CN114849708B - 一种三维大孔碳锚定的单原子铁催化剂及其制备方法与应用 - Google Patents
一种三维大孔碳锚定的单原子铁催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种三维大孔碳锚定的单原子铁催化剂及其制备方法与应用,将单原子铁锚定在三维大孔碳上作为微波催化剂用于去除土壤中的氯霉素等有机污染物。具体而言,以多巴胺作为碳源、氯化钠作为模板、氯化铁水溶液作为离子源制备3D Fe‑NC;首先经过冷冻干燥,再高温煅烧,之后使用水和0.5M的硫酸洗去氯化钠模板,即可得到3D Fe‑NC。本发明选择自然土壤作为实验土壤,加入污染物,再加入催化剂,在微波的辐射下引发反应;去除效率高(5min达到99.9%),修复后土壤毒性小,适用pH范围广,节省能源。
Description
技术领域
本发明属于微波催化剂材料技术领域,具体涉及一种3D Fe-NC作为微波吸附剂和催化剂,其制备方法,及其在土壤中去除氯霉素的用途。
背景技术
在日常生活环境中,氯霉素(2,4-DCP)是一种由人工合成的抗菌素, 通过与细菌的核糖体进行结合而抑制蛋白质合成达到抑菌的目的。由于其成本低廉、抗菌效果优良,氯霉素还被广泛用于畜牧业和水产品的养殖, 在土壤、地表水和地下水中都曾被检测出,一旦进入食物链, 就对人们健康带来风险。由于它的高毒性,持久性和生物积累性,迫切需要发展生态友好型和高效型从污染土壤中去除氯霉素的方法。目前,从土壤中去除氯霉素的方法研究也成为了研究热点,常见的去除方法包括生物去除、吸附、芬顿氧化,但存在有去除时间长,去除效率低,能量消耗大等缺陷。为了满足目前市场对土壤不产生二次污染、实用、效率高等方面的要求,亟需开发出一种新型去除土壤中2,4-DCP的方法。
发明内容
针对上述情况,本发明采用新型3D Fe-NC作为微波吸附剂和催化剂,通过负载不同的单原子铁的含量,在微波的辐射下去除土壤中的有机污染物,比如氯霉素,5min内去除99.9%。
具体而言,本发明采用如下技术方案:
一种三维大孔碳锚定的单原子铁催化剂(3D Fe-NC),其制备方法为,将多巴胺、水溶性无机盐与铁盐混合后冷冻干燥,然后煅烧,再去模板,得到三维大孔碳锚定的单原子铁催化剂。本发明以多巴胺作为碳源,氯化钠作为模板,氯化铁溶液作为离子源经过冷冻干燥,高温煅烧,再使用水溶液和0.5M 的硫酸洗去氯化钠模板,即可得到催化剂3D Fe-NC,比表面积为597m2/g,孔径1μm。此催化剂是微波吸附剂,又是微波催化剂,可提高微波能量的利用率,成为催化中心快速产生微波热点。
本发明中,水溶性无机盐为氯化钠;铁盐为FeCl3·6H2O;三维大孔碳锚定的单原子铁催化剂中,铁的负载量为2~5wt%。
具体的,将多巴胺、水溶性无机盐与铁盐混合1~5小时后冷冻干燥,然后煅烧,再水洗与酸洗去模板,得到三维大孔碳锚定的单原子铁催化剂;优选的,冷冻干燥的温度为-60℃~-50℃、时间为2~8天;煅烧的温度为700~900℃,时间为1~5h;本发明将多巴胺、水溶性无机盐与铁盐在水中混合;酸为0.2~0.6M的硫酸。
本发明公开了上述三维大孔碳锚定的单原子铁催化剂在去除土壤中有机污染物的应用;或者上述三维大孔碳锚定的单原子铁催化剂作为微波催化剂在去除有机污染物中的应用。
本发明公开了一种去除物质中有机污染物的方法,包括以下步骤,将上述三维大孔碳锚定的单原子铁催化剂与含有有机污染物的物质混合,在微波作用下实现物质中有机污染物的去除,优选的,所述物质为污染土壤;催化剂的用量为1~5%;微波功率为500W~2000W。有机污染物为氯霉素、2,4-二氯苯酚、邻苯二甲酸二正丙酯、菲或者苯甲醛。
本发明中,水溶性铁盐为FeCl3·6H2O;将多巴胺作为碳源,氯化钠作为模板,氯化铁溶液为离子源加入到水中,常规超声1~5h后,经过冷冻干燥数天,将得到的白色粉末在氩气环境中煅烧。优选的,煅烧温度为700~900℃,升温速率为2~4℃/min,煅烧时间为1~5h。煅烧后的黑色粉末经过水和0.5M硫酸溶液洗去模板氯化钠,在烘箱中70℃干燥一夜,即为3D Fe-NC,铁的负载量为2~5wt%,优选为0.4~2.5wt%;以铁的质量/三维大孔碳锚定的单原子铁催化剂质量计算,铁的质量根据ICP测试。
本发明去除有机污染物的方法中,物质为土壤,pH=3.41~11.58,含水量0~20%;优选催化剂用量30mg∶1g,即3%;微波功率800~1400W,时间为1~15分钟,比如2~10分钟。
与现有技术相比,利用上述技术方案的本发明具有如下优点:
(1)催化剂3D Fe-NC即是微波吸收剂又是催化剂;
(2)去除效率高,对比传统的活性炭,去除速率常数是活性炭的2倍;
(3)单原子催化剂的活性高,也提高了铁离子的利用率。
(4)适用的pH范围广。
(5)修复后的土壤莴苣种子的发芽率达到70%。
附图说明
图1为1.7wt%3D Fe-NC的SEM谱图。
图2为1.7wt%3D Fe-NC的高角度环形暗场-扫描透射电子显微镜图。
图3为3D Fe-NC的XRD谱图。
图4为不同催化剂对于初始污染浓度100 mg/kg土壤的去除结果,a为去除效率,b为去除k值。
图5为不同污染物去除结果。
图6为不同功率去除结果。
图7为不同铁负载量去除结果。
图8为不同pH去除结果。
图9为不同含水量去除结果。
具体实施方式
下文将结合附图和具体实施例来进一步说明本发明的技术方案。除非另有说明,下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得;除非有特殊说明,实施例参数、环境都为常规技术;选择自然土壤作为实验土壤,加入一定浓度的氯霉素或者其他污染物配制污染土壤,再加入一定量的催化剂在微波的辐射下,从而引发反应,实现污染物的去除。具体制备操作、实验方法以及结果分析,都是常规技术。
实施例一 催化材料3D Fe-NC的合成
多巴胺(0.5g)、氯化钠(1g)、FeCl3·6H2O (20mg) 加入到100ml 水中,常规超声2h后,经过-54℃冷冻干燥5天,将得到的白色粉末在氩气环境中煅烧,煅烧温度为800℃,升温速率为3℃/min,煅烧时间为2 h;煅烧后的黑色粉末依次经过水、0.5M硫酸溶液洗,去除模板氯化钠,然后在烘箱中70℃干燥一夜,即为3D Fe-NC,铁负载量为17.wt%,称为1.7% 3DFe-NC。
3D Fe-NC SEM显微结构如图1所示,高角度环形暗场-扫描透射电子显微镜图如图2所示;由图1可以看出3D Fe-NC为三维大孔状,孔径大约1μm;图2可以看出铁原子的均匀分布。
在实施例一的基础上,采用不同FeCl3·6H2O用量,得到不同铁的负载量的3D Fe-NC;以铁的质量/三维大孔碳锚定的单原子铁催化剂质量计算,铁的质量根据ICP测试。
各催化剂的X射线衍射图谱如图3所示,上述合成的3D Fe-NC只存在两个石墨烯碳峰。
以上测试可以确定3D Fe-NC合成成功。
对比例一
多巴胺(0.5g)、氯化钠(1g)加入到100ml 水中,常规超声2h后,经过-54℃冷冻干燥5天,将得到的粉末在氩气环境中煅烧,煅烧温度为800℃,升温速率为3℃/min,煅烧时间为2 h;煅烧后的粉末依次经过水、0.5M硫酸溶液洗,去除模板氯化钠,然后在烘箱中70℃干燥一夜,即为NC。
实施例二 催化剂材料3D Fe-NC用于土壤中氯霉素的去除
(a)取1 g初始污染物氯霉素浓度为100 mg/kg的土壤放入石英管中,此时pH=7.60,含水量为15%;
(b)加入30mg催化剂材料(实施例一)或者对比催化剂材料,然后在1200W功率下微波催化5min;
(c)将微波催化后的土壤加入5ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定氯霉素的浓度。
不同催化剂对于初始污染浓度100 mg/kg土壤的去除结果如图4,AC为市售活性炭,MW为微波;可以看出,本发明催化剂1.7% 3D Fe-NC达到最佳去除率,5min内去除99.9%。
按照国际标准(ISO 17126)进行修复后的土壤质量验证。具体的:3组土壤(自然土壤,污染土壤 (100mg/kg),按实施例二方法得到的微波修复后的土壤)各250g,分别放入培养皿,播撒30粒莴苣种子,浇水使其获得85%的保水能力,放入超净工作台25℃培育5天;污染土壤的土壤莴苣种子的发芽率为13%,修复后的土壤莴苣种子的发芽率达到70%,较自然土壤略少,说明本发明方法不仅有效去除氯霉素等污染物,而且修复的土壤具有好的种植质量。
实施例三 不同污染物的去除
(a)取10 g初始污染物浓度为100 mg/kg的土壤放入石英管中,在混匀搅拌器上搅动;初始污染物为2,4-二氯苯酚、邻苯二甲酸二正丙酯、菲或者苯甲醛;
(b)加入300 mg上述催化剂材料1.7% 3D Fe-NC,在1200W功率下微波催化5min;
(c)将微波催化后的土壤加入50ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定各污染物的浓度;不同污染物去除结果见图5,可以看出,本发明催化剂1.7% 3D Fe-NC对苯甲醛在5min内也达到99.9%去除率。
实施例四 不同微波功率用于土壤中氯霉素的去除
(a)取1 g初始污染物氯霉素浓度为100 mg/kg的土壤放入石英管中;
(b)加入30mg上述催化剂材料1.7% 3D Fe-NC,不同微波功率下微波催化5min;
(c)将微波催化后的土壤加入5ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定氯霉素的浓度;不同功率去除结果见图6。
实施例五 不同铁负载量用于土壤中氯霉素的去除
a)取1 g初始污染物氯霉素浓度为100 mg/kg的土壤放入石英管中;
(b)加入30mg不同铁比例的催化剂材料3D Fe-NC,然后在1200W功率下微波催化5min;
(c)将微波催化后的土壤加入5ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定氯霉素的浓度;不同铁含量催化剂的去除结果见图7。
实施例六 不同pH下土壤中氯霉素的去除
(a)取1 g初始污染物氯霉素浓度为100 mg/kg的土壤放入石英管中,通过加入H2SO4调节pH,保持含水量15%;
(b)加入30mg催化剂材料(实施例一)或者对比催化剂材料,然后在1200W功率下微波催化5min;
(c)将微波催化后的土壤加入5ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定氯霉素的浓度;不同pH去除结果见图8。
实施例七 不同含水量下土壤中氯霉素的去除
(a)取1 g初始污染物氯霉素浓度为100 mg/kg的土壤放入石英管中,保持pH=7.60,通过加入水或者干燥调节含水量;
(b)加入30mg催化剂材料(实施例一)或者对比催化剂材料,然后在1200W功率下微波催化5min;
(c)将微波催化后的土壤加入5ml甲醇进行超声浸取30min然后离心,将得到的清夜装入液相小瓶,通过HPLC测定氯霉素的浓度;不同含水数量去除结果见图9。
综上所述,本发明通过将新型的3D-Fe-NC作为微波催化剂去除土壤中的氯霉素,实现了初始污染浓度100 mg/kg的高效去除,去除率达99.9%,实现了铁剂催化剂在微波催化实验中的高效利用,本发明的基于微波催化剂3D-Fe-NC对于土壤中有机污染物的去除具有很高的应用价值。
Claims (8)
1.一种三维大孔碳锚定的单原子铁催化剂作为微波催化剂在去除有机污染物中的应用,其特征在于,所述三维大孔碳锚定的单原子铁催化剂的制备方法为,将多巴胺、水溶性无机盐与铁盐混合后冷冻干燥,然后煅烧,再水洗与酸洗去模板,得到三维大孔碳锚定的单原子铁催化剂;所述水溶性无机盐为氯化钠。
2.根据权利要求1所述的应用,其特征在于,水溶性无机盐为氯化钠;铁盐为FeCl3·6H2O。
3.根据权利要求1所述的应用,其特征在于,三维大孔碳锚定的单原子铁催化剂中,铁的负载量为2~5wt%。
4.根据权利要求1所述的应用,其特征在于,将多巴胺、水溶性无机盐与铁盐混合1~5小时后冷冻干燥,然后煅烧,再水洗与酸洗去模板,得到三维大孔碳锚定的单原子铁催化剂。
5.根据权利要求4所述的应用,其特征在于,冷冻干燥的温度为-60℃~-50℃、时间为2~8天;煅烧的温度为700~900℃,时间为1~5h。
6.根据权利要求4所述的应用,其特征在于,将多巴胺、水溶性无机盐与铁盐在水中混合;酸为0.2~0.6M的硫酸。
7.一种去除物质中有机污染物的方法,其特征在于,包括以下步骤,将三维大孔碳锚定的单原子铁催化剂与含有有机污染物的物质混合,在微波作用下实现物质中有机污染物的去除;所述三维大孔碳锚定的单原子铁催化剂的制备方法为,将多巴胺、水溶性无机盐与铁盐混合后冷冻干燥,然后煅烧,再水洗与酸洗去模板,得到三维大孔碳锚定的单原子铁催化剂;所述水溶性无机盐为氯化钠;催化剂的用量为1~5%;微波功率为500W~2000W。
8.根据权利要求7所述去除物质中有机污染物的方法,其特征在于,所述物质为污染土壤。
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