Multichannel Porous TiO2 Hollow Nanofibers with Rich Oxygen Vacancies and High Grain Boundary Density Enabling Superior Sodium Storage Performance

TiO₂ as an anode for sodium‐ion batteries (NIBs) has attracted much recent attention, but poor cyclability and rate performance remain problematic owing to the intrinsic electronic conductivity and the sluggish diffusivity of Na ions in the TiO₂ matrix. Herein, a simple process is demonstrated to improve the sodium storage performance of TiO₂ by fabricating a 1D, multichannel, porous binary‐phase anatase‐TiO₂–rutile‐TiO₂ composite with oxygen‐deficient and high grain‐boundary density (denoted as a‐TiO_2?x /r‐TiO_2?x ) via electrospinning and subsequent vacuum treatment. The introduction of oxygen vacancies in the TiO₂ matrix enables enhanced intrinsic electronic conductivity and fast sodium‐ion diffusion kinetics. The porous structure offers easy access of the liquid electrolyte and a short transport path of Na⁺ through the pores toward the TiO₂ nanoparticle. Furthermore, the high density of grain boundaries between the anatase TiO₂ and rutile TiO₂ offer more interfaces for a novel interfacial storage. The a‐TiO_2?x /r‐TiO_2?x shows excellent long cycling stability (134 mAh g^?1 at 10 C after 4500 cycles) and superior rate performance (93 mAh g^?1 after 4500 cycles at 20 C) for sodium‐ion batteries. This simple and effective process could serve as a model for the modification of other materials applied in energy storage systems and other fields.     

Homologous Heterostructured NiS/NiS2@C Hollow Ultrathin Microspheres with Interfacial Electron Redistribution for High-Performance Sodium Storage

Nickel sulfides with high theoretical capacity are considered as promising anode materials for sodium-ion batteries (SIBs); however, their intrinsic poor electric conductivity, large volume change during charging/discharging, and easy sulfur dissolution result in inferior electrochemical performance for sodium storage. Herein, a hierarchical hollow microsphere is assembled from heterostructured NiS/NiS₂ nanoparticles confined by in situ carbon layer (H-NiS/NiS₂@C) via regulating the sulfidation temperature of the precursor Ni-MOFs. The morphology of ultrathin hollow spherical shells and confinement of in situ carbon layer to active materials provide rich channels for ion/electron transfer and alleviate the effects of volume change and agglomeration of the material. Consequently, the as-prepared H-NiS/NiS₂@C exhibit superb electrochemical properties, satisfactory initial specific capacity of 953.0 mA h g⁻¹ at 0.1 A g⁻¹, excellent rate capability of 509.9 mA h g⁻¹ at 2 A g⁻¹, and superior longtime cycling life with 433.4 mA h g⁻¹ after 4500 cycles at 10 A g⁻¹. Density functional theory calculation shows that heterogenous interfaces with electron redistribution lead to charge transfer from NiS to NiS₂, and thus favor interfacial electron transport and reduce ion-diffusion barrier. This work provides an innovative idea for the synthesis of homologous heterostructures for high-efficiency SIB electrode materials.     

以PSA-A乳胶粒为模板批量制备TiO2空心球

以表面富载马来酸羧基的聚（苯乙烯-丙烯酸酯）阴离子（PSA-A）乳胶粒为模板,硫酸钛为原料,水为分散介质,制备了PSA-A/钛水解产物核壳微球,然后在空气中适当温度下煅烧得到粒径约为450nm的TiO2空心球壳,用TG、SEM、TEM、IR和XRD对样品进行了分析表征,并研究了核壳结构形成的过程和各实验条件对陈化过程中体系pH值变化速率的影响.得出影响核壳结构的关键因素为体系的pH值变化速率,以此依据设计出钛盐浓度为1mol/L,乳胶粒浓度为230g/L的高浓度条件下批量制备TiO2空心球壳的新实验方案,最终产物保持良好的空心球结构.     

Hierarchical TiO2/SnO2 Hollow Spheres Coated with Graphitized Carbon for High‐Performance Electrochemical Li‐Ion Storage

A self‐templated strategy is developed to fabricate hierarchical TiO₂/SnO₂ hollow spheres coated with graphitized carbon (HTSO/GC‐HSs) by combined sol–gel processes with hydrothermal treatment and calcination. The as‐prepared mesoporous HTSO/GC‐HSs present an approximate yolk‐double–shell structure, with high specific area and small nanocrystals of TiO₂ and SnO₂, and thus exhibit superior electrochemical reactivity and stability when used as anode materials for Li‐ion batteries. A high reversible specific capacity of about 310 mAh g^?1 at a high current density of 5 A g^?1 can be achieved over 500 cycles indicating very good cycle stability and rate performance.     

Er3+掺杂TiO2空心球的制备及其光催化性能研究

以钛酸四丁酯、氧化铒、硝酸等为原料, 采用碳球模板法制备了TiO₂: Er³⁺空心球材料, 利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试方法, 对样品的结构和形貌进行了表征。并利用紫外-可见(UV-Vis)分光光度计考察了TiO₂: Er³⁺空心球材料在催化染料罗丹明B、亚甲基蓝、茜素红、甲基橙的脱色降解过程中的应用性能。系统研究了Er³⁺掺杂浓度、不同离子型染料和染料水溶液的pH等因素对催化降解效率的影响。实验结果表明: 经600℃煅烧3 h制备的TiO₂: Er³⁺为锐钛矿晶型, 空心球结构, 尺寸均匀, 粒径约为120 nm, 比表面积约为60.5 m²/g; Er³⁺掺杂量为0.5mol%的样品对甲基橙染料的催化降解效率最高; 对四种不同离子型染料, 茜素红的催化降解效果显著, 在紫外光照射下, 催化效率较未掺杂Er³⁺的TiO₂提高了约30%。     

Heterostructured TiO2 Spheres with Tunable Interiors and Shells toward Improved Packing Density and Pseudocapacitive Sodium Storage

Insertion‐type anode materials with beneficial micro‐ and nanostructures are proved to be promising for high‐performance electrochemical metal ion storage. In this work, heterostructured TiO₂ shperes with tunable interiors and shells are controllably fabricated through newly proposed programs, resulting in enhanced pseudocapacitive response as well as favorable Na⁺ storage kinetics and performances. In addition, reasonably designed nanosheets in the extrinsic shells are also able to reduce the excess space generated by hierarchical structure, thus improving the packing density of TiO₂ shperes. Lastly, detailed density functional theory calculations with regard to sodium intercalation and diffusion in TiO₂ crystal units are also employed, further proving the significance of the surface‐controlled pseudocapacitive Na⁺ storage mechanism. The structure design strategies and experimental results demonstrated in this work are meaningful for electrode material preparation with high rate performance and volume energy density.     

Facile synthesis of defected TiO2-x (B) nanosheet/graphene oxide hybrids with high photocatalytic activity

TiO2 (B) nanosheets/GO (graphene oxide) hybrids are considered to be outstanding performance pho-tocatalysts for high efficiency of H2 evolution.However,they still suffer severe challenges during the synthetic processes,such as a large amount of the capping agents adhering on the surface and easy occurrence of aggregation.To figure out these obstacles,Ar plasma treatment as a modified method in this study not only enable the TiO2 (B) nanosheets distributed uniformly on the GO sheets but also engi-neer defects within TiO2 (B) nanosheetsto significantly improve the photocatalytic activity for the water splitting.The hydrogen evolution rate of the TiO2-x (B)/GO sheets is 1.4 times higher compared with that of original TiO2 (B)/GO sheets without Ar plasma treatment.The improved photocatalytic proper-ties were owing to the synergetic effects of oxygen vacancies and the heterojunction between GO and TiO2 (B),which can promote the visible light utilization and accelerate separation and transportation of photogenerated electron-holes.This study can provide a facile pathway to prepare the two-dimensional hybrid photocatalysts with high photocatalytic H2 activity.     

具有高活性(001)晶面的TiO2纳米方块的制备及光催化性能

采用水热法制备了尺寸为70~100 nm, 具有高活性(001)晶面的锐钛矿相TiO₂纳米方块, 利用FE-SEM、TEM、XRD和UV-Vis DRS等手段对催化剂结构和光吸收性能进行分析, 同时考察了水热反应温度和溶液pH对TiO₂形貌和(001)晶面暴露率的影响。以酸性红染料为目标污染物, 对催化剂的光催化活性进行研究。实验结果表明, 合成TiO₂纳米方块的最佳条件为水热温度180℃、溶液pH=4~5。(001)晶面的光催化活性优于(101)晶面, 具有33%(001)晶面暴露率的TiO₂纳米方块的光催化活性是普通TiO₂的1.6倍。     

Photocatalytic degradation of mixed pollutants in aqueous wastewater using mesoporous 2D/2D TiO2(B)-BiOBr heterojunction

There are multiple contaminants in practical wastewater;and the photodegradation of mixed pollutants is a challenge in the field of photocatalysis.Herein,we design a mesoporous 2D/2D TiO2(B)-BiOBr hetero-junction photocatalyst for the photodegradation of mixed pollutants.Such a coupling structure results in an enhancement in the disconnection of photoexcited carriers,and the increase of absorption and reaction sites.The 2D/2D TiO2(B)-BiOBr demonstrates outstanding photocatalytic activity for photode-grading rhodamine B(RhB),methyl orange(MO),tetracycline hydrochloride(TCH),and bisphenol A(BPA)simultaneously under visible light,which is 4.7.1.4,23 and 16.4 times as high as that of original BiOBr,respectively.Our work represents a possible solution to devise promising and efficient photocatalysts for the treatment of practical wastewater in the near future.     

TiO_2-NTs/rGO复合材料的制备及电化学性能

通过碱液水热法制备TiO_2纳米管(TiO_2-NTs)前驱体,并将其与氧化石墨烯复合得到二氧化钛纳米管/还原氧化石墨烯(TiO_2-NTs/rGO)复合材料。利用X射线衍射仪(XRD),透射电子显微镜(TEM),电化学测试等分析技术对复合物进行表征。结果表明:复合物中TiO_2-NTs晶相为B型(TiO_2(B)),其管径约为25~30nm;与单纯TiO_2-NTs相比,石墨烯负载的TiO_2-NTs的倍率性能和循环性能都得到显著改善,在放电倍率为1C(335mA/g)时,TiO_2-NTs/rGO和TiO_2-NTs首次放电容量分别为258.5mAh/g和214.9mAh/g;电化学阻抗谱测试显示,复合材料的电荷转移电阻明显小于纯相TiO_2-NTs。     

Na2Ti3O7@N‐Doped Carbon Hollow Spheres for Sodium‐Ion Batteries with Excellent Rate Performance

Uniform Na₂Ti₃O₇ hollow spheres assembled from N‐doped carbon‐coated ultrathin nanosheets are synthesized. A unique multilayer structure of nanosheets is presumed to significantly reduce energy consumption during the diffusion process of sodium ions, while the carbon‐coated structure can increase the overall conductivity. The as‐prepared sample used as an anode in sodium‐ion batteries exhibits the best rate performance ever reported for Na₂Ti₃O₇, delivering more than 60 mAh g^?1 after 1000 continuous cycles at the high rate of 50 C, which was achieved due to its unique structure.     

Identifying the Origin and Contribution of Surface Storage in TiO2(B) Nanotube Electrode by In Situ Dynamic Valence State Monitoring

Fundamental insight into the surface charging mechanism of TiO₂(B) nanomaterials is limited due to the complicated nature of lithiation behavior, as well as the limitations of available characterization tools that can directly probe surface charging process. Here, an in situ approach is reported to monitor the dynamic valence state of TiO₂(B) nanotube electrodes, which utilizes in situ X‐ray absorption spectroscopy (XAS) to identify the origin and contribution of surface storage. A real‐time correlation is elucidated between the rate‐dependent electrode performance and dynamic Ti valence‐state change. A continuous Ti valence state change is directly observed through the whole charging/discharging process regardless of charging rates, which proves that along with the well‐known non‐faradaic reaction, the surface charging process also originates from a faradaic reaction. The quantification of these two surface storage contributions at different charging rates is further realized through in situ dynamic valence state monitoring combined with traditional cyclic voltammetry measurement. The methodology reported here can also be applied to other electrode materials for the real‐time probing of valence state change during electrochemical reactions, the quantification of the faradaic and non‐faradaic reactions, and the eventual elucidation of electrochemical surface charging mechanisms.