CN113275040B - 一种Fe3O4@C限域界面负载Ce-MOFs催化剂的制备及其在电芬顿中的应用 - Google Patents
一种Fe3O4@C限域界面负载Ce-MOFs催化剂的制备及其在电芬顿中的应用 Download PDFInfo
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Abstract
本发明公开了一种Fe3O4@C界面限域负载Ce‑MOFs催化剂(Ce‑MOFs/Fe3O4@C)的制备方法，及将其负载于阴极应用于非均相电芬顿水处理方法中实现污染物的高效去除。本发明催化剂的特征是：通过溶剂热法同时合成了铈‑金属有机框架和铁‑金属有机框架(Ce/Fe‑MOFs)，利用两种MOFs分解温度的不同，实现了Ce‑MOFs沉积于碳包裹Fe3O4颗粒的表面，实现了Ce‑MOFs与碳之间的界面限域以及多层结构表现的多反应中心。利用氧空位及Ce‑MOFs与Fe3O4@C之间的强作用力促进O2还原为H2O2和O2 ·‑，而Fe2+及Ce3+活化产生的H2O2产生·OH，同时Ce4+活化O2 ·‑产生1O2，从而实现多种自由基对污染物的催化。Ce‑MOFs/Fe3O4@C催化剂表现出高的H2O2选择率，高的电流效率及低的溶出铁的特点。同时该催化剂可在低电势，宽pH下对多种污染物实现高效去除，解决了常规均相芬顿反应pH适应范围窄以及不能重复使用的问题。
Description
技术领域
本发明涉及材料、环境领域，具体地，本发明涉及Fe3O4@C限域界面负载 Ce-MOFs催化剂的制备方法及其在非均相电芬顿中的应用。
背景技术
均相电芬顿技术由于可以产生强氧化性的·OH高效降解各种污染物而备受欢迎。但均相电芬顿也存在一定的局限性：(1)pH适用范围窄(pH～3)，中碱性下易产生大量铁泥，增加后续处理费用；(2)均相催化剂无法回收，导致使用量大。因此，目前发展的铁基催化剂可既为非均相催化剂又为阴极材料，同时实现H2O2的产生及污染物的降解，并且可以拓宽pH范围，实现催化剂的重复使用，但仍面临着需要的阴极电势高，H2O2产量低，铁溶出较大的问题。
目前，有研究表明，铈(Ce)可以在H2O2存在的情况下发生Ce4+/Ce3+转化过程，同时CeO2的晶格中可产生氧空位有利于氧气的储存和H2O2的产生。 Ce4+/Ce3+之间的相互转化类似于Fe2+/Fe3+在芬顿过程中的行为。另外，有研究表明，CeO2可以提高Fe3O4的催化活性。因此，在铁基催化剂基础上引入Ce，同时高效发挥Ce与Fe之间的耦合关系，增强ORR活性及电化学催化活性，从而实现污染物的高效去除是至关重要的。
发明内容
本发明的目的旨在制备Fe3O4@C限域界面负载Ce-MOFs催化剂 (Ce-MOFs/Fe3O4@C)，并将其应用于非均相电芬顿水处理中，在较低电势下原位实现H2O2的高效产生及污染物的有效去除。本发明提出Ce、Fe、C、O组分间的多反应活性中心及Ce-MOFs与Fe3O4@C界面限域的结构，可促进O2的吸附及转化，实现多种自由基共同催化降解污染物。
Fe3O4@C限域界面负载Ce-MOFs催化剂的制备方法，其特征在于以下步骤：
(1)将乙酰丙酮铁、硝酸铈和对苯二甲酸溶解于N,N-二甲基甲酰胺和乙醇的混合溶液中，将其放入反应釜后，在120℃下保持24h,自然冷却到室温，甲醇清洗后在200℃中活化6h，得到Fe/Ce-MOFs；(2)将步骤(1)得到的Fe/Ce-MOFs 置于惰性气体气氛下，在400℃煅烧1-2h，Fe-MOFs中的有机物逐渐碳化，得到Fe3O4@C限域界面负载Ce-MOFs催化剂(Ce-MOFs/Fe3O4@C)。
上述的Fe3O4@C限域界面负载Ce-MOFs催化剂的制备方法，其特征在于得到的Ce-MOFs/Fe3O4@C催化剂中Ce-MOFs负载于碳包裹Fe3O4颗粒的表面。
上述的Fe3O4@C限域界面负载Ce-MOFs催化剂的制备方法，其特征在于乙酰丙酮铁和硝酸铈的比例可为5：1至1：1。
上述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于：将权力要求1所述的催化剂粉末负载于碳基底作为阴极；调节待处理废水pH为 3-7，控制阴极电势为-0.15V-0.45V(vs可逆氢电极)进行非均相电芬顿降解。
上述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于碳基底为碳毡、碳布、碳纸或碳纤维等碳材料基底。
上述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于催化剂负载量为1至4mg cm-2。
本发明具有以下突出特点：
(1)该催化剂制备方法简单，且该催化剂表现出多反应活性中心及 Ce-MOFs及Fe3O4@C间界面限域效应等结构特点
(2)该催化剂表现出90％的H2O2选择率，80％的电流效率及0.29mg L-1溶出铁的特点
(3)该催化剂表现出在-0.15V-0.45V的阴极电势下可产生·OH及1O2多种活性物种实现中性环境下高效降解污染物的特点。
附图说明
图1本发明制备的乙酰丙酮铁和硝酸铈为2：1的Ce-MOFs/Fe3O4@C催化剂应用于非均相电芬顿工艺原位降解磺胺二甲基嘧啶的效果图；
图2为本发明制备的Ce-MOFs/Fe3O4@C催化剂的X射线衍射谱图；
图3为本发明制备的Ce-MOFs/Fe3O4@C阴极产生的羟基自由基和单线氧图；
图4为本发明制备的乙酰丙酮铁和硝酸铈为5：1的Ce-MOFs/Fe3O4@C催化剂应用于非均相电芬顿工艺原位降解磺胺二甲基嘧啶的效果图；
图5为本发明制备的乙酰丙酮铁和硝酸铈为1：1的Ce-MOFs/Fe3O4@C催化剂应用于非均相电芬顿工艺原位降解磺胺二甲基嘧啶的效果图；
图6为本发明制备的Ce-MOFs/Fe3O4@C催化剂与Ce-MOFs和Fe3O4@C混合后催化剂的H2O2选择率图；
图7为本发明制备的Ce-MOFs/Fe3O4@C催化剂与Ce-MOFs和Fe3O4@C混合后催化剂作为阴极应用于非均相电芬顿工艺原位降解磺胺二甲基嘧啶及产 H2O2时的电流效率图；
图8为本发明制备的Ce-MOFs/Fe3O4@C阴极降解多种污染物的效果图；
图9为本发明制备的Ce-MOFs/Fe3O4@C阴极重复使用10次降解磺胺二甲基嘧啶的效果图和铁溶出图；
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
将硝酸铈、乙酰丙酮铁和对苯二甲酸溶解于N,N-二甲基甲酰胺和乙醇的混合溶液中，将其放入反应釜后，在120℃下保持24h,自然冷却到室温，甲醇清洗后在200℃中活化6h，得到Fe/Ce-MOFs；将得到的Fe/Ce-MOFs置于惰性气体气氛下，在400℃煅烧1-2h，Fe-MOFs中的有机物逐渐碳化，得到Fe3O4@C 限域界面负载Ce-MOFs催化剂(Ce-MOFs/Fe3O4@C)。
实施案例1
本实施例的Ce-MOFs/Fe3O4@C阴极催化性能测试如下：配置50mL含有 10mg L-1磺胺二甲基嘧啶的50mM硫酸钠溶液，且pH为7。当 Ce-MOFs/Fe3O4@C负载量为2mg cm-2，阴极电势为0.05V(vs可逆氢电极) 以及曝气量为0.4L min-1时，从图1可以看出当乙酰丙酮铁和硝酸铈为2：1，磺胺二甲基嘧啶的去除为94％。采用透射电子显微镜观察到Ce-MOFs/Fe3O4@C的多层结构，这证明Fe3O4@C界面负载Ce-MOFs催化剂(结果见图2)。在测试反应过程中产生的活性氧物种时，发现Ce-MOFs/Fe3O4@C@C阴极产生的活性氧物种为·OH和1O2，这可能是因为氧空位的存在可以富集O2产生H2O2及O2 ·-，而Fe2+/Fe3+和Ce3+/Ce4+之间的相互作用将其定向转化为·OH和1O2(结果见图 3)。
实施案例2
实施案例2的步骤基本与实施案例1相同，除了制备乙酰丙酮铁和硝酸铈为5：1的Ce-MOFs/Fe3O4@C，当该催化剂作为阴极时，2小时磺胺二甲基嘧啶的去除为77％，结果见图4。
实施案例3
实施案例3的步骤基本与实施案例1相同，除了制备乙酰丙酮铁和硝酸铈为1：1的Ce-MOFs/Fe3O4@C，当该催化剂作为阴极时，2小时磺胺二甲基嘧啶的去除降为70％，结果见图5。
实施案例4
将Fe3O4@C和Ce-MOFs按照2：1机械混合后，与实施案例1中制备的 Ce-MOFs/Fe3O4@C在旋转圆盘电极测试过程中比较发现，制备的 Ce-MOFs/Fe3O4@C催化剂表现出良好的电子传递过程，以及计算得到的H2O2选择率可达90％，而Fe3O4@C和Ce-MOFs机械混合催化剂的H2O2选择率仅为 76％，结果见图6，表明Ce-MOFs/Fe3O4@C是一种良好的实现两电子ORR产生H2O2的催化剂。
参考图7，当Ce-MOFs和Fe3O4@C机械混合的催化剂作为阴极时，磺胺二甲基嘧啶仅去除仅为50％，且铁溶出从0.29mg L-1增加至1.26mg L-1。同时， Ce-MOFs/Fe3O4@C及Ce-MOFs和Fe3O4@C机械混合的催化剂产生H2O2时的电流效率分别为80.68％和33.43％，这也表明本发明制备的Ce-MOFs/Fe3O4@C 在低电势下可以高效产生H2O2及实现磺胺二甲基嘧啶的去除。
实施案例5
实施案例5的步骤基本与实施案例1相同，除了污染物为10mg L-1的苯酚、卡马西平以及罗丹明B。从图8中可看出，针对三种不同种类的污染物， Ce-MOFs/Fe3O4@C阴极在中性条件下，对三种污染物均可实现85％以上的去除。说明Ce-MOFs/Fe3O4@C阴极非均相电芬顿水处理方法可适用于多种污染物降解及其废水。
实施案例6
实施案例6的步骤基本与实施案例1相同。参考图9，当Ce-MOFs/Fe3O4@C 阴极重复使用10次后，磺胺二甲基嘧啶的去除仍可达80％，且溶出铁浓度均低于0.3mg L-1。因此Ce-MOFs/Fe3O4@C阴极既可以实现重复使用，并且可以减少铁溶出，从而减少铁泥的产生。
Claims (5)
1.一种Fe3O4@C限域界面负载Ce-MOFs催化剂的制备方法，其特征在于以下步骤：
（1）将乙酰丙酮铁、硝酸铈和对苯二甲酸溶解于N, N-二甲基甲酰胺和乙醇的混合溶液中，其中乙酰丙酮铁和硝酸铈的比例为5：1至1：1，将其放入反应釜后，在120℃下保持24 h,自然冷却到室温，甲醇清洗后在200℃中活化6 h，得到Fe/Ce-MOFs；
（2）将步骤（1）得到的Fe/Ce-MOFs置于惰性气体气氛下，在400℃煅烧1 - 2 h，Fe-MOFs中的有机物逐渐碳化，得到Fe3O4@C限域界面负载Ce-MOFs的催化剂Ce-MOFs/Fe3O4@C。
2.根据权利要求1所述的Fe3O4@C限域界面负载Ce-MOFs催化剂的制备方法，其特征在于得到的Ce-MOFs/Fe3O4@C催化剂中Ce-MOFs负载于碳包裹Fe3O4颗粒的表面。
3.根据权利要求1所述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于：将权利要求1所述的催化剂粉末负载于碳基底作为阴极；调节待处理废水pH为3-7，控制阴极电势相对可逆氢电极为-0.15 V - 0.45 V进行非均相电芬顿降解。
4.根据权利要求3所述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于碳基底为碳毡、碳布、碳纸或碳纤维。
5.根据权利要求3所述的Ce-MOFs/Fe3O4@C催化剂在非均相电芬顿中的应用，其特征在于催化剂负载量为1至4 mg·cm-2。
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