Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.     

Phase analysis in Zn1− x Cr x O through charge density

Cr-doped zinc oxide Zn_{1? x} Cr _x O powder samples are synthesized by a standard high-temperature solid-state reaction technique with x?=?0.00, 0.04, and 0.08. The powders are analyzed for the electron densities using X-ray diffraction. The electron densities of observed wurtzite phase ZnO as well as the spinel phase ZnCr₂O₄ are mapped and analyzed for Cr doping concentration. The charge density study reveals that the Cr atom is added in the lattice as Cr³⁺ rather than Cr²⁺.     

Structural studies of Cr-doped mullite derived from single-phase precursors

Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr₂O₃ using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and b (Δc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr₂O₃). A second phase, namely θ-(Al,Cr)₂O₃, was revealed by XRD in the sample containing 9.60 wt% Cr₂O₃. The structure of mullites was refined by the Rietveld method, location of Cr³⁺ was performed by the EPR spectroscopy. At low chromium doping level (Cr₂O₃ content less than ∼5 wt%) Cr³⁺ ions were substituted for Al³⁺ in the AlO₆ octahedra of the mullite structure (M1 site). For higher doping level, Cr³⁺ ions were additionally substituted for Al³⁺ in the AlO₆ octahedra of the second phase [θ-(Al,Cr)₂O₃ at 1400 °C, or α-(Al,Cr)₂O₃ at 1600 °C] which segregated in the system. Substitution of Cr³⁺ for Al³⁺ on M1 site in the mullite structure resulted in increase of average distances in (M1)O₆ octahedron and decrease of average distances in T*O₄ tetrahedron, while average distances in TO₄ tetrahedron stayed almost constant.     

Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

A novel Cr₂O₃/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr₂O₃ on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr₂O₃ nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV–visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr₂O₃. The 2.5Cr₂O₃/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H₂ evolution for Cr₂O₃/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr³⁺ and a probably photocatalytic mechanism was proposed.     

Non-adiabatic polaron hopping conduction in CaMn1−xCrxO3 (0?x?0.3)

DC electrical conductivity (σ_dc) of electron-doped antiferromagnetic CaMn_1−xCr_xO₃ (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σ_dc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr³⁺ has larger ionic size compared to that of Mn⁴⁺. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO₃ manganites.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

Photo(electro)catalytic Activity of Cu-Modified TiO2 Nanorod Array Thin Films under Visible Light Irradiation

In the present study, a two-step method was applied to synthesise Cu²⁺-modified TiO₂ nanorod array thin films for photocatalytic processes. TiO₂ nanorod array thin films were synthesised by a hydrothermal method and then modified with an ultrasonic-assisted sequential cation adsorption method. The samples were characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and inductively coupled plasma mass spectroscopy (ICP-MS) analysis. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry and Mott–Schottky analysis; photocatalytic activities were tested by methylene blue degradation under visible light. The photocurrent density of the TiO₂/FTO sample modified with 50 mM Cu²⁺ solution was 26 times higher than that of the unmodified TiO₂/FTO sample. Additionally, methylene blue degradation efficiency under visible light was increased 40% with respect to the efficiency of the unmodified sample. The mechanism of the photocatalytic activity enhancement of Cu²⁺-modified TiO₂ nanorod films was discussed.     

Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles

The Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr³⁺) ions at least partially substitute Zn (Zn²⁺) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr₂O₄ was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.     

Influence of Cr3+ doping on photoelectronic processes of La2Ti2O7 pyrochlore and La23TiO3 perovskite anodes

Photoelectrical properties of La₂TiO₂O₇ and La_{$\text{2}\text{3}$}TiO₃ anodes undoped and Cr³⁺—doped have been investigated. The onset of photocurrent for both the undoped and Cr³⁺ doped pyrochlore is at 400 nm while for undoped perovskite it is at 420 n.m. A shift of the spectral photoresponse down to 550 n.m. is observed for the Cr-doped perovskite. The experimental data have been analyzed according to the Schottky barrier model of the semiconductor-electrolyte junction. This analysis has allowed us to propose a photoconduction mechanism.     

Cu-doped flower-like hematite nanostructures for efficient water splitting applications

This study reports the successful preparation of Cu-doped hematite (α-Fe₂O₃) flower-like nanostructures with different Cu concentrations on FTO glass substrates using a facile hydrothermal method. The Cu-doped α-Fe₂O₃ flower-like nanostructure combines the advantage of p-type doping with the feature of a flower-like architecture. The prepared nanostructure film was applied as a photocathode in a photoelectrochemical (PEC) water splitting experiment and achieved a significantly improved photocurrent density of −5.34 mA cm⁻² at −0.6 V vs. reversible hydrogen electrode (RHE) for 1 mol% Cu doping. The obtained photocurrent is about 4.85 times higher than that of the pure α-Fe₂O₃ based photoelectrode. The incorporation of Cu into α-Fe₂O₃ results in a dramatic enhancement in the water splitting performance. The enhancement is gained through an improvement in light harvesting and charge carrier separation. The copper-modified α-Fe₂O₃ sample also exhibited an up shift in the conduction band edge potential, which is energetically favorable for the water reduction reaction. This result demonstrated high performance PEC water splitting as a potential route for the production of hydrogen gas using a single Cu-doped α-Fe₂O₃ photoelectrode without the need for other catalysts and hybrid structures.     

Charge states of transition metal in “Cr, Co and Ni” doped Ln0.5Ca0.5MnO3 CMR manganites

The XAS study at Cr, Co, Ni and Mn K-edges was performed for the doped CMR manganites Ln_0.5Ca_0.5Mn_1-xB_xO₃ with Ln=La, Nd, Sm and B= Cr, Co, Ni (), on the samples that were studied previously for their ferromagnetic-metallic to antiferromagnetic-insulator transition. We observed that the formal charges of the doping elements are Ni²⁺, Co²⁺ and Cr³⁺. It is also evidenced that the average formal charge of the manganese is increased after doping, in agreement with the charge compensation keeping “O₃” stoichiometry. These results suggest that the doping elements participate directly to the band structure. Received: 9 January 1998 / Received in final form: 6 April 1998 / Accepted: 7 April 1998     

Magnetic exchange interactions induced by Cr-doping in perovskite manganites

The effect of Cr-doping on the structural, magnetic and transport properties of perovskite manganites La_0.8Ca_0.2Mn_1−xCr_xO₃ (0≤x≤0.7) has been investigated. The Curie temperature (T_C) of the Cr-doped samples is almost unchanged up to 30% of Cr-doping. The Cr-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_C. The dc and ac magnetization data suggest that ferromagnetic clusters induced by double exchange interaction between Cr³⁺ and Mn³⁺ ions and antiferromagnetic components driven by Cr³⁺/Mn⁴⁺ and Cr³⁺/Cr³⁺ interactions are present in the Cr-doped system, which is supported by comparative studies on magnetic and transport properties of LaMnO_3+δ and LaMn_0.75Cr_0.25O_3+δ.     

Preparation and characterization of visible light responsive Fe2O3-TiO2 composites

In this study we present the effects of iron oxide (Fe₂O₃) on titanium dioxide (TiO₂) in synthesising visible-light reactive photocatalysts. A Fe₂O₃-TiO₂ composite photocatalyst was synthesized from Fe₂(SO₄)₃ and Ti(SO₄)₂ by a ethanol-assisted hydrothermal method. The preparation conditions were optimized through the investigation of the effects of hydrothermal temperature and time as well as molar ratio of Ti to Fe on the photocatalytic activity. The visual, physical and chemical properties of the Fe₂O₃-TiO₂ composites were investigated. The results showed that α-Fe₂O₃ and anatase TiO₂ were present in the composites. The Fe₂O₃-TiO₂ synthesized under optimum condition consisted of mesoporous structure with an average pore size of 4 nm and a surface area of 43 m²/g. Under visible and solar light irradiation, the photocatalytic activity of optimized sample was significantly higher than that of pure TiO₂. This sample led to a photodegradation efficiency of 90% and 40% of auramine under visible light and solar light, respectively.     

Scanning transmission X-ray microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry study on the enhanced visible photocatalytic mechanism of carbon-TiO2 nanohybrids

Carbon-TiO₂ nanohybrids (CTs, 5-10 nm TiO₂ nanocrystals evenly dispersed on carbon film) have been successfully prepared via a mild, one-step hydrothermal approach. The interactions and electronic structures of carbon and TiO₂ nanoparticles and the enhanced visible photocatalytic mechanism were investigated by scanning transmission X-ray microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry in detail. Meanwhile, it was demonstrated that the as-obtained CTs had a large BET specific surface area of 304.6 m²/g and showed excellent photocatalytic abilities towards organic (Rhodamine B, benzene) and inorganic pollutant (K₂Cr₂O₇) degradation in visible light. This work provided a new approach for the high performance catalyst design towards new energy sources and environmental issues.     

Effects of Gd<Superscript>3+</Superscript> modifications on the photoelectrochemical properties of TiO<Subscript>2</Subscript>-based dye-sensitized solar cells

In this paper, TiO₂ particles (~30 nm) modified with Gd₂O₃-coating layer (~2 nm) for dye-sensitized solar cells (DSSCs) were fabricated via the hydrothermal method. Among the solar cells based on the Gd³⁺-doped TiO₂ photoanodes, the optimal conversion efficiency was obtained from the 0.025Gd³⁺-modified TiO₂-based cell, with a 17.7% improvement in the efficiency as compared to the unmodified one (7.18%). This enhancement was probably due to the improved UV radiation harvesting via a down-conversion luminescence process by Gd³⁺ ions, enhancement of visible light absorption and improved dye loading capacity. In addition, after Gd modification, a thin coating could be formed on the TiO₂ nanoparticles, which worked as an energy barrier and resulted in a lower charge recombination.     

Preparation and characterization of TiO2 photocatalysts co-doped with iron (III) and lanthanum for the degradation of organic pollutants

Titanium dioxide photocatalysts co-doped with iron (III) and lanthanum were prepared by a facile sol-gel method. The structure of catalysts was characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by the degradation of methylene blue in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. Doping with Fe³⁺ results in a lower anatase to rutile (A-R) phase transformation temperature for TiO₂ particles, while doping with La³⁺ inhibits the A-R phase transformation, and co-doping samples indicate that Fe³⁺ partly counteracts the effect of La³⁺ on the A-R transformation property of TiO₂. Fe-TiO₂ has a long tail extending up the absorption edges to 600 nm, whereas La-TiO₂ results in a red shift of the absorption. However, Fe and La have synergistic effect in the absorption of TiO₂. Compared with Fe³⁺ and La³⁺ singly doped TiO₂, the co-doped simple exhibits excellent visible light and UV light activity and the synergistic effect of Fe³⁺ and La³⁺ is responsible for improving the photocatalytic activity.     

Reversible photochromic effects in doped single crystals of bismuth germanium (Bi12GeO20) and bismuth silicon oxide (Bi12SiO20)

Absorption of Bi₁₂GeO₂₀ and Bi₁₂SiO₂₀ single crystals doped with Mn and Cr were investigated before and after illumination with visible light. Pronounced photochromic effects were found. The effects are explained in terms of light induced charge transfer Mn⁴⁺→Mn⁵⁺ and Cr³⁺→Cr²⁺.     

Structural, optical and magnetic properties of Cr doped ZnO microrods prepared by spray pyrolysis method

A series of Cr-doped ZnO micro-rod arrays were fabricated by a spray pyrolysis method. X-ray diffraction patterns of the samples showed that the undoped and Cr-doped ZnO microrods exhibit hexagonal crystal structure. Surface morphology analysis of the samples has revealed that pure ZnO sample has a hexagonal microrod morphology. From X-ray photoelectron spectroscopy studies, the Cr 2p3/2 binding energy is found to be 577.3 eV indicating that the electron binding energy of the Cr in ZnO is almost the same as the binding energy of Cr³⁺ states in Cr₂O₃. The optical band gap E_g decreases slightly from 3.26 to 3.15 eV with the increase of actual Cr molar fraction from x = 0.00 to 0.046 in ZnO. Photoluminescence studies at 10 K show that the incorporation of chromium leads to a relative increase of deep level band intensity. It was also observed that Cr doped samples clearly showed ferromagnetic behavior; however, 2.5 at.% Cr doped ZnO showed remnant magnetization higher than that of 1.1 at.% and 4.6 at.% Cr doped samples, while 4.6 at.% Cr doped ZnO samples had a coercive field higher than the other dopings.     

Titanium atoms dimerization phenomenon and magnetic properties of titanium-antisite (TiO) and chromium doped rutile TiO2, ab-initio calculation

The ab-initio calculations based on the Korringa Kohn Rostoker approximation approach combined with coherent potential approximation (KKR-CPA), were used to study the magnetic properties of the titanium anti-site (Ti_O) and chromium (Cr) doped TiO₂. In the considered systems, we used different concentrations for Ti_O defect and Cr doping. In TiO_2(0.98)(Ti_O)_0.02, the obtained results indicate that Ti_O is a donor having half-metal behavior. Ti_O[3d] band is located at the Fermi level, although isn’t 100% polarized, the ferromagnetic (FM) state is verified as being more stable than disordered local moment (DLM) state. For Ti_0.98Cr_0.02O₂ the Cr doping introduced new states which give the material half-metallic feature. The majority spin of Cr impurities are located at the Fermi level and the conduction electrons around the Fermi level are 100% spin polarized. This indicates the stability of (FM) state. Moreover, in Ti_0.98Cr_0.02O_2(0.98)(Ti_O)_0.02, the top of the valence band is shifted to lower energy compared to pure TiO₂, and the n-type of TiO₂ is verified. The majority spin of Cr[3d] are located at 0.025 Ry close to the Fermi level. The predicted Curie temperatures (Tc) were calculated using the mean field approximation (MFA) and we predicted that Ti_O defect in Cr doped TiO₂ makes Tc higher. This kind of defect makes the material useful for spinotronics's applications and devices.     

Study on the mechanisms of photoinduced carriers separation and recombination for Fe-TiO2 photocatalysts

The iron(III)-ion doped TiO₂ (Fe³⁺-TiO₂) with different doping Fe³⁺ content were prepared via a sol-gel method. The as-prepared Fe³⁺-TiO₂ nanoparticles were investigated by means of surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and the photoelectrochemical properties of Fe³⁺-TiO₂ catalysts with different Fe³⁺ content are performed by electrical impedance spectroscopy (EIS) as well as photocatalytic degradation of RhB are studied under illuminating. Based on the experiment results, the mechanism of photoinduced carriers separation and recombination of Fe³⁺-TiO₂ was revealed: that is, the Fe³⁺ captures the photoinduced electrons, inhibiting the recombination of photoinduced electron-hole pairs, this favors to the photocatalytic reaction at low doping concentration (Fe/Ti ≤ 0.03 mol%); while Fe³⁺ dopant content exceeds 0.03 mol%, Fe₂O₃ became the recombination centers of photoinduced electrons and holes because of that the interaction of Fe₂O₃ with TiO₂ leads to that the photoinduced electrons and holes of TiO₂ transfer to Fe₂O₃ and recombine quickly, which is unfavorable to the photocatalytic reaction.