CN105833913A - 一种化学改性的二氧化钛光催化剂及其制备方法 - Google Patents
一种化学改性的二氧化钛光催化剂及其制备方法 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明公开了一种化学改性的二氧化钛光催化剂,所述光催化剂是通过将一定量的二氧化钛负载到石墨烯和磺化酞菁钴合成物上而制得。本发明化学改性的二氧化钛光催化剂通过将石墨烯、磺化酞菁钴和二氧化钛有机的结合起来,不仅降低了二氧化钛的禁带宽度,增强了电子的转移效率,提高了催化剂的可见光响应范围,改性后的二氧化钛光催化剂对波长≥460nm的可见光均有响应,还能活化氧气;本发明化学改性的二氧化钛光催化剂在紫外光和可见光下均能通过对氧分子的活化快速降解水中的有机污染物。本发明化学改性的二氧化钛光催化剂的制备方法工艺简单、成本低,适用于工业化生产。
Description
技术领域
本发明涉及一种二氧化钛光催化剂,尤其涉及一种化学改性的二氧化钛光催化剂,还涉及上述化学改性二氧化钛光催化剂的制备方法,属于光催化剂领域。
背景技术
近年来光催化领域迅速发展,光催化降解有机物更是光催化研究领域的一个重要分支。利用TiO2光催化降解有机染料不仅效率高、成本低而且环保可靠。但是由于TiO2的禁带宽度为3.2ev,只能被波长小于380nm的紫外光所激发;而太阳光中大约只有4%的紫外光,对其余大部分可见光均不能产生响应。另外,当TiO2受到太阳光辐射时,被太阳光所激发的电子-空穴对很容易在内部迅速复合,这大大阻碍了TiO2在实际光催化领域的应用。
石墨烯是从石墨材料中剥离出来,由碳原子组成的只有一层原子厚度的二维晶体。石墨烯具有优质的导电性,是良好的电子受体,在一定程度上弥补了二氧化钛的电子-空穴易复合的缺陷。
磺化酞菁钴是由具有18个电子的大共轭体系的化合物酞菁经过磺化而得到的,其化学性质稳定,中心金属离子为钴离子。当磺化酞菁钴被一定能量的光子激发后,可以发生氧化还原反应。磺化酞菁钴易与氧气形成超氧络合物,位于中心的钴离子轨道(d2z或者dxy)可以与氧轨道相互作用,氧分子在磺化酞菁钴分子表面形成Co--O2键。但是纯磺化酞菁钴在可见光下并没有响应。
发明内容
发明目的:本发明所要解决的技术问题是提供一种化学改性的二氧化钛光催化剂,该光催化剂在紫外光和可见光下均能通过对氧分子的活化快速降解水中的有机污染物。
本发明还要解决的技术问题是提供上述化学改性的二氧化钛光催化剂的制备方法。
为解决上述技术问题,本发明所采用的技术方案为:
一种化学改性的二氧化钛光催化剂,所述光催化剂是通过将一定量的二氧化钛负载到石墨烯和磺化酞菁钴合成物上而制得。
上述化学改性的二氧化钛光催化剂的制备方法,包括如下步骤:
步骤1,将一定量的石墨烯和磺化酞菁钴加入水中,超声反应得到石墨烯-磺化酞菁钴合成物;
步骤2,将一定量的钛酸丁酯、乙醇和乙酸混合搅拌均匀;
步骤3,将步骤1的石墨烯-磺化酞菁钴合成物加入到步骤2的混合溶液中,持续搅拌下得到溶胶;
步骤4,将步骤3的溶胶置于反应釜中,于160~200℃下反应16~20h后,将产物分别用盐酸和水清洗并干燥即可得到石墨烯-磺化酞菁钴-二氧化钛。
其中,步骤1中,所述石墨烯和磺化酞菁钴的加入质量比为1∶50;对于每1ml水,加入石墨烯的质量为0.1667mg,加入磺化酞菁钴的质量为8.33mg。
其中,步骤1中,所述超声时间为8~10h。
其中,步骤2中,所述钛酸丁酯、乙醇和乙酸的加入体积比为17∶34∶4.8。
其中,步骤3中,所述石墨烯-磺化酞菁钴合成物的加入量为14.2mg,所述混合溶液的体积为55.8ml。
其中,步骤4中,所述盐酸的质量百分浓度为5%。
其中,步骤4中,所述干燥温度为80℃,所述干燥时间为8h。
本发明制备方法首先通过长时间超声将石墨烯和磺化酞菁钴合成到一起,再通过水热合成法将二氧化钛负载到石墨烯和磺化酞菁钴合成物上,通过这样的改性大大提高了二氧化钛的光响应范围,并起到了对氧气分子活化的作用。
本发明化学改性的二氧化钛光催化剂(石墨烯-磺化酞菁钴-二氧化钛)的制备原理:本发明通过水热合成法制备化学改性的二氧化钛光催化剂G-CoPcS-TiO2,通过添加石墨烯(G),促进二氧化钛和石墨烯之间的电子传递,作为良好电子受体的石墨烯很好地抑制了光激发二氧化钛所形成的电子-空穴对的复合;通过添加磺化酞菁钴(CoPcS),与二氧化钛形成共价键,并且中心过渡金属离子Co通过与氧分子的转移使得O-O键拉长,从而将三线态的氧活化为单线态的氧、超氧离子和羟基离子,大大提高了氧气的活化性能,进而也提高了光催化剂的催化能力。
有益效果:本发明化学改性的二氧化钛光催化剂是将石墨烯、磺化酞菁钴和二氧化钛有机的结合起来,不仅降低了二氧化钛的禁带宽度,增强了电子的转移效率,提高了催化剂的可见光响应范围,改性后的二氧化钛光催化剂对波长≥460nm的可见光均有响应,还能活化氧气;本发明化学改性的二氧化钛光催化剂的制备方法工艺简单、成本低,适用于工业化生产。
附图说明
图1为本发明化学改性的二氧化钛光催化剂制备方法的工艺流程图;
图2为本发明化学改性的二氧化钛光催化剂改性前后的吸附-紫外光催化氧化亚甲基蓝的效果对比图;
图3为本发明化学改性的二氧化钛光催化剂改性前后的吸附-可见光催化氧化亚甲基蓝效果对比图。
具体实施方式
以下结合附图对本发明的技术方案做进一步说明,但是本发明要求保护的范围并不局限于此。
实施例1
一种化学改性的二氧化钛光催化剂的制备方法,包括如下步骤:
步骤1,将6mg石墨烯、300mg磺化酞菁钴加入到36mL去离子水中,超声反应8h后离心并去除上清液,烘干后得到14.2mg石墨烯-磺化酞菁钴合成物;
步骤2,边搅拌边将17mL钛酸丁酯缓慢滴入34ml乙醇和4.8mL乙酸的混合液中,60分钟滴完,混合均匀得到溶液B;
步骤3,边搅拌边将14.2mg石墨烯-磺化酞菁钴合成物加入混合溶液B中,磁力搅拌2h得到溶胶;
步骤4,将溶胶置于100mL反应釜中,于160℃下反应16h后,将产物分别用50mL质量百分浓度为5%的盐酸和去离子水冲洗,然后再置于80℃烘箱中干燥8小时,最后研磨至粉末状即得石墨烯-磺化酞菁钴-二氧化钛(G-CoPcS-TiO2)。
实施例2
一种化学改性的二氧化钛光催化剂的制备方法,包括如下步骤:
步骤1,将6mg石墨烯、300mg磺化酞菁钴加入到36mL去离子水中,超声反应10h后离心并去除上清液,烘干后得到14.2mg石墨烯-磺化酞菁钴合成物;
步骤2,边搅拌边将17mL钛酸丁酯缓慢滴入34ml乙醇和4.8mL乙酸的混合液中,60分钟滴完,混合均匀得到溶液B;
步骤3,边搅拌边将14.2mg石墨烯-磺化酞菁钴合成物加入混合溶液B中,磁力搅拌2h得到溶胶;
步骤4,将溶胶置于100mL反应釜中,于200℃下反应20h后,将产物分别用50mL质量百分浓度为5%的盐酸和去离子水冲洗,然后再置于80℃烘箱中干燥8小时,最后研磨至粉末状即得石墨烯-磺化酞菁钴-二氧化钛(G-CoPcS-TiO2)。
将实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2与改性前二氧化钛光催化剂TiO2进行亚甲基蓝的吸附-紫外光催化实验:
分别取两份100mL初始浓度为20mg/L亚甲基蓝溶液,往两份溶液中分别加入0.05g实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2和改性前二氧化钛光催化剂TiO2,恒温振荡120min,待吸附达到平衡后,通入空气并开启汞灯,紫外光光源照射3h,进行紫外光光催化实验,实验中,每隔60min分别从两份溶液中取样3mL,离心分离(离心5min,4000r/min),取1mL上清液,稀释至10mL,用紫外分光光度计测定吸光度,计算出各个时间点亚甲基蓝的浓度,从而计算出各个时间点亚甲基蓝的降解率,结果如图2所示。
从图2可以看出,G-CoPcS-TiO2和TiO2降解亚甲基蓝实验过程中,吸附2h后,亚甲基蓝浓度和初始浓度的比值分别为93.91%、88.40%,计算去除率分别为6.09%、11.60%;紫外光照射3h后,亚甲基蓝的浓度和初始浓度的比值分别为1.26%、9.20%,计算去除率分别为98.74%、90.8%。数据表明,改性后所得的G-CoPcS-TiO2对亚甲基蓝的吸附-紫外光光催化能力得到了提升,降解率接近100%。
将实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2与改性前二氧化钛光催化剂TiO2进行亚甲基蓝的吸附-可见光催化实验:
分别取两份100mL初始浓度为20mg/L亚甲基蓝溶液,往两份溶液中分别加入0.05g实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2和改性前二氧化钛光催化剂TiO2,恒温振荡120min,待吸附达到平衡后,通入空气并开启金卤灯,滤去紫外光照射3h,进行可见光光催化实验;实验中,每隔60min分别从两份溶液中取样3mL,离心分离(离心5min,4000r/min),取1mL上清液,稀释至10mL,用紫外分光光度计测定吸光度,计算出各个时间点的亚甲基蓝的浓度,从而计算出各个时间点亚甲基蓝的降解率,结果如图3所示。
从图3可以看出,G-CoPcS-TiO2和TiO2降解亚甲基蓝实验过程中,吸附2h后,亚甲基蓝的浓度和初始浓度的比值分别为93.61%、88.94%,计算去除率分别为6.39%、11.06%,可见光照射3h后,亚甲基蓝的浓度和初始浓度的比值分别为26.82%、88.20%,计算去除率分别为73.18%、11.80%。数据表明,改性后所得的G-CoPcS-TiO2对亚甲基蓝的吸附-可见光光催化能力得到了大幅提升,改性后所得的G-CoPcS-TiO2在可见光下仍具有很强的光催化活性,而改性前的TiO2在可见光下几乎没有光催化活性。
本发明化学改性的TiO2光催化剂不仅在紫外光条件下对亚甲基蓝溶液具有接近100%的降解能力,而且其可见光活性明显,改性后所得的G-CoPcS-TiO2可见光活性达到70%以上。因此本发明化学改性后的二氧化钛光光催化剂在紫外光和可见光下均有很强的光催化活性,均能通过对氧分子的活化快速降解水中的有机染料。
将实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2进行亚甲基蓝的吸附-可见光催化实验:
分别取两份100mL初始浓度为20mg/L亚甲基蓝溶液,往两份溶液中分别加入0.05g实施例1制得的改性后二氧化钛光催化剂G-CoPcS-TiO2,恒温振荡120min,待吸附达到平衡后,其中一份溶液通入空气并开启金卤灯,滤去紫外光,另一份溶液通入氮气并开启金卤灯,滤去紫外光,照射3h,进行可见光光催化实验,实验中,每隔60min分别从两份溶液中取样3mL,离心分离(离心5min,4000r/min),取1mL上清液,稀释至10mL,用紫外分光光度计测定吸光度,计算出亚甲基蓝的浓度,从而计算出亚甲基蓝的降解率。
G-CoPcS-TiO2在通入空气和通入氮气进行降解亚甲基蓝实验过程中,在有氧条件、可见光下G-CoPcS-TiO2对亚甲基蓝溶液的降解率为73.18%,而无氧条件、可见光下其降解率仅为40.48%。
数据表明,在光催化过程中,改性后的光催化剂不仅增强了对可见光的吸收,也使氧化还原反应中的氧气得到了活化。石墨烯-磺化酞菁钴-二氧化钛在光催化过程中,将惰性较强的三线态氧活化成了单线态氧、羟基自由基和超氧离子,大大提高了氧气的活性,进而也提高了光催化剂的催化能力,促进了对溶液中亚甲基蓝的降解。
显然,上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而这些属于本发明的精神所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (8)
1.一种化学改性的二氧化钛光催化剂,其特征在于:所述光催化剂是通过将一定量的二氧化钛负载到石墨烯和磺化酞菁钴合成物上而制得。
2.权利要求1所述化学改性的二氧化钛光催化剂的制备方法,其特征在于,包括如下步骤:
步骤1,将一定量的石墨烯和磺化酞菁钴加入水中,超声反应得到石墨烯-磺化酞菁钴合成物;
步骤2,将一定量的钛酸丁酯、乙醇和乙酸混合搅拌均匀;
步骤3,将步骤1的石墨烯-磺化酞菁钴合成物加入到步骤2的混合溶液中,持续搅拌下得到溶胶;
步骤4,将步骤3的溶胶置于反应釜中,于160~200℃下反应16~20h后,将产物分别用盐酸和水清洗并干燥即可得到石墨烯-磺化酞菁钴-二氧化钛。
3.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤1中,所述石墨烯和磺化酞菁钴的加入质量比为1∶50;对于每1ml水,加入石墨烯的质量为0.1667mg,加入磺化酞菁钴的质量为8.33mg。
4.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤1中,所述超声时间为8~10h。
5.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤2中,所述钛酸丁酯、乙醇和乙酸的加入体积比为17∶34∶4.8。
6.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤3中,所述石墨烯-磺化酞菁钴合成物的加入量为14.2mg,所述混合溶液的体积为55.8ml。
7.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤4中,所述盐酸的质量百分浓度为5%。
8.根据权利要求2所述化学改性的二氧化钛光催化剂的制备方法,其特征在于:步骤4中,所述干燥温度为80℃,所述干燥时间为8h。
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