CN106824195B - 多孔Fe3Co7@C纳米球及催化降解有机污染物的应用 - Google Patents
多孔Fe3Co7@C纳米球及催化降解有机污染物的应用 Download PDFInfo
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Abstract
本发明提供了一种制备石墨烯包裹的Fe3Co7合金(Fe3Co7@C)多孔纳米球的方法。通过在氮气气氛下煅烧掺杂型Fe‑Co普鲁士蓝类似物(FeyCo1‑y‑Co PBA)可以制备得到Fe3Co7@C多孔纳米球。该Fe3Co7@C纳米球具有很好的稳定性，其零价铁和钴在石墨烯的包裹下十分稳定，在空气中可以长期保存。另外，该Fe3Co7@C纳米球可以作为芬顿、类芬顿反应催化剂，通过活化PMS、PS或者H2O2产生活性自由基物种降解污水中的有机污染物。
Description
技术领域
本发明涉及利用一种多孔Fe3Co7@C多孔纳米球的制备方法，以及其在芬顿反应中催化降解有机污染物中的应用。
背景技术
近年来纳米零价铁(nZVI)在光催化、芬顿反应、重金属吸附、电化学等领域有着广泛的应用。制备nZVI的方法也有很多，包括硼氢化钠还原法、氢气还原法、以及氮气气氛焙烧等。但是制备得到的nZVI往往存在较差的稳定性，在空气气氛下极易被氧化生成惰性氧化膜。而大多数催化反应均发生在催化剂的表面，零价铁表层的惰性氧化膜则会大幅度降低其催化性能。因此，如何制备具有较高稳定性的纳米零价铁依旧存在着挑战。
铁钴合金纳米材料由于其存在双金属协同催化的效果，可以发挥更好的催化活性。但通过传统方法制备得到的铁钴合金存在比表面积小，颗粒大，易氧化等缺点。通过在纳米零价金属表面包裹一层碳材料则可以大幅度提高其稳定性。但是传统的制备方法存在着制备步骤繁琐等缺点，制备出来的材料具有碳包裹不均匀、分散性差等弊端。因此，开发新的合成方法制备稳定的碳包裹的铁钴合金纳米颗粒具有重要的意义。
铁和钴均为芬顿反应的主要活性物种，因此，将铁钴合金用于芬顿、类芬顿反应降解有机污染物对对环境净化有着重要的意义。
发明内容
本发明旨在开发一种新型的多孔Fe3Co7@C多孔纳米球，并开发其在芬顿催化领域的用途。
一种新型的多孔Fe3Co7@C纳米球的制备，其具体步骤为：
以FeyCo1-y[Co(CN)6]0.67·nH2O(FeyCo1-y-Co PBAs)为前驱体，在氮气气氛下煅烧可得。
在氮气气氛下煅烧，其特征为：
煅烧温度为600-1000度，半小时以上,升温速率为1-10度/min。
将所制备的多孔Fe3Co7@C纳米球在H2O2、PS或者PMS存在下对污水中有机污染物降解，可以取得较好的降解效果。
本发明具有如下优点：
1)制备得到的多孔Fe3Co7@C纳米球具有较高的比表面积，因此在催化应用中可以表现出较高的活性。
2)该纳米笼同时具有很强的铁磁性，在水溶液催化反应后，可以方便的利用磁铁吸附回收再利用。
3)该制备方案简单易行。
4)制备得到的Fe3Co7@C在空气气氛可以稳定保存。
附图说明
图1是实施例1中制备得到的Fe3Co7@C纳米球的SEM(扫描电镜)照片。从图中可以看出，制备得到的纳米弄分散均匀，形貌规则且具有多孔的性质。
图2是实施例2中制备得到的Fe3Co7@C纳米球的SEM(扫描电镜)照片。从图中可以看出，制备得到的纳米弄分散均匀，形貌规则且具有多孔的性质。
图3是实施例1中制备得到的Fe3Co7@C纳米球的XRD谱图。从图中可以看出，得到的Fe3Co7@C纳米球为纯相的铁钴合金，并无杂质峰的出现。
图4是实施例3中，利用Fe3Co7@C纳米球作为芬顿反应催化剂降解双酚A 的活性图，可以看去，30分钟，其对双酚A的降解率超过99％。说明其在有机污染物降解催化中的应用。
具体实施方式
实施例1
将Fe0.5Co0.5-Co PBAs纳米球前体在650度氮气气氛焙烧1h，升温速率为2 度/min，即可制备出多孔Fe3Co7@C纳米球。
实施例2
将Fe0.5Co0.5-Co PBAs纳米球前体在800度氮气气氛焙烧1h，升温速率为2 度/min，同样可制备出多孔Fe3Co7@C纳米球。
实施例3
取0.01g实施例1得到的Fe3Co7@C纳米球加入50ml的双酚A有机污染物中，之后加入0.01g PMS。考察Fe3Co7@C纳米球作为芬顿反应催化剂活化PMS 降解有机污染物的活性。反应条件为：催化剂浓度0.1g/L、双酚A浓度20mg/L，PMS浓度0.2g/L的水溶液，pH＝6.0。结果发现，其对双酚A的降解率30分钟可以达到99％。
以上所述，仅为本发明的具体实施方式之一，但本发明的保护范围并不局限与此，任何熟悉本领域的技术人员在本发明所揭露的技术范围内，未经过创造性思想的变动和替换，均应包涵在保护范围之内。因此，本发明的保护范围应该以权力要求书所限定的保护范围为准。
Claims (4)
1.一种多孔Fe3Co7@C纳米球在类芬顿反应降解有机污染物中的应用，其特征在于：
所述多孔Fe3Co7@C纳米球，Fe：Co金属比例为3:7，以Fe0.5Co0.5[Co(CN)6]0.67•nH2O为前驱体，其中n为0-1，在氮气气氛下煅烧得到，在H2O2、PS或者PMS中的一种或二种以上存在下对污水中有机污染物降解。
2.按照权利要求1所述的应用，其特征在于：
煅烧温度为600-1000℃，从室温到煅烧温度的升温速率为1-10℃/min。
3.按照权利要求1所述的应用，其特征在于：
其中铁和钴均为零价，Fe3Co7合金颗粒均匀包裹在薄层的碳中，堆积形成多孔纳米球；纳米球尺寸为50-300 nm。
4.按照权利要求2所述的应用，其特征在于：煅烧时间为0.5-4 h。
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| CN112911915B (zh) * | 2021-01-18 | 2022-08-09 | 江南大学 | 一种耐腐蚀性石墨烯基磁性复合泡沫吸波材料及制备方法 |
| CN113206230B (zh) * | 2021-04-25 | 2022-07-05 | 华中科技大学 | 一种碳包覆普鲁士蓝或其类似物及它们的制备与应用 |
| CN114950450B (zh) * | 2022-04-15 | 2023-05-16 | 兰州大学 | 一种催化降解四环素的双金属氧化物及其制备方法和应用 |
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| CN115090287B (zh) * | 2022-06-02 | 2024-02-27 | 中国科学技术大学 | 一种铁钴掺杂的臭氧活化催化剂Fe-CoOx及制备方法 |
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