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.     

Photoelectrochemical water splitting on highly smooth and ordered TiO2 nanotube arrays for hydrogen generation

To improve the photoelectrochemical (PEC) water splitting efficiency for hydrogen production, we reported the fabrication of lotus-root-shaped, highly smooth and ordered TiO₂ nanotube arrays (TiO₂ NTs) by a simple and effective two-step anodization method. The TiO₂ NTs prepared in the two-step anodization process (2-step TiO₂ NTs) showed better surface smoothness and tube orderliness than those of TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). Under illumination of 100 mW/cm² (AM 1.5, simulated solar light) in 1 M KOH solution, water was oxidized on the 2-step TiO₂ NTs electrode with higher efficiency (incident-photon-to-current efficiency of 43.4% at 360 nm and photocurrent density of 0.90 mA/cm² at 1.23 V_RHE) than that on the 1-step TiO₂ NTs electrode. The effective photon-to-hydrogen conversion efficiency was found to be 0.18% and 0.49% for 1-step TiO₂ NTs and 2-step TiO₂ NTs, respectively. These results suggested that the structural smoothness and orderliness of TiO₂ NTs played an important role in improving the PEC water splitting application for hydrogen generation.     

A ternary Ag/TiO2/CNT photoanode for efficient photoelectrochemical water splitting under visible light irradiation

A ternary Ag/TiO₂/CNT photoanode was prepared by grafting Ag nanoparticles on the surface of as-synthesized TiO₂/CNT nanocomposite for the photoelectrochemical (PEC) water splitting under visible light irradiance. The ternary composite photoanode was observed to generate four times higher photocurrent density compared to binary TiO₂/CNT nanocomposite under visible light irradiance. The Ag nanoparticles on the surface of nanocomposite act as a surface plasmon resonance (SPR) photosensitizer under visible light. The enhanced photocurrent density of Ag/TiO₂/CNT ternary photoanode is attributed to the increased light absorption in the visible region, decrease in band-bending and effective interfacial electron transfer due to the synergetic effect of Ag nanoparticles and CNTs. The enhanced charge transfer within the Ag/TiO₂/CNT was also confirmed by the electrochemical impedance spectroscopy. This work demonstrates a feasible route to improve the PEC performance of TiO₂ towards water splitting under sunlight irradiation.     

Electrosynthesis of dendritic palladium supported on Ti/TiO2NTs/Ni/CeO2 as high-performing and stable anode electrocatalyst for methanol electrooxidation

Liquid-fueled direct methanol fuel cell (DMFC) is highly promising for low-carbon transportation, but is hindered by high cost and short lifespan of conventional Pt-based electrocatalysts. Herein, we propose a new Pt-free catalyst strategy to exploit high-performing and stable electrocatalyst of DMFC, achieving enhanced electrocatalytic activity and high stability for methanol oxidation reaction (MOR) in alkaline media. A new Pt-free anode catalysts consisting of titanium/reduced-titanium dioxide nanotubes/nickel/cerium dioxide (Ti/r-TiO₂NTs/Ni/CeO₂) nanosupport and uniformly-dispersed Pd dendrites is successfully prepared by a facile three-step electrodeposition route without applying any template or surfactant. Noticeably, the as-prepared Ti/r-TiO₂NTs/Ni/CeO₂–Pd as an anode electrode exhibits superior activity than commercial Pd/C and other electrodes. The obtained large mass activity for Ti/r-TiO₂NTs/Ni/CeO₂–Pd electrode is 1752 mA mg_Pd^?1 for MOR. After successive CV tests of 1000 cycles, Ti/r-TiO₂NTs/Ni/CeO₂–Pd electrode still retained 88.9% of its initial current. The superior performance of Ti/r-TiO₂NTs/Ni/CeO₂–Pd attributes to the large surface area and excellent conductivity, as well as the synergistic effects among nanosupport and Pd dendrites. Therefore, this study will open a new door for high-performance fuel cell applications.     

Facile synthesis of Ti3+ doped Ag/AgITiO2 nanoparticles with efficient visible-light photocatalytic activity

We successfully synthesized novel Ti³⁺ doped TiO₂ and Ti³⁺ doped Ag/AgITiO₂ nanoparticles with efficient visible-light photocatalytic activity for hydrogen production by facile one-step solvothermal method. The as-prepared Ti³⁺ doped TiO₂ nanoparticles displayed excellent visible-light absorption and visible-light driven hydrogen production activity (115.3 μmol g^?1 h^?1), while the commercial TiO₂ had no visible-light response. Moreover, the as-prepared Ti³⁺ doped Ag/AgITiO₂ nanoparticles in this experiment showed highly enhanced visible-light absorption and efficient visible-light driven activity for hydrogen (571.0 μmol g^?1 h^?1), which was 4.95 times as high as that of the as-prepared TiO₂ nanoparticles. And the surface areas of the as-prepared TiO₂ and Ti³⁺ doped Ag/AgITiO₂ catalysts were up to 138.829 m² g^?1 and 102.988 m² g^?1, much higher than that of the commercial TiO₂ (55.516 m² g^?1). Finally, the visible-light photocatalytic mechanism of the Ti³⁺ doped Ag/AgITiO₂ nanoparticles for hydrogen generation was also proposed in detail.     

Direct formation of dendritic Ag catalyst on a gas diffusion layer for electrochemical CO2 reduction to CO and H2

Dendritic Ag (a CO₂-to-CO reduction catalyst) has been synthesized on carbon paper (CP) using pulse electrodeposition to fabricate a gas diffusion electrode. A combination of sonication and pulse deposition facilitated mass transfer of Ag ions to the CP, enlarging the catalyst active surface area without significantly changing the Ag crystalline structure. The current density of CO₂ reduction was proportional to the surface area of dendritic Ag. Further improvements in performance were achieved by adding polyethylene glycol to the CO₂ reduction cell catholyte that removed the CO gas bubbles produced at the electrode surface. The fabrication methods presented herein suggest an effective gas diffusion electrode for application in the membrane-electrode-assembly-type single cell for electrochemical CO₂ reduction.     

Effect of anodization voltage on performance of TiO2 nanotube arrays for hydrogen generation in a two-compartment photoelectrochemical cell

Highly ordered TiO₂ nanotube arrays were prepared by anodic oxidation of Ti foil under different anodization voltages in ethylene glycol electrolyte. The morphology and photoelectrochemical performance of the TiO₂ nanotubes (NTs) samples were characterized by FESEM and electrochemical working station. Hydrogen production was measured by splitting water in the two-compartment photoelectrochemical (PEC) cell without any external applied voltage or sacrificial agent. The results indicated that anodization voltage significantly affects morphology structures, photoelectrochemical properties and hydrogen production of TiO₂ NTs. The pore diameter and layer thickness of TiO₂ samples increased linearly with the anodization voltage, which led to the enhancement of active surface area. Accordingly, the photocurrent response, photoconversion efficiency and hydrogen production of TiO₂ nanotubes were also linearly correlated with the anodization voltage.     

Flexible TCO-free counter electrode for dye-sensitized solar cells using graphene nanosheets from a Ti–Ti(III) acid solution

A rapid and simple route to synthesize highly conductive graphene-based nanosheets for use as a flexible counter electrode in dye-sensitized solar cells is presented. The flexible counter electrode is free of transparent conductive oxide layer, i.e., TCO-free. A clean graphene with high quality is obtained by the chemical reduction of graphene oxide (GO) using titanium metallic powders in a hydrochloric acid solution. The Ti⁺³ ions that dissociated from metallic Ti particles in a hydrochloric acid solution result in a clean graphene material with no formation of TiO₂ nanoparticles, which are always present on graphene when only Ti⁺³ ions are used for the reduction, i.e., an anatase TiO₂ nanoparticle by-product will be always left on the graphene product when not using metallic Ti particles. The chemical reaction mechanisms for these differences are revealed in this report. The reduced materials are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, thermo-gravimetric analysis, Fourier transform infrared spectrometry, UV–vis spectroscopy and X-ray photoelectron spectroscopy. The four-point probe method is also employed to characterize the surface conductivity of the graphene films. This high quality graphene film exhibits comparable or better performance than those obtained using conventional sputtered Pt counter electrode when used as a flexible counter electrode of dye-sensitized solar cells.     

Pt nanoparticles supported on titanium iron nitride nanotubes prepared as a superior electrocatalysts for methanol electrooxidation

Titanium iron nitride (Ti_0.95Fe_0.05N) supports with one-dimensional (1D) hollow and porous nanotubes(Ti_0.95Fe_0.05N NTs)are prepared by a two-step method, including hydrothermal method followed post-nitriding treatment. Pt nanoparticles (NPs) are further supported on Ti_0.95Fe_0.05N NTs for methanol electrooxidation. The experimental results reveal that the prepared material is Ti_0.95Fe_0.05N NTs with high purity, and this support is characterized by a porous tubular structure with hollow walls and large specific surface area. The X-ray photoelectron spectroscopy (XPS) pattern shows the strong interaction between the robust Ti_0.95Fe_0.05N NTs support and uniform Pt NPs catalyst. In addition, the electrochemical data demonstrate that Ti_0.95Fe_0.05N NTs loaded Pt NPs (Pt/Ti_0.95Fe_0.05N) display greatly improved activity and stability than that of Pt/C catalyst. The significantly enhanced durability of the hybrid electrocatalysts and electrochemical surface area (ECSA) preservation of the catalyst are observed after the accelerated durability test (ADT). The experimental data verify that the introducing of Fe can tune the electronic structure of Pt atoms, which contributes to the strengthened activity and stability of the Pt catalyst for the methanol oxidation reaction.     

Photoelectrochemical water splitting with black Ni/Si-doped TiO2 nanostructures

Black Ni/Si-doped TiO₂ nanostructures were successfully fabricated through electrochemical anodization of Ti–1Ni–5Si alloy and Sn-reduction treatment. After Sn-reduction treatment, the band gap of Ni/Si-doped TiO₂ became much smaller compared to other samples, which can be attributed to the synergetic effect of Ni/Si doping and the large quantity of Ti³⁺/oxygen vacancy species induced by Sn-reduction treatment. The black Ni/Si-doped TiO₂ nanostructures exhibited a remarkable enhancement in the photoelectrochemical (PEC) water splitting in comparison with the pure TiO₂ and Ni/Si-doped TiO₂. The highest photocurrent reached 2.15 mA/cm² (at 0 V versus Ag/AgCl), corresponding to a conversion efficiency (~1.10%) which was 5.8 times that of the pure TiO₂ nanotubes. The first-principles calculations using density-functional theory (DFT) showed that ion doping and self-doped Ti³⁺ defect levels in the forbidden gap induced through Sn-reduction treatment could improve the mobility of photogenerated carriers and suppress charge recombination, which was in well agreement with the experimental results.     

Photo-induced CO2 reduction by hydrogen for selective CO evolution in a dynamic monolith photoreactor loaded with Ag-modified TiO2 nanocatalyst

Ag-promoted TiO₂ nanoparticles immobilized over the cordierite monolithic support for dynamic and selective photo-reduction of CO₂ to CO by the use of hydrogen has been investigated. Ag-loaded TiO₂ NPs synthesized by a facile sol–gel method were coated over the monolith channels by dip-coating method. The samples were characterized by XRD, Raman, FTIR, SEM, TEM, XPS, N₂ adsorption–desorption, UV–Vis and PL spectroscopy. The photo-activity test of Ag-modified TiO₂ NPs was conducted for dynamic photocatalytic CO₂ reduction with H₂ as a reductant via a reverse water gas shift (RWGS) reaction in a cell type and monolith photo-reactors. Using 5 wt. % Ag/TO₂ NPs, CO₂ was energetically converted to CO with a yield rate 1335 μmole g-catal.^?1 h^?1, a 111 fold-higher than the amount of CO produced over the pure TiO₂ catalyst. More importantly, photo-activity of Ag/TiO₂ catalyst for CO evolution can be improved by 209 fold using monolith photo-reactor than the cell type reactor under the same operating conditions. This enactment was evidently due to the efficient light harvesting with larger illuminated surface area inside monolith micro-channels and efficient charges separation in the presence of Ag-metal. The reusability of Ag/TiO₂ NPs loaded over the monolithic support showed favorable recycling capability than the catalyst dispersed in a cell reactor. A possible reaction mechanism for this observation has been discussed in detail.     

Test of conductor and semiconductor electrocatalysts in high voltage alkaline electrolyzer as production media for green hydrogen

Despite the restricted success of conductor and semiconductor electrodes in solving hydrogen production problems, they provide a promising alternative to expensive conventional electrodes in water electrolysis investigations. Titanium dioxide (TiO₂) and silver (Ag) are widely used as photocatalysts in water splitting systems for hydrogen generation. Though TiO₂ is an inactive chemical semiconductor with poor conductivity, it has not been entirely investigated as an electrocatalyst yet. Two criteria were used to achieve this target: supplying high voltage to overcome the TiO₂ large band gap and immersing it in an alkaline solution to activate its inert surface. For comparison study, Ag noble metal nanoparticles coating was employed as a competitive electrocatalyst. In this regard, the application of Ag and TiO₂ coated on Ti electrodes in a hydrogen production system operated under high voltage was reported. The nanoparticles were synthesized using cost-effective and simple methods based on UV-deposition for Ag nanoparticles and the chemical precipitation method for TiO₂ nanoparticles. Then the synthesized nanoparticles were deposited on the Ti electrodes by simple immersion. The synthesized nanoparticles and coated electrodes were tested by XRD, SEM, and EDS to study their morphology, structure, particle size, and surface composition. Based on these results, TiO₂ nano-powder and coated electrodes exhibited homogenous spheres with a mixture of rutile and anatase phases, the majority being the anatase phase. The Ag-coated Ti substrate possessed a smaller crystallite size compared to TiO₂ coated substrate. To evaluate the performance of Ag/Ti and TiO₂/Ti electrodes toward hydrogen production, H₂ flow rates were measured in a 3.6 M KOH electrolytic solution at 6 V. Hydrogen flow rates obtained for pure Ti, Ag, and TiO₂ electrodes at a steady state were 21, 35, and 37 SCCM (standard cm³/min), respectively. Also, it was found that energy consumption was reduced when the electrodes were coated with nanoparticles. Furthermore, the electrolyzer's performance was assessed by calculating the hydrogen production efficiency and the voltage efficiency. The results showed that using TiO₂ electrodes gave the best hydrogen production and voltage efficiencies of 27% and 23%, respectively. This study brings new insights about Ag and TiO₂ coated electrodes in alkaline water electrolysis at high voltage regarding nanoparticle performance, hydrogen production, system performance, and energy consumption. In addition, minimizing the fabrication and operation costs of hydrogen production is the major enabler for the broad commercialization of water electrolysis devices.     

Self-doped Ti@TiO2 visible light photocatalyst: Influence of synthetic parameters on the H2 production activity

Self-doped TiO₂ shows visible light photocatalytic activity, while pristine TiO₂ is only UV responsive. Ti³⁺ has been demonstrated to be responsible for this improvement. We systematically studied various experimental parameters, such as the amount of reducing agent imidazole, types of imidazoles and Ti sources, and determined effects of these parameters on the combustion process and final materials. The phase composition, Ti³⁺ concentration, light absorption, surface area, and crystallinity of the product are significantly affected by the amount of imidazoles. Through comparing different imidazoles, we found that only flammable/combustible imidazoles are able to convert Ti⁴⁺ into Ti³⁺. This result is very helpful in understanding the mechanism and reactions in combustion process. Titanium precursors also have a great influence in production of Ti³⁺ doped TiO₂ materials. Titanium alkoxides allow the successful synthesis of blue partially reduced TiO₂, while TiCl₄ only lead to white pristine TiO₂.     

Building three-dimensional Pt catalysts on TiO2 nanorod arrays for effective ethanol electrooxidation

Pt nanoparticles on TiO₂ nanorod arrays have been prepared and used for the electrooxidation of ethanol in acidic and alkaline media. The vertically aligned TiO₂ nanorod arrays provide a three-dimensional frame for supporting Pt nanoparticles. FESEM and TEM show that the Pt nanoparticles about 3 nm in diameter are evenly distributed on the surface of TiO₂ nanorods. Cyclic voltammetry and chronoamperometry are performed to investigate electrochemical properties of Pt/TiO₂/Ti, Pt/C, and Pt/Ti electrocatalysts. The Pt/TiO₂/Ti electrocatalyst shows better catalytic activity and higher catalytic stability compared with other electrocatalysts.     

Composite sodium p-toluenesulfonate/polypyrrole/TiO2 nanotubes/Ti anode for sodium ion battery

Composite sodium p-toluenesulfonate/polypyrrole/TiO₂ nanotubes/Ti was designed and synthesized for sodium ion battery anode via facile electrochemical methods. The obtained composite sodium p-toluenesulfonate/polypyrrole/TiO₂ nanotubes/Ti (TsONa/PPy/TiO₂NT/Ti) electrode was investigated in terms of SEM, EDX, FTIR, galvanostatic charge/discharge and AC impedance. As expected, the composite TsONa/PPy/TiO₂NT/Ti electrode displayed higher electrochemical performances than the bare TiO₂NT/Ti electrode. For example, the reversible capacity after 50 cycles was still as high as about 200 mAh/g, higher than 170 mAh/g of TiO₂NT/Ti electrode. High Na-storage activities of both TiO₂NT and TsONa/PPy, high conductivity of TsONa-doped PPy and the synergy effect among the various components may be responsible for the improved electrochemical performances.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

Investigation of plasmonic Cu with controlled diameter over TiO2 photoelectrode for solar-to-hydrogen conversion

Plasmonic metal nanoparticles (NPs) have been used to improve the solar-to-hydrogen conversion efficiency. Relative to Au and Ag, Cu is cheaper and more abundant. In the present work, Cu NPs with the controlled diameter were deposited on TiO₂ nanotube arrays (TNTAs) by using a pulse electrochemical deposition method. When the deposition was cycled 3600 times, the size of Cu NPs can be tuned to approximately 30 nm with the most uniform distribution, resulting in the remarkable characteristic peak of surface plasmon resonance and higher photocurrent density. The hydrogen production rates remained unchanged during irradiation (AM 1.5, 100 mW/cm²) of 2 h, indicating a good stability of the resultant Cu/TNTAs electrode. The photoelectrochemical performances of as-prepared Cu/TNTAs can also be comparable to those of Ag/TNTAs electrode fabricated by the same method.     

Hydrogen adsorption properties of Ag decorated TiO2 nanomaterials

In this work, we present the synthesis of Ag doped TiO₂ materials. The products are characterized by powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption, and hydrogen adsorption. The Ag/TiO₂ materials exhibit 3.65 times higher in hydrogen adsorption capability compared with the non-doped TiO₂ materials thank to the existence of Ti³⁺ species, which are Kubas-type hydrogen adsorption centers, and the Ag nanoparticles which provide spillover effects. We believe that this is the first time that both Kubas-type adsorption and spillover are exploited in the design of novel hydrogen storage materials.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.     

Modification of the photocatalytic properties of self doped TiO2 nanoparticles for hydrogen generation using sunlight type radiation

Synthetic approaches/methodologies can change the properties of nanoparticles significantly. In this study, the photocatalytic property of self (Ti³⁺) doped TiO₂ nanoparticles was modified by synthesizing through different routes. Solvothermal (T-Sol), sonochemical (T-Son) and polyol (T-Pol) methods were employed to prepare TiO₂ nanoparticles and the photocatalytic activities of these samples were compared with that of the sample prepared by precipitation using ammonia solution (T-Ppt). All samples had particle size below 30 nm except T-Son, where small nanoparticles existed as large spherical agglomerates with size around 500 nm. Surface area and porosity measurements of these different TiO₂ samples showed a significant dependency on the synthesis method. UV–Visible absorption spectra showed the onset of absorption at ∼440 nm for all samples due to the presence of defect levels originating from anion vacancies. Photocatalytic activity for hydrogen generation decreased in the order T-Sol > T-Son > T-Pol > T-Ppt and the observed activity is correlated with their physical properties such as surface area and crystallinity. The hydrogen yield was highly enhanced by the addition of Pd metal as co-catalyst on the surface of TiO₂ photocatalysts. Present experiments clearly demonstrate the importance of synthesis route to improve the photocatalytic activity of TiO₂.