F-doped orthorhombic Nb_(2)O_(5) exposed with 97% (100) facet for fast reversible Liþ-Intercalation

Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(2)O_(5))are rationally synthesized through topotactic conversion.Specifically,F-Nb_(2)O_(5) are assembled by single-crystal nanoflakes with nearly 97%exposed(100)facet,which maximizes the exposure of the feasible Li^(+)transport pathways along loosely packed 4g atomic layers to the electrolytes,thus effectively enhancing the Li^(+)-intercalation performance.Besides,the band gap of F-Nb_(2)O_(5) is reduced to 2.87 eV due to the doping of F atoms,leading to enhanced electrical conductivity.The synergetic effects between tailored exposed crystal facets,F-doping,and ultrathin building blocks,speed up the Li^(+)/electron transfer kinetics and improve the pseudocapacitive properties of F-Nb_(2)O_(5).Therefore,F-Nb_(2)O_(5) exhibit superior rate capability(210.8 and 164.9 mAh g^(-1) at 1 and 10 C,respectively)and good long-term 10 C cycling performance(132.7 mAh g^(-1) after 1500 cycles).

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.

Synthesis and Optimization of TiO_(2)/Graphene with Exposed {001} Facets Based on Response Surface Methodology and Evaluation of Enhanced Photocatalytic Activity

Response surface methodology(RSM)was employed to optimize the control parameters of TiO_(2)/graphene with exposed{001}facets during synthesis,and its enhanced photocatalytic activities were evaluated in the photodegradation of toluene.Experimental results were in good agreement with the predicted results obtained using RSM with a correlation coefficient(R^(2))of 0.9345.When 22.06 mg of graphite oxide(GO)and 2.09 mL of hydrofluoric acid(HF)were added and a hydrothermal time of 28 h was used,a maximum efficiency in the degradation of toluene was achieved.X-ray diffraction(XRD),transmission electron microscopy(TEM),and scanning electron microscopy(SEM)were employed to characterize the obtained hybrid photocatalyst.The electron transferred between Ti and C retarded the combination of electron–hole pairs and hastened the transferring of electrons,which enhanced the photocatalytic activity.

Au Nanoparticles Loaded on Hollow TiO2 Microspheres with （001） Exposed Facets： a Strategy for Promoting Photocatalytic Performance

Au nanoparticles loaded TiO2 hollow microspheres with exposed （001） facets（Au-HTFs） were synthesized through template-free hydrothermal process combined with a chemical reduction role. Au-HTFs displayed excellent photocatalytic activity in catalyzing oxidization reaction in organic pollutant system, which originates from the synergistic effect of the reactive （001） facets and Au nanoparticles with a wide range of absorption in visible region based on localized surface plasmon resonance effect. The unique synergistic effect could largely increase the photocatalytic performance resulting from the improvements of both the visible light aborption and the recombination of electron-hole pairs. Our findings revealed that among Au-HTFs with different Au loading percentages, Au-HTFs with 2%（mass fraction） Au loading possessed the superior photocatalytic activity.

SnO_2 nano-sheet as an efficient catalyst for CO oxidation

Polycrystalline SnO2 fine powder consisting of nano-particles （SnO2-NP）, SnO2 nano-sheets （SnO2-NS）, and SnO2 containing both nano-rods and nano-particles （SnO2-NR＋NP） were prepared and used for CO oxidation. SnO2-NS possesses a mesoporous structure and has a higher surface area, larger pore volume, and more active species than SnO2-NP, and shows improved activity. In contrast, although SnO2-NR＋NP has only a slightly higher surface area and pore volume, and slightly more active surface oxygen species than SnO2-NP, it has more exposed active （110） facets, which is the reason for its improved oxidation activity. Water vapor has only a reversible and weak influence on SnO2-NS, therefore it is a potential catalyst for emission control processes.

Lithium storage performance of {010}-faceted and [111]-faceted anatase TiO2 nanocrystals

As a popular anode material for lithium-ion batteries,anatase TiO2 nanoparticles with exposed{001}facets usually exhibit exceptional lithium storage performance owing to more accessible sites and fast migration of lithium ions along the good crystalline channels.However,there are few researches on the lithium storage capability of TiO2 nanocrystals with other high-energy facets owing to lack of effective synthesis method for controlling crystal facets.Herein,anatase TiO2 nanocrystals with exposed{010}-and[111]-facets are successfully prepared by using the delaminated tetratitanate nanoribbons as precursors.The electrochemical properties of these TiO2 nanocrystals with high-energy surfaces and the comparison with commercial TiO2 nanoparticles(P25)are studied.It is found that the cycle and rate performance of TiO2 nanocrystals is highly improved by reducing the particle size of nanocrystals.Moreover,TiO2 nanocrystals with exposed{010}-and[111]-facets exhibit better lithium storage capacities in comparison with P25 without a specific facet though P25 has smaller particle size than these TiO2 nanocrystals,indicating that the exposed facets of TiO2 nanocrystals have an important impact on their lithium storage capacity.Therefore,the synthesis design of high-performance TiO2 materials applied in the next-generation secondary batteries should both consider the particle size and the exposed facets of nanocrystals.

Photocatalytic mechanism of high-activity anatase TiO2 with exposed （001） facets from molecular-atomic scale： HRTEM and Raman studies

Anatase TiO2 with a variant percentage of exposed （001） facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that： 1） From HRTEM observations, the surface of original TiO2 with exposed （001） facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue （MB） solution, there were many 1 nm molecular absorbed at the surface of TiO2; after the photocatalytic experiment, MB molecules disappeared and the TiO2 lattice image became fuzzy. 2） The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO2 during photocatalyzation.

Facet-dependent transformation and toxicity of nanoscale zinc oxide in the synthetic saliva

The nanoscale zinc oxide(n-ZnO)was used in food packages due to its superior antibac terial activity,resulting in potential intake of n-ZnO through the digestive system,wherein n-ZnO interacted with saliva.In recent,facet engineering,a technique for controlling the exposed facets,was applied to n-ZnO,whereas risk of n-ZnO with specific exposed facets in saliva was ignored.ZnO nanoflakes(ZnO-0001)and nanoneedles(ZnO-1010)with the pri mary exposed facets of{0001}and{1010}respectively were prepared in this study,investigat ing stability and toxicity of ZnO-0001 and ZnO-1010 in synthetic saliva.Both ZnO-0001 and ZnO-1010 partially transformed into amorphous Zn_(3)(PO_(4))_(2)within 1 hr in the saliva even containing orgnaic components,forming a ZnO-Zn_(3)(PO_(4))_(2)core-shell structure.Neverthe less,ZnO-1010 relative to ZnO-0001 would likely transform into Zn_(3)(PO_(4))_(2),being attributed to superior dissolution of{1010}facet due to its lower vacancy formation energy(1.15 eV than{0001}facet(3.90 eV)).The toxicity of n-ZnO to Caco-2 cells was also dependent on the primary exposed facet;ZnO-0001 caused cell toxicity through oxidative stress,whereas ZnO-1010 resulted in lower cells viability than ZnO-0001 through oxidative stress and mem brane damage.Density functional theory calculations illustrated that·O_(2)^(-)was formed and released on{1010}facet,yet O_(2)^(2-)instead of·O_(2)^(-)was generated on{0001}facet,leading to low oxidative stress from ZnO-0001.All findings demonstrated that stability and toxicity of n-ZnO were dependent on the primary exposed facet,improving our understanding o health risk of nanomaterials.

Protein Corona Formation on Cadmium-Bearing Nanoparticles:Important Role of Facet-Dependent Binding of Cysteine-Rich Proteins

Cadmium-bearing nanoparticles,such as nanoparticulate cadmium selenide(CdSe)and cadmium sulfide(CdS),widely exist in the environment and originate from both natural and anthropogenic sources.Risk assessment of these nanoparticles cannot be accurate without taking into account the properties of the protein corona that is acquired by the nanoparticles upon biouptake.Here,we show that the compositions of the protein corona on CdSe/CdS nanoparticles are regulated collectively by the surface atomic arrangement of the nanoparticles and the abundance and distribution of cysteine moieties of the proteins in contact with the nanoparticles.A proteomic analysis shows that the observed facet-dependent preferential binding of proteins is mostly related to the cysteine contents of the proteins,among commonly recognized protein properties controlling the formation of the protein corona.Theoretical calculations further demonstrate that the atomic arrangement of surface Cd atoms,as dictated by the exposed facets of the nanoparticles,controls the specific binding mode of the S atoms in the disulfide bonds of the proteins.Supplemental protein adsorption experiments confirm that disulfide bonds remain intact during protein adsorption,making the binding of protein molecules sensitive to the abundance and distribution of Cd-binding moieties and possibly molecular rigidity of the proteins.The significant conformational changes of adsorbed proteins evidenced from a circular dichroism spectroscopy analysis suggest that disrupting the structural stability of proteins may be an additional risk factor of Cd-bearing nanoparticles.These findings underline that the unique properties and behaviors of nanoparticles must be fully considered when evaluating the biological effects and health risks of metal pollutants.

Formation of Oxygen Vacancies on the {010} Facets of BiOCl and Visible Light Activity for Degradation of Ciprofloxacin

BiOC1 nanosheets with oxygen vacancies on the exposed {010} facets were assistant-synthesized by triethanolamine（TEOA） via hydrothermal method. We explored the surface properties, crystal structure, morphology and optical absorption ability of the prepared samples via various characterization technologies. The results indicate that the morphologies and microstructures of the obtained samples depend on the amount of TEOA in the synthesis. The addition of TEOA induces the production of oxygen vacancy on the surface of the samples. Therefore, the synthesized samples with TEOA-assistance hold higher photoactivity for the degradation of colorless antibiotic agent ciprofloxacin（CIP） under visible light（λ≥420 nm）. The obtained sample upon the addition of 20 mL of TEOA exhibits the highest photocatalytic performance, which is nearly 14 times as high as that of the sample prepared without TEOA and twice as high as that of the prepared samples with NaOH or NH3·H2O. The possible degradation mechanism was discussed on the basis of the experiment results.

Influences of CeO_(2)morphology on enhanced performance of electro-Fenton for wastewater treatment

As a kind of rare-earth oxide,CeO_(2)has been considered as a great potential material for its abundant oxygen vacancies and catalysis activity in wastewater treatment.In this study,three ceria samples with different morphological structure were prepared,and their effect on contaminates degradation in electro-Fenton(E-Fenton)system was investigated.It is found that the morphology of CeO_(2)has great influence on promoting the performance of E-Fenton process.The rod-like CeO_(2)(R-CeO_(2))induced EFenton system shows higher azo dye X3 B removal and mineralization rates than cubs(C-CeO_(2))and octahedrons(O-CeO_(2)),and the degradation kinetic rate constants are 0.28,0.169 and 0.181 min^(-1)respectively,already surpass that of the blank one(0.120 min^(-1)).The H_(2)O_(2)generation capacity of R-CeO_(2)induced E-Fenton system is also superior to the others,and the corresponding Faraday current efficiency even increases to 166.2%at 2.5 min.Characterizations by scanning-transmission electron microscopy(STEM),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),electron spin resonance(ESR),Raman spectroscopy were conducted to disclose the mystery behind this phenomenon.The results indicate that the difference of surface oxygen vacancy density in different shaped CeO_(2)acts as a magic driving force for the accelerated oxygen reduction,and then leads to the enhanced degradation efficiency of E-Fenton system.This work provides a new insight into the development and application of rare-earth elements based catalyst in E-Fenton technology.