CN111437885A - 一种多孔磁性掺杂量子点生物复合光催化剂的制备方法 - Google Patents
一种多孔磁性掺杂量子点生物复合光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种多孔磁性掺杂量子点生物复合光催化剂的制备方法，其特征在于，以蚕丝为碳源，以氯化钙、氯化铜、乙醇、水作为溶剂制备铜、钙掺杂碳量子点，采用铜、钙掺杂碳量子点修饰磷钼酸银，制得量子点修饰磷钼酸银；在反应器中，分别加入，去离子水：62~68%，蛋清：6~10%，黄原胶：3~6%，搅拌溶解，量子点修饰磷钼酸银：16~20%，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：3~5%，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。本发明具有制备方法简单，催化剂稳定性好、可降解特点；催化剂容易回收，其反应条件温和、催化活性高等特点。
Description
技术领域
本发明关于负载催化剂制备技术领域，特别涉及一种多孔磁性掺杂量子点生物复合光催化剂的制备方法及在有机污染物降解中的应用。
背景技术
环境污染问题是当今人类亟待解决的重大问题之一。光催化氧化法对环境污染的治理具有能耗低、净化条件温和无二次污染等优势，因而作为一 种绿色化学工艺倍受关注。传统的半导体光催化剂如TiO2和ZnO，具有较宽的禁带宽度，只能吸收3%~5%的太阳光能量.。Bi系及Ag系半导体则分别存在可见光吸收范围窄、光腐蚀性强等问题，而且大多数半导体的光生载流子复合率较高，限制了半导体光催化剂的潜在应用。因此，越来越多的研究致力于拓宽光催化剂的可见光吸收范围并促进载流子的分离效率，以提高其光催化活性和稳定性.
蚕丝是熟蚕结茧时所分泌丝液凝固而成的连续长纤维，也称天然丝。蚕丝主要由动物蛋白组成，富含十八种人体所必须的氨基酸，能促进皮肤细胞活力。蚕茧的丝纤很细，只有20到30微米，是十分宝贵的生态资源之一，是一种可再生资源，是十分珍贵的长纤维原料。这种天然高分子材料应用制作吸附具有天然、绿色、可生物降解的特点。
碳量子点(Carbon quantum dots, CQDs)是最近发现的一类具有突出荧光性的新型碳纳米材料，由尺寸小于10 nm的准离散球形碳纳米粒子组成，是一种兼具优异水溶性、高生物相容性和低毒性的环境友好材料。研究表明，由于CQDs独特的结构和物理化学性质，使得它能与半导体光催化剂复合后大大改善半导体的光催化性能。 CQDs表面的羟基和羧基可以作为反应的成核位点，通过较强的界面键合作用与光催化剂形成复合体系，并表现出诸多优势：①CQDs具有近红外光吸收特性，可拓宽催化剂对太阳光的吸收范围；②CQDs具有上转换光致发光特性，可激发半导体形成更多光生电子空穴对；③CQDs具有较强的电子传输性能，可有效转移和存储催化剂中的光生电子，达到改善电荷分离效率的效果，而且光生电子与其表面的吸附O2结合，可形成超氧自由基，实现多位点催化；④π-π共轭结构有利于有机污染物在光催化剂表面的吸附；⑤对Ag系等不稳定的光催化剂，CQDs层与其形成核壳结构后，不但可以阻止催化剂溶解，还可有效防止光腐蚀。因而将CQDs与半导体复合，是改善光催化剂性能的重要途径。
本申请采用蚕丝作为碳源，以氯化钙、氯化铜、乙醇、水作为溶剂制备铜、钙掺杂碳量子点，然后修饰半导体光催化剂磷钼酸银，在黄原胶中添加蛋清和磁性微粒，冷冻干燥制备得到多孔磁性半导体复合光催化剂，具有多孔、比表面积大、催化效率高、质轻价廉、稳定性好、可降解和环境友好等特点，并且是再生资源，有良好的物理化学稳定性和优异的机械稳定性，可见光催化效率高。
发明内容
本发明的目的在于提供一种多孔磁性掺杂量子点生物复合光催化剂的制备方法。
一种多孔磁性掺杂量子点生物复合光催化剂的制备方法，其特征在于，该方法具有以下工艺步骤：
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，按如下组成质量百分比加入，去离子水与乙醇的体积比为7:3的混合溶液：80~85%，氯化钙：6~10%，搅拌溶解，硝酸铜：1~2%，预处理蚕丝粉：6 ~10%，各组分质量百分比之和为百分之百，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，按如下组成质量百分比加入，去离子水：68~72%，钼酸钠：17~21%，铜、钙掺杂碳量子点：0.5~2.0%，搅拌溶解，滴加6mol/L硝酸银溶液：8~11%，各组分质量百分比之和为百分之百，避光搅拌反应4 h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，按如下组成质量百分比加入，去离子水：62~68%，蛋清：6~10%，黄原胶： 3~6%，搅拌溶解，量子点修饰磷钼酸银：16~20%，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：3~5%，超声分散20 min，各组分质量百分比之和为百分之百，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
步骤（1）中所述的预处理蚕丝粉为：蚕茧用水洗涤去除杂质和蚕蛹，放入容器中用水浸泡24h，将蚕茧剪成小块清水洗净，真空干燥后进行粉碎，用120目的筛子过筛，将蚕丝按固液比为1：40mL，用质量百分浓度为3%的碳酸钠水溶液浸泡12h，煮沸30min，冷却后用去离子水洗涤至中性，固液分离，干燥，得预处理蚕丝粉；
步骤（2）中所述钼酸钠与硝酸银的摩尔比为1:3~3.3之间。
步骤（3）中所述挤压成球体，球体的粒径在1.0~3.0mm之间。
本发明的另一目的是将一种多孔磁性掺杂量子点生物复合光催化剂应用到废水中甲基橙、罗丹明B、偶氮类染料、双酚A、四环素、有机污染物等的催化降解进行分析评价。
本发明的有益效果是：
（1）本申请提供的一种多孔磁性掺杂量子点生物复合光催化剂是以蚕丝为碳源，氯化钙、水和乙醇为溶剂的溶剂热法合成水溶性铜、钙掺杂碳量子点，采用量子点修饰磷钼酸银，然后将催化剂固载到生物磁性多孔材料中，相比传统工艺更为绿色、经济、环保。蚕丝作为一种分布广泛、生长周期短，蚕丝为碳源原料廉价易得。
（2）本申请采用溶剂热方法制备的一种多孔磁性掺杂量子点生物复合光催化剂操作简单、采用量子点修饰磷钼酸银，然后将催化剂固载到生物磁性多孔材料中，颗粒分散均匀，具有多孔、比表面积大、催化效率高、质轻价廉、稳定性好、可降解和环境友好等特点，并且是再生资源，有良好的物理化学稳定性和优异的机械稳定性，可拓宽催化剂对太阳光的吸收范围；有上转换光致发光特性，可激发半导体形成更多光生电子空穴对；可见光催化效率高。
（3）本申请采用溶剂热方法制备的一种多孔磁性掺杂量子点生物复合光催化剂具有磁性容易分离，催化剂不损失，密度轻可以漂浮在水中，。
具体实施方式
实施例1
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，分别加入，去离子水与乙醇的体积比为7:3的混合溶液：82 mL，氯化钙：8g，硝酸铜：1g，搅拌溶解，预处理蚕丝粉：9g，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，分别加入，去离子水：70 mL，钼酸钠：19g，铜、钙掺杂碳量子点：1g，搅拌溶解，滴加6mol/L硝酸银溶液：10 mL，避光搅拌反应4 h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，分别加入，去离子水：65 mL，蛋清：8g，黄原胶：5g，搅拌溶解，量子点修饰磷钼酸银：18g，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：4g，超声分散20 min，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
实施例2
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，分别加入，去离子水与乙醇的体积比为7:3的混合溶液：800 mL，氯化钙：85g，硝酸铜：15g，搅拌溶解，预处理蚕丝粉：100g，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，分别加入，去离子水：680 mL，钼酸钠：210g，铜、钙掺杂碳量子点：5g，搅拌溶解，滴加6mol/L硝酸银溶液：110 mL，避光搅拌反应4h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，分别加入，去离子水：620mL，蛋清：100g，黄原胶：60g，搅拌溶解，量子点修饰磷钼酸银：170g，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：50g，超声分散20 min，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
实施例3
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，分别加入，去离子水与乙醇的体积比为7:3的混合溶液：170 mL，氯化钙：12g，硝酸铜：4g，搅拌溶解，预处理蚕丝粉：14g，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，分别加入，去离子水：144 mL，钼酸钠：36g，铜、钙掺杂碳量子点：4g，搅拌溶解，滴加6mol/L硝酸银溶液：16 mL，避光搅拌反应4 h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，分别加入，去离子水：136 mL，蛋清：12g，黄原胶：8g，搅拌溶解，量子点修饰磷钼酸银：32g，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：10g，超声分散20 min，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
实施例4
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，分别加入，去离子水与乙醇的体积比为7:3的混合溶液：332 mL，氯化钙：40g，硝酸铜：4g，搅拌溶解，预处理蚕丝粉：24g，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，分别加入，去离子水：288 mL，钼酸钠：68g，铜、钙掺杂碳量子点：6g，搅拌溶解，滴加6mol/L硝酸银溶液：36 mL，避光搅拌反应4 h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，分别加入，去离子水：256mL，蛋清：36g，黄原胶：12g，搅拌溶解，量子点修饰磷钼酸银：80g，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：12g，超声分散20 min，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
实施例5
催化剂活性评价，把300 W氙灯加λ≥420 nm的滤光片作为光源，并且所有试管都浸于恒温水浴（25℃）中。进行光催化活性测试实验时，10 mg本申请实施例所制备光催化剂分散在100 mL的偶氮氯膦Ⅲ（10 mg/L）当中。光照前，为了达到吸附/解吸平衡，所有溶液在黑暗中磁力搅拌30分钟。用分光光度计测定上清液的吸光度。不同时刻上清液的吸光度与初始溶液吸光度的比值就是其浓度的比值（c/c 0），用来表征光催化剂的降解率。反应1小时，偶氮氯膦Ⅲ的降解率达到85%，反应3小时，偶氮氯膦Ⅲ的降解率达到96%以上，降解的pH值至4.5~6.5之间降解率最高且稳定。而取相同浓度和体积的甲基橙的溶液不加催化剂，在相同条件下进行催化反应，偶氮氯膦Ⅲ的降解率为2.82%。
Claims (4)
1.一种多孔磁性掺杂量子点生物复合光催化剂的制备方法，其特征在于，该方法具有以下工艺步骤：
（1）铜、钙掺杂碳量子点的制备：在带有聚四氟乙烯衬套中反应釜中，按如下组成质量百分比加入，去离子水与乙醇的体积比为7:3的混合溶液：80~85%，氯化钙：6~10%，搅拌溶解，硝酸铜：1~2%，预处理蚕丝粉：6 ~10%，各组分质量百分比之和为百分之百，盖好密封盖，置于恒温箱中，温度在120±2℃恒温，反应2 h，得到前换色透明液体，透析袋透析24 h，干燥，得到水溶性铜、钙掺杂碳量子点；
（2）量子点修饰磷钼酸银制备：在反应器中，按如下组成质量百分比加入，去离子水：68~72%，钼酸钠：17~21%，铜、钙掺杂碳量子点：0.5~2.0%，搅拌溶解，滴加6mol/L硝酸银溶液：8~11%，各组分质量百分比之和为百分之百，避光搅拌反应4 h，静止6 h，固液分离，洗涤，干燥，制得量子点修饰磷钼酸银；
（3）多孔磁性掺杂量子点生物复合光催化剂的制备：在反应器中，按如下组成质量百分比加入，去离子水：62~68%，蛋清：6~10%，黄原胶： 3~6%，搅拌溶解，量子点修饰磷钼酸银：16~20%，聚乙烯亚胺修饰的四氧化三铁磁性纳米颗粒：3~5%，超声分散20 min，各组分质量百分比之和为百分之百，得粘稠悬浮液，挤压成球体，于10%的氯化镁溶液中固化12 h，固液分离，洗涤，冷冻干燥，制得多孔磁性掺杂量子点生物复合光催化剂。
2.根据权利要求1所述的一种多孔磁性掺杂量子点生物复合光催化剂的制备方法，其特征在于，步骤（2）中所述钼酸钠与硝酸银的摩尔比为1:3~3.3之间。
3.根据权利要求1所述的一种多孔磁性掺杂量子点生物复合光催化剂的制备方法，其特征在于，步骤（3）中所述挤压成球体，球体的粒径在1.0~3.0mm之间。
4.根据权利要求1所述的一种多孔磁性掺杂量子点生物复合光催化剂的制备方法所制备的多孔磁性掺杂量子点生物复合光催化剂。
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