四(4-羟基-3-苯偶氮基)苯基卟啉的合成、表征及光谱性能

以苯胺和对羟基苯甲醛为原料合成偶氮醛,并进一步与吡咯缩合得到一种新型的偶氮卟啉。通过元素分析、质谱、^1HNMR、UV-Vis表征了其结构。探讨了其荧光性能。通过与四对羟基苯基卟啉的荧光性能的对比,发现有较大程度的荧光猝灭。可能是偶氮苯基与卟啉环相互作用发生分子内电子转移的结果。     

电-Fenton法废水处理技术的研究现状与进展

电-Fenton法是一种新兴的废水处理技术,在水处理中的应用越来越受到关注。作者综述了电-Fenton技术的特性、动力学特征、各种形式及其特点,以及国内外电-Fenton废水处理技术的试验研究现状。同时提出了该技术亟待解决的突出问题和发展动向．指出高效催化性能的阴极材料的开发应用是电-Fenton法最具潜力的发展方向。     

Anchoring hydroxyl intermediate on NiCo(OOH)x nanosheets to enable highly efficient electrooxidation of benzyl alcohols

Selective oxidation of alcohols to the carboxylic acid plays an important role in the production of valuable chemicals. Herein, NiCo hydroxide (NiCo(OOH)_x) nanosheets with a thickness of ~4 nm were controllably fabricated in a facile way efficient for the electrooxidation of benzyl alcohol (BAL) to benzoic acid (BAD). Mechanistic studies confirmed the hydroxyl active intermediate ( OH*) generated on the surface of NiCo(OOH)_x nanosheets through operando electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy analysis during the electrooxidation process. Importantly, we discovered that the  OH* was crucial to boost the selective oxidation of BAL by attacking the hydroxyl end group to achieve carboxylic acid. The early onset potential of 1.16 V_RHE in the presence of BAL was below 1.23 V_RHE for oxygen evolution reaction. The rotating ring-disk electrode further revealed that the electrocatalytic BAL oxidation reaction occurred earlier in the oxygen evolution reaction. In 150 mM BAL, NiCo(OOH)_x nanosheets generated a high BAD selectivity of >99% and full conversion of BAL in 3 h. The experimental and theoretical calculation revealed that the dominant pathway of BAL oxidation was the interaction between nucleophilic BAL with  OH* to form BAL-OH* directly by dehydrogenates, thereby producing BAD with high efficiency. This research sheds mechanism insights on the electrocatalytic alcohols oxidation reaction.     

荧光法测定镧银二氧化钛无机纳米复合材料中的羟基自由基

目的 为了增进TiO2光催化材料的实用性,使其在药学、生物学、医学以及免疫学等领域可以广泛应用,采用掺杂稀土元素镧,提高其光催化性能.方法 应用苯基荧光酮荧光法,通过测定苯基荧光酮反应前后的荧光变化,间接地测定自由基的产生,找到体系的最佳实验条件,方法简单,测定快捷,灵敏度高,无需昂贵的仪器,可作为一种筛选抗氧化剂的方法,研究稀土元素掺杂二氧化钛所产生的羟基自由基.结果 合成出了具有优异抗菌活性和光学活性的新型纳米抗菌剂,苯基荧光酮荧光法测定出La-Ag-TiO2体系中产生的羟基.结论 双元素掺杂的样品的荧光强度在一定条件下低于单元素掺杂的样品,由此可知,双元素掺杂的样品产生的羟基自由基多于单元素掺杂,且镧的掺杂促进了羟基自由基的产生,降低了样品的荧光强度.     

A Method for Evaluating Lignin Mobility Distributions Obtained by Capillary Zone Electrophoresis

Abstract

The profile of the mobility distribution of lignin-containing samples depends on type of sample. To facilitate comparison, a procedure for determining the average mobility (μ_av), i.e. the average charge density, of lignin is presented. The procedure is applied to black liquor (Sb), isolated dissolved lignin (Sd) and isolated residual (Sr) lignin samples, obtained from flow-through kraft cooks of softwood. The μ_av of the isolated lignin samples is compared with the concentration of phenol and carboxyl groups and relative molecular size. As the cook proceeds the μ_av for a particular type of lignin sample increases, reflecting an increase in average charge density. The μ_av, measured at pH 12, decreases in the order Sd>Sb>Sr, except at the end of the cook, when the average charge densities of the Sb and Sr samples are similar. Associations between lignin and carbohydrate fragments are proposed to cause the lower mobility of black liquor compared to isolated dissolved lignin. Characterisations performed at pH 10 indicate that the isolated dissolved lignin samples may have a higher pK_a in the middle of the cook than the other samples.     

BDD电极电催化降解苯酚废水的研究

采用直流等离子体化学气相沉积方法制备了硼掺杂金刚石(BDD)薄膜电极。以苯酚为目标污染物,研究了苯酚废水在电极上的电化学降解规律及降解历程。结果表明,不同浓度的苯酚在电极上均能够完全矿化成CO2。高浓度条件下,苯酚先转化成中间产物,然后中间产物再氧化成CO2;低浓度条件下,苯酚氧化反应迅速,直接矿化成CO2。提高电流密度能够加速苯酚的降解,但会导致电流效率下降。苯酚的降解历程为对位首先受到·OH自由基的攻击,生成对苯二酚,再开环形成顺、反丁烯二酸与乙酸,然后顺、反丁烯二酸在阴极还原为丁二酸,丁二酸氧化脱羧形成丙二酸、乙酸、草酸或甲酸,最终氧化成CO2。     

钙法化学混凝工艺处理海底钢管酸洗废水

针对海底钢管酸洗废水成分复杂、酸度高、含磷量高的特点,采用钙法化学混凝工艺对其进行处理。通过单因素试验考察了体系pH值、反应时间、生石灰投量和静置时间等因素对除磷效果的影响。试验结果表明,酸洗废水磷酸盐的质量浓度为124.3 mg/L时,在生石灰的投加量是理论投加量的2.5倍,反应体系pH值大于或等于11.0,25℃下恒温搅拌反应30 min、静置30 min的条件下,出水磷酸盐的质量浓度(以磷计)降至1.0 mg/L,达到了GB 18918—2002《城镇污水处理厂污染物排放标准》中一级B排放标准的要求。pH值是钙法化学混凝除磷的控制性因素,用生石灰做混凝剂可以补充溶液的碱度,进而减少了氢氧化钠的用量,节约了处理成本。     

罗汉果提取液对自由基的清除作用

以邻苯三酚自氧化产生超氧自由基(02-),Fenton反应产生羟自由基(.OH),用分光光度法测定罗汉果提取物对O2-和.OH的清除作用。结果表明,罗汉果提取物对O2-和.0H均有显著清除作用。     

催化高压脉冲放电降解水中苯酚

采用向高压脉冲放电反应器中投加催化剂的方式来强化降解苯酚的效果,并考察了不同催化剂及其投量对苯酚处理效果的影响。与单独高压脉冲放电进行比较,Fe2+投量为0.05 mmol/L时,催化效果最好,可以使苯酚的去除率由15.45%提高到94.94%,其次是Fe3+,投量为0.061mmol/L时,苯酚的去除率提高了3倍。这主要是因为Fe2+和Fe3+诱发放电过程中产生的H2O2发生芬顿和类芬顿反应,生成HO.。另外,由于放电过程中紫外光解的作用,投加0.1mmol/LH2O2可以使苯酚的去除率提高1倍。粉末活性炭的良好吸附性能也使它具有一定的催化作用,投量5 mg/L可使苯酚的去除率提高1.3倍。     

具有纳米结构的TiO_2纤维光催化氧化活性

研究了具有纳米结构,高比表面的锐钛矿TiO2纤维在光催化降解苯酚体系中的氧化性能,发现其活性与P25相当;通过加羟基自由基猝灭剂证实了羟基自由基(HO.)对苯酚降解的贡献;而通过加空穴猝灭剂则观察到明显的空穴(h )效应。并通过K I氧化反应进一步研究了催化剂表面上的空穴效应,结果表明,TiO2纤维上的光生空穴比P25稳定,其空穴量子产率是后者的3.3倍。