Fa-tang Li

Enhanced visible-light photocatalytic activity of active Al2O3/g-C3N4 heterojunctions synthesized via surface hydroxyl modification

Novel Al2O3/g-C3N4 heterojunction photocatalysts were fabricated through ultrasonic dispersion method. Al2O3, obtained via solution combustion, contained amorphous ingredient with lots of defect sites and was used as active component for transferring photo-induced electrons of g-C3N4. G-C3N4 was grafted surface hydroxyl groups in the presence of ammonia aqueous solution to combine with Al2O3 possessing positive charges via hydrogen bond. The XRD, SEM, element map, TEM, HRTEM, FT-IR, and XPS results indicate that these synthesized materials are two-phase hybrids of Al2O3 and g-C3N4 with interaction. The photocatalytic results for the degradation of rhodamine B (RhB) indicate that the most active heterojunction proportion is 60wt.% g-C3N4:40wt.% Al2O3, the visible light photocatalytic activity of which is 3.8 times that of a mechanical mixture. The enhanced performance is attributed to the high separation efficiency of photo-induced electrons from the LUMO of g-C3N4 injected into the defect sites of Al2O3, which is verified by photoluminescence spectroscopy (PL) and surface photovoltage (SPV) measurements. The electron paramagnetic resonance (EPR) signals and radical scavengers trapping experiments reveal holes (h(+)) and superoxide anion radical (O2(-)) are the main active species responsible for the degradation of RhB.

Desulfurization of dibenzothiophene by chemical oxidation and solvent extraction with Me3NCH2C6H5Cl·2ZnCl2 ionic liquid

Desulfurization of dibenzothiophene (DBT) by a combination of both chemical oxidation and solvent extraction was investigated. Me3NCH2C6H5Cl·2ZnCl2 ionic liquid was prepared from cheap starting materials and used as extractant for oxidative desulfurization of DBT in n-octane. DBT in oil phase was extracted into ionic liquid phase and then oxidized to its corresponding sulfone by H2O2 and equal volume of acetic acid. The desulfurization yield of DBT in n-octane was 94% at 30 min under the conditions of H2O2/DBT molar ratio at 6 and V (ionic liquid) : V (n-octane) = 1 : 5, which was remarkably higher than that by mere extraction with ionic liquid (28.9%). The Me3NCH2C6H5Cl·2ZnCl2 ionic liquid could be recycled six times without a significant decrease in activity. Kinetics of oxidative desulfurization of DBT by H2O2 and acetic acid was first-order with an apparent rate constant of 0.0842 min−1 and half-time of 8.23 min.

N-doped P25 TiO2–amorphous Al2O3 composites: One-step solution combustion preparation and enhanced visible-light photocatalytic activity

Nitrogen-doped Degussa P25 TiO2-amorphous Al2O3 composites were prepared via facile solution combustion. The composites were characterised using X-ray diffraction, high-resolution transmission microscopy, scanning electron microscopy, nitrogen adsorption-desorption measurements, X-ray photoelectron spectroscopy, UV-vis light-diffusion reflectance spectrometry (DRS), zeta-potential measurements, and photoluminescence spectroscopy. The DRS results showed that TiO2 and amorphous Al2O3 exhibited absorption in the UV region. However, the Al2O3/TiO2 composite exhibited visible-light absorption, which was attributed to N-doping during high-temperature combustion and to alterations in the electronic structure of Ti species induced by the addition of Al. The optimal molar ratio of TiO2 to Al2O3 was 1.5:1, and this composite exhibited a large specific surface area of 152 m2/g, surface positive charges, and enhanced photocatalytic activity. These characteristics enhanced the degradation rate of anionic methylene orange, which was 43.6 times greater than that of pure P25 TiO2. The high visible-light photocatalytic activity was attributed to synthetic effects between amorphous Al2O3 and TiO2, low recombination efficiency of photo-excited electrons and holes, N-doping, and a large specific surface area. Experiments that involved radical scavengers indicated that OH and O2- were the main reactive species. A potential photocatalytic mechanism was also proposed.

Deep extractive and oxidative desulfurization of dibenzothiophene with C5H9NO·SnCl2 coordinated ionic liquid

A new C5H9NO·SnCl2 coordinated ionic liquid (IL) was prepared by reacting N-methyl-pyrrolidone with anhydrous SnCl2. Desulfurization of dibenzothiophene (DBT) via extraction and oxidation with C5H9NO·SnCl2 IL as extractant, H2O2 and equal mol of CH3COOH as oxidants was investigated. The Nernst partition coefficients k(N) of C5H9NO·SnCl2 IL for the DBT in n-octane was above 5.0, showing its excellent extraction ability. During the oxidative desulfurization process, the optimal molar ratio of H2O2/DBT was six. Sulfur removal of DBT in n-octane was 94.8% in 30 min at 30 °C under the conditions of H2O2/DBT molar ratio of six and V (IL):V (oil)=1:3. Moreover, the sulfur removal increased with increasing temperature because of the high reaction rate constant, low viscosity, and high solubility of dibenzothiophene-sulfone in the IL. The kinetics of oxidative desulfurization of DBT was also investigated, and the apparent activation energy was found to be 32.5 kJ/mol. The IL could be recycled six times without a significant decrease in activity.

Construction of amorphous TiO2/BiOBr heterojunctions via facets coupling for enhanced photocatalytic activity

Facets coupled BiOBr with amorphous TiO2 composite photocatalysts are synthesized via an in situ direct growth approach under microwave irradiation. XRD, SEM and HRTEM characterizations indicate that the heterointerface between BiOBr and amorphous TiO2 occurs mainly on the {001} facets of BiOBr. BET and TEM verify that the heterojunctions possess higher specific surface areas and smaller amorphous TiO2 particle size than bare BiOBr and amorphous TiO2, exhibiting the inhibition function of BiOBr on the growth of TiO2 particles. XPS verifies the interaction between the two components. The degradation of methyl orange (MO) and phenol are used as the objective reaction to evaluate the photocatalytic activity of the as-prepared samples. The reaction rate constant of 15% TiO2/BiOBr composite is 3.4 times greater than that of pure BiOBr, which is attributed to its higher surface area, and efficient separation of photo-generated electron-hole pairs between BiOBr and amorphous TiO2.

Synthesis and photocatalytic performances of the TiO2 pillared montmorillonite

TiO(2) pillared clay materials were prepared by montmorillonite (Mt) and acidic solutions of hydrolyzed Ti alkoxides in the presence of high-molecular-weight polyoxypropylene (POP)-backboned di-quaternary salts (POP). The as-prepared materials were characterized by means of XRD, FTIR, TG-DTA, XRF, specific surface area and porosity determinations, TEM and SEM, respectively. The experiments showed that the resulting material was a porous delaminated structure containing pillared fragments and nano-scaled TiO(2) particles well dispersed among each other. Introducing polymer surfactant POP as an expanding agent of Mt cannot only promote the formation of the delaminated structure, but significantly improve the porosity and surface area of the composites. The resulting TiO(2) pillared Mt exhibited a good thermal stability as indicated by its surface area after calcination at 800 °C. No phase transformation from anatase to rutile was observed even under calcination at 900 °C. The grain size of anatase in as-prepared sample decreased with the increase of the POP concentration, but increased with the increment of calcination temperature. The photocatalytic performances of these new porous materials were evaluated by using methylene blue degradation. The composite solid exhibited superior photocatalyic property and the maximum removal efficiency was up to 98% within 90 min.

Structure Modification Function of g-C3N4 for Al2O3 in the In Situ Hydrothermal Process for Enhanced Photocatalytic Activity†

Heterojunctions of g-C3 N4 /Al2 O3 (g-C3 N4 =graphitic carbon nitride) are constructed by an in situ one-pot hydrothermal route based on the development of photoactive γ-Al2 O3 semiconductor with a mesoporous structure and a high surface area (188 m(2) g(-1) ) acting as electron acceptor. A structure modification function of g-C3 N4 for Al2 O3 in the hydrothermal process is found, which can be attributed to the coordination between unoccupied orbitals of the Al ions and lone-pair electrons of the N atoms. The as-synthesized heterojunctions exhibit much higher photocatalytic activity than pure g-C3 N4 . The hydrogen generation rate and the reaction rate constant for the degradation of methyl orange over 50 % g-C3 N4 /Al2 O3 under visible-light irradiation (λ>420 nm) are 2.5 and 7.3 times, respectively, higher than those over pristine g-C3 N4 . The enhanced activity of the heterojunctions is attributed to their large specific surface areas, their close contact, and the high interfacial areas between the components as well as their excellent adsorption performance, and efficient charge transfer ability.

Photocatalytic oxidative desulfurization of dibenzothiophene under simulated sunlight irradiation with mixed-phase Fe2O3 prepared by solution combustion

Mixed-phase Fe2O3 was prepared from Fe(NO3)3 and (C2H5)3NHCl via solution combustion. Photocatalytic oxidative desulfurization of dibenzothiophene (DBT) under simulated sunlight irradiation using mixed-phases of α- and β-Fe2O3 as catalysts was investigated. The DBT in the oil phase was extracted into water phase and then photooxidized to CO2 and SO42− by Fe2O3 and O2 dissolved in water. The Fe2O3 containing 36.6% β-Fe2O3 and 63.4% α-Fe2O3 exhibited the highest photocatalytic activity. Sulfur removal of DBT in n-octane was 92.3% for 90 min irradiation under the conditions of V(water) : V(n-octane) = 1 : 1, air flow rate at 150 mL min−1, and Fe2O3 addition at 0.05 g. The kinetics of photooxidative desulfurization of DBT was a pseudo-first-order with an apparent rate constant of 0.0287 min−1 and half-time of 24.15 min. The sulfur content of the actual diesel could be reduced from 478 μg mL−1 to 44.5 μg mL−1 after 90 min. The radical scavengers experiments and terephthalic acid fluorescence technique indicated that ˙OH and O2˙− were the main reactive species in the DBT photocatalytic degradation. A potential photocatalytic desulfurization mechanism using mixed-phase Fe2O3 was proposed.

A Chelation Strategy for In-situ Constructing Surface Oxygen Vacancy on {001} Facets Exposed BiOBr Nanosheets.

Surface defect of nanomaterials is an important physical parameter which significantly influences their physical and chemical performances. In this work, high concentration of surface oxygen vancancies (SOVs) are successfully introduced on {001} facets exposed BiOBr nanosheets via a simple surface modification using polybasic carboxylic acids. The chelation interaction between carboxylic acid anions and Bi3+ results in the weakness of Bi-O bond of BiOBr. Afterwards, under visible-light irradiation, the oxygen atoms would absorb the photo-energy and then be released from the surface of BiOBr, leaving SOVs. The electron spin resonance (ESR), high-resolution transmission electron microscopy (HRTEM), and UV–vis diffuse reflectance spectra (DRS) measurements confirm the existence of SOVs. The SOVs can enhance the absorption in visible light region and improve the separation efficiency of photo-generated charges. Hence, the transformation rate of adsorbed O2 on the as-prepared BiOBr with SOVs to superoxide anion radicals (•O2−) and the photocatalytic activity are greatly enhanced. Based on the modification by several carboxylic acids and the photocatalytic results, we propose that carboxylic acids with natural bond orbital (NBO) electrostatic charges absolute values greater than 0.830 are effective in modifying BiOBr.

One-step construction of {001} facet-exposed BiOCl hybridized with Al2O3 for enhanced molecular oxygen activation

{001} facet-exposed BiOCl with surface oxygen vacancies (SOVs) is developed via a facile ionic liquid (IL) self-combustion route using diethylamine hydrochloride (DLH, (C2H5)2NH·HCl) as a fuel and a source of the IL cation. It is found for the first time that an excess of DLH can not only facilitate the growth of {001} facets, but also create a reducing atmosphere for combustion, resulting in the release of oxygen atoms on the surface of BiOCl and thus the formation of SOVs. The existence of SOVs lifts the energy band potentials of BiOCl and narrows its energy band gap. To improve the separation efficiency of the photo-generated electrons and holes in BiOCl, amorphous Al2O3 is introduced to construct a heterojunction via an in situ combustion strategy by mixing their aqueous precursors. The heterostructured BiOCl/Al2O3 photocatalysts exhibit noticeable molecular oxygen activation and photocatalytic degradation of Rhodamine B. The conduction band (CB) position of amorphous Al2O3 is proposed for the first time, which matches well with that of BiOCl with SOVs and contributes to the effective transfer of electrons from BiOCl to Al2O3.