CN108404995B - 多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备 - Google Patents
多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
本发明公开了一种多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备方法,其特征在于,采用1‑烯丙基‑3‑甲基咪唑溴盐溶解羊毛添加聚乙烯醇和纳米四氧化三铁,得到多孔磁性复合羊毛颗粒;采用燃烧法制得膨松的铑掺杂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:72~78%,失水山梨糖醇脂肪酸酯:4~8%,剧烈搅拌下加入铑掺杂BiOBr粉体:2~5%,加入多孔磁性复合羊毛颗粒:12~18%,搅拌、反应固液分离,在用无水乙醇洗涤,干燥,制得多孔磁性复合羊毛负载铑掺杂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羊毛负载铑掺杂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
羊毛属天然蛋白质纤维,作为纺织品的原材料,其具有吸湿性强、保暖、耐磨、光泽柔和等优点。但值得关注的是,在毛纺行业存在大量的羊毛在纺织过程中被废弃,丢掉的现象.据报道”,我国每年约有十几万吨的废弃羊毛,这不仅导致大量羊毛角蛋白资源的浪费,也给环境保护带来了一定的压力。过去对羊毛的溶解,一般都是用强碱或强酸性溶液作为溶剂来溶解粗短或废弃羊毛,这样不仅使角朊大分子链基本上被破坏掉,所使用的化学试剂也给环境带来了一定的污染.随着绿色化学的发展和环保的要求,离子液体作为绿色可设计性溶剂,越来越受到关注.与现在所使用的传统分子溶剂相比较,离子液体本身特殊的结构决定了它具有独特的溶解特征。
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。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。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。贵金属铑元素掺杂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。
本申请采用1-烯丙基-3-甲基咪唑溴盐溶解羊毛与聚乙烯醇混合添加加入纳米四氧化三铁制备多孔磁性复合羊毛颗粒作为催化剂的载体制备负载型铑掺杂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羊毛负载铑掺杂BiOBr光催化剂的制备方法。
一种多孔磁性复合羊毛负载铑掺杂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, 1-烯丙基-3-甲基咪唑溴盐:70~75%,脱脂羊毛:25~30%,密封,置于烘箱中,温度升至140±2℃恒温反应13~15 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:85~88%,聚乙烯醇:5~8%,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40 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合羊毛颗粒制备:在反应器中,按如下组成质量百分比加入,A液:50~54%,B悬浮液:42~45%,四硼酸铵:1~3%,搅拌混合均匀,搅拌,温度升至45℃,滴加卤水:2~5%,各组分质量百分比之和为百分之百,温度在55±2℃继续恒温放置10 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合羊毛颗粒;
(4)铑掺杂BiOBr粉体的制备:在反应器中,按如下组成质量百分比加入,3.0mol/LHNO3:64~68%,硝酸铑:0.5~1.0%,搅拌溶解,再加入Bi(NO3)3:10~14%,十二烷基三甲基溴化铵:6~10%,丙氨酸叔丁酯:12~16%,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,制得膨松的铑掺杂BiOBr粉体;
(5)多孔磁性复合羊毛负载铑掺杂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:72~78%,失水山梨糖醇脂肪酸酯:4~8%,剧烈搅拌下加入铑掺杂BiOBr粉体:2~5%,超声分散40 min,加入多孔磁性复合羊毛颗粒:12~18%,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2~4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,制得多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂。
步骤(1)中所述的脱脂羊毛处理方法:在反应器中,采用质量百分浓度为5~8%碳酸钠溶液,搅拌均匀浸泡洗净的羊毛16~20h,再煮沸30min,冷却后用去离子水洗涤至中性,固液分离,在放入异丙醇中浸泡5h,固液比为1g:5~15mL,温度为60℃,冷却后,固液分离, 用水洗涤至中性,干燥,得脱脂羊毛;
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羊毛负载铑掺杂BiOBr光催化剂中铑掺杂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羊毛负载铑掺杂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羊毛负载铑掺杂BiOBr光催化剂所用的载体是多孔磁性复合羊毛,羊毛来源广泛,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,在羊毛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羊毛负载铑掺杂BiOBr光催化剂操作简单、铑掺杂BiOBr负载率高、颗粒分散均匀、铑掺杂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羊毛,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,采用冷冻干燥形成多孔,增加载体的比表面积,提高了铑掺杂BiOBr的负载量,增加光的照射强度而提高催化剂的催化效率,催化剂中在铑掺杂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, 1-烯丙基-3-甲基咪唑溴盐:72g,脱脂羊毛:28g,密封,置于烘箱中,温度升至140±2℃恒温反应14 h,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:87 mL,聚乙烯醇:6g,加热搅拌溶解,加入纳米四氧化三铁:7g,超声分散40 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合羊毛颗粒制备:在反应器中,分别加入,A液:52g,B悬浮液:44g,四硼酸铵:1.0g,搅拌均匀,搅拌,温度升至45℃,滴加卤水:3mL,温度在55±2℃继续恒温放置10 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合羊毛颗粒;
(4)铑掺杂BiOBr粉体的制备:在反应器中,分别加入,3.0mol/L HNO3:66mL,硝酸铑:0.8g,搅拌溶解,再加入Bi(NO3)3:12g,十二烷基三甲基溴化铵:8g,丙氨酸叔丁酯:13.2g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的铑掺杂BiOBr粉体;
(5)多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:87mL,失水山梨糖醇脂肪酸酯:6g,剧烈搅拌下加入铑掺杂BiOBr粉体4g,超声分散40 min,加入多孔磁性复合羊毛颗粒:15g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入2~4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,制得多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂。
实施例2
(1)A液配制:在反应釜中,分别加入, 1-烯丙基-3-甲基咪唑溴盐:75g,脱脂羊毛:25g,密封,置于烘箱中,温度升至140±2℃恒温反应13 h,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:85 mL,聚乙烯醇:7g,加热搅拌溶解,加入纳米四氧化三铁:8g,超声分散40 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合羊毛颗粒制备:在反应器中,分别加入,A液:50g,B悬浮液:43g,四硼酸铵:2g,搅拌均匀,搅拌,温度升至45℃,滴加卤水:5mL,温度在55±2℃继续恒温放置10 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合羊毛颗粒;
(4)铑掺杂BiOBr粉体的制备:在反应器中,分别加入,3.0mol/L HNO3:64mL,硝酸铑:1g,搅拌溶解,再加入Bi(NO3)3:14g,十二烷基三甲基溴化铵:6g,丙氨酸叔丁酯:15g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的铑掺杂BiOBr粉体;
(5)多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:84mL,失水山梨糖醇脂肪酸酯:8g,剧烈搅拌下加入铑掺杂BiOBr粉体2g,超声分散40 min,加入多孔磁性复合羊毛颗粒:18g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入2~4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,制得多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂。
实施例3
(1)A液配制:在反应釜中,分别加入, 1-烯丙基-3-甲基咪唑溴盐:70g,脱脂羊毛:30g,密封,置于烘箱中,温度升至140±2℃恒温反应15 h,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:8g,加热搅拌溶解,加入纳米四氧化三铁:5g,超声分散40 min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合羊毛颗粒制备:在反应器中,分别加入,A液:54g,B悬浮液:42g,四硼酸铵:1.5g,搅拌均匀,搅拌,温度升至45℃,滴加卤水:3mL,温度在55±2℃继续恒温放置10 h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合羊毛颗粒;
(4)铑掺杂BiOBr粉体的制备:在反应器中,分别加入,3.0mol/L HNO3:68mL,硝酸铑:0.5g,搅拌溶解,再加入Bi(NO3)3:10g,十二烷基三甲基溴化铵:10g,丙氨酸叔丁酯:12g,低温加热,温度在130℃之间,蒸发水分,形成黏稠胶体,点燃燃烧,制得膨松的铑掺杂BiOBr粉体;
(5)多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备:在反应器中,分别加入,液体石蜡:90mL,失水山梨糖醇脂肪酸酯:4g,剧烈搅拌下加入铑掺杂BiOBr粉体5g,超声分散40 min,加入多孔磁性复合羊毛颗粒:12g,温度升至85±2℃恒温、搅拌、反应60min,温度降低至50±2℃,加入2~4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,制得多孔磁性复合羊毛负载铑掺杂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多孔磁性复合羊毛负载铑掺杂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=0.015,偶氮胂Ⅲ的降解率达到98.02%。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多孔磁性复合羊毛负载铑掺杂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=0.018,双酚A的降解率达到96.91%。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 (4)
1.一种多孔磁性复合羊毛负载铑掺杂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,1-烯丙基-3-甲基咪唑溴盐:70~75%,脱脂羊毛:25~30%,密封,置于烘箱中,温度升至140±2℃恒温反应13~15h,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:85~88%,聚乙烯醇:5~8%,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40min,冷却到室温,制得B悬浮液;
(3)多孔磁性复合羊毛颗粒制备:在反应器中,按如下组成质量百分比加入,A液:50~54%,B悬浮液:42~45%,四硼酸铵:1~3%,搅拌混合均匀,搅拌,温度升至45℃,滴加卤水:2~5%,各组分质量百分比之和为百分之百,温度在55±2℃继续恒温放置10h,冷至室温,固液分离,洗涤,反复冷冻干燥,得到多孔磁性复合羊毛颗粒;
(4)铑掺杂BiOBr粉体的制备:在反应器中,按如下组成质量百分比加入,3.0mol/LHNO3:64~68%,硝酸铑:0.5~1.0%,搅拌溶解,再加入Bi(NO3)3:10~14%,十二烷基三甲基溴化铵:6~10%,丙氨酸叔丁酯:12~16%,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,制得膨松的铑掺杂BiOBr粉体;
(5)多孔磁性复合羊毛负载铑掺杂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:72~78%,失水山梨醇脂肪酸酯:4~8%,剧烈搅拌下加入铑掺杂BiOBr粉体:2~5%,超声分散40min,加入多孔磁性复合羊毛颗粒:12~18%,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2~4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,制得多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂。
2.根据权利要求1所述的一种多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备方法,其特征在于,骤(1)中所述的脱脂羊毛处理方法:在反应器中,采用质量百分浓度为5~8%碳酸钠溶液,搅拌均匀浸泡洗净的羊毛16~20h,再煮沸30min,冷却后用去离子水洗涤至中性,固液分离,在放入异丙醇中浸泡5h,固液比为1g:5~15mL,温度为60℃,冷却后,固液分离,用水洗涤至中性,干燥,得脱脂羊毛。
3.根据权利要求1所述的一种多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备方法所制备的多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂,其特征在于,所述的多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂中铑掺杂BiOBr的质量百分含量大于2%。
4.根据权利要求1所述的一种多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂的制备方法所制备的多孔磁性复合羊毛负载铑掺杂BiOBr光催化剂。
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CN106563472B (zh) * | 2016-11-07 | 2019-01-11 | 中国科学院合肥物质科学研究院 | 金-氯氧铋纳米复合材料及其制备方法 |
CN106732689B (zh) * | 2016-12-21 | 2019-02-22 | 郑州师范学院 | 一种光催化降解有机小分子的BiOI-Ru-B协同光催化剂及其制备方法和应用 |
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