TiO2 Surface Research Articles

Characterization and comparison of titanium dioxide nanoparticles prepared by microwave and pulse laser ablation liquid methods

This study synthesized titanium dioxide (TiO2) quickly and cheaply using microwaves and pulsed laser ablation. Titanium isopropoxide (Ti[OCH(CH3)2]4) was the precursor and deionized water (DIW) was the solvent and reducer for sub-micrometer particle production in microwave technique. TiO2 nanoparticles were synthesized in pulsed laser ablation liquid medium after a 5-minute preparation period in a 1200 W commercial microwave and a 1-hour annealing at 400°C. A Q-switched Nd:YAG laser with 480 mJ energy per pulse was used for 100, 200, and 300 pulses. Multiple methods, including XRD, BET, and EDX. XRD showed anatase TiO2 in microwave-synthesised nanoparticles. Pulsed laser ablation produced pure TiO2 nanoparticles with a brookite crystalline structure. In microwave BET analysis, TiO2 has a large surface area of 72.727 to 108.28 m2/g. BET analysis indicated 82.44 to 98.67 m2/g of TiO2 surface area by pulsed laser ablation. Strong titanium (Ti) and oxygen (O) peaks in microwave and pulsed laser ablation EDX tests showed nanoparticle purity.

Investigating the Electronic Properties and Stability of Rh3 Clusters on Rutile TiO2 for Potential Photocatalytic Applications.

Addressing the pressing needs for alternatives to fossil fuel-based energy sources, this research explores the intricate interplay between Rhodium (Rh3) clusters and titanium dioxide (TiO2) to improve photocatalytic water splitting for the generation of eco-friendly hydrogen. This research applies the density functional theory (DFT) coupled with the Hartree-Fock theory to meticulously examine the structural and electronic structures of Rh3 clusters on TiO2 (110) interfaces. Considering the photocatalytic capabilities of TiO2 and its inherent limitations in harnessing visible light, the potential for metals such as Rh3 clusters to act as co-catalysts is assessed. The results show that triangular Rh3 clusters demonstrate remarkable stability and efficacy in charge transfer when integrated into rutile TiO2 (110), undergoing oxidation in optimal adsorption conditions and altering the electronic structures of TiO2. The subsequent analysis of TiO2 surfaces exhibiting defects indicates that Rh3 clusters elevate the energy necessary for the formation of an oxygen vacancy, thereby enhancing the stability of the metal oxide. Additionally, the combination of Rh3-cluster adsorption and oxygen-vacancy formation generates polaronic and localized states, crucial for enhancing the photocatalytic activity of metal oxide in the visible light range. Through the DFT analysis, this study elucidates the importance of Rh3 clusters as co-catalysts in TiO2-based photocatalytic frameworks, paving the way for empirical testing and the fabrication of effective photocatalysts for hydrogen production. The elucidated impact on oxygen vacancy formation and electronic structures highlights the complex interplay between Rh3 clusters and TiO2 surfaces, providing insightful guidance for subsequent studies aimed at achieving clean and sustainable energy solutions.

TiO2 thermal stress deformation induced to promote photocatalytic CO2 reduction

Semiconductor photocatalytic reduction of CO2 is an effective means to achieve the goal of double carbon. TiO2 has received extensive attention as an excellent photocatalyst, but the adsorption of CO2 on the surface of TiO2 is not stable, which greatly inhibits the yield and selectivity of reduction products. In this work, wollastonite was used to reduce the melting temperature of TiO2 and in turn induce thermal stress deformation on the surface of the TiO2 lattice. Characterization and DFT results certified that the lattice stress deformation caused by the contraction of oxygen vacancy enables TiO2 to obtain better carrier transport efficiency and lower activation energy barrier, and also stabilizes the adsorption state of CO2 on the surface of TiO2 crystal, which effectively improved the reduction yield and selectivity of CO2. The CO yield is increased by 5.1 times, reaching up to 2.09 μmolg-1h−1, and the CO selectivity is as high as 91 %. These findings provide valuable insights for the development of efficient and selective photocatalysts for carbon dioxide transformation and pave the way for novel avenues in this research field.

How to construct the most stable structure of (110) surface from rutile TiO2 bulk?

XRD pattern of rutile TiO2 bulk and surface energy of possible terminated (110) planes were investigated using the DFT+U method. The (110) surface was demonstrated to be the most popular facet of rutile TiO2, which is in good agreement with data of the JCPDS card No. 21-1276. The difference in surface energy among possible terminated (110) planes is attributed to structure of top and bottom atomic layers. We have found that the P5 plane is the most stable. It represents structure of (110) surface. Rutile TiO2 (110) surface has calculated surface energy of 0.98 J/m2. The value compares well with previous publications. Besides, DFT calculations were also performed. In comparison with DFT+U, surface energy obtained from DFT calculation for (110) surface is very small, about 0.48 J/m2.

Investigation of TiO2/PPy nanocomposite for photocatalytic applications; synthesis, characterization, and combination with various substrates: a review.

The use of photocatalysis technology, specifically visible light photocatalysis that relies on sustainable solar energy, is the most promising for the degradation of contaminants. The interaction of conducting polymer and titanium dioxide (TiO2) leads to the exchange that enhances the alteration of the semiconductor's surface and subsequently decreases the bandgap energy. Polypyrrole (PPy) and TiO2 nanocomposites have promising potential for photocatalytic degradation. Chemically and electrochemical polymerization are two predominant methods for adding inorganic nanoparticles to a conducting polymer host matrix. The most commonly utilized method for producing PPy/TiO2 nanocomposites is the in-situ chemical oxidative polymerization technique. Immobilizing PPy/TiO2 on substrates causes more charge carriers (electron/hole pairs) to be produced on the surface of TiO2 and enhances the rate of photocatalytic degradation compared to pure TiO2. The increased surface charge affects how electron/hole pairs are formed when visible light is used. This study provides a comprehensive investigation into the synthesis, characterization, application, efficiency, and mechanism of PPy/TiO2 nanocomposites in the photocatalytic degradation process of various pollutants. Furthermore, the effect of stabilizing the TiO2/PPy nanocomposite on various substrates will be investigated. In conclusion, the review outlines the ongoing challenges in utilizing these photocatalysts and highlights the essential concerns that require attention in future research. Its objective is to help researchers better understand photocatalysts and encourage their use in wastewater treatment.

Comprehensive spectroscopy and photocatalytic activity analysis of TiO2-Pt systems under LED irradiation

This study presents a thorough spectroscopic analysis of TiO2-Pt systems under LED irradiation, with a focus on elucidating the photodeposition process of Pt nanoparticles onto TiO2 surfaces. The methodology leverages an innovative LED photoreactor tailored to a specific spectral range, enabling precise characterization of the excitation spectrum of TiO2-Pt composites. Through the identification of Pt precursor species and their excitation under LED-UV light, a photodeposition mechanism is proposed involving concurrent excitation of both the TiO2 semiconductor and the H2PtCl6 precursor. The LED photoreactors are employed to scrutinize the excitation profile of TiO2-Pt materials, revealing that the incorporation of Pt nanoparticles does not expand TiO2's absorption spectrum. Furthermore, UV-A exposure in the absence of Pt did not induce the formation of surface defects, underscoring the lack of visible light activity in TiO2-Pt systems. Spectroscopic analyses, complemented by naproxen photooxidation experiments, indicate the absence of a significant plasmonic effect in Pt nanoparticles within the experimental framework. Mass spectroscopy results corroborate the presence of distinct naproxen degradation pathways, suggesting minimal influence from photocatalyst properties. This research provides a detailed spectroscopic insight into TiO2-Pt photocatalysis, enriching the knowledge of photocatalytic materials in LED lighting.

Enhancing Efficiency of Dye Sensitized Solar Cells by Coinage Metal Doping of Cyanidin-Silver Trimer Hybrids at TiO2 Support Based on Theoretical Study.

Identification of a natural-based sensitizer with optimal stability and efficiency for dye-sensitized solar cell (DSSC) application remains a challenging task. Previously, we proposed a new class of sensitizers based on bio-nano hybrids. These systems composed of natural cyanidin dyes interacting with silver nanoclusters (NCs) have demonstrated enhanced opto-electronic and photovoltaic properties. In this study, we explore the doping of silver nanocluster within a cyanidin-Ag3 hybrid employing Density Functional Theory (DFT) and its time-dependent counterpart (TDDFT). Specifically, we investigate the influence of coinage metal atoms (Au and Cu) on the properties of the cyanidin-Ag3 system. Our findings suggest that cyanidin-Ag2Au and cyanidin-AgAuCu emerge as the most promising candidates for improved light harvesting efficiency, increased two-photon absorption, and strong coupling to the TiO2 surface. These theoretical predictions suggest the viability of replacing larger silver NCs with heterometallic trimers such as Ag2Au or AgAuCu, presenting new avenues for utilizing bio-nano hybrids at the surface for DSSC application.

Round-the-Clock Adsorption-Degradation of Tetracycline Hydrochloride by Ag/Ni-TiO2.

The synergy of adsorption and photocatalysis is a good method to remove organic pollutants in wastewater. In recent decades, persistent photocatalysis has gained considerable interest for its ability to sustain the catalytic degradation of organic pollutants in the dark. Herein, we report three different TiO2 nanomaterials to remove tetracycline hydrochloride (TCH) in solution. We found that the removal ability of TiO2, Ni-TiO2, and Ag/Ni-TiO2 is 8.8 mg/g, 13.9 mg/g and 23.4 mg/g, respectively, when the initial concentration of TCH is 50 mg/L. Chemical adsorption could be the rate-determining step in the TCH adsorption process. Moreover, Ag nanoparticles dispersed on Ni doped TiO2 surface act as traps to capture photo-generated electrons upon illumination with indoor light. The holes in Ag/Ni-TiO2 serve as critical oxidative species in TCH degradation under dark conditions. This work provides new insights into the design of persistent photocatalysts that can be activated by weak illumination and degrade organic pollutants in wastewater after sunset.

Implementing a Two‐in‐One Defect Passivation Strategy Utilizing CsX for High‐Performance Printable Carbon‐Based Perovskite Solar Cells

AbstractIn the rapidly advancing realm of perovskite solar cells, the rectification of defects has surfaced as a crucial scientific challenge. The control over defect states, especially in printable mesoscopic perovskite solar cells (p‐MPSCs), is hindered by the complexities of screen‐printing technology. Here a novel “two‐in‐one” defect passivation strategy is presented, through doping TiO2 paste with cesium halide salts (CsX, where X = F, Cl, Br, I) to integrate all‐inorganic Cs halides, particularly CsF, into the electron transport layer in p‐MPSCs. Owing to the robust interaction between F− ions and TiO2 compared to Cs+ ions, and the inability of F− to infiltrate the perovskite lattice, F− and Cs+ play distinct roles starting from the buried interface of the p‐MPSCs. Specifically, F− can rectify the oxygen vacancies on the TiO2 surface, thus alleviating the residual stress at the perovskite's buried interface. Simultaneously, Cs+ diffuses to the top perovskite and mends the methylamine vacancies. As a result, the PCE of the optimal device, based on F‐doped TiO2, witnesses a significant improvement from 16.18% (control) to 18.24%. The two‐in‐one strategy utilizing CsX from the buried interface can well realize the all‐inorganic defect rectification, thereby offering a promising prospect for the enhancement of p‐MPSC performance.

Real-time and operando observation of intermediates on TiO2 photoelectrocatalysis by soft X-ray absorption spectroscopy

The oxygen evolution reaction (OER) on the TiO2 surface at the solid–liquid interface was observed in real-time and operando using fluorescence-yield X-ray absorption spectroscopy (XAS) in the soft X-ray region. The OER was observed during a potential sweep with UV light on or off, focusing on the oxygen K-edge XAS. Although conventional XAS measurements require long measurement times, the spectra during the reaction were obtained every 3 s in the present experiment via wavelength-dispersive XAS technique. An increase in the X-ray absorption intensity at approximately 533.8 eV was observed during the potential sweep only with UV light on. The observed spectral change is discussed in relation to the reaction mechanism of the OER. The present technique can be applied to a wide range of analyses of (photo-) electrocatalysis and electrochemical reactions at solid–liquid interfaces to observe their products and intermediates during the reaction.

Prediction of Feasibility of Polaronic OER on the (110) Surface of Rutile TiO2.

The front cover artwork is provided by Dr. Hori Pada Sarker from Dr. Frank Abild-Pedersen's research group at the SLAC National Accelerator Laboratory. The image shows the generation of photoexcited carriers (electrons and holes) and the subsequent formation of hole polaron in rutile TiO2 during oxygen evolution reaction (OER). Read the full text of the Research Article at 10.1002/cphc.202400060.

Prediction of electronic density of states in guanine-TiO2 adsorption model based on machine learning

The electronic density of states is a property of the material that is extensively used in quantum systems in condensed matter physics. It refers to the energy level of the electrons in a solid crystal. One of the most current ways to compute it is by Density Functional Tight Binding (DFTB), given the geometry of the material. Nevertheless, this computation could be very computationally demanding, although applied to some materials with a very reduced number of atoms. This paper presents a method to deduce the electronic density of states, which is based on a neural network, thus, almost linear with respect to the number of atoms in the material. Specifically, we have applied our method to a metal oxide structure interacting with a nucleic base guanine. We have focused on stoichiometric and O-defective anatase TiO2 (101) surfaces. The data set of the electronic density of states needed to train the neural network has been obtained by a DFTB+ numerical solver given an initial molecular geometry model, which computed a track of time-dependent geometry and their associated electronic density of states. We validated that the predicted electronic density of states deduced by our method and by DFTB tends to be very similar, thus, opening the door to other computations such that introducing our method in the process of generating the time-dependent geometry analysis.

Interaction of phenolic compounds with functionalized TiO2: Enhanced catechol adsorption and cooperative phenol adsorption

A commercial TiO2 sample functionalized with 3-aminopropyltrimethoxysilane (APTMS) and 4-carboxyphenylboronic acid (CPBA), has been previously proposed as a suitable photocatalyst to perform selective photocatalytic degradation of pollutants in aqueous streams, while avoiding the oxidation of valuable catechol simultaneously present in the reacting medium. In the present study, we highlight the adsorption mechanisms underlying the higher affinity of catechol, compared to phenol, with the surface of modified TiO2, quantitatively justifying the photocatalytic selective degradation results previously obtained. Moreover, a cooperative adsorption mechanism of phenol onto the TiO2 sample modified with APTMS has been for the first time observed. The resulting sigmoidal adsorption isotherms, satisfactorily fitted with the Hill model, could be attributed to the enhanced surface hydrophobicity and, more importantly, to alterations of the folding of APTMS molecules on the TiO2 surface occurring upon increasing the concentration of the phenolic compounds.Photocatalytic tests revealed that the existence of boronate groups on the surface of TiO2 hinders the photocatalytic degradation of catechol and facilitates a swifter oxidation of phenol. These findings confirm the potential for selective photocatalytic degradation, in line with modern conceptions of innovative and environmentally sustainable wastewater treatments.

Photocatalytic Degradation of Naproxen: Intermediates and Total Reaction Mechanism.

Photochemical and photocatalytic oxidation of naproxen (NPX) with UV-A light and commercial TiO2 under constant flow of oxygen have been investigated. Adsorption experiments indicated that 90% of the solute remained in the solution. Combined chemical analysis of samples on the photochemical degradation indicated that NPX in an aqueous solution (20 ppm) is efficiently transformed into other species but only 18% of the reactant is mineralized into CO2 and water after three hours of reaction. Performing the photocatalytic oxidation in the presence of TiO2, more than 80% of the organic compounds are mineralized by reactive oxidation species (ROS) within four hours of reaction. Analysis of reaction mixtures by a combination of analytical techniques indicated that naproxen is transformed into several aromatic naphthalene derivatives. These latter compounds are eventually transformed into polyhydroxylated aromatic compounds that are strongly adsorbed onto the TiO2 surface and are quickly oxidized into low-molecular-weight acids by an electron transfer mechanism. Based on this and previous studies on NPX photocatalytic oxidation, a unified and complete degradation mechanism is presented.

A systematic DFT study of structure and electronic properties of titanium dioxide.

DFT functionals are of paramount importance for an accurate electronic and structural description of transition metal systems. In this work, a systematic analysis using some well-known and commonly used DFT functionals is performed. A comparison of the structural and energetic parameters calculated with the available experimental data is made in order to find the adequate functional for an accurate description of the TiO2 bulk and surface of both anatase and rutile structures. In the absence of experimental data on the surface energy, the theoretical predictions obtained using the high-accuracy HSE06 functional were used as a reference to compare against the surface energy values calculated with the other DFT functionals. A clear improvement in the electronic description of both anatase and rutile was observed by introducing the Hubbard U correction term to PBE, PW91, and OptPBE functionals. The OptPBE-U4 functional was found to offer a good compromise between accurately describing the structural and electronic properties of titania.

Combustion Behavior of Cellulose Ester Fibrous Bundles from Used Cigarette Filters: Kinetic Analysis Study.

This study is focused on the detailed examination of the combustion properties and kinetic analysis of a cellulose acetate fibrous bundle (CAFB), separated from used cigarette filters. It was shown that the faster rate of CAFB heating allows a large amount of heat to be supplied to a combustion system in the initial stages, where the increase in heating rate has a positive response to ignition behavior. The best combustion stability of CAFB is achieved at the lowest heating rate. Through the use of different kinetic methods, it was shown that combustion takes place through two series of consecutive reaction steps and one independent single-step reaction. By optimizing the kinetic parameters within the proposed reaction models, it was found that the steps related to the generation of levoglucosenone (LGO) (by catalytic dehydration of levoglucosan (LG)) and acrolein (by breakdown of glycerol during CAFB burning-which was carried out through glycerol adsorption on a TiO2 surface in a the developed dehydration mechanism) represent rate-controlling steps, which are strongly controlled by applied heating rate. Isothermal predictions have shown that CAFB manifests very good long-term stability at 60 °C (which corresponds to storage in a sea shipping container), while at 200 °C, it shows a sudden loss in thermal stability, which is related to the physical properties of the sample.

Thermal-Stabilized Protonated TiO2 for Heat-Accelerated Photoelectrochemical Water Splitting.

Enhancing the charge separation efficiency is a big challenge that limits the energy conversion efficiency of photoelectrochemical (PEC) water splitting. Surface states generated by protonation of TiO2 are the efficient charge separation passageways to massively accept or transfer the photogenerated electrons. However, a challenge is to avoid the deprotonation of a protonated TiO2 photoelectrode at the operation temperature. Here, we found that the terminal hydroxyl group (OHT) as surface states on the TiO2 surface generated via electrochemical protonation of TiO2 at 90 °C [90-TiO2-x-(OH)x] is thermally stable. As a result, the thermally enhanced photocurrent of the 90-TiO2-x-(OH)x electrode reached 1.05 mA cm-2 under 80 °C, and the stability was maintained up to 10 h with a slight photocurrent decrease of 3%. The thermally stable surface states as charge separation paths provide an effective method to couple the heat field with the PEC process via thermal-stimulating hopping of polarons.

Influence of micro and nanoporous TiO2 surface modifications on physical-chemical and biological interactions

Titanium is widely used in implants but can cause adverse reactions like inflammation and tissue rejection. Surface modifications like acid-etching and anodization improve implant properties and osseointegration. This study investigated how micro and nanoporous TiO2 films affect the implant-host interaction, focusing on physical–chemical and biological aspects. Surface treated implants were obtained by acid-etched and anodization of commercially pure titanium (CPTi). Samples were characterized by FE- and FIB-SEM, XRD, EDX, WCA, profilometry, and electrochemical behavior was also investigated. Biocompatibility was accessed by protein adsorption (albumin and serum proteins), hemolysis, and in vitro fibroblast interaction. Anodic samples exhibited the highest corrosion resistance and apatite deposition. Protein adsorption was related to surface roughness and wettability. Samples followed the Langmuir model isotherm (Type I), except for galvanostatic samples (Type III isotherm). Kinetic adsorption was modeled by a pseudo-first-order model, wherein rate-limiting step is albumin diffusion into pores. All surfaces met the hemocompatibility requirements for its use as biomaterial (hemolysis index < 2 %). The upper surface roughness threshold was identified at approximately Sa ≈ 1 µm for better fibroblast viability, adhesion, and proliferation. Combining the results, nanoporous samples present optimized surface conditions that enhance body-fluid contact and improve cell adhesion, thereby contributing to long-term stability.

Unlocking ethane production in photocatalytic methanol reforming based on a novel carbon–carbon coupling mechanism

Photocatalytic methanol reforming represents a promising solution to energy and environmental challenges, yet the CO2 by-product poses significant environmental concerns. Recent advancements enhance the economic and environmental sustainability of this process by yielding valuable by-products like ethylene and ethylene–glycol. However, synthesizing ethane (C2H6), a crucial material, remains unattainable through this reaction, with an unclear mechanism. Herein, we synthesized oxygen-deficient two-dimensional TiO2 nanosheets to achieve ethane production via methanol reforming. Through theoretical calculations and in situ characterization, we unveil a novel carbon–carbon (C–C) coupling mechanism driving ethane production. It is discovered that methanol preferentially adsorbs on the oxygen vacancies of the defective TiO2 surface, forming methoxy radicals (*CH3O), facilitating C–C coupling for ethane formation. Furthermore, prolonged hydrogenation creates additional oxygen vacancies, leading to more adjacent oxygen vacancies. This results in more neighboring *CH3O, facilitating C–C coupling and elevating C2H6 production. Our study clarifies ethane production feasibility in photocatalytic methanol reforming, providing valuable references for future research.

Gradient gyroid Ti6Al4V scaffolds with TiO2 surface modification: Promising approach for large bone defect repair

Large bone defects, particularly those exceeding the critical size, present a clinical challenge due to the limited regenerative capacity of bone tissue. Traditional treatments like autografts and allografts are constrained by donor availability, immune rejection, and mechanical performance. This study aimed to develop an effective solution by designing gradient gyroid scaffolds with titania (TiO2) surface modification for the repair of large segmental bone defects. The scaffolds were engineered to balance mechanical strength with the necessary internal space to promote new bone formation and nutrient exchange. A gradient design of the scaffold was optimized through Finite Element Analysis (FEA) and Computational Fluid Dynamics (CFD) simulations to enhance fluid flow and cell adhesion. In vivo studies in rabbits demonstrated that the G@TiO2 scaffold, featuring a gradient structure and TiO2 surface modification, exhibited superior healing capabilities compared to the homogeneous structure and TiO2 surface modification (H@TiO2) and gradient structure (G) scaffolds. At 12 weeks post-operation, in a bone defect representing nearly 30 % of the total length of the radius, the implantation of the G@TiO2 scaffold achieved a 27 % bone volume to tissue volume (BV/TV) ratio, demonstrating excellent osseointegration. The TiO2 surface modification provided photothermal antibacterial effects, enhancing the scaffold's biocompatibility and potential for infection prevention. These findings suggest that the gradient gyroid scaffold with TiO2 surface modification is a promising candidate for treating large segmental bone defects, offering a combination of mechanical strength, bioactivity, and infection resistance.