CN106111053B - 一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂及其制备方法和应用 - Google Patents
一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种短孔道有序介孔氧化硅‑硫铟锌复合光催化剂及其制备方法和应用。所述短孔道有序介孔氧化硅‑硫铟锌复合光催化剂是将正硅酸乙酯、ZrOCl2、锌盐、铟盐和还原剂混合后，在表面活性剂存在下，经溶胶‑凝胶‑水热‑醇超声依次处理以及抽滤清洗和烘干后制得。该光催化剂实现了吸附与光催化氧化的一体化，对挥发性有机物(VOCs)具有较强的吸附性能和光催化活性，使得催化剂表面产生的羟基自由基在原位就能有效地降解材料所吸附和富集的VOCs，从而大幅增强光催化降解VOCs的反应速率和效率，在环保领域可作为有机污染物的吸附剂或光催化剂，具有广阔的环境保护应用潜力。
Description
技术领域
本发明属于吸附型催化材料技术领域，更具体地，涉及一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂及其制备方法和应用。
背景技术
挥发性有机物(Volatile organic compounds,VOCs)给我们带来了大量的环境问题，同时也严重地威胁到了人类的生命安全。由于光催化氧化技术能在光照射和催化剂的存在下，将VOCs最终氧化成CO2和H2O，而受到广泛的关注。目前，一些已报道的半导体光催化剂只能利用太阳光中的紫外光(紫外光只占太阳光总能量的约5％激发下才表现出活性，这极大地限制了它们的实际应用。因而，大量的科研人员开始致力于研发具有可见光响应的光催化剂，并且已经合成出了大量的可见光活性催化剂，但其催化效率要低于紫外光响应的催化剂，而且在太阳光照射下由于紫外光会引起严重的光腐蚀，从而导致这些已报道的可见光催化剂很不稳定。因此，为了实现太阳光催化剂的实际应用，则需光催化剂既要提高可见光时的催化活性，又要在太阳光下具有稳定性。
为了更好地吸附挥发性有机物，通常采用有序介孔材料，它是利用自组装方法得到的一类重要具有有序孔道结构的材料，如SBA-15等有序介孔氧化硅。这类材料具有比表面积和孔体积大、孔径分布窄、且在2-50nm尺度内均匀可调，孔道结构规则、可控，表面易于修饰以及热稳定性好等一系列特性。然而，传统有序介孔碳呈棒状或纤维状，孔道较长，且颗粒往往呈聚集状，不利于VOCs在孔道内的扩散和传输，使得VOCs在催化剂表面扩散慢，不能迅速达到催化剂的活性位点，从而限制了其催化活性，同时也存在着吸附剂原位的再生难题，造成吸附剂的后处置和二次污染问题。因此，如何有效地吸附挥发性有机物并提高对其光催化效率，制备出在太阳光下具有稳定、高效的太阳光催化剂，能够增强催化剂对光的吸收和利用的同时，进一步提高催化剂的稳定性是亟待解决的技术问题。
截至目前，未见关于短孔道有序介孔氧化硅-硫铟锌复合光催化剂的制备及其在VOCs降解方面的相关研究和报道。
发明内容
本发明所要解决的技术问题是克服现有技术中VOCs在孔道内的扩散和传输的缺陷和不足，提供一种具有较强的吸附性能和光催化活性的短孔道有序介孔氧化硅-硫铟锌复合光催化剂的制备方法，能够解决反应物在催化剂表面能够快速扩散的问题，迅速达到催化剂的活性位点，大幅度地提高其催化活性。
本发明的目的是提供一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂的制备方法。
本发明的另一目的是提供上述方法制备得到的短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
本发明的再一目的是提供上述短孔道有序介孔氧化硅-硫铟锌复合光催化剂的应用。
本发明上述目的通过以下技术方案予以实现：
一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂的制备方法，包括如下步骤：
S1.将0.1～10g表面活性剂加入到6～100mL体积比为1～10：1的水和浓盐酸溶液中，在30～90℃下搅拌0.5～24h，得到混合溶液A；
S2.将0.1～10mL正硅酸乙酯、50～500mgZrOCl2、20～200mg锌盐、60～400mg铟盐和30～300mg还原剂依次添加到步骤S1所得混合溶液A中，在30～90℃下搅拌2～72h，得到混合溶液B；
S3.将步骤S2所得混合溶液B装入25～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待冷却至室温后，收集沉淀物，用50～2000mL水冲洗沉淀物，将沉淀物在50～180℃下烘干1～36h，得到短孔道有序介孔氧化硅；
S4.将步骤S3制得的短孔道有序介孔氧化硅与醇以0.1～10mg/mL的比例混匀，超声处理0.5～60min，通过抽滤回收溶液中颗粒物，用50～2000mL醇冲洗，然后在50～180℃下烘干1～36h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
优选地，步骤S1中所述表面活性剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
优选地，步骤S2中所述锌盐为氯化锌、硝酸锌或硫酸锌。
优选地，步骤S2中所述铟盐为氯化铟、硝酸铟或硫酸铟。
优选地，步骤S2中所述还原剂为硫脲、尿素或硫代乙酰胺。
优选地，步骤S4中所述醇为乙醇或甲醇。
优选地，步骤S1和S3中所述水为去离子水。
另外，上述方法制备的短孔道有序介孔氧化硅-硫铟锌复合光催化剂及其在在环保领域作为VOCs的选择性吸附剂或光催化剂中的应用，也在本发明的保护范围之内。
本发明中以硫铟锌作为催化剂与短孔道有序介孔碳材料进行复合，制备出一种新型高效的吸附-光催化复合材料。在太阳光下既能有效地吸附挥发性有机物，又能增强催化剂对光的吸收和利用，进一步提高催化剂的稳定性。这是由于硫铟锌具有较窄的带隙能(2.34-2.48eV)，可以有效地吸收可见光，进而产生更多光生电子-空穴对，提高其光催化性能。而短孔道介孔材料因其孔道较短，易于VOCs在孔道内的传质与扩散。将短孔道有序介孔氧化硅对VOCs的吸附富集作用与硫铟锌光催化剂的光催化作用相结合，使VOCs在催化剂硫铟锌表面能够快速扩散，迅速达到催化剂的活性位点，提高了对VOCs的吸附。同时短孔道有序介孔硅的加入可以提高光生电子的传输速率，使光生电子从硫铟锌传递到介孔硅上，这样可以抑制其对硫铟锌的光腐蚀，提高催化剂的稳定性，从而显著提高了光催化性能。因此，短孔道有序介孔氧化硅-硫铟锌复合光催化剂不仅可以提高硫铟锌对挥发有机物的吸附富集，还能进一步提高催化剂的太阳光稳定性和光催化性能，从而实现了吸附与光催化氧化VOCs的一体化。
与现有技术相比，本发明具有以下有益效果：
本发明将短孔道有序介孔氧化硅对VOCs的吸附富集作用与硫铟锌光催化剂的光催化矿化作用相结合，制备出一种新型高效的吸附-光催化一体化材料，即短孔道有序介孔氧化硅-硫铟锌复合光催化剂，能够解决VOCs在催化剂表面能够快速扩散的问题，迅速达到催化剂的活性位置，大幅度地提高其催化活性。
本发明制备出的短孔道有序介孔氧化硅-硫铟锌复合光催化剂对气相二甲苯表现出良好的吸附和光催化活性，具有吸附时间短，降解率高的优点。其中，对二甲苯的吸附率在40min内达到了36.6％，对气相二甲苯的降解率也在60min内高达96.9％，从而实现了吸附与光催化氧化VOCs的一体化。
另外，催化剂表面产生的羟基自由基在原位就可有效地降解材料所吸附和富集的VOCs，大幅度增强光催化降解有机污染物的反应速率和效率，同时解决了吸附剂原位的再生难题，避免了吸附剂的后处置和二次污染问题。
附图说明
图1为短孔道有序介孔氧化硅-硫铟锌复合光催化剂对气相二甲苯的吸附动力学曲线和光催化降解动力学曲线。
具体实施方式
下面结合说明书附图和具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.制备：
S1.将0.1g聚乙二醇加入到6mL体积比为10：1的水和浓盐酸溶液中，在90℃下搅拌24h，得到澄清溶液；
S2.将10mL正硅酸乙酯、50mgZrOCl2、20mg氯化锌、60mg氯化铟和30mg硫脲依次缓慢添加到步骤S1所得澄清溶液，在30℃下搅拌2h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入25mL聚四氟乙烯罐中，在60℃下水热反应72h，待聚四氟乙烯罐中冷却后，收集沉淀物，用50mL水冲洗沉淀物，将水洗后的沉淀物在50℃下烘干36h，得到短孔道有序介孔氧化硅；
S4.将S3所得的短孔道有序介孔氧化硅与甲醇以0.1mg/mL的比例混匀，超声处理0.5min，通过抽滤回收溶液中颗粒物，用50mL甲醇冲洗，然后在50℃下烘干1h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
2.性能测试：
图1为短孔道有序介孔氧化硅-硫铟锌复合光催化剂对气相二甲苯的吸附动力学曲线和光催化降解动力学曲线。由图1可以看出，该光催化剂具有良好的吸附和光催化活性，对二甲苯的吸附率在40min内达到了36.6％，对二甲苯的降解率在60min内可达到96.9％。实验结果表明，本发明制备的短孔道有序介孔氧化硅-硫铟锌复合光催化剂是一种具有高吸附和光催化活性的新型材料。实施例2
S1.将10g聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物加入到100mL体积比为1：1的水和浓盐酸溶液中，在30℃下搅拌24h，得到澄清溶液；
S2.将0.1mL正硅酸乙酯、500mgZrOCl2、200mg硝酸锌、400mg硝酸铟和30mg尿素依次缓慢添加到步骤S1所得澄清溶液，在90℃下搅拌72h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入200mL聚四氟乙烯罐中，在250℃下水热反应2h，待聚四氟乙烯罐中冷却后，收集沉淀物，用2000mL水冲洗沉淀物，将水洗后的沉淀物在180℃下烘干1h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得的短孔道有序介孔氧化硅与乙醇以10mg/mL的比例混匀，超声处理60min，通过抽滤回收溶液中颗粒物，用2000mL乙醇冲洗，然后在180℃下烘干36h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
实施例3
S1.将5g十六烷基三甲基溴化铵加入到80mL体积比为5：1的水和浓盐酸溶液中，在50℃下搅拌6h，得到澄清溶液；
S2.将2mL正硅酸乙酯、100mgZrOCl2、150mg硫酸锌、200mg硫酸铟和190mg硫代乙酰胺依次缓慢添加到步骤S1所得澄清溶液，在50℃下搅拌12h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入100mL聚四氟乙烯罐中，在120℃下水热反应18h，待聚四氟乙烯罐中冷却后，收集沉淀物，用1000mL水冲洗沉淀物，将水洗后的沉淀物在100℃下烘干8h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得的短孔道有序介孔氧化硅与乙醇以0.5mg/mL的比例混匀，超声处理30min，通过抽滤回收溶液中颗粒物，用1000mL乙醇冲洗，然后在100℃下烘干8h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
实施例4
S1.将6g聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物加入到100mL体积比为9：1的水和浓盐酸溶液中，在45℃下搅拌3h，得到澄清溶液；
S2.将5.6mL正硅酸乙酯、152mgZrOCl2、143mg氯化锌、300mg硝酸铟和34mg硫代乙酰胺依次缓慢添加到步骤S1所得澄清溶液，在45℃下搅拌24h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入100mL聚四氟乙烯罐中，在90℃下水热反应24h，待聚四氟乙烯罐中冷却后，收集沉淀物，用500mL去离子水冲洗沉淀物，将沉淀物在60℃下烘干12h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得的短孔道有序介孔氧化硅与甲醇以2mg/mL的比例混匀，超声处理5min，通过抽滤回收溶液中颗粒物，用500mL甲醇冲洗，然后在60℃下烘干12h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (7)
1.一种短孔道有序介孔氧化硅-硫铟锌复合光催化剂的制备方法，其特征在于，包括如下步骤：
S1.将0.1～10g表面活性剂加入到6～100mL体积比为1～10：1的水和浓盐酸溶液中，在30～90℃下搅拌0.5～24h，得到混合溶液A；
S2.将0.1～10mL正硅酸乙酯、50～500mgZrOCl2、20～200mg锌盐、60～400mg铟盐和30～300mg还原剂依次添加到步骤S1所得混合溶液A，在30～90℃下搅拌2～72h，得到混合溶液B；其中，所述锌盐为氯化锌、硝酸锌或硫酸锌；所述铟盐为氯化铟、硝酸铟或硫酸铟；所述还原剂为硫脲、尿素或硫代乙酰胺；
S3.将步骤S2所得混合溶液B装入25～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待冷却至室温后，收集沉淀物，用50～2000mL水冲洗沉淀物，将沉淀物在50～180℃下烘干1～36h，得到短孔道有序介孔氧化硅；
S4.将步骤S3制得的短孔道有序介孔氧化硅与醇以0.1～10mg/mL的比例混匀，超声处理0.5～60min，通过抽滤回收溶液中颗粒物，用50～2000mL醇冲洗，然后在50～180℃下烘干1～36h，即得短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
2.根据权利要求1所述的制备方法，其特征在于，步骤S1中所述表面活性剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
3.根据权利要求1所述的制备方法，其特征在于，步骤S4中所述醇为乙醇或甲醇。
4.根据权利要求1所述的制备方法，其特征在于，步骤S1和S3中所述水为去离子水。
5.一种由权利要求1～4任一项所述方法制备的短孔道有序介孔氧化硅-硫铟锌复合光催化剂。
6.权利要求5所述的短孔道有序介孔氧化硅-硫铟锌复合光催化剂在环保领域降解挥发有机物中的应用。
7.根据权利要求6所述应用，其特征在于，所述挥发有机物为二甲苯。
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