TiO2 nanotubes modified with electrochemically reduced graphene oxide for photoelectrochemical water splitting

The photocatalytic water splitting into hydrogen and oxygen using solar light is a promising method to provide clean energy carriers in the future. Herein we report on an experimental investigation of TiO₂ nanotubes (NTs) modified with electrochemically reduced graphene oxide (ERGO) for photoelectrochemical water splitting. A photocurrent density of 1.44 mA cm⁻² at 1.23 V vs. RHE has been achieved for ERGO–TiO₂ NTs photoanode under standard reporting conditions, i.e., simulated AM 1.5G sunlight (intensity 100 mW cm⁻²), which is notably increased by ∼140% compared to the bare TiO₂ NTs. This efficiency is nearly ten times higher than that of the P25 nanoparticles based device. The enhanced photocurrent densities can be attributed to the reduced graphene oxide and Ti^{3 +} self-doping produced by an electrochemical reduction treatment. The ERGO modified photoanodes show excellent stability during light soaking under full sunlight.     

Novel one-step preparation of tungsten loaded TiO2 nanotube arrays with enhanced photoelectrocatalytic activity for pollutant degradation and hydrogen production

Highly ordered tungsten doped TiO₂ nanotube arrays (W-TiO₂NTs) were prepared in glycerol/fluoride electrolyte solution containing sodium tungstate via the electrochemical oxidation of a Ti substrate. The resulting arrays were characterized by XRD, SEM, and XPS. The 15 mM W-TiO₂NTs exhibited better photoelectrochemical activity than the TiO₂NTs and W-TiO₂NTs fabricated using other W concentrations under Xe illumination. The W ion was successfully introduced into the TiO₂ crystal lattice in the W^6 + form according to the XPS analysis, which enhanced the photoelectrocatalytic activity of the W-TiO₂NTs, as indicated by the efficient removal of Rhodamine B and the production of hydrogen.     

The effects of substitution on the electrochemical reduction of naphthacenetetrone in N,N-Dimethylformamide

The polarographic reduction of 5,6,11,12-naphthacenetetrone (NT) and several of its chloromethyl, and nitro derivatives were investigated. The electrochemical behavior of NT was compared with 6, 11-dihydroxy-5, 12-naphthacencequinone (DHNQ) previously studied. Like DHNQ, NT exhibits two reduction waves in N,N-dimethylformamide. However, two additional post adsorption waves which were not present in DHNQ reduction were also observed. The first step reduction of NT, representing the formation of the radical anion NT^?, has a potential (0.01 V vs sce) much more anodic than that of its DHNQ counterpart ( ?0.75 V vs sce). The substituent effects of NTs were noted. A linear Hammett relationship similar to that of the DHNQ series was also found for the NTs. In both cases, the averaged values of σ_meta and σ_para were used as the substituent constants     

SnO2–graphene–carbon nanotube mixture for anode material with improved rate capacities

SnO₂–graphene–carbon nanotube (SnO₂–G–CNT) mixture is synthesized using graphene oxide as precursor for application as anode material in rechargeable Li ion batteries. It is shown that the SnO₂ nanoparticles of 3–6 nm in diameter are not only attached onto the surface of graphene sheets by anchoring with surface functional groups, but they also are encapsulated in pore channels formed by entangled graphene sheets. The incorporation of carbon nanotubes reduces the charge transfer resistance of the anode made from the mixture through the formation of 3D electronic conductive networks. The SnO₂–G–CNT anodes deliver remarkable capacities of 345 and 635 mAh g⁻¹ at 1.5 and 0.25 A g⁻¹, respectively. Flexible electrodes consisting of highly-aligned SnO₂–G–CNT papers are also prepared using a simple vacuum filtration technique. They present a stable capacity of 387 mAh g⁻¹ at 0.1 A g⁻¹ after 50 cycles through the synergy of the high specific capacity of SnO₂ nanoparticles and the excellent cycleability of G–CNT paper.     

High-efficiency photoelectrochemical performance of PbS nanoparticles sensitized TiO2 nanotube arrays

TiO₂ nanotube arrays sensitized by PbS nanoparticles (TiO₂ NTs/PbS) with enhanced visible-light activity were synthesized by a two-step approach including an electrochemical anodization technique followed by an in situ photodeposition approach. The structural investigations indicated that PbS nanoparticles grew uniformly on the walls of the TiO₂ NTs. The TiO₂ NTs/PbS exhibited more excellent photoelectrochemical properties than that of the TiO₂ NTs under visible-light irradiation. The enhanced photoelectrochemical activity of the TiO₂ NTs/PbS could be attributed to the improvement of visible-light absorption and charge separation derived from the coupling effect of the PbS nanoparticles and TiO₂ NTs.     

TiO2-graphene nanocomposite for electrochemical sensing of adenine and guanine

TiO₂-graphene nanocomposite was prepared by hydrolysis of titanium isopropoxide in colloidal suspension of graphene oxide and in situ hydrothermal treatment. It provides an efficient and facile approach to yield nanocomposite with TiO₂ nanoparticles uniformly embedded on graphene substrate. The electrochemical behavior of adenine and guanine at the TiO₂-graphene nanocomposite modified glassy carbon electrode was investigated. The results show that the incorporation of TiO₂ nanoparticles with graphene significantly improved the electrocatalytic activity and voltammetric response towards these species comparing with that at the graphene film. The TiO₂-graphene based electrochemical sensor exhibits wide linear range of 0.5–200 μM with detection limit of 0.10 and 0.15 μM for adenine and guanine detection, respectively. The excellent performance of this electrochemical sensor can be attributed to the high adsorptivity and conductivity of TiO₂-graphene nanocomposite, which provides an efficient microenvironment for electrochemical reaction of these purine bases.     

Nanoflower-like CdS and SnS2 loaded TiO2 nanotube arrays for photocatalytic wastewater treatment and hydrogen production

In this work, nanoflower-like CdS/SnS₂/TiO₂ NTs ternary heterojunction photocatalysts were synthesized by a hydrothermal method, the relationship between the morphology, microscopic morphology, crystallinity, elemental presence state and hydrogen production performance of the ternary photocatalysts were investigated by SEM, TEM, XRD and XPS, respectively. The photocatalytic performance, electrochemical property and hydrogen production capacity of CdS/SnS₂/TiO₂ NTs were compared with pure TiO₂ NTs, CdS/TiO₂ NTs and SnS₂/TiO₂ NTs. After 2 h of photocatalytic reaction, the removal efficiency of MB wastewater reached 100%, and the photocatalytic efficiencies toward RhB and Cr(VI) removal reached 86.08% and 80.93% after 3 h, respectively. The electron spin resonance (ESR) technique certified the active radical groups that played a role in the catalytic process and further investigated the possible photocatalytic mechanism. Hydrogen production per unit time achieved 97.14 μmol h^?1 cm^?2, this work provides the new technique to achieve solar energy conversion for hydrogen generation.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

Increasing of Photocatalytic Performance of TiO2 Nanotubes by Doping AgS and CdS

Highly ordered titanium nanotubes (TiO₂ NTs) photocatalyst was prepared by the anodic oxidation method, and AgS, CdS, and AgS/CdS nanoparticles were doped on the surface of TiO₂ NTs by the successive ion adsorption and reaction (SILAR) method. The photocatalysts were characterized by SEM, EDS, XRD, and potentiostat system. The SEM and EDS analyses respectively show that the average outer diameter of prepared photocatalysts is in the range of 50–120?nm, and the presence of Ti, O, Ag, and Cd is successfully proved. The photocatalytic properties of TiO₂ NTs and doped TiO₂ NTs were studied by measuring the degradation of Methylene Blue (MB) solution. The experimental results show that AgS/CdS/TiO₂ photocatalyst exhibited most efficient photocatalytic activity with 340?µA/cm² photocurrent value. AgS/CdS/TiO₂ NTs photocatalyst shows up to 22.20% higher than TiO₂ NTs, 16.42% higher than CdS/TiO₂ NTs, and 4.3% higher than AgS/TiO₂ NTs.     

Improved activity of a graphene–TiO2 hybrid electrode in an electrochemical supercapacitor

We present a simple and fast approach for the synthesis of a graphene–TiO₂ hybrid nanostructure using a microwave-assisted technique. The microstructure, composition, and morphology were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, Raman microscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. The electrochemical properties were evaluated using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. Structural analysis revealed a homogeneous distribution of nanosized TiO₂ particles on graphene nanosheets. The material exhibited a high specific capacitance of 165 F g⁻¹ at a scan rate of 5 mV s⁻¹ in 1 M Na₂SO₄ electrolyte solution. Theenhanced supercapacitance property of these materials could be ascribed to the increased conductivity of TiO₂ and better utilization of graphene. Moreover, the material exhibited long-term cycle stability, retaining ∼90% specific capacitance after 5000 cycles, which suggests that it has potential as an electrode material for high-performance electrochemical supercapacitors.     

Binder-free combination of graphene nanosheets with TiO<Subscript>2</Subscript> nanotube arrays for lithium ion battery anode

Binder-free combination of graphene nanosheets with oriented TiO₂ nanotube arrays was designed and achieved via one-step facile electrodeposition. The structure and morphology of as-prepared composite graphene nanosheets/TiO₂ nanotube arrays were studied in terms of SEM, FESEM, EDX, TEM, Raman and FTIR. Furthermore, the corresponding electrochemical performances were evaluated in terms of galvanostatic charge/discharge, cycle stability and AC impedance. As expected, the composite graphene nanosheets/TiO₂ nanotube arrays displayed higher discharge capacity, cycle stability and Li⁺ diffusion coefficient than bare TiO₂ nanotube arrays. High Li-storage activity, superior conductivity and large surface area of graphene nanosheets should be responsible for improved electrochemical performances.     

Fabrication of plasmonic Au/TiO2 nanotube arrays with enhanced photoelectrocatalytic activities

Uniformly dispersed Au nanoparticles (NPs) deposited on the surface of highly ordered TiO₂ nanotube arrays (Au/TiO₂ NTs) were synthesized through a two-step process including anodization method and microwave-assisted chemical reduction route. The investigation indicated that Au NPs grew uniformly on the walls of TiO₂ NTs. Au/TiO₂ NTs exhibited excellent visible light absorption due to the LSPR effect of Au NPs. Au/TiO₂ NTs exhibited much higher photocurrent density and the photoconversion efficiency of Au decorated TiO₂ NTs was about 2.05 times greater than that of bare TiO₂ NTs. Besides, the PL intensity of Au/TiO₂ NTs was much lower than that of TiO₂ NTs, revealing a decrease in charge carrier recombination. The prepared Au/TiO₂ NTs exhibited superior photoelectrocatalytic activity and stability in the degradation of MB under simulated solar light irradiation. The synergy effect between nanotubular structures of TiO₂ and uniformly dispersed Au nanoparticles, as well as the small bias potential and strong interaction between Au and TiO₂, facilitated the Au plasmon-induced charge separation and transfer, which lead to highly efficient and stable photoelectrocatalytic activity.     

High performance PPO/Ti3+/TiO2NT membrane/electrode for lithium ion battery

In order to improve the electrical conductivity and electrochemical performances of lithium ion battery, the electrodeposition of poly(phenylene oxide) (PPO) on Ti³⁺-doped TiO₂ nanotube arrays (Ti³⁺/TiO₂NT) was designed and achieved via self-doping of Ti³⁺ and the following electropolymerization of phenol monomers. The as-synthesized PPO/Ti³⁺/TiO₂NT membrane/electrode was investigated in terms of SEM, EDX, XPS, galvanostatic charge/discharge, cycle voltammetry (CV) and AC impedance. As expected, PPO film indeed grew onto the surface of Ti³⁺/TiO₂NT electrode via one-step electrodeposition; furthermore, PPO/Ti³⁺/TiO₂NT membrane/electrode delivered satisfactory rate performances and cycle stability, mainly attributed to the joint contributions from higher electrical conductivity of Ti³⁺/TiO₂NT electrode and the synergy effects between Ti³⁺/TiO₂NT electrode and loose PPO film.     

Fabrication and characterization of copper doped TiO2 nanotube arrays by in situ electrochemical method as efficient visible-light photocatalyst

Highly ordered copper doped TiO₂ nanotube arrays (CuTiO₂NTs) thin-film were prepared in an aqueous solution containing NH₄F and different concentrations of copper nitrate via the electrochemical oxidation of titanium substrates. The resulting nanotubes were characterized by FE-SEM, XRD, XPS and EDX. The CuTiO₂NTs showed a tube diameter of 40–90 nm and wall thickness of 20–30 nm. Diffuse reflectance spectra showed a shift toward longer wavelengths relative to pure TiO₂ nanotubes (TiO₂NTs). The visible light photo-catalytic activity of the CuTiO₂NTs electrodes was evaluated by the removal of methylene blue (MB) dye and the production of hydrogen. The results showed that CuTiO₂NTs samples exhibited better photo-catalytic activity than the TiO₂NTs. This work demonstrated a feasible and simple anodization method to fabricate an effective, reproducible, and inexpensive visible-light-driven photo-catalyst for hydrogen evolution and environmental applications.     

Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells

This study employed a solution-based method to prepare a 3-D hybrid material comprising graphene and acid-treated multi-walled carbon nanotubes (MWCNTs). The adsorption of MWCNTs on graphene reduces the π–π interaction between graphene sheets resulting from steric hindrance, providing a subsequent reduction in aggregation. Optimal proportions of MWCNTs to graphene (2:1) enabled the even distribution of individual MWCNTs deposited on the surface of the graphene. The hybrid 3-D material was incorporated within a TiO₂ matrix and used as a working electrode in dye-sensitized solar cells (DSSCs). The hybrid material provides a number of advantages over electrodes formed of either MWCNTs or graphene alone, including a greater degree of dye adsorption and lower levels of charge recombination. In this study, DSSCs incorporating 3-D structured hybrid materials demonstrated a conversion efficiency of 6.11%, which is 31% higher than that of conventional TiO₂-based devices.     

Hydrothermal preparation of Sn3O4/TiO2 nanotube arrays as effective photocatalysts for boosting photocatalytic dye degradation and hydrogen production

The efficient TiO₂ NTs/Sn₃O₄ photocatalysts were synthesized by the hydrothermal deposition of Sn₃O₄ on TiO₂ nanotube arrays (TiO₂ NTs), and the morphology, microstructure and photocatalytic property were adjusted by changing the alkali kind. The TiO₂ NTs/Sn₃O₄ prepared with NaOH exhibited the outstanding photoelectric conversion and photocatalytic environment remediation/H₂ evolution. The methylene blue (MB) dye and Cr(VI) could be removed by the as-prepared photocatalysts under visible light irradiation, and ?O₂^?/?OH radicals were the main active species for MB photodegradation. Furthermore, the high photocatalytic H₂ evolution rate was as high as 6.49 μmol cm^?2 h^?1. The outstanding photocatalytic activity and stability of TiO₂ NTs/Sn₃O₄ photocatalysts would exhibit attractive prospect in the wastewater remediation and electric energy/hydrogen generation.     

Preparation and electrochemical characterization of MnOOH nanowire–graphene oxide

MnOOH nanowire–graphene oxide composites are prepared by hydrothermal reaction in distilled water or 5% ammonia aqueous solution at 130 °C with MnO₂–graphene oxide composites which are synthesized by a redox reaction between KMnO₄ and graphene oxide. Powder X-ray diffraction (XRD) analyses and energy dispersive X-ray analyses (EDAX) show MnO₂ is deoxidized to MnOOH on graphene oxide through hydrothermal reaction without any extra reductants. The electrochemical capacitance of MnOOH nanowire–graphene oxide composites prepared in 5% ammonia aqueous solution is 76 F g⁻¹ at current density of 0.1 A g⁻¹. Moreover, electrochemical impedance spectroscopy (EIS) suggests the electrochemical resistance of MnOOH nanowire–graphene oxide composites is reduced when hydrothermal reaction is conducted in ammonia aqueous solution. The relationship between the electrochemical capacitance and the structure of MnOOH nanowire–graphene oxide composites is characterized by cyclic voltammetry (CV) and field emission scanning electron microscopy (FESEM). The results indicate the electrochemical performance of MnOOH nanowire–graphene oxide composites strongly depends on their morphology.     

Microwave-assisted synthesis of Ag–TiO2/graphene composite for hydrogen production under visible light irradiation

Novel photocatalysts based on silver (Ag), TiO₂, and graphene were successfully synthesized by microwave-assisted hydrothermal method. The prepared photocatalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The influence of silver loading and graphene incorporation on photocatalytic hydrogen (H₂) production of as-prepared samples was investigated in methanolic aqueous solution under visible light irradiation (λ≥420 nm). The results showed that Ag–TiO₂/graphene composite had appreciably enhanced photocatalytic H₂ production performance under visible light illumination compared to pure TiO₂, Ag–TiO₂ and TiO₂/graphene samples. The enhanced photocatalytic hydrogen production activity of Ag–TiO₂/graphene composite under visible light irradiation could be attributed to increased visible light absorption, reduced recombination of photogenerated charge carriers and high specific surface area. This novel study provides more insight for the development of novel visible light responsive TiO²⁻ graphene based photocatalysts for energy applications.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Hydrothermal deposition of AgCl/AgBr co-sensitizers to modify TiO2 NTs for enhanced photocatalytic performance

AgCl/AgBr co-sensitizers were prepared on TiO₂ nanotube arrays (TiO₂ NTs/AgCl/AgBr) by the hydrothermal method. The composition, morphology, optical absorption, photoelectric and photoelectrocatalytic (PEC) performances of TiO₂ NTs/AgCl/AgBr were influenced by the concentration ratio of KCl/KBr. The investigation results revealed that the TiO₂ NTs/AgCl/AgBr photocatalyst exhibited dramatically strong visible light absorption and outstanding photoelectrochemical capacity. The photoelectrode produced high visible light surface photovoltage (-0.43 V), transient photocurrent (0.47 mA/cm²) and carrier concentration (4.39 × 10²⁰ cm^-3). The sample also showed high PEC activity in the organic dye and Cr(VI) removal, and the photocatalytic mechanism and charge carrier transfer path were described based on PEC results. The investigation would offer prospective insight to the sensitization of TiO₂ NTs, which would result in extensive attraction in the preparation and application of semiconductor materials as photoelectrodes and photocatalysts with superior photoelectrochemical performances.