铝基阳极氧化铝模板水热法制备TiO2纳米管阵列

在(NH4)2TiF6的水溶液中,以铝基阳极氧化铝为模板,采用水热法制备了TiO2纳米管阵列. 使用场发射扫描电镜和X射线衍射对水热合成产物进行了表征. 实验结果表明,水热处理所得TiO2纳米管阵列具有特殊的形貌,其表面为连续的多孔状,断面为不连续、相互分离的管状;管口和管壁分别由平均粒度约45和25 nm的微细TiO2颗粒紧密堆积而成. 采用本方法制备的TiO2纳米管阵列无需热处理便已具有明显的锐钛矿型晶相特征.     

氮掺杂TiO2纳米管阵列的制备及其可见光光电催化活性研究

联用电化学阳极氧化和湿化学法制备氮掺杂的TiO2纳米管阵列膜.应用SEM、XPS、DRS分析、表征,并研究该膜层的形貌、组成和光学性质以及在卤钨灯照射下降解甲基橙水溶液的光电催化活性.结果表明:氮以取代掺杂的形式进入TiO2晶格,掺氮的TiO2纳米管阵列在可见光区有较强的吸收,其光电催化性能优于纯的TiO2纳米管阵列膜.     

二氧化钛纳米管阵列光电催化同时降解苯酚和Cr(VI)

采用电化学阳极氧化法在纯钛箔基底上制备了TiO2纳米管阵列,并运用X射线衍射、扫描电镜和电化学工作站对其进行了表征.结果表明,所制样品是锐钛矿相,管径约为100nm,管长约为2μm,在0.5V偏压下光电流最大.以苯酚和Cr(VI)混合溶液为目标污染物,考察了TiO2纳米管阵列光电催化同时去除苯酚和Cr(VI)的反应性能...     

淬火处理对TiO2纳米管阵列电极性能影响

为使TiO2纳米管阵列电极更好地应用于太阳能电池中,通过恒压阳极氧化法以0.5%(w,质量分数)NH4F/甘油作为电解液,在钛基体上制备出了TiO2纳米管阵列.随后将TiO2纳米管阵列电极在水中进行不同温度淬火处理,通过x射线衍射(XRD)仪、场发射扫描电子显微镜(FESEM)、X射线光电子能谱(XPS)和循环伏安法(CV)研究经淬火处理的TiO2纳米管阵列的形貌、晶体结构和电化学性能.研究得出TiO2纳米管阵列经淬火处理其表面获得更多Ti3+缺陷点和TiO2纳米碎片.经0℃淬火处理的TiO2纳米管阵列电极出现了更多Ti3+缺陷点和OH基团,且有更多的纳米碎片出现,其光电化学性能得到了大幅度提高,其40 min光照对甲基橙的光催化降解率高达96.2%.     

淬火处理对TiO2纳米管阵列电极性能影响

为使TiO2纳米管阵列电极更好地应用于太阳能电池中, 通过恒压阳极氧化法以0.5%(w, 质量分数)NH4F/甘油作为电解液, 在钛基体上制备出了TiO2纳米管阵列. 随后将TiO2纳米管阵列电极在水中进行不同温度淬火处理, 通过X射线衍射(XRD)仪、场发射扫描电子显微镜(FESEM)、X射线光电子能谱(XPS)和循环伏安法(CV)研究经淬火处理的TiO2纳米管阵列的形貌、晶体结构和电化学性能. 研究得出TiO2纳米管阵列经淬火处理其表面获得更多Ti3+缺陷点和TiO2纳米碎片. 经0 ℃淬火处理的TiO2纳米管阵列电极出现了更多Ti3+缺陷点和OH 基团, 且有更多的纳米碎片出现, 其光电化学性能得到了大幅度提高, 其40 min光照对甲基橙的光催化降解率高达96.2%.     

基于铜基底的TiO2纳米管阵列储锂性能

研究了基于铜基底的TiO2纳米管阵列直接作为锂离子电池电极的储锂性能。以铜基底上生长的Cu(OH)2纳米棒阵列为模板,采用自牺牲模板法,通过外向包覆与内向刻蚀,制备了非晶态的TiO2纳米管阵列,然后将其在500℃下退火处理4 h,获得锐钛矿型TiO2纳米管阵列。采用X射线衍射、场发射扫描电镜、透射电镜、热重分析对样品进行表征;采用恒电流充放电、循环伏安和交流阻抗谱测试对退火前后TiO2纳米管阵列的电化学性能进行研究。结果表明:与非晶态的TiO2纳米管阵列相比,锐钛矿型TiO2纳米管阵列吸附水的含量低,结晶度高,电荷迁移阻力小,锂离子扩散系数大,结构稳定,具有更好的循环性能和倍率性能;在0.2C下,其首次放电比容量为353 mAh·g-1,经过40次循环后的放电比容量仍为243 mAh·g-1,在8C下的放电比容量为90 mAh·g-1。     

电化学阻抗谱法研究铈改性TiO2纳米管阵列光电极裂解水产氢动力学

通过阳极氧化法在纯钛板上制备TiO2纳米管阵列电极.在光电化学电解池阳极中加入供电子物质乙二醇,显著减小了TiO2纳米管的电荷传递阻抗,促进了光电催化裂解水产氢反应.采用阴极电沉积和阳极氧化法制备了单质铈和氧化铈共同改性的TiO2纳米管阵列半导体光阳极,其平带电位向电负方向移动.采用电化学阻抗谱法(EIS)对改性后TiO2纳米管阵列在光电催化裂解水产氢中的电子传输性能以及界面性质进行了表征,确定了各阻抗弧对应的电极过程.采用合理的等效电路模型计算了电极的电子传输动力学参数.结果表明,经铈改性后的TiO2纳米管阵列膜电阻明显减小,有利于氢气的产生.探讨了单质铈与氧化铈促进TiO2纳米管阵列电荷传输的作用机理.     

TiO_2纳米管阵列光电催化制氢研究进展

以TiO2纳米管阵列为光阳极组成的光电解池光电催化分解水是目前光催化制氢领域内研究最广泛的体系之一。本文综述了近年来TiO2纳米管阵列在光电催化分解水制氢领域的最新研究进展,重点阐述了提高TiO2纳米管阵列光电转换效率和产氢速率的方法,指出了目前存在的问题,并对今后的发展提出了展望。     

甘油-DMSO-H2O中阳极氧化TiO2纳米管阵列的生长与性能

采用NH4F-甘油-DMSO(二甲基亚砜)-H2O溶液体系的电化学阳极氧化法, 在金属钛基板上形成厚度为0.4-1.5 μm的有序TiO2纳米管阵列薄膜. 利用场发射电子扫描显微镜(FESEM)技术, 研究了电解液的组成及阳极氧化电压对TiO2纳米管阵列生长形貌的影响. 结果表明, 阳极氧化电压可以影响TiO2纳米管的径向尺寸和长度；通过改变电解液中DMSO/H2O的体积比, 能够调控纳米管的生成速率与形貌. 利用X射线衍射(XRD)对经过不同温度热处理的TiO2纳米管阵列薄膜的物相进行了分析. TiO2纳米管阵列薄膜的光电催化分解水过程的电压-电流特性测量显示, 光电流密度大于0.2 mA·cm-2.     

Eu2O3修饰对纳米TiO2热稳定性及光催化活性的影响

通过浸渍过程实现了Eu2O3对溶胶水热法合成的锐钛矿相TiO2纳米粒子的表面修饰改性.重点研究了表面修饰对纳米锐钛矿相热稳定性及光催化活性的影响.结果表明,Eu2O3表面修饰抑制了锐钛矿相向金红石相的转变,相变温度由550℃左右升高到700℃左右,提高了纳米锐钛矿相TiO2的热稳定性,这与Eu2O3修饰在表面而阻碍了锐钛矿纳米粒子的直接接触有关.与未修饰的TiO2相比,经过700℃高温热处理的Eu2O3修饰的TiO2样品表现出了较高的光催化活性,这与其结晶度提高而有利于光生电荷分离有关.     

新型N-TiO2的固相法制备及其光催化性能

以纳米管钛酸为前驱体,以NH4HCO3为N源,先机械研磨使二者混合均匀,再在Ar保护下,于不同温度焙烧4h制得N掺杂TiO2 (N-TiO2),并采用X射线粉末衍射、X射线光电子能谱、紫外-可见吸收光谱、透射电镜及N2吸附-脱附对样品进行了表征.结果显示,N以间隙掺杂方式进入TiO2晶格内.在热处理过程中,生成中间体(...     

氢氟酸腐蚀对α-Fe2O3薄膜光解水电极光电化学性质的影响

使用溶胶-凝胶法制备了α-Fe₂O₃薄膜,研究了氢氟酸腐蚀薄膜表面对其光电化学性质的影响. 实验发现,薄膜表面的孔洞和间隙随着氢氟酸浸蚀时间的增长而发生变化. 氢氟酸浸蚀5 min,α-Fe₂O₃电极的光电流降低;随后随浸蚀时间增加而迅速增加;当浸蚀时间大于15 min时,其光电流再次下降,但对浸蚀过的样品再次退火可以使光电流大幅增加. 通过电化学交流阻抗谱、拉曼和X射线光电子能谱分析,提出了两个影响光电流的因素：氢氟酸表面浸蚀造成薄膜表面的多孔性和结晶度降低. 为此,通过示意图解释了结合浸蚀和退火后处理两个步骤来增强α-Fe₂O₃薄膜光解水电极光电活性的原理. 相对于初始的α-Fe₂O₃电极,浸蚀并且再退火处理后,其光电性质更加稳定.     

Quantitative characterization of hydroxyl radicals produced by various photocatalysts

Hydroxyl radicals ((·)OH) have been deemed to be the major active species during the photocatalytic oxidation reaction. In this study, (·)OH produced on various semiconductor photocatalysts in aqueous solution under Xenon lamp irradiation was quantitatively investigated by the photoluminescence (PL) technique using coumarin (COU) as a probe molecule. The results indicated that the formation rate of (·)OH on the surface of irradiated commercial Degussa P25 (P25) was much higher than that of other semiconductor. The pH values of the solution and phase structure of TiO(2) significantly influenced the production rate of (·)OH. The acidic pH environment of the solutions and bi-phase structure (anatase and rutile) of TiO(2) were beneficial to enhancing the formation rate of (·)OH. In addition, the formation rate of (·)OH on anatase TiO(2) and P25 was much faster than that of (·)OH on the other semiconductors (such as rutile TiO(2), ZnO, WO(3), CdS, Bi(2)WO(4) and BiOCl, etc.). A new concept "OH-index" was first proposed to compare photocatalytic activity of photocatalysts, which would provide new insight into the investigation of semiconductor photocatalysts.     

Visible light photocatalyst: iodine-doped mesoporous titania with a bicrystalline framework

Iodine-doped (I-doped) mesoporous titania with a bicrystalline (anatase and rutile) framework was synthesized by a two-step template hydrothermal synthesis route. I-doped titania with anatase structure was also synthesized without the use of a block copolymer as a template. The resultant titania samples were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared, nitrogen adsorption, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible absorption spectroscopy. Both I-doped titania samples, with and without template, show much better photocatalytic activity than commercial P25 titania in the photodegradation of methylene blue under the irradiation of visible light (>420 nm) and UV-visible light. Furthermore, I-doped mesoporous titania with a bicrystalline framework exhibits better activity than I-doped titania with anatase structure. The effect of rutile phase in titania on the adsorptive capacity of water and surface hydroxyl, and photocatalytic activity was investigated in detail. The excellent performance of I-doped mesoporous titania under both visible light and UV-visible light can be attributed to the combined effects of bicrystalline framework, high crystallinity, large surface area, mesoporous structure, and high visible light absorption induced by I-doping.     

CeO2/NaNbO3复合物的水热合成及其光催化性能的提高

钙钛矿型NaNbO3由于其非线性光学、铁电、离子导电性、高声速、光催化性能和光折变等优良性能而备受关注. 在光催化反应中, 宽禁带宽度(≈ 3.24 eV)使NaNbO3具有较高的导带底(CBM)和较低的价带顶(VBM). 因此, 它表现出强烈的光氧化和光还原能力. 众所周知, 钙钛矿型光催化剂光电子激发和传输能力的增强归因于其较高的对称性. 因此, 具有高对称性的立方NaNbO3有利于电子激发和转移. 但是, 一些固有的缺点, 包括电荷分离效率低、量子产率差和光催化活性差等, 限制了其在光催化领域的实际应用. 为了解决这些问题, 一种有效的方法是与其他半导体结合, 形成具有改善光催化活性的异质结复合物. CeO2作为传统的催化剂在光催化领域得到了广泛研究. CeO2具有稳定、无毒的特点, 是一种n型半导体. 目前, 研究人员已经发现CeO2与不同半导体的耦合可以提高CeO2的光催化活性. 这归因于能级水平的适当匹配.本文通过简易水热法制备了高活性的CeO2/NaNbO3异质结复合物, 并采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM, HRTEM)和紫外-可见漫反射光谱(DRS)等表征技术研究了所制光催化剂的物相结构、样品形貌和光学性能. 所制样品的光催化活性通过光催化降解无色抗菌环丙沙星(CIP)和染料罗丹明B(RhB)证实. 结果表明,在紫外和可见光照射, CeO2/NaNbO3复合物比纯NaNbO3具有更高的光催化活性. 此外, CeO2/NaNbO3复合物中CeO2的最佳质量比为2.0 wt%. 紫外光照射下光催化性能的显著提高是由于CeO2/NaNbO3异质结的形成不仅提高了光生电荷在界面范围内的迁移速率, 而且降低了光激发产生的电子和空穴的复合率. 可见光照射下内置电场的存在促进了电子和空穴的分离, 提高了光催化性能. 此外, 利用光致发光(PL)光谱、光电流、电化学阻抗谱和捕获实验证明了样品的光催化反应机理.捕获实验结果表明, ·OH自由基、·O2-自由基和空穴都参与了RhB的光催化降解过程. 最后, 探讨了提高光催化活性的可能机理.     

水热法制备铂掺杂二氧化钛及其可见光催化性能

以纳米管钛酸为前驱体,采用水热法制备了Pt掺杂TiO2样品.水热反应过程中,纳米管钛酸表面羟基与氯铂酸发生酸碱中和反应,导致反应后pH值升高;在130°C开始纳米管钛酸晶体结构由正交晶系转变为锐钛矿相TiO2.表面化学组成分析表明,掺杂的Pt主要以+2价形式存在.以丙烯为模型污染物,评价样品的可见光(λ≥420nm)光催化活性.结果表明,Pt-TiO2具有明显的可见光光催化降解丙烯的活性,其中160°C水热处理制得的Pt-TiO2活性最高.最后讨论了低温水热法Pt掺杂的形成机理及Pt-TiO2具有可见光响应的原因.     

Boron and nitrogen-codoped TiO2 nanorods: Synthesis, characterization, and photoelectrochemical properties

Boron and nitrogen codoped TiO₂ nanorods (BNTRs) were synthesized via two-step hydrothermal reactions using TiN as a starting material. The as-prepared samples were characterized by X-ray diffraction, field-emission scanning electron microscope (SEM), transmission electron microscopy and X-ray photoelectron spectroscopy techniques. The results showed that TiO₂ nanorods with the diameter of approximately 50–100 nm and the length of several micrometers were doped by the interstitial N and B. The nanorods were firstly formed in the hydrothermal synthesis of nitrogen doped TiO₂. The growing process of nanorods was observed by SEM and a most probable formation mechanism of the trititanate nanorods was proposed. The BNTRs showed a higher photocatalytic activity and a bigger photocurrent response than N–TiO₂ nanorods under visible light irradiation.     

钛酸纳米管前驱体水热制备TiO2：水热媒介对结晶度及光催化活性的影响

以钛酸纳米管为先驱体,180℃24 h同一水热条件下,利用H2O、HNO3、KBF4以及HNO3+KBF4的4种水热媒介溶液,制备了高结晶度高光催化活性的TiO2,并研究了水热媒介对TiO2结晶度、表面羟基和光催化活性的影响。通过扫描电镜(SEM)、X射线衍射(XRD)、红外测试(FTIR)、X射线光电子能谱(XPS)、紫外可见漫反射吸收光谱(UV-Vis)进行了结构表征。光催化活性通过降解甲基橙溶液进行了评价。结果表明,与其他3种媒介相比,HNO3+KBF4溶液为水热媒介制备的锐钛矿晶型TiO2,结晶度高,表面羟基含量高,因此,呈现高的光催化活性。     

CuCrO2的合成及其复合催化剂的光催化性能

以硝酸铬和硝酸铜为原料,通过半湿法经两种不同路径合成了CuCrO₂半导体物质。分别采用热重-差示扫描（TG-DSC）、X射线衍射（XRD）、紫外-可见漫反射（UV-vis DR）、扫描电镜（SEM）及X射线光电子能谱（XPS）对样品进行了表征分析。确立了以氨水为Cr³⁺沉淀剂制得的氢氧化铬沉淀中加入硝酸铜溶液是合成CuCrO₂较适宜的路径。借助TG-DSC和XRD的分析结果确立前驱体在热处理的过程中,含Cr物相的变化历程为Cr（OH）₃ → CuCrO₄ → CuCr₂O₄ → CuCrO₂。通过机械研磨的方法合成了CuCrO₂-WO₃和CuCrO₂-ZnO复合型催化剂,对其进行了XRD、SEM和XPS表征分析,并测试了复合催化剂的光催化活性。结果表明,与单独使用CuCrO₂相比,无论是以高压汞灯,还是以氙灯为光源,CuCrO₂-WO₃和CuCrO₂-ZnO的光催化产氢活性都有显著提高。     

Electrocatalytic oxidation of nucleobases by TiO2 nanobelts

Two kinds of TiO(2) nanobelts were prepared from commercial P-25 powders via an alkaline hydrothermal method with and without an acid etching process. The uncauterized nanobelts (TNs) exhibited a smooth surface, and mixed phases of anatase and TiO(2) (B), whereas the cauterized ones (CTNs) displayed a rough surface and a pure anatase structure. TNs and CTNs were then deposited onto a glassy carbon electrode (GCE) surface with a conductive adhesive (CA), and the resulting chemically modified electrodes exhibited electrocatalytic activities in the oxidation of nucleobases in a 0.1 M phosphate buffer solution (PBS) at pH 7.4. For guanine and adenine, well-defined oxidation peaks were observed in voltammetric measurements at about +0.62 and +0.89 V, respectively, at a potential sweep rate of 100 mV s(-1), whereas for cytosine, uracil and thymine, the voltammetric features were not obvious. The average surface coverages (Γ) of guanine and adenine on the CTNs/CA/GCE electrode were estimated to be 4.75 × 10(-10) and 7.44 × 10(-10) mol cm(-2), respectively, which were about twice those at the TNs/CA/GCE electrode. The enhanced activity of the CTN-based electrode towards purine nucleobase oxidation was ascribed to the large specific surface area and anatase structures with enhanced (001) facets of the CTN that facilitated adsorption of the analytes onto the electrode surface and charge transport through the electrode surface layer.