CN108404981B - 多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备 - Google Patents
多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备 Download PDFInfo
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Abstract
本发明公开了一种多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备方法,其特征在于,采用蚕丝与聚乙烯醇添加加入纳米四氧化三铁,得到多孔磁性复合蚕丝;采用燃烧法制得膨松的钐掺杂BiOBr粉体;然后在反应器中,按如下组成质量百分比加入,液体石蜡:70~76%,山梨坦单硬脂酸酯:4~8%,剧烈搅拌下加入镨掺杂BiOBr粉体:2~5%,超声分散30 min,加入多孔磁性复合蚕丝:16~20%,搅拌、反应,固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。本发明具有制备方法简单,催化剂稳定性好、可降解和环境友好等特点;催化剂容易回收,其反应条件温和、催化活性高、用量少等特点。
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复合蚕丝负载镨掺杂BiOBr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
蚕丝(silk)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,是一种天然纤维。人类利用最早的动物纤维之一,蚕丝是自然界中最轻最柔最细的天然纤维。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。
随着工业的快速发展,染料的用量也越来越大,合成染料与天然染料相比,具有使用方便、性质稳定、成本低、品种多等优点被广泛应用于纺织、造纸、制药和食品工业。染料废水已经成为我国目前主要污染废水之一,解决环境污染问题是十分迫切的问题。目前大多数合成染料的结构具有复杂的芳环结构,性质很稳定,难以生物降解。这些染料会对人类的健康造成威胁。染料的广泛使用导致染料污水的大量排放到自然水体中,造成水体污染,即便是少量的染料废水排放也会导致水体着色,严重破坏了水体的自然生态链。因此,如何去除工业废水中的染料是国内外专家学者研究的热点。研制光催化剂加入后在太阳光照射下,可以降解水体中的染料和有机污染物,研制从水体中容易分离,不造成二次污染的光催化剂,成为一种有效途径。
半导体光催化技术,作为一种新型“绿色化学方法”,在能源转化及环境修复应用中已经得到广泛研究。传统的半导体光催化剂如TiO2和ZnO氧化性强、光诱导性好且已经被广泛应用于水体中各种污染物降解,但由于较宽的带隙( 如TiO2带隙能为3.2 eV) ,只能利用仅占太阳光谱的4%的紫外光,明显限制了其应用。因此,开发新型可见光响应的半导体光催化剂越来越引起人们的重视。近年来,卤氧化铋化合物( BiOX,X = Cl、Br、I) 半导体光催化剂因其优良的可见光响应的光催化活性而引起广泛的关注。卤氧化铋层状结构具有足够的空间来极化相应的原子和原子轨道,空穴与电子能够被诱导偶极矩有效地分离从而降低光生电子空穴的复合率并有效分离和转移。但是BiOBr 较大的禁带宽度同样限制了它对可见光的利用,因此常通过将其与窄禁带半导体复合构建异质结型光催化剂,一方面,窄禁带半导体能够有效地吸收可见光,大大加强对太阳能的利用;另一方面,不同材料复合后形成的异质结可以促进光生载流子的分离,提高其光催化效率。目前,对于BiOBr 光催化剂的研究主要集中于BiOBr 粉末,而对BiOBr /Fe3O4纳米磁性复合结构的制备和光催化活性的研究却鲜有报道。粉末光催化剂具有比表面大、反应速率高、容易制得等特点,但存在分散性不佳、与溶液难分离、难回收等缺点,特别是对具有微纳结构的细小颗粒,因此将催化剂磁性化可回收,有利于固液分离以及重复利用,更加方便用于处理水中有机污染物。
BiOBr具有较大的应用潜力,但其禁带宽度较宽,只能吸收波长≤387nm的光子,无法利用占太阳光能量大部分的可见光。为拓宽BiOBr光催化材料的光响应范围和提高其量子效率,对此类光催化剂进行修饰和改性引起了国内外越来越多学者的关注。主要方法有非金属掺杂、金属掺杂、半导体复合、染料敏化及贵金属表面修饰等。稀土镨元素掺杂BiOBr中可以大大提高太阳光能的利用,吸收波长可达到可见光范围。
负载型催化剂载体的作用,载体可将催化剂固定,克服了悬浮相催化剂粉体易流失、分离回收难的缺点;用载体将粉体催化剂固定,便于对催化剂进行表面修饰并制成各种形状的光催化剂反应容器;将催化剂负载于载体表面,能够避免悬浮项中催化剂的团聚,增加了比表面积,提高利用率。目前文献报道的制备负载型BiOBr光催化剂的较少。
本申请利用蚕丝与聚乙烯醇制备多孔磁性复合蚕丝颗粒作为催化剂的载体制备负载型镨掺杂BiOBr光催化剂,具有质轻价廉、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复合蚕丝负载镨掺杂BiOBr光催化剂的制备方法。
一种多孔磁性复合蚕丝负载镨掺杂BiOBr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)A液配制:在反应釜中,按如下组成质量百分比加入,溴化1-乙基-3-甲基咪唑:55~60%,脱胶蚕丝:40~45%,密封,置于烘箱中,温度升至120±2℃恒温反应10~12 h,取出自然冷却至室温,制得A液;
(2)B悬浮液制备:在反应器中,按如下组成质量百分比加入,去离子水:84~88%,聚乙烯醇:6~10%,加热搅拌溶解,加入纳米四氧化三铁:5~8%,各组分质量百分比之和为百分之百,超声分散20 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合蚕丝制备:在反应器中,按如下组成质量百分比加入,A液:45~50%,B悬浮液:44~48%,四硼酸铵:1~3%,搅拌混合均匀,搅拌,温度升至50℃,滴加质量体积百分浓度为8%的氯化镁溶液:2~6%,各组分质量百分比之和为百分之百,在50±2℃继续恒温放置8 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合蚕丝;
(4)镨掺杂BiOBr粉体的制备:在反应器中,按如下组成质量百分比加入,4.5mol/LHNO3:70~75%,三氧化二镨:0.5~1.0%,加热溶解,再加入Bi(NO3)3:8~12%,溴化铵:4~8%,丙氨酸叔丁酯:10~14%,各组分质量百分比之和为百分之百,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的镨掺杂BiOBr粉体;
(5)多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备:在反应器中,按如下组成质量百分比加入,液体石蜡:70~76%,山梨坦单硬脂酸酯:4~8%,剧烈搅拌下加入镨掺杂BiOBr粉体:2~5%,超声分散30 min,加入多孔磁性复合蚕丝:16~20%,各组分质量百分比之和为百分之百,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入4倍液体体积的无水乙醇,搅拌,固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
步骤(1)中所述的脱胶蚕丝为:蚕茧用水洗涤去除杂质和蚕蛹,放入容器中用水浸泡50 h,将蚕茧剪成小块清水洗净,真空干燥后进行粉碎,用100目的筛子过筛,将蚕丝按固液比为1:35mL,用质量百分浓度为6%的碳酸氢钠水溶液浸泡12h,煮沸20min,冷却后用去离子水洗涤至中性,固液分离,干燥,得脱胶蚕丝;
步骤(5)中所述固液分离后的液相可以重复使用。
所制备的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂中镨掺杂BiOBr的质量百分含量大于2%。
本发明的另一目的是将多孔磁性复合蚕丝负载镨掺杂BiOBr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、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)本申请提供的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂所用的载体是多孔磁性复合蚕丝,蚕丝来源广泛,具有质轻价廉、稳定性好、可降解和环境友好等特点,并且是再生资源,在蚕丝中添加聚乙烯醇增加载体的机械强度,所以说该催化剂具有良好的物理化学稳定性和优异的机械稳定性,可重复使用10次以上。
(2)本申请采用溶剂热方法制备的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂操作简单、镨掺杂BiOBr负载率高、颗粒分散均匀、镨掺杂BiOBr不脱落,催化活性高,具有磁性容易分离。
(3)本申请提供的催化剂所用的载体是多孔磁性复合蚕丝,其比重轻同时具有吸附作用,在废水处理中使用这种负载型催化剂时可悬浮在水中,采用冷冻干燥使蚕丝形成多孔,增加载体的比表面积,提高了镨掺杂BiOBr的负载量,增加光的照射强度而提高催化剂的催化效率,催化剂中在镨掺杂BiOBr大大提高了太阳光能的利用,对可见光有良好吸收。
具体实施方式
实施例1
(1)A液配制:在反应釜中,分别加入,溴化1-乙基-3-甲基咪唑:58g,脱胶蚕丝:42g,密封,置于烘箱中,温度升至120±2℃恒温反应11 h,取出自然冷却至室温,制得A液;
(2)B悬浮液制备:在反应器中,分别加入,去离子水:86 mL,聚乙烯醇:9g,加热搅拌溶解,加入纳米四氧化三铁:5g,超声分散20 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合蚕丝制备:在反应器中,分别加入,A液:48g,B悬浮液:46g,四硼酸铵:2g,搅拌混合均匀,搅拌,温度升至50℃,滴加质量体积百分浓度为8%的氯化镁溶液:4mL,在50±2℃继续恒温放置8 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合蚕丝;
(4)镨掺杂BiOBr粉体的制备:在反应器中,分别加入,4.5mol/L HNO3:73 mL,三氧化二镨:0.8g,加热溶解,再加入Bi(NO3)3:10g,溴化铵:6g,丙氨酸叔丁酯:11.2g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的镨掺杂BiOBr粉体;
(5)多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:85 mL,山梨坦单硬脂酸酯:3g,剧烈搅拌下加入镨掺杂BiOBr粉体:3g,超声分散30 min,加入多孔磁性复合蚕丝:19g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入4倍液体体积的无水乙醇,搅拌,固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
实施例2
(1)A液配制:在反应釜中,分别加入,溴化1-乙基-3-甲基咪唑:55g,脱胶蚕丝:45g,密封,置于烘箱中,温度升至120±2℃恒温反应10 h,取出自然冷却至室温,制得A液;
(2)B悬浮液制备:在反应器中,分别加入,去离子水:84 mL,聚乙烯醇:8g,加热搅拌溶解,加入纳米四氧化三铁:8g,超声分散20 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合蚕丝制备:在反应器中,分别加入,A液:45g,B悬浮液:48g,四硼酸铵:1g,搅拌混合均匀,搅拌,温度升至50℃,滴加质量体积百分浓度为8%的氯化镁溶液:6mL,在50±2℃继续恒温放置8 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合蚕丝;
(4)镨掺杂BiOBr粉体的制备:在反应器中,分别加入,4.5mol/L HNO3:70 mL,三氧化二镨:1.0g,加热溶解,再加入Bi(NO3)3:12g,溴化铵:4g,丙氨酸叔丁酯:13g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的镨掺杂BiOBr粉体;
(5)多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:81mL,山梨坦单硬脂酸酯:8g,剧烈搅拌下加入镨掺杂BiOBr粉体:5g,超声分散30min,加入多孔磁性复合蚕丝:17g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入4倍液体体积的无水乙醇,搅拌,固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
实施例3
(1)A液配制:在反应釜中,分别加入,溴化1-乙基-3-甲基咪唑:60g,脱胶蚕丝:44g,密封,置于烘箱中,温度升至120±2℃恒温反应12h,取出自然冷却至室温,制得A液;
(2)B悬浮液制备:在反应器中,分别加入,去离子水:88 mL,聚乙烯醇:6g,加热搅拌溶解,加入纳米四氧化三铁:6g,超声分散20 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合蚕丝制备:在反应器中,分别加入,A液:50g,B悬浮液:44g,四硼酸铵:3g,搅拌混合均匀,搅拌,温度升至50℃,滴加质量体积百分浓度为8%的氯化镁溶液:3mL,在50±2℃继续恒温放置8 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合蚕丝;
(4)镨掺杂BiOBr粉体的制备:在反应器中,分别加入,4.5mol/L HNO3:75mL,三氧化二镨:0.5g,加热溶解,再加入Bi(NO3)3:8g,溴化铵:6.5g,丙氨酸叔丁酯:10g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的镨掺杂BiOBr粉体;
(5)多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:87mL,山梨坦单硬脂酸酯:7g,剧烈搅拌下加入镨掺杂BiOBr粉体:2g,超声分散30min,加入多孔磁性复合蚕丝:16g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入4倍液体体积的无水乙醇,搅拌,固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
实施例4
催化剂活性评价,将100 mL含20mg/L偶氮胂Ⅲ,放入250 mL烧杯中,调节溶液的pH值至6.0~8.0之间,加入1.0g多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂,在太阳光下进行催化反应。采用分光光度法分别测定初始溶液的吸光度为A0=0.756,太阳光照射2小时后,吸光度A=0.022,偶氮胂Ⅲ的降解率达到97.09%。光降解率以脱色率D(%)表示:D=(A0-A)/A0×100%。而取相同浓度和体积的孔雀石绿的溶液不加催化剂,在相同太阳光下进行催化反应,采用分光光度法分别测定初始溶液的吸光度为A0=0.756,太阳光照射2小时后,吸光度A=0.741,偶氮胂Ⅲ的降解率达到1.98%。
实施例5
催化剂活性评价,将100 mL含20mg/L双酚A,放入250 mL烧杯中,用0.5mol/L盐酸调节溶液的pH值至5.0~7.5之间,加入1.0g多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂,在太阳光下进行催化反应。采用紫外分光光度法分别测定初始溶液的吸光度为A0=0.582,太阳光照射2小时后,吸光度A=0.022,双酚A的降解率达到96.22%。光降解率以脱色率D(%)表示:D=(A0-A)/A0×100%。而取相同浓度和体积的双酚A的溶液不加催化剂,在相同太阳光下进行催化反应,采用紫外分光光度法分别测定初始溶液的吸光度为A0=0.582,太阳光照射2小时后,吸光度A=0.566,双酚A的降解率达到2.75%。
Claims (3)
1.一种多孔磁性复合蚕丝负载镨掺杂BiOBr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)A液配制:在反应釜中,按如下组成质量百分比加入,溴化1-乙基-3-甲基咪唑:55~60%,脱胶蚕丝:40~45%,密封,置于烘箱中,温度升至120±2℃恒温反应10~12 h,取出自然冷却至室温,制得A液;
(2)B悬浮液制备:在反应器中,按如下组成质量百分比加入,去离子水:84~88%,聚乙烯醇:6~10%,加热搅拌溶解,加入纳米四氧化三铁:5~8%,各组分质量百分比之和为百分之百,超声分散20 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合蚕丝制备:在反应器中,按如下组成质量百分比加入,A液:45~50%,B悬浮液:44~48%,四硼酸铵:1~3%,搅拌混合均匀,搅拌,温度升至50℃,滴加质量体积百分浓度为8%的氯化镁溶液:2~6%,各组分质量百分比之和为百分之百,在50±2℃继续恒温放置8h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合蚕丝;
(4)镨掺杂BiOBr粉体的制备:在反应器中,按如下组成质量百分比加入,4.5mol/LHNO3:70~75%,三氧化二镨:0.5~1.0%,加热溶解,再加入Bi(NO3)3:8~12%,溴化铵:4~8%,丙氨酸叔丁酯:10~14%,各组分质量百分比之和为百分之百,低温加热,温度在130℃,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的镨掺杂BiOBr粉体;
(5)多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备:在反应器中,按如下组成质量百分比加入,液体石蜡:70~76%,山梨坦单硬脂酸酯:4~8%,剧烈搅拌下加入镨掺杂BiOBr粉体:2~5%,超声分散30 min,加入多孔磁性复合蚕丝:16~20%,各组分质量百分比之和为百分之百,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入4倍液体体积的无水乙醇,搅拌,固液分离,再用无水乙醇洗涤,干燥,制得多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
2.根据权利要求1所述的一种多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备方法所制备的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂,其特征在于,所述的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂中镨掺杂BiOBr的质量百分含量大于2%。
3.根据权利要求1所述的一种多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂的制备方法所制备的多孔磁性复合蚕丝负载镨掺杂BiOBr光催化剂。
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