TiO_2光催化剂的形貌与晶面调控

二氧化钛(TiO2)具有化学稳定性高、无毒、价格低廉、来源广泛及光电性能优异等优点,被广泛应用于太阳能电池和光催化等领域,尤其是在污染物的光催化降解方面,可很好地解决当前的环境污染问题。但一方面受带隙宽度限制,使其对太阳光的利用率不足5%,不能充分利用太阳光中的可见光;另一方面由于光生电子-空穴容易结合,催化效率低,从而使TiO2的实际应用受到限制。因此必须采取合适的措施,一方面要增强TiO2对可见光的吸收,提高对太阳光的利用率;另一方面要抑制光生电子-空穴的复合,提高光催化效率。目前越来越多的科学家通过控制TiO2的形貌、晶型、特殊晶面暴露等手段来提高TiO2光生电子-空穴的传输速率和光电转换效率。本文主要综述了近年来在TiO2光催化剂的特殊形貌和特殊晶面暴露等方面的研究进展,对未来的研究和发展方向作了展望。     

Preparation and characterization of Ti0.7Sn0.3O2 as catalyst support for oxygen reduction reaction

Sn-doped TiO_2 nanoparticles with high surface area of 125.7 m~2·g~(-1) are synthesized via a simple one-step hydrothermai method and explored as the cathode catalyst support for proton exchange membrane fuel cells.The synthesized support materials are studied by X-ray diffraction analysis,energy dispersive X-ray spectroscopy and transmission electron microscopy.It is found that the conductivity has been greatly improved by the addition of 30 mol%Sn and Pt nanoparticles are well dispersed on Ti_(0.7)Sn_(0.3)O_2 support with an average size of 2.44 run.Electrochemical studies show that the Ti_(0.7)Sn_(0.3)O_2 nanoparticles have excellent electrochemical stability under a high potential compared to Vulcan XC-72.The as-synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 exhibits high and stable electrocatalytic activity for the oxygen reduction reaction.The Pt/Ti_(0.7)Sn_(0.3)O_2 catalyst reserves most of its electrochemically active surface area(ECA),and its half wave potential difference is 11 mV,which is lower than that of Pt/XC-72(36 mV) under 10 h potential hold at 1.4 V vs.NHE.In addition,the ECA degradation of Pt/Ti_(0.7)Sn_(0.3)O_2is 1.9 times lower than commercial Pt/XC-72 under 500 potential cycles between 0.6 V and 1.2 V vs.NHE.Therefore,the as synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 can be considered as a promising alternative cathode,catalyst for proton exchange membrane fuel cells.     

卟啉化聚合物纤维膜负载TiO_2光催化剂的制备及其光催化性能研究

通过烯基铁卟啉分别和苯乙烯、丙烯腈及甲基丙烯酸甲酯共聚制备三种卟啉化聚合物,然后利用静电纺丝技术将这三种卟啉共聚物与TiO2颗粒共纺制备卟啉共聚物纤维膜负载TiO2光催化剂。扫描电子显微镜(SEM)表征结果显示卟啉共聚物纤维负载TiO2催化剂都具有良好的纤维结构,纤维直径约为1.0-2.0μm。X-射线衍射仪(XRD)则表明TiO2的晶型在纺丝前后都没有受到明显影响。对甲基橙溶液的催化降解实验结果显示:铁卟啉-丙烯腈共聚物负载TiO2催化剂的光催化活性最高,而且铁卟啉的含量对催化剂催化活性起着非常重要的作用。优化后的铁卟啉-丙烯腈共聚物纤维膜负载TiO2光催化剂对甲基橙溶液的脱色率达到76.3%,同时纤维膜结构有利于催化剂的回收和重复使用。     

纳米复合材料CdS/TiO2制备与不同模式光催化降解多种染料

采用化学水浴沉淀法再结合溶胶-凝胶和程序升温溶剂热两步法制备了一系列不同比例的CdS/TiO2。通过XRD、XPS、SEM、UV-Vis/DRS等手段对所合成纳米复合材料的组成、结构和形貌等进行了表征。结果表明,该系列CdS/TiO2为锐钛矿TiO2和六方相CdS的混合晶相,其在可见光有较强吸收,并且随着复合材料中TiO2比例的增加,BET值明显增大。另外,所合成CdS/TiO2呈圆球形,颗粒比较均匀。紫外光催化降解甲基橙的实验结果表明,摩尔比为1:4的CdS/TiO2的活性明显高于CdS、P25以及其它不     

TiO_2/12-磷钨杂多酸/金复合纳米材料的制备及电化学性能

采用水热法制备TiO2纳米管(TNTs),然后以12-磷钨杂多酸(PTA)作为交联剂,运用光催化方法在TiO2纳米管表面负载金纳米颗粒(GNPs),从而得到新型复合纳米材料——TNTs-PTA-GNPs;借助傅立叶变换红外光谱仪,X射线衍射仪和透射电子显微镜分析了新型复合纳米材料的结构及形貌,并利用循环伏安法测试了其电化学性能.结果表明,GNPs均匀分布在TNTs表面,从而大幅度改善纳米材料的导电性;但复合纳米材料中无游离的金纳米颗粒.与此同时,TNTs-PTA-GNPs纳米材料具有良好的生物相容性,且可促进酶与电极之间的直接电子转移.     

部分还原二氧化钛的NMR和EPR研究

Partially reduced TiO₂ nanomaterials have attracted significant interest because of their visible-light activity for catalysis and photodegradation. Herein, we prepared a partially reduced anatase TiO₂ (Re-A-TiO₂) nanoparticle material using a fast combustion method, demonstrating good activity toward decomposing methyl orange under visible light irradiation. The surface structure of the prepared material, after being surface-selectively ¹⁷O-labeled with H₂¹⁷O (¹⁷O-enriched water), was studied via ¹⁷O and ¹H solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and electron paramagnetic resonance (EPR) spectroscopy, and the obtained results were compared to those of non-reduced anatase TiO₂ (A-TiO₂). The EPR results showed that the concentrations of paramagnetic species (i.e., oxygen vacancies (OV) and Ti³⁺) in Re-A-TiO₂ were much higher than that in A-TiO₂, while the former was associated with a higher OV/Ti³⁺ ratio. The intensities of the EPR signals were significantly affected by the adsorbed water, and this phenomenon was explored in combination with ¹H NMR spectroscopy. The ¹H species on Re-A-TiO₂ appeared at larger chemical shifts, denoting the increased acidity of the sample, and these ¹H species on Re-A-TiO₂ were more difficult to remove than those on A-TiO₂. On the other hand, different features were observed for the signals arising from the two-coordinated oxygen atoms (μ₂-O) in ¹⁷O NMR, suggesting a typical anatase TiO₂(101) surface on A-TiO₂, but a more complex surface environment for Re-A-TiO₂. Furthermore, a larger amount of hydroxyl groups (OH) were observed on Re-A-TiO₂ compared to that on A-TiO₂, indicating a larger proportion of exposed (001) facets on Re-A-TiO₂. However, the μ₂-O signals broadened and became similar when the drying temperature was increased to 100 ℃, indicating a non-faceted anatase TiO₂ surface in such conditions. Based on the EPR and NMR results, a significant fraction of the OH species is believed to be formed from the reaction of the paramagnetic centers and adsorbed water molecules. The ¹H→¹⁷O cross polarization (CP) MAS and two-dimensional heteronuclear correlation (2D HETCOR) NMR spectra were used to verify the spatial proximity of the hydrogen and oxygen species, confirming the spectral assignments of a strongly adsorbed water and one type of surface OH species. In particular, the ¹H NMR signals at approximately 11 ppm were ascribed to the hydrogen species in the intramolecular hydrogen bond. In summary, this study investigated the paramagnetic species and surface structure of anatase TiO₂ materials by combining EPR along with ¹H and ¹⁷O solid-state NMR spectroscopy. The differences in the surface structures of Re-A-TiO₂ and A-TiO₂ should be closely related to their different properties toward the photodegradation of methyl orange.     

TiO_2纳米阵列光阳极光电催化水分解研究进展

光电催化水分解制氢是目前解决能源危机与环境污染最理想的技术之一.设计和构筑高效的光阳极是实现光电催化技术实际应用的关键.在众多半导体光阳极材料中,TiO_2纳米阵列由于其快的电荷传输速率,高的光热稳定性,无毒和成本低等优点,已经被广泛用于光电催化水分解反应的研究.但是TiO_2本征的光吸收范围窄、光生电荷复合率高、表面水氧化动力学缓慢严重地制约了其太阳能-氢能转换效率.我们结合近年来国内外及本课题组的研究工作详细论述了TiO_2纳米阵列的改性策略,主要包括利用元素掺杂来拓展TiO_2的光吸收范围并提高导电性,构筑异质结促进光电极电荷的分离与转移,半导体敏化增加光电极的可见光吸收并促进电荷转移,表面处理用于增加表面水氧化反应速率.最后指出了该材料发展现状,并对其发展前景做出展望.我们为进一步提高TiO_2纳米阵列的光电催化水分解活性提供了理论指导和实践借鉴.     

硝酸根接枝诱导组装金红石相TiO2纳米束以增强光催化产氢（英文）

化石燃料的快速消耗加速了全球能源危机和环境污染等问题.光催化产氢直接利用清洁和可持续的太阳能实现向化学燃料的转化,因而成为一种有前景的技术.众多半导体光催化剂中,二氧化钛因其高光催化活性、稳定的化学性质、低成本和无毒等优势而被广泛用作分解水产氢的光催化剂.最近,金红石相TiO2纳米晶体在某些情况下被证明具有光催化的潜力,然而其光生电子-空穴对的快速复合显著抑制了光催化效率.表面修饰、构建异质结和负载助催化剂等策略被用来提高光生载流子的分离效率以减少复合损失,从而提升光催化活性.由于光催化反应通常发生在光催化剂的表面活性位点上,因此通过改善表面性质改变电荷转移途径对光催化活性具有重要影响.磷酸、硫酸、硼酸和盐酸等无机酸的修饰可以改变光催化剂的表面基团,分别通过促进表面羟基的形成和氧气的吸附以及改变表面电荷性质更有效地捕获空穴,实现光生电子和空穴的分离,有助于光催化降解有机污染物.然而,这种影响机制显然不适用于光催化产氢体系,目前对无机酸修饰用于分解水产氢的研究鲜有报道.因此,通过酸改性策略制备高效产氢的光催化剂仍然是一个相当大的挑战.本文利用硝酸诱导策略合成纺锤状金红石相二氧化钛纳米束(R-TiO2).首先,制备层状质子化钛酸盐(LPT)作为TiO2的前体,随后,加入浓硝酸以诱导向金红石相TiO2的转变,并组装形成纺锤状纳米束.对照实验显示,硝酸的酸化可以诱导LPT向金红石相TiO2的转变,而相同条件下浓硝酸后处理不会引起晶相的转变.纺锤形纳米束的形成源于,硝酸诱导R-TiO2沿(110)方向生长并彼此粘附,硝酸诱导组装过程成功在TiO2表面修饰上硝酸根,同时扩大了光吸收范围,有效减少了电荷复合损失.光催化产氢测试证明了R-TiO2光催化剂具有高效的产氢性能,产氢速率为402.4μmol h-1,是Degussa P25的3.1倍,并且显著高于未经浓硝酸处理的锐钛矿(52.0μmol h^-1)或金红石相(110.8μmol h^-1)光催化剂.为了说明表面硝酸根的影响,分别从晶体和化学结构、形态以及表面电荷性质方面比较了光催化反应前后的变化,结果表明,R-TiO2增强的光催化效率可归因于硝酸根基团的负场效应,有利于在表面上捕获带正电的质子以促进载流子分离,提高光催化产氢的效率.总之,本工作不仅对于发展表面修饰策略制备高效产氢光催化剂的研究具有重要意义,而且提出了一种不同于文献报道的无机酸影响机制.     

Insight into Superior Visible Light Photocatalytic Activity for Degradation of Dye over Corner-truncated Cubic Ag2O Decorated TiO2 Hollow Nanofibers

Ag2O/TiO2 heterostructure has been constructed by loading corner-truncated cubic Ag2O on the TiO2 hollow nanofibers via an electrospinning-precipitation method. Compared to individual Ag2O and TiO2, Ag2O/TiO2 heterostructure exhibits obviously enhanced photocatalytic activity for the photodegradation of methyl orange(MO) under visible light irradiation. The composite with molar ratio of Ag2O to TiO2 at 4:10 exhibits the best photocatalytic performance with MO degraded 93% in 6 min. The superior activity is mainly attributed to the surface plasmon resonance(SPR) effect of metallic Ag in-situ produced during the photocatalytic process, which can favor electron transfer to the conduction band of TiO2. This leads to the efficient separation of photogenerated carriers, thus a superior photodegradation activity. Moreover, the energy band alignments of Ag2O/TiO2 heterostructure are calculated, which provides strong support for the proposed mechanism.