CN114797865B - 一种类芬顿复合催化剂膜材料及其制备方法和应用 - Google Patents
一种类芬顿复合催化剂膜材料及其制备方法和应用 Download PDFInfo
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Abstract
一种类芬顿复合催化剂膜材料及其制备方法和应用,室温下,将CNF和氧化石墨烯混合掺杂改性制成柔性石墨烯薄膜;配制含(NH4)2TiF6和H3BO3的混合水溶液,加入锐钛矿型TiO2纳米晶,搅拌后过滤得沉积用反应溶液;将柔性石墨烯薄膜浸没于沉积用反应溶液中,静置沉积TiO2薄膜,干燥后焙烧得TiO2/石墨烯薄膜;配制含有硝酸铁和硝酸钴的前驱体溶液,加入γ‑Al2O3原位浸渍负载,所得混合液超声使均匀分散;以TiO2/石墨烯薄膜为基底,加入混合液,静置使其均匀沉积到石墨烯膜另一面,压实后再干燥,焙烧后使用无水乙醇冲洗制得。本发明催化材料可在紫外光和外加适量双氧水反应条件下催化氧化降解水中有机污染物。
Description
技术领域
本发明涉及水污染物处理领域,具体涉及一种紫外光协同类芬顿复合催化剂膜材料及其制备方法和应用。
背景技术
随着化工、制药与印染等工业的快速发展,水中有机污染物的治理问题已经成为制约社会可持续发展的重要因素。传统处理废水的方法如吸附,絮凝,沉淀等对其降解效果一般。而近些年发展起来的高级氧化技术如芬顿法,臭氧氧化法,光催化技术等,利用具有强氧化能力的羟基自由基,臭氧等,可以有效降解难生化处理的污染物。单一的高级氧化法往往无法达到预期的效果,因此常用两种或两种以上高级氧化技术协同催化降解。
光催化技术具有二次污染小,操作难度低,降解性能好等优点,但因其常用的光催化剂如二氧化钛等具有光响应范围窄,光生电子和空穴复合率高等缺点。芬顿氧化法是利用二价铁离子和过氧化氢之间的链反应催化生成具有较强氧化能力的羟基自由基,它能氧化各种难降解的有机化合物,以达到去除污染物的目的。传统芬顿氧化法只能在酸性条件下才能发挥作用,且会引入亚铁离子杂质,因此产生了通过外加条件或催化剂活化过氧化氢产生自由基的类芬顿技术。因此,发现一种可用于类芬顿技术的高效催化剂,且结合光催化等其他高级氧化技术实现更高效,二次污染更小的催化氧化,具有重要的意义。
发明内容
解决的技术问题:针对以上技术问题,本发明提供了一种紫外光协同类芬顿复合催化剂膜材料及其制备方法和应用,催化材料可在紫外光和外加适量双氧水反应条件下催化氧化降解水中有机污染物。膜材料两面分别为不同的催化剂,对光面负载光催化剂二氧化钛,与紫外光响应发生光催化反应,采用液相沉积法使催化剂表面的羟基和柔性石墨烯材料表面的羟基和羧基脱水缩合,实现有效负载;中间基底材料为柔性石墨烯,使用碳纳米纤维掺杂改性;石墨烯表面为电负性,通过静电作用可在背光面原位沉积负载Co/Fe-γAl2O3复合催化剂使其与水中过氧化氢发生类芬顿反应以降解有机污染物。
技术方案:一种类芬顿复合催化剂膜材料的制备方法,室温下,将CNF和氧化石墨烯按质量比1:1-7:13混合掺杂改性制成柔性石墨烯薄膜;配制含(NH4)2TiF6浓度0.1-0.2mol·L-1和H3BO3浓度0.3-0.4 mol·L-1的混合水溶液,按1.5-2.0 g/L加入锐钛矿型TiO2纳米晶,搅拌后过滤得沉积用反应溶液;将柔性石墨烯薄膜浸没于沉积用反应溶液中,在40-60 ℃下静置沉积TiO2薄膜,6-8小时后取出,用去离子水冲洗干净,60-80 ℃烘箱中干燥,200-400 ℃焙烧处理2 h得TiO2/石墨烯薄膜;配制含有硝酸铁和硝酸钴的前驱体溶液,其中Co:Fe的摩尔比为1:1-1:2,前驱体溶液中的硝酸根浓度为0.05mol/L,按100g/L加入γ-Al2O3原位浸渍负载,所得混合液超声使均匀分散;以TiO2/石墨烯薄膜为基底,加入混合液,静置8-12 h使其均匀沉积到石墨烯膜另一面,压实后再干燥,250 ℃-350 ℃焙烧,使用无水乙醇冲洗制得紫外光协同类芬顿复合催化剂膜材料。
优选的,上述TiO2/石墨烯薄膜的焙烧温度为400℃。
优选的,上硝酸铁和硝酸钴按照摩尔比Co:Fe=1:1混合配制成前驱体溶液。
优选的,上述压实后再干燥的温度为80 ℃,干燥24 h,再在350 ℃中焙烧3 h。
上述制备方法制得的紫外光协同类芬顿复合催化剂膜材料。
上述紫外光协同类芬顿复合催化剂膜材料在通过光催化氧化降解水中有机污染物产品制备中的应用。
有益效果:表面负载二氧化钛克服了传统复合光催化剂遮盖光反应位点的弊端,提高了光催化反应效率;掺杂碳纳米纤维增强了石墨烯的柔性,耐温性和孔道结构,石墨烯电导率较高,在对光面二氧化钛发生光催化反应时,可以有效降低光生电子和空穴的复合率,且将光生电子有效利用到降解污染物和助类芬顿反应;γ-Al2O3拥有较大的比表面积和反应活性,将活性组分钴和铁负载其上可增加反应位点,从而增强催化效率,并降低反应过程中钴和铁的浸出,增强了背光面催化剂的负载效果和分散性。复合催化剂为膜材料,可多次重复利用,有利于催化剂和反应液的分离。
附图说明
图1是本发明实施例1~4制备的类芬顿复合催化剂膜材料结合对比实验1~4催化降解污染物图(自下而上依次为对比实验1、对比实验2、对比实验3、对比实验4、实施例1、实施例2、实施例3、实施例4)。
具体实施方式
实施例1
本实施例中,紫外光协同类芬顿复合催化剂膜材料具体制备方法如下:
(1)取100 mL 3.5 g/L的氧化石墨烯分散液,加入3.5 g纳米纤维素,在室温下搅拌6 h,再将混合液超声30 min,使用Bucher漏斗过滤,将得到的氧化石墨烯/CNF薄膜在使用重物压实放在滤纸之间,并在室温下干燥;在80 ℃水浴密封烧杯中,将制备的氧化石墨烯膜浸入到质量分数为45 %的HI溶液中,还原10 min,取出用无水乙醇冲洗,在80 ℃烘箱中使用重物按压12 h,得到柔性石墨烯薄膜。
(2)配制含(NH4)2TiF6浓度0.1 mol·L-1和H3BO3浓度0.3 mol·L-1的混合水溶液,加入1.5 g/L锐钛矿型TiO2纳米晶,搅拌后过滤得反应溶液。
(3)以柔性石墨烯薄膜为基底放置在沉积用反应溶液中,在40 ℃下静置沉积TiO2薄膜,12 h取出,用去离子水冲洗干净,在烘箱中干燥,再经200 ℃焙烧2 h。
(4)称取10 gγ-Al2O3,1.21 g硝酸铁和0.87 g硝酸钴,加入盛有100mL去离子水的烧杯中,搅拌12 h,再放入40kHz超声水浴锅中超声1 h,得Co/Fe-γAl2O3前驱体溶液。
(5)柔性石墨烯薄膜为基底,空白面朝上,倒入Co/Fe-γAl2O3前驱体溶液,原位沉积Co/Fe-γAl2O3复合催化剂30 min,成膜后在80 ℃烘箱中干燥,再放入马弗炉中在200℃焙烧形成复合催化剂膜材料。
将制备好的紫外光协同类芬顿复合催化剂膜材料用于紫外光芬顿催化氧化降解水中有机污染物,水中COD为5000 mg/L。
催化材料投加方式如下:取5 g紫外光协同类芬顿复合催化剂膜材料使用金属夹具固定,伸入反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000 mg/L的有机废水,加入10 mL 30wt.%双氧水,反应30min,取出水样检测其剩余COD含量。
实施例2
本实施例中,紫外光协同类芬顿复合催化剂膜材料具体制备方法如下:
(1)取100 mL3.5 g/L的氧化石墨烯分散液,加入4.5 g纳米纤维素,在室温下搅拌6 h,再将混合液超声30 min,使用Bucher漏斗过滤,将得到的氧化石墨烯/CNF薄膜在使用重物压实放在滤纸之间,并在室温下干燥;在80 ℃水浴密封烧杯中,将制备的氧化石墨烯膜浸入到质量分数为45 %的HI溶液中,还原10 min,取出用无水乙醇冲洗,在80 ℃烘箱中使用重物按压12 h,得到柔性石墨烯薄膜。
(2)配制含(NH4)2TiF6浓度0.1 mol·L-1和H3BO3浓度0.3 mol·L-1的混合水溶液,加入2.0 g锐钛矿型TiO2纳米晶,搅拌后过滤得反应溶液。
(3)以柔性石墨烯薄膜为基底放置在沉积用反应溶液中,在40 ℃下静置沉积TiO2薄膜,12 h后取出,用去离子水冲洗干净,在烘箱中干燥,再经300 ℃焙烧2 h。
(4)称取10 gγ-Al2O3,1.21 g硝酸铁和0.87 g硝酸钴,加入盛有100mL去离子水的烧杯中,搅拌12 h,再放入40 kHz超声水浴锅中超声1 h,得Co/Fe-γAl2O3前驱体溶液。
(5)柔性石墨烯薄膜为基底,空白面朝上,倒入Co/Fe-γAl2O3前驱体溶液,原位沉积Co/Fe-γAl2O3复合催化剂30 min,成膜后在80 ℃烘箱中干燥,再放入马弗炉中在300 ℃焙烧形成复合催化剂膜材料。
将制备好的紫外光协同类芬顿复合催化剂膜材料用于紫外光芬顿催化氧化降解水中有机污染物,水中COD为5000 mg/L。
催化材料投加方式如下:取5 g紫外光协同类芬顿复合催化剂膜材料使用金属夹具固定,伸入反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000 mg/L的有机废水,加入10 mL 30 wt.%双氧水,反应30 min,取出水样检测其剩余COD含量。
实施例3
本实施例中,紫外光协同类芬顿复合催化剂膜材料具体制备方法如下:
(1)取100 mL3.5 g/L的氧化石墨烯分散液,加入5.5 g纳米纤维素,在室温下搅拌6 h,再将混合液超声30 min,使用Bucher漏斗过滤,将得到的氧化石墨烯/CNF薄膜使用重物压实放在滤纸之间,并在室温下干燥;在80 ℃水浴密封烧杯中,将制备的氧化石墨烯膜浸入到质量分数为45 %的HI溶液中,还原10 min,取出用无水乙醇冲洗,在80 ℃烘箱中使用重物按压12 h,得到柔性石墨烯薄膜。
(2)配制含(NH4)2TiF6浓度0.1 mol·L-1和H3BO3浓度0.3 mol·L-1的混合水溶液,加入少量锐钛矿型TiO2纳米晶,搅拌后过滤得反应溶液。
(3)以柔性石墨烯薄膜为基底放置在沉积用反应溶液中,在40 ℃下静置沉积TiO2薄膜,12 h后取出,用去离子水冲洗干净,在烘箱中干燥,再经350 ℃焙烧2 h。
(4)称取10 gγ-Al2O3,1.21 g硝酸铁和0.87 g硝酸钴,加入盛有100mL去离子水的烧杯中,搅拌12 h,再放入40 kHz超声水浴锅中超声1 h,得Co/Fe-γAl2O3前驱体溶液。
(5)柔性石墨烯薄膜为基底,空白面朝上,倒入Co/Fe-γAl2O3前驱体溶液,原位沉积Co/Fe-γAl2O3复合催化剂30 min,成膜后在80 ℃烘箱中干燥,再放入马弗炉中在350 ℃焙烧形成复合催化剂膜材料。
将制备好的紫外光协同类芬顿复合催化剂膜材料用于紫外光芬顿催化氧化降解水中有机污染物,水中COD为5000 mg/L。
催化材料投加方式如下:取大约5 g紫外光协同类芬顿复合催化剂膜材料使用金属夹具固定,伸入反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000mg/L的有机废水,加入10 mL 30 wt.%双氧水,反应30 min,取出水样检测其剩余COD含量。
实施例4
本实施例中,紫外光协同类芬顿复合催化剂膜材料具体制备方法如下:
(1)取100 mL3.5 g/L的氧化石墨烯分散液,加入6.5 g纳米纤维素,在室温下搅拌6 h,再将混合液超声30 min,使用Bucher漏斗过滤,将得到的氧化石墨烯/CNF薄膜在一定的压力下放在滤纸之间,并在室温下干燥;在80 ℃水浴密封烧杯中,将制备的氧化石墨烯膜浸入到质量分数为45 %的HI溶液中,还原10 min,取出用无水乙醇冲洗,在80 ℃烘箱中使用重物按压12 h,得到柔性石墨烯薄膜。
(2)配制含(NH4)2TiF6浓度0.1 mol·L-1和H3BO3浓度0.3 mol·L-1的混合水溶液,加入少量锐钛矿型TiO2纳米晶,搅拌后过滤得反应溶液。
(3)以柔性石墨烯薄膜为基底放置在沉积用反应溶液中,在40 ℃下静置沉积TiO2薄膜,12 h后取出,用去离子水冲洗干净,在烘箱中干燥,再经400 ℃焙烧2 h。
(4)称取10 gγ-Al2O3,1.21 g硝酸铁和0.87 g硝酸钴,加入盛有100mL去离子水的烧杯中,搅拌12 h,再放入40 kHz超声水浴锅中超声1 h,得Co/Fe-γAl2O3前驱体溶液。
(5)柔性石墨烯薄膜为基底,空白面朝上,倒入Co/Fe-γAl2O3前驱体溶液,原位沉积Co/Fe-γAl2O3复合催化剂30 min,成膜后在80 ℃烘箱中干燥,再放入马弗炉中在400 ℃焙烧形成复合催化剂膜材料。
将制备好的紫外光协同类芬顿复合催化剂膜材料用于紫外光芬顿催化氧化降解水中有机污染物,水中COD为5000 mg/L。
催化材料投加方式如下:取大约5 g紫外光协同类芬顿复合催化剂膜材料使用金属夹具固定,伸入反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000mg/L的有机废水,加入10 mL 30wt.%双氧水,反应30 min,取出水样检测其剩余COD含量。
对比实验1
无催化材料投加条件下,将有机废水在紫外光照和外加双氧水条件下进行降解处理,反应30 min,对水中COD含量进行检测分析。
对比实验2
按照实施例2中的方法制备二氧化钛/石墨烯膜材料,将其按照5 g/L的用量夹取固定在反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000 mg/L的有机废水,加入10 mL 30%双氧水,反应30 min,取出水样检测其剩余COD含量。
对比实验3
按照实施例2中的方法制备石墨烯/Co/Fe-γAl2O3复合材料,将其按照5 g/L的用量夹取固定在反应器中,空白面朝向紫外光,在反应器中加入1 L COD含量为5000 mg/L的有机废水,加入10 mL 30%双氧水,反应30 min,取出水样检测其剩余COD含量。
对比实验4
按照实施例2中的方法制备柔性石墨烯膜材料,将其按照5 g/L的用量夹取固定在反应器中,二氧化钛面朝向紫外光,在反应器中加入1 L COD含量为5000 mg/L的有机废水,加入10 mL 30%双氧水,反应30 min,取出水样检测其剩余COD含量。
本发明并不限于上述实施方式,对于本技术领域的普通技术人员来说,在获知本发明中记载内容后,在不脱离本发明原理的前提下,还可以对其作出若干同等变换和替代,这些同等变换和替代也应视为属于本发明的保护范围。
Claims (6)
1.一种类芬顿复合催化剂膜材料的制备方法,其特征在于:室温下,将CNF和氧化石墨烯按质量比1:1-7:13混合掺杂改性制成柔性石墨烯薄膜;配制含(NH4)2TiF6浓度0.1-0.2mol·L-1和H3BO3浓度0.3-0.4 mol·L-1的混合水溶液,按1.5-2.0 g/L加入锐钛矿型TiO2纳米晶,搅拌后过滤得沉积用反应溶液;将柔性石墨烯薄膜浸没于沉积用反应溶液中,在40-60 ℃下静置沉积TiO2薄膜,6-8小时后取出,用去离子水冲洗干净,60-80 ℃烘箱中干燥,200-400 ℃焙烧处理2 h得TiO2/石墨烯薄膜;配制含有硝酸铁和硝酸钴的前驱体溶液,其中Co:Fe的摩尔比为1:1-1:2,前驱体溶液中的硝酸根浓度为0.05mol/L,按100g/L加入γ-Al2O3原位浸渍负载,所得混合液超声使均匀分散;以TiO2/石墨烯薄膜为基底,加入混合液,静置8-12 h使其均匀沉积到石墨烯膜另一面,压实后再干燥,250 ℃-350 ℃焙烧,使用无水乙醇冲洗制得紫外光协同类芬顿复合催化剂膜材料。
2.根据权利要求1所述类芬顿复合催化剂膜材料的制备方法,其特征在于,所述TiO2/石墨烯薄膜的焙烧温度为400℃。
3.根据权利要求1所述类芬顿复合催化剂膜材料的制备方法,其特征在于:硝酸铁和硝酸钴按照摩尔比Co:Fe=1:1混合配制成前驱体溶液。
4.根据权利要求1所述类芬顿复合催化剂膜材料的制备方法,其特征在于:所述压实后再干燥的温度为80 ℃,干燥24 h,再在350 ℃中焙烧3 h。
5.权利要求1-4任一所述制备方法制得的紫外光协同类芬顿复合催化剂膜材料。
6.权利要求5所述紫外光协同类芬顿复合催化剂膜材料在通过光催化氧化降解水中有机污染物中的应用。
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