CN108786923B - 一种核壳结构可见光催化剂的制备方法 - Google Patents
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Abstract
本发明公开了一种核壳结构可见光催化剂的制备方法,先制备出具有正八面体形貌的MOF材料UiO‑66;然后,通过水热法,利用十二胺的弱的还原作用,将单质硫还原为能与In3+结合的S2‑离子,同时使用木质素磺酸钠作为UIO‑66的包覆剂,使形成的In2S3纳米颗粒能均匀负载在UiO‑66的表面,得到以UiO‑66为核,In2S3为壳的核壳结构可见光催化剂。本发明所制备的可见光催化剂稳定性好,吸附以及催化效率高,对有机染料具有较好的降解效果,在可见光照射下,能在60min内将甲基橙(MO)降解97%,该种可见光催化材料有望在光催化降解有机染料、抗生素等领域得到大规模的应用。
Description
技术领域
本发明属于光催化领域,涉及一种光催化剂,具体来说是一种In2S3/UiO-66核壳结构可见光催化剂的制备方法。
背景技术
随着工业化进程加剧,环境污染成为当今社会一个越来越严重的问题,其中,水体污染尤其严重。工业用水和生活污水的大量排放,使得水体中污染物含量逐渐增大,严重威胁到人类健康以及生态平衡。而其中的有机污染物,因其具有毒性高,浓度大和难降解等特点而尤其危害严重。在解决水体污染问题的众多手段中,光催化降解因其降解效率高、不产生二次污染物以及节能环保的优点而被认为是最具前景的方法。在过去的几十年间,半导体材料在光催化领域受到了越来越多的关注,但是,单一组分的半导体材料存在较多缺点,如光响应范围小、稳定性差以及催化效率低等,这些缺点使得其已不能满足实际功能应用的需求,因此,开发出性能优异、环境友好和制备方法简单的复合半导体光催化材料迫在眉睫。
金属有机框架材料(MOFs)是一类由金属中心离子和有机配体通过自组装形成的三维网状晶体材料,因其具有孔隙率高、比表面积大以及可功能修饰等优点,而被广泛研究应用于催化、气体存储及药物传输等领域。此外,MOFs本身也具有半导体性质,但是,大多数MOFs材料的能带间隙较宽,导致其只能对紫外光进行响应。因此,研究人员致力于将MOFs材料与半导体材料复合,希望得到一种稳定性好,可见光响应,催化效率高的复合光催化剂。UiO-66是一种由锆(IV)离子和对苯二甲酸自组装形成的MOFs材料,研究表明,UiO-66的比表面积可达1347.9m2g-1,在450℃时依然保持结构稳定,并且在水中具有较好的稳定性,这些优点使得UiO-66被广泛研究于催化领域,例如光催化降解有机染料、光解水制氢以及催化有机合成反应等。
硫化铟(In2S3)是重要的III-VA族硫化物,是典型的III-VI型半导体,In2S3存在三种晶相结构:缺陷立方结构α-In2S3,缺陷尖晶石结构β-In2S3和层状结构γ-In2S3,其中,β-In2S3是典型的n-型半导体,具有高载流子迁移率、低毒性和高稳定性的特点。β-In2S3的带隙宽度约为1.9-2.2eV,可对较宽范围内的可见光响应,因此,β-In2S3在太阳能染料电池、可见光降解有机染料以及光解水制氢等方面有着广泛的应用。但是,单一的In2S3在受光照后,光生载流子容易重新复合,使得催化效率降低;并且,颗粒状的In2S3容易发生团聚,使得比表面积减少,从而使光催化反应时活性位点减少,催化效率降低,且不易回收再利用;此外,铟盐价格相对昂贵,这些缺点限制了单一组分的In2S3在实际中的大规模应用。为此,科研人员进行了许多研究。
专利CN 103990486 A中公布了一种In2S3/g-C3N4复合纳米材料的制备方法,在降解亚甲基蓝(MB)的实验中,该种复合可见光催化剂比单一的In2S3有更好的降解效果,但是g-C3N4的制备需在550℃高温下通过煅烧尿素获得,制备工艺复杂,成本较高,不利于节能环保;专利CN 106732686 A中公布了一种硫化铟掺杂溴氧化铋复合光催化剂的制备方法,在该种复合催化剂中,光生电子可以从高费米能级的硫化铟迁移至低费米能级的溴氧化铋上,一定程度上抑制光生载流子的重新复合,但是,溴氧化铋的比表面积较低,二者复合后并不能有效增加反应活性位点,该复合光催化剂在可见光下90min内对10mg/L的罗丹明B的降解率为88.5%,其催化效率仍然有待提高,且容易发生团聚,不利于回收再利用。目前,关于In2S3/UiO-66复合光催化剂还未见相关文献报道。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种核壳结构可见光催化剂的制备方法,所述的这种核壳结构可见光催化剂主要解决现有技术中的可见光催化剂制备工艺复杂,制备条件苛刻以及催化效果有限的技术问题。
本发明提供了一种核壳结构可见光催化剂的制备方法,包括如下步骤:
1)按照ZrCl4和对苯二甲酸的摩尔比为1:1~1.2的比例分别称取ZrCl4和对苯二甲酸,分散于N,N-二甲基甲酰胺中,然后,按照N,N-二甲基甲酰胺与乙酸的体积比为10~12:1的比例加入乙酸,搅拌后移至微波反应釜中,反应温度为120~160℃,反应时间为0.5~1.5h。反应结束后待冷却至室温,抽滤,并用N,N-二甲基甲酰胺和去离子水交替洗涤1-4次,干燥研磨后获得UiO-66基体材料;
2) 将UiO-66基体材料分散在去离子水中,按照In(NO3)3•5H2O和UiO-66的质量比为0.5~1:1的比例将In(NO3)3•5H2O加入到UiO-66的水分散液中,搅拌后,按照十二胺、硫单质、木质素磺酸钠与In(NO3)3•5H2O的摩尔比为0.1~0.3:1.5~3:0.1~0.3:1的比例依次加入上述物质,并用0.5mol/L的硝酸将体系PH调至3;
3)将步骤3)的混合液在120-160℃的油浴锅中回流反应12-16h,反应结束后待冷却至室温,抽滤,并用去离子水和乙醇交替洗涤1-4次,干燥研磨后获得In2S3/UiO-66核壳结构可见光催化材料。
本发明创新性提出利用微波辅助的方式合成形状规则的UiO-66基体材料,并通过十二胺的弱的还原作用,将单质硫还原为能与In3+结合的S2-离子,同时使用了木质素磺酸钠作为UiO-66的包覆剂,使得形成的In2S3纳米颗粒能均匀负载在UiO-66的表面。该种复合材料一方面具备In2S3可见光响应,光生载流子迁移率高的特点,另一方面具备UiO-66结构稳定,孔隙率高,比表面积大特点。同时,在受光照后,光生电子由In2S3的导带向UiO-66的导带转移,延长了光生电子的转移路径,抑制了光生电子-光生空穴的重新复合,另一方面,In2S3由于负载在UiO-66表面,减少了团聚现象,增加了反应活性位点,这些使得复合材料的光催化能力得到较大的提高。此外,相对于单一组分的In2S3,In2S3/UiO-66复合材料更利于回收再利用。这些优点使In2S3/UiO-66核壳结构可见光催化材料在光催化领域有极大的应用价值。
本发明先通过微波辅助合成法制备出UiO-66前驱体,利用UiO-66作为基体,然后,以In(NO3)3•5H2O作为铟源,利用十二胺的弱还原性将硫单质还原成S2-作为硫源,同时以木质素磺酸钠作为UiO-66的包覆剂,接着通过水热法,在木质素磺酸钠包覆的UiO-66表面原位生长In2S3纳米颗粒,得到以UiO-66为核,In2S3纳米颗粒为壳的In2S3/UiO-66核壳结构可见光催化材料。本发明和已有发明相比,进步是显著的。本发明的In2S3/UiO-66核壳结构可见光催化材料制备工艺简单,制备条件温和,环保无污染,设备要求低,可操作性强。本发明的In2S3/UiO-66核壳结构可见光催化材料在可见光驱动下对有机污染物,以及抗生素等具有良好的降解效果,无二次污染物产生,可大规模工业化应用。
附图说明
图1实施例1,2,3的 XRD图。
图2实施例1,2,3的UV-vis图。
图3实施例2的SEM图。
具体实施方式
下面通过具体实施例对本发明进一步阐述,但并不限制本发明。
本发明中,采用15mg/L的甲基橙作为目标降解物,以加装滤光片(λ>420nm)的500W氙灯作为光源,考察光催化剂的催化性能。在光照之前,先在暗处搅拌40min,使体系达到吸-脱附平衡。光催化实验是在一个特制的双层容器中进行,容器隔层通有循环水以保证体系温度保持在室温,同时加以磁力搅拌。每隔10分钟取3mL反应液,使用离心机在8000rpm离心5分钟,将上清液用0 .22微米的过滤器过滤,利用岛津UV-3600紫外分光光度计检测,根据溶液465nm处吸光度的变化来确定溶液中甲基橙的浓度变化。
实施例1
1)按照ZrCl4和对苯二甲酸(H2BDC)的摩尔比为1:1的比例分别称取ZrCl4和对苯二甲酸,分散于N,N-二甲基甲酰胺中,然后,按照N,N-二甲基甲酰胺与乙酸的体积比为10:1的比例加入乙酸,搅拌30min后移至微波反应釜中,反应温度为120℃,反应时间为0.5h。反应结束后待冷却至室温,抽滤,并用N,N-二甲基甲酰胺和去离子水交替洗涤三次,干燥研磨后获得UiO-66基体材料。
2)将UiO-66分散在去离子水中,按照In(NO3)3•5H2O和UiO-66的质量比为0.5:1的比例将In(NO3)3•5H2O加入到UiO-66的水分散液中,搅拌30min后,按照十二胺、硫单质、木质素磺酸钠与In(NO3)3•5H2O的摩尔比为0.1:1.5:0.1:1的比例依次加入上述物质,并用0.5mol/L的硝酸将体系PH调至3。
3)将上述混合液在120℃的油浴锅中回流反应12h,反应结束后待冷却至室温,抽滤,并用去离子水和乙醇交替洗涤三次,干燥研磨后获得In2S3/UiO-66核壳结构可见光催化材料。
利用德国布鲁克D8 Advance对所得样品进行XRD谱图测试,结果如图1所示,所得样品的XRD谱图中同时出现UiO-66和In2S3的特征峰,说明UiO-66和In2S3复合成功。
利用澳大利亚的Agilent Cary 5000对所得样品进行紫外-可见漫反射光谱分析,结果如图所示,所得样品在紫外-可见光范围都能进行响应,说明可用于可见光催化。
将本实施例所制备的In2S3/UiO-66核壳结构可见光催化剂,以0.5g/L的比例加入到15mg/L的甲基橙溶液中,经暗反应40min后,接着在可见光下照射下,甲基橙溶液在60min内可降解96%。
实施例2
1) 按照ZrCl4和对苯二甲酸(H2BDC)的摩尔比为1~1的比例分别称取ZrCl4和对苯二甲酸,分散于N,N-二甲基甲酰胺中,然后,按照N,N-二甲基甲酰胺与乙酸的体积比为10~11:1的比例加入乙酸,搅拌后30min移至微波反应釜中,反应温度为140℃,反应时间为1h。反应结束后待冷却至室温,抽滤,并用N,N-二甲基甲酰胺和去离子水交替洗涤三次,干燥研磨后获得UiO-66基体材料。
2) 将UiO-66分散在去离子水中,按照In(NO3)3•5H2O和UiO-66的质量比为0.75:1的比例将In(NO3)3•5H2O加入到UiO-66的水分散液中,搅拌后,按照十二胺、硫单质、木质素磺酸钠与In(NO3)3•5H2O的摩尔比为0.2:2:0.2:1的比例依次加入上述物质,并用0.5mol/L的硝酸将体系PH调至3。
3)将上述混合液在140℃的油浴锅中回流反应14h,反应结束后待冷却至室温,抽滤,并用去离子水和乙醇交替洗涤三次,干燥研磨后获得In2S3/UiO-66核壳结构可见光催化材料。
利用德国布鲁克D8 Advance对所得样品进行XRD谱图测试,结果如图1所示,所得样品的XRD谱图中同时出现UiO-66和In2S3的特征峰,说明UiO-66和In2S3复合成功。
利用澳大利亚的Agilent Cary 5000对所得样品进行紫外-可见漫反射光谱分析,结果如图所示,所得样品在紫外-可见光范围都能进行响应,说明可用于可见光催化。
利用日本的Hitachi S-4800 II对所得样品进行SEM形貌分析,结果如图2所示,UiO-66位正八面体形状,分散良好, In2S3纳米颗粒均匀的负载在UiO-66表面,没有发生明显的团聚。
将本实施例所制备的In2S3/UiO-66核壳结构可见光催化剂,以0.5g/L的比例加入到15mg/L的甲基橙溶液中,经暗反应40min后,接着在可见光下照射下,甲基橙溶液在60min可降解97%。
实施例3
1) 按照ZrCl4和对苯二甲酸(H2BDC)的摩尔比为1:1.2的比例分别称取ZrCl4和对苯二甲酸,分散于N,N-二甲基甲酰胺中,然后,按照N,N-二甲基甲酰胺与乙酸的体积比为12:1的比例加入乙酸,搅拌后移至微波反应釜中,反应温度为160℃,反应时间为1.5h。反应结束后待冷却至室温,抽滤,并用N,N-二甲基甲酰胺和去离子水交替洗涤三次,干燥研磨后获得UiO-66基体材料。
2) 将UiO-66分散在去离子水中,按照In(NO3)3•5H2O和UiO-66的质量比为1:1的比例将In(NO3)3•5H2O加入到UiO-66的水分散液中,搅拌后,按照十二胺、硫单质、木质素磺酸钠与In(NO3)3•5H2O的摩尔比为0.3:3:0.3:1的比例依次加入上述物质,并用0.5mol/L的硝酸将体系PH调至3。
3)将上述混合液在160℃的油浴锅中回流反应16h,反应结束后待冷却至室温,抽滤,并用去离子水和乙醇交替洗涤三次,干燥研磨后获得In2S3/UiO-66核壳结构可见光催化材料。
利用德国布鲁克D8 Advance对所得样品进行XRD谱图测试,结果如图1所示,所得样品的XRD谱图中同时出现UiO-66和In2S3的特征峰,说明UiO-66和In2S3复合成功。
利用澳大利亚的Agilent Cary 5000对所得样品进行紫外-可见漫反射光谱分析,结果如图所示,所得样品在紫外-可见光范围都能进行响应,说明可用于可见光催化。
将本实施例所制备的In2S3/UiO-66核壳结构可见光催化剂,以0.5g/L的比例加入到15mg/L的甲基橙溶液中,经暗反应40min后,接着在可见光下照射下,甲基橙溶液在60min内可降解95%。
Claims (1)
1.一种核壳结构可见光催化剂的制备方法,其特征在于包括如下步骤:
1)按照ZrCl4和对苯二甲酸的摩尔比为1:1~1.2的比例分别称取ZrCl4和对苯二甲酸,分散于N,N-二甲基甲酰胺中,然后,按照N,N-二甲基甲酰胺与乙酸的体积比为10~12:1的比例加入乙酸,搅拌后移至微波反应釜中,反应温度为120~160℃,反应时间为0.5~1.5h,反应结束后待冷却至室温,抽滤,并用N,N-二甲基甲酰胺和去离子水交替洗涤1-4次,干燥研磨后获得UiO-66基体材料;
2)将UiO-66基体材料分散在去离子水中,按照In(NO3)3•5H2O和UiO-66的质量比为0.5~1:1的比例将In(NO3)3•5H2O加入到UiO-66的水分散液中,搅拌后,按照十二胺、硫单质、木质素磺酸钠与In(NO3)3•5H2O的摩尔比为0.1~0.3:1.5~3:0.1~0.3:1的比例依次加入上述物质,并用0.5mol/L的硝酸将体系p H调至3;
3)将步骤3)的混合液在120-160℃的油浴锅中回流反应12-16h,反应结束后待冷却至室温,抽滤,并用去离子水和乙醇交替洗涤1-4次,干燥研磨后获得In2S3/UiO-66核壳结构可见光催化材料。
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Application publication date: 20181113 Assignee: SHANGHAI SUPERHIGH ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. Assignor: SHANGHAI INSTITUTE OF TECHNOLOGY Contract record no.: X2022310000099 Denomination of invention: A kind of preparation method of visible light catalyst of core-shell structure Granted publication date: 20210420 License type: Common License Record date: 20220830 |