CN115254166B - 可磁分离的氮掺杂二氧化钛光催化剂及其制备方法与应用 - Google Patents
可磁分离的氮掺杂二氧化钛光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磁分离的氮掺杂二氧化钛光催化剂及其制备方法与应用,该光催化剂制备步骤为S1、向醇溶剂中加入六水氯化铁、硼酸和单宁酸混匀制备络合物溶液A;S2、向醇溶剂中加入钛酸四丁酯和二甲基咪唑混匀得溶液B,再与S1所得溶液A混合搅拌反应,固化得到催化剂前驱体;S3、将干燥后的前驱体在惰性气氛下煅烧,冷却后得到产物使用沸水进行洗涤、过滤、干燥,即得到可磁分离的氮掺杂二氧化钛光催化剂。本发明通过一步煅烧法得到了可磁分离的氮掺杂二氧化钛光催化剂,该方法制备过程简单,制备的光催化剂磁性回收效率高,可见光催化性能优于商业的P25,在污水处理方面具有潜在的利用价值。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种可磁分离的氮掺杂二氧化钛光催化剂及其制备方法与应用。
背景技术
光催化剂二氧化钛(TiO2)具有光催化性能高、热稳定性好、产量高、生产成本低等优点。但其作为光催化剂也存在一定缺陷。其一是普通TiO2的带隙宽度为3.2eV,只能响应紫外光,对太阳光的利用效率较低;其二是纳米TiO2的超细粒子形态造成了纳米TiO2在反应体系中呈稳定的悬浮分散状态,TiO2在降解过程中难分离、回收困难,易泄露到环境中并成为新的纳米污染物,有证据表明TiO2纳米粒子与微生物细胞表面的相互作用会诱导微生物细胞活性氧水平的升高,进而诱导破坏微生物细胞膜。
采用过渡金属阳离子或者非金属元素掺杂是提高载流子寿命并同时减小带隙的最有效方法,CN113769725A以氯化铁、氯化亚铁和氨水为原料,利用水热法制备Fe3O4,再水解正硅酸乙酯在Fe3O4表面上负载上SiO2,最后利用钛酸四丁酯水解继续包覆一层TiO2,水热晶化得到白色的TiO2@SiO2@Fe3O4复合催化剂。CN102319564A首先在乙二醇溶液中溶剂热制备Fe3O4微球,接着采用溶胶凝胶法在Fe3O4表面依次包覆SiO2和TiO2,最后利用氢氧化钠刻蚀、盐酸溶液处理、高温煅烧得到锐钛矿型的双层空腔结构及海胆状的二氧化钛磁性微球。CN104624189A通过称取一定量的聚乙二醇和聚乙烯吡咯烷酮加入到乙醇水溶液中,待充分溶解后,向溶液中加入纳米TiO2和Fe3O4,机械搅拌分散后利用蠕动泵送入到等离子体焰流中,得到磁性二氧化钛复合中空微球。CN113877548A利用溶剂热合成的Fe3O4作为磁性载体,再负载上TiO2得到应用于环境治理的磁性纳米颗粒。
上述技术中的赋磁方法过程较为繁琐,制备成本较高,所得的磁性载体没有进行有效包覆,在使用过程中易形成团聚体,会导致光催化剂光催化性能的降低。此外,文献中在赋磁的同时没有解决TiO2的宽带隙缺陷。
发明内容
本发明提供一种可磁分离的氮掺杂二氧化钛光催化剂及其制备方法与应用,催化剂的可见光催化性能和稳定性优于传统二氧化钛,同时具备易回收的特点,避免二氧化钛材料向环境中的泄露。
本发明的技术方案是,一种可磁分离的氮掺杂二氧化钛光催化剂制备方法,包括以下步骤:
S1、向醇溶剂中加入六水氯化铁、硼酸和单宁酸混匀制备络合物溶液A;
S2、向醇溶剂中加入钛酸四丁酯和二甲基咪唑混匀得溶液B,再与S1所得溶液A混合搅拌反应,固化得到催化剂前驱体;
S3、将干燥后的前驱体在惰性气氛下煅烧,冷却后得到产物使用沸水进行洗涤、过滤、干燥,即得到可磁分离的氮掺杂二氧化钛光催化剂。
进一步地,S1中氯化铁的浓度为0.3-1.0 mol/L,硼酸的浓度为1-3.5 mol/L,单宁酸的浓度为0.02-0.1 mol/L。
进一步地,S2溶液B中钛酸四丁酯的浓度为1-3.5 mol/L,二甲基咪唑的浓度为1-4mol/L。
进一步地,S2中溶液A和溶液B等体积混合。
进一步地,S2混合物中Fe与Ti的摩尔比为1~3:10。
进一步地,所述的醇溶液为甲醇、乙醇、异丙醇中的一种或几种组合。
进一步地,S2中烘干温度为40-80℃。
进一步地,S3中煅烧温度为650-750℃,升温速度为3-10℃/min,保温时间0.5-2h;煅烧气氛为氮气氛,流速为0.02-0.55L/min。
本发明涉及所述制备方法得到的可磁分离的氮掺杂二氧化钛光催化剂。
本发明还涉及所述可磁分离的氮掺杂二氧化钛光催化剂在污水处理中的应用。
本发明具有以下有益效果:
本发明S1中采用单宁酸作为碳源,单宁酸结构中的邻苯二酚和邻苯三酚与三价铁离子发生强烈的相互作用,形成铁离子-单宁酸骨架;进一步的当铁离子-单宁酸骨架与S2中2-甲基咪唑生成絮状沉淀能够与S2中钛源充分的混合,进而在S3的煅烧步骤形成均匀复合的可磁分离的氮掺杂二氧化钛光催化剂。单宁酸在煅烧过程中转变为衍生碳包覆在催化剂表面,碳材料具有较大的孔隙度,且表面富含羧基、羟基、羰基等官能团,有助于提高催化剂对污染物的吸附和降解能力。碳材料在TiO2表面的包覆还能缓解TiO2纳米粒子的硬团聚,而且碳材料的三维特性及复合催化剂中的磁性粒子也能降低TiO2的回收难度。此外,单宁酸衍生的碳材料对磁性粒子和TiO2进行包覆,解决了磁性粒子TiO2粒子的腐蚀和泄露问题,提高了催化剂的使用稳定性。
由于氮元素和氧元素的原子半径大小相当,氮元素可以掺杂TiO2的晶体结构,从而减小TiO2的能带间隙,本发明采用氮元素的掺入增强了TiO2的可见光催化性能。引入磁性粒子为TiO2提供了可磁回收利用的功能,磁性离子中的铁元素在TiO2晶格中的掺杂可以产生更多的氧空位,导致形成新的能级,进一步缩小带隙,拓宽光吸收范围,加速光生电荷的转移,表现出优异可见光催化性能,可以快速的降解有机染料和抗生素类污染物。
本发明通过一步煅烧法得到了可磁分离的氮掺杂二氧化钛光催化剂,该方法制备过程简单,制备的光催化剂磁性回收效率高,可见光催化性能优于商业的P25,在污水处理方面具有潜在的利用价值。
附图说明
图1是实施例1所得光催化剂的XRD谱图;
图2是实施例2所得光催化剂的SEM照片;
图3为实施例2所得光催化剂的元素分布照片;
图4为实施例3所得光催化剂通过外加磁场实现催化剂分离的效果图,其中左图为外加磁场分离后效果,右图为磁分离前效果;
图5为实施例3所得催化剂与商业P25在氙灯照射下对盐酸四环素的降解效果图;
图6为实施例4所得光催化剂降解亚甲基蓝的循环效果图。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。
实施例1
在10mL的异丙醇中分别加入0.811g六水氯化铁、0.618g硼酸和0.34g单宁酸得到溶液A;在另一份10mL乙醇中加入3.4mL钛酸四丁酯和0.82g 2-甲基咪唑得到溶液B;搅拌下快速混合溶液A和溶液B得到固化的蓬松状的前驱体材料,60℃干燥4h;称取3g干燥的前驱体材料转移到石英舟中,再将石英舟置于管式炉中,设置升温速度为3℃/min,升温至650℃保温2h,氮气流速为0.02L/min;将冷却后的催化剂材料转移到200mL去离子水中,煮沸30min后过滤、干燥得到可磁分离的氮掺杂二氧化钛光催化剂。其XRD谱图见图1,本催化剂中的TiO2为锐钛矿和金红石相TiO2构成的异质结构,异质结构颗粒可提高光的吸收、改善光生载流子的分离效率,进而提高TiO2的光催化性能。
将50mg制得的催化剂加入到50mL 20mg/L的亚甲基蓝溶液中,搅拌30min后利用氙灯光源照射1h,紫外可见分光光度计测定上层清液浓度,去除率为98.7%。
实施例2
在10mL的乙醇中分别加入2.7g六水氯化铁、2.2g硼酸和1.7g单宁酸得到溶液A;在另一份10mL乙醇中加入12mL钛酸四丁酯和3.2g 2-甲基咪唑得到溶液B;搅拌下快速混合溶液A和溶液B得到固化的蓬松状的前驱体材料,80℃干燥3h;称取5g干燥的前驱体材料转移到石英舟中,再将石英舟置于管式炉中,设置升温速度为10℃/min,升温至750℃保温0.5h,氮气流速为0.5L/min;将冷却后的催化剂材料转移到200mL去离子水中,煮沸30min后过滤、干燥得到可磁分离的氮掺杂二氧化钛光催化剂。将50mg制得的催化剂加入到50mL 20mg/L的甲基蓝溶液中,搅拌30min后利用氙灯光源照射1h,紫外可见分光光度计测定上层清液浓度,去除率为95.3%。图2和图3为该光催化剂的SEM照片;可磁分离的氮掺杂二氧化钛光催化剂是由纳米粒子构成的聚集体,元素分布显示催化剂材料中氧元素、碳元素、钛元素、铁元素和氮元素分布均匀,说明催化剂材料中各组分复合均匀。
实施例3
在10mL的甲醇中分别加入1.35g六水氯化铁、2g硼酸和1g单宁酸得到溶液A;在另一份10mL乙醇中加入8mL钛酸四丁酯和2g 2-甲基咪唑得到溶液B;搅拌下快速混合溶液A和溶液B得到固化的蓬松状的前驱体材料,60℃干燥3h;称取4g干燥的前驱体材料转移到石英舟中,再将石英舟置于管式炉中,设置升温速度为5℃/min,升温至680℃保温1h,氮气流速为0.08L/min;将冷却后的催化剂材料转移到200mL去离子水中,煮沸30min后过滤、干燥得到可磁分离的氮掺杂二氧化钛光催化剂。将50mg制得的催化剂加入到50mL 20mg/L的盐酸四环素溶液中,搅拌30min后利用氙灯光源照射1h,紫外可见分光光度计测定上层清液浓度,去除率为99.3%。
该光催化剂通过外加磁场实现催化剂分离的效果如图4,其与市售二氧化钛P25在氙灯照射下对盐酸四环素的降解效果图见图5。结果证实可磁分离的氮掺杂二氧化钛光催化剂在使用后具有磁场分离效果,且与商业P25相比,具有更佳优异的吸附和可见光催化性能。
实施例4
在6mL乙醇和4mL甲醇的混合溶剂中分别加入1.5g六水氯化铁、2g硼酸和1.2g单宁酸得到溶液A;在另一份4mL甲醇、4mL乙醇和2mL的异丙醇混合溶剂中加入10mL钛酸四丁酯和2g 2-甲基咪唑得到溶液B;搅拌下快速混合溶液A和溶液B得到固化的蓬松状的前驱体材料,40℃干燥6h;称取5g干燥的前驱体材料转移到石英舟中,再将石英舟置于管式炉中,设置升温速度为10℃/min,升温至700℃保温1h,氮气流速为0.05L/min;将冷却后的催化剂材料转移到200mL去离子水中,煮沸30min后过滤、干燥得到可磁分离的氮掺杂二氧化钛光催化剂。将50mg制得的催化剂加入到50mL 20mg/L的亚甲基蓝溶液中,搅拌30min后利用氙灯光源照射1h,紫外可见分光光度计测定上层清液浓度,去除率为98.1%。该光催化剂降解亚甲基蓝的循环效果见图6,说明可磁分离的氮掺杂二氧化钛光催化剂具有良好的重复使用性。
上述的实施例仅为本发明的优选技术方案,而不应视为对于本发明的限制,本申请中的实施例及实施例中的特征在不冲突的情况下,可以相互任意组合。本发明的保护范围应以权利要求记载的技术方案,包括权利要求记载的技术方案中技术特征的等同替换方案为保护范围。即在此范围内的等同替换改进,也在本发明的保护范围之内。
Claims (10)
1.一种可磁分离的氮掺杂二氧化钛光催化剂制备方法,其特征在于,包括以下步骤:
S1、向醇溶剂中加入六水氯化铁、硼酸和单宁酸混匀制备络合物溶液A;
S2、向醇溶剂中加入钛酸四丁酯和二甲基咪唑混匀得溶液B,再与S1所得溶液A混合搅拌反应,固化得到催化剂前驱体;
S3、将干燥后的前驱体在惰性气氛下煅烧,冷却后得到产物使用沸水进行洗涤、过滤、干燥,即得到可磁分离的氮掺杂二氧化钛光催化剂。
2. 根据权利要求1所述的制备方法,其特征在于:S1中氯化铁的浓度为0.3-1.0 mol/L,硼酸的浓度为1-3.5 mol/L,单宁酸的浓度为0.02-0.1 mol/L。
3. 根据权利要求1所述的制备方法,其特征在于:S2溶液B中钛酸四丁酯的浓度为1-3.5 mol/L,二甲基咪唑的浓度为1-4 mol/L。
4.根据权利要求1所述的制备方法,其特征在于:S2中溶液A和溶液B等体积混合。
5.根据权利要求1~4任意一项所述的制备方法,其特征在于:S2混合物中Fe与Ti的摩尔比为1~3:10。
6.根据权利要求1所述的制备方法,其特征在于:所述的醇溶剂为甲醇、乙醇、异丙醇中的一种或几种组合。
7.根据权利要求1所述的制备方法,其特征在于:S2中固化得到催化剂前驱体的烘干温度为40-80℃。
8.根据权利要求1所述的制备方法,其特征在于:S3中煅烧温度为650-750℃,升温速度为3-10℃/min,保温时间0.5-2h;煅烧气氛为氮气氛,流速为0.02-0.55L/min。
9.权利要求1~8任意一项所述制备方法得到的可磁分离的氮掺杂二氧化钛光催化剂。
10.权利要求9所述可磁分离的氮掺杂二氧化钛光催化剂在污水处理中的应用。
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