Xiao-jing Wang

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.

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.

Ionic liquid self-combustion synthesis of BiOBr/Bi24O31Br10 heterojunctions with exceptional visible-light photocatalytic performances

Heterostructured BiOBr/Bi24O31Br10 nanocomposites with surface oxygen vacancies are constructed by a facile in situ route of one-step self-combustion of ionic liquids. The compositions can be easily controlled by simply adjusting the fuel ratio of urea and 2-bromoethylamine hydrobromide (BTH). BTH serves not only as a fuel, but also as a complexing agent for ionic liquids and a reactant to supply the Br element. The heterojunctions show remarkable adsorptive ability for both the cationic dye of rhodamine B (RhB) and the anionic dye of methylene orange (MO) at high concentrations, which is attributed to the abundant surface oxygen vacancies. The sample containing 75.2% BiOBr and 24.8% Bi24O31Br10 exhibits the highest photocatalytic activity. Its reaction rate constant is 4.0 and 9.0 times that of pure BiOBr in degrading 50 mg L(-1) of RhB and 30 mg L(-1) of MO under visible-light (λ > 400 nm) irradiation, respectively, which is attributed to the narrow band gap and highly efficient transfer efficiency of charge carriers. Different photocatalytic reaction processes and mechanisms over pure BiOBr and heterojunctions are proposed.

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.

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.

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.

Synthesis of {111} Facet-Exposed MgO with Surface Oxygen Vacancies for Reactive Oxygen Species Generation in the Dark

Seeking a simple and moderate route to generate reactive oxygen species (ROS) for antibiosis is of great interest and challenge. This work demonstrates that molecule transition and electron rearrangement processes can directly occur only through chemisorption interaction between the adsorbed O2 and high-energy {111} facet-exposed MgO with abundant surface oxygen vacancies (SOVs), hence producing singlet oxygen and superoxide anion radicals without light irradiation. These ROS were confirmed by electron paramagnetic resonance, in situ Raman, and scavenger experiments. Furthermore, heat plays a crucial role for the electron transfer process to accelerate the formation of ·O2-, which is verified by temperature kinetic experiments of nitro blue tetrazolium reduction in the dark. Therefore, the presence of oxygen vacancy can be considered as an intensification of the activation process. The designed MgO is acquired in one step via constructing a reduction atmosphere during the combustion reaction process, which has an ability similar to that of noble metal Pd to activate molecular oxygen and can be used as an effective bacteriocide in the dark.

Ultrathin porous nanosheet-assembled hollow cobalt nickel oxide microspheres with optimized compositions for efficient oxygen evolution reaction

Hollow cobalt nickel oxide microspheres assembled by ultrathin porous nanosheets with tunable Co/Ni molar ratios have been successfully synthesized via a facile “self-template” method, taking solid bimetallic alkoxide microspheres as a precursor. The compositions and the sizes of the hollow cavities of cobalt nickel oxides can be easily controlled by the Co/Ni molar ratios and the size of bimetallic alkoxide microspheres, respectively. The electrochemical measurements indicate that the cobalt nickel oxide catalysts exhibit greatly enhanced oxygen evolution reaction (OER) activity in alkaline media, and Co2–Ni1–O microspheres with the optimal composition show the lowest overpotential (∼310 mV for 10 mA cm−2) and the smallest Tafel slope (57 mV per decade). This is attributed to the large electrochemically reactive surface and good charge conduction offered by the synergetic effects between their unique structural features and tunable compositions. The hollow cobalt nickel oxide microspheres may serve as promising noble-metal-free OER electrocatalysts to replace IrOx material, and the synthetic strategy that directs structural design can be applied to prepare other multifunctional materials.