TiO2 Surface Research Articles

Coupling interface, electronic and conjugation effects in C-COFs/TiO2 composite structure toward boosting photocatalytic hydrogen evolution

Hydrogen energy, recognized as a pivotal clean energy source, has attracted considerable attention in the realm of photocatalytic hydrogen production. Nevertheless, inorganic materials were difficult to regulate band gaps, resulting in limited photogenerated carrier rates. Additionally, organic materials frequently suffer from insufficient stability and a propensity for electron recombination. Therefore, fully utilizing the interface effect will become an important breakthrough for novel and efficient catalysts. Herein, hydroxylate covalent organic frameworks (H-COFs) were formed by direct synthesis method, in addition, titanium dioxide (TiO2) was used as an inorganic substrate, and TiO2 was transformed titanium acid under weakly acidic conditions, meanwhile, chloride covalent organic frameworks (C-COFs) growth on TiO2 surface by interface effect when H-COFs were formed into C-COFs under titanium acid. The structure characteristics, photoelectric performance, bandgap width and stability of C-COFs/TiO2 were confirmed through characterization analysis. C-COFs/TiO2 exhibit strong stability, conjugation effects, electron deficiency effects, and catalytic efficiency. Hydrogen production rate up to 5598 μmol g−1 h−1 by C-COFs/TiO2 as photocatalyst. C-COFs/TiO2 lead to 161 times improvement in photocatalytic activity for TiO2 and 3.6 times improvement in photocatalytic activity for H-COFs. The catalytic reaction mechanism was obtained by utilizing experimental data and DFT calculation. This synergistic integration of organic inorganic combined catalyst provides a foundational framework for advancing research into novel photocatalysts.

Impact of copper on activity, selectivity, and deactivation in the photocatalytic reduction of CO2 over TiO2

The photocatalytic reduction of CO2 to hydrocarbons may be a promising mechanistic route to reduce greenhouse gas CO2, convert it into useful products, and limit the direct emission of CO2. The photocatalytic reduction of CO2 is a reaction in which photons activate the photocatalyst by generating reduced and oxidized sites, that are re-oxidized and re-reduced by the reactants. The photocatalytic reduction of CO2 can produce various products, including CO, formic acid, formaldehyde, methanol, methane, etc.Here, the activity/selectivity of produced hydrocarbons in the presence of oxygen on various photocatalysts (TiO2, 5 wt%Cu-TiO2, 5 wt%Cu-C-TiO2) was determined.The reaction rate increased with increasing reaction time up to the first half an hour of the reaction but then started to decrease with photocatalysts, indicating photocatalyst deactivation, a rate-limiting step by hydroxyl radicals and adsorption of intermediates on TiO2. Carbon deposition as the origin of photocatalyst deactivation was confirmed using the TGA of the spent photocatalyst. Additionally, absorption of intermediates on spent catalysts were confirmed by FTIR. On the other hand, the conversion increased with time when copper was used as a promoter on a TiO2 compared with TiO2 due to its larger surface area and having more active sites.The photocatalysts were characterized using BET, ICP-OES, XRD, TGA, XPS, Fourier-Transform Infrared Spectroscopy (FTIR), and UV–Vis. The focus of this study was to determine the activity and efficacy of different photocatalysts (TiO2, 5 wt%Cu-TiO2, 5 wt%Cu-C-TiO2) by gas phase measurement, with a particular emphasis on obtaining reproducible data on conversion and selectivity as a function of irradiation time.The copper on TiO2 was found to be more selective towards sodium formate/formic acid with a maximum selectivity of ∼90 % in 4 h and had higher activity (74.3 µmol gcat-1 h-1). A maximum CO with a selectivity of 86 % was found when TiO2 was used in 4 h.Copper transfer electrons on the TiO2 surface enhance CO2 adsorption on the catalytic surface and is the reason for having higher valuable product on Cu-C-TiO2 and Cu-TiO2 compared with TiO2. Carbon in this experiment did not have a role and its effect was negligible.

Laser ablation and chemical vapor deposition to prepare a nanostructured PPy layer on the Ti surface

Abstract The deposition of polypyrrole (PPy) on a Ti surface is commonly employed to enhance the material’s properties for different applications such as supercapacitors, biomedicine, and corrosion resistance. Instead of complex or costly polymerization procedures for the PPy synthesis on the Ti metal surface, we utilized the effect of a simple and inexpensive laser ablation of the Ti surface in the open-air environment to prepare a hydrophilic TiO2 surface. In this condition, a thin PPy layer with remarkable nanostructures such as nanorings (∼80 nm) and nanotubes (∼245 nm) was deposited on a selective and desired pattern of ablated Ti areas through the chemical vapor deposition process using ferric chloride (FeCl3) solution as a pyrrole oxidizer. Raman and X-ray photoelectron spectroscopy (XPS) analyses confirmed the PPy formation on the Ti surface. The creation of these nanostructures was due to the micro/nanomorphology of the ablated Ti substrate. Water contact angle (WCA) measurements indicated the hydrophobic behavior of the PPy/Ti surface by the aging effect after 24 weeks with the change of WCA from 20° to 116°. The change in the surface chemical composition upon adsorption of airborne organic compounds with the long-term storage of PPy/Ti surface in air was studied by the XPS test.

Molecular Engineering Strategies of Spectral Matching and Structure Optimization for Efficient Metal-Free Organic Dyes in Dye-Sensitized Solar Cells: A Theoretical Study.

Metal-free organic dyes are promising dyes that can be applied widely in dye-sensitized solar cells (DSSCs). The rational design and selection of dyes with complementary absorption can promote the development of methods that can enhance the utilization of incident light by DSSCs, such as cosensitization and tandem devices. Based on these opinions, the structure of the reported high-performance metal-free organic dye ZL003 is used as a template to design two new metal-free organic dyes, HX-1 and HX-2, by replacing its donor unit with a 2-phenothiazine-phenylamine unit and fusing its three independent π-bridge units into a whole with the aim of driving the red shift and the blue shift of the absorption spectra of ZL003, respectively. Through theoretical investigation, it is demonstrated that the perfect complementary optical absorption of HX-1 and HX-2 can be realized as the shift of the absorption spectra of ZL003 to different directions, which means their feasibility to the application in cosensitization or tandem dye-sensitized solar cells (T-DSSCs). Furthermore, it is hypothesized that HX-1 may be the dye with better photovoltaic performance than ZL003 by modeling their intramolecular charge-transfer (ICT) processes, TiO2 surface adsorption, and photovoltaic parameters. The short-circuit current density (Jsc) and photoelectric conversion efficiency (PCE) of HX-1 are 23.10 mA·cm-2 and 21.26% in theory, compared to those of 20.68 mA·cm-2 and 19.64% in ZL003 at the same computational level, respectively. In view of the complementary optical properties, the combination of HX-1 with HX-2 may be a reasonable option for dyes for the development of a highly efficient cosensitization system or T-DSSCs in the future. In terms of such findings, these two novel metal-free organic dyes may have bright prospects in the research of highly efficient DSSCs, and this work can provide a reference for the design of dyes with complementary absorption through simple structural adjustments of the realistic dyes with high photovoltaic performance.

Synthesis and Characterization of Multifunctional Symmetrical Squaraine Dyes for Molecular Photovoltaics by Terminal Alkyl Chain Modifications

Novel far-red sensitive symmetric squaraine (SQ) dyes with terminal alkyl chain modifications were designed, synthesized, and characterized, aiming towards imparting multifunctionalities such as photosensitization, dye aggregation prevention, and source of electrolyte components. The dye sensitizer SQ-80 with alkyl chain terminal modifications consisting of 1-methylimidazolium iodide was designed and synthesized as a new dye sensitizer for DSSCs based on symmetric SQ-4 without any terminal modification used as reference. Upon adsorption on the mesoporous TiO2 surface, SQ-80 demonstrated reduced dye aggregation and stronger binding to the TiO2 surface, leading to enhanced durability of DSSCs. Apart from the most common photosensitization behavior, the newly designed dye demonstrated multifunctionalities such as aggregation prevention and electrolyte functionality, utilizing iodine-based redox electrolytes in the presence and absence of I2 and LiI additives. In the absence of LiI and I2, a mixture of SQ-77 with alkyl chain terminal modifications consisting of iodide and SQ-80 demonstrated a photoconversion efficiency of 1.54% under simulated solar irradiation, which was about six times higher compared with the reference dye SQ-4 (0.24%) (having no alkyl chain terminal modification).

Manganese-rhodium nanoparticles: Adsorption on titanium oxide surfaces and catalyst for syngas reactions.

Manganese-rhodium (Mn-Rh) nanoparticles have emerged as a promising candidate for catalytic applications in the production of syngas, a critical precursor for a wide range of industrial processes. This study employs a comprehensive, theoretical, and computational approach to investigate the structural and electronic properties of Mn-Rh nanoparticles, with a specific focus on their interaction with titanium oxide (TiO2) surfaces and their potential as catalysts for syngas reactions. The density functional theory calculations are employed to explore the adsorption behavior of Mn-Rh nanoparticles on TiO2 surfaces. By analyzing the adsorption energies, geometries, and electronic structure at the nanoscale interface, we provide valuable insights into the stability and reactivity of Mn-Rh nanoparticles when immobilized on TiO2 supports. Furthermore, the catalytic performance of Mn-Rh nanoparticles in syngas production is thoroughly examined. Through detailed reaction mechanism studies and kinetic analysis, we elucidate the role of Mn and Rh in promoting syngas generation via carbon dioxide reforming and partial oxidation reactions. The findings demonstrate the potential of Mn-Rh nanoparticles as efficient catalysts for these crucial syngas reactions. This research work not only enhances our understanding of the fundamental properties of Mn-Rh nanoparticles but also highlights their application as catalysts for sustainable and industrially significant syngas production.

Effect of water on formic acid and formaldehyde decomposition on the TiO2 (110) surface

The catalytic and photocatalytic performance of TiO2 in air pollutant degradation is significantly influenced by the adsorption of water. Here, we explore the molecular mechanism of formic acid and formaldehyde decomposition and their interaction with water on the TiO2 (110) surface, employing density functional theory (DFT) calculations and reactive molecular dynamics (RMD) simulations. RMD simulations indicate that due to the competitive adsorption of water at the surface Ti site, formic acid predominantly exists in a monodentate dissociative adsorption form on the TiO2 (110) surface. Moreover, on the TiO2 (110) surface, water molecules inhibit the adsorption and dissociation of formic acid, but they facilitate that of formaldehyde, forming methanediol (*CH2OHO) and dioxymethylene (*CH2O2). DFT calculations suggest that the formation pathway of *CH2OHO or *CH2O2 is energetically favorable, but the formation of formate is difficult. This contrasts with the adsorption of formaldehyde on the anatase surface, where formate species are formed.

Antimicrobial Activity against Fusarium oxysporum f. sp. dianthi of TiO2/ZnO Thin Films under UV Irradiation: Experimental and Theoretical Study.

We deposited bare TiO2 and TiO2/ZnO thin films to study their antimicrobial capacity against Fusarium oxysporum f. sp. dianthi. The deposit of TiO2 was performed by spin coating and the ZnO thin films were deposited onto the TiO2 surface by plasma-assisted reactive evaporation technique. The characterization of the compounds was carried out by scanning electron microscopy (SEM) and powder X-ray diffraction techniques. Furthermore, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were performed to support the observed experimental results. Thus, the removal of methylene blue (MB) by adsorption and posterior photocatalytic degradation was studied. Adsorption kinetic results showed that TiO2/ZnO thin films were more efficient in MB removal than bare TiO2 thin films, and the pseudo-second-order model was suitable to describe the experimental results for TiO2/ZnO (q e = 12.9 mg/g; k 2 = 0.14 g/mg/min) and TiO2 thin films (q e = 12.0 mg/g; k 2 = 0.13 g/mg/min). Photocatalytic results under UV irradiation showed that TiO2 thin films reached 10.9% of MB photodegradation (k = 1.0 × 10-3 min-1), whereas TiO2/ZnO thin films reached 20.6% of MB photodegradation (k = 3.9 × 10-3 min-1). Both thin films reduced the photocatalytic efficiency by less than 3% after 4 photocatalytic tests. DFT study showed that the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap decreases for the mixed nanoparticle system, showing its increased reactivity. Furthermore, the chemical hardness shows a lower value for the mixed system, whereas the electrophilicity index shows the biggest value, supporting the larger reactivity for the mixed nanoparticle system. Finally, the antimicrobial activity against F. oxysporum f. sp. dianthi showed that bare TiO2 reached a growth reduction of 68% while TiO2/ZnO reached a growth reduction of 90% after 250 min of UV irradiation.

Elucidating mechanisms and DFT analysis of monometallic Vanadium incorporated nanoporous TiO2 as advanced material for enzyme-free electrochemical blood glucose biosensors with exceptional performance tailored for point-of-care applications

Diabetes is a chronic condition that can last a lifetime and has claimed a great number of lives in recent years. This motivated scientists to design a glucose biosensor to monitor and control blood glucose levels in diabetic patients. Herein, hydrothermal derived Vanadium (V), Nickel (Ni), and Cobalt (Co)-dopedTiO2 (MxTi1-xO2 (x = 0.01, 0.02, and 0.03)) was synthesized to achieve the best material to answer the pertaining problem. Of all the materials synthesized, V0.03Ti0.97O2@NF demonstrated the highest level of sensitivity, and selectivity, and has higher electrochemical cycling stability in 0.1 M KOH. It exhibits a very high sensitivity of 1129.31 μAmM-1cm-2 and Limits of Detection (LOD) and Limits of Quantification (LOQ) of 1.8 μM (S/N = 3) and 6.2 μM, respectively, with a broad linear range from 20 μM to 2 mM. The DFT approach was employed computationally to analyze the adsorption of glucose on surfaces of pure TiO2 and TiO2 doped with V, Ni, and Co respectively. The research findings highlight that when it comes to its interaction with glucose, pure TiO2 exhibits significantly less reactivity compared to transition metal-doped TiO2. Experimentally it shows thattheV0.03Ti0.97O2@NF surface has the most sensitiveglucose detection capability and it alsoexhibited significant selectivity towards glucose in the presence of additional interference. Itdemonstrated 100% retention after cycling stability and had a shelf life of ≃30 days. The V0.03Ti0.97O2@NF-based sensor exhibits accurate glucose sensing, even for human serum samples.

Atom Pairing Enhances Sulfur Resistance in Low-Temperature SCR via Upshifting the Lowest Unoccupied States of Cerium.

Environmentally benign cerium-based catalysts are promising alternatives to toxic vanadium-based catalysts for controlling NOx emissions via selective catalytic reduction (SCR), but conventional cerium-based catalysts unavoidably suffer from SO2 poisoning in low-temperature SCR. We develop a strongly sulfur-resistant Ce1+1/TiO2 catalyst by spatially confining Ce atom pairs to different anchoring sites of anatase TiO2(001) surfaces. Experimental results combined with theoretical calculations demonstrate that strong electronic interactions between the paired Ce atoms upshift the lowest unoccupied states to an energy level higher than the highest occupied molecular orbital (HOMO) of SO2 so as to be catalytically inert in SO2 oxidation but slightly lower than HOMO of NH3 so that Ce1+1/TiO2 has desired ability toward NH3 activation required for SCR. Hence, Ce1+1/TiO2 shows higher SCR activity and excellent stability in the presence of SO2 at low temperatures with respect to supported single Ce atoms. This work provides a general strategy to develop sulfur-resistant catalysts by tuning the electronic states of active sites for low-temperature SCR, which has implications for practical applications with energy-saving requirements.

Facet-engineered ruthenium oxide on titanium oxide oxygen evolution electrocatalysts for proton-exchange membrane water electrolysis

Ruthenium oxide-based catalysts exhibit an active oxygen evolution reaction (OER) in acidic media but suffer from low stability, limiting their practical application in proton-exchange membrane water electrolyzers (PEMWEs). Herein, we present an effective acidic OER catalyst comprising RuO2 nanolayers on an isostructural rutile TiO2 support (NL-RuO2-250) that maximizes exposure to specific crystal orientations. RuO2 morphology and growth mechanism on the TiO2 surface were affected by the interfacial charge states during hydrothermal process, with the crystal structure similarity between the RuO2 catalyst and TiO2 support advantageous for maximizing compatibility at the interface. Density functional theory combined with experimental analyses revealed that NL-RuO2-250 is an optimized form for improving OER performance. As-prepared NL-RuO2-250 required a low overpotential (230 mV at 10 mA cm−2) and a PEMWE single cell assembled with NL-RuO2-250 exhibited an insignificant voltage drop for 24 h under 0.2 A cm−2, demonstrating a practical design strategy for acidic OER catalysts.

Titanium dioxide modified by polydopamine used as stabilizer of Pickering emulsion and characterized for its sunscreen properties

The high hydrophilicity of titanium dioxide (TiO2) caused by surface hydroxyl groups limited their application in Pickering emulsions. Inspired by the structure and function of mussel adhesion protein, polydopamine-modified TiO2 (PDA-TiO2) was successfully prepared in this study. The effect of modified conditions on emulsifying capacity of Pickering emulsions stabilized by PDA-TiO2 were investigated, including pH, material ratio, reaction time, and temperature. The morphology and structure properties of modified TiO2 were characterized by SEM, TEM, FTIR, UV, TG, XPS, and XRD. The results suggested that PDA were successfully bonded to the TiO2 surface, which might improve the hydrophilicity of TiO2. PDA-TiO2 could stabilized Pickering emulsion with more uniform emulsified drops when m(TiO2)/m(DA) was 1/0.1, the reaction pH was 8.5, the reaction time was 3 h, and the reaction temperature was 50 °C. In addition, the introduction of polydopamine effectively improved the sun protection ability of TiO2. Compared to traditional sunscreen emulsion, Pickering emulsion stabilized by polydopamine-modified TiO2 could increase the sunscreen value by 55%, which broadened its application in cosmetic and other fields.

Light-Induced Transformation of Virus-Like Particles on TiO2.

Titanium dioxide (TiO2) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO2 surface. The in situ GISAXS measurements under an N2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

Study of Microstructure, Morphology and Functional Groups of Titanium Dioxide (Tio2) Impregnated With Copper (Cu)

This research aims to determine the differences in the microstructure, morphology, and functional groups of TiO2 (P-25) after being impregnated with Cu. Cu-impregnated TiO2 samples are synthesized using the impregnation method with TiO2 (P-25) and copper sulfate as precursors. The microstructure and functional groups of TiO2 (P-25) and Cu-TiO2 were investigated using X-ray diffraction (XRD), scanning electron microscope-energy dispersive x-ray (SEM-EDX), and Fourier transform infrared (FTIR) analysis. The lattice parameters (a, b, and c) of the TiO2 sample were found to be a = b = 0.3778 nm, c = 0.9494 nm, and these values increased to a = b = 0.3779 nm, c = 0.9496 nm after the addition of Cu. The distance between the lattices of the TiO2 sample was measured at 0.3505 nm and increased to 0.3509 nm after Cu addition. The average crystallite size of the TiO2 sample was 33 nm, which increased to 43 nm after Cu impregnation. The strain value decreased from 2.76×10^(-3) to 1.82×10^(-3) after Cu addition. SEM results revealed that the morphology of the particles from the Cu-doped synthesis showed agglomeration. The success of Cu doping was confirmed by EDX mapping, which showed the presence of Ti, O, and Cu evenly distributed on the TiO2 surface. The FTIR spectrum indicated that TiO2 (P-25) and Cu-TiO2 particles had absorption peaks at similar wave numbers. However, in the absorption area of 1000 cm^-1 to 1250 cm^-1, new absorption bands affiliated with Cu-O bonds appeared in the Cu-TiO2 sample, resulting from TiO2 vibrations after Cu addition.

Titanium Superoxide as a Carrier of a "Long-Lived" Superoxide Anion: An Ab Initio Investigation.

The photoinduced generation of a superoxide anion on the surface of a semiconductor photocatalyst is usually attributed to the reduction of O2 with conduction-band electrons. In the current work, the reaction of TiO2 with O2 giving rise to TiO4 in superoxide and peroxide states has been investigated with ab initio (CAS, CCSD) and DFT (B3LYP) calculations. The ground triplet state and two substates (open-shell singlet (OSS) and closed-shell singlet (CSS)) of a doubly degenerate excited singlet state (a1Δg) are considered as reactive states of oxygen, participating in spontaneous or photoinduced processes, respectively. The triplet and OSS singlet states of TiO4 contain O2- as structural units and can be defined as titanium superoxides. Both states have energy less than the level of the initial pair TiO2+O2 by about 30 kcal/mol. The CSS state of TiO4 has a diperoxide structure Ti4+(O22-)2 and also lies in energy below the initial pair TiO2+3O2. Titanium superoxide is considered to be the carrier of an "exceptionally stable" and "long-lived" superoxide anion, which was earlier synthesized or detected on the surface of TiO2. The low-energy location of the conical intersections on the way from reagents to 3TiO4 allows us to explain the literature data on the spontaneous generation of the "long-lived" superoxide anion on the TiO2 surface.

Preparation of Pt and bamboo charcoal co-modified TiO2 for formaldehyde sensing at room temperature.

Anatase TiO2 has evolved into one of the most attractive materials for gas sensing owing to its strong oxidation activity and excellent sensing properties. In this study, we prepared Pt and bamboo charcoal co-modified nano-TiO2 using a one-pot hydrothermal process and applied it to detect formaldehyde. The successful incorporation of the precious metal Pt and bamboo charcoal onto TiO2 was confirmed by scanning electron microscope, transmission electron microscopy, energy dispersive spectrometer, X-ray diffraction and X-ray photoelectron spectroscopy. Detailed analysis revealed a homogeneous distribution of Pt nanoparticles and bamboo charcoal on the TiO2 surface, which significantly improved the surface area and facilitated gas adsorption. These modifiers significantly enhanced the response of TiO2 to formaldehyde, for instance, the response signal increased fourfold, while the response time decreased from 91 to 68 s. The sample with 0.5@Pt and 0.5@C bamboo charcoal performed the best, showcasing the synergistic effect of metal nanoparticles and carbonaceous materials on gas-sensing properties. Our work highlighted the potential of using biomass-derived carbon to enhance the detection of formaldehyde and demonstrated the importance of material characteristics in designing effective gas sensors.

The effect of applying lead ion to the surface of TiO2 on dye-adsorption rate and photovoltaic properties of solar cells

Lead ion was incorporated into TiO2 layers prepared on an F-doped tin oxide (FTO) substrate. The resulting electrodes (Pb2+-TiO2/FTO) were sensitized with N719 dye and put to use in dye-sensitized solar cells (DSCs). Owing to the electrostatic attraction between the positively charged TiO2 and the carboxylate anions (–COO−) in the N719 dye, more dye was adsorbed into the Pb2+-TiO2/FTO, which required only 2 h for sensitization, than in a reference TiO2/FTO electrode that was sensitized for 8 h. The power conversion efficiency of a DSC with the Pb2+-TiO2/FTO rose to 10.01 % over the efficiency (9.29 %) of the reference device. It was found that the increased dye adsorption in the Pb2+-TiO2/FTO allowed the cells to more efficiently harvest light and collect electrons, resulting in a higher short-circuit current in the DSC. The larger amount of dye also induced a higher open-circuit voltage in the cell by increasing the total number of photoinjected electrons and prolonging their lifetime.

Preparation and Performance Evaluation of Microporous Transport Layers for Proton Exchange Membrane (PEM) Water Electrolyzer Anodes

In this work, ≈25 μm thin titanium microporous layers (MPLs) with ≈2 μm small pores and low surface roughness were coated and sintered on top of ≈260 μm thick commercial titanium-powder-sinter sheets with ≈16 μm pores, maintaining a porosity of ≈40% in both layers. Serving as porous transport layers (PTLs) on the anode side in proton exchange membrane water electrolyzers (PEMWEs), these pore-graded, two-layer sheets (“PTL/MPL”) are compared to single-layer PTLs in single-cell PEMWEs. The PTL/MPL samples prepared here give a 3–6 mΩ cm2 lower high-frequency resistance (HFR) compared to the as-received single-layer PTL, which is attributed to a partial reduction of the TiO2 surface passivation layer during the MPL sintering process. For ≈1 μm thin anodes with an iridium loading of ≈0.2 mgIr cm−2, the use of an MPL leads to a ≈24 mV improvement in HFR-free cell voltage at 6 A cm−2. As no such benefit is observed for ≈9 μm thick anodes with ≈2.0 mgIr cm−2, mass transport resistances within the PTL/MPL play a minor role. Possible reasons for the higher catalyst utilization in ultra-thin electrodes when using an MPL are discussed. Furthermore, an MPL provides superior mechanical membrane support, which is particularly relevant for thin membranes.

Examining the dual effect of copper nanoparticles and nitrogen doping on Cu@N-TiO2

Abstract The study of six compositions of Cu@N-TiO2 with different amounts of copper and nitrogen synthesized using a sol–gel method is reported. X-ray diffraction patterns and Raman spectra indicated the formation of a single anatase TiO2 phase in all materials without evidence of secondary phases including copper or nitrogen. Electron microscopy images showed a homogeneous distribution of the copper particles around a TiO2 matrix, just as that the insertion of nitrogen did not have a significant effect on the morphology of the particles. X-ray photoelectron spectroscopy analysis confirmed that nitrogen was inserted in the atomic arrangement of titanium dioxide, while copper was presented mainly as metallic element on the TiO2 surface. Characterization of the optical properties and photoactivity test confirm that band gap strongly depends on the copper and nitrogen content phenomenon attributed to the combined presence of modifiers over the TiO2 surface and the promotion of a plasmonic effect, which displaced the absorption UV bands to higher wavelengths with respect to un-doped TiO2. The catalytic test performed using rhodamine-B as probe molecule, confirm that TiCuN2 and TiCuN3 samples exhibit the best decomposition percentages of 38 and 36 % respectively. Such results confirm the surface plasmon resonance effect associated to Cu particles on the TiO2 as main cause in the increase in current along synthesized samples and the use of cyclic voltammetry technique to identify these effects between 0.0 and 1.5 V.

Investigation of scale formation and degeneration of silicide coating on Nb–Si based alloy in the temperature range from 1250 °C to 1560 °C

Nb silicide coatings modified with active elements have good oxidation resistance, but there is a lack of systematic research on their oxidation behavior at high temperatures above 1250 °C. The aim of this work is to investigate the oxidation behavior of an Al–Y modified silicide coating on Nb–Si based alloy in the temperature range from 1250 °C to 1560 °C. After oxidation at 1250 °C, the scale displays a typical layered structure consisting mainly of a TiO2 outer layer, an amorphous SiO2 matrix layer embedded with TiO2 and ZrSiO4, and an inner layer consisting of SiO2 and Cr2O3. Above 1350 °C, the evaporation reaction of Cr2O3 into CrO3 (g) is significantly accelerated and Cr2O3 disappeared gradually with temperature or time. The TiO2 layers covering on the scales formed at 1250–1500 °C grow along the crystallographic orientation of [100]. The micropores formed on the surface of TiO2 should be attributed to the further oxidation of Cr2O3 into volatile oxide CrO3 (g). The scales exhibit a similar structure consisting mainly of a SiO2 glass matrix embedded with ZrSiO4 and a surface TiO2 layer until 1500 °C. Above the eutectic temperature of SiO2–TiO2 system, the scale is mainly composed of a matrix layer of SiO2–TiO2 eutectic embedded with block TiO2 particles, and a thin SiO2 interface layer at 1560 °C. The degeneration path of the (Nb,X)Si2 coating is (Nb,X)Si2 → (Ti,Nb)5Si4 → γ-(Nb,X)5Si3.