N‐doped porous carbon nanofibers inlaid with hollow Co_(3)O_(4) nanoparticles as an efficient bifunctional catalyst for rechargeable Li‐O_(2) batteries

Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.

Sulfur-doped g-C3N4/TiO2 S-scheme heterojunction photocatalyst for Congo Red photodegradation

Constructing step-scheme(S-scheme)heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials.In this work,a series of sulfur-doped g-C3N4(SCN)/TiO2 S-scheme photocatalysts were synthesized using electrospinning and calcination methods.The as-prepared SCN/TiO2 composites showed superior photocatalytic performance than pure TiO2 and SCN in the photocatalytic degradation of Congo Red(CR)aqueous solution.The significant enhancement in photocatalytic activity benefited not only from the 1D well-distributed nanostructure,but also from the S-scheme heterojunction.Furthermore,the XPS analyses and DFT calculations demonstrated that electrons were transferred from SCN to TiO2 across the interface of the SCN/TiO2 composites.The built-in electric field,band edge bending,and Coulomb interaction synergistically facilitated the recombination of relatively useless electrons and holes in hybrid when the interface was irradiated by simulated solar light.Therefore,the remaining electrons and holes with higher reducibility and oxidizability endowed the composite with supreme redox ability.These results were adequately verified by radical trapping experiments,ESR tests,and in situ XPS analyses,suggesting that the electron immigration in the photocatalyst followed the S-scheme heterojunction mechanism.This work can enrich our knowledge of the design and fabrication of novel S-scheme heterojunction photocatalysts and provide a promising strategy for solving environmental pollution in the future.

La^(3+)、Nd^(3+)与非金属氮共掺杂TiO_2光催化剂的制备及其性能研究

采用溶胶-凝胶法制备了Ti O2、1%La/Ti O2、1%Nd/Ti O2和系列稀土La3+和Nd3+共掺杂Ti O2光催化剂,进而结合水热法制备了双稀土La3+、Nd3+和非金属氮共掺杂多元体系Ti O2光催化剂,并采用XRD、UV-Vis、SEM和XPS等测试手段对制备样品的微观结构、光谱学性能和离子掺杂形式进行了表征。研究表明,实验所制备样品均为锐钛矿型Ti O2光催化剂,稀土离子La3+或Nd3+的掺杂能有效抑制Ti O2颗粒尺寸的生长,而且双稀土离子的共掺杂更有效抑制Ti O2光催化剂颗粒尺寸的生长;非金属离子N的掺杂,能有效拓宽Ti O2光催化剂的光响应范围;多元体系Ti O2光催化剂中,稀土钕以+3形式掺杂,非金属氮以-3形式掺杂。实验以甲基橙为目标污染物研究其光催化性能,研究表明,所制备的光催化剂均有较高的紫外光光催化性能,其中样品1%(La∶Nd,1∶7),N/Ti O2的紫外光光催化性能最高,而且有较强的可见光光催化活性。

固体超强酸SO_4^(2-)/TiO_2/Nd^(3+)催化合成糠酸乙酯

采用稀土元素Nd3+对固体超强酸SO24-/TiO2进行改性,制备出固体超强酸SO24-/TiO2/Nd3+为催化剂,以自制糠酸和乙醇为原料合成糠酸乙酯。通过正交法设计实验方案,对各种因素与收率的影响进行了讨论。实验结果表明,最佳反应条件为:催化剂用量为1.0g,醇酸物质的量比1∶4,反应时间为4h,该催化剂可再生重复多次使用,产品的收率达92.2%。

水热法制备Nd^(3+)-介孔TiO_2/GO复合材料及光催化性能研究

采用水热法首先制备稀土Nd^(3+)掺杂介孔TiO_2,进而复合氧化石墨烯(GO)合成了系列Nd^(3+)-介孔TiO_2/GO复合材料。通过X射线衍射(XRD)、透射电镜(TEM)、孔结构分析(BJH与BET)、X射线光电子能谱(XPS)和紫外-可见漫反射(UV-vis)等测试手段对样品的微观结构、形貌、样品表面各元素价态及谱学性质进行表征,并以甲基橙模拟污染物测试其光催化性能。结果表明,所制样品均为锐钛矿结构TiO_2,晶粒尺寸在3~4 nm之间;从UV-vis测试结果分析可知,与Nd^(3+)-介孔TiO_2和TiO_2/GO相比,稀土Nd^(3+)和GO的协同效应更能有效减小TiO_2半导体禁带宽度,从而增加其对可见光的吸收。此外,不同光照射下光催化降解甲基橙的实验表明,所制备样品均有较强的紫外及可见光光催化性能,其中系列Nd^(3+)-介孔TiO_2/GO复合体系可见光光催化性能更为显著。

Metal-doped Mo2C(metal=Fe,Co,Ni,Cu)as catalysts on TiO2 for photocatalytic hydrogen evolution in neutral solution

The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.

Enhanced Pseudo‑Capacitive Contributions to High‑Performance Sodium Storage in TiO2/C Nanofibers via Double Effects of Sulfur Modification

Pseudo-capacitive mechanisms can provide higher energy densities than electrical double-layer capacitors while being faster than bulk storage mechanisms.Usually,they suffer from low intrinsic electronic and ion conductivities of the active materials.Here,taking advantage of the combination of TiS2 decoration,sulfur doping,and a nanometer-sized structure,as-spun TiO2/C nanofiber composites are developed that enable rapid transport of sodium ions and electrons,and exhibit enhanced pseudo-capacitively dominated capacities.At a scan rate of 0.5 mV s−1,a high pseudo-capacitive contribution(76%of the total storage)is obtained for the S-doped TiS2/TiO2/C electrode(termed as TiS2/S-TiO2/C).Such enhanced pseudocapacitive activity allows rapid chemical kinetics and significantly improves the high-rate sodium storage performance of TiO2.The TiS2/S-TiO2/C composite electrode delivers a high capacity of 114 mAh g−1 at a current density of 5000 mA g−1.The capacity maintains at high level(161 mAh g−1)even after 1500 cycles and is still characterized by 58 mAh g−1 at the extreme condition of 10,000 mA g−1 after 10,000 cycles.

Fe_2O_3掺杂TiO_2薄膜对甲基紫溶液光催化降解

甲基紫是一种相当稳定的有机物 ,能被 Ti O2 光催化降解 .本文采用 sol-gel工艺在玻璃表面制得了均匀透明的 Ti O2 薄膜 ,研究了热处理温度、涂覆层数、掺杂 Fe2 O3 等制备工艺 ,以及溶液 p H值和助催化剂H2 O2 等因素对 Ti O2 薄膜的光催化性能和稳定性的影响 .结果表明 ,掺 Fe2 O3 的 Ti O2 薄膜对甲基紫的降解率明显优于未掺 Fe2 O3 的 Ti O2 薄膜 .

3d过渡金属掺杂TiO_2纳米晶膜电极的光电化学研究

应用原子力显微镜和X射线粉末法对 3d过渡金属离子Cr(Ⅲ ) ,Fe(Ⅲ ) ,Mn(Ⅱ ) ,Co(Ⅱ ) ,Ni(Ⅱ ) ,Cu(Ⅱ )和Zn(Ⅱ )掺杂TiO2 纳米晶粒 (简写为M3d TiO2 )作了表征 ,并用光电化学方法研究了M3d TiO2 纳米结构多孔膜电极 .实验结果表明 ,M3d TiO2 纳米粒子的颗粒较均匀 ,粒径约为 1 5nm ,其晶型为锐钛矿和板钛矿的混晶 .在所研究的M3d TiO2 中 ,只有Zn2 + TiO2 电极的光电流大于未掺杂的TiO2 纳米结构多孔膜电极 .3d金属离子的掺杂引起各电极的光电流信号在一定波长范围内出现 p

微波法合成纳米TiO_2及Fe^(3+)掺杂纳米TiO_2粉体的研究

通过控制盐的水解和微波辐射制备出晶粒尺寸为 6～ 2 5nm的TiO2 、Fe/TiO2 粉体。对水解温度、陈化时间、微波辐射的影响进行研究 ,发现TiO2 水解温度在 70～ 80℃、Fe/TiO2 水解温度在 6 5℃时 ,晶粒尺寸较小 ,而室温陈化时间的长短对晶粒尺寸没有大的影响 ,样品未微波辐射与微波辐射的晶粒尺寸、热性质等存在明显不同。通过XRD、TG DSC。

掺杂Fe_2O_3对吸附相反应技术制备TiO_2的形貌和光催化性能的影响

利用吸附相反应技术制备得到了掺杂不同浓度的Fe2O3的TiO2复合光催化剂。通过透射电子显微镜(TEM)、紫外可见光谱和X射线衍射(XRD)研究不同掺杂浓度对TiO2形貌和结晶过程的影响,并利用3种波长光源下的甲基橙光降解实验考评了各个复合光催化剂的催化活性。结果表明,掺杂后复合光催化剂中Fe2O3分散性较好较均匀。在TiO2紫外可见吸收光谱中由于Fe2O3的掺杂而出现了红移,而且随着掺杂浓度增加红移越来越明显,复合光催化剂的禁带宽度也越来越小。在焙烧过程中无定形Fe2O3或Fe3+进入了TiO2的晶格结构,从而抑制了TiO2的结晶过程。半导体禁带宽度的减少以及TiO2结晶过程的抑制作用,都导致紫外光下复合光催化剂催化活性的降低。但Fe2O3的掺杂也使得复合光催化剂在可见光区出现了一定的光催化活性。

Improving the denitration performance and K-poisoning resistance of the V_2O_5-WO_3/TiO_2 catalyst by Ce^(4+) and Zr^(4+) co-doping

A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.

Ultrasonic Degradation of Methyl Orange in Presence of Y2O3 Doping Anatase TiO2 Catalyst

Various affecting factors and degradation mechanism were studied on ultrasonic degradation of methyl orange adopting Y2O3 doping anatase TiO2 catalyst prepared in laboratory.In the experiment, the UV-VIS spectrophotometer was used to follow and inspect the degradation process of methyl orange.The results indicate that the ultrasonic degradation ratios of methyl orange in the presence of anatase TiO2 catalyst are much better than those without catalyst.Moreover, the catalytic performance of Y2O3 doping anatase TiO2 catalyst is obviously higher than that of anatase TiO2 catalyst without doping.The optimal conditions were adopted in this work and the degradation and COD elimination ratio of methyl orange got to98% and 99.0% in 90 min, respectively.

掺Fe3+A-TiO2紫外光下催化降解乙基紫

以掺Fe^3+A-TiO2粉末为催化剂对乙基紫溶液进行光催化降解,并确定降解的最佳条件,同时开展了暗吸附研究。结果表明,乙基紫溶液的起始质量浓度为10mg/L(溶液自身pH=6),加入2g/L掺Fe^3+5%(摩尔比)的A-TiO2粉末,在室温下(20℃)经254nm的紫外光照射,恒温快速搅拌反应1.5h,乙基紫降解率为33.70%。同上条件下撤去光源进行暗吸附试验,2h达到吸附平衡,催化剂对乙基紫吸附量为1.472mg/g。

掺Nd^(3+)玻璃微球发射光谱研究

采用粉末喷烧法制备了掺Nd3 + 高折射率TiBa玻璃微球,主要成分为TiO2 ,BaO和SiO2 ,微球直径在30 μm左右。在带有显微镜的光谱仪上,用5 14nm激光照射微球的边缘,测量了它们的发射光谱,观察到了微球腔效应导致的光谱结构共振。在较低泵浦阈值(2mW )下,获得了Nd3 + 的激射发光。利用光学微腔理论讨论了玻璃微球荧光光谱中的形貌共振,实验结果与计算结果相符。

Microstructure and bidirectional dielectric tunability behaviour of Nd^(3+)-doped KSr_(2)Nb_(5)O_(15) lead-free ceramics

The luminescence modulation behaviour under the in-situ electric field of rare-earth doped KSr_(2)Nb_(5)O_(15) ceramics opened a new door for the development of dielectric materials.Where the understanding the effect of rare-earth doping on the electric properties of host,especially at the similar doping concentration with luminescence researches(low concentrations)is very important for the exploration of mechanism of electric-luminescent coupling effect.In this work,Nd^(3+)-doped KSr_(2)Nb_(5)O_(15)(KSN-xNd)ceramics were synthesized,and the electric properties were investigated systematically.Our results suggest that the Nd^(3+) doping slightly increased the phase transition temperatures and improved the piezoelectric response of KSr_(2)Nb_(5)O_(15).Most importantly,a bidirectional dielectric tunability is revealed in KSr_(2)Nb_(5)O_(15).The dielectric permittivity can be adjusted by the DC electric bias,with tunability ranging from12.3% to 21.9%.The related mechanism and relationship between the bidirectional dielectric tunability and ferroelectricity are revealed by temperature-dependent dielectric and ferroelectric characterization.The researches of electric properties and bidirectional dielectric tunability of KSN-based ceramics paved the way to further exploration of electric-luminescent coupling mechanism.

High-performance enhancement-mode thin-film transistors based on Mg-doped In2O3 nanofiber networks

Although In2O3 nanofibers （NFs） are well-known candidates as active materials for next-generation, low-cost electronics, these NF based devices still suffer from high leakage current, insufficient on-off current ratios （Ion/Ioff）, and large, negative threshold voltages （VTH）, leading to poor device performance, parasitic energy consumption, and rather complicated circuit design. Here, instead of the conventional surface modification of In2O3 NFs, we present a one-step electrospinning process （i.e., without hot-press） to obtain controllable Mg-doped In2O3 NF networks to achieve high-performance enhancement-mode thin-film transistors （TFTs）. By simply adjusting the Mg doping concentration, the device performance can be manipulated precisely. For the optimal doping concentration of 2 mol%, the devices exhibit a small VTH （3.2 V）, high saturation current （1.1 × 10^-4 A）, large on/off current ratio （〉 10^8）, and respectable peak carrier mobility （2.04 cm2/（V.s））, corresponding to one of the best device performances among all 1D metal-oxide NFs based devices reported so far. When high-K HfOx thin films are employed as the gate dielectric, their electron mobility and VTH can be further improved to 5.30 cm^2/（V.s） and 0.9 V, respectivel）, which demonstrates the promising prospect of these Mg-doped In2O3 NF networks for high- performance, large-scale, and low-power electronics.

Ultrafast one-step synthesis of N and Ti^3＋ codoped TiO2 nanosheets via energetic material deflagration

An energetic-material （NAN3） deflagration method for preparing N- and Ti3＋-codoped TiO2 nanosheets （NT-TiO2） was developed. In this method, N radicals filled the crystal lattice, and Na clusters captured partial O from TiO2. The deflagration process was fast and facile and can be completed within 〈 I s after ignition. The obtained NT-TiO2 exhibited rough surfaces with nanopits and nanoholes. The doping concentration can be regulated by controlling the NaN3 addition. The NT-TiO2 samples showed significant enhancements in the visible-light absorption and photoelectric response. The simultaneously produced N radicals and Na clusters from NaN3 deflagration served as N sources and reduction agents, respectively. Additionally, the high deflagration temperature/ pressure improved the reactivity of N radicals and Na dusters. Thus, the present NaN3 deflagration method was demonstrated as an ultrafast and effective approach to fabricate NT-TiO2 with a visible-light response. The proposed NaN3 deflagration method allows the ultrafast synthesis of new functional materials via the efficient deflagration of energetic materials.

Heterostructured Nitrogen and Sulfur co-Doped Black TiO2/g-C3N4 Photocatalyst with Enhanced Photocatalytic Activity

Conventional titanium dioxide(TiO2)photocatalyst could absorb only ultraviolet light due to its wide bandgap.In this paper,black TiO2 with narrow bandgap was prepared by introducing oxygen vacancies.Meanwhile.nitrogen(N)and sulfur(S)elements were doped to further broaden the visible light response range of TiOx(NS-BT),and then heterostructured N.S-doped black TiOz/g-C3Na(CN/NS-BT)was successfully constructed by easily accessible route.The formation of CN/NS-BT heteroiunction structure increased the generation and separation efficiency of photogenerated electron-hole pairs,as well as accelerated the transfer rate of the carriers.The as-prepared CN/NS-BT exhibited excellent photocatalytic performance towards the degradation of Rhodamine B(RhB)under visible light irradiation with satisfactory stability.The apparent reaction rate constant of CN/NS-BT(0.0079)was 15.8-fold higher than that of commercial P25(0.0005),The structure,morphology,chemical composition and optical properties of the as-prepared CN/NS-BT were characterized by various analytical methods,and possible photocatalytic enhancement mechanism was proposed.Overall,CN/NS-BT composites look promising as photocatalytic material for future environmental treatment.

Aligning Fe_(2)O_(3)photo-sheets on TiO_(2)nanofibers with hydrophilic and aerophobic surface for boosting photoelectrochemical performance

Photoelectrochemical(PEC)nanomaterials are critical to producing clean oxygenation or value-added chemical production by utilizing sustainable solar energy,but are always limited by simultaneous integration of architectural engineering and electronic regulation in one structure.Directed by density functional theory(DFT)calculations and finite element analysis(FEA),the bioinspired ivy-like Fe_(2)O_(3)heterostructures with enriched oxygen defects on TiO_(2)nanofibers are designed for boosting PEC performances.Ivy-like Fe_(2)O_(3)photo-sheets remarkably enhanced the light harvesting by multiple light-mater interactions.The oxygen vacancies on Fe_(2)O_(3)photo-sheets could aid the photons catching and promote the reactivity at active sites.More importantly,demonstrated by a well-designed dynamic observation,the abundant tip-edges within ivy-like Fe_(2)O_(3)photo-sheets enabled the surface of heterostructure with hydrophilic and aerophobic properties.The functionalized surface allowed the rapid desorption of produced bubbles and thus ensured a high density of unoccupied active sites for electrolyte accessing.Featured by these attributes,the Fe_(2)O_(3)@TiO_(2)nanofibers delivered an excellent photocurrent of 40.8 mA/mg,high donor density(1.2×10^(18)cm^(−3)),and rapid oxygen production rate(1 mmol/(L∙h)).This work demonstrates a new strategy on nano-structural design for enhancing light-harvesting and making a hydrophilic/aerophobic surface on low-dimensional oxide nanomaterial,holding great potential on designing high-performance PEC devices for producing survival source gas,carbon-neutral fuel,and valuedchemicals.