Electron spin resonance spin-trapping detection of radical intermediates in N-doped TiO2-assisted photodegradation of 4-chlorophenol

The electron spin resonance (ESR) spin-trapping technique using 5,5-dimethyl-1-pyrroline-N-oxide as the spin-trap reagent has been applied to detect free radical intermediates generated during in situ ultraviolet or visible irradiation of aqueous 4-chlorphenol (4-CP)/N-doped TiO(2) suspensions. ESR measurements gave the first direct evidence that the active species ((*)OH and O(2*-)) are responsible for the photodecomposition of 4-CP over N-doped TiO(2) under visible-light irradiation, strongly suggesting that the photocatalytic reaction of organic compounds in powdered N-doped TiO(2) systems proceed via surface intermediates of oxygen reduction or water oxidation, not via direct reaction with holes trapped at the N-induced midgap level. These results have important implications for the evaluation of the oxidative powder of TiO(2-x)N(x) catalysts.     

氮掺杂二氧化钛薄膜的光催化性能研究

采用溶胶-凝胶法制备了氮掺杂Ti O2薄膜;利用X射线光电子能谱仪、紫外-可见光谱仪表征了所制备的薄膜的化学状态和光吸收性能;并考察了可见光照射下薄膜的亲水性能和光催化性能.结果表明:N通过取代部分O的方式进入到Ti O2薄膜中,且掺杂后在可见光区的光吸收增强;最优条件下,Ti O2-xNx薄膜的接触角由31°降到12°,亲水化速度常数为0.018,可见光照射3 h,亚甲基蓝的降解率达到45%.     

具有可见光响应的C、N共掺杂TiO2纳米管光催化剂的制备

为了提高二氧化钛对可见光的利用效率,采用等离子体电解方法对二氧化钛实现了C、N共掺杂.掺杂通过等离子体电解HCONH2、NaNO2、(NH2)2CO产生活性N、C实现.XPS结果表明,C、N掺杂进入了氧化钛晶格.紫外漫反射光谱分析表明,氧化钛对可见光(＞400 nm)的响应增强,其光催化降解能力也大大增强.C、N共掺杂TiO2是一种利用太阳能的理想的光催化剂.     

One-step solvothermal synthesis of N-doped TiO2 nanoparticles with high photocatalytic activity in the reduction of aqueous Cr（Ⅵ）

N-doped TiO2 （N-TiO2） nanoparticles were synthesized via a one-step low temperature （180℃） solvothermal route, which adopted NH4NO3 as the nitrogen source. The structure, composition, BET specific surface area, and optical properties of the as-synthesized product were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N2 adsorption- desorption isotherms, and UV-vis diffuse reflectance spectroscopy. In addition, its photocatalytic properties were tested by the reduction of aqueous Cr（VI） under UV and visible light （x 〉 420 rim） irradiation. It was observed that for the reduction of aqueous Cr（VI）, the as-synthesized N-TiO2 nanoparticles not only exhibited much higher photocatalytic activity than P25 TiO2 under UV light, but also exhibited remarkably high photocatalytic activity under visible light （λ 〉 420 nm）.     

具有可见光响应的C、N共掺杂TiO2纳米管光催化剂的制备

为了提高二氧化钛对可见光的利用效率, 采用等离子体电解方法对二氧化钛实现了C、N共掺杂. 掺杂通过等离子体电解HCONH2、NaNO2、(NH2)2CO产生活性N、C实现. XPS结果表明, C、N掺杂进入了氧化钛晶格. 紫外漫反射光谱分析表明, 氧化钛对可见光(>400 nm)的响应增强, 其光催化降解能力也大大增强. C、N共掺杂TiO2是一种利用太阳能的理想的光催化剂.     

Fe、N共掺杂TiO2纳米管阵列的制备及可见光光催化活性

应用电化学阳极氧化法结合浸渍和退火后处理制备了Fe和N共掺杂的TiO2纳米管阵列光催化剂,并用场发射扫描电镜(FESEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和俄歇电子能谱(AES)仪对其进行了表征.结果表明,Fe、N共掺杂对TiO2纳米管阵列的形貌和结构没有明显影响,Fe和N均掺入了TiO2晶格.紫外-可见(UV-Vis)漫反射光谱显示Fe和N共掺杂TiO2纳米管阵列的吸收带边较纯TiO2纳米管阵列和单一掺杂TiO2纳米管阵列红移,可见光吸收增强.以可见光催化降解罗丹明B(RhB)考察了材料的光催化活性,Fe和N共掺杂TiO2纳米管阵列对RhB的降解速率较纯TiO2纳米管阵列和单一掺杂TiO2纳米管阵列明显提高,证明了Fe、N共掺杂产生的协同效应提高了TiO2纳米管阵列在可见光照射下的光催化活性.     

N掺杂纳米TiO2可见光催化氧化丙烯的动力学行为

通过在不同温度的氨气气氛中处理纳米管钛酸(NTA)制得具有可见光响应的氮掺杂纳米二氧化钛. X射线衍射(XRD)谱表征结果显示, 当温度高于400 ℃时, 样品由正交晶系向锐钛矿相转变, 700 ℃处理得到的样品除了锐钛矿相TiO2外还有TiN 新相存在; 紫外-可见扩散漫反射(DRS)结果表明, 氮掺杂纳米TiO2在整个可见光区都有明显的吸收. 不同波长可见光及不同气体流速的光催化氧化丙烯动力学研究表明, 活性最好的N掺杂纳米TiO2催化剂(600 ℃ NH3处理)对可见光的利用范围可扩展至500 nm, 低浓度丙烯光催化氧化反应为一级反应.     

Characterization and mechanism analysis of Mo-N-co-doped TiO2 nano-photocatalyst and its enhanced visible activity

In this study, Mo-N-co-doped TiO(2) nano-photocatalysts have been synthesized through hydrolysis-precipitation method, combined with sonication posttreatment. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). XRD showed that co-doping with Mo and N favored the formation of anatase and retarded the growth of crystallite size. XPS revealed that N was incorporated into the lattice of TiO(2) through substituting oxygen atoms and coexisted in the forms of β-N and γ-N in co-doped TiO(2). Meanwhile, Mo was also incorporated into the lattice of TiO(2) through substituting titanium atoms and existed in the form of Mo(6+). DRS indicated that the light absorbance in visible region was improved by co-doping with Mo and N, leading to a narrower band gap and higher visible light photocatalytic activity for the degradation of phenol than that of pure and N-doped TiO(2). The enhanced visible light photocatalytic activity of Mo-N-co-doped TiO(2) nano-photocatalyst was attributed to the small crystallite size, narrow band gap and intense light absorbance in visible region. This study provides a new method to synthesize visible light active TiO(2)-based photocatalyst.     

N掺杂TiO_2纳米粒子表面光生电荷特性与光催化活性

以尿素为氮源,采用水热法制备了不同N掺杂量的TiO2(N-TiO2)光催化剂.利用X射线衍射(XRD),紫外-可见漫反射光谱(UV-Vis DRS),X射线光电子能谱(XPS)及荧光(PL)光谱等技术对其进行了系统的表征.以罗丹明B(RhB)和甲基橙(MO)溶液的脱色降解为模型反应,分别考察了N-TiO2光催化剂在紫外和可见光区的光催化活性.利用表面光伏(SPV)和瞬态光伏(TPV)技术研究了N-TiO2纳米粒子表面光生电荷的产生和传输机制,并探讨了光生电荷与光催化活性之间的关系.结果显示,随着N含量的增大,TiO2表面光伏响应阈值红移,可见光部分光电压响应强度逐渐增强,瞬态光伏响应达到最大值的时间亦有着不同程度的延迟.这表明适量的N掺杂能够提高TiO2纳米粒子中光生载流子的分离效率,相应地延长载流子的传输时间,增加光生电荷的寿命,从而促进其光催化活性;而过量的N掺杂则增加了TiO2纳米粒子中光生载流子的复合中心,抑制其光催化活性.     

N、F共掺杂TiO2可见光响应光催化剂的酸催化水解法制备及表征

采用酸催化水解法由TiCl4、NH4F混合液合成N、F共掺杂可见光响应TiO2光催化剂(TONF). 以苯酚为模型物, 考察了催化剂在可见光区、紫外光区的催化活性. 采用X射线光电子能谱(XPS)、紫外-可见漫反射光谱(DRS)、X射线衍射(XRD)、扫描电子显微镜(SEM)及低温氮物理吸附对光催化剂的晶相结构、光谱特征和表面结构等进行表征. 结果表明, 适量的N、F共掺杂TONF催化剂表现出较高的可见光催化活性. N、F共掺杂可显著提高TiO2分散性能, 促进锐钛矿相的形成, 抑制其向金红石相转变, 提高相转变温度. N掺杂可提高TiO2在可见光区的吸收; F掺杂可使TiO2能隙变窄.     

Characterization of paramagnetic species in N-doped TiO2 powders by EPR spectroscopy and DFT calculations

Electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations are combined for the first time in an effort to characterize the paramagnetic species present in N-doped anatase TiO2 powders obtained by sol-gel synthesis. The experimental hyperfine coupling constants are well reproduced by two structurally different nitrogen impurities: substitutional and interstitial N atoms in the TiO2 anatase matrix. DFT calculations show that the nitrogen impurities induce the formation of localized states in the band gap. Substitutional nitrogen states lie just above the valence band, while interstitial nitrogen states lie higher in the gap. Excitations from these localized states to the conduction band may account for the absorption edge shift toward lower energies (visible region) observed in the case of N-doped TiO2 with respect to pure TiO2 (UV region). Calculations also show that nitrogen doping leads to a substantial reduction of the energy cost to form oxygen vacancies in bulk TiO2. This suggests that nitrogen doping is likely to be accompanied by oxygen vacancy formation. Finally, we propose that the relative abundance of the two observed nitrogen-doping species depends on the preparation conditions, such as the oxygen concentration in the atmosphere and the annealing temperature during synthesis.     

负载金的掺氮二氧化钛的制备及其可见光催化性能

以纳米管钛酸为前驱体,采用水热法先制备得到新型N掺杂二氧化钛,然后用沉积沉淀法在N掺杂二氧化钛表面负载微量贵金属Au,制备得到负载Au的掺N二氧化钛.利用TEM、XRD、XPS、ESR和DRS等手段研究了样品的形貌、晶体结构、元素化学态和光谱吸收性质.样品光催化活性通过可见光催化降解丙烯进行评价,结果表明,样品N-TiO₂和Au/N-TiO₂具有明显的可见光(λ≥420 nm)催化活性.ESR结果表明,掺氮过程中生成的束缚单电子的氧空位是样品具有可见光响应的原因.     

掺杂改性纳米TiO2降解挥发性污染物及产物研究

本文系统研究了水热法制备的铁掺杂纳米TiO₂和氮掺杂纳米TiO₂在可见光照射下对挥发性有机物(volatile organic compounds,VOCs)的降解能力和降解产物.铁掺杂纳米TiO₂和氮掺杂TiO₂对光的吸收边分别红移到540 nm和580 nm;在可见光下具有良好的催化活性,24 h内对挥发性有机物的降解率达20%—50%,降解后的最终产物可能主要为CO₂.     

Photodegradation of toluene over TiO(2-x)N(x) under visible light irradiation

We report the photooxidation of toluene over nitrogen doped TiO(2) (TiO(2-x)N(x)) under visible light irradiation. The photocatalytic oxidation of toluene in air over TiO(2-x)N(x) powders was studied using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), gas chromatography (GC), ion chromatography (IC), and gas chromatography mass spectrometry (GC-MS), focusing on the photocatalytic decomposition processes of toluene. Results obtained indicate that toluene, weakly adsorbed on the catalyst surface, is initially photooxidized to benzaldehyde which adsorbs onto the TiO(2-x)N(x) surface more strongly, leading to the formation of ring-opening products such as carboxylic acids and aldehydes. No gaseous intermediates were detected during the photooxidation. Major intermediates adsorbed at the catalyst surface were oxalic acid, (COOH)(2), acetic acid, CH(3)COOH, formic acid, HCOOH, and pyruvic acid, CH(3)COCOOH, whereas more complicated carboxylic species, including propionic acid, CH(3)CH(2)COOH, isovaleric acid, (CH(3))(2)CHCH(2)COOH, and succinic acid, (CH(2)COOH)(2), were also found in the early stage of the photooxidation. These intermediate products were gradually photodegraded to CO(2) and H(2)O under visible light irradiation.     

Hierarchical N-doped TiO2 hollow microspheres consisting of nanothorns with exposed anatase {101} facets

A green solvothermal synthesis approach employing water as a hollowing controller and diethylenetriamine as both crystal growth stabilizer and N dopant source to the preparation of hierarchical N-doped TiO(2) hollow microspheres comprised of nanothorns with exposed anatase {101} facets is established. The superstructured TiO(2) shows excellent photocatalytic activities in degrading dyes under visible light irradiation.     

Synthesis, property characterization and photocatalytic activity of the novel composite polymer polyaniline/Bi2SnTiO7

A novel polyaniline/Bi(2)SnTiO(7 )composite polymer was synthesized by chemical oxidation in-situ polymerization method and sol-gel method for the first time. The structural properties of novel polyaniline/Bi(2)SnTiO(7) have been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray spectrometry. The lattice parameter of Bi(2)SnTiO(7) was found to be a = 10.52582(8) ?. The photocatalytic degradation of methylene blue was realized under visible light irradiation with the novel polyaniline/Bi(2)SnTiO(7) as catalyst. The results showed that novel polyaniline/Bi(2)SnTiO(7 )possessed higher catalytic activity compared with Bi(2)InTaO(7) or pure TiO(2) or N-doped TiO(2) for photocatalytic degradation of methylene blue under visible light irradiation. The photocatalytic degradation of methylene blue with the novel polyaniline/Bi(2)SnTiO(7) or N-doped TiO(2) as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01504 or 0.00333 min(-1). After visible light irradiation for 220 minutes with novel polyaniline/Bi(2)SnTiO(7 )as catalyst, complete removal and mineralization of methylene blue was observed. The reduction of the total organic carbon, the formation of inorganic products, SO(4)2- and NO(3-), and the evolution of CO(2) revealed the continuous mineralization of methylene blue during the photocatalytic process. The possible photocatalytic degradation pathway of methylene blue was obtained under visible light irradiation.     

A series of highly efficient photocatalysts for organic contaminants degradation under visible light irradiation

Antimonic acid and N-doped antimonic acid, solid acids with d(10) electron configuration, are reported as novel photocatalysts for rhodamine B (RhB) degradation under visible light irradiation. They show much higher activities in comparison with P25 and photolysis. However, the extent of degradation abilities for RhB was not consistent with the formation rate of the active ˙OH radicals under visible light irradiation.     

Nitrogen and sulfur co-doped TiO2 nanosheets with exposed {001} facets: synthesis, characterization and visible-light photocatalytic activity

Nitrogen and sulfur co-doped TiO(2) nanosheets with exposed {001} facets (N-S-TiO(2)) were prepared by a simple mixing-calcination method using the hydrothermally prepared TiO(2) nanosheets powder as a precursor and thiourea as a dopant. The resulting samples were characterized by transmission electron microscope, X-ray diffraction, N(2) adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The electronic properties of N,S co-doped TiO(2) were studied using the first-principle density functional theory (DFT). The photocatalytic activity of N-S-TiO(2) was evaluated by degradation of 4-chlorophenol (4-CP) aqueous solution under visible light irradiation. The production of hydroxyl radicals (˙OH) on the surface of visible-light-irradiated samples was detected by photoluminescence technique using terephthalic acid as a probe molecule. The results show that nitrogen and sulfur atoms were successfully incorporated into the lattice of TiO(2), which resulted in N-S-TiO(2) samples exhibiting stronger absorption in the UV-visible range with a red shift in the band gap transition. The first-principle DFT calculations further confirm that N and S co-dopants can induce the formation of new energy levels in the band gap, which is associated with the response of N-S-TiO(2) nanosheets to visible light irradiation. Surprisingly, pure TiO(2) nanosheets show the visible-light photocatalytic activity for the degradation of 4-CP mainly due to the substrate-surface complexation of TiO(2) and 4-CP, which results in extending absorption of titania to visible light region through ligand-to-titanium charge transfer. The N-S-TiO(2) samples studied exhibited an enhanced visible-light photocatalytic activity than pure TiO(2). Especially, the doped TiO(2) sample at the nominal weight ratio of thiourea to TiO(2) powder of 2 showed the highest photocatalytic activity, which was about twice greater than that of Degussa P25. The enhanced activity of N-S-TiO(2) can be primarily attributed to the synergetic effects of two factors including the intense absorption in the visible-light region and the exposure of highly reactive {001} facets of TiO(2) nanosheets. The former is beneficial for the photogeneration of electrons and holes participating in the photocatalytic reactions, and the latter facilitates adsorption of 4-CP molecules on the surface of TiO(2) nanosheets.     

N(4S) formation following the 193.3-nm ArF laser irradiation of NO and NO2 and its application to kinetic studies of N(4S) reactions with NO and NO2

Formation of the ground-state nitrogen atom, N((4)S), following 193.3-nm ArF laser irradiation of NO and NO(2) was detected directly by a technique of laser-induced fluorescence (LIF) spectroscopy at 120.07 nm. Tunable vacuum ultraviolet (VUV) laser radiation around 120.07 nm was generated by two-photon resonance four-wave sum frequency mixing in Hg vapor. Photoexcitation processes of NO and NO(2) giving rise to the N((4)S) formation are discussed on the basis of the Doppler profiles of the nascent N((4)S) atoms produced from the photolysis of NO and NO(2) and the photolysis laser-power dependence of the N((4)S) signal intensities. Using laser flash photolysis and vacuum ultraviolet laser-induced fluorescence detection, the kinetics of the reactions of N((4)S) with NO and NO(2) have been investigated at 295 +/- 2 K. The rate constants for the reactions of N((4)S) with NO and NO(2) were determined to be (3.8 +/- 0.2) x 10(-11) and (7.3 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), respectively, where the quoted uncertainties are 2sigma statistical uncertainty including estimated systematic error.     

具可见光活性的氮掺杂二氧化钛光催化剂

以氮掺杂为代表的非金属掺杂型TiO₂光催化剂被誉为“第二代光催化材料”。本文首先系统评述了氮掺杂二氧化钛的制备方法，然后详细阐述了在N掺杂TiO₂研究中关于其可见光活性机制以及掺杂N在TiO₂晶格中的存在状态等方面的争议。N掺杂TiO₂粉末的制备方法主要有氨气气氛下的热处理工艺、水解沉淀法、溶胶－凝胶法以及机械化学法等；N掺杂TiO₂薄膜的制备方法主要包括磁控溅射法、脉冲激光沉积法以及金属有机化学气相沉积法等。已提出的关于N掺杂TiO₂可见光活性机制的观点有N2P与O2P能级相杂化、形成N 2p孤立能态、氧空位的作用以及具顺磁性特征的杂质敏化。关于掺杂N在TiO₂晶格中存在状态的分歧在于XPS N 1s谱中特征峰的位置及其归属的解析。文章最后指出了氮掺杂二氧化钛催化剂研究中有待解决的问题及今后的发展方向。