蛋氨酸改性TiO2空心纳米盒高效可见光催化RhB分解和NO氧化

由高能面 TiO2纳米片 (TiO2-NSs) 组装成的 TiO2空心纳米盒 (TiO2-HNBs)显示出比单独 TiO2-NSs 更强的光催化性能, 但是 TiO2-HNBs 依然属于紫外光催化剂, 无法充分利用太阳能. 因此, 开发具有可见光响应的由高能面 TiO2-NSs 组装而成的 TiO2-HNBs 具有重要意义. 本文将立方体 TiOF2与含有 N 和 S 元素的生物分子蛋氨酸混合, 通过一步焙烧制备了具有可见光响应活性的 N 和 S 元素共掺杂的 TiO2-HNBs(掺杂催化剂标记为 TMx, 未掺杂催化剂标记为 Tx, x 代表焙烧温度).由立方体 TiOF2到锐钛矿相 TiO2空心纳米盒的转变是一个自模板转化过程. 氟离子的存在降低了 TiO2高能面(001)面的表面能, 从而使得高能面 TiO2纳米片的形成变得可能. 因此, 热处理立方体 TiOF2可得到由高能面 TiO2纳米片组装的 TiO2空心纳米盒.本文系统研究了焙烧温度 (300-500 ℃) 对所制 TiO2-HNBs 结构与光催化性能的影响. 结果发现, 在 350 ℃下焙烧, TiOF2完全转化成锐钛矿相 TiO2-HNBs. 但是焙烧蛋氨酸与 TiOF2的混合物, 需 400 ℃才能完全实现 TiOF2到锐钛矿相TiO2-HNBs 的转变. 这说明蛋氨酸的加入阻碍了 TiOF2向锐钛矿相 TiO2-HNBs 的转变. XPS 结果显示, 经过 400 ℃焙烧的蛋氨酸改性样品 (TM400), N 和 S 元素成功掺入了 TiO2-HNBs 晶格, 使其产生可见光催化活性.相对于 400 ℃焙烧 TiOF2所得样品 T400, 蛋氨酸改性的 TM400 催化剂可见光降解罗丹明 B 染料 (RhB) 和 NO 氧化的性能分别提升了 1.55 倍和 2.0 倍, 这与其更强的可见光吸收性能和光生载流子分离效率有关. 400 ℃焙烧的蛋氨酸改性的 TM400 可见光催化活性稳定, 连续 5 次可见光催化 RhB 降解后, 其活性没有明显改变, 显示了潜在的应用前景.     

S-doped graphene quantum dots as nanophotocatalyst for visible light degradation

S-doped graphene quantum dots (S-GQDs) with well crystallization and monodispersity were prepared and applied as novel nanophotocatalyst for visible light degradation of basic fuchsin.     

Fe2O3/carbon quantum dots complex photocatalysts and their enhanced photocatalytic activity under visible light

In this study, we report the facile fabrication of Fe(2)O(3)/CQDs nanocomposites, and investigate their effective photocatalytic activity for the photodegradation of toxic gas (gas-phase benzene and methanol) under visible light. The crucial roles of CQDs in the enhancement of photocatalytic activity of the Fe(2)O(3)/CQDs composites are illustrated.     

Double-shell structural polyaniline-derived TiO2 hollow spheres for enhanced photocatalytic activity

Transition Metal Chemistry - Polyaniline (PANI) is a conducting polymer which has been employed as a photosensitizer for enhancing the performance of a number of photocatalysts. Herein, we describe...     

高结晶氮化碳空心球的制备及其增强光催化产氢活性

石墨烯型氮化碳(g-C3N4)已经成为解决环境污染和能源危机问题的较为理想的光催化剂,但由于其较低的比表面积和较高的光生载流子重组效率而表现出较弱的光催化活性.因此,研究者们已经提出了许多策略,例如纳米结构设计,杂原子掺杂和增加结晶度,用来克服氮化碳的这些缺点,从而提高其光催化性能.其中,引起了较多关注的是增加g-C3...     

Urchin-like cobalt incorporated manganese oxide OMS-2 hollow spheres: Synthesis,characterization and catalytic degradation of RhB dye

Urchin-like K_xCo_yMn_8−yO₁₆ hollow spheres assembled from nanoplate building blocks were successfully fabricated via a one-pot hydrothermal route using cobalt acetate and potassium permanganate as raw material. The products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrometer, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) measurement. The thermal stability and surface areas of cobalt ion in the manganese sites of KMn₈O₁₆ structures were clearly evidenced by TGA and N₂ adsorption–desorption isotherms curves. Based on time depended experiment results, a possible formation mechanism for this structures was proposed. The catalytic degradation of Rhodamine B (RhB) on K_xCo_yMn_8−yO₁₆ materials has, therefore been dependent for the molar precursor ratio and specific surface area of the as-fabricated products. UV–vis, LC–MS and barium hydroxide methods were utilized to monitor the temporal course of the catalytic reaction.     

N-Doped, porous TiO2 with rutile phase and visible light sensitive photocatalytic activity

Nitrogen-doped, porous rutile has been prepared by hydrothermal reaction of TiN in nitric acid, with the nitrogen atoms present in the interstitial sites and in the form of adsorbed nitrate ions. The N-rutile powder exhibits outstanding photocatalytic activity toward degradation of adsorbed methylene blue under visible light irradiation.     

中空碳球负载TiO2纳米颗粒用于增强光催化抗菌性能

以聚吡咯包覆聚苯乙烯核壳结构衍生的中空碳球(hollow carbon spheres,HCS)为载体,乙酰丙酮钛(TOAC)为钛源,通过湿化学法和可控热解法制备了HCS负载纳米二氧化钛(HCS@TiO₂)复合材料。通过粉末X射线衍射、紫外可见光谱、X射线光电子能谱、热重分析、扫描电子显微镜、透射电子显微镜、光致发光光谱和Mott-Schottky曲线对HCS@TiO₂的晶态结构、微观形貌、光学性能等进行表征,并通过调控TiO₂的负载量和热解温度对HCS@TiO₂复合材料进行了结构优化。在模拟太阳光照射条件下,以大肠杆菌(E. coli)和金黄色葡萄球菌(S. aureus)为实验对象,研究了不同TiO₂负载量的HCS@TiO₂复合材料及TiO₂和HCS对照样品的光催化抗菌性能,以及光照时间对抗菌性能的影响。结果表明,当TOAC与HCS质量比为15∶1、热解温度为650℃时,最优化的HCS@TiO₂-15复合材料...     

SPR effect of Au nanoparticles on the visible photocatalytic RhB degradation and NO oxidation over TiO2 hollow nanoboxes

Three-dimensional (3D) TiO₂ hollow structures have attracted much attention due to their unique properties. However, the large bandgap of (3.2 eV) results in the fact that anatase TiO₂ photocatalyst can only be excited by UV light, which only accounts for 3–5% of the solar energy. On considering that nobel metallatic nanomaterials can harvest visible light due to surface plasmon resonance (SPR) effect, in this paper, three kinds of Au nanoparticles with different morphologies, namely Au nanospheres (Au-NSs), Au nanorods (Au-NRs) and Au nanopentogons (Au-NPs) were prepared and used as photosensitizers to modified TiO₂ hollow nanoboxes (TiO₂-HNBs), aiming to explore high efficient visible-light-responsive photocatalyst. The photoreacitivty of Au/TiO₂-HNBs was evaluated by photoctalytic oxidation of Rhodamine B (RhB) and NO under visible irradiation (λ > 420 nm). It was found that the visible photoreactivity of TiO₂-HNBs was greatly enhanced after modified with Au nanoparticles, and TiO₂-HNBs loaded with Au-NRs exhibit the highest visible photocatalytic activity towards both RhB degradation and NO oxidation. Upon visible irradiation, SPR effect induces the production of hot electrons from the Au nanoparticles, which can further transfer to the conduction band of TiO₂-HNBs to produce superoxide radicals (O₂⁻), resulting in an efficient separation of photo-generated electron-hole pairs. The photoreactivity of Au-NRs/TiO₂-HNBs towards RhB degradation almost keeps unchanged even after recycling used for 5 times, indicating that it is promising to be use in practical applications.     

Synthesis of hierarchical nanoporous F-doped TiO2 spheres with visible light photocatalytic activity

Hierarchical porous F-doped TiO2 microspheres exhibiting high visible light photocatalytic activity have been fabricated by a one-step low-temperature hydrothermal approach without using any templates.     

A metal-free carbon dots for wastewater treatment by visible light active photo-Fenton-like reaction in the broad pH range

Carbon dots (Cdots) has been proved to possess the catalytic decomposition of H2O2 in the photocatalytic system. It is a potential photo-Fenton catalyst. Since ...     

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce³⁺ ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.     

Electrospun nanofibers of TiO2/CdS heteroarchitectures with enhanced photocatalytic activity by visible light

Herein, we have demonstrated that the electrospun nanofibers of TiO(2)/CdS heteroarchitectures could be fabricated through combining electrospinning technique with hydrothermal process. The configuration, crystal structure, and element composition of the as-prepared TiO(2)/CdS heteroarchitectures were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), resonant Raman spectrometer, X-ray photoelectron spectroscopy (XPS). The results indicated that the high-density hexagonal wurtzite CdS crystalline particles of ca. 6-40 nm in diameter were uniformly and closely grown on anatase TiO(2) nanofibers. Especially, the light-absorption properties as well as photocatalytic characteristics of pure TiO(2) nanofibers and TiO(2)/CdS heteroarchitectures with different amount loading of CdS were also investigated. The absorption of TiO(2)/CdS heteroarchitectures was extended to the visible due to effective immobilization of sensitizing agent CdS on TiO(2). In contrast with the pure TiO(2) nanofibers, the TiO(2)/CdS heteroarchitectures showed excellent photocatalytic activity by using rhodamine B dye as a model organic substrate under visible-light irradiation. It was worth noting that the cooperative photocatalytic mechanism of the TiO(2)/CdS heteroarchitectures was also discussed.     

Preparation of AgBr/DyVO<Subscript>4</Subscript> composite and its excellent photocatalytic activity in RhB degradation under visible light

A AgBr/DyVO₄ composite photocatalyst was synthesized by a hydrothermal method for the first time. The physical and chemical structure and optical properties of the composite catalysts were investigated by XRD, XPS, SEM, TEM and UV–Vis. It was found that the prepared photocatalyst is a ternary composite of DyVO₄, AgBr and Ag. A photodegradation experiment and a cyclic test verified that the composite catalyst has high activity and stability, indicating that the photocatalyst has a wide application potential. The optimal AgBr/DyVO₄ sample can degrade 85% of RhB (20 ppm) under visible light irradiation for 12 min. The degradation rate reaches 0.290 min^?1, which is 14.5 times higher than that of AgBr. The high activity can be ascribed to the coupling effect between AgBr, DyVO₄ and Ag, which leads to high separation efficiency of electrons and holes.     

Nanoparticle self-assembled hollow TiO(2) spheres with well matching visible light scattering for high performance dye-sensitized solar cells

Submicrometer-sized hollow TiO(2) spheres are directly self-assembled from TiO(2) nanoparticles without using any template or surfactant as a scattering layer for dye-sensitized solar cells, showing good visible light scattering match to significantly improve the photoconversion efficiency.     

Phenylenediamine-formaldehyde chemistry derived N-doped hollow carbon spheres for high-energy-density supercapacitors

Porous carbon spheres represent an ideal family of electrode materials forsupercapacitors because of the high surface area,ideal conductivity,negligible aggregation,and ability to achieve space efficient packing.However,the development of new synthetic methods towards porous carbon spheres still remains a great challenge.Herein,N-doped hollow carbon spheres with an ultrahigh surface area of2044 m²/g have been designed based on the phenylenediamine-formaldehyde chemistry.When applied in symmetric supercapacitors with ionic electrolyte(EMIBF_4),the obtained N-doped hollow carbon spheres demonstrate a high capacitance of 234 F/g,affording an ultrahigh energy density of 114.8 Wh/kg.Excellent cycling stability has also been achieved.The impressive capacitive performances make the phenylenediamine-formaldehyde resin derived N-doped carbon a promising candidate electrode material for supercapacitors.     

Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries

Going into their shell: A novel carbon-sulfur nanocomposite has been synthesized by confining sulfur in double-shelled "soft" carbon hollow spheres with high surface area and porosity. This carbon-sulfur nanocomposite shows outstanding electrochemical performance when evaluated as a cathode material for lithium-sulfur batteries.     

氮自掺杂暴露（001）晶面TiO2微米片的可见光光催化CO2还原性能增强

化石能源的使用可产生大量CO2,带来严重的温室效应。光催化CO2还原生产太阳燃料技术既有望缓解温室效应,又可以将低能量密度的太阳能转化为高能量密度的化学能储存起来方便使用。高效光催化材料的开发是发展光催化技术的关键。迄今,在已开发的所有半导体光催化材料中, TiO2仍是广泛研究的明星材料。在实际使用中, TiO2的光催化效率仍受限于其极弱的可见光利用率和较高的电子-空穴复合几率。近年来,越来越多的研究表明TiO2的结构与形貌特征极大地影响其光催化效率。尤其, TiO2的外露晶面设计与晶面效应研究引起了广泛关注。由于具有较高表面能和较多表面不饱和键,起初大多数理论和实验研究认为锐钛矿TiO2(001)晶面是光催化活性晶面。后来,越来越多研究表明并非锐钛矿TiO2(001)晶面的暴露比例越高其光催化活性就越高。最近,我们发现锐钛矿TiO2(001)晶面与(101)晶面在调控光催化CO2还原性能上具有良好的协同效应。密度泛函理论计算表明,锐钛矿TiO2的(001)晶面与(101)晶面的能带结构有差异,(001)晶面的导带位置相对于(101)晶面而言较高,而(101)晶面的价带位置相对于(001)晶面而言较低。基于此我们提出,具有合适比例的锐钛矿TiO2的(001)晶面与(101)晶面的交界处可以形成最佳的表面异质结或晶面异质结。表面异质结的形成导致光生电子倾向于向(101)扩散,光生空穴倾向于向(001)扩散,从而促进光生电子-空穴分离,降低光生电子-空穴复合几率。在此工作基础上,我们直接以氮化钛为原料,氢氟酸为添加剂,通过简单的水热反应一步合成了氮自掺杂的TiO2微米片。利用X射线粉末衍射、扫描电镜、X射线光电子能谱、紫外-可见漫反射光谱、氮气吸附-脱附以及电化学阻抗谱等方法手段对所制备的光催化剂进行了基本结构与理化性质表征分析,并研究了其可见光光催化CO2还原性能。电镜照片结果表明,我们所制备的氮自掺杂锐钛矿TiO2微米片的(001)晶面与(101)晶面比例分别为65%和35%。基于我们前期研究结果, TiO2微米片的(001)晶面与(101)晶面可以形成表面异质结,具有良好的电荷分离效率,这也得到了电化学阻抗谱研究结果的证明。同时,由于N的原位掺杂,所制备的TiO2微米片具有优异的可见光捕获能力。由于可见光利用效率增强与光生电子-空穴分离效率提高这两方面的综合作用,所制备的氮自掺杂TiO2微米片具有非常好的可见光光催化CO2还原制甲醇性能,比商用P25及氮掺杂TiO2纳米粒子等参考样品的可见光光催化性能更优异。研究表明,通过原位自掺杂方法与晶面设计方法相结合,可以同时改善TiO2的可见光利用效率和光生电子-空穴分离效率,优化TiO2的可见光光催化性能,这也为后续开发新型高效光催化材料提供了新思路。