In-situ decoration of metallic Bi on BiOBr with exposed(110)facets and surface oxygen vacancy for enhanced solar light photocatalytic degradation of gaseous n-hexane

Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is still rare.Here,a series of Bi/BiOBr composites were solvothermally synthe-sized and applied in solar-light-driven photocatalytic degradation of gaseous n-hexane.The charac-terization results revealed that both increasing number of functional groups of alcohol solvent(from methanol and ethylene glycol to glycerol)and solvothermal temperature(from 160 and 180to 200℃)facilitated the in-situ formation of metallic Bi nanospheres on BiOBr nanoplates withexposed(110)facets.Meanwhile,chemical bonding between Bi and BiOBr was observed on theseexposed facets that resulted in the formation of surface oxygen vacancy.Furthermore,the synergis-tic effect of optimum surface oxygen vacancy on exposed(110)facets led to a high visible light re-sponse,narrow band gap,great photocurrent,low recombination rate of the charge carriers,andstrong·O2-and h*formation,all of which resulted in the highest removal efficiency of 97.4%within120 min of 15 ppmv of n-hexane on Bi/BiOBr.Our findings efficiently broaden the application ofBi-based photocatalysis technology in the purification of gaseous straight-chain pollutants emittedby the petrochemical industry.

Engineering surface oxygen vacancy of mesoporous CeO_(2) nanosheets assembled microspheres for boosting solar-driven photocatalytic performance

Surface oxygen vacancy defects of mesoporous CeO_(2)nanosheets assembled microspheres(D-CeO_(2))are engineered by polymer precipitation,hydrothermal and surface hydrogenation strategies.The resultant D-CeO_(2)with a main pore diameter of 9.3 nm has a large specific surface area(~102.3 m^(2)/g)and high thermal stability.The mesoporous nanosheets assembled microsphere structure prevents the nanosheets from aggregation,which is beneficial to effective mass transfer and shortens the migration distance of charge carriers.After surface hydrogenation,the photoresponse extends to long wavelength region,combing with the band gap from 2.63 eV reduced to 2.39 eV.Under AM 1.5 G radiation,the photocatalytic degradation rate of tetracycline(TC)can be up to 99.99%,which is three times as high as that of pristine CeO_(2)microspheres.The excellent solar-driven photocatalytic performance can be attributed to the efficient surface oxygen vacancy engineering and the mesoporous nanosheets assembled microsphere structure,which narrows the band gap,shortens the migration distance of carriers,promotes the spatial separation of photogenerated electron-hole pairs and favors mass transfer.The strategy provides new insights for fabricating other high-efficient oxide photocatalysts.

Effect of Calcination Temperature on Surface Oxygen Vacancies and Catalytic Performance Towards CO Oxidation of Co3O4 Nanoparticles Supported on SiO2

Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）, laser Raman spectroscopy, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR） and X-ray absorption fine structure （XAFS） spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2＋ ions are present on the surface of Co3O4 in Co3O4（200）/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4（200）/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4（200）/SIO2 contains excess Co2＋. Increasing calcination temperature results in oxidation of excess Co2＋ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4（200）/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2＋ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.

Zn‐doping mediated formation of oxygen vacancies in SnO2 with unique electronic structure for efficient and stable photocatalytic toluene degradation

To optimize the electronic structure of photocatalyst,a facile one‐step approach is developed for the simultaneous realization of Zn‐doping and surface oxygen vacancies(SOVs)formation on SnO_(2).The Zn‐doped SnO_(2)with abundant SOVs exhibits efficient and stable performance for photocatalytic degradation of toluene under both low and high relative humidity.Experimental and theoretical calculations results show that the synergistic effects of Zn‐doping and SOVs on SnO_(2)can considerably boost the charge transfer and separation efficiency.Utilizing the in situ DRIFTS and theoretical calculations methods,it is revealed that the benzene ring of toluene is opened at benzoic acid on the SnO_(2)surface and selectively at benzaldehyde on the Zn‐doped SnO_(2)surface.This implies that Zn‐doped SnO_(2)photocatalysts shorten the pathway of toluene degradation,and toxic intermediates can be significantly inhibited.This work could provide a promising and sustainable route for safe and efficient removal of aromatic VOCs with photocatalytic technology.

Oxygen vacancy O-terminated surface:The most exposed surface of hexagonal WO3(001)surface

It is known that exposed surface determines material’s performance.WO3 is widely used in gas sensing and its working surface is proposed to control its sensitivity.However,the working surface,or most exposed surface with detailed surface structure remain unclear.In this paper,DFT calculation confirmed that oxygen vacancy O-terminated surface is the most exposed hexagonal WO3(001)surface,judging from competitive adsorption of CO and O2,working surface determination for CO sensing and comparison of oxygen vacancy formation ene rgies on different h-WO3(001)surfaces.It is found that DFT can be a useful alternate for exposed surface determination.Our results provide new perspectives and performance explanations for material research.

Enhanced CO catalytic oxidation by Sr reconstruction on the surface of LaxSr1-xCoO3-δ

Surface electronic structure of solid materials plays a critical role in heterogeneous catalysis. However, surface chemical composition of the perovskite oxides is usually dominated by segregated A-site cations and the amount of oxygen vacancies is relatively low, which seriously restricts their catalytic oxidation property. Here, we prepare perovskite LaxSrl xCO03 ~ （x = 0.3, 0.5, 0.7） with different Sr doping amount and experiment results show that perovskite LSCO with higher content of surface Sr possesses more oxy- gen vacancies and better catalytic activity. On this basis, we develop a new experimental strategy to cre- ate more surface oxygen vacancies to promote their CO catalytic activity. In this method, we use high active hydrogen atoms （BHa-） as reductant to realize surface in-situ chemical composite modification of LaxSrl xCo03 ~s （x = 0.3, 0.5, 0.7）, which causes their surface reconstruction （surface Sr enrichment）. The regulation mainly focuses on the atomic layer level without damaging their bulk phase structure. Different from traditional high temperature annealing under reducing atmosphere, this method is high-efficiency, green and controllable. Furthermore, we study the surface reconstruction process and demonstrated that it is atomic layer engineering on the surface of LaxSr1-xCoO3-δ （x = 0.3, 0.5, 0.7） by X-ray photoelectron spectroscopy （XPS） and X-ray absorption fine structure （XAFS）. Our experiment results also show that these samples treated by this method exhibit superior activity for CO oxidation compared with original samples.

Catalytic oxidation of CO over Pt/Fe3O4 catalysts:Tuning O2 activation and CO adsorption

The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation.It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance.In this work,we used in situ reductions of chloroplatinic acid on commercial Fe3O4 powder to prepare heterogeneousstructured Pt/Fe3O4 catalysts in the solution of ethylene glycol.The heterogeneous Pt/Fe3O4 catalysts achieved a better catalytic performance of CO oxidation compared with the Fe3O4 powder.The temperatures of 50%and 90%CO conversion were achieved above 260℃and 290℃at Pt/Fe3O4,respectively.However,they are accomplished on Fe3O4 at temperatures higher than 310℃.XRD,XPS,and H2-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe3O4 supports.TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe3O4.The combined results of O2-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe3O4 catalysts.The reaction pathway involves a Pt-assisted Mars-van Krevelen(MvK)mechanism.

A2B2O7 pyrochlore compounds:A category of potential materials for clean energy and environment protection catalysis

A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of special compounds has rarely been documented,though a few researchers have tried to synthesize some pyrochlore compounds with different chemical compositions for a variety of green energy production and air pollution control reactions in the history.With the expectation to help catalysis scientists to get better acquaintance with,and gain deeper understanding on this type of compounds as heterogeneous catalysts,the major publications over the past several decades have been screened and reviewed in this paper,based also on our own experience of studying on this type of catalytic materials.The crystalline phase transformations of the compounds with the change of the A and B site cations,the phase change’s influences on the surface and bulk properties,and their subsequent impact on the catalytic performance for different reactions have been summarized.Furthermore,the future work which needs to be performed to perceive in depth this kind of important materials as catalysts has been proposed and suggested.We trust that this short review contains valuable information,which will provide great help for people to get better cognition for A2 B2 O7 pyrochlore compounds,and assist them to develop better catalysts for various reactions.

Diffusion-controlled synthesis of Cu-based catalysts for the Rochow reaction

The properties of materials are strongly dependent on their structures. The diffusion effect is a main kinetic factor that can be used to regulate the growth and structure of materials. In this work, we developed a systematic and feasible strategy to synthesize Cu2O solid spheres and hexahedrons by controlling the diffusion coefficients. These Cu2O products can be successively transformed into corresponding Cu hollow spheres and hexahedrons as well as CuO porous spheres and hexahedrons by controlling hydrogen diffusion in hydrazine hydrate solution and controlling oxygen diffusion in air, respectively. The formation of these transformations was also discussed in detail. Tested for Rochow reaction, the as-prepared Cu2O solid and CuO porous spheres exhibit higher dimethyldichlorosilane selectivity and Si conversion than Cu hollow spheres, which is attributed to the active sites for CH3Cl adsorption formed in CuxSi phase after the removal of oxygen atoms in Cn2O and CuO in the formation of dimethylchlorosilane. The present work not only develops a feasible method for preparing well shape-defined Cu2O solid spheres and hexahedrons but also clarifies the respective roles of Cu, Cu2O and CuO in dimethyldichlorosilane synthesis via Rochow reaction.