CN112138722B - 一种三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法 - Google Patents
一种三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开一种三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，采用三苯胺基树枝配体取代硅酞菁在有机溶剂中与二氧化硅反应，制备得到了以共价键结合的、具有催化氧化有机污染物能力的三苯胺基树枝配体取代硅酞菁（TPA‑SiPc）负载SiO2光催化剂。其制备方法是：在碱性条件下，将正硅酸乙酯水解的同时，加入三苯胺基树枝配体取代硅酞菁的N，N‑二甲基甲酰胺溶液，搅拌并在一定温度下反应，将水解后产物经沉淀、离心、洗涤、干燥后即可得到该催化剂。本方法所制备的三苯胺基树枝配体取代硅酞菁负载SiO2（TPA‑SiPc@SiO2）光催化剂具有光催化降解有机物的性能，可应用于空气、土壤及污水中有机污染物的光催化处理。
Description
技术领域
本发明涉及催化材料，具体涉及一种三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，属于功能材料技术领域。
背景技术
酞菁，是一类具有共扼大π键的类卟啉大环化合物，其大环内有一个空穴，可以容纳许多金属及其非金属原子，生成酞菁金属配合物。酞菁分子上的苯环可以引入多种取代基，从而得到各种功能化的衍生物。加之酞菁生产成本较低、着色性能优异；光、热及化学稳定性良好，对太阳光中可见光区具有较强的吸收，而且在吸收光能后能够产生活性态氧，如单线态氧、羟基自由基、超氧自由基等。因此，酞菁类化合物在光催化、光动力学治疗、化学传感器等方面具有很广阔的研究和应用前景。
但由于酞菁类化合物是具有刚性、平面的、共扼大环芳香体系，而芳香环的疏水性强，且芳香性大环间存在强烈的π-π相互作用，分子之间易形成聚集体，从而降低酞菁分子的荧光量子产率，缩短单线态和三线态量子产率和寿命，从而降低其光敏化效率。众多学者研究酞菁的负载，负载载体一般为传统分子筛、纤维素和溶胶凝胶，一方面能提高酞菁的分散性能，增加催化剂使用效率；另一方面，采用传统负载载体制备的负载型酞菁存在负载率低、催化活性不高、分离困难等缺点。如樊亚芳等采用首先高温活化Y型分子筛，然后Fe2+置换Na+的方法制备成金属Fe2+离子修饰的Y型分子筛，最后原位合成制备Y型分子筛负载型铁酞菁，但由于Fe2+置换困难而含量低，而且孔道结构固定，制备出的负载型酞菁种类少，催化选择性低，不能满足实用要求。
本发明利用三苯胺基树枝配体取代硅酞菁负载在SiO2上可有效地调整酞菁的聚集程度，使其更有效的产生单线态氧，从而更有效应用于在光动力治疗或光催化应用中。本发明将可能从以下几个方面影响多相光催化反应过程，从而提高光催化过程效率：1）引入具有聚集诱导发光（AIE）性能、空穴传输和供电子体特性的三苯胺（TPA）基团，赋予酞菁较大的空间位阻，阻止聚集体形成并且提高其溶解性。2）树枝配体的结构呈单分散状态，以酞菁化合物为中心在其周围接上树枝结构，树枝上接上亲水基团，使亲水性提高，并有效降低酞菁化合物的聚集，减少其自猝灭现象。3）亲水性基团的接入能够使其与SiO2更好的结合，三苯胺基树枝配体取代硅酞菁负载在SiO2上能够使光生电子转移到酞菁分子上，从而可有效提高电子转移，转移到半导体导带的电子可以进一步与氧气反应生成活性氧，如超阳自由基，有上述所产生的活性氧进一步与水体中的有机污染物反应将其矿化成CO2和H2O。4）酞菁分子周围的亲水性官能团能够与SiO2上的氢氧键形成作用力，更好的固定在SiO2上。同时，酞菁分子中的金属原子可与SiO2形成轴向络合增强分子之间的作用力。5）SiO2与树枝状酞菁络合后可以降低酞菁分子之间的聚集，同时有利于回收。
发明内容
本发明的目的在于提供一种三苯胺基树枝配体取代硅酞菁负载SiO2（TPA-SiPc@SiO2）光催化剂的制备方法。本发明目的在于为土壤、空气和水质的光催化净化处理过程提供一种具有光催化降解有机污染物的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂，该光催化剂利用三苯胺的空间位阻在一定程度上能抑制酞菁的自聚集行为；又可以提高SiO2对可见光的吸收能力，以及减少电子空穴对的复合几率，显著提高了其可见光光催化性能。
本发明所述的一种三苯胺基树枝配体取代硅酞菁负载SiO2催化剂的制备方法，包括如下步骤：（1）将不同配比异丙醇、乙醇和水的母液和三苯胺基树枝配体取代硅酞菁的N，N-二甲基甲酰胺贮备液在pH值为中性或碱性以及一定水浴温度的条件下搅拌混合均匀；（2）向溶液中加入正硅酸乙酯，继续搅拌得到所需要的催化剂。
本发明所述的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，其特征在于：配置不同配比异丙醇、乙醇和水的母液，配比如（异丙醇与乙醇的比例选2:0、2:1、4:1等，水的体积固定不变 )。
本发明所述的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，其特征在于：向溶液中加入浓氨水调节pH值7~12，混合溶液在一定温度水浴条件（30~80℃）下搅拌混合均匀。
本发明所述的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，其特征在于：向上所述溶液中加入不同量的三苯胺基树枝配体取代硅酞菁的N，N-二甲基甲酰胺贮备液（0.02 mol/L，0.2~1.5 mL）搅拌5~8 min使其混合均匀。
本发明所述的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，其特征在于：向上述溶液中加入正硅酸乙酯，继续搅拌8~12 h使其充分水解，最后将溶液过滤，洗涤，80~100℃干燥即得到所需要的催化剂。
将本发明制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂用于可见光或太阳光照射下的光催化反应，具有光催化降解有机物的性能。
本发明有益效果：
（1）通过调节母液调控SiO2的粒径大小。
（2）本发明可见光催化剂制备方法工艺简单，所需原料量少，易于控制，适于工业化生产和应用。
（3）制备出的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂，可以显著提高量子效率，可用于处理工业污水、降解染料废水及室内有毒气体等。
附图说明
图１是实施例１制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的SEM图。
图2是实施例1制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂降解对氯苯酚活性图。
具体实施方式
实施例1
（1）将10 mL蒸馏水加入到100 mL的异丙醇中，70℃水浴条件下搅拌均匀。
（2）向步骤（1）所述混合溶液中加入浓氨水调节pH值为12，待pH稳定后再加入1 mL的三苯胺基树枝配体取代硅酞菁储备液（0.02 mol/L），继续搅拌5 min。
（3）向溶液中加入10mL的正硅酸乙酯，继续搅拌使其充分水解，最后将溶液过滤，洗涤（每次用10mL异丙醇洗涤3次、10 mL蒸馏水洗涤5次），将固体在80~100 ℃条件下烘干，得到所需的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂，图１是实施例１制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的SEM图。
实施例2
可见光光催化反应的光源为置于双层玻璃夹套(通冷凝水)中的500 Ｗ卤钨灯，使用滤光片保证入射光为可见光(420 nm<λ<800 nm)，以实施例1制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂 50mg 为光催化剂，取200 mL 10 mg/L对氯苯酚溶液进行紫外-可见光谱分析，在紫外最大吸收波长λ为279 nm处测定溶液吸光值，来计算得到三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂对对氯苯酚水溶液的降解能力。在反应时间6 h后，三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂对对氯苯酚水溶液的降解率可达52.4%；图2是实施例1制备的三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂降解对氯苯酚活性图。
Claims (3)
1.一种三苯胺基树枝配体取代硅酞菁负载SiO2光催化剂的制备方法，包括如下步骤：
（1）将不同配比异丙醇、乙醇和水的母液和三苯胺基树枝配体取代硅酞菁的N，N-二甲基甲酰胺贮备液在pH值为中性或碱性以及一定水浴温度的条件下搅拌混合均匀，获得溶液；（2）向溶液中加入正硅酸乙酯，继续搅拌得到所需要的催化剂；
所述母液为将10mL蒸馏水加入到100mL的异丙醇中；
步骤（1）的溶液中加入浓氨水调节pH值7～12，混合溶液在30～80℃温度水浴条件下搅拌混合均匀；
步骤（1）的溶液中加入浓度为0.02mol/L、0.2～1.5mL不同量的三苯胺基树枝配体取代硅酞菁的N，N-二甲基甲酰胺贮备液搅拌5～8min使其混合均匀；
步骤（2）中的向溶液中加入10mL正硅酸乙酯，继续搅拌8～12h使其充分水解，最后将溶液过滤，洗涤，80～100℃干燥即得到所需要的催化剂。
2.权利要求1所述的方法制备的三苯胺基树枝配体取代硅酞菁负载SiO2可见光光催化剂用于可见光或太阳光照射下的光催化反应，具有光催化降解有机物的性能。
3.根据权利要求2所述的应用，其特征在于：降解有机物为对氯苯酚水溶液。
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