CN108906037B - 一种GOQDs/TiO2/Ag光催化剂的制备及其在废水中的应用 - Google Patents
一种GOQDs/TiO2/Ag光催化剂的制备及其在废水中的应用 Download PDFInfo
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Abstract
本发明涉及的是一种GOQDs/TiO2/Ag光催化剂的制备及其在废水中的应用。该材料以二氧化钛（TiO2）纳米片为载体，Ag单质分布在TiO2纳米片上，且氧化石墨烯量子点（GOQDS）均匀的散布在TiO2纳米片周围，制备方法为通过水热法将氧化石墨烯溶液制备成尺寸大小均匀的GOQDs，然后利用一步水热法合成GOQDs/TiO2/Ag光催化剂材料，TiO2与Ag形成半导体‑贵金属异质结构体系提高了TiO2光催化效率；再对反渗透浓水中的重金属类内分泌干扰物进行光催化工艺处理，根据光生电子的还原性将重金属离子还原成单质。本发明的光催化剂催化效率高，绿色环保，方法简单可控，加快了光催化技术在污水处理中的应用。
Description
技术领域
本发明属于光催化材料、水处理领域，涉及一种GOQDs/TiO2/Ag光催化剂的制备及其在废水处理中的应用。
背景技术
反渗透技术在石化、制药等行业的废水处理中应用逐渐广泛，在净化水质的同时产生了高浓缩的反渗透浓水，成分复杂、包含多种新型污染物，其中，重金属类内分泌干扰物是能干扰人体内分泌系统、对环境产生严重危害的一类物质。
光催化剂在紫外光的激发下可产生氧化、还原性较强的空穴和光生电子，可与光催化剂表面吸附的污染物质发生氧化还原反应，不仅能够还原重金属离子，还可以将有机污染物氧化为无害物质，本专利采用光催化方法实现对重金属类内分泌干扰物的高效去除。
由于二氧化钛（TiO2）的带隙较宽、量子产率较低，使其使用受到制约，若将TiO2与贵金属Ag复合，形成半导体-贵金属异质结构体系，TiO2产生的光生电子能够迅速转移到Ag单质上，且Ag表面具有较低的还原反应电位，光生电子可以迅速与周围的重金属离子发生反应，提高了光催化效率，达到了去除重金属类内分泌干扰物的目的。同时，氧化石墨烯量子点（GOQDs）具有十分优异的性能，比如说较高的电子迁移率和量子尺寸效应，有利于降低TiO2的光生载流子的复合率，提高TiO2的光催化性能。
发明内容
本发明采用光催化方法去除反渗透浓水中的重金属类内分泌干扰物，流程简单、安全可控、去除率较高，拓宽了光催化方法在环境治理中的应用；制备的GOQDs/TiO2/Ag光催化剂，具有较高的催化性能。
本发明的技术方案是：
（一）利用Hummers氧化法将石墨粉制成氧化石墨烯，通过进一步的水热处理制备出GOQDs溶液；（二）通过一步水热法合成GOQDs/TiO2/Ag光催化剂，该材料以TiO2纳米片为基底，单质Ag均匀的负载在TiO2纳米片上，GOQDs分布在TiO2纳米片上及四周；（三）以反渗透浓水为处理水样，取一定质量的GOQDs/TiO2/Ag光催化剂进行光催化处理，对结果进行检测。
具体步骤如下：
（1）GOQDs的制备：采用水热法制备GOQDs，量取70~90ml的氧化石墨烯溶液，调节其pH为11并加入1~2ml的H2O2，然后转移至100ml的聚四氟乙烯内衬的水热反应釜中进行水热处理（反应温度在180℃~200℃，反应时间为18h~24h），最后将反应产物用孔径为0.22μm的微孔滤膜过滤，并用透析的方法将杂质截留，透析袋的截留分子量为3000-3500Da，透析产物为GOQDs溶液，烘干得到GOQDs。
（2）GOQDs/TiO2/Ag光催化剂的制备：采用一步水热法制备GOQDs/TiO2/Ag光催化剂，称取150~250mg的硝酸银并溶于3~10ml去离子水中，缓慢加入0.25ml的氨水，将得到的溶液与30~50ml的GOQDs溶液混合，室温下搅拌20~40 min，将混合液升温至80℃~100℃，继续反应1 h，得到溶液A；在烧杯中加入80ml的无水乙醇，边搅拌边滴加1ml的钛酸丁酯，体系出现白色沉淀后滴加0.4ml氢氟酸，搅拌30min，得到溶液B；将上述所得的A溶液逐滴加入到B溶液中，溶液全部混合后继续搅拌2 h，转移至水热反应釜中进行水热处理（反应温度在160~180℃，反应时间为18h~24h），将所得产品用去离子水和无水乙醇洗涤多次至中性，然后在60℃下于恒温干燥箱中干燥，得到GOQDs/TiO2/Ag光催化剂。
（3）由上述制备方法制备的光催化剂在废水处理中的应用：取反渗透浓水并加入一定质量的GOQDs/TiO2/Ag光催化剂，使其在反渗透浓水中的浓度为0.2~0.8mg/l，进行0.5h~1.5h的暗反应，然后转移至光催化反应装置中，在紫外灯的照射下并不断搅拌20min~2h，使光催化剂与反渗透浓水充分混合以去除重金属类内分泌干扰物。
本发明的特点及有益效果是：
1.本发明制备的GOQDs/TiO2/Ag光催化剂，具有良好清晰的形貌、较高的电子传输能力，以TiO2纳米片为基底，同时载有单质Ag和GOQDs，一步水热即可合成，方法简单，操作可控。
2.本发明制备的GOQDs/TiO2/Ag光催化剂中GOQDs大小较均匀皆在10nm以下，有较大的比表面积和良好的性能，且作为TiO2的电子受体能够降低光生载流子的复合率，达到了提高光催化效率的目的。
3.本发明为去除反渗透浓水中重金属类内分泌干扰物提供了新思路，减少了对生物体的危害，操作简单、绿色环保、环境友好，实现了从材料制备到应用的良好衔接，拓宽了光催化材料在环境中的应用。
附图说明
图1.制备的GOQDs/TiO2/Ag光催化剂的透射电镜图片：(a)、(b) 氧化石墨烯量子点，(c)、(d) GOQDs/TiO2/Ag光催化剂。
具体实施方式
下面结合实施例对本发明作进一步解释，选用的反渗透浓水来自齐鲁石化公司炼化废水，其中Cd2+浓度为0.386mg/l，Pb2+浓度为0.351mg/l。
实施例1
通过改进的Hummers氧化法制备出GO并按比例1:3稀释成GO溶液，超声分散15min，滴加适量NaOH溶液使pH为11，加入1ml的H2O2后移至聚四氟乙烯内衬的水热反应釜中进行处理（200℃，24h），反应结束后，待水热反应釜在真空干燥箱中自然冷却到室温后再取出，将溶液用0.22μm的微孔滤膜过滤后，放在透析袋中透析3天即得到淡棕色的GOQDs溶液。
称取375mg硝酸银，溶于10ml去离子水中，缓慢加入 0.25ml的氨水，得到新配制的银氨溶液，取30ml GOQDs 溶液与银氨溶液混合，室温下搅拌 20 min，然后升温至 100 ℃，继续反应 1 h，得到溶液A；在200ml的烧杯中加入80ml无水乙醇，放在磁力搅拌仪上面，边搅拌边滴加1ml钛酸丁酯，体系出现白色沉淀，然后滴加0.4ml氢氟酸，搅拌30min，得到B溶液；在不断搅拌的前提下，将上述所得的A溶液逐滴加入到B溶液中，溶液全部混合后继续搅拌2 h，并转移到水热高压反应釜中进行处理（160℃，24h）；将所得产品用蒸馏水和无水乙醇洗涤多次至中性，然后在60℃下于恒温真空干燥箱中干燥，得到GOQDs/TiO2/Ag光催化剂。
称取35.2mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为6，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应80min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.031mg/l、0.102mg/l，去除率分别为95.27%、73.31%。
实施例2
GOQDs溶液和GOQDs/TiO2/Ag光催化剂制备方法如实施例1。
称取41.6mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为7，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应60min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.067mg/l、0.099mg/l，去除率分别为89.98%、74.15%。
实施例3
GOQDs溶液和GOQDs/TiO2/Ag光催化剂制备方法如实施例1。
称取48mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为4，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应40min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.067mg/l、0.109mg/l，去除率分别为89.98%、71.64%。
实施例4
GOQDs溶液和GOQDs/TiO2/Ag光催化剂制备方法如实施例1。
称取54.4mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为5，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应20min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.032mg/l、0.103mg/l，去除率分别为95.27%、73.00%。
实施例5
GOQDs溶液制备方法如实施例1。
称取500mg硝酸银，溶于10ml去离子水中，缓慢加入 0.25ml的氨水，得到新配制的银氨溶液，取30ml GOQDs 溶液与银氨溶液混合，室温下搅拌 20 min，然后升温至100℃，继续反应1 h，得到溶液A；在200ml的烧杯中加入80ml的无水乙醇，放在磁力搅拌仪上面，边搅拌边滴加1ml钛酸丁酯，体系出现白色沉淀，然后滴加0.4ml氢氟酸，搅拌30min，得到B溶液；在不断搅拌的前提下，将上述所得的A溶液逐滴加入到B溶液中，溶液全部混合后继续搅拌2h，并转移到水热高压反应釜中进行处理（160℃，24h）；将所得产品用蒸馏水和无水乙醇洗涤多次至中性，然后在60℃下于恒温真空干燥箱中干燥，得到GOQDs/TiO2/Ag光催化剂。
称取35.2mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为7，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应40min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.102mg/l、0.140mg/l，去除率分别为84.69%、63.49%。
实施例6
GOQDs溶液制备方法如实施例1，GOQDs/TiO2/Ag光催化剂制备方法如实施例5。
称取41.6mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为6，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应20min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.138mg/l、0.125mg/l，去除率分别为79.39%、67.28%。
实施例7
GOQDs溶液制备方法如实施例1，GOQDs/TiO2/Ag光催化剂制备方法如实施例5。
称取48mg GOQDs/TiO2/Ag光催化剂溶于80ml反渗透浓水中，调节反渗透浓水的pH为5，先避光搅拌0.5h使吸附平衡，然后在汞灯照射下反应80min，通过火焰原子吸收分光光度计测定反渗透浓水中Cd2+和Pb2+浓度分别为0.102mg/l、0.122mg/l，去除率分别为84.69%、68.23%。
Claims (4)
1.一种GOQDs/TiO2/Ag光催化剂的制备方法，其特征在于，具体步骤如下：
（1）氧化石墨烯量子点GOQDs的制备：采用水热法制备GOQDs，量取70~90 ml的氧化石墨烯GO溶液，调节其pH为11并加入1~2 ml的H2O2，然后转移至100 ml聚四氟乙烯内衬的水热反应釜中进行水热处理，水热处理反应温度在180~200℃，反应时间为18~24 h，最后将产物用孔径为0.22 μm的微孔滤膜过滤，并用透析的方法将杂质截留，透析产物为GOQDs溶液，将其干燥可得到GOQDs；
（2）GOQDs/TiO2/Ag光催化剂的制备：采用一步水热法制备GOQDs/TiO2/Ag光催化剂，称取150~250 mg的硝酸银并溶于3~10 ml去离子水中，缓慢加入0.25 ml的氨水，将得到的溶液与30~50 ml的GOQDs溶液混合，室温下搅拌20~40 min，将混合液升温至80~100℃继续反应1 h，得到溶液A；在烧杯中加入80 ml的无水乙醇，边搅拌边滴加1 ml的钛酸丁酯，体系出现白色沉淀后滴加0.4 ml氢氟酸，搅拌30 min，得到溶液B；将上述所得的A溶液逐滴加入到B溶液中，溶液全部混合后继续搅拌2 h，转移至水热反应釜中进行水热处理，水热处理反应温度在160~180℃，反应时间为18~24 h，将所得产品用去离子水和无水乙醇洗涤多次至中性，然后在60℃下于恒温干燥箱中干燥，得到GOQDs/TiO2/Ag光催化剂。
2.按权利要求1所述的GOQDs/TiO2/Ag光催化剂的制备方法，其特征在于，步骤（1）中透析袋的截留分子量为3000~3500 Da，透析时间为1~3天，干燥方式为烘干或者冻干。
3.按权利要求1所述的GOQDs/TiO2/Ag光催化剂的制备方法，其特征在于，步骤（2）制备的GOQDs/TiO2/Ag光催化剂中元素占比为：Ti：60~70%，Ag：10~20%，C：10~20%，O：20~30%。
4.由权利要求1~3中任一项所述的制备方法制备的GOQDs/TiO2/Ag作为光催化剂在废水处理中的应用。
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