氮掺杂二氧化钛负载钒磷氧催化氧化NO的实验研究

以VPO为活性组分,N掺杂TiO 2为载体,采用浸渍法制备了VPO/TiN催化剂,基于单因素实验研究了其对NO的选择性催化氧化(SCO)性能以及抗硫抗水性能。研究表明:当P/V为1/5、N/Ti为1、活性组分负载量为10%、焙烧温度为350℃时,催化剂的SCO活性最好,NO氧化率达到61%;光致发光光谱(PL)表征显示N掺杂TiO 2在催化剂表面形成的氧空位可增强催化剂对O 2的吸附;VPO/TiN催化剂抗硫抗水性能较强,反应后的催化剂表面未发现硫酸根的特征峰,水蒸气主要通过与NO竞争吸附占据活性位点来抑制催化剂的SCO活性。     

钴掺杂二氧化钛的制备及光催化性能的研究

钴掺杂制备超细TiO2粒子,并进行了表征。CoO与TiO2形成固溶体抑制了TiO2晶粒的长大并促进相变。钴掺杂有利于提高TiO2光催化剂的寿命。     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

La3+掺杂对吸附相反应制备TiO2复合催化剂的结晶过程及弱紫外光下活性的影响

利用吸附相反应技术制备弱紫外光响应的高效催化剂,并通过XRD、XPS以及HRTEM探索了不同焙烧温度下La3+掺杂量对TiO2结晶过程的影响.结合弱紫外光下甲基橙的降解反应,深入研究催化剂结晶过程的变化对弱紫外光下催化剂活性的影响.结果表明,La3+掺杂会抑制TiO2的结晶过程.当焙烧温度或者掺杂量较低时,La3+不能进入TiO2的晶格结构但会轻微地抑制TiO2的结晶过程;未进入晶格结构的La3+存在会引入光生载流子的浅能级捕获中心,在弱光体系中极大提升了催化剂的活性.当La3+的掺杂量为0.05%(原子分数)时,经过900℃焙烧后催化剂降解能力最高,其活性超过商用P25的2倍多.在较高La3+掺杂量(超过0.20%)时,900℃焙烧后一定量La3+进入TiO2的晶格结构而大大抑制了TiO2结晶;这种强烈的抑制作用使得催化剂中存在大量无定形结构TiO2,无定形TiO2甚至多于700℃焙烧后的催化剂,反而大大抑制了弱光体系中催化剂活性.     

Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

氮掺杂TiO2可见光光催化剂的制备及性能

以尿素和钛酸丁酯为原料,通过溶胶-凝胶法低温下制备了高可见光催化活性的氮掺杂TiO2(NDT)光催化剂,采用XRD、TEM、BET和UV-Vis DRS等测试手段对其进行了表征,并在自制光催化反应器中降解甲基橙评价了样品的光催化活性。结果表明,当氮与钛的摩尔比为0.5∶1时,350℃焙烧的样品(NDT350)具有最佳的可见光光谱吸收和光催化活性,该催化剂为锐钛矿晶相,平均粒径为21 nm,比表面积为89.13 m2/g。可见光辐照下,NDT350降解甲基橙的表观反应速率常数为1.381×10-2min-1,是商业P25催化剂的16.85倍。NDT350优良的可见光催化活性与其大的比表面积和强烈的可见光光谱吸收有关。     

N掺杂TiO_2光催化剂的制备及其H_2O_2改性的研究

以钛酸四丁酯为前驱物,采用水解沉淀法制备了N掺杂TiO_2光催化剂和H_2O_2改性的N掺杂TiO_2光催化剂.实验表明,H_2O_2改性的N掺杂TiO_2光催化剂的最佳制备条件为:氨水(质量分数28%)加入量20 mL,焙烧温度500 ℃,H_2O_2(质量分数30%)加入量2.0 mL.日光下,N掺杂TiO_2光催化剂及H_2O_2改性的N掺杂TiO_2光催化剂在反应90 min时的活性红紫去除率达99%,它们对活性红紫的去除率远高于P_(25)TiO_2光催化剂.H_2O_2改性的N掺杂TiO_2光催化剂中N质量分数比改性前明显提高,制备的两种催化剂中不仅含有N元素,同时还含有C和H元素.     

Fabrication of ion doped WO3 photocatalysts through bulk and surface doping

Na⁺ doped WO₃ nanowire photocatalysts were prepared by using post-treatment (surface doping) and in situ (bulk doping) doping methods. Photocatalytic degradation of Methyl Blue was tested under visible light irradiation, the results showed that 1 wt.% Na⁺ bulk-doped WO₃ performed better, with higher photoactivity than surface-doped WO₃. Photoelectrochemical characterization revealed the differences in the photocatalytic process for surface doping and bulk doping. Uniform bulk doping could generate more electron–hole pairs, while minimizing the chance of electron–hole recombination. Some bulk properties such as the bandgap, Fermi level and band position could also be adjusted by bulk doping, but not by surface doping.     

Modified titanium oxide (TiO2) nanocomposites and its array of applications: a review

Titania (TiO₂) has been the focus of attention of researchers since the first demonstration of its capability to generate the photocatalytic splitting of water into hydrogen and oxygen. However, there seems to be a recent surge in the research activity, involving modified TiO₂ nanoparticles (NP), which are considered to be more effective due to different physicochemical properties in comparison to unmodified fine particle analogs. Several strategies have been employed to modify TiO₂ to reduce recombination rates of photogenerated charge carriers to enhance the optimal functioning of TiO₂. Doping with cations and anions and coupling it with another semiconductor are the most well-known modification methods used. Titania nanocomposites are known to have a plethora of applications. Photoexcitation of these particles are seen to be extraordinarily effective in eliciting microbial death which makes it an attractive candidate for the manufacturing of antimicrobial coatings. On the other hand, TiO₂ induces the oxidation of various organic refractory compounds like tetracycline, sulfamethazine, and bisphenol. The photo-electrocatalytic oxidation technique which amalgamates the principle of photocatalysis and electrolysis serves as a newer, unswerving, and cost effective water treatment process. In the biomedical arena, use is now acknowledged for the photodynamic therapy of cancer, cell imaging, biological sensors, drug delivery system, and as endonucleases. In the commercial front, it is utilized in creams owing to its small particle size, which facilitates absorption through skin. It is also employed as ultraviolet blocking agents in sunscreen and commonly encountered as a brilliant white pigment in paint due to its brightness, high refractive index and resistance to discoloration. Its use in solar cells has also been reported. This review aims to encompass the new progress of modified TiO2 nanocomposites for efficient applications, emphasizing the future trends of TiO2 in arenas like healthcare, environment, biomedical, food, personal care, and pharmacy and also highlights the commercial implications of this promising nanomaterial.     

物理气相沉积硬质耐腐蚀磨损防护涂层研究进展

叙述了用物理气相沉积技术制备的硬质耐腐蚀磨损防护涂层的研究进展。重点介绍了腐蚀磨损耦合工况特性和作用机理,单元、多元掺杂氮化物涂层,高熵氮化物涂层,多层、纳米多层、纳米复合、梯度氮化物涂层耐腐蚀磨损性能研究,非金属元素/金属元素掺杂DLC涂层、多层复合DLC涂层耐腐蚀磨损性能研究,并对涂层改性、强化机理和腐蚀磨损失效机制进行了总结。最后,提出了未来物理气相沉积硬质耐腐蚀磨损防护涂层重点发展的方向,应重点发展涂层组元/结构设计、力–电耦合损伤机理研究、高效率研发设计、涂层先进制备装备与评估体系等方面的能力。