Plasma synthesis of various polymorphs of tungsten trioxide nanoparticles using gliding electric discharge in humid air:characterization and photocatalytic properties

A gliding electric arc(glidarc)discharge generates a low-temperature plasma at atmospheric pressure.When the discharge occurs in humid air as the feed gas,the chemistry of a glidarc plasma consists of in situ formation of HO°and NO°as the primary chemical species.Tungsten trioxide(WO_(3))nanoparticles were successfully prepared by exposure of a liquid precursor to glidarc plasma.The WO_(3)samples were calcined at three different temperatures(300℃,500℃and 800℃),resulting in different pure polymorphs:γ-WO_(3)(at 300℃),β-WO_(3)(at 500℃)andα-WO_(3)(at 800℃)according to x-ray diffraction analysis.The identification of WO_(3)compounds was also confirmed by attenuated total reflection Fourier transform infrared spectroscopy analysis.Increase in the calcination temperature of WO_(3)induced a decrease in its specific surface area according to Brunauer–Emmett–Teller nitrogen physisorption analysis.The UV-visible results showed that the absorption bands of plasma-WO_(3)samples were more intense than those of WO_(3)samples obtained by a precipitation route,a classical method used for comparison.Consequently,this parameter can improve the photocatalytic properties of WO_(3)under visible light.The photodegradation(in sunlight conditions)of gentian violet,chosen as a model pollutant,confirmed the photocatalytic properties of plasma-WO_(3)samples.This novel synthesis method has great potential to improve the efficiency of advanced tungsten trioxide-based functional material preparation,as well as in pollution-reducing and energy-saving tungsten extractive metallurgy.

Low-temperature catalytic methane deep oxidation over sol-gel derived mesoporous hausmannite (Mn_(3)O_(4)) spherical particles

In this study,Mn_(3)O_(4) spherical particles(SPs)were synthesized by the sol-gel process,after which they were thermally annealed at 400℃,and comprehensively characterized.X-ray Diffraction(XRD)revealed that Mn_(3)O_(4) exhibited a tetragonal spinel structure,and Fourier transformed infrared(FTIR)spectroscopy identified surfaceadsorbed functional groups.Scanning electron microscopy(SEM)and the specific surface area analyses by Brunauer−Emmett−Teller(BET)revealed a porous,homogeneous surface composed of strongly agglomerated spherical grains with an estimated average particle size of∼35 nm,which corresponded to a large specific surface area of∼81.5 m^(2)/g.X-ray photoelectron spectroscopy(XPS)analysis indicated that Mn_(3)O_(4) was composed of metallic cations(Mn^(4+),Mn^(3)+,and Mn^(2+))and oxygen species(O_(2)−,OH−and CO_(3)^(2−)).The optical bandgap energy is∼2.55 eV.Assessment of the catalytic performance of the Mn_(3)O_(4) SPs indicated T90 conversion of CH4 to CO_(2) and H_(2)O at 398℃ for gas hourly space velocity(GHSV)of 72000 mL^(3) g^(−1) h^(−1).This observed performance can be attributed to the cooperative effects of the smallest spherical grain size with a mesoporous structure,which is responsible for the larger specific surface area and available surface-active oxygenated species.The cooperative effect of the good reducibility,higher ratio of active species(OLat/OAds),and results of density functional theory(DFT)calculations suggested that the total oxidation of CH_(4) over the mesoporous Mn_(3)O_(4) SPs might take place via a two-term process in which both the Langmuir−Hinshelwood and Mars−van Krevelen mechanisms are cooperatively involved.