Boosting the photoconversion efficiency of TiO2 nanotubes using UV radiation-assisted anodization as a prospective method: An efficient photocatalyst for eliminating resistant organic pollutants

1D TiO₂ nanotube arrays (TNTs), as versatile nanostructures, have attracted a considerable amount of scientific attention, particularly in photocatalytic applications. In the present study, UV radiation-assisted anodization method with various irradiation times (30–120 min) was employed as a preferable approach to fabricating TNTs with remarkable optical property and photocatalytic activity. The results revealed that in situ irradiation not only improved the surface area (from 30.10 to 48.5 m²), but also increased the roughness factor (from 77.27 to 124.73). Furthermore, UV radiation had a significant impact on optical property and by altering elemental composition, led to a red shift in absorption edge (from 3.2 to 1.4eV). Meanwhile, voltammetric experiments showed that 120 min UV radiation during anodization was able to substantially cause a surge of the photocurrent density and the photoconversion efficiency of TNTs from 0.15 to 0.55 mA cm⁻² and from 13% to 40%, respectively. As a consequence of the improvement in optical property and photochemical features, anodic TNTs fabricated under 120 min UV radiation could increase the photocatalytic degradation of 2,4-DCP from 75% to 100%. Moreover, the kinetics study showed that all photocatalytic reactions followed zero-order kinetics which rate constant over the synthesized TNTs under 120 min UV radiation was about 5.1 times greater than that of conventionally fabricated TNTs. Likewise, the pathway of photocatalytic degradation and the proportion of reactive species in this process were assessed by scavenging tests. The results confirmed that holes (h⁺) play the main role that 53% of photocatalytic degradation occurred via both direct and indirect reactions with h⁺ species. The rest of the degradation pathways were also allocated to e⁻ and ^•O₂⁻ species by accounting for 37% and 10%, respectively.     

甲磺酸铜催化合成草酸二异戊酯

制备了甲磺酸铜催化剂,对其结构进行了IR和热重分析,并用于催化草酸和异戊醇的酯化反应。结果表明,甲磺酸铜具有催化活性高、稳定,易分离,重复使用性能优良,对环境友好的特点。最佳酯化工艺条件为:n(异戊醇):n(草酸)=2．8:1,w(甲磺酸铜)=0．3％,以过量的异戊醇为带水剂,回流反应2．0 h,酯化率可达到96．8％。     

向日葵壳水解-氧化-水解法制取草酸新工艺研究

研究了以植物纤维向日葵壳为原料，采用水解-氧化-水解法制取草酸（乙二酸）的新工艺。与用同类原料，其他方法制草酸相比，本工艺在提高产率，降低生产成本以及易于业化方面有很大突破。在H2SO4质量分数为70%，原料浸泡时间3h以上，m(HNO3):m（向日葵壳）=方面有很大突破，在H2SO4质量分数为70%，原料浸泡时间3h以上，m(HNO3):m(向日葵壳）=2.1:1.0；氧化-水解反应时间5h，反应温度65-70℃的条件下，草酸二水合物收率可达78.5%。     

臭氧化合成乙醛酸技术研究 Ⅱ.马来酸酯臭氧化过程

对马来酸酯臭氧化合成乙醛酸的技术进行了研究,重点考察了臭氧化过程中的工艺参数对反应的影响。获得优化的工艺条件为,马来酸酯臭氧化反应的适宜温度应小于-5℃,臭氧浓度约30gO3/m3时,马来酸酯浓度为6~10g/100mL。通过后续的催化加氢还原和水解,获得高纯度的乙醛酸产品,总收率达到80%以上。     

乙醛酸和草酸的高效液相色谱分析

采用高效液相色谱法测定了草酸电合成乙醛酸中乙醛酸和草酸的含量,方法简便,成本低廉,效果良好。色谱柱为VP-ODS(150 mm×4.6 mm),流动相为稀磷酸水溶液(pH=2.7),流速为0.5 mL/min,柱温40℃,检测波长为212 nm。探讨了pH值及其它条件对色谱分离的影响。乙醛酸的线性方程为:Y=1.226×102X-7.053×102,线性相关系数R=0.999 6,相对标准偏差为1.5%,检出限为3.0×10-9g;草酸的线性方程为:Y=1.670×103X-5.563×104,线性相关系数R=0.999 9,相对标准偏差为0.8%,检出限为2.3×10-10g。     

草酸镁分解法制备纳米氧化镁

以草酸和氯化镁为原料，采用固液法制备了纳米级氧化镁粉体。优化了试验条件，并用TEM和XRD对纳米氧化镁的粒子结构和形貌进行了研究。结果表明，在600℃焙烧，得到的纳米氧化镁粒度分布均匀，平均粒径为15nm。并对固液法生成纳米氧化镁的机理进行了初步探讨。     

草酸二乙酯水解宏观动力学研究

在65～80℃对草酸二乙酯水解生成草酸的反应宏观动力学进行了研究,得到的草酸二乙酯水解反应速率方程可表示为rc=dcc/dt=kc0.5acc1-kc1.5c k=2.117×105exp(-3.479×104/RT) k=5.273×102exp(-1.398×104/RT) 并用实验数据对模型进行了检验.     

载锰氮化碳催化臭氧法降解水中草酸研究

草酸是废水中多种有机物氧化降解的中间产物,与臭氧反应速率很低,难以直接氧化去除。本研究通过热解法煅烧不同摩尔比例的三聚氰胺与醋酸锰(Ⅲ)二水合物,制备出不同负载量的载锰氮化碳催化剂,并研究了不同条件下载锰氮化碳催化臭氧法对草酸的降解效果,考察三聚氰胺与醋酸锰摩尔比、催化剂投加量、p H值、臭氧浓度等因素以及叔丁醇对草酸去除效果的影响。实验结果表明:相对于单独臭氧氧化而言,载锰氮化碳催化臭氧法可以极大的提高草酸的去除率,在投加0.15 g/L三聚氰胺与醋酸锰20∶1的催化剂后,草酸在60 min的TOC去除率可达到89.1%。叔丁醇加入对草酸的去除率影响较小,表明·OH在载锰氮化碳催化氧化草酸的过程中起作用但不是唯一因素。     

Photocatalytic degradation rate of oxalic acid on the semiconductive layer of n-TiO2 particles in the batch mode plate reactor Part I: Mass transfer limits

Organic compounds dissolved in water can be decomposed on a layer of n-TiO2 particles irradiated by u.v. light, which generates holes and electrons in the TiO2 material. Dissolved oxygen was used as electron scavenger and holes reacted with water to give OH radicals. The rate of degradation of the dissolved organic compounds by OH radicals is limited by the transfer of either oxygen or of theorganic compounds to the surface of n-TiO2 particles. The consequence of these limits is that, in the batch mode reactor with recirculation of the liquid, the dependence of the concentration of an organic compound on time has either a linear or an exponential form. Experiments with decomposition of oxalic acid in aqueous solutions using a plate reactor (60 cm × 120 cm) confirmed the analysis. Equations for evaluation of the mass transfer coefficient of the dissolved species to the surface of the plate reactor with a moving liquid fil m were developed for the case of the thickness of the Nernst diffusion layer being thinner than the thickness of the liquid. The experimentally obtained decomposition rate of oxalic acid was about 60 to 80% of the theoretical decomposition rate limited by oxygen flux through the film of a moving liquid. The present theory neglects the diffusion of oxygen into the porous layer of n-TiO2.     

EDTA在尿素换热设备清洗中的应用

草酸法清洗换热设备垢层时对设备腐蚀严重。EDTA能与积垢中的铁离子反应生成溶于水的络合离子,达到清洗积垢的目的,对设备腐蚀程度也小,通过EDTA、Fe含量的变化可判断清洗程度。