CN113042105B - 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法 - Google Patents
一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法 Download PDFInfo
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- CN113042105B CN113042105B CN202110387237.XA CN202110387237A CN113042105B CN 113042105 B CN113042105 B CN 113042105B CN 202110387237 A CN202110387237 A CN 202110387237A CN 113042105 B CN113042105 B CN 113042105B
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Abstract
本发明涉及一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,该方法是指:首先制备钴离子分散液和配体溶液;然后将羟基磷灰石纳米线加入到钴离子分散液中,超声分散形成均一的粉色悬浮溶液;其次以100~1600 r/min的磁力搅拌速度下,在粉色悬浮溶液中逐滴加入配体溶液,继续搅拌后,得到紫色悬浮体系,该紫色悬浮体系经室温静置、离心分离,得到紫色产物;最后,紫色产物经洗涤、真空干燥至恒重即得。本发明方法简单、成本低廉,所得的串珠状催化剂应用于催化活化过一硫酸盐降解抗生素、有机染料等典型的有机污染物时,其表现出优异的降解去除率与循环稳定性。
Description
技术领域
本发明涉及复合材料科学领域和污染废水处理技术领域,尤其涉及一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法。
背景技术
水环境保护是当前人类社会广泛关注的一个问题,随着我国国民经济的快速发展,高浓度的有机废水对我国宝贵的水资源造成了严重威胁。有机污染物的种类多样、性质和污染源广泛,比如染料(罗丹明B(RhB)、亚甲基兰(MB)、结晶紫(CV)、酸性橙(AO7)、茜素红(AZR)和孔雀石绿(MG)等)、有机溶剂(N,N'-二甲基甲酰胺(DMF)等)、有机化合物(苯酚(PL)和乙二胺(EDA)等);洗涤剂、多环芳烃、杀虫剂、除草剂(双酚A(BPA)和对硝基苯酚(PNP)等)和抗生素(盐酸四环素(TC)、阿奇霉素、卡那霉素等)以及个人护理产品(PPCPs等)等是排放到水体中最为常见的有机污染物。由于这些污染物是稳定且持久的环境污染物,不能自然消失即难以生化降解,而且有机污染物通常具有致癌、致畸、致突变的严重危害,对人类健康和环境构成了巨大威胁。
在这种情况下,迫切需要深入研究水污染处理技术,开发能够快速、高效和经济的材料去除水中的有机污染物,使废水能够回收和再利用,从而有助于重新建立地球的环境平衡。目前,对有机污染物废水的处理方法主要有物理法、生物法、化学法三大类,各种类型的处理技术均有其优势与不足。如:发明专利CN 112121771 A公开了一种负载金属离子的生物质吸附剂,具有废物再利用、原材料来源广泛、制备简便,对左氧氟沙星、盐酸四环素等水中难降解有机污染物吸附能力强等特点,该吸附剂存在金属离子浸出率大,吸附的污染物范围窄,吸附剂吸附后容易造成二次污染的缺点。发明专利CN 103627653 A公开了一种赤红球菌菌株及其在含有机污染物的废水处理中的应用,本发明的菌株及菌剂应用于高盐苯酚废水、含烃类废水和香料废水的处理中时,降低了污水处理的成本,但是微生物降解对人类最重要的影响之一是导致传染病的流行。发明专利CN 111908563 A公开了一种液相阴极等离子体放电快速降解水体中有机污染物的方法,通过在不同直径的阴极镍钛合金丝上外加较低的脉冲电压,在阴极试样周围放电产生等离子体区域,短时间内降解溶液中的有机污染物;产生的阴极等离子体具有高活性、强氧化性、无选择性等优点,能够快速彻底地降解水体中的有机污染物,该种方法成本较高,不能够大面积推广使用。发明专利CN112121821 A公开了一种硫化镉/氧化锌复合材料,研究了其在压电-光催化去除有机污染物中的应用,该复合材料对水中双酚A的降解速率有非常明显的提高,在20 min就可以降解100%的双酚A,该复合材料在超声条件下效果才有显著提高,其成本较高,实际应用很难达到。发明专利CN 112121797 A公开了一种磁性TiO2氧化石墨烯复合材料的制备方法,将TiO2-Fe3O4制成核壳结构,有效预防了水体中强氧化物质对Fe3O4磁性的破坏,而氧化石墨烯表面基团不仅增强了该复合材料在水中的分散性,也增强了该复合材料对水体中有机污染物的吸附,有利于TiO2的光催化降解;该光催化剂制备过程复杂,通过简单的物理作用将TiO2-Fe3O4与氧化石墨烯复合,将导致光催化剂使用效率不高。发明专利CN 111921562 A公开了一种非均相光催化剂g-C3N4@α-FOD,该催化剂表现出较好的光催化活性,同时材料结构的稳定性也使其表现出较优的循环重复利用性,而该光催化剂存在降解时间长的问题。
研究表明:在化学法中,高级氧化技术(AOPs)是以产生活性氧(ROSs)使难降解大分子有机物氧化成低毒或无毒的小分子物质的方法。在各种ROSs中,与羟基自由基(•OH)相比,硫酸根自由基(SO4 -•)具有更高的氧化还原电势(E0 = 2.5~3.1 V)、更长的寿命、更好的选择性和更强的降解能力。几十年来,基于过一硫酸盐(KHSO5,PMS)活化的AOPs引起了人们越来越多的关注。PMS可以通过加热、紫外线/可见光、超声波以及各种催化剂来激活。在这些方法中,过渡金属离子和氧化物通常被认为是在PMS存在下降解有机污染物的有效催化剂。但是这种类型的催化剂也并不是最完美的,例如发明专利CN 103464166 A公开了一种以铁尾矿为载体的负载型过渡金属(Co、Mn或Cu)催化剂,催化降解有机污染物效果好、降解率高,且方法简单、成本低廉,达到了“以废治污”的目的,并存在显著的重金属离子浸出的风险。发明专利CN 112156804 A公开了一种MQDs/NCDs/TiO2复合材料,该复合材料与过硫酸盐组成的复合催化体系能够产生协同催化作用,进一步促进了对有机污染物的降解,该复合材料制备过程复杂,降解时间缓慢。发明专利CN 112076754 A公开了一种高孔隙率和高铁磁性Co-Fe3O4催化剂,该催化剂对水中的盐酸四环素(TC)具有较高的催化活化过硫酸盐降解有机污染物的效果,该催化剂降解率较低。发明专利CN 111871422 A公开了一种钙锰氧化物催化剂,该催化剂制备简单、环境友好,所含元素为低毒、廉价和地球富含的Ca、Mn元素,在反应过程中金属溶出率低,无二次污染问题。所述催化剂与过硫酸盐形成的反应体系可快速降解苯酚、双酚A、2,6-二氯苯酚、对氯酚、扑热息痛等难降解有机污染物,在较宽的pH范围内表现出良好的性能,具有很大的应用潜力,但是该催化剂制备成本较高,并且降解时间缓慢。
因此,如何寻找一种降解速度快、降解率高、降解污染物广泛、循环稳定性好的催化剂已经迫在眉睫。
羟基磷灰石(HA,Ca10(PO4)6(OH)2)作为骨骼和牙齿的主要无机成分,由于其良好的生物相容性、稳定性和高比表面积等,已广泛用于生物医用和环境修复方面等。发明专利CN108424138A公开了一种含硅晶界相改性羟基磷灰石陶瓷、骨损伤修复材料,通过溶胶渗透法制备的含硅晶界相改性羟基磷灰石陶瓷,烧结过程中形成的含硅晶界相包裹羟基磷灰石晶粒,改善了羟基磷灰石晶粒间的结合,使材料具有好的力学性能;含硅晶界相为羟基磷灰石陶瓷引入硅元素,改善了羟基磷灰石的降解性能,并提高了材料的成骨性能。发明专利CN 107185500 A公开了一种利用大豆分离蛋白杂化羟基磷灰石用于吸附重金属离子的多孔材料,这种新型吸附剂材料环境友好、可生物降解、制备方法简单,原料成本低,且绿色环保。同时具有特殊线型形貌的羟基磷灰石纳米线的成功合成,拓宽了羟基磷灰石的应用范围。例如:发明专利CN 111087836A公开了一种BN/羟基磷灰石纳米线复合导热绝缘阻燃界面材料,羟基磷灰石纳米线的加入显著提高了复合导热绝缘阻燃的性能。发明专利CN107574705A公开了一种基于羟基磷灰石纳米线的防火耐磨可修复的超疏水纸,该超疏水纸具备良好的稳定性能,对水的接触角均大于150°,滚动角小于10°,且对于生活中的常见水系液体也具有极好的抗浸润能力。修饰后的纸张表现出了很好的耐火性、耐磨性和化学稳定性。目前羟基磷灰石纳米线在AOPs中的应用较少,因此,在活化PMS的催化剂中引入羟基磷灰石纳米线,以发挥其强大的离子交换性能就显得尤为重要。
发明内容
本发明所要解决的技术问题是提供一种工艺简单、成本低廉的羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法。
为解决上述问题,本发明所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:首先制备钴离子分散液和配体溶液;然后将羟基磷灰石纳米线加入到所述钴离子分散液中,超声分散20~40 min,形成均一的粉色悬浮溶液;其次以100~1600 r/min的磁力搅拌速度下,在所述粉色悬浮溶液中逐滴加入所述配体溶液,继续搅拌10~15 h后,得到紫色悬浮体系,该紫色悬浮体系经室温静置3~5 h后,于7500~8500 r/min离心分离5~15 min,得到紫色产物;最后,所述紫色产物经醇水混合液进行洗涤4~8次,于50~80℃真空干燥至恒重即得;所述钴离子分散液中的钴盐与所述羟基磷灰石纳米线的质量比为1:0.5~1:5;所述配体溶液中的配体与所述羟基磷灰石纳米线的质量比为1:0.5~1:3。
所述钴离子分散液是指将钴盐均匀分散于醇水混合液中,形成10~70 g/L的溶液;所述钴盐是指Co(NO3)2•6H2O、CoSO4•7H2O或CoCl2•6H2O中的一种。
所述配体溶液是指将配体均匀分散于醇水混合液中,形成10~100 g/L的溶液;所述配体是指2-甲基咪唑(C4H6N2)、1,2-二甲基咪唑(C5H8N2)或苯并咪唑(C7H6N2)中的一种。
所述醇水混合液是指将醇与水按20:1~5:1的体积比混合均匀所得的溶液;所述醇指甲醇、乙醇、丙醇中的一种或两种。
所述羟基磷灰石纳米线按下述方法制得:
⑴将5~30 mL醇-水-油酸混合溶液放置在冰水浴中,在磁力搅拌速度为100~1700r/min的条件下,缓慢滴加5~50 mL浓度为1.20 mol/L的NaOH溶液,10~45 min内滴加完毕,得到白色的前驱体溶液;
⑵依次将1~40 mL浓度为0.20 mol/L的钙盐溶液和1~40 mL浓度为0.40 mol/L的磷酸盐溶液均匀分散于所述前驱体溶液中,得到淡黄色粘稠溶液;
⑶将所述淡黄色粘稠溶液转入到水热反应釜中,静置0.5~3 h,然后放置在均相水热反应器中,升温到120~200℃后,持续反应16~26 h;待反应釜冷却至室温后,得到反应物;
⑷所述反应物于7500~8500 r/min离心分离5~15 min后用醇水混合溶液洗涤4~8次,最后于50~80℃真空干燥12~36 h,即得长径比为23:1的白色固体粉末状羟基磷灰石纳米线。
所述步骤⑴中醇-水-油酸混合溶液是指将醇、水、油酸按0.5:1:1~1:10:10的体积比混合均匀的溶液。
所述步骤⑵中钙盐溶液是指CaCl2溶液、Ca(NO3)2溶液或者Ca(HCO3)2溶液中的一种。
所述步骤⑵中磷酸盐溶液指NaH2PO4溶液、KH2PO4溶液、K2HPO4溶液或Na2HPO4溶液中的一种。
所述步骤⑷中醇水混合溶液是指将醇与水按1:1~10:1的体积比混合均匀所得的溶液。
所述醇指甲醇、乙醇、丙醇中的一种或两种。
本发明与现有技术相比具有以下优点:
1、本发明以油酸、钙盐和磷酸盐混合溶液为前驱体溶液,醇水混合溶液为分散剂,采用溶剂热法制备出具有高水热稳定性,长径比为23:1的羟基磷灰石纳米线后,并分散于合成钴MOFs材料的前驱体溶液中,在原位生长的过程中,通过离子交换作用进入羟基磷灰石纳米线晶格内部的钴离子与配体形成骨架结构,进而形成了结合体材料。
2、对本发明所制备的羟基磷灰石纳米线结合钴MOFs串珠状催化剂进行SEM能谱分析,其宏观形貌和微观形貌如图1所示。可以看出,其宏观照片为紫色状固体(左图)。从SEM照片可以看出,羟基磷灰石纳米线与钴MOFs很好的结合在一起(右图),长径比为23:1羟基磷灰石纳米线穿过八面体形的钴MOFs,形成了串珠结构,并且没有出现堆积团聚现象。而羟基磷灰石纳米线的线性结构也并没有发生改变。并且在结合体中钴MOFs的轮廓较为圆滑,这是由于在羟基磷灰石纳米线表面原位生长形成正八面体骨架时,有一部分的Co2+与羟基磷灰石纳米线中的Ca2+发生了离子交换反应,形成了Co-OH,因而缺失了部分的骨架位点。综上所述,说明已成功制备了羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
3、对本发明所制备的羟基磷灰石纳米线结合钴MOFs串珠状催化剂进行形貌分析,可以发现钴MOFs与羟基磷灰石纳米线以串珠的方式结合在一起,这种两者牢固结合的形貌将会导致在复合材料表面存在更多的活性位点,使得该催化剂能充分发挥协同高效降解、循环稳定性好的性能,并有望降低钴离子溶出率。
【EDS元素分析】
通过EDS面扫分析所选区域各元素的分布,结果如图2所示。可明显看出在羟基磷灰石纳米线结合钴MOFs串珠状催化剂中主要含有Ca、P、O、C、N、Co元素,其中C、N、Co元素来源于复合材料中的钴MOFs,Ca、P、O元素来源于催化剂中的羟基磷灰石纳米线。而且,可以看到这些元素均匀分布在所选区域,说明该催化剂是均一的结合体,并不是单纯的复合在一起。
【X射线衍射(XRD)分析】
对所制备的催化剂进行了XRD分析,以测定羟基磷灰石纳米线结合钴MOFs串珠状催化剂的晶体结构及结晶度等信息,如图3所示。从图中可以得出,羟基磷灰石纳米线的特征衍射峰出现在2θ = 26.7°、32.2°、33.7°、40°和46.1°,分别对应于羟基磷灰石纳米线单晶的(002)、(211)、(300)、(310)和(222)晶面。钴MOFs材料中主要的特征衍射峰的位置出现在2θ = 7.2°、10.9°、12.7°、18.1°和27.0°,分别对应于(011)、(002)、(112)、(222)和(134)晶面。以上特征衍射峰均出现在催化剂中,说明羟基磷灰石纳米线结合钴MOFs串珠状催化剂是由羟基磷灰石纳米线和钴MOFs组成的。
4、为了考察羟基磷灰石纳米线结合钴MOFs串珠状催化剂的降解性能,以抗生素盐酸四环素(TC)、有机染料罗丹明B(RhB)、结晶紫(CV)、亚甲基兰(MB)和孔雀石绿(MG)为模拟有机污染物进行降解性能测试。
在25℃,各种污染物初始浓度为15 mg/L,PMS浓度为1.8 mmol/L时,测试其降解效率。实验结果显示,羟基磷灰石纳米线结合钴MOFs串珠状催化剂在5 min之内对各种污染物的降解率均达到95%以上,结果如图4所示。并且对RhB的降解可达到100%(5 min),远远高于文献报道的结果。说明羟基磷灰石纳米线结合钴MOFs串珠状催化剂在有机污染物去除方面具有优良的降解性能,降解效率高、降解迅速、循环使用率高(重复使用5次后,其降解率依然保持不变)。因此,所得的羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备思路可为AOPs中重金属离子容易溶出的问题提供借鉴作用,进一步拓宽了羟基磷灰石纳米线的应用范围,并可推广其用作工业废水中有机污染的处理材料。
5、本发明工艺简单、原料易得、成本低廉,整个制备过程中无有毒有机溶剂参与,绿色环保、安全可靠。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明实施例1羟基磷灰石纳米线结合钴MOFs串珠状催化剂的SEM图。
图2为本发明实施例1羟基磷灰石纳米线结合钴MOFs串珠状催化剂的EDS图。
图3为本发明实施例1羟基磷灰石纳米线结合钴MOFs串珠状催化剂的XRD图。
图4为本发明实施例1羟基磷灰石纳米线结合钴MOFs串珠状催化剂对各种有机污染物的降解效果图。
具体实施方式
一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
首先制备钴离子分散液和配体溶液;然后将羟基磷灰石纳米线加入到钴离子分散液中,超声分散20~40 min,形成均一的粉色悬浮溶液;其次以100~1600 r/min的磁力搅拌速度下,在粉色悬浮溶液中逐滴加入配体溶液,继续搅拌10~15 h后,得到紫色悬浮体系,该紫色悬浮体系经室温静置3~5 h后,于7500~8500 r/min离心分离5~15 min,得到紫色产物;最后,紫色产物经醇水混合液进行洗涤4~8次,于50~80℃真空干燥至恒重即得。
其中:钴离子分散液中的钴盐与羟基磷灰石纳米线的质量比(g/g)为1:0.5~1:5。钴离子分散液是指将钴盐均匀分散于醇水混合液中,形成10~70 g/L的溶液;钴盐是指Co(NO3)2•6H2O、CoSO4•7H2O或CoCl2•6H2O中的一种。
配体溶液中的配体与羟基磷灰石纳米线的质量比(g/g)为1:0.5~1:3。配体溶液是指将配体均匀分散于醇水混合液中,形成10~100 g/L的溶液;配体是指2-甲基咪唑(C4H6N2)、1,2-二甲基咪唑(C5H8N2)或苯并咪唑(C7H6N2)中的一种。
醇水混合液是指将醇与水按20:1~5:1的体积比(mL/mL)混合均匀所得的溶液。
羟基磷灰石纳米线按下述方法制得:
⑴将5~30 mL醇-水-油酸混合溶液放置在冰水浴中,在磁力搅拌速度为100~1700r/min的条件下,缓慢滴加5~50 mL浓度为1.20 mol/L的NaOH溶液,10~45 min内滴加完毕,得到白色的前驱体溶液。
醇-水-油酸混合溶液是指将醇、水、油酸按0.5:1:1~1:10:10的体积比(mL/mL)混合均匀的溶液。
⑵依次将1~40 mL浓度为0.20 mol/L的钙盐溶液和1~40 mL浓度为0.40 mol/L的磷酸盐溶液均匀分散于前驱体溶液中,得到淡黄色粘稠溶液。
钙盐溶液是指CaCl2溶液、Ca(NO3)2溶液或者Ca(HCO3)2溶液中的一种。磷酸盐溶液指NaH2PO4溶液、KH2PO4溶液、K2HPO4溶液或Na2HPO4溶液中的一种。
⑶将淡黄色粘稠溶液转入到水热反应釜中,静置0.5~3 h,然后放置在均相水热反应器中,升温到120~200℃后,持续反应16~26 h;待反应釜冷却至室温后,得到反应物。
⑷反应物于7500~8500 r/min离心分离5~15 min后用醇水混合溶液洗涤4~8次,最后于50~80℃真空干燥12~36 h,即得长径比为23:1的白色固体粉末状羟基磷灰石纳米线。醇水混合溶液是指将醇与水按1:1~10:1的体积比(mL/mL)混合均匀所得的溶液。
上述醇指甲醇、乙醇、丙醇中的一种或两种。
实施例1 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将5 mL蒸馏水、5 mL乙醇和5 mL油酸置于冰水浴中,在磁力搅拌速度为200r/min下搅拌5 min,缓慢滴加5 mL 1.20 mol/L NaOH溶液,10 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入5 mL 0.20 mol/L的Ca(HCO3)2溶液、5 mL 0.20mol/L的Na2HPO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100 mL聚四氟乙烯内衬的水热反应釜中静置0.5 h。随后将水热反应釜转移到均相反应器中,升温至140℃,并在此温度下保持20 h。待反应釜冷却至室温,并在7500 r/min反应物离心分离15 min,用乙醇水体积比1:1的混合溶液洗涤4次,再在55℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将0.750 g Co(NO3)2•6H2O分散于20 mL乙醇水体积比为5:1的混合溶液中,将1.700 g 1,2-二甲基咪唑分散于30 mL上述体积比的乙醇水混合溶液中,然后将1.250 g羟基磷灰石纳米线加入到钴离子分散液中,超声分散30 min,形成均一的粉色悬浮溶液;接着在磁力搅拌100 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌12 h后,得到紫色悬浮体系;经静置4 h后,7500 r/min离心分离15 min,得到紫色产物;最后,紫色产物经上述体积比的乙醇水混合溶液进行洗涤4次,于55℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为95.1%;对RhB的降解率为98.5%;对CV的降解率为95.4%;对MB的降解率为97.3%;对MG的降解率为96.6%。
实施例2 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将8 mL蒸馏水、5 mL甲醇和8 mL油酸置于冰水浴中,在磁力搅拌速度为500r/min下搅拌10 min,缓慢滴加8 mL 1.20 mol/L NaOH溶液,15 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入8 mL 0.20 mol/L的Ca(NO3)2溶液、8 mL 0.20mol/L的KH2PO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100 mL聚四氟乙烯内衬的水热反应釜中静置1 h。随后将水热反应釜转移到均相反应器中,升温至150℃,并在此温度下保持16 h。待反应釜冷却至室温,并在8000 r/min反应物离心分离10 min,用甲醇水体积比2:1的混合溶液洗涤4次,再在60℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将0.850 g CoSO4•7H2O分散于15 mL甲醇水体积比为6:1的混合溶液中,将2.100 g 2-甲基咪唑分散于25 mL上述体积比的甲醇水混合溶液中,然后将1.050 g羟基磷灰石纳米线加入到钴离子分散液中,超声分散20 min,形成均一的粉色悬浮溶液;接着在磁力搅拌300 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌10 h后,得到紫色悬浮体系;经静置3 h后,8000 r/min离心分离8 min,得到紫色产物;最后,紫色产物经上述体积比的甲醇水混合溶液进行洗涤5次,于50℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为95.3%;对RhB的降解率为100%;对CV的降解率为98.5%;对MB的降解率为99.5%;对MG的降解率为98.6%。
实施例3 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将10 mL蒸馏水、5 mL丙醇和15 mL油酸置于冰水浴中,在磁力搅拌速度为800 r/min下搅拌15 min,缓慢滴加10 mL 1.20 mol/L NaOH溶液,20 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入10 mL 0.20 mol/L的CaCl2溶液、10 mL0.20 mol/L的K2HPO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100 mL聚四氟乙烯内衬的水热反应釜中静置1.5 h。随后将水热反应釜转移到均相反应器中,升温至155℃,并在此温度下保持24 h。待反应釜冷却至室温,并在8000 r/min反应物离心分离10 min,用丙醇水体积比5:1的混合溶液洗涤5次,再在65℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将0.724 g CoCl2•6H2O分散于30 mL丙醇水体积比为10:1的混合溶液中,将1.500g 苯并咪唑分散于20 mL上述体积比的丙醇水混合溶液中,然后将1.500 g羟基磷灰石纳米线加入到钴离子分散液中,超声分散40 min,形成均一的粉色悬浮溶液;接着在磁力搅拌500 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌15 h后,得到紫色悬浮体系;经静置5 h后,8500 r/min离心分离5 min,得到紫色产物;最后,紫色产物经上述体积比的丙醇水混合溶液进行洗涤6次,于60℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为95.6%;对RhB的降解率为98.9%;对CV的降解率为96.5%;对MB的降解率为98.1%;对MG的降解率为97.6%。
实施例4 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将8 mL蒸馏水、4 mL乙醇、4 mL甲醇和8 mL油酸置于冰水浴中,在磁力搅拌速度为1000 r/min下搅拌20 min,缓慢滴加10 mL 1.20 mol/L NaOH溶液,25 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入15 mL 0.20 mol/L的Ca(HCO3)2溶液、15 mL 0.20 mol/L的NaH2PO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100mL聚四氟乙烯内衬的水热反应釜中静置2 h。随后将水热反应釜转移到均相反应器中,升温至160℃,并在此温度下保持26 h。待反应釜冷却至室温,并在7500 r/min反应物离心分离15 min,用体积比甲醇:乙醇:水=1:1:1的混合溶液洗涤4次,再在70℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将0.980 g CoCl2•6H2O分散于20 mL醇水混合溶液(乙醇:甲醇:水=2:2:1)中,将1.000 g 2-甲基咪唑分散于20 mL上述体积比的醇水混合溶液中,然后将2.000 g羟基磷灰石纳米线加入到钴离子分散液中,超声分散20 min,形成均一的粉色悬浮溶液;接着在磁力搅拌600 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌10 h后,得到紫色悬浮体系;经静置3 h后,8300 r/min离心分离5 min,得到紫色产物;最后,紫色产物经上述体积比的醇水混合溶液进行洗涤5次,于80℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为95.9%;对RhB的降解率为99.8%;对CV的降解率为98.5%;对MB的降解率为98.1%;对MG的降解率为97.6%。
实施例5 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将12 mL蒸馏水、5 mL丙醇、4 mL乙醇和9 mL油酸置于冰水浴中,在磁力搅拌速度为1200 r/min下搅拌30 min,缓慢滴加20 mL 1.20 mol/L NaOH溶液,30 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入20 mL 0.20 mol/L的CaCl2溶液、10 mL 0.20 mol/L的KH2PO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100 mL聚四氟乙烯内衬的水热反应釜中静置2.5 h。随后将水热反应釜转移到均相反应器中,升温至180℃,并在此温度下保持22 h。待反应釜冷却至室温,并在8000 r/min反应物离心分离10min,用体积比丙醇:乙醇:水=2:1:1的混合溶液洗涤5次,再在75℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将0.650 g Co(NO3)2•6H2O分散于25 mL醇水混合溶液(乙醇:丙醇:水=1:3:1)中,将0.800 g 1,2-二甲基咪唑分散于30 mL上述体积比的醇水混合溶液中,然后将0.900g羟基磷灰石纳米线加入到钴离子分散液中,超声分散30 min,形成均一的粉色悬浮溶液;接着在磁力搅拌800 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌12 h后,得到紫色悬浮体系;经静置3.5 h后,7500 r/min离心分离12 min,得到紫色产物;最后,紫色产物经上述体积比的醇水混合溶液进行洗涤4次,于70℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为96.5%;对RhB的降解率为99.5%;对CV的降解率为95.7%;对MB的降解率为97.8%;对MG的降解率为95.9%。
实施例6 一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法:
【制备羟基磷灰石纳米线】
首先,将12 mL蒸馏水、4 mL甲醇、3 mL丙醇和8 mL油酸置于冰水浴中,在磁力搅拌速度为1500 r/min下搅拌20 min,缓慢滴加10 mL 1.20 mol/L NaOH溶液,45 min内滴加完毕,形成白色混合溶液。依次在上述混合溶液中逐滴加入10 mL 0.20 mol/L的Ca(NO3)2溶液、15 mL 0.20 mol/L的NaH2PO4溶液,搅拌10 min,形成淡黄色粘稠溶液。之后转入到100mL聚四氟乙烯内衬的水热反应釜中静置3 h。随后将水热反应釜转移到均相反应器中,升温至200℃,并在此温度下保持20 h。待反应釜冷却至室温,并在8500 r/min反应物离心分离5min,用体积比丙醇:甲醇:水=2:2:1的混合溶液洗涤4次,再在80℃真空烘箱中干燥,即得到白色粉末状羟基磷灰石纳米线。
【制备羟基磷灰石纳米线结合钴MOFs串珠状催化剂】
首先将1.000 g CoSO4•7H2O分散于20 mL醇水混合溶液(甲醇:丙醇:水=4:2:1)中,将1.200 g苯并咪唑分散于20 mL上述体积比的醇水混合溶液中,然后将1.500 g羟基磷灰石纳米线加入到钴离子分散液中,超声分散25 min,形成均一的粉色悬浮溶液;接着在磁力搅拌1500 r/min下在粉色悬浮溶液中逐滴加入配体溶液,磁力搅拌14 h后,得到紫色悬浮体系;经静置4.5 h后,8000 r/min离心分离8 min,得到紫色产物;最后,紫色产物经上述体积比的醇水混合溶液进行洗涤5次,于80℃真空干燥至恒重,即得羟基磷灰石纳米线结合钴MOFs串珠状催化剂。
该催化剂在5 min之内对TC的降解率为97.5%;对RhB的降解率为98.5%;对CV的降解率为96.1%;对MB的降解率为98.5%;对MG的降解率为97.3%。
Claims (7)
1.一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:首先制备钴离子分散液和配体溶液;然后将羟基磷灰石纳米线加入到所述钴离子分散液中,超声分散20~40 min,形成均一的粉色悬浮溶液;其次以100~1600 r/min的磁力搅拌速度下,在所述粉色悬浮溶液中逐滴加入所述配体溶液,继续搅拌10~15 h后,得到紫色悬浮体系,该紫色悬浮体系经室温静置3~5 h后,于7500~8500 r/min离心分离5~15 min,得到紫色产物;最后,所述紫色产物经醇水混合液进行洗涤4~8次,于50~80℃真空干燥至恒重即得;所述钴离子分散液中的钴盐与所述羟基磷灰石纳米线的质量比为1:0.5~1:5;所述配体溶液中的配体与所述羟基磷灰石纳米线的质量比为1:0.5~1:3;所述钴离子分散液是指将钴盐均匀分散于醇水混合液中,形成10~70 g/L的溶液;所述钴盐是指Co(NO3)2•6H2O、CoSO4•7H2O或CoCl2•6H2O中的一种;所述配体溶液是指将配体均匀分散于醇水混合液中,形成10~100 g/L的溶液;所述配体是指2-甲基咪唑、1,2-二甲基咪唑或苯并咪唑中的一种;
所述羟基磷灰石纳米线按下述方法制得:
⑴将5~30 mL醇-水-油酸混合溶液放置在冰水浴中,在磁力搅拌速度为100~1700 r/min的条件下,缓慢滴加5~50 mL浓度为1.20 mol/L的NaOH溶液,10~45 min内滴加完毕,得到白色的前驱体溶液;
⑵依次将1~40 mL浓度为0.20 mol/L的钙盐溶液和1~40 mL浓度为0.40 mol/L的磷酸盐溶液均匀分散于所述前驱体溶液中,得到淡黄色粘稠溶液;
⑶将所述淡黄色粘稠溶液转入到水热反应釜中,静置0.5~3 h,然后放置在均相水热反应器中,升温到120~200℃后,持续反应16~26 h;待反应釜冷却至室温后,得到反应物;
⑷所述反应物于7500~8500 r/min离心分离5~15 min后用醇水混合溶液洗涤4~8次,最后于50~80℃真空干燥12~36 h,即得长径比为23:1的白色固体粉末状羟基磷灰石纳米线。
2.如权利要求1所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述醇水混合液是指将醇与水按20:1~5:1的体积比混合均匀所得的溶液;所述醇指甲醇、乙醇、丙醇中的一种或两种。
3.如权利要求1所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述步骤⑴中醇-水-油酸混合溶液是指将醇、水、油酸按0.5:1:1~1:10:10的体积比混合均匀的溶液。
4.如权利要求1所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述步骤⑵中钙盐溶液是指CaCl2溶液、Ca(NO3)2溶液或者Ca(HCO3)2溶液中的一种。
5.如权利要求1所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述步骤⑵中磷酸盐溶液指NaH2PO4溶液、KH2PO4溶液、K2HPO4溶液或Na2HPO4溶液中的一种。
6.如权利要求1所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述步骤⑷中醇水混合溶液是指将醇与水按1:1~10:1的体积比混合均匀所得的溶液。
7.如权利要求3或6所述的一种羟基磷灰石纳米线结合钴MOFs串珠状催化剂的制备方法,其特征在于:所述醇指甲醇、乙醇、丙醇中的一种或两种。
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