CN111841620B - 一种毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)及其制备方法与应用 - Google Patents
一种毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)及其制备方法与应用 Download PDFInfo
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- CN111841620B CN111841620B CN202010579105.2A CN202010579105A CN111841620B CN 111841620 B CN111841620 B CN 111841620B CN 202010579105 A CN202010579105 A CN 202010579105A CN 111841620 B CN111841620 B CN 111841620B
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 69
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Abstract
本发明公开了一种毫米级过一硫酸氢盐活化剂ZSM‑5‑(C@Fe)及其制备方法与应用。该方法首次合成毫米级稳定结构的PMS活化剂ZSM‑5‑(C@Fe),利用ZSM‑5易于羧基化的特性和金属有机骨架材料(MOFs)中的游离的羧基聚合,然后在氮气的氛围下热解,形成了既有ZSM‑5极佳水稳定性,又有热解MOFs形成的具有活化位点的Fe掺杂C结构的新型毫米级PMS活化剂。该催化剂活化效果良好,易于回收循环使用,在降解持久性有机污染物方面具有很大的应用前景。
Description
技术领域
本发明属于水污染控制技术领域,具体涉及毫米级过一硫酸氢盐(PMS)活化剂ZSM-5-(C@Fe)的制备及降解新兴污染物的方法。
背景技术
新兴污染物(ECs)一般是指没有排放标准,但由于其潜在的危害而被纳入控制对象的一类有机污染物。近年来,随着农药、抗生素和化妆品的广泛应用,地表水中ECs明显增多,对水生环境造成了巨大的威胁。然而,由于ECs具有稳定的化学结构和生物蓄积的特性,生物处理工艺不能有效地去除废水中的ECs。因此,高级氧化技术作为有效的废水三级处理技术引起了人们的注意。
随着研究的深入,利用碳基为主的非均相催化剂活化PMS不仅可以产生硫酸根(SO4 -·)为基础自由基降解路径,还可以发生以单线氧(1O2)为基础的非自由基降解路径,可以高速降解废水中的ECs。在传统方法中,碳基材料的元素掺杂(Fe,N,S)往往是提高非均相催化剂活性的主要方法,非金属元素掺杂形成的催化剂在氧化降解过程中容易发生副反应(W.Tian,H.Zhang,X.Duan,H.Sun,M.O.Tade,H.M.Ang,S.Wang,Nitrogen-and Sulfur-Codoped Hierarchically Porous Carbon for Adsorptive and Oxidative Removal ofPharmaceutical Contaminants,(2016).doi:10.1021/acsami.6b01748.),而Fe的现有掺杂方法大多为浸渍法,这种方法掺杂的Fe容易脱落(M.Pagano,A.Volpe,G.Mascolo,A.Lopez,V.Locaputo,R.Ciannarella,Chemosphere Peroxymonosulfate–Co(II)oxidation system for the removal of the non-ionic surfactant Brij 35fromaqueous solution,Chemosphere.86(2012)329–334.doi:10.1016/j.chemosphere.2011.09.010.),因此目前的技术易于造成催化剂的失活,制约了催化剂的循环使用情况。此外,现有的非均相催化剂均为纳米级别材料,在水处理工艺中无论是形成流化床结构还是制作专门的反应器中,均极易流失,造成催化剂的浪费(G.Ye,Z.Yu,Y.Li,L.Li,L.Song,L.Gu,X.Cao,Ef fi cient treatment of brine wastewater through aflow-through technology integrating desalination and photocatalysis,157(2019)134–144.doi:10.1016/j.watres.2019.03.058.)。因此,合成一种毫米级别的稳定的PMS活化剂对PMS高级氧化体系的工业推广至关重要。
发明内容
本发明的目的是针对传统碳基材料的元素掺杂方法的不稳定且多为纳米材料,极易发生副反应、脱落等现象造成催化剂的失活,供一种毫米级PMS盐活化剂ZSM-5-(C@Fe)的制备及降解新兴污染物的方法。
本发明提供的制备方法,成功首次合成毫米级PMS活化剂ZSM-5-(C@Fe),在活化PMS高效降解新兴污染物的实验中取得了良好解效果。
本发明的目的至少采用如下技术方案之一实现。
本发明提供的一种毫米级PMS活化剂ZSM-5-(C@Fe)的制备方法,包括如下步骤:
(1)利用羧基化的方法预处理ZSM-5,得到ZSM-5-COOH;
(2)利用热法合成亚铁基金属有机骨架材料,得到前驱体Fe(II)-MOF-74;
(3)将步骤(1)所述ZSM-5-COOH和二甲基丙烯酸乙二醇酯分散于乙腈中,混合均匀,得到混合溶液;将步骤(2)所述前驱体Fe(II)-MOF-74加入所述混合溶液中,在引发剂的作用下进行搅拌反应,过滤取沉淀,所述沉淀为颗粒状,洗涤,在真空炉中进行真空干燥,得到ZSM-5-MOFs(白色前驱体);
(4)在氮气气氛下,将步骤(3)所述ZSM-5-MOFs升温进行高温热解处理,得到所述毫米级PMS活化剂ZSM-5-(C@Fe)。
进一步地,步骤(3)所述ZSM-5-COOH与前驱体Fe(II)-MOF-74的质量比为10:1-10:2。
进一步地,步骤(3)所述ZSM-5-COOH与乙腈的质量体积比为(5-15):100g/mL。
进一步地,步骤(3)所述二甲基丙烯酸乙二醇酯与乙腈的摩尔体积比为(25-75):100mmol/mL。
进一步地,步骤(3)所述搅拌反应的温度为40-80℃;搅拌反应的时间为20-28h。
进一步地,步骤(3)所述引发剂为偶氮二异丁腈。
优选地,步骤(3)所述引发剂的加入量为10-20mg。
优选地,步骤(3)所述洗涤为用甲醇洗涤。
进一步地,步骤(3)所述真空干燥的温度为50-80℃,真空干燥的时间为10-12小时。
进一步地,步骤(4)所述高温热解处理的温度为400-600℃,高温热解处理的时间为1-3h。
本发明提供一种由上述的制备方法制得的毫米级PMS活化剂ZSM-5-(C@Fe)。本发明得到的毫米级PMS活化剂ZSM-5-(C@Fe)为毫米级黑色固体小球,球径为1-5mm。
本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)在处理废水中ECs的应用,包括如下步骤:
向含有ECs的废水中加入所述毫米级PMS活化剂ZSM-5-(C@Fe)和PMS,然后在摇床中进行催化活化反应(常温条件下),得到处理后的废水。
本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)在处理废水中ECs的应用中,所述PMS(PMS)与废水中的ECs的摩尔比为10:1-50:1;所述毫米级PMS活化剂ZSM-5-(C@Fe)的投加量为1-5g L-1;所述ECs为四溴双酚A、磺胺甲恶挫、三氯苯酚及环丙沙星中一种以上;所述摇床的转速为50-200rpm,催化活化反应的时间为10-30min。
优选地,催化活化反应的时间为15min。
优选地,所述ZSM-5-(C@Fe)的投加量为4g L-1。
优选地,所述PMS与废水中的ECs的摩尔比为40:1。
本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)在处理废水中ECs的应用中,是利用ZSM-5-(C@Fe)上的活化位点活化PMS,在常温下产生强氧化性的硫酸根自由基和单线氧,降解废水中新兴污染物。
本发明提供的ZSM-5-(C@Fe)具有优秀的活化能力去除水中ECs,而且所述ZSM-5-(C@Fe)结构稳定,易于回收,可以多次循环利用。
本发明中利用ZSM-5易于羧基化的特性和金属有机骨架材料(MOFs)中的游离的羧基聚合,然后在氮气的氛围下热解,形成了既有ZSM-5极佳水稳定性,又有热解MOFs形成的具有活化位点的Fe掺杂C结构的新型毫米级PMS活化剂ZSM-5-(C@Fe)。ZSM-5-(C@Fe)可以在水处理过程中稳定的存在,不易流失,经过多次重复利用后活化效果依然很好。利用Fe掺杂C形成的活化稳点,既可以产生以硫酸根自由基为主的自由基降解途径,也可以产生以单线氧为主的非自由基降解途径,提高了活化效率和新兴污染物的降解速率。
本发明中,利用ZSM-5极佳的水稳定性和易于羧基化的特性、热解金属有机骨架材料(MOFs)可形成稳定的Fe掺杂C材料的特性首次合成毫米级PMS活化剂ZSM-5-(C@Fe),该催化剂具有可以高效活化位点的C@Fe结构,同时也具有高水稳定性结构的ZSM-5结构,在实现新兴污染物高效降解的同时,也能持续的循环使用,为处理持久性有机污染物提供了广泛的应用前景。
与现有技术相比,本发明具有如下优点和有益效果:
(1)本发明首次提供了合成毫米级PMS活化剂ZSM-5-(C@Fe)的制备方法;
(2)本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)具有良好的水稳定性,易于回收循环使用;
(3)本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)增强了PMS的活化能力,加快了新兴污染物的去除效率;
(4)本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)对目标污染物无选择性,适用性广泛;
(5)本发明提供的毫米级PMS活化剂ZSM-5-(C@Fe)应用于催化活化PMS处理ECs的方法,不需要额外附件能量,降低了成本;而且工艺流程十分简单,效果好,时间短,具有广阔的实际应用前景。
附图说明
图1为实例1中ZSM-5-(C@Fe)的X射线晶体衍射图(XRD);
图2为实例1中ZSM-5-(C@Fe)的扫描电镜图(SEM)。
具体实施方式
以下结合实例对本发明的具体实施作进一步说明,但本发明的实施和保护不限于此。需指出的是,以下若有未特别详细说明之过程,均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者,视为可以通过市售购买得到的常规产品。
实施例1
本实施例考察制备的ZSM-5-(C@Fe)具有良好的降解新兴污染物的能力。
(1)ZSM-5-(C@Fe)的制备:将10g ZSM-5、150mmol 3-氨基丙基三乙氧基硅烷和150mmol顺丁烯二酸酐均匀分散于100mLN,N-二甲基甲酰胺中,室温下搅拌24h;然后用甲醇洗涤颗粒样品,50℃干燥12h,得到前驱体ZSM-5-COOH。分别取对苯二甲酸(1.065g)与FeCl2·4H2O(2.65g)置于500ml的三口瓶中,加入250ml的N,N-二甲基甲酰胺使其溶解,再次加入30ml甲醇,逐滴加入8ml氢氟酸使溶液呈淡绿色,然后加热到140℃,反应24h,得到亚铁MOFs前驱体(Fe(II)-MOF-74)。将10gZSM-5-COOH和50mmol二甲基丙烯酸乙二醇酯分散于100mL乙腈中,得到混合溶液。然后将1gFe(II)-MOF-74和20mg偶氮二异丁腈放入所述混合溶液中,在60℃下搅拌24h。过滤出颗粒状样品,用甲醇洗涤,然后在50℃的真空炉中干燥12小时,得到白色前驱体ZSM-5-MOFs。然后将ZSM-5-MOFs在管式炉中进行高温热解,在氮气氛围下,热解温度为500℃热解2h,最终得到所述毫米级PMS活化剂ZSM-5-(C@Fe)。图1为实例1中ZSM-5-(C@Fe)的X射线晶体衍射图(XRD),发现ZSM-5-(C@Fe)具有ZSM-5和Fe两种晶体的特征峰;图2为实例1中ZSM-5-(C@Fe)的扫描电镜图(SEM),发现ZSM-5-(C@Fe)的毫米小球的表面分布了微米级的棒状结构。
(2)配制浓度为0.036mmol L-1的环丙沙星溶液作为ECs污染物,备用;
(3)采用锥形瓶为反应器,向反应器1中分别加入的100mL环丙沙星溶液(浓度为0.036mol L-1),往反应器1中加入0.036mmolPMS和0.05g ZSM-5,将反应器放置在180rpm的摇床中,在常温(25℃)进行降解反应。
(4)反应器2中加入0.1g ZSM-5-COOH,但不加入ZSM-5,其他条件同步骤(3)。
(5)反应器3中加入0.1g ZSM-5-MOFs,但不加入ZSM-5,其他条件同步骤(3)。
(6)反应器4中加入0.1g ZSM-5-(C@Fe),但不加入ZSM-5,其他条件同步骤(3)。
不同催化剂下环丙沙星的去除率如表1所示。
表1
由表1可知:ZSM-5-(C@Fe)催化活化PMS降解环丙沙星的去除效果十分显著,这是由于ZSM-5-(C@Fe)中的活化位点既可以产生以硫酸根自由基为主的自由基降解途径,也可以产生以单线氧为主的非自由基降解途径,提高了活化效率和新兴污染物的降解速率。
实施例2
本实施例比较ZSM-5-(C@Fe)的投加量对催化活化降解环丙沙星的影响。
(1)ZSM-5-(C@Fe)的制备方法同实施例1中的步骤(1);
(2)配制0.036mmol L-1的环丙沙星溶液备用;
(3)采用锥形瓶为反应器,向反应器1中加入0.036mmolPMS和浓度为0.036mmol L-1环丙沙星溶液100mL,同时往反应器中投加0.1g ZSM-5-(C@Fe),将锥形瓶放置在180rpm的摇床中,在常温(25℃)条件下进行反应,定点取样分析;
(4)反应器2中ZSM-5-(C@Fe)的加入量变为0.2g,其他条件同(3);
(5)反应器3中ZSM-5-(C@Fe)的加入量变为0.3g,其他条件同(3);
(6)反应器4中ZSM-5-(C@Fe)的加入量变为0.4g,其他条件同(3);
(7)反应器5中ZSM-5-(C@Fe)的加入量变为0.5g,其他条件同(3);
不同ZSM-5-(C@Fe)的投加量下的环丙沙星去除率如下表2所示。
表2
由表2可知:在30min时,随着ZSM-5-(C@Fe)投加量越来越大,降解效率先是上升,当催化剂投加量达到0.4g以后呈现平缓趋势,从反应效率和成本方面考虑在ZSM-5-(C@Fe)的投加量为4gL-1时,是最佳选择。
实施例3
本实施例比较PMS和环丙沙星的摩尔比不同对ZSM-5-(C@Fe)催化活化反应的影响。
(1)ZSM-5-(C@Fe)的制备方法同实施例1中的步骤(1);
(2)配制0.036mmol L-1的环丙沙星溶液备用;
(3)采用锥形瓶为反应器,向反应器1中加入0.036mmolPMS和浓度为0.036mmol L-1环丙沙星溶液100mL,同时往反应器中投加0.4g ZSM-5-(C@Fe),将锥形瓶放置在180rpm的摇床中,在常温(25℃)条件下进行反应,定点取样分析;
(4)反应器2中PMS的加入量变为0.072mmol,其他条件同(3);
(5)反应器3中PMS的加入量变为0.108mmol,其他条件同(3);
(6)反应器4中PMS的加入量变为0.144mmol,其他条件同(3);
(7)反应器5中PMS的加入量变为0.180mmol,其他条件同(3);
不同PMS和环丙沙星的摩尔比下ZSM-5-(C@Fe)催化活化PMS降解环丙沙星的去除率如表3所示。
表3
由表3可知:随着n PMS/n环丙沙星比值增大,环丙沙星去除速率呈现先上升后下降趋势,当比例超过40:1(摩尔比)以后,去除速率增长缓慢,从反应效率和成本方面考虑,nPMS/n环丙沙星=40:1是最佳选择。
实施例4
本实施例考察ZSM-5-(C@Fe)活化PMS降解4种ECs的效果。
(1)ZSM-5-(C@Fe)的制备方法同实施例1中的步骤(1);
(2)分别配制浓度为0.036mmol L-1的四溴双酚A溶液、磺胺甲恶挫溶液、三氯苯酚溶液和环丙沙星溶液作为ECs污染物备用;
(3)采用锥形瓶为反应器,向反应器1中加入0.144mmolPMS和浓度为0.036mmol L-1环丙沙星溶液100mL,同时往反应器中投加0.4g ZSM-5-(C@Fe),将锥形瓶放置在180rpm的摇床中,在常温(25℃)条件下进行反应,定点取样分析;
(4)反应器2中加入0.036mmol L-1四溴双酚A溶液100mL,不加环丙沙星溶液,其他条件同(3);
(5)反应器3中加入0.036mmol L-1磺胺甲恶挫溶液100mL,不加环丙沙星溶液,其他条件同(3);
(6)反应器4中加入0.036mmol L-1三氯苯酚溶液100mL,不加环丙沙星溶液,其他条件同(3);
ZSM-5-(C@Fe)活化PMS降解4种ECs的效果如下表4所示。
表4
由表4可知:在30min时,ZSM-5-(C@Fe)催化活化PMS降解多种ECs的去除效果均比较良好。
实施例5
本实施例考察ZSM-5-(C@Fe)催化活化PMS降解四溴双酚A反应的循环利用情况。
(1)ZSM-5-(C@Fe)的制备方法同实施例1中的步骤(1);
(2)0.036mmol L-1环丙沙星溶液备用;
(3)采用锥形瓶为反应器,向反应器1中加入0.144mmolPMS和浓度为0.036mmol L-1环丙沙星溶液100mL,同时往反应器中投加0.4g ZSM-5-(C@Fe),将锥形瓶放置在180rpm的摇床中,在常温(25℃)条件下进行反应,定点取样分析;
(4)步骤(3)结束后,回收反应器1中的ZSM-5-(C@Fe),继续进行降解反应,条件如(3);
(5)步骤(4)结束后,回收反应器1中的ZSM-5-(C@Fe),继续进行降解反应,条件如(3);
(6)步骤(5)结束后,回收反应器1中的ZSM-5-(C@Fe),继续进行降解反应,条件如(3);
(7)步骤(6)结束后,回收反应器1中的ZSM-5-(C@Fe),继续进行降解反应,条件如(3)。
五种工艺得到的环丙沙星的去除率如表5所示。
表5
由表5可知:ZSM-5-(C@Fe)催化活化PMS降解环丙沙星的循环降解实验中,可以明显的发现,随着循环次数的增加,环丙沙星去除率基本保持稳定,并且催化剂几乎可以完全回收,因此ZSM-5-(C@Fe)可以在多次循环后仍能有效的催化活化PMS降解ECs。
以上实施例仅为本发明较优的实施方式,仅用于解释本发明,而非限制本发明,本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。
Claims (10)
1.一种毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,包括如下步骤:
(1)利用羧基化的方法预处理ZSM-5,得到ZSM-5-COOH;
(2)利用溶剂热法合成亚铁基金属有机骨架材料,得到前驱体Fe(II)-MOF-74;
(3)将步骤(1)所述ZSM-5-COOH和二甲基丙烯酸乙二醇酯分散于乙腈中,混合均匀,得到混合溶液;将步骤(2)所述前驱体Fe(II)-MOF-74加入所述混合溶液中,在偶氮二异丁腈的作用下进行搅拌反应,过滤取沉淀,洗涤,真空干燥,得到ZSM-5-MOFs;
(4)在氮气气氛下,将步骤(3)所述ZSM-5-MOFs升温进行高温热解处理,得到所述毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe);所述高温热解处理的温度为400-600℃;
所述过一硫酸氢盐活化剂ZSM-5-(C@Fe)用于处理废水中新兴污染物。
2.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(3)所述ZSM-5-COOH与前驱体Fe(II)-MOF-74的质量比为10 : 1 - 10:2。
3.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(3)所述ZSM-5-COOH与乙腈的质量体积比为(5 -15):100 g/mL。
4.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(3)所述二甲基丙烯酸乙二醇酯与乙腈的摩尔体积比为(25-75):100 mmol/mL。
5.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(3)所述搅拌反应的温度为40-80 ℃;搅拌反应的时间为20-28 h。
6.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(3)所述真空干燥的温度为50-80℃,真空干燥的时间为10-12小时。
7.根据权利要求1所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的制备方法,其特征在于,步骤(4)中所述高温热解处理的时间为1-3 h。
8.一种由权利要求1-7任一项所述的制备方法制得的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)。
9.权利要求8所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)在处理废水中新兴污染物的应用,其特征在于,包括如下步骤:
向含有新兴污染物的废水中加入所述毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)和过一硫酸氢盐,然后在摇床中进行催化活化反应,得到处理后的废水。
10.根据权利要求9所述的毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)在处理废水中新兴污染物的应用,其特征在于,所述过一硫酸氢盐与废水中的新兴污染物的摩尔比为10:1-50:1;所述毫米级过一硫酸氢盐活化剂ZSM-5-(C@Fe)的投加量为1-5 g· L-1;所述新兴污染物为四溴双酚A、磺胺甲恶唑、三氯苯酚及环丙沙星中一种以上;所述摇床的转速为50-200 rpm,催化活化反应的时间为10-30 min。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105148882A (zh) * | 2015-06-30 | 2015-12-16 | 河北大学 | 一种金属有机骨架材料为壳的核壳型亲水色谱固定相及其制备方法与应用 |
US9308517B1 (en) * | 2013-03-15 | 2016-04-12 | The United States Of America As Represented By The Secretary Of The Army | Composite filtration media for removing broad spectrum toxic chemicals |
CN106957438A (zh) * | 2017-03-21 | 2017-07-18 | 华南理工大学 | 一种改性MIL‑53(Fe)金属有机骨架的制备及其活化过硫酸盐处理有机废水的方法 |
CN110615444A (zh) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | 一种丝光沸石分子筛、其制备方法及应用 |
CN110947385A (zh) * | 2019-11-30 | 2020-04-03 | 华南理工大学 | 一种碳封装缺陷铁纳米催化剂及其制备方法与其催化过一硫酸氢盐降解新兴污染物的应用 |
-
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2021
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9308517B1 (en) * | 2013-03-15 | 2016-04-12 | The United States Of America As Represented By The Secretary Of The Army | Composite filtration media for removing broad spectrum toxic chemicals |
CN105148882A (zh) * | 2015-06-30 | 2015-12-16 | 河北大学 | 一种金属有机骨架材料为壳的核壳型亲水色谱固定相及其制备方法与应用 |
CN106957438A (zh) * | 2017-03-21 | 2017-07-18 | 华南理工大学 | 一种改性MIL‑53(Fe)金属有机骨架的制备及其活化过硫酸盐处理有机废水的方法 |
CN110615444A (zh) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | 一种丝光沸石分子筛、其制备方法及应用 |
CN110947385A (zh) * | 2019-11-30 | 2020-04-03 | 华南理工大学 | 一种碳封装缺陷铁纳米催化剂及其制备方法与其催化过一硫酸氢盐降解新兴污染物的应用 |
Non-Patent Citations (1)
Title |
---|
Chiral Metal-Organic Framework D-His-ZIF-8@SiO2 Core-Shell Microspheres Used for HPLC Enantioseparations;Yu Yunyan et al.;《ACS APPLIED MATERIALS & INTERFACES》;20200316;第12卷(第14期);摘要、实验部分 * |
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