Light and nitrogen vacancy-intensified nonradical oxidation of organic contaminant with Mn (III) doped carbon nitride in peroxymonosulfate activation.

Recently, Mn-based materials have a great potential for selective removal of organic contaminants with the assistance of oxidants (PMS, H2O2) and the direct oxidation. However, the rapid oxidation of organic pollutants by Mn-based materials in PMS activation still presents a challenge due to the lower conversion of surface Mn (III)/Mn (IV) and higher reactive energy barrier for reactive intermediates. Here, we constructed Mn (III) and nitrogen vacancies (Nv) modified graphite carbon nitride (MNCN) to break these aforementioned limitations. Through analysis of in-situ spectra and various experiments, a novel mechanism of light-assistance non-radical reaction is clearly elucidated in MNCN/PMS-Light system. Adequate results indicate that Mn (III) only provide a few electrons to decompose Mn (III)-PMS* complex under light irradiation. Thus, the lacking electrons necessarily are supplied from BPA, resulting in its greater removal, then the decomposition of the Mn (III)-PMS* complex and light synergism form the surface Mn (IV) species. Above Mn-PMS complex and surface Mn (IV) species lead to the BPA oxidation in MNCN/PMS-Light system without the involvement of sulfate (SO4• ̶) and hydroxyl radicals (•OH). The study provides a new understanding for accelerating non-radical reaction in light/PMS system for the selective removal of contaminant.

Surface-defect-rich mesoporous NH2-MIL-125 (Ti)@Bi2MoO6 core-shell heterojunction with improved charge separation and enhanced visible-light-driven photocatalytic performance.

Mesoporous NH2-MIL-125(Ti)@Bi2MoO6 core-shell heterojunctions with surface defects were fabricated through a facile solvothermal method. The mesoporous core-shell structure with a large relative surface area of 87.7 m2 g-1 and narrow pore size of 8.2 nm extends the photoresponse to the range of visible light due to the narrow band gap of ∼1.89 eV. The visible-light-driven photocatalytic degradation efficiency of highly toxic dichlorophen and trichlorophenol were 93.28 and 92.19%, respectively, and the corresponding rate constants were approximately 8 and 17 times higher than the rates achieved by pristine NH2-MIL-125(Ti). The photocatalytic oxygen production rate was increased to 171.3 µmol g-1. Recycling for several cycles indicates high stability, which is favorable for practical applications. The excellent photocatalytic performance can be ascribed to the formation of the core-shell heterojunctions and to the surface defects that favor charge separation and visible light absorption; the mesoporous structure offers an adequate number of surface active sites and mass transfer. This novel mesoporous core-shell photocatalyst will have potential applications in the environment, and this strategy offers a new insight into fabrication of other high-performance core-shell structure photocatalysts.

Surface plasma Ag-decorated single-crystalline TiO2-x(B) nanorod/defect-rich g-C3N4 nanosheet ternary superstructure 3D heterojunctions as enhanced visible-light-driven photocatalyst.

Ag-TiO2-x(B)/g-C3N4 ternary heterojunctions photocatalysts are fabricated by hydrothermal-calcination, photo-deposition procedure, and followed by in-situ solid-state chemical reduction procedure. As-obtained photocatalysts are consisted with heterojunctions between 2D g-C3N4 sheets and 1D TiO2(B) single-crystalline nanorods. The band gap of Ag-TiO2-x(B)/g-C3N4 ternary heterojunctions photocatalysts is reduced to ∼2.23 eV due to plasma Ag and surface engineering. Under visible light irradiation, it has an optimal photocatalytic property for the reduction of Cr6+ (95%) and degradation of NH4+ (93%). The apparent reaction rate constants (k) of ternary heterojunctions photocatalysts for NH4+ and Cr6+ are 25 and 12 folds higher than that of original TiO2(B). Furthermore, Ag-TiO2-x(B)/g-C3N4 also has excellent hydrogen production efficiency, which is up to 410 µmol h-1 g-1. This enhancement can be attributed to the unique heterojunction formed by 1D single-crystalline TiO2(B) nanorods and 2D g-C3N4 sheets, surface plasma resonance effect of plasma Ag nanoparticle, and surface engineering. A possible photocatalytic mechanism is also proposed by analysizing the XPS valence-band spectra and the Mott-Schottky.

Assembly of surface-defect single-crystalline strontium titanate nanocubes acting as molecular bricks onto surface-defect single-crystalline titanium dioxide (B) nanorods for efficient visible-light-driven photocatalytic performance.

Ti3+ self-doped single-crystalline SrTiO3-x nanocubes acting as molecular bricks are successfully assembled onto Ti3+ self-doping single-crystalline TiO2-x(B) nanorods through an effortless two-step hydrothermal process coupled with an in situ solid-state chemical reduction method. SrTiO3-x nanocubes act as molecular bricks, which are uniformly assembled onto the surface of TiO2-x(B) nanorods due to lattice matching. The band gap of the resultant SrTiO3-x/TiO2-x(B) sample is ∼2.97 eV, which exhibits excellent photocatalytic performance for the reduction of Cr(VI) and hydrogen production under visible light. The apparent rate constant k value for the photocatalytic reaction of SrTiO3-x/TiO2-x(B) for Cr(VI) reduction is ∼8 times higher than that of white TiO2(B). The photocatalytic hydrogen production rate for SrTiO3-x/TiO2-x(B) is ∼160.2 µmol g-1 h-1, which is ∼5 times higher than that of white TiO2(B). The enhanced photocatalytic activity can be considered to be caused by a synergetic effect of heterojunction formation and the introduction of Ti3+ self-doping, which can not only facilitate the separation of photogenerated charge carriers between TiO2-x(B) and SrTiO3-x, but also broaden the photoresponse from the UV to visible-light region.

Plasmon Ag decorated 3D urchinlike N-TiO2-x for enhanced visible-light-driven photocatalytic performance.

Plasmon Ag decorated 3D urchinlike N-TiO2-x photocatalysts are successfully synthesized by a facile hydrothermal treatment (180 °C) and combined with a photo-deposition approach, followed by a reduction treatment. The results show that the resultant Ag/N-TiO2-x sample possesses a three-dimensional (3D) urchinlike nanostructure with high crystallinity of anatase. Meanwhile, it exhibits the narrow optical band gap (Eg ∼ 2.61 eV) and the excellent visible-light-driven photocatalytic performance. Moreover, the hydrogen generation rate and photocatalytic degradation rate of phenol are up to 186.2 µmol h-1 g-1 and 97.7% under visible light irradiation, which are about 4.2 and 5.4 folds greater than that of N-TiO2. The mechanism of photocatalytic process is also proposed, and the enhanced photocatalytic property is mainly due to the synergistic reaction of the Ti3+ and N codoping, which narrows the band gap and favors the utilization of visible light, and the plasmon effect of Ag nanoparticles and unique 3D urchinlike architecture, which are propitious to the separation and transmission of photogenerated carriers.

Mercury removal from coal combustion flue gas by modified fly ash.

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2, CuCl2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2, CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.