CN114950498B - 一种可循环利用的高效光催化材料及其制备方法和应用 - Google Patents
一种可循环利用的高效光催化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种可循环利用的高效光催化材料及其制备方法和应用，所述可循环利用的高效光催化材料是通过引入氧化石墨烯材料，并利用阴离子型天然高分子多糖水溶液与二价阳离子形成稳定凝胶的性质，采用化学偶联和原位沉积法负载AgCl，再通过光致还原制备而成的Ag@AgCl/GO光催化材料。本发明所述光催化材料在实际光催化剂生产中具有极大应用潜力。
Description
技术领域
本发明涉及一种光催化材料及其制备方法和应用，具体涉及一种可循环利用的高效光催化材料及其制备方法和应用。
背景技术
近年来，Ag@AgCl等离子体光催化剂引起了广泛的关注。Ag@AgCl是指AgCl在光照条件下分解出的单质态的Ag0负载于AgCl表面，因此Ag@AgCl光催化剂是一种基于纳米金属表面等离子体效应和半导体光催化效应的新型可见光催化材料。虽然Ag@AgCl等离子体有很好的光催化活性，但由于AgCl光化学稳定性差，易团聚，光生电子-空穴高复合率。因此，其在光催化研究中的应用受到限制。
氧化石墨烯(GO)是一种新型的碳基材料，是由羧基、羟基、环氧基等含氧官能团组成的单层石墨烯片，表面呈褶皱状，是石墨烯的衍生物，具有优异的亲水性、较大的比表面积和低毒性等特性，其与光催化剂形成的复合材料在光催化等领域受到了极大的关注，如GO与TiO2、Ag3PO4、BiOI、BiVO4、ZnO。
2018年专利CN201410492455.X公开了一种制备Ag@AgCl/GO自清洁型表面拉曼增强基底的方法。AgCl溶胶在高压釜160-180℃下保温12-36h后获得Ag@AgCl溶胶，然后利用GO带负电荷的特点以及强的吸附功能和模板效应，通过自组装吸附带正电荷的Ag@AgCl纳米粒子获得了Ag@AgCl/GO复合薄膜并应用于自清洁型拉曼增强基底。2020年专利CN111905774A公开了一种应用于降解甲基橙的光催化剂的制备方法，将一定量的TiO2在管式炉高温得到C-TiO2，然后将适量的硝酸银、氨水、C-TiO2和GO加入到容器中，再先后加入酸性溶液和醇溶液，通过可见光光照得催化剂Ag/AgCl/C-TiO2/GO。
目前，制备的GO负载的Ag@AgCl复合光催化材料中，有些制备工艺复杂，有些需要高温煅烧制备，有些制备的为粉体催化材料不易从水中分离，回收较困难，难以循环使用，易造成二次污染。
发明内容
发明目的：本发明的目的在于提供一种可循环利用的高效光催化材料及其制备方法和应用，有效解决粉体催化剂难分离回收问题。本发明另一个目的是提供所述可循环利用的高效光催化材料的制备方法。本发明还有一个目的是提供所述的可循环利用的高效光催化材料在制备水体清洁剂中的应用。
技术方案：本发明所述的可循环利用的高效光催化材料，其是通过引入氧化石墨烯材料，并利用阴离子型天然高分子多糖水溶液与二价阳离子形成稳定凝胶的性质，采用化学偶联和原位沉积法负载AgCl，并通过光致还原法制备而成的Ag@AgCl/GO光催化材料。
所述的可循环利用的高效光催化材料，所述阴离子型天然高分子多糖为海藻酸钠或海藻酸钾。
所述的可循环利用的高效光催化材料，所述二价阳离子选自Ca2+、Cu2+或Zn2+，优选Ca2+。
所述的可循环利用的高效光催化材料的制备方法，包括以下步骤：
(1)取氧化石墨烯分散液，加入海藻酸钠或海藻酸钾溶液，超声分散使充分混合；
(2)于(2)所得的混合液中加入十六烷基三甲基溴化铵，超声分散；由于氢键的作用和CTAB的表面活性剂作用，海藻酸根离子会被吸附在GO上。
(3)在搅拌下，缓慢滴加AgNO3溶液，滴加完毕，继续搅拌；由于静电引力作用，带正电的银离子(Ag+)会吸引带负电的海藻酸根离子和GO上的羧酸根基团(-COO-)，从而使Ag+被紧密包围在GO内部。
(4)在搅拌下，于(3)所得的混合悬浮液中缓慢滴加CaCl2溶液，形成不溶性小颗粒，搅拌后静置；利用Ca2+的交联作用和AgCl沉淀形成不溶性小颗粒。
(5)纱布过滤(4)所得的产物，将所得小颗粒沉淀物用水洗涤，然后把小颗粒沉淀物加入容器中，再加水，在搅拌下，置于太阳光照或置于氙灯光源下照射，纱布过滤，再用水洗涤，真空冷冻干燥，即得到Ag@AgCl/GO光催化材料。
所述的可循环利用的高效光催化材料的制备方法，所述纱布为双层纱布。
所述的可循环利用的高效光催化材料在制备水体清洁剂中的应用。
所述的可循环利用的高效光催化材料在制备光催化剂中的应用。
所述的可循环利用的高效光催化材料在降解罗丹明B、亚甲基蓝及甲基橙中的应用。
所述的可循环利用的高效光催化材料在降解四环素中的应用。
本发明所制备的易分离且可循环利用的高效可见光催化材料，有效解决粉体催化剂难分离回收问题。发明针对AgCl光稳定性差且难回收的问题，引入氧化石墨烯(GO)材料，并利用阴离子型天然高分子多糖海藻酸钠(SA)水溶液与二价阳离子(如Ca2+)能形成稳定凝胶的性质，采用化学偶联和原位沉积负载AgCl，再通过光致还原法制备Ag@AgCl/GO不溶性颗粒光催化材料，然后用于处理染料废水和抗生素废水等污染物。该光催化材料呈小颗粒状，光催化效率高，可见光波响应范围广，易与水相分离，可循环利用。
本发明主要解决AgCl光化学稳定性差，易团聚，吸附能力不足以及难回收循环利用的问题。通过引入氧化石墨烯(GO)材料，并利用海藻酸钠(SA)水溶液与二价阳离子(如Ca2+)能形成稳定凝胶的性质，采用化学偶联和原位沉积法负载AgCl，并通过光致还原法制备Ag@AgCl/GO不溶性颗粒光催化材料。该光催化材料呈小颗粒状，具有制备工艺简单，所制备得到的催化材料吸附能力强、光催化降解时间短、催化效率高以及易回收循环使用等优点，可用于实际多种有机污染废水的降解。
有益效果：(1)制备工艺简单，无需过多的设备投入，无需复杂的技术手段和工艺条件就能得到。(2)对紫外和可见光响应均响应，尤其是在可见光下吸收带较宽。(3)对多种有机污染物都具有较好的催化效果，且催化效率高，催化时间短，一级反应动力学拟合表明，催化材料对罗丹明B(RhB)、亚甲基蓝(MB)及甲基橙(MO)光催化降解速率常数(k)分别为0.5381min-1、0.4989min-1及0.2573min-1。(4)催化材料呈小颗粒状，易回收循环使用，稳定性能好，复合材料经过5次循环使用后，对RhB仍然具有大于91.0％的脱色率。表明该催化材料具有良好的光催化稳定性及可重复使用性，作为一种可见光催化剂应用于实际生产中具有极大潜力。
附图说明
图1是高分辨场发射扫描电镜(SEM)观察到的催化剂催化材料形貌图；
图2是透射电子显微镜(TEM)观察到的催化剂催化材料形貌图；
图3是催化材料的EDS图；
图4是测定催化材料的红外光谱图；
图5是测定催化材料的拉曼光谱图；
图6是测定催化材料的比表面积；
图7是测定催化材料的孔径分布；
图8是光催化材料对RhB降解的紫外-可见光谱；
图9是光催化材料对MB降解的紫外-可见光谱；
图10是光催化材料对MO降解的紫外-可见光谱；
图11是光催化材料RhB降解的循环使用稳定性测试曲线；
图12是光催化材料对四环素降解的紫外-可见光谱。
具体实施方式
实施例1
Ag@AgCl/GO的制备
1、取浓度1g/L氧化石墨烯(GO)分散液60mL，加入浓度4g/L海藻酸钠(SA)溶液3mL，超声分散15min使GO分散液与SA溶液充分混合。
2、于上述混合液中加入浓度为10g/L的十六烷基三甲基溴化铵(CTAB)1.5mL，超声分散30min，由于氢键的作用和CTAB的表面活性剂作用，海藻酸根离子会被吸附在GO上。
3、在磁力搅拌下，缓慢滴加浓度50g/L的AgNO3溶液9mL，滴加完毕，继续磁力搅拌20min。由于静电引力作用，带正电的银离子(Ag+)会吸引带负电的海藻酸根离子和GO上的羧酸根基团(-COO-)，从而使Ag+被紧密包围在GO内部。
4、在磁力搅拌下，于上述混合悬浮液中缓慢滴加9mLCaCl2溶液，利用Ca2+的交联作用和AgCl沉淀，进一步形成不溶性小颗粒，CaCl2溶液浓度为20g/L，磁力搅拌30min后静置24h。
5、双层纱布过滤，所得小颗粒沉淀物用去离子水洗涤5次，然后把小颗粒沉淀物加入250mL三角瓶中，加入50mL去离子水，在磁力搅拌下，置于太阳光照30min或置于350W氙灯光源下照射1h。双层纱布过滤，得到的颗粒再用去离子水洗涤3次，真空冷冻干燥，即得到Ag@AgCl/GO光催化材料。
实施例2
将实施例1所制得的光催化材料分别用高分辨场发射扫描电镜(SEM)和透射电子显微镜(TEM)观察，结果如图1和图2所示。图3是将实施例1所制得的光催化材料检测EDS，结果见图3，将实施例1所制得的光催化材料进行红外光谱检测，结果如图4所示，再将实施例1所制得的光催化材料进行拉曼光谱检测，结果如图5所示。测定催化材料的比表面积，结果如图6所示。测定催化材料的孔径分布，结果如图7所示。
实施例3
取所制备的光催化材料0.2g，加入到含有50mL去离子水中的三角瓶中，并加入罗丹明B(RhB)，使其浓度为10mg/L，调pH值6.5，温度控制在40℃，先于暗处在磁力搅拌下吸附30min，再置于350W的氙灯可见光处，在磁力搅拌下照射10min，光源距液面2cm，其对RhB的吸附和降解情况见图8。RhB在可见光区域554nm处(C＝O，C＝N上的n→π＊的电子跃迁)和紫外光区域270nm处(苯环上π→π＊的电子跃迁)的特征吸收，随反应时间的延长，在可见区最大吸收峰迅速降低，说明发色基团苯氨基、羰基键逐渐被破坏，10min后，RhB的主要结构物质被完全分解。
实施例4
取所制备的光催化材料0.2g，加入到含有50mL去离子水中的三角瓶中，并加入亚甲基蓝(MB)，使其浓度为10mg/L，调pH值6.5，温度控制在40℃，先于暗处在磁力搅拌下吸附30min，再置于350W的氙灯可见光处，在磁力搅拌下照射10min，光源距液面2cm，其降解情况见图9。MB在664、609、291.8及246.4nm处有特征吸收峰，其中664nm和291.8nm处分别对应于MB的超大共轭结构及苯环的π→π*跃迁所产生的吸收峰。经过10min，这些特征吸收峰消失，表明反应后，废水中的MB已被降解。
实施例5
取所制备的光催化材料0.2g，加入到含有50mL去离子水中的三角瓶中，并加入甲基橙(MO)，使其浓度为10mg/L，调pH值6.5，温度控制在40℃，先于暗处在磁力搅拌下吸附30min，再置于350W的氙灯可见光处，在磁力搅拌下照射12min，光源距液面2cm，其降解情况见图10。MO在465.2nm及271.6nm处有特征吸收峰，分别是MO的-N＝N-偶氮显色基团和苯环共轭体系产生的吸收峰。随着催化降解反应时间的延长，2个吸收峰均不断减弱，12min后，可见区和紫外区已无明显的吸收峰，说明MO已被催化降解。
实施例6
取所制备的光催化材料0.1g，加入到含有50mL去离子水中的三角瓶中，并加入RhB，使其浓度为10mg/L，调pH值6.5，温度控制在40℃，磁力搅拌下，置于350W的氙灯可见光照射20min。过滤后所得颗粒，经去离子水洗涤2次，再重复上述操作，经过5次循环使用后的降解效果如图11。光催化材料经过5次循环使用后，对RhB仍然具有大于90.0％以上的降解率，表明该催化材料具有良好的光催化稳定性及可重复使用性。
实施例7
分别取所制备的光催化材料0.2g，加入到含有50mL去离子水中的2个三角瓶中，并加入四环素，使其浓度为10mg/L，调pH值6.5，温度控制在40℃，先于暗处在磁力搅拌下吸附30min后，1瓶加浓度30％(w/w)的双氧水(H2O2))0.2mL，另一瓶不加双氧水，并同时置于350W的氙灯可见光处，在磁力搅拌下照射20min，光源距液面2cm，其吸附和降解情况见图12。光照20min时，未加H2O2的四环素在267nm处显示还有弱的吸收峰，表明仍存在少量芳香环A结构，而在体系中加入少量H2O2，四环素在267nm和355nm(芳香环B～D与其所连接的发色基团)引起的峰消失，表明四环素完全降解。
Claims (7)
1.一种可循环利用的高效光催化材料的制备方法，其特征在于，其是通过引入氧化石墨烯材料，并利用阴离子型天然高分子多糖水溶液与二价阳离子形成稳定凝胶的性质，采用化学偶联和原位沉积负载AgCl，再通过光致还原制备而成的Ag@AgCl/GO光催化材料；所述阴离子型天然高分子多糖为海藻酸钠或海藻酸钾；所述二价阳离子为Ca2+；包括以下步骤：
（1）取氧化石墨烯分散液，加入海藻酸钠或海藻酸钾溶液，超声分散使充分混合；
（2）于（1）所得的混合液中加入十六烷基三甲基溴化铵，超声分散；
（3）在搅拌下，缓慢滴加AgNO3溶液，滴加完毕，继续搅拌；
（4）在搅拌下，于（3）所得的混悬液中缓慢滴加CaCl2溶液，形成不溶性小颗粒，搅拌后静置；
（5）纱布过滤（4）所得的产物，将所得小颗粒沉淀物用水洗涤，然后把小颗粒沉淀物加入容器中，再加水，在搅拌下，置于太阳光照或置于氙灯光源下照射，纱布过滤，再用水洗涤，真空冷冻干燥，即得到Ag@AgCl / GO光催化材料。
2.根据权利要求1所述的可循环利用的高效光催化材料的制备方法，其特征在于，所述纱布为双层纱布。
3.权利要求1所述的可循环利用的高效光催化材料的制备方法得到的可循环利用的高效光催化材料在制备水体清洁剂中的应用。
4.权利要求1所述的可循环利用的高效光催化材料的制备方法得到的可循环利用的高效光催化材料在制备光催化剂中的应用。
5.权利要求1所述的可循环利用的高效光催化材料的制备方法得到的可循环利用的高效光催化材料在降解罗丹明B、亚甲基蓝及甲基橙中的应用。
6.权利要求1所述的可循环利用的高效光催化材料的制备方法得到的可循环利用的高效光催化材料在降解四环素中的应用。
7.权利要求1所述的可循环利用的高效光催化材料的制备方法得到的可循环利用的高效光催化材料和双氧水联用在降解四环素中的应用。
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