and application. Ti_nO_2n−1 (3 ≤ n ≤ 10) is a series of titanium sub-oxide materials with excellent electrical conductivity, electrochemical activity, and stability, which have been widely applied in the field of energy storage and catalysis. Herein, we design and synthesize Ti₄O₇/Ti₃O₅ (T4/T3) dual-phase nanofibers with excellent ORR catalytic performance through hydrothermal growth, which is followed by a precisely controlled calcination process. The H₂Ti₃O₇ precursor with uniform size can be first obtained by optimizing the hydrothermal growth parameters. By precisely controlling the amount of reducing agent, calcination temperature, and holding time, the T4/T3 dual-phase nanofibers with uniform morphology and coherent interfaces can be obtained. The orientation relationships between T4 and T3 are confirmed to be

{[001]}_{T 3} / / {[031]}_{T 4}

{(100)}_{T 3} / / {(92 \bar{6})}_{T 4}

, and

{(010)}_{T 3} / / {(1 \bar{2} 6)}_{T 4}

, respectively, based on comprehensive transmission electron microscopy (TEM) investigations. Furthermore, such dual-phase nanofibers exhibit the onset potential and half-wave potential of 0.90 V and 0.75 V as the ORR electrocatalysts in alkaline media, respectively, which illustrates the excellent ORR catalytic performance. The rotating ring-disk electrode (RRDE) experiment confirmed the electron transfer number of 3.0 for such catalysts, which indicates a mixture of two electron and four electron transfer reaction pathways. Moreover, the methanol tolerance and cycling stability of the catalysts are also investigated accordingly. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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15 pages, 2799 KiB

Open AccessArticle

The Photocatalytic Activity of Titania Coatings Produced by Electrochemical and Chemical Oxidation of Ti6Al4V Substrate, Estimated According to ISO 10678:2010

by Michalina Ehlert, Aleksandra Radtke, Adrian Topolski, Julia Śmigiel and Piotr Piszczek

Materials 2020, 13(11), 2649; https://doi.org/10.3390/ma13112649 - 10 Jun 2020

Cited by 8 | Viewed by 2031

Abstract

The last twenty years have been a period of intense investigations of materials based on titanium dioxide, which have unique properties and functionalities, and which can be used in various areas of medicine. As a part of this issue, the results of our works for the assessment of the photocatalytic activity of titanium dioxide nanocoatings of different nanoarchitecture (nanoporous, nanotubular, nanosponge-like and nanofibrous examples), which were earlier checked in terms of their biocompatibility and usability for the modification of medical devices’ surfaces, are presented. The studied materials were produced on the surface of Ti6Al4V substrates using electrochemical and chemical oxidation methods. The activity of produced titania materials was studied on the base of the methylene blue (MB) degradation effect, in accordance to ISO 10678:2010. In our works, we have focused on the analysis of the correlation between the photocatalytic activity of nanoarchitecturally different TiO₂ coatings, their morphology and structure. The obtained results prove that all studied coatings, both amorphous and amorphous containing crystalline domains, revealed photocatalytic activity in the photoinduced degradation of the organic pollution standard. This activity may be an additional advantage of medical device coatings, being adequate for use in sterilization processes applying UVA light. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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22 pages, 8691 KiB

Open AccessArticle

Hybrid TiO₂–Polyaniline Photocatalysts and their Application in Building Gypsum Plasters

by Agnieszka Sulowska, Izabela Wysocka, Daniel Pelczarski, Jakub Karczewski and Anna Zielińska-Jurek

Materials 2020, 13(7), 1516; https://doi.org/10.3390/ma13071516 - 26 Mar 2020

Cited by 20 | Viewed by 2752

Abstract

Hybrid materials of conjugated polymer and titanium(IV) oxide have attracted considerable attention concerning their potential benefits, including (i) efficient exploitation of visible light, (ii) a high adsorption capacity for organic contaminants, (iii) and effective charge carriers separation. The new class of the photocatalysts is promising for the removal of environmental pollutants in both aqueous and gaseous phases. For the first time, in this study, the polyaniline (PANI)–TiO₂ hybrid composite was used for the degradation of phenol in water and toluene in the gas phase. Polyaniline–TiO₂ was prepared by the in situ polymerization of aniline on the TiO₂ surface. The obtained hybrid material was characterized by diffuse reflectance spectroscopy (DR/UV-Vis), X-ray diffraction (XRD), fast-Fourier transformation spectroscopy (FTIR), photoluminescence (PL) spectroscopy, microscopy analysis (SEM/TEM), and thermogravimetric analysis (TGA). An insight into the mechanism was shown based on the photodegradation analysis of charge carrier scavengers. Polyaniline is an efficient TiO₂ photosensitizer for photodegradation in visible light (λ > 420 nm). The trapping experiments revealed that mainly h+ and ˙OH were the reactive oxygen species that were responsible for phenol degradation. Furthermore, the PANI–TiO₂ hybrid nanocomposite was used in gypsum plaster to study the self-cleaning properties of the obtained building material. The effect of PANI–TiO₂ content on the hydrophilic/hydrophobic properties and crystallographic structure of gypsum was studied. The obtained PANI–TiO₂-modified gypsum plaster had improved photocatalytic activity in the reaction of toluene degradation under Vis light. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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12 pages, 23403 KiB

Open AccessArticle

Processing and Mechanical Properties of Ti₂AlC MAX Phase Reinforced AE44 Magnesium Composite

by Xufeng Pi, Wenbo Yu, Chaosheng Ma, Xiaojun Wang, ShouMei Xiong and Antoine Guitton

Materials 2020, 13(4), 995; https://doi.org/10.3390/ma13040995 - 23 Feb 2020

Cited by 5 | Viewed by 3414

Abstract

AE44 alloys and nanolaminated Ti₂AlC particle-reinforced AE44 magnesium composites were synthesized by stir casting techniques and textured by hot extrusion methods. It was found that lamellar Al₁₁RE₃ precipitates spheroidized with the introduction of Ti₂AlC into the AE44 matrix. Both transmission electron microscope and planar disregistries calculations reveal a good match for interfacial lattice transition between Mg (0001) and the basal plane (0001) of Ti₂AlC. This suggests that Ti₂AlC is an efficient potent nucleating substrate for Mg, thus fertilizing the formation of strong interfacial bonds. After hot extrusion treatment, Ti₂AlC particles were reoriented in the textured magnesium matrix, as confirmed by X-ray diffraction. This texture effect on the composite’s mechanical properties was carefully studied by tensile and compressive tests. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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12 pages, 1437 KiB

Open AccessArticle

Optical Properties of Titanium in the Regime of the Limited Light Penetration

by Lukasz Skowronski

Materials 2020, 13(4), 952; https://doi.org/10.3390/ma13040952 - 20 Feb 2020

Cited by 3 | Viewed by 2221

Abstract

In this study, the titanium layers from 12 to 1470 nm thick were fabricated by using the method involving dynamically changed working gas pressure (gas injection magnetron sputtering). The influence of the deposition time on the optical and electrical properties of Ti films, as well as on their microstructure, are considered. The samples are investigated by means of spectroscopic ellipsometry, atomic force microscopy, X-ray diffraction, and confocal optical microscopy. Additionally, for the Ti layers, the sheet resistance was determined. The produced coatings exhibit privileged direction of growth (002). The obtained results show a gradual increase in the mean relaxation time of free-carriers with the increase in the thickness of titanium film. However, the plasma energy exhibits maximum for the coating with the thickness of 93 nm. For such thickness, the lowest value of optical resistivity (about 200

μ Ω

cm) was observed. It was found that the dc- and optical resistivity exhibit similar values for titanium films with thickness up to 93 nm. For thicker Ti layers, significant differences in resistivities (dc- and optical) were noticed. The behavior of the Drude parameter (the plasma energy), calculated optical resistivity, and discrepancies between values of optical and dc-resistivities for thicker Ti coatings can be explained as a result of the limited light penetration. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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13 pages, 4574 KiB

Open AccessArticle

Ni/Si-Codoped TiO₂ Nanostructure Photoanode for Enhanced Photoelectrochemical Water Splitting

by Ting Li and Dongyan Ding

Materials 2019, 12(24), 4102; https://doi.org/10.3390/ma12244102 - 08 Dec 2019

Cited by 11 | Viewed by 2834

Abstract

We synthesized Ni/Si-codoped TiO₂ nanostructures for photoelectrochemical (PEC) water splitting, by electrochemical anodization of Ti-1Ni-5Si alloy foils in ethylene glycol/glycerol solutions containing a small amount of water. The effects of annealing temperature on PEC properties of Ni/Si-codoped TiO₂ photoanode were investigated. We found that the Ni/Si-codoped TiO₂ photoanode annealed at 700 °C had an anatase-rutile mixed phase and exhibited the highest photocurrent density of 1.15 mA/cm² at 0 V (vs. Ag/AgCl), corresponding to a photoconversion efficiency of 0.70%, which was superior to Ni-doped and Si-doped TiO₂. This improvement in PEC water splitting could be attributed to the extended light absorption, faster charge transfer, possibly lower charge recombination, and longer lifetime. Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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17 pages, 3146 KiB

Open AccessArticle

Trinuclear Oxo-Titanium Clusters: Synthesis, Structure, and Photocatalytic Activity

by Maciej Janek, Tadeusz M. Muzioł and Piotr Piszczek

Materials 2019, 12(19), 3195; https://doi.org/10.3390/ma12193195 - 29 Sep 2019

Cited by 11 | Viewed by 2321

Abstract

The interest in titanium (IV) oxo-complexes is due to their potential application in photodegradation processes and environmental pollutants reduction. Titanium (IV) oxo-complexes (TOCs) of the general formula [Ti₃O(OⁱPr)₈(OOCR’)₂] (R’ = -C₁₃H₉ (1), -p-PhCl (2), -m-PhNO₂ (3), -C₄H₇ (4)) were synthesized and structurally characterized. The use of the different carboxylate ligands allowed modulating the optical band gaps of the produced microcrystals, which were measured via diffuse reflectance ultraviolet and visible spectroscopy (UV-Vis-DRS) and calculated using the density functional theory (DFT) method. The dispersion of TOCs (1–3) in the poly (methyl methacrylate) matrix (PMMA) led to the formation of polymer/TOCs composites, which in the next stage of our works have been applied in the photocatalytic activity estimation of synthesized trinuclear Ti(IV) oxo-complexes. Studies of the photocatalytic degradation of methylene blue (MB) induced by UV irradiation exhibit that the PMMA-TOCs composite containing (1) oxo-clusters is the most active, followed by the system containing the complex (3). Full article

(This article belongs to the Special Issue Functional Titanium-Based Materials: Complexes, Composites and Coatings)

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