Zhenxuan Zhao

High-performance porous spherical or octapod-like single-crystalline BiVO4 photocatalysts for the removal of phenol and methylene blue under visible-light illumination

Monoclinic BiVO(4) single-crystallites with a polyhedral, spherical or porous octapod-like morphology were selectively prepared using the triblock copolymer P123 (HO(CH(2)CH(2)O)(20)(CH(2)CH(CH(3))O)(70)(CH(2)CH(2)O)(20)H)-assisted hydrothermal method with bismuth nitrate and ammonium metavanadate as metal source and various bases as pH adjustor. The BiVO(4) materials were well characterized and their photocatalytic activities were evaluated for the removal of methylene blue (MB) and phenol in the presence of a small amount of H(2)O(2) under visible-light illumination. It is shown that the pH value of the precursor solution, surfactant, and hydrothermal temperature had an important impact on particle architecture of the BiVO(4) product. The introduction of P123 favored the generation of BiVO(4) with porous structures. The BiVO(4) derived hydrothermally with P123 at pH 3 or 6 possessed good optical absorption performance both in UV- and visible-light regions and hence showed excellent photocatalytic activities for the degradation of MB and phenol. It is concluded that the high visible-light-driven catalytic performance of the porous octapod-like BiVO(4) single-crystallites is associated with the higher surface area, porous structure, lower band gap energy, and unique particle morphology. Such porous BiVO(4) materials are useful in the solar-light-driven photocatalytic treatment of organic-containing wastewater.

P123-PMMA dual-templating generation and unique physicochemical properties of three-dimensionally ordered macroporous iron oxides with nanovoids in the crystalline walls.

Three-dimensionally (3D) ordered macroporous (3DOM) iron oxides with nanovoids in the rhombohedrally crystallized macroporous walls were fabricated by adopting the dual-templating [Pluronic P123 and poly(methyl methacrylate) (PMMA) colloidal microspheres] strategy with ferric nitrate as the metal precursor in an ethanol or ethylene glycol and methanol mixed solution and after calcination at 550 °C. The possible formation mechanisms of such architectured materials were discussed. The physicochemical properties of the materials were characterized by means of techniques such as XRD, TGA/DSC, FT-IR, BET, HRSEM, HRTEM/SAED, UV-vis, XPS, and H(2)-TPR. The catalytic properties of the materials were also examined using toluene oxidation as a probe reaction. It is shown that 3DOM-structured α-Fe(2)O(3) without nanovoids in the macroporous walls was formed in the absence of P123 during the fabrication process, whereas the dual-templating strategy gave rise to α-Fe(2)O(3) materials that possessed high-quality 3DOM structures with the presence of nanovoids in the polycrystalline macropore walls and higher surface areas (32-46 m(2)/g). The surfactant P123 played a key role in the generation of nanovoids within the walls of the 3DOM-architectured iron oxides. There was the presence of multivalent iron ions and adsorbed oxygen species on the surface of each sample, with the trivalent iron ion and oxygen adspecies concentrations being different from sample to sample. The dual-templating fabricated iron oxide samples exhibited much better low-temperature reducibility than the bulk counterpart. The copresence of a 3DOM-structured skeleton and nanovoids in the macropore walls gave rise to a drop in the band-gap energy of iron oxide. The higher oxygen adspecies amounts, larger surface areas, better low-temperature reducibility, and unique nanovoid-containing 3DOM structures of the iron oxide materials accounted for their excellent catalytic performance in the oxidation of toluene.

Controlled Generation of Uniform Spherical LaMnO3, LaCoO3, Mn2O3, and Co3O4 Nanoparticles and Their High Catalytic Performance for Carbon Monoxide and Toluene Oxidation

Uniform hollow spherical rhombohedral LaMO3 and solid spherical cubic MOx (M = Mn and Co) NPs were fabricated using the PMMA-templating strategy. Hollow spherical LaMO3 and solid spherical MOx NPs possessed surface areas of 21-33 and 21-24 m(2)/g, respectively. There were larger amounts of surface-adsorbed oxygen species and better low-temperature reducibility on/of the hollow spherical LaMO3 samples than on/of the solid spherical MOx samples. Hollow spherical LaMO3 and solid spherical MOx samples outperformed their nanosized counterparts for oxidation of CO and toluene, with the best catalytic activity being achieved over the solid spherical Co3O4 sample for CO oxidation (T50% = 81 °C and T90% = 109 °C) at space velocity = 10,000 mL/(g h) and the hollow spherical LaCoO3 sample for toluene oxidation (T50% = 220 °C and T90% = 237 °C) at space velocity = 20,000 mL/(g h). It is concluded that the higher surface areas and oxygen adspecies concentrations and better low-temperature reducibility are responsible for the excellent catalytic performance of the hollow spherical LaCoO3 and solid spherical Co3O4 NPs. We believe that the PMMA-templating strategy provides an effective route to prepare uniform perovskite-type oxide and transition-metal oxide NPs.

Mesoporous LaFeO3 catalysts for the oxidation of toluene and carbon monoxide

Abstract Wormhole-like orthorhombic LaFeO3 catalysts (LFO-1 and LFO-2) were prepared using the KIT-6 and SiO2 nanospheres as template, respectively. LFO-1 showed better catalytic activity with T50% and T90% of 155 and 180 °C for CO oxidation, and of 200 and 253 °C for toluene oxidation at 20000 mL/(g·h). The excellent catalytic performance was associated with its larger surface area (138 m2/g), higher adsorbed oxygen concentration, and better low-temperature reducibility as well as a wormhole-like mesoporous structure.

Effect of Sulfur Doping on the Photocatalytic Performance of BiVO4 under Visible Light Illumination

Porous monoclinic bismuth vanadate (BiVO(subscript 4-δ)) and sulfur‐doped bismuth vanadates (BiVO(subscript 4-δ)S(subscript 0.05), BiVO(subscript 4-δ)S(subscript 0.08), and BiVO(subscript 4-δ)S(subscript 0.12)) were synthesized by a dodecylamine‐assisted alcohol‐hydrothermal route in the absence and presence of thiourea or Na2S. The physicochemical properties of the materials were characterized and their photocatalytic performance for the degradation of methylene blue and formaldehyde under visible light was evaluated. The samples have a single phase monoclinic scheetlite crystal structure with a porous olive‐like morphology, surface areas of 8.4-12.5 m^2/g, and bandgap energies of 2.40-2.48 eV. Surface Bi^(5+), Bi^(3+), V^(5+), and V^(4+) species were present on the S‐doped BiVO(subscript 4-δ) samples. Sulfur doping influenced the surface Bi^(5+)/Bi^(3+), V^(5+)/V^(4+), and Oads/Olatt molar ratios, and the amount of sulfur doped had an important effect on the photocatalytic performance. Under visible light, BiVO(subscript 4-δ)S(subscript 0.08) performed the best in the photodegradation of methylene blue and formaldehyde. A higher surface oxygen species concentration and a lower bandgap energy were responsible for the excellent visible light photocatalytic performance of BiVO(subscript 4-δ)S(subscript 0.08).

Porous FeOx/BiVO4–δS0.08: Highly efficient photocatalysts for the degradation of Methylene Blue under visible-light illumination

Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide (y wt.% FeOx/BiVO4-deltaS0.08, y = 0.06, 0.76, and 1.40) photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-deltaS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi5+, Bi3+, V5+, V3+, Fe3+, and Fe2+ species in y wt.% FeOx/BiVO4-deltaS0.08. The 1.40 wt.% FeOx/BiVO4-deltaS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower bandgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-deltaS0.08.