Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

Strontium-substituted calcium phosphates prepared by hydrothermal method under linoleic acid–ethanol solution

Strontium-incorporated calcium phosphates show potential in biomedical application, particularly the doped strontium may help to new bone formation. In this study, the particle was synthesized by hydrothermal treatment at 120 °C for 15 h. It was found that the phase purity and aspect ratio was significantly affected by the addition of linoleic acid due to reduction of solution pH. In particular, strontium played important role in the transformation of minerals. Below 20% solution of calcium substituted by strontium, only apatite was formed; above it, a mixture of apatite and DCPA was detected, and α-SrHPO₄ was formed if all calcium solutions were replaced by strontium. Meanwhile, the adsorption of fatty acid on crystal was detected by FTIR. In summary, the incorporated fatty acid not only affected the morphology, but also its composition.     

Photocatalytic reduction of CO2 to energy products using Cu–TiO2/ZSM-5 and Co–TiO2/ZSM-5 under low energy irradiation

Copper or cobalt incorporated TiO₂ supported ZSM-5 catalysts were prepared by a sol–gel method, and then were characterized by XRD, BET, XPS and UV–vis diffuse reflectance spectroscopy. Ti^3 + was the main titanium specie in TiO₂/ZSM-5 and Cu–TiO₂/ZSM-5, which will be oxide to Ti^4 + after Co was doped. With the deposition of Cu or Co, the efficiency of the CO₂ conversion to CH₃OH was increased under low energy irradiation. The peak production rate of CH₃OH reached 50.05 and 35.12 μmol g^− 1 h^− 1, respectively. High photo energy efficiency (PEE) and quantum yield (φ) were also reached. The mechanism was discussed in our study.     

Ba0.6Sr0.4TiO3–MgO ceramics from ceramic powders prepared by improved aqueous gelcasting-assisted solid-state method

Based on aqueous gelcasting-assisted solid-state method (AGASSM), improved aqueous gelcasting-assisted solid-state method (IAGASSM) was proposed to prepare the 45 wt% Ba_0.6Sr_0.4TiO₃–55 wt% MgO (BSTM) ceramic powders. It is found that the BSTM ceramic powders prepared by IAGASSM are the most uniform with the smallest particles (D_av = 0.83 μm) than those prepared by solid-state method (SSM) and AGASSM. The phase compositions of the BSTM ceramic powders and ceramics from the prepared ceramic powders are the same whatever ceramic powder preparation method is adopted. Compared with SSM and AGASSM, the BSTM green samples and ceramics from ceramic powders prepared by IAGASSM are the most uniform. Furthermore, it is found that adopting IAGASSM to prepare ceramic powders could not only improve the dielectric properties of the BSTM ceramics considerably, but also decrease their sintering temperature.     

Methanol synthesis from carbon monoxide and hydrogen catalyzed over Pd/CeO2 prepared by the deposition–precipitation method

Ceria‐supported palladium catalysts prepared by the deposition–precipitation method are highly active for the methanol synthesis from carbon monoxide and hydrogen in comparison with the catalyst prepared by the conventional impregnation method. Analyses by EXAFS show that palladium particles can be dispersed very well on the surface of ceria by both the methods, implying that the higher activity of the catalysts prepared by deposition–precipitation is not simply due to the particle size of palladium. Cationic palladium species are present in the samples prepared by deposition–precipitation after reduction with hydrogen at 300 °C, suggesting that the active species are produced by strong contact between palladium particles and the support. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Optical properties of Nb-doped TiO2 thin films prepared by sol–gel method

In this work, we studied optical properties of pure and Nb-doped TiO₂ synthesized using a sol–gel method and deposited as thin films by spin-coating followed by annealing in air at 500 °C for 1 h. The surface elemental composition was derived from X-ray photoelectron spectra, while structure and surface morphology were investigated using X-ray diffraction and atomic force/scanning electron microscopy. Finally, the optical properties were investigated by means of UV–vis spectrophotometry and spectroscopic ellipsometry.The Nb content was determined from XPS measurements to vary between 1.8 and 4.3 at%. The XRD patterns of the deposited thin films, with a maximum thickness of about 56 nm, showed no diffraction peaks. As proven both by microscopy and spectroscopic ellipsometry studies doping TiO₂ with Nb modified the surface morphology of the samples; the grain size is increasing while the surface roughness decreases with the increase in Nb content. This is accompanied by a decrease in the refractive index and an increase of the extinction coefficient.     

The preparation of core–shell Al2O3/Ni composite powders by electroless plating

Core–shell nanostructured Ni-coated Al₂O₃ composite powders were synthesised by using the electroless plating method. The influence of the chemical components and powder concentration in the Ni coating was investigated by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction techniques. The results show that the concentration of the plating components plays an important role in the formation of core–shell Al₂O₃/Ni composite powders. The nickel content in the composite powders could be effectively controlled by adjusting the nickel chloride content and the concentration of NaH₂PO₂·H₂O in the plating solution. The nanostructure of the crystalline Ni coatings was observed to be very attractive for achieving good bonding between ceramic particles and matrices for composite production.     

Hydrogen production via methanol steam reforming over Au/CuO,Au/CeO2, and Au/CuO–CeO2 catalysts prepared by deposition–precipitation

The production of hydrogen (H₂) with a low concentration of carbon monoxide (CO) via steam reforming of methanol (SRM) over Au/CuO, Au/CeO₂, (50:50)CuO–CeO₂, Au/(50:50)CuO–CeO₂, and commercial MegaMax 700 catalysts were investigated over reaction temperatures between 200 °C and 300 °C at atmospheric pressure. Au loading in the catalysts was maintained at 5 wt%. Supports were prepared by co-precipitation (CP) whilst all prepared catalysts were synthesized by deposition–precipitation (DP). The catalysts were characterized by Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM). Au/(50:50)CuO–CeO₂ catalysts expressed a higher methanol conversion with negligible amount of CO than the others due to the integration of CuO particles into the CeO₂ lattice, as evidenced by XRD, and a interaction of Au and CuO species, as evidenced by TPR. A 50:50 Cu:Ce atomic ratio was optimal for Au supported on CuO–CeO₂ catalysts which can then promote SRM. Increasing the reaction time, by reducing the liquid feed rate from 3 to 1.5 cm³ h^?1, resulted in a catalytic activity with complete (100%) methanol conversion, and a H₂ and CO selectivity of ～82% and ～1.3%, respectively. From stability testing, Au/(50:50)CuO–CeO₂ catalysts were still active for 540 min use even though the CuO was reduced to metallic Cu, as evidenced by XRD. Therefore, it can be concluded that metallic Cu is one of active components of the catalysts for SRM.     

Photocatalytic CO2 reduction in gas–solid regime in the presence of H2O by using GaP/TiO2 composite as photocatalyst under simulated solar light

GaP/TiO₂ composites exhibited a remarkable photocatalytic activity for CO₂ reduction in the presence of water vapor producing methane. By decreasing the GaP:TiO₂ mass ratio an increase in the photocatalytic activity of the composite was observed for up to a 1:10 mass ratio. The photocatalytic activity of the composite can be attributed to the band structures of the solids as well as to the efficient charge transfer between GaP and TiO₂ heterojunction.     

Use of a nickel-boride–silica nanocomposite catalyst prepared by in-situ reduction for hydrogen production from hydrolysis of sodium borohydride

Hydrogen was produced by hydrolysis of sodium borohydride (NaBH₄) using nickel-boride–silica nanocomposite catalyst. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectrometry (EDX). The Ni-B–silica nanocomposite catalyst was found to consist of amorphous Ni-B nanoparticles attached to the surface of amine-modified silica nanosphere. The kinetics of hydrolysis of NaBH₄ by Ni-B–silica composite catalyst was investigated. The effects of temperature, NaBH₄ concentration, and catalyst concentration on hydrogen generation were also investigated. A rate of hydrogen generation as high as 1916 ml H₂/min/g Ni was achieved by catalytic hydrolysis of NaBH₄. The stability of the composite catalyst was also explored.     

Environmental remediation from thiophene solution by photocatalytic oxidation using a Pd/ZrO2–chitosan nanocomposite

A modified sol–gel technique was used to prepare ZrO₂ nanoparticles through impregnation of ZrO₂ with Pd and/or chitosan (CS). The composite photocatalyst of Pd/ZrO₂ was characterized by XRD, TEM, UV–vis, Pl, and BET and the photocatalytic activity was investigated under visible light irradiation by using a thiophene solution as a model pollutant. The results revealed the influence of the type and amount of the catalyst where CS can effectively prevent the agglomeration of ZrO₂ nanoparticles. UV–vis spectroscopic investigation indicated also that the ability of the composite to absorb visible light is greatly improved. The catalyst was reproducible without significant loss in its activity during the first five cycles.     

Production of hydrogen by steam reforming of methanol over Cu/CeO2 catalysts derived from Ce1−xCuxO2−x precursors

The Ce_1−xCu_xO_2−x mixed oxides were synthesized using the coprecipitation method, and were reduced to form the Cu/CeO₂ (cop) catalysts for the steam reforming of methanol. All the Cu-containing catalysts tested in this study showed high selectivities to CO₂ (over 97%) and H₂. A 3.9 wt% Cu/CeO₂ (cop) catalyst showed a conversion of 53.9% for the steam reforming of methanol at 513 K, which was higher than those over Cu/ZnO (37.9%), Cu/Zn(Al)O (32.3%) and Cu/Al₂O₃ (11.2%) with the same Cu loading under the same reaction conditions. It is likely that the high activity of the 3.9 wt% Cu/CeO₂ (cop) catalyst was due to the highly dispersed Cu metal particles and the Cu⁺ species stabilized by the CeO₂ support.     

Photocatalytic hydrogen generation of ZnO rod–CdS/reduced graphene oxide heterostructure prepared by Pt-induced oxidation and light irradiation-assisted methods

A synthesis method including Pt-induced oxidation and light irradiation-assisted routes has been developed to prepare a ZnO rod–CdS/reduced graphene oxide (RGO) heterostructure. Here, graphene oxide nanosheets are reduced and loaded onto the surface of Zn spheres using a redox process. ZnO rods are generated from Zn spheres by a Pt-induced oxidation method, and CdS nanoparticles are then loaded onto the surface of RGO via a light irradiation-assisted method. The ZnO rod–CdS/RGO heterostructure exhibits 3.8 times higher photocatalytic hydrogen generation rate from an aqueous solution containing Na₂S/Na₂SO₃ than the reference ZnO rod–CdS heterostructure under simulated solar light irradiation. The optimal contents of RGO nanosheets and CdS nanoparticles are 2 wt% and 20 at.%, respectively.     

Photocatalytic H2 Production from Ethanol–Water Mixtures Over Pt/TiO2 and Au/TiO2 Photocatalysts: A Comparative Study

Pt/TiO₂ (Pt loadings 0–4 wt%) and Au/TiO₂ (Au loadings 0–4 wt%) photocatalysts were synthesized, characterized and tested for H₂ production from ethanol–water mixtures (80 vol% ethanol, 20 vol% H₂O) under UV excitation. Average metal nanoparticle sizes determined by TEM were 1–3 nm for Pt in the Pt/TiO₂ photocatalysts and 5–7 nm for Au in the Au/TiO₂ photocatalysts. Au/TiO₂ showed an intense localized surface plasmon resonance feature at ~570 nm, typical for metallic Au nanoparticles of diameter ~5 nm supported on TiO₂. X-ray photoelectron spectroscopy and X-ray diffraction analyses established that Pt and Au were present in metallic form on the TiO₂ support. X-ray fluorescence revealed close accord between nominal and actual Pt and Au loadings. The Au/TiO₂ and Pt/TiO₂ photocatalysts both displayed very high activities for H₂ production under UV irradiation, with the Au/TiO₂ samples affording slightly superior rates of H₂ production at most metal loadings. The 2 wt% Au/TiO₂ and 1 wt% Pt/TiO₂ photocatalysts showed the highest H₂ production rates (32–34 mmol g^?1 h^?1). Photoluminescence studies confirmed that Pt and Au nanoparticles positively enhance the photocatalytic properties of P25 TiO₂ for H₂ production by acting as electron acceptors and thereby suppressing electron–hole pair recombination in TiO₂.     

Low-temperature methanol synthesis catalyzed over Cu/γ-Al2O3–TiO2 for CO2 hydrogenation

A titanium-modified -alumina-supported CuO catalyst has been prepared and used for methanol synthesis from CO₂ hydrogenation. XRD and TPR were used to characterize the phase, reduction property and particle size of the reduced catalyst. The addition of Ti to the CuO/-Al₂O₃ catalyst made the copper in the catalyst exist in much smaller crystallites and exhibit an amorphous-like structure. The adding of Ti made the reduction peak shift toward lower temperature in comparison with the CuO/-Al₂O₃ catalyst. The effect of the addition of Ti and the reaction conditions on the activity and selectivity to methanol from CO₂ hydrogenation were investigated. The activity was found to increase with increasing surface area of metallic copper, but it is not a linear relationship. This indicated that the catalytic activity of the catalysts depends on both the metallic copper area and the synergy between the copper and titanium dioxide. The effect of contact time on the relative selectivity (=SCH₃0H /S_CO) and selectivity of methanol were also investigated. The results indicated that methanol was formed directly from the hydrogenation of CO₂.     

WGS activity of a novel Cu–ZrO2 catalyst prepared by a reflux method. Comparison with a conventional impregnation method

The activity in the WGS reaction of Cu/ZrO₂ catalysts prepared by a method of refluxing in an aqueous NH₄OH solution is studied. It is shown that at 3% Cu load the methods of impregnation over monoclinic or tetragonal ZrO₂ do not produce active catalysts for the WGS reaction. However, the method of refluxing generates highly active catalysts with Cu loads of 3% (w/w) or higher. The activity of the catalysts prepared by refluxing is associated with the formation of small Cu clusters, which would allow the regrouping of the H atoms to generate molecular H₂ in the presence of the crystalline tetragonal ZrO₂.     

Core–shell structured Cu@m-SiO2 and Cu/ZnO@m-SiO2 catalysts for methanol synthesis from CO2 hydrogenation

The core–shell catalysts with Cu and Cu/ZnO nanoparticles coated by mesoporous silica shells are prepared for CO₂ hydrogenation to methanol. With the confined effect of silica shell, the size of Cu nanoparticles is only about 5.0 nm, which results in high activity for CO₂ conversion. The CH₃OH selectivity is enhanced significantly with the introduction of ZnO. The core–shell structured catalysts endow the Cu nanoparticles trapped inside with excellent anti-aggregation and no deactivation is observed with time-on-stream. Therefore, the core–shell Cu/ZnO@m-SiO₂ catalyst exhibits the maximum CH₃OH yield with high stability.     

Microstructure–thermal properties of Cu/Al2O3 bilayer prepared by direct bonding

The thermal conductivity of Cu/Al₂O₃ bilayers prepared by a direct-bonding technique was determined. The direct-bonding process started with the pre-oxidation treatment of a Cu plate at a temperature less than 600 °C. Though a thin oxide layer was located on the surface of the plate after treatment, the oxygen solutes began to diffuse into the interior of Cu plate prior to bonding. Bonding occurred by a eutectic liquid formed at 1075 °C. No reaction interphase was observed at the Cu–Al₂O₃ interface. The thermal resistance of the Cu/Al₂O₃ interface is very low. The extremely low thermal resistance can be related to the clean interface between the two materials.