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).

Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO_(2) nanosheets for enhancing photocatalytic H_(2) evolution

Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.

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.

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.

One-step synthesized SO_4^(2-)-TiO_2 with exposed(001) facets and its application in selective catalytic reduction of NO by NH_3

A sample of sulfated anatase TiO2 with high‐energy(001)facets(TiO2‐001)was prepared by a simple one‐step hydrothermal route using SO42-as a morphology‐controlling agent.After doping ceria,Ce/TiO2‐001 was used as the catalyst for selective catalytic reduction(SCR)of NO with NH3.Compared with Ce/P25(Degussa P25 TiO2)and Ce/P25‐S(sulfated P25)catalysts,Ce/TiO2‐001 was more suitable for medium‐and high‐temperature SCR of NO due to the high surface area,sulfation,and the excellent properties of the active‐energy(001)facets.All of these facilitated the generation of abundant acidity,chemisorbed oxygen,and activated NOx‐adsorption species,which were the important factors for the SCR reaction.

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.

Photocatalytic Activity of Hierarchical Flower-Like TiO_(2) Superstructures with Dominant {001} Facets

The fabrication of well defined hierarchical structures of anatase TiO_(2) with a high percentage of reactive facets is of great importance and challenging.Hierarchically flower-like TiO_(2) superstructures(HFTS)self-assembled from anatase TiO_(2) nanosheets with exposed{001}facets(up to 87%)were synthesized by a simple alcohothermal strategy in a HF-H_(2)O-C_(2)H_(5)OH mixed solution using titanate nanotubes as precursor.The samples were characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,and N2 adsorption-desorption isotherms.The photocatalytic activity was evaluated by the photocatalytic oxidation decomposition of acetone in air and methyl orange in aqueous solution under UV illumination.The photocatalytic activity of HFTS was much higher than that of commercial Degussa P25 and tabular-shaped anatase TiO_(2) obtained using pure water as the synthesis medium.The enhancement in photocatalytic activity was related to several factors,including the hierarchically porous structure,exposed{001}facets,and increased light harvesting ability.The HFTS was also of interest for use in solar cells,photocatalytic H_(2) production,optoelectronic devices,sensors,and catalysis.

Dye-Sensitized Solar Cells with An Electrophoresis-Deposited Layer of {001} Exposed Nanosheet-Based Hierarchical TiO_(2) Spheres

Anatase Ti0_(2) nanosheet-based hierarchical spheres(HSs)with nearly 100%exposed{001}facets were synthesized via a facile solvothermal process.Using these hierarchical spheres as a scattering layer on nanocrystaline TiO_(2)film,hi-layered dye-sensitized solar cells(DSSCs)have been fabricated by electrophoresis deposition method,which well preserved the fragile hierarchical structure.Owing to the superior dye adsorption and light scattering effect of HSs,an overall energy conversion efficiency of 7.38%is achieved,which is 26%higher than that of nanoparticle-based photoanode.

Surface Modification of (001) Facets Dominated TiO2 with Ozone for Adsorption and Photocatalytic Degradation of Gaseous Toluene

This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated（001） facets for toluene degradation.The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modification, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation.The surface modification with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5 c-Ti sites on（001）facets act as the adsorption sites for ozone. The formed Ti–O bonds reacted with H2O to generate a large amount of isolated Ti5 c-OH which act as the adsorption sites for toluene,and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO2 is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH·radicals under irradiation. Furthermore, the O2 generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.

Pt/TiO_(2) Nanosheets Array Dominated by {001} Facets with Enhanced Photocatalytic Activity

{001}facets dominated single crystalline anatase TiO_(2) nanosheet array(TNSA)was synthe-sized through an optimized organic solvothermal route on uorine-doped tin oxide substrate.The field emission scanning electron microscopy images and X-ray diffraction patterns re-vealed that the{001}synthesized facets dominated TNSA exhibited much higher orientation than that synthesized by hydrothermal route.The TNSAs were loaded with Pt nanoparti-cles in uniformly size by using a photodecomposition method,which were further con rmed by high resolution transmission electron microscopy(HRTEM).The HRTEM images also revealed that Pt nanoparticles preferred to deposit on{001}facets.With loading of Pt nanoparticles,the optical absorbance was significantly enhanced,while the photolumines-cence(PL)was inhibited.The photocatalytic activity of TNSA was signi cantly improved by Pt loading and reached the maximum with optimal amount of Pt loading.The optimal amount of Pt on{001}facets is far less than that on TiO_(2) nanoparticles,which may be attributed to the specific atom structure of reactive{001}facets.

(001)/(101)晶面暴露TiO_(2)光催化氧化甘油制备甲酸研究

采用水热法制备了(001)/(101)晶面暴露的TiO_(2)催化剂,对其光催化氧化甘油制备甲酸性能进行了研究。利用SEM、TEM、XRD、XPS、EPR、Raman、UV-vis DRS和PL对TiO_(2)的结构和光学性能进行表征。结果表明,以钛酸异丙酯为Ti源,以氢氟酸为形貌控制剂,通过水热法合成的TiO_(2)暴露出(001)晶面。氢氟酸加入量为2 mL的样品(TiO_(2)-2F)同时暴露锐钛矿(001)和(101)晶面,表现出最高的催化活性和选择性。紫外光照射4 h,TiO_(2)-2F催化剂上甘油转化率为49.0%,甲酸选择性为55.6%。界面接触的(001)和(101)晶面形成表面异质结,抑制光生载流子的复合,提高甘油光催化氧化活性。(001)晶面的氧空位和配位不饱和O_(2c)-Ti_(5c)-O_(2c)键合方式使甘油及其中间产物深度氧化,提高甲酸选择性。机理分析表明,·OH和·O^(-)_(2)是甘油选择性氧化制备甲酸的关键活性物种。

TiO_(2) nanosheets with exposed {001} facets for photocatalytic applications

TiO_(2) nanosheets with highly reactive{001}facets({001}-TiO_(2))have attracted great attention in the fields of science and technology because of their unique properties.In recent years,many efforts have been made to synthesize{001}-TiO_(2) and to explore their applications in photocatalysis.In this review,we summarize the recent progress in preparing{001}-TiO_(2) using different techniques such as hydrothermal,solvothermal,alcohothermal,chemical vapor deposition(CVD),and sol gel-based techniques.Furthermore,the enhanced efficiency of{001}-TiO_(2) by modification of carbon materials,surface deposition of transition metals,and non-metal doping is reviewed.Then,the applications of{001}-TiOR-based photocatalysts in the degradation of organic dyes,hydrogen evolution,carbon dioxide(CO_(2))reduction,bacterial disinfection,and dye-sensitized solar cells are summarized.We believe this entire review on TiO_(2) nanosheets with{001}facets can further inspire researchers in associated fields.

Self-assembly of nitrogen-doped TiO_(2) with exposed {001} facets on a graphene scaffold as photo-active hybrid nanostructures for reduction of carbon dioxide to methane

Tailored synthesis of well-defined anatase TiO_(2)-based crystals with exposed{001}facets has stimulated incessant research interest worldwide due to their scientific and technological importance.Herein,anatase nitrogen-doped TiO_(2)(N-TiO_(2))nanoparticles with exposed{001}facets deposited on the graphene(GR)sheets(N-TiO_(2)-001/GR)were synthesized for the first time via a one-step solvothermal synthetic route using NH4F as the morphology-controlling agent.The experimental results exemplified that GR was uniformly covered with anatase N-TiO_(2) nanoparticles(10-17 nm),exposing the{001}facets.The percentage of exposed{001}facets in the N-TiO_(2)-001/GR nanocomposites was calculated to be ca.35%.Also,a red shift in the absorption edge and a strong absorption in the visible light range were observed due to the formation of Ti-O-C bonds,resulting in the successful narrowing of the band gap from 3.23 to 2.9 eV.The photocatalytic activities of the as-prepared photocatalysts were evaluated for CO_(2) reduction to produce CH,in the presence of water vapor under ambient temperature and atmospheric pressure using a low-power 15 W energy-saving daylight lamp as the visible light source--in contrast to the most commonly employed high-power xenon lamps--which rendered the process economically and practically feasible.Among all the studied photocatalysts,the N-TiO_(2)-001/GR nanocomposites exhibited the greatest CH4 yield of 3.70 p-mol'gcatalyst 1,approxi-mately 11-fold higher activity than the TiO_(2)-001.The enhancement of photocatalyfic performance was ascribed to the effective charge anti-recombination of graphene,high absorption of visible light region relative to the{101}facets.and high catalytic activity of{001}facets.

Synthesis of anatase TiO_(2) with exposed {001} and {101} facets and photocatalytic activity

Anatase titanium(IV)oxide(TiO_(2))particles with exposed{001}and{101}facets were prepared by hydrothermal treatment of amorphous TiO_(2) with H_(2)O_(2)-NH_(3) solution.Crystal phase,shape,and size of TiO_(2) particles are found to be greatly dependent on the ratio of H_(2)O_(2)-NH_(3) solution.The prepared TiO_(2) particles with specific exposed crystal faces show higher photocatalytic activity for acetaldehyde decomposition than commercial spherical TiO_(2) particles.This result implies that recombination is prevented by spatial separation of redox sites in the particles because of selective migration of electrons and positive holes to specific exposed crystal faces and/or different reactivity of electrons and positive holes on the specific exposed crystal face.

Effect of defects in TiO_(2) nanoplates with exposed {001} facets on the gas sensing properties

The exposed crystal facet of TiO_(2) is a crucial factor influencing the gas sensing properties.TiO_(2) with high-energy{001}crystal facets that have higher surface energy and reactivity is expected to exhibit excellent gas-sensing properties.In this paper,TiO_(2) nanoplates with defective{001}facets were synthesized by chemical etching via one-step hydrothermal method.We carefully explored the gas-sensing performance of TiO_(2) nanoplates with defective and complete{001}facets towards acetone.The results show that the sensing response of TiO_(2) nanoplates with complete{001}facets is 70%higher than that of defective TiO_(2) nanoplates,which proves that the{001}facets plays a vital role in improving the gas sensing performance of TiO_(2).It is speculated that the poor gas sensitivity of defective TiO_(2) can be contributed to fewer adsorption sites and blocked electron transfer.This work presents a more direct evidence for explaining the important role of the complete{001}crystal facets in high sensitivity of TiO_(2) and also provides a new insight for preparing high sensitivity sensing materials.

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.

The preparation of nitrogen-doped TiO_2 nanocrystals with exposed {001} facets and their visible-light photocatalytic performances

Anatase TiO2with exposed{001}facets has been deepgoingly studied for optimizing its photocatalytic activity.In this study,we synthesized N-doped TiO2 nanocrystals with exposed{001}facets by sol–gel method and solvothermal method,respectively.The physical and chemical properties of as-synthesized samples,such as morphology,crystal phase,surface elements composition,porous structure,specific surface area,and optical response,were characterized in detail.The photocatalytic performances of all samples were evaluated by photocatalytic decoloration of methylene blue under visible-light irradiation(k[420 nm).The results showed that the as-prepared samples present high visible-light photocatalytic performances,which can be ascribed to the excellent crystallization,the enhancement of absorbance in the visible-light region,and the strong adsorption performance,and calcination treatment is helpful to further improve the visible-light photocatalytic performance of N-doped TiO2 nanocrystals with exposed{001}facets.

Mesocrystalline TiO_(2) nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystaUine anatase TiO_(2) nanosheets with highly exposed{001}facets was developed through topotactic transformation.Unique mesocrystalline{001}-faceted TiO_(2) nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the{001}-faceted TiO_(2) nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed{001}facets,in addition to the advantageous features of low-dimensional structure arrays(e.g.,fast electron transport and efficient charge collection),the obtained TiO_(2) nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells(DSSCs).Particularly,{001}-faceted TiO_(2) nanosheet arrays-15μm long annealed at 500℃showed a power conversion efficiency of 7.51%.Furthermore,a remarkable efficiency of 8.85%was achieved for a DSSC based on doubleqayered TiO_(2) nanosheet arrays-35μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.

非水溶剂热法制备(001)面暴露的F/TiO_2纳米晶及其光催化活性

采用非水体系溶剂热法制备了(001)面暴露的锐钛矿相F/TiO2纳米光催化剂.结果表明,F的掺杂对TiO2纳米单晶的形成影响很大.一方面,F离子作为晶面导向剂稳定(001)晶面,形成(001)面暴露的锐钛矿相TiO2;另一方面,F离子也起到稳定剂作用,抑制纳米粒子的快速生长.以光催化降解甲基橙为模型反应比较了不同F/TiO2样品和商业P25样品的光催化活性.同时,通过选用不同捕获剂,研究了F/TiO2和P25样品在甲基橙降解反应中的活性物种.

可见光响应(001)晶面纳米TiO_2光催化剂的制备及性能研究

以钛酸丁酯为钛源,氢氟酸为形貌控制剂,采用水热法合成了具有高表面能(001)晶面的锐钛矿相TiO_2纳米材料。利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及紫外-可见漫反射光谱分析(UV-vis)对样品的形貌、结构和谱学性能进行表征,并以甲基橙溶液为目标污染物,研究其光催化性能和最佳制备条件。结果表明,以氢氟酸为形貌控制剂时,可制备锐钛矿相(001)晶面纳米TiO_2纳米材料,能拓宽TiO_2体系光响应范围,并具有较高的光催化性能;当反应温度为180°C、时间为24 h、F/Ti摩尔比为1.5时,样品对甲基橙溶液光催化降解率最高,在紫外光照射条件下1 h内降解率可达99.08%,其可见光降解率为66.79%。