CN111921558A - 一种可见光响应的MIL-125/BiOBr复合催化剂及其制备方法与应用 - Google Patents
一种可见光响应的MIL-125/BiOBr复合催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明提供了一种可见光响应的MIL‑125/BiOBr复合催化剂及其制备方法。该复合催化剂是由平均粒径为15‑25nm的纳米粒子组成的微观形貌;禁带宽度为2.81eV,吸收边带为441nm,具有可见光响应。MIL‑125/BiOBr复合催化剂的制备方法为:将Bi(NO3)3·5H2O分散加入至EG溶液中,搅拌至溶解;将CTAB分散至水溶液中,搅拌至溶解;上述溶液混合后,调节pH值,超声处理,得到BiOBr前驱体;将Ti(O‑iPr)4、H2BDC、CH3OH和DMF混合搅拌溶解,得到MIL‑125前驱体;将BiOBr前驱体滴入MIL‑125前驱体中,超声处理后,转入水热反应釜中,在130~180℃反应30~60h;冷却室温后,离心、洗涤、干燥,得到MIL‑125/BiOBr复合催化剂。此催化剂在可见光照射下,实现目标污染物Cr6+的高效还原。该方法合成路线简单易控,形貌重现性好,适用于工业大批量生产的需求。
Description
技术领域
本发明涉及可见光响应的MIL-125/BiOBr复合催化剂,属于环境化工光催化水处理技术领域,特别涉及可见光处理Cr6+废水。
背景技术
世界卫生组织将镉列入对人体毒性最强的重金属之一,镉元素大量存在于自然界中。镉容易进入人体的肾脏,与蛋白酶发生螯合作用,螯合物在肾脏中反应,发生镉的二次释放,破坏肾脏系统。此外,镉离子与钙离子的原子半径相近,当人补充钙离子时,镉离子能够进入钙通道,抑制G-ATP酶活性,影响钙离子的转运,导致钙离子浓度急剧升高,产生癌基因。因此,面对镉离子等有毒有害性较强的污染物,相应的去除方法研究日益成为热点。光催化技术是一种环保的、高效的、无二次污染的高级氧化技术,在能源开发和环境污染治理领域都显示出广阔的应用前景,吸引了国内外学者广泛关注及研究。
金属-有机骨架(metal-organic frameworks,MOFs),也被称为多孔配位聚合物(porous coordination polymers,PCPs),具有超高的孔隙率(>90%的自由体积)、较高的比表面积、可调的孔径和内表面特性,使其在气体的储存和分离、传感、催化、质子传导和药物运输等方面均有着广泛的应用。但MOFs材料对水敏感,限制了其在许多领域中的应用。
发明内容
针对上述问题,本发明旨在提供一种具有可见光响应的、对Cr6+具有高效还原能力、稳定性好的MIL-125/BiOBr复合纳米催化剂的制备工艺。
本发明技术方案如下:
一方面,本发明提供了一种MIL-125/BiOBr复合催化剂的制备方法,所述制备方法为原位超声水热法,所述原位超声水热法包括以下步骤:
步骤1、将Bi的金属盐分散加入至EG(乙二醇)溶液中,室温搅拌至溶解,得混合溶液A;
步骤2、将CTAB(十六烷基三甲基溴化铵)分散至水中,搅拌至溶解,得溶液B;
步骤3、将所述溶液B滴入混合溶液A中,加入碳酸钠溶液至pH=3~6,室温超声处理,得溶液C;
步骤4、将Ti(O-iPr)4、H2BDC、CH3OH和DMF(二甲基甲酰胺)混合,搅拌,形成溶液D;
步骤5、将溶液D滴入溶液C中,形成混合溶液,室温超声处理,得混合溶液E;
步骤6、将溶液E在130~180℃反应30~60h,冷却至室温后,洗涤、干燥得到所述MIL-125/BiOBr复合催化剂。
基于上述方案,优选地,所述Bi的金属盐为Bi(NO3)3·5H2O;所述溶液A中Bi3+的浓度为0.1~0.5g/L;所述CTAB与Bi3+的摩尔比为1:1;所述溶液B中Br-的浓度为0.1~0.5g/L;所述混合溶液B的滴加速度为1~5mL/min,所述混合溶液B采用微量注射泵滴加;所述碳酸钠溶液的浓度为0.1M;所述步骤3中超声处理时间为20~120min。
基于上述方案,优选地,所述溶液D中Ti(O-iPr)4、H2BDC、CH3OH和DMF的质量比为1:2:4:35;所述步骤4中搅拌时间为1h;所述溶液D的滴加速度为1~5mL/min;所述溶液D采用微量注射泵滴加;所述步骤5中超声处理时间为20~120min;所述混合溶液E中Ti与Bi的摩尔比为10:1~5:1。
基于上述方案,优选地,所述溶液E于水热反应釜中进行反应;所述洗涤步骤为:用去离子水和无水乙醇各洗涤三次;所述干燥步骤为:于真空烘箱中在50~100℃下干燥12~24h。
另一方面,本发明提供了一种MIL-125/BiOBr复合催化剂,所述复合催化剂采用上述的方法制备。
基于上述方案,优选地,所述催化剂由纳米粒子组成;所述纳米粒子的平均粒径为15-25nm。
基于上述方案,优选地,所述催化剂的禁带宽度为2.81eV,吸收边带为441nm;所述催化剂具有可见光响应。
再一方面,本发明将上述催化剂应用于光催化还原Cr6+的反应。
基于上述方案,优选地,所述MIL-125/BiOBr催化剂与Cr6+底物的质量比为7:1~2:1;所述Cr6+底物溶液的浓度为50mg/L;所述反应采用氙灯为光源。
有益效果
1、本发明提供的原位超声水热法具有操作简单、合成步骤少、能耗低等优点,更适于工业生产。
2、本发明的方法制备的催化剂与现有的方法制备的催化剂,在形貌上具有纳米粒子小且均匀的特点,在复合形式上MIL-125与BiOBr接触充分的特点,有效的抑制光生电子的复合,提高光催化还原Cr6+能力。
附图说明
图1为实施例1中的MIL-125/BiOBr复合催化剂的扫描电镜图。
图2为实施例1中的MIL-125/BiOBr复合催化剂与纯BiOBr和MIL-125光催化降解Cr6+效果对比图。
图3为实施例1中的MIL-125/BiOBr复合催化剂与两步水热法制得的MIL-125/BiOBr复合催化剂光催化降解Cr6+效果对比图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
MIL-125/BiOBr-1复合催化剂的制备方法具体如下:
步骤1、将Bi(NO3)3·5H2O分散加入至EG溶液中,室温磁力搅拌至溶解,得混合溶液A,溶液A中Bi3+的浓度为0.1g/L;
步骤2、将与Bi(NO3)3·5H2O的摩尔比为1:1的CTAB分散至水溶液中,磁力搅拌至溶解,得混合溶液B,溶液B中Br-的浓度为0.1g/L;
步骤3、采用微量注射泵将混合溶液B以1mL/min的速度滴入混合溶液A中,加入0.1M碳酸钠溶液至pH=3,室温超声处理20min,得溶液C;
步骤4、将质量比为的1:2:4:35的Ti(O-iPr)4、H2BDC、CH3OH和DMF混合搅拌1h,形成溶液D;
步骤5、采用微量注射泵将溶液D以1mL/min的速度滴入溶液C中形成混合溶液,室温超声处理20min,得混合溶液E,混合溶液E中Ti与Bi的摩尔比为10:1。
步骤6、将溶液E转入水热反应釜中,在130℃反应60h;冷却至室温后,用去离子水和无水乙醇各洗涤三次,在真空烘箱中在50℃下干燥24h,得到MIL-125/BiOBr-1复合催化剂。MIL-125/BiOBr-1复合催化剂的扫描电镜图如图1所示,复合催化剂的的形貌为20nm左右的纳米粒子,粒径均匀。
实施例2
MIL-125/BiOBr-2复合催化剂的制备方法具体如下:
步骤1、将Bi(NO3)3·5H2O分散加入至EG溶液中,室温磁力搅拌至溶解,得混合溶液A,溶液A中Bi3+的浓度为0.5g/L;
步骤2、将与Bi(NO3)3·5H2O的摩尔比为1:1的CTAB分散至水溶液中,磁力搅拌至溶解,得混合溶液B,溶液B中Br-的浓度为0.5g/L;
步骤3、采用微量注射泵将混合溶液B以5mL/min的速度滴入混合溶液A中,加入0.1M碳酸钠溶液至pH=6,室温超声处理120min,得溶液C;
步骤4、将质量比为的1:2:4:35的Ti(O-iPr)4、H2BDC、CH3OH和DMF混合搅拌1h,形成溶液D;
步骤5、采用微量注射泵将溶液D以5mL/min的速度滴入溶液C中形成混合溶液,室温超声处理120min,得混合溶液E,混合溶液E中Ti与Bi的摩尔比为5:1。
步骤6、将溶液E转入水热反应釜中,在180℃反应30h;冷却至室温后,用去离子水和无水乙醇各洗涤三次,在真空烘箱中在100℃下干燥12h,得到MIL-125/BiOBr-2复合催化剂。
实施例3
MIL-125/BiOBr-3复合催化剂的制备方法具体如下:
步骤1、将Bi(NO3)3·5H2O分散加入至EG溶液中,室温磁力搅拌至溶解,得混合溶液A,溶液A中Bi3+的浓度为0.25g/L;
步骤2、将与Bi(NO3)3·5H2O的摩尔比为1:1的CTAB分散至水溶液中,磁力搅拌至溶解,得混合溶液B,溶液B中Br-的浓度为0.25g/L;
步骤3、采用微量注射泵将混合溶液B以2mL/min的速度滴入混合溶液A中,加入0.1M碳酸钠溶液至pH=4,室温超声处理60min,得溶液C;
步骤4、将质量比为的1:2:4:35的Ti(O-iPr)4、H2BDC、CH3OH和DMF混合搅拌1h,形成溶液D;
步骤5、采用微量注射泵将溶液D以2mL/min的速度滴入溶液C中形成混合溶液,室温超声处理60min,得混合溶液E,混合溶液E中Ti与Bi的摩尔比为8:1。
步骤6、将溶液E转入水热反应釜中,在150℃反应45h;冷却至室温后,用去离子水和无水乙醇各洗涤三次,在真空烘箱中在80℃下干燥18h,得到MIL-125/BiOBr-3复合催化剂。
应用例1
首先,将实施例1中的0.05g的MIL-125/BiOBr复合纳米材料分散于200mL重铬酸钾溶液中(0.05g/L);
再次,暗光下,上述溶液磁力搅拌1h,让MIL-125/BiOBr复合催化剂吸附饱和;
最后,以氙灯为光源,进行光催化降解Cr6+实验,并通过吸光光度法计算的Cr6+去除率,实验结果见图2所示。
实施例2和实施例3制备的催化剂同样的条件下应用于以上光催化降解Cr6+实验,Cr6+去除率分别为83.2%和82.7%。
对比例1-2
作为对比,同样反应条件下,将自制的MIL-125(采用实施例1中步骤4、6制备)和BiOBr(采用实施例1中步骤1、2、3、6制备)分别用于光催化还原Cr6+中的反应。
实验结果见图2所示,经过5h降解,MIL-125/BiOBr复合纳米材料可见光降解Cr6+的效率是MIL-125的2倍、BiOBr的4倍。
对比例3
采用两步水热法合成的MIL-125/BiOBr,两步水热合成MIL-125/BiOBr复合催化剂过程中各物料的用量与实施例1相同,具体步骤如下:
①MIL-125
步骤1、将质量比为的1:2:4:35的Ti(O-iPr)4、H2BDC、CH3OH和DMF混合搅拌1h,形成溶液A;
步骤2、将溶液A转入水热反应釜中,在130℃反应60h;冷却至室温后,用去离子水和无水乙醇各洗涤三次,在真空烘箱中在50℃下干燥24h,得到MIL-125催化剂。
②MIL-125/BiOBr复合催化剂
步骤1、将Bi(NO3)3·5H2O分散加入至EG溶液中,室温磁力搅拌至溶解,得混合溶液A,溶液A中Bi3+的浓度为0.1g/L;
步骤2、将与Bi(NO3)3·5H2O的摩尔比为1:1的CTAB分散至水溶液中,磁力搅拌至溶解,得混合溶液B,溶液B中Br-的浓度为0.1g/L;
步骤3、采用微量注射泵将混合溶液B以1mL/min的速度滴入混合溶液A中,加入0.1M碳酸钠溶液至pH=3,室温超声处理20min,得溶液C;
步骤4、将①中制得的MIL-125催化剂加入至溶液C中,超声处理30min,得溶液D;
步骤5、将溶液D转入水热反应釜中,在130℃反应60h;冷却至室温后,用去离子水和无水乙醇各洗涤三次,在真空烘箱中在50℃下干燥24h,得到MIL-125/BiOBr-1复合催化剂。
将上述方法制备的催化剂用于光催化还原Cr6+中的反应,反应条件同应用例1。
与实施例1的对比实验结果见图3所示,经过5h降解,原位超声水热法制得的复合纳米材料可见光降解Cr6+的效率是两步水热法制得的复合催化剂的1.5倍。
Claims (9)
1.一种MIL-125/BiOBr复合催化剂的制备方法,其特征在于,所述制备方法为原位超声水热法,所述原位超声水热法包括以下步骤:
步骤1、将Bi3+的金属盐分加入至EG溶液中,室温搅拌至溶解,得混合溶液A;
步骤2、将CTAB分散至水中,搅拌至溶解,得溶液B;
步骤3、将所述溶液B滴入混合溶液A中,加入碳酸钠溶液至pH=3~6,室温超声处理,得溶液C;
步骤4、将Ti(O-iPr)4、H2BDC、CH3OH和DMF混合,搅拌,形成溶液D;
步骤5、将溶液D滴入溶液C中,形成混合溶液,室温超声处理,得混合溶液E;
步骤6、将溶液E在130~180℃反应30~60h,冷却至室温后,洗涤、干燥得到所述MIL-125/BiOBr复合催化剂。
2.根据权利要求1所述的催化剂的制备方法,其特征在于,
所述Bi的金属盐为Bi(NO3)3·5H2O;所述溶液A中Bi3+的浓度为0.1~0.5g/L;
所述CTAB与Bi3+的摩尔比为1:1;所述溶液B中Br-的浓度为0.1~0.5g/L;
所述混合溶液B的滴加速度为1~5mL/min,所述混合溶液B采用微量注射泵滴加;所述碳酸钠溶液的浓度为0.1M;所述步骤3中超声处理时间为20~120min。
3.根据权利要求1所述的催化剂的制备方法,其特征在于,
所述溶液D中Ti(O-iPr)4、H2BDC、CH3OH和DMF的质量比为1:2:4:35;所述步骤4中搅拌时间为1h;
所述溶液D的滴加速度为1~5mL/min;所述溶液D采用微量注射泵滴加;所述步骤5中超声处理时间为20~120min;所述混合溶液E中Ti与Bi的摩尔比为10:1~5:1。
4.根据权利要求1所述的催化剂的制备方法,其特征在于,
所述溶液E于水热反应釜中进行反应;所述洗涤步骤为:用去离子水和无水乙醇各洗涤三次;所述干燥步骤为:于真空烘箱中在50~100℃下干燥12~24h。
5.一种MIL-125/BiOBr复合催化剂,其特征在于:所述复合催化剂采用权利要求1-4所述的方法制备。
6.根据权利要求5所述的催化剂,其特征在于,所述催化剂由纳米粒子组成;所述纳米粒子的平均粒径为15-25nm。
7.根据权利要求5所述的催化剂,其特征在于,所述催化剂的禁带宽度为2.81eV,吸收边带为441nm;所述催化剂具有可见光响应。
8.一种权利要求5所述的催化剂在光催化还原Cr6+中的应用。
9.根据权利要求8所述的应用,其特征在于,所述MIL-125/BiOBr催化剂与Cr6+底物的质量比为7:1~2:1;所述Cr6+底物溶液的浓度为50mg/L;所述反应采用氙灯为光源。
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