CN107715916A - 一种MIL‑100(Fe)纳米催化剂的制备方法及其应用 - Google Patents
一种MIL‑100(Fe)纳米催化剂的制备方法及其应用 Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013291 MIL-100 Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
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- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 9
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- 239000003054 catalyst Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000013144 Fe-MIL-100 Substances 0.000 claims 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
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Abstract
本发明涉及一种MIL‑100(Fe)纳米催化剂的制备方法及其应用,它包括以下步骤:(a)将均苯三甲酸和无机碱溶于水中形成第一溶液;(b)将铁源溶于水中形成含有Fe2+或/和Fe3+的第二溶液;(c)将所述第一溶液滴加至所述第二溶液中,搅拌反应后过滤,用乙醇冲洗,烘干,收集滤饼即可;所述均苯三甲酸、所述无机碱和铁元素的摩尔比为1:2~3.5:1~1.5。在室温条件下即可快速合成具有高度结晶的MIL‑100(Fe);反应溶剂为水,避免了大量有机溶剂的使用,且无需HF等腐蚀性极强的添加剂,反应条件温和,无需高压反应釜,操作简单,易于工业化大量合成,极大降低了MIL‑100(Fe)合成条件。
Description
技术领域
本发明属于纳米催化剂领域,涉及一种MIL-100(Fe)纳米催化剂,具体涉及一种MIL-100(Fe)纳米催化剂的制备方法及其在光降解有机染料中的应用。
背景技术
金属-有机框架材料(Metal-Organic Frameworks,MOFs)是一类由有机多配位配体连结金属离子节点或团簇形成的有机-无机杂化多孔性晶体材料,在气体存储、气体分离、催化、分子识别、化学传感器等领域取得了令人瞩目的成果。近年来,MOFs与纳米科学的交叉使得MOFs研究进入纳米领域,即金属-有机框架纳米材料(nano-scale metal-organicframeworks,NMOFs)成为新的研究热点。与传统大尺寸MOFs相比,NMOFs不仅具有传统MOFs的结构优势,如丰富的孔结构、功能化的骨架结构以及超高比表面积等特点,同时兼备形貌规则、尺寸可控、易于在溶剂中分散、结构多样、客体分子在孔隙传输迅速等独特优点。
环境污染是当今中国社会发展面临的最重大问题,其中尤以水污染最为严重,水污染治理已刻不容缓。由于工业污水、废水具有的污染物组成繁杂、污染物毒性强,以及难以生物降解等特点,导致污水治理难度大、成本高、低效高能,致使某些企业铤而走险,减排、偷排现象较为严重。因此如何高效、节能地处理水体污染是一个亟待解决的重要问题。太阳能取之不尽、用之不竭、安全可靠,是人类最理想的绿色清洁能源。开发可用于光催化降解废水中的有机染料催化剂是目前绿色化学研究领域的热点之一。得益于NMOFs优异的吸附分离、离子交换、分子识别等新颖特点,近年来,NMOFs成为废水净化技术新的研究热点,特别是具有光催化性能的NMOFs,在废水净化领域具有独特的优势。然而,目前合成MOFs的方法通常采用溶剂热或水热法,即有机配体与金属离子置于高压反应釜中或其它耐高温的密封容器中,反应温度100~200℃,反应持续数小时至数天,有机配体与金属离子通过配位自组装形成MOFs晶体。然而,有机溶剂包不仅价格昂贵,需要高压反应釜等设备,且在大量合成时容易排放大量有机污染物。因此,开发一种以水为溶剂、在室温条件下、快速合成NMOFs的方法对实现MOFs工业化应用具有极其重要的研究意义。
发明内容
本发明目的是为了克服现有技术的不足而提供一种MIL-100(Fe)纳米催化剂的制备方法。
为解决以上技术问题,本发明采取的一种技术方案是:一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将均苯三甲酸和无机碱溶于水中形成第一溶液;
(b)将铁源溶于水中形成含有Fe2+或/和Fe3+的第二溶液;
(c)将所述第一溶液滴加至所述第二溶液中,搅拌反应后过滤,用乙醇冲洗,烘干,收集滤饼即可;所述均苯三甲酸、所述无机碱和铁元素的摩尔比为1:2~3.5:1~1.5。
优化地,所述无机碱为选自NaOH和KOH中的一种或两种。
优化地,所述铁源为选自FeCl2·4H2O、FeSO4·7H2O、Fe(OAc)2、FeCl3·6H2O、Fe(NO3)3·9H2O和Fe2(SO4)3中的一种或多种组成的混合物。
进一步地,所述铁源为选自FeCl2·4H2O和FeSO4·7H2O中的一种或两种。
优化地,步骤(c)中,在10~40℃搅拌反应2~24h。
优化地,步骤(c)中,所述滴加速度为1~5滴/s。
优化地,步骤(c)中,所述均苯三甲酸和水的摩尔比为1:800~1500。
本发明的又一目的在于提供一种MIL-100(Fe)纳米催化剂的应用,MIL-100(Fe)纳米催化剂由上述制备方法制得,所述MIL-100(Fe)纳米催化剂用于光降解污水中的有机染料。
优化地,将所述MIL-100(Fe)纳米催化剂置于含有有机染料的污水中,在紫外光照射下进行搅拌即可。
进一步地,在紫外光照射前还向污水中加入H2O2
本发明带来的有益效果是:本发明MIL-100(Fe)纳米催化剂的制备方法,在室温条件下即可快速合成具有高度结晶的MIL-100(Fe);反应溶剂为水,避免了大量有机溶剂的使用,且无需HF等腐蚀性极强的添加剂,反应条件温和,无需高压反应釜,操作简单,易于工业化大量合成,极大降低了MIL-100(Fe)合成条件;所合成的MIL-100(Fe)具有高比表面积,比表面积(BET)高达1500m2/g,合成的颗粒尺寸为500~1000nm。采用该MIL-100(Fe)纳米粒子对有机染料具有超高的光降解性能,特别是对于高浓度有机染料,光降解效率高,且MIL-100(Fe)纳米粒子具有高的水稳定性,样品可重复利用。
附图说明
图1为实施例1中制得的MIL-100(Fe)SEM图;
图2为实施例1中制得的MIL-100(Fe)XRD图;
图3为实施例1中制得的MIL-100(Fe)FT-IR图;
图4为实施例1中制得的MIL-100(Fe)对罗丹明B光降解UV-Vis谱图及溶液颜色变化照片;
图5为实施例1中制得的MIL-100(Fe)对罗丹明B光降解效率图。
具体实施方式
本发明MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:(a)将均苯三甲酸和无机碱溶于水中形成第一溶液;(b)将铁源溶于水中形成含有Fe2+或/和Fe3+的第二溶液;(c)将所述第一溶液滴加至所述第二溶液中,搅拌反应后过滤,用乙醇冲洗,烘干,收集滤饼即可;所述均苯三甲酸、所述无机碱和铁元素的摩尔比为1:2~3.5:1~1.5。本发明MIL-100(Fe)纳米催化剂的制备方法,通过使均苯三甲酸和无机碱进行反应形成均苯三甲酸根离子而能与铁离子或亚铁离子进行配合形成具有高度结晶的MIL-100(Fe),该反应在室温条件下即可快速合成具有高度结晶的MIL-100(Fe),反应溶剂为水,避免了大量有机溶剂的使用,且无需HF等腐蚀性极强的添加剂,反应条件温和,无需高压反应釜,操作简单,易于工业化大量合成,极大降低了MIL-100(Fe)合成条件;所合成的MIL-100(Fe)具有高比表面积,比表面积(BET)高达1500m2/g,合成的颗粒尺寸为500~1000nm。
无机碱选用常规的即可,如可以选自NaOH和KOH中的一种或两种。铁源为选自FeCl2·4H2O、FeSO4·7H2O、Fe(OAc)2、FeCl3·6H2O、Fe(NO3)3·9H2O和Fe2(SO4)3中的一种或多种组成的混合物;优选使用FeCl2·4H2O和FeSO4·7H2O中的一种或两种。步骤(c)中,在10~40℃搅拌反应2~24h;滴加速度为常规的即可,使用滴管进行转移即可,通常为1~5滴/s。步骤(c)中,所述均苯三甲酸和水的摩尔比为1:800~1500。
上述制得的MIL-100(Fe)纳米催化剂的应用,它用于光降解污水中的有机染料。具体为:将所述MIL-100(Fe)纳米催化剂置于含有有机染料的污水中,在紫外光照射下进行搅拌即可。在紫外光照射前还优选向污水中加入H2O2。采用该MIL-100(Fe)纳米粒子对有机染料具有超高的光降解性能,特别是对于高浓度有机染料,光降解效率高,且MIL-100(Fe)纳米粒子具有高的水稳定性,样品可重复利用。
下面将结合附图对本发明优选实施方案进行详细说明:
实施例1
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将NaOH(10.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeSO4·7H2O(31.7g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌12小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。对获得的产品进行SEM、XRD和红外测试,其结果分别如图1至图3所示;可见制得的MIL-100(Fe)颗粒粒径为500-1000nm,结晶度高。
实施例2
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将NaOH(10.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeCl2·4H2O(22.6g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌10小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。
实施例3
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将NaOH(10.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeCl3·6H2O(30.7g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌10小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。
实施例4
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将KOH(14.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeSO4·7H2O(31.7g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌10小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。
实施例5
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将KOH(14.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeCl2·4H2O(30.7g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌10小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。
实施例6
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它包括以下步骤:
(a)将KOH(7.0g)、NaOH(5.0g)加入圆底烧瓶中,加250mL水溶解,将均苯三甲酸(H3btc,16.7g)分次加入,搅拌获得澄清溶液(即第一溶液);
(b)将FeCl2·4H2O(15.3g)和FeSO4·7H2O(15.3g)溶于1000mL水,得第二溶液;
(c)将第一溶液在室温(25℃)搅拌下滴加到第二溶液(使用常规的滴管滴加,约1~5滴/秒,下同),并搅拌10小时;将上述滤液过滤,用水、乙醇冲洗滤饼,烘干,收集滤饼即可。
实施例7
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它与实施例1中的步骤基本一致,不同的是:均苯三甲酸的使用量为26.3g,FeSO4·7H2O的使用量为34.75g。
实施例8
本实施例提供一种MIL-100(Fe)纳米催化剂的制备方法,它与实施例1中的步骤基本一致,不同的是:均苯三甲酸的使用量为15g,FeSO4·7H2O的使用量为29.79g。
对比例1
本例提供一与实施例1类似的方法,不同的是:未加入均苯三甲酸,最终未能得到MIL-100(Fe)纳米催化剂。
实验例1
取20mg罗丹明B溶解于适量水中,转移至100ml容量瓶中,定容,配制成200mg/l的罗丹明B溶液;取配制好的200mg/l的罗丹明B溶液50ml(6份),分别加入10mg实施例1-实施例6中制得的MIL-100(Fe)样品,再分别加入100μl H2O2,在紫外灯照射下搅拌,取不同照射时间的溶液样品,离心,利用紫外-可见分光光度计测试清液的紫外吸收谱(其中实施例1中的测试效果如图4和图5所示)。
表1g实施例1-实施例6中制得的MIL-100(Fe)样品的性能表
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种MIL-100(Fe)纳米催化剂的制备方法,其特征在于,它包括以下步骤:
(a)将均苯三甲酸和无机碱溶于水中形成第一溶液;
(b)将铁源溶于水中形成含有Fe2+或/和Fe3+的第二溶液;
(c)将所述第一溶液滴加至所述第二溶液中,搅拌反应后过滤,用乙醇冲洗,烘干,收集滤饼即可;所述均苯三甲酸、所述无机碱和铁元素的摩尔比为1:2~3.5:1~1.5。
2.根据权利要求1所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:所述无机碱为选自NaOH和KOH中的一种或两种。
3.根据权利要求1所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:所述铁源为选自FeCl2·4H2O、FeSO4·7H2O、Fe(OAc)2、FeCl3·6H2O、Fe(NO3)3·9H2O和Fe2(SO4)3中的一种或多种组成的混合物。
4.根据权利要求3所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:所述铁源为选自FeCl2·4H2O和FeSO4·7H2O中的一种或两种。
5.根据权利要求1所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:步骤(c)中,在10~40℃搅拌反应2~24h。
6.根据权利要求1所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:步骤(c)中,所述滴加速度为1~5滴/s。
7.根据权利要求1所述MIL-100(Fe)纳米催化剂的制备方法,其特征在于:步骤(c)中,所述均苯三甲酸和水的摩尔比为1:800~1500。
8.一种MIL-100(Fe)纳米催化剂的应用,所述MIL-100(Fe)纳米催化剂由权利要求1至7中任一所述MIL-100(Fe)纳米催化剂的制备方法制得,其特征在于:所述MIL-100(Fe)纳米催化剂用于光降解污水中的有机染料。
9.根据权利要求8所述MIL-100(Fe)纳米催化剂的应用,其特征在于:将所述MIL-100(Fe)纳米催化剂置于含有有机染料的污水中,在紫外光照射下进行搅拌即可。
10.根据权利要求9所述MIL-100(Fe)纳米催化剂的应用,其特征在于:在紫外光照射前还向污水中加入H2O2。
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