Enhanced electrochemical hydrogen storage capacity of multi-walled carbon nanotubes by TiO2 decoration

Electrochemical hydrogen storage of multi-walled carbon nanotubes (MWCNTs) decorated by TiO₂ nanoparticles (NPs) has been studied by the galvanostatic charge and discharge method. The TiO₂ NPs are deposited on the surface of MWCNTs by sol-gel method. Structural and morphological characterizations have been carried out using XRD, SEM and TEM, respectively. TiO₂ NPs can significantly enhance the discharge capacity of MWCNTs. The cyclic voltammograms analysis indicates that the electrical double layer contributes little to the discharge capacity of TiO₂-decorated MWCNTs. The MWCNTs modified with a certain amount of TiO₂ NPs have a discharge capacity of 540 mAh/g, corresponding to an electrochemical hydrogen storage capacity of about 2.02 wt%, which is quite interesting for the battery applications. The enhancement effect of TiO₂ NPs on the discharge capacity of MWCNTs could be related to the increased effective area for the adsorption of hydrogen atoms in the presence of TiO₂ NPs on MWCNTs and the preferable redox ability of TiO₂ NPs.     

Photocatalytic hydrogen production over CuO and TiO2 nanoparticles mixture

Cheap and efficient photocatalysts were fabricated by simply mixing TiO₂ nanoparticles (NPs) and CuO NPs. The two NPs combined with each other to form TiO₂/CuO mixture in an aqueous solution due to the opposite surface charge. The TiO₂/CuO mixture exhibited photocatalytic hydrogen production rate of up to 8.23 mmol h⁻¹ g⁻¹ under Xe lamp irradiation when the weight ratio of P25 to CuO was optimized to 10. Although the conduction band edge position of CuO NPs is more positive than normal hydrogen electrode, the TiO₂/CuO mixture exhibited good photocatalytic hydrogen production performance because of the inter-particle charge transfer between the two NPs. The detailed mechanism of the photocatalytic hydrogen production is discussed. This mixing method does not require a complicated chemical process and allows mass production of the photocatalysts.     

The decoration of TiO2/reduced graphene oxide by Pd and Pt nanoparticles for hydrogen gas sensing

Reduced graphene oxide (RGO) was used to improve the hydrogen sensing properties of Pd and Pt-decorated TiO₂ nanoparticles by facile production routes. The TiO₂ nanoparticles were synthesized by sol–gel method and coupled on GO sheets via a photoreduction process. The Pd or Pt nanoparticles were decorated on the TiO₂/RGO hybrid structures by chemical reduction. X-ray photoelectron spectroscopy demonstrated that GO reduction is done by the TiO₂ nanoparticles and Ti–C bonds are formed between the TiO₂ and the RGO sheets as well. Gas sensing was studied with different concentrations of hydrogen ranging from 100 to 10,000 ppm at various temperatures. High sensitivity (92%) and fast response time (less than 20 s) at 500 ppm of hydrogen were observed for the sample with low concentration of Pd (2 wt.%) decorated on the TiO₂/RGO sample at a relatively low temperature (180 °C). The RGO sheets, by playing scaffold role in these hybrid structures, provide new pathways for gas diffusion and preferential channels for electrical current. Based on the proposed mechanisms, Pd/TiO₂/RGO sample indicated better sensing performance compared to the Pt/TiO₂/RGO. Greater rate of spill-over effect and dissociation of hydrogen molecules on Pd are considered as possible causes of the enhanced sensitivity in Pd/TiO₂/RGO.     

TiO2 nanorods decorated on RGO sheet for an excellent energy storage performance

Herein, we report nanocomposite of titanium dioxide (TiO₂) nanorods decorated reduced graphene oxide (TiO₂/RGO) nanocomposite prepared using the simple, one-pot hydrothermal route for electrode material in supercapacitor applications. A systematic comparison study was carried out for the TiO₂ nanorods coated on graphite foil in presence of alkaline media 3 M KOH, NaCl, and Na₂SO₄ using the three-electrode method. The TiO₂/RGO composite shows an excellent specific capacitance (C_sp) of 330 Fg^-1 at the discharge current density 0.5 Ag^-1 in presence of 3 M KOH electrolyte solution. The obtained highest specific capacitance values in order by various electrolytes are observed as KOH > NaCl > Na₂SO₄. The long-term cycle stability of charge and discharge cycle at current density 0.5 Ag^-1 over 1000 cycles and only 8% decay in the specific capacitance of TiO₂/RGO nanocomposite was observed in 3 M KOH electrolyte. The improved electrochemical performance TiO₂/RGOcomposite in presence of KOH electrolyte is shown to be the most suitable electrode for the supercapacitors.     

Photo-induced reforming of alcohols with improved hydrogen apparent quantum yield on TiO2 nanotubes loaded with ultra-small Pt nanoparticles

Photo-induced reforming of methanol, ethanol, glycerol and phenol at room temperature for hydrogen production was investigated with the use of ultra-small Pt nanoparticles (NPs) loaded on TiO₂ nanotubes (NTs). The Pt NPs with diameters between 1.1 and 1.3 nm were deposited on TiO₂ NTs by DC-magnetron sputtering (DC-MS) technique. The photocatalytic hydrogen rate achieved an optimum value for a loading of about 1 wt% of Pt. Apparent quantum yield for hydrogen generation was measured for methanol and ethanol water solutions reaching a maximum of 16% under irradiation with a wavelength of 313 nm in methanol/water solution (1/8 v/v). Pt NPs loaded on TiO₂ NTs represented also a true water splitting catalyst under UV irradiation and pure distilled water. DC-MS method appears to be a technologically simple, ecologically benign and potentially low-cost process for production of an efficient photocatalyst loaded with ultra-small NPs with precise size control.     

Electrospun Pt/TiO2 hybrid nanofibers for visible-light-driven H2 evolution

One-dimensional (1D) Pt/TiO₂ hybrid nanofibers (HNFs) with different concentrations of Pt were fabricated by a facile two-step synthesis route combining an electrospinning technique and calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) results showed that the Pt nanoparticles (NPs) with the size of 5–10 nm were well dispersed in the TiO₂ nanofibers (NFs). Further investigations from the UV–Vis diffuse reflectance (DR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that some Pt ions were incorporated into the TiO₂ lattice as Pt⁴⁺ state, which contributed to the visible light absorption of TiO₂ NFs. Meanwhile, the Pt²⁺ ions existing on the surface of Pt NPs resulted in the formation of Pt–O–Ti bond at Pt NPs/TiO₂ NFs interfaces that might serve as an effective channel for improving the charge transfer. The as-electrospun Pt/TiO₂ HNFs exhibited remarkable activities for photocatalytic H₂ evolution under visible light irradiation in the presence of l-ascorbic acid as the sacrificial agent. In particular, the optimal HNFs containing 1.0 at% Pt showed the H₂ evolution rate of 2.91 μmol h⁻¹ and apparent quantum efficiency of 0.04% at 420 nm by using only 5 mg of photocatalysts. The higher photocatalytic activity could be ascribed to the appropriate amount of Pt ions doping and excellent electron-sink effect of Pt NPs co-catalysts.     

Three-dimensional ZnO@TiO2 core-shell nanostructures decorated with plasmonic Au nanoparticles for promoting photoelectrochemical water splitting

A novel three-dimensional (3D) core-shell nanostructure decorated with plasmonic Au nanoparticles (NPs) was prepared for photoelectrochemical water splitting. In the new nanostructure, ZnO nanorods (NRs) are perpendicular to ZnO nanosheets (NSs), and the ZnO NSs-NRs are coated with a thin TiO₂ shell formed by liquid phase deposition. The plasmonic Au NPs were formed in situ on the surface of ZnO NSs-NRs@TiO₂ by thermal reduction. A thin TiO₂ shell and uniformly distributed Au NPs were successfully obtained. The photoconversion efficiency and photocurrent density of the 3D ZnO NSs-NRs@TiO₂-Au nanostructure respectively reached 0.48% and 1.73 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode, 4.80 and 4.33 times higher than those of ZnO NSs, respectively. The thin TiO₂ shell effectively promoted charge separation, while the surface plasmon resonance effects of the Au NPs improved the photocurrent density. The findings suggest that the 3D ZnO NSs-NRs@TiO₂-Au nanostructure is a promising photoanode for photoelectrochemical water splitting.     

Facile synthesis and electrochemical hydrogen storage of bentonite/TiO2/Au nanocomposite

In this study, the electrochemical hydrogen storage of bentonite composites containing TiO₂ and Au nanoparticles (NPs) has been investigated by cyclic voltammetry (CV) analysis. TiO₂ NPs were first deposited on the bentonite substrate by reflux technique. Au NPs were then prepared by laser ablation in liquid (LAL) method under different laser irradiation times (6, 12, and 18 min), and utilized in the decoration of bentonite/TiO₂ nanocomposite by physical mixing. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, and elemental mapping were carried out in the characterization of the prepared bentonite/TiO₂/Au nanocomposite. The surface and chemical properties of the acquired nanocomposite were analyzed by Brunauer-Emmett-Teller and Fourier transform infrared spectroscopy, respectively. Electrochemical measurement was performed on stainless steel mesh prefabricated electrodes in 1 M KOH electrolyte solution. The B-T/Au nanocomposite prepared under 12 min laser irradiation displayed the highest hydrogen storage capacity (15 Cg^-1).     

Photoelectrochemical hydrogen production from water/methanol decomposition using Ag/TiO2 nanocomposite thin films

Though less frequently studied for solar-hydrogen production, films are more convenient to use than powders and can be easily recycled. Anatase TiO₂ films decorated with Ag nanoparticles are synthesized by a rapid, simple, and inexpensive method. They are used to cleave water to produce H₂ under UV light in the presence of methanol as a hole scavenger. A simple and sensitive method is established here to monitor the time course of hydrogen production for ultralow amounts of TiO₂. The average hydrogen production rate of Ag/TiO₂ anatase films is 147.9 ± 35.5 μmol/h/g. Without silver, it decreases dramatically to 4.65 ± 0.39 μmol/h/g for anatase TiO₂ films and to 0.46 ± 0.66 μmol/h/g for amorphous TiO₂ films fabricated at room temperature. Our method can be used as a high through-put screening process in search of high efficiency heterogeneous photocatalysts for solar-hydrogen production from water-splitting.     

Properties and H2 production ability of Pt photodeposited on the anatase phase transition of nitrogen-doped titanium dioxide

The effect of calcination temperature on the properties and H₂ production ability of nitrogen-doped (N-doped) titanium dioxide (TiO₂) photodeposited with 0.2 wt% Pt (platinum) was studied. The increase in crystallinity of pre-calcinated N-doped TiO₂ initiated at temperatures higher than 131 °C transformed the morphology from anomalous nanostructure to texture composed of nanoparticles and enhanced the specific surface areas. At 200-400 °C, the anatase peaks gradually became sharper and the visible light absorption region decreased due to the growth of crystallites and the decrease of N-doping content, respectively. Maximum H₂ production was reached when N-doped TiO₂ was calcined at 200 °C followed by Pt photodeposition. The maximum condition is brought about by the formation of textures consisting of nanoparticles and a broad absorption region, thus creating superior active sites for photocatalytic H₂ production.     

Optimisation of the electrochromic properties of Nb2O5 thin films produced by sol–gel route using factorial design

Electrochemical and electrochromical properties of oxide films are dependent on their microstructure and morphological properties. Thus, the effects of three preparation variables on the electrochemical and electrochromical properties of Nb₂O₅ thin films prepared by the Pechini method were investigated. In order to minimise the number of experiments, a factorial design 2³ was used. The effects of the following variables: CA/EG molar ratio, CA/[Nb] molar ratio and calcination temperature were evaluated. Films prepared with the resin composition CA/EG=1 : 4, CA/[Nb]=10 : 1 and calcined at 500°C, showed the highest values of intercalation charge, transmittance variation and coloration efficiency, 22 mC/cm², 84% and 23 cm² C⁻¹, respectively.     

Hierarchical Gd–La codoped TiO2 microspheres as robust photocatalysts

Robust Gd–La codoped TiO₂ microspheres with diameter of 2∼3 μm were successfully synthesized via a hydrothermal method using poly(ethylene glycol)-block–poly(propylene glycol)-block–poly(ethylene glycol) as a template. The photocatalytic activity of the Gd–La codoped TiO₂ microspheres evaluated by photodegrading methyl orange (MO) has been significantly enhanced compared to that of undoped TiO₂ microspheres. Ti⁴⁺ may substitute for La³⁺ and Gd³⁺ in the lattices of rare earth oxides to create abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and MO photodegradation. The formation of an exciton energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂ microspheres, resulting in robust photocatalysts. The results suggest that Gd–La codoped TiO₂ microspheres calcined at 350 °C are very promising for enhancing the photocatalytic activity of photocatalysts.     

Photocorrosion-less stable heterojunction photoanode for efficient visible-light driven solar hydrogen generation

In this work, a heterostructure CdS/TiO₂ nanotubes (TNT) photoelectrode is decorated with Ni nanoparticles (NPs) to enhance hydrogen generation via the photoelectrochemical method. Herein, we report a systematic study of the effect of Ni NPs heterostructure photoelectrode to improve light absorption and photoelectrochemical (PEC) performance. The fabricated photoelectrodes were evaluated for photoelectrochemical hydrogen generation under simulated sunlight. The optimized Ni/CdS/TNT photoelectrode exhibited an improved photocurrent density of 6.5 mA cm^?2 in poly-sulfide aqueous media at a low potential of 0 V. Owing to the enhanced photocurrent density, Ni NPs also played a significant role in improving the stability of the photoelectrode. The synergistic effect with semiconductor ternary junction incites the surface plasmon resonance (SPR) for light-harvesting to enhance photoelectrochemical hydrogen generation.     

Pt modified TiO2 nanotubes electrode: Preparation and electrocatalytic application for methanol oxidation

Pt nanoparticles decorated TiO₂ nanotubes (Pt/TiO₂NTs) modified electrode has been successfully synthesized by depositing Pt in TiO₂NTs, which were prepared by anodization of the Ti foil. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize their structures and properties. The Pt/TiO₂NTs electrode shows excellent electrocatalytic activity toward methanol oxidation reaction (MOR) in alkaline electrolyte without UV irradiation.     

Role of electronically coupled in situ grown silver sulfides (Ag2S) nanoparticles with TiO2 for the efficient photoelectrochemical H2 evolution

A solution-processed in situ grown synthesis method has been developed to grow electronically coupled silver sulfide (Ag₂S) nanoparticles (NPs) inside a titanium oxide (TiO₂) thin film. Taking the advantage of better charge transport between Ag₂S and TiO₂, this composite thin film has been utilized for electro-photocatalytic H₂ generation. This thin film growth requires three successive steps, including sol-gel derived ion-conducting thin film fabrication containing loosely bound light ion (Li⁺) followed by ion-exchange (with Li⁺↔Ag⁺) and subsequent sulfurization process. This entire solution-processed deposition technique is capable to fabricate cost-effective large area Ag₂S–TiO₂ thin film containing Ag₂S NPs ranging ~10–70 nm. Since, Ag₂S has a lower band gap and consider as a promising material for photoelectrochemical H₂ generation, therefore Ag₂S (NPs)-TiO₂ thin film is grown on three different substrates, including fluorine-doped tin oxide (FTO), FTO/TiO₂ (sol-gel), and FTO/TiO₂ (NPs) to fabricate photoanode for this study. A comparative photo-electrocatalytic measurement of these three different Ag₂S(NPs)-TiO₂ thin film coated photoanodes showed that sample on FTO/TiO₂ (NPs) substrate generate highest photocurrent of density ~50 mA cm⁻² at 0.5 V vs NHE in 1 M KOH solution which is three orders higher than pure TiO₂ and stable for more than 1.5 h, indicating it's excellent potential application for photoelectrochemical water splitting. The photocurrent generation of this Ag₂S–TiO₂ thin film is significantly higher than earlier reported Ag₂S–TiO₂ system, which is originated due to the reduced carrier recombination from electronically coupled Ag₂S/TiO₂ interface state of such in situ grown Ag₂S NPs.     

Kinetic study of oxygen reduction reaction and PEM fuel cell performance of Pt/TiO2-C electrocatalyst

The electrochemical activity and thermal stability of the Pt/TiO₂-C were evaluated in the oxygen reduction reaction (ORR) in acid medium at different temperatures. The platinum was selectively deposited onto the TiO₂ (E_bg = 2.3 eV) by the photo-irradiation of platinum precursor (Pt⁴⁺→Pt⁰). The Pt/TiO₂-C electrocatalyst prepared was characterized by XRD, TEM/EDS, cyclic and lineal voltammetry techniques. TEM images indicated that platinum nanoparticles (<5 nm) were deposited in agglomerates form around the oxide sites. EDS and XRD results confirm the composition and crystalline structure of Pt/TiO₂-C. The thermal stability and electrochemical activity of the Pt/TiO₂-C for ORR at different temperatures (298–343 K) is higher than Pt/C commercial sample (Pt-Etek). A more favorable apparent enthalpy of activation for Pt/TiO₂-C was greatly influenced by addition of oxide in the catalyst compare to Pt-Etek. Single H₂/O₂ fuel cell performance results of Pt/TiO₂-C show an improvement of the power density with the increase of the temperature.     

Synthesis of strontium chromate-nitrogen and sulfur co-doped graphene and its potential for electrochemical hydrogen storage

In the present study, monazite-type strontium chromate (SrCrO₄) as a ternary metal oxide was prepared by the sol-gel method. Nitrogen and sulfur co-doped graphene decorated with SrCrO₄ nanocrystals was synthesized successfully, and the electrochemical hydrogen storage performance of the SrCrO₄ and its relative nanocomposites also were investigated by chronopotentiometry (CHP) technique. The effect of doped graphene as a substrate of the SrCrO₄ sample on the improvement of the electrochemical hydrogen storage performance was considered as well. The SrCrO₄-nitrogen and sulfur co-doped graphene (SrCrO₄/NSG) displayed the highest discharge capacity in comparison to SrCrO₄-reduced graphene oxide (SrCrO₄/rGO), SrCrO₄ calcined at 1000 °C (SrCrO₄ (1000)) and SrCrO₄ calcined at 800 °C (SrCrO₄ (800)). Also, increasing the hydrogen storage capacity of the samples by repeating the cycles indicated the excellent cycle stability of the nanoparticles. In monazite-type structures, oxygen vacancies can be created by thermal treatment. Creating oxygen vacancies can improve redox reactions, which increase the conductivity of the samples and hydrogen storage capacity.     

Concentrated solar photocatalysis for hydrogen generation from water by titania-containing gold nanoparticles

Photocatalysis is an effective way to utilize solar energy to produce hydrogen from water. Au/TiO₂ nanoparticles (NPs) have a better performance in photocatalytic hydrogen generation because of the localized surface plasmon resonance (LSPR) effect of Au/TiO₂ NPs. In the photocatalytic hydrogen generation experiments, it was found that light intensity plays a key role in the photocatalytic reaction rate of Au/TiO₂ NPs. At a light intensity of 0–7 kW/m², the reaction rate has a super-linear law dependence on the light intensity (Rate ∝ Intensityⁿ, with n > 1). However, at a light intensity of 7–9 kW/m², the dependency becomes sub-linear (n < 1). This means that the increase rate of photocatalytic rate is smaller than that of light intensity when the light intensity exceeds 7 kW/m². In addition, the finite element method (FEM) was utilized to further elucidate the role of light intensity by calculating the absorption power and nearfield intensity mapping of a Au/TiO₂ nanoparticle. The variation trend of the calculated total absorption power agrees with the photocatalytic experimental results for different light intensities. These results shed light on the utilization of concentrated solar photocatalysis to increase the solar-to-hydrogen performance of Au/TiO₂ NPs.     

Investigation of IrO2 electrocatalysts prepared by a sulfite-couplex route for the O2 evolution reaction in solid polymer electrolyte water electrolyzers

IrO₂ electrocatalysts were prepared and electrochemically characterized for the oxygen evolution reaction in a Solid Polymer Electrolyte (SPE) electrolyzer. By using a sulfite complex-based preparation procedure, an amorphous iridium oxide precursor was obtained at 80 °C, which was, successively, calcined at different temperatures: 350 °C, 400 °C and 450 °C. A physico-chemical characterization was carried out by X Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray-photoelectron spectroscopy (XPS). The various IrO₂ catalysts were sprayed onto a Nafion 115 membrane with a loading of 2.5 mg cm⁻² to form the anode. A Pt/C catalyst (Pt loading 0.5 mg cm⁻²) was used as cathode. The best electrochemical performance was obtained for the cell based on the IrO₂ calcined at 350 °C. The maximum current density at high potentials (1.8  V) was about 1.75 A cm⁻². Accelerated time-tests at 2 A cm⁻² demonstrated a suitable stability of the IrO₂ calcined at 350 °C; however, the intrinsic stability appeared to increase with the calcination temperature. The sample calcined at 400 °C could represent a good compromise between performance and intrinsic stability.     

Electrocatalytic performance of TiO2 with different phase state towards V2+/V3+ reaction for vanadium redox flow battery

In this paper, titanium dioxide (TiO₂) nanoparticles were employed as catalysts towards V²⁺/V³⁺ redox couple of vanadium redox flow battery (VRFB). The effect of TiO₂ phase on the electrocatalytic performance for negative couple was systematically investigated. The electrochemical properties of TiO₂ with different phase were assessed via cyclic voltammetry and electrochemical impedance spectroscopy by using AB as conductive agent. Obtained from the results, anatase TiO₂ (α‐TiO₂) exhibits superior electrocatalytic activity to rutile TiO₂ (γ‐TiO₂). The VRFB cell performs well at discharge capacity, voltage efficiency, and energy efficiency by employing α‐TiO₂‐modified negative electrode with current density varying between 50 and 100 mA cm^?2. The discharge capacity of α‐TiO₂‐modified cell with vanadium ion concentration of 1.6 M comes up to 113.5 mA h at 100 mA cm^?2 current density, which is increased by 39.1 mA h after modification for negative electrode. Moreover, the corresponding energy efficiency increases by 7.5% after modification of α‐TiO₂. Experimental results show that TiO₂ is an ideal catalyst for VRFB. Moreover, α‐TiO₂ demonstrates superior electrocatalytic performance to γ‐TiO₂ towards V²⁺/V³⁺ reaction.