CN114904536A - 一种多孔生物炭基MnFe2O4复合物的制备方法 - Google Patents
一种多孔生物炭基MnFe2O4复合物的制备方法 Download PDFInfo
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Abstract
本发明公开了一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：紫花苜蓿用超纯水冲洗，烘干，搅碎，筛分，得到尺寸均一的紫花苜蓿粉末；紫花苜蓿粉末与活化剂混合后，进行共热解反应；将反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；将黑色粉末生物炭置于超纯水中超声分散，然后与摩尔比为2～4：1的FeCl3·6H2O和MnCl2·4H2O均匀混合，调节pH为碱性，进行高温高压水热反应；用超纯水、乙醇依次冲洗步骤四反应后的混合物，真空干燥。本发明制备原料为农业废弃物紫花苜蓿，来源广，成本低，能够实现废弃物充分再利用，有利于提高物紫花苜蓿附加值。
Description
技术领域
本发明涉及MnFe2O4复合物制法，具体为一种多孔生物炭基MnFe2O4复合物的制备方法。
背景技术
近年来，由于农业和制药厂的快速发展，在河流和饮用水中频繁检出抗生素。最新的研究结果表明，抗生素难以降解，在环境中可长期保持。水环境中的抗生素可引发人和动物体内抗生素耐药基因的增加，对生态环境造成潜在的基因污染。如今，抗生素耐药性问题已成为全球公共卫生问题之一。
通过激活过氧单硫酸盐或过氧二硫酸盐的高级氧化技术(AOT)已被广泛用于去除抗生素，并显示出良好的性能。活性氧(ROS)如硫酸盐自由基和羟基自由基可以通过紫外线、过渡金属活化和热活化在原位形成。在储存和运输方面，过硫酸盐比过氧化氢具有更高的稳定性和便利性。虽然过硫酸盐活化法具有上述优点，但基于过硫酸盐的 AOT仍有很大的缺点，如成本高，处理后的水可能会产生毒性。亚硫酸盐作为烟气脱硫过程的副产物，近年来被认为是一种可行的替代品。此外，多种过渡金属，包括锰、铁和钴，已被应用于过硫酸盐的活化。显然，与钴相比，含铁和锰的催化剂成本低、毒性低，是更好的选择。
MnFe2O4作为一种磁性材料，在外加磁场的作用下很容易从水溶液中分离出来，为实际应用提供了一种经济有效的方法。然而，由于颗粒之间的磁性相互作用，磁性纳米颗粒容易在水中聚集，这大大降低了催化活性。有必要选择合适的载体来提高MnFe2O4的应用性能。
现有MnFe2O4制备方法存在以下缺点：催化剂的利用率低，表面活性位点少，容易发生聚集。
发明内容
发明目的：为了克服现有技术中存在的不足，本发明的目的是提供一种来源广泛、成本低廉的多孔生物炭基MnFe2O4复合物的制备方法。
技术方案：本发明所述的一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
步骤一，紫花苜蓿用超纯水冲洗，去除表面杂质，烘干，搅碎，筛分，得到尺寸均一的紫花苜蓿粉末；
步骤二，紫花苜蓿粉末与活化剂混合后，放入管式炉中进行共热解反应；
步骤三，将步骤二反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；
步骤四，将步骤三中的黑色粉末生物炭置于超纯水中超声分散，然后与摩尔比为2～4：1的FeCl3·6H2O和MnCl2·4H2O均匀混合，调节pH为碱性，进行高温高压水热反应；
步骤五，用超纯水、乙醇依次冲洗步骤四反应后的混合物，真空干燥，得到多孔生物炭基MnFe2O4复合物。
进一步地，步骤一中，紫花苜蓿的氮含量为4～4.5wt％。烘干是在80～110℃烘箱中干燥12～24h，搅碎使用粉碎机，筛分用20～40目筛。
进一步地，步骤二中，活化剂为氢氧化钾、氢氧化钙、氢氧化钠中的一种或多种。活化剂优选为氢氧化钾和氢氧化钙的混合物，其质量比为1～3：1，优选为1：1。紫花苜蓿粉末与活化剂的质量比为1：1～3。共热解反应在管式炉中进行，反应气氛为氮气，温度为500～800℃，升温速率为1～10℃/分钟，时间为1～10h。
进一步地，步骤四中，超声分散时间为10～60分钟，pH用1M浓度的氢氧化钠溶液调节为11～13，优选为12。高温高压水热反应在高温高压釜中进行，反应温度为 150～200℃，反应时间为2～24小时。
进一步地，步骤五，干燥温度为80～120℃，时间为12～24h。多孔生物炭基MnFe2O4复合物的比表面积为655～660m2/g，总孔体积为0.7～0.8cm3/g。
反应原理：Mn、Fe、O在反应过程中容易聚集，通过本申请步骤二到步骤四的处理，能够使其分散均匀。在高级氧化与光催化协同作用过程中，由于生物炭中大量氮掺杂构型的存在，光生电子和空穴对的分离效率提高。由于生物炭表面的孔径，以及生物炭与金属的界面相互作用使其不易聚集。
有益效果：本发明和现有技术相比，具有如下显著性特点：
1、制备原料为农业废弃物紫花苜蓿，来源广，成本低，能够实现废弃物充分再利用，两种不同类型的碱共活化，有利于生成不同尺寸的孔径，有利于四环素的传质与吸附；
2、有利于提高物紫花苜蓿的附加值，利用其富含氮元素的特点，制得的生物炭原位生成了氮掺杂构型，有较大的比表面积、类石墨结构和分级多孔结构，吸附容量大；
3、MnFe2O4中锰元素和铁元素可催化过硫酸盐反应，用于降解废水中的抗生素；且MnFe2O4是磁性材料，在外磁场的作用下易分离，便于回收再利用；
4、生物炭作为MnFe2O4的载体，可以抑制磁性MnFe2O4的聚集，提高其分散性，加速污染物与活性位点的接触，提高降解效率，在高级氧化与光催化协同作用过程中，由于生物炭中大量氮掺杂构型的存在，光生电子和空穴对的分离效率提高。
附图说明
图1是本发明的XRD谱图；
图2是本发明实施例4NBCs的扫描电镜图；
图3是MnFe2O4的扫描电镜图；
图4是本发明实施例5所得产品的扫描电镜图；
图5是本发明实施例4、实施例5所得产品的N2吸附-解吸附等温线图；
图6是本发明实施例4、实施例5所得产品的孔径尺寸分布图；
图7是本发明实施例8的材料在吸附四环素前后的FTIR对比图，其中，a为实施例4所得产品，b为实施例6所得产品，c为实施例7所得产品，d为实施例5所得产品；
图8是本发明实施例8的材料对于四环素的吸附动力学曲线，其中，a为实施例4 所得产品，b为实施例6所得产品，c为实施例7所得产品，d为实施例5所得产品；
图9是本发明实施例9中的材料与其对照样品的降解动力学曲线；
图10是本发明实施例9中的材料的准一级降解速率常数对比图。
具体实施方式
以下各实施例中，紫花苜蓿的氮含量为4～4.5wt％。
实施例1
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在80℃烘箱中干燥12h，用粉碎机搅碎，用20目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与10g活化剂氢氧化钾，混合后，放入管式炉中进行共热解反应1h，反应气氛为氮气，温度为500℃，升温速率为1℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；
(4)将步骤(3)中的0.05893g黑色粉末生物炭置于超纯水中超声分散10～60分钟，然后与0.1081g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为11，在高温高压釜中进行150℃高压水热反应2小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，80～120℃真空干燥12h，得到多孔生物炭基MnFe2O4复合物。
所得多孔生物炭基MnFe2O4复合物的比表面积为655.36m2/g，总孔体积为0.72cm3/g。
实施例2
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在110℃烘箱中干燥24h，用粉碎机搅碎，用40目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与30g活化剂，活化剂为15g氢氧化钾和15g氢氧化钠混合后，放入管式炉中进行共热解反应10h，反应气氛为氮气，温度为800℃，升温速率为10℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；
(4)将步骤(3)中的黑色粉末生物炭置于超纯水中超声分散10～60分钟，然后与0.2162g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为13，在高温高压釜中进行200℃高压水热反应24小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，80～120℃真空干燥24h，得到多孔生物炭基MnFe2O4复合物。
所得多孔生物炭基MnFe2O4复合物的比表面积为659.76m2/g，总孔体积为0.79cm3/g。
实施例3
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在95℃烘箱中干燥18h，用粉碎机搅碎，用40目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与20g活化剂氢氧化钠混合后，放入管式炉中进行共热解反应5h，反应气氛为氮气，温度为650℃，升温速率为5℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；
(4)将步骤(3)中的黑色粉末生物炭置于超纯水中超声分散10～60分钟，然后与0.1081g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为12，在高温高压釜中进行180℃高压水热反应13小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，80～120℃真空干燥1h，得到多孔生物炭基MnFe2O4复合物。
所得多孔生物炭基MnFe2O4复合物的比表面积为657.18m2/g，总孔体积为0.75cm3/g。
实施例4
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在100℃烘箱中干燥12h，用粉碎机搅碎，用20目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与20g活化剂混合，活化剂为10g氢氧化钾和10g氢氧化钙的混合物，放入管式炉中进行共热解反应1h，反应气氛为氮气，温度为700℃，升温速率为8℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭，记为NBCs。
由图2可以看出，NBCs表面光滑，缺陷位点多，孔结构发达。
实施例5
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在100℃烘箱中干燥12h，用粉碎机搅碎，用20目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与20g活化剂混合，活化剂为10g氢氧化钾和10g氢氧化钙的混合物，放入管式炉中进行共热解反应1h，反应气氛为氮气，温度为700℃，升温速率为8℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭，记为NBCs；
(4)将步骤(3)中的黑色粉末生物炭(NBCs)0.117852g置于超纯水中超声分散 20分钟，然后与0.10812g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为12，在高温高压釜中进行180℃高压水热反应6小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，100℃真空干燥18h，得到多孔生物炭基MnFe2O4复合物，记为NBCs/MnFe2O4-2:1。
图3为常规的MnFe2O4的扫描电镜图，呈准球形，并伴有少量棒状和板状结构，直径为50-200nm。图4是本实施例所得MnFe2O4复合物的扫描电镜图。由图4可以看出，最终制得的MnFe2O4复合物为多孔结构，使用NBCs作为载体来装载小尺寸的MnFe2O4纳米颗粒，并且在NBCs/MnFe2O4中，NBCs和MnFe2O4的形态没有显著变化。
图5是实施例4、实施例5所得产品的N2吸附-解吸附等温线图。从图5可以看出：根据IUPAC分类，NBCs和NBCs/MnFe2O4均具有明显回滞环的IV型吸附等温线，这证明制备的样品含有介孔，有利于污染物的传质。当相对压力小于0.01时，由于样品中存在微孔，吸附体积急剧增加。
图6是实施例4、实施例5所得产品的孔径尺寸分布图。从图6可以看出：样品同时含有微孔和介孔，这与吸附等温线分析结果一致。
实施例6
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在100℃烘箱中干燥12h，用粉碎机搅碎，用20目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与20g活化剂混合，活化剂为10g氢氧化钾和10g氢氧化钙的混合物，放入管式炉中进行共热解反应1h，反应气氛为氮气，温度为700℃，升温速率为8℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭，记为NBCs；
(4)将步骤(3)中的黑色粉末生物炭(NBCs)0.058926g置于超纯水中超声分散 20分钟，然后与0.10812g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为12，在高温高压釜中进行180℃高压水热反应6小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，100℃真空干燥18h，得到多孔生物炭基MnFe2O4复合物，记为NBCs/MnFe2O4-1:1。
实施例7
一种多孔生物炭基MnFe2O4复合物的制备方法，包含以下步骤：
(1)紫花苜蓿用超纯水冲洗，去除表面杂质，在100℃烘箱中干燥12h，用粉碎机搅碎，用20目筛筛分，得到尺寸均一的紫花苜蓿粉末；
(2)将10g紫花苜蓿粉末与20g活化剂混合，活化剂为10g氢氧化钾和10g氢氧化钙的混合物，放入管式炉中进行共热解反应1h，反应气氛为氮气，温度为700℃，升温速率为8℃/分钟；
(3)将步骤(2)反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭，记为NBCs；
(4)将步骤(3)中的黑色粉末生物炭(NBCs)0.029463g置于超纯水中超声分散 20分钟，然后与0.10812g的FeCl3·6H2O和0.0396g MnCl2·4H2O均匀混合，用1M浓度的氢氧化钠溶液调节pH为12，在高温高压釜中进行180℃高压水热反应6小时；
(5)用超纯水、乙醇依次冲洗步骤(4)反应后的混合物，100℃真空干燥18h，得到多孔生物炭基MnFe2O4复合物，记为NBCs/MnFe2O4-1:2。
将实施例4～7中得到的NBCs、NBCs/MnFe2O4-1:1、NBCs/MnFe2O4-1:2、 NBCs/MnFe2O4-2:1分别进行XRD测试，如图1，可以看出：纯MnFe2O4的典型衍射峰为尖晶石相，具有较高的结晶度，在制备过程中无杂质生成。对于NBCs，在2θ＝26.46°和42.42°处存在特征衍射峰，分别属于石墨的(0 0 2)面和(1 0 0)面。此外，在NBCs/ MnFe2O4-2:1的XRD光谱中，MnFe2O4的特征衍射峰分别位于35.25°和62.46°处。这些结果表明，成功地制备了NBCs/MnFe2O4。
实施例8
S1：配置4份50mg/L的四环素溶液100mL于带塞的烧瓶；
S2：将实施例4～7中得到的NBCs、NBCs/MnFe2O4-1:1、NBCs/MnFe2O4-1:2、 NBCs/MnFe2O4-2:1，在避光条件下置于25℃，200rpm的磁力水浴搅拌锅，在特定时间点取样(5分钟、10分钟、20分钟、30分钟、40分钟、50分钟、60分钟、80分钟、 100分钟、120分钟、150分钟、180分钟、240分钟、300分钟、360分钟和420分钟)
S3：取样3000rpm离心后，通过紫外-可见分光光度计测定上清液浓度。
材料对四环素的吸附能力用以下方程计算：
其中：V(L)表示四环素溶液的体积；C0(mg/L)和Ct(mg/L)分别表示四环素溶液的初始浓度和平衡浓度。m(g)表示生物炭的质量；Qt(mg/g)表示生物炭对四环素的吸附量。在计算吸附动力学后，分别运用准一级动力学模型与准二级动力学模型模拟。模型方程如下：
准一级动力学模型：
准二级动力学模型：
式中，Qe为平衡吸附量拟合值，单位mg/g；Qt为t时刻吸附量，单位mg/g；k1为准一级吸附速率常数，单位min-1；k2为准二级吸附速率常数，单位g·mg-1·min-1。
从图8可以看出：准二级动力学更能准确的描述吸附动力学实验数据，这意味着TC在NBCs和NBCs/MnFe2O4上的吸附遵循化学吸附机理。
实施例9
S1：配置7份30mg/L的四环素溶液100mL于带塞的烧瓶，并在第1、2、3、4、6、 7号烧瓶中加入3mmol的Na2SO3；
S2：分别取实施例2-4中得到的NBCs/MnFe2O4-1:1、NBCs/MnFe2O4-1:2、 NBCs/MnFe2O4-2:1、各10mg于S1配置的第1-3号烧瓶中，并向第4、5号烧瓶中加入 10mg的MnFe2O4，置于25℃，200rpm的磁力水浴搅拌锅，用低压汞灯向1-6号烧瓶照射波长为254nm的紫外光。在特定时间点取样(5分钟、10分钟、20分钟、30分钟、40分钟、50分钟、60分钟、80分钟、100分钟、120分钟、150分钟、180分钟、 240分钟、300分钟、360分钟和420分钟)。
S3：取样3000rpm离心后，通过紫外-可见分光光度计测定上清液浓度。
从图9～10可以看出：NBCs/MnFe2O4-2:1对TC的催化降解效果最好，且其速率常数更大。
Claims (10)
1.一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于，包含以下步骤：
步骤一，紫花苜蓿用超纯水冲洗，烘干，搅碎，筛分，得到尺寸均一的紫花苜蓿粉末；
步骤二，紫花苜蓿粉末与活化剂混合后，进行共热解反应；
步骤三，将步骤二反应得到的混合物冷却至室温，用稀盐酸和超纯水反复冲洗，干燥得黑色粉末生物炭；
步骤四，将步骤三中的黑色粉末生物炭置于超纯水中超声分散，然后与摩尔比为2～4：1的FeCl3·6H2O和MnCl2·4H2O均匀混合，调节pH为碱性，进行高温高压水热反应；
步骤五，用超纯水、乙醇依次冲洗步骤四反应后的混合物，真空干燥，得到多孔生物炭基MnFe2O4复合物。
2.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤一中，紫花苜蓿的氮含量为4～4.5wt％。
3.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤一中，烘干是在80～110℃烘箱中干燥12～24h，搅碎使用粉碎机，筛分用20～40目筛。
4.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤二中，活化剂为氢氧化钾、氢氧化钙、氢氧化钠中的一种或多种。
5.根据权利要求4所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤二中，活化剂为氢氧化钾和氢氧化钙的混合物，其质量比为1～3：1。
6.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤二中，紫花苜蓿粉末与活化剂的质量比为1：1～3。
7.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤二中，共热解反应在管式炉中进行，反应气氛为氮气，温度为500～800℃，升温速率为1～10℃/分钟，时间为1～10h。
8.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤四中，超声分散时间为10～60分钟，pH用氢氧化钠溶液调节为11～13，高温高压水热反应在高温高压釜中进行，反应温度为150～200℃，反应时间为2～24小时。
9.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤五，干燥温度为80～120℃，时间为12～24h。
10.根据权利要求1所述的一种多孔生物炭基MnFe2O4复合物的制备方法，其特征在于：所述步骤五中，多孔生物炭基MnFe2O4复合物的比表面积为655～660m2/g，总孔体积为0.7～0.8cm3/g。
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