CN106881141B - 钴/六方氮化硼复合核壳结构纳米催化剂及其制备与应用 - Google Patents
钴/六方氮化硼复合核壳结构纳米催化剂及其制备与应用 Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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Abstract
本发明公开了一种钴/六方氮化硼复合核壳结构纳米催化剂Co@BN及其制备方法和应用,属于材料制备和环境净化技术领域。所述复合纳米催化剂是采用氨气一次常压高温焙烧法,制得的以六方氮化硼包裹钴纳米颗粒形成的核壳结构纳米催化剂。所得催化剂具有大比表面积和高活性位点,可用于高效催化还原硝基化合物,且其具有磁性,易回收再利用,能够有效解决传统金属纳米催化剂不稳定、易团聚等问题。本发明制备方法简单,原料廉价易得,有利于大规模的工业生产,具备显著的经济和社会效益。
Description
技术领域
本发明属于材料制备和环境净化技术领域,具体涉及一种钴/六方氮化硼复合核壳结构纳米催化剂Co@BN及其制备方法和应用。
背景技术
随着我国化学工业的发展,工业废水也在不断地增加,其中含硝基化合物的废水也是有害化工废水之一。如何有效地处理含硝基化合物的废水,对环境保护有着重要的意义。在目前众多的处理硝基化合物废水手段(如生化法、吸附法、液膜法、化学氧化法和催化法)中,催化还原硝基化合物技术由于成本低、反应条件相对温和以及还原产物用途广泛等优点成为一种比较理想的环境治理技术。目前,催化还原硝基化合物技术研究主要集中于贵金属纳米催化,但是贵金属稀缺昂贵,不利于广泛应用。过渡金属钴含量丰富、廉价易得,是一种广泛使用的催化材料。同时,纳米尺寸的金属催化剂由于比表面大、表面活性中心多,因此展现非常好催化性能。但是纳米尺寸的金属粒子由于高表面能容易导致粒子之间的团聚,从而降低了催化剂的催化性能。因此开发具有较高稳定性和活性的催化剂对还原硝基化合物及其废水的治理有重大的意义。
发明内容
本发明的目的在于提供一种钴/六方氮化硼复合核壳结构纳米催化剂Co@BN及其制备方法和应用,所得催化剂具有高比表面积,适用于高效催化还原硝基化合物,且其具有磁性,易回收再次利用,可解决传统金属纳米催化剂不稳定、易团聚等问题,同时其制备方法简单,原料廉价易得,有利于大规模的工业生产,具备显著的经济和社会效益。
为实现上述目的,本发明采用如下技术方案:
一种钴/六方氮化硼复合核壳结构纳米催化剂,其是以六方氮化硼包裹钴纳米颗粒形成所述核壳结构,所得催化剂具有大的比表面积和高的活性位点。
所述钴/六方氮化硼复合核壳结构纳米催化剂是采用氨气一次常压高温焙烧法进行制备;其具体操作为:将氧化硼、尿素和硝酸钴按质量比10:20:0.3、10:20:3、10:20:6或10:20:12混合,研磨成粉末,然后置于刚玉瓷舟里,再放入卧式高温管式炉中,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,保持5h,所得产物取出后经研磨,即得所述钴/六方氮化硼复合核壳结构纳米催化剂。
所述的钴/六方氮化硼复合核壳结构纳米催化剂适用于硝基化合物的催化还原。
本发明的有益效果在于:
(1)本发明首次制备获得一种Co@BN核壳结构,其利用六方氮化硼包裹钴纳米颗粒,可使钴纳米粒子得到长期保存。
(2)本发明在氨气气氛下,经一步高温焙烧制备所述钴/六方氮化硼复合核壳结构纳米催化剂,该制备方法具有很好的可控性和重复性,制备过程简单、低环境污染,有利于大规模的工业生产。
(3)本发明所得复合核壳结构纳米催化剂Co@BN能高效催化还原硝基化合物,同时具有良好的活性稳定性,且其具有磁性,重复利用率高,具有很高的实用价值和应用前景。
附图说明
图1为实施例1-4制备的具有不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂的XRD图。
图2为实施例1-4制备的具有不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂的FTIR图。
图3为实施例1-4制备的具有不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂的Raman图。
图4为本发明钴/六方氮化硼复合核壳结构纳米催化剂的TEM图(a、b)、HRTEM图(c)和SAED图(d)。
图5为实施例1-4制备的具有不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂催化还原对硝基苯酚的Ct/C0图。
图6为本发明钴/六方氮化硼复合核壳结构纳米催化剂催化还原不同硝基化合物的性能图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
将氧化硼、尿素和硝酸钴按质量比10:20:0.3混合,研磨成粉末;取混合样品于刚玉瓷舟里,再将其置于卧式高温管式炉里,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,再保持5h;产物取出后经研磨得10:20:0.3 Co@BN。
实施例2
将氧化硼、尿素和硝酸钴按质量比10:20:3混合,研磨成粉末;取混合样品于刚玉瓷舟里,再将其置于卧式高温管式炉里,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,再保持5h;产物取出后经研磨得10:20:3 Co@BN。
实施例3
将氧化硼、尿素和硝酸钴按质量比10:20:6混合,研磨成粉末;取混合样品于刚玉瓷舟里,再将其置于卧式高温管式炉里,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,再保持5h;产物取出后经研磨得10:20:6 Co@BN。
实施例4
将氧化硼、尿素和硝酸钴按质量比10:20:12混合,研磨成粉末;取混合样品于刚玉瓷舟里,再将其置于卧式高温管式炉里,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,再保持5h;产物取出后经研磨得10:20:12 Co@BN。
图1-3分别为实施例1-4制备的不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂的X射线衍射图(XRD)、红外光谱图(FTIR)及拉曼光谱图(Raman)。图1中,位于26.7°和42°的衍射峰分别代表的是h-BN的(002)和(100)特征衍射,在44.2°、51.5°和75.8°的衍射峰分别对应于Co的(111)、(200)和(220)晶面,此外,Co的衍射峰强度随着它的含量增加而逐渐增加。图2中,位于786和1387 cm-1处的峰分别是由于B-N-B平面外的弯曲振动和B-N平面内的伸缩振动,没有观察到氧化钴的峰,与XRD分析结合,说明制备的是单质钴。晶体的掺杂、缺陷、晶格无序都可由拉曼图分析得到。如图3中,位于1368 cm-1处的峰是由于氮化硼层间高频振动形成的峰,也没有观察到氧化钴的峰,拉曼分析结果与XRD和红外峰一致。
图4为实施例3制备的10:20:6 Co@BN复合核壳结构纳米催化剂的透射电镜图(TEM)、高分辨透射电镜图(HRTEM)及选区电子衍射图(SAED)。从透射电镜图(a、b)可以看出高度分散的Co纳米粒子的直径在100-200 nm之间,并且被h-BN包裹形成了核壳结构,氮化硼壳的厚度约为30-50 nm。而从相应的高分辨率透射电镜图像(c)看出,图中有两种晶格间距0.33 nm和0.20 nm,分别对应于h-BN的(002)晶面和Co的(111)晶面;更进一步可以看出Co纳米粒子被h-BN晶格环绕包裹,表明形成了Co@h-BN的核壳结构。由选区电子衍射图(d)可以看出,制备的钴是立方相,单晶。
实施例5
在100 mL的烧杯中,依次加入35 mL去离子水、4 mL 100 ppm的对硝基苯酚溶液,3mL 0.2M的硼氢化钠溶液、10 mg Co@BN复合纳米催化剂。每隔一定时间,取1.5 mL的反应混合溶液,用滤头过滤使催化剂与反应液隔离,以达到终止反应的目的,所得滤液用紫外可见分光光度计测定其吸光度。
图5为实施例1-4制备的具有不同钴含量的钴/六方氮化硼复合核壳结构纳米催化剂催化还原对硝基苯酚的Ct/C0图(对硝基苯酚的初始浓度和任意时刻的浓度分别为C0和Ct,根据朗伯比而定律,Ct/C0即At/A0)。从图5曲线斜率可以看出10:20:6 Co@BN的催化性能最好。
实施例6
在100 mL干净的烧杯中,依次加入35 mL去离子水、4mL 100 ppm的硝基化合物(对硝基苯酚、对硝基氯苯、对硝基甲苯、对硝基苯甲醚、对硝基苯胺)溶液,3 mL 0.2M 的硼氢化钠溶液、10 mg 制备好的10:20:6 Co@BN 复合纳米催化剂。利用Cary-500型分光光度计检测Co@BN 复合纳米催化剂对不同硝基化合物的催化还原情况。
图6为实施例3制备的10:20:6 Co@BN复合核壳结构纳米催化剂催化还原不同硝基化合物的性能图。如图6所示,10:20:6 Co@BN对不同硝基化合物的催化性能都很好,反应30分钟,对硝基苯酚、对硝基苯甲醚、对硝基苯胺的转化率均达到100%,对硝基甲苯和对硝基氯苯的转化率分别为74%和82%,转化率不同的原因可能是因为官能团的差异引起的。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (1)
1.一种钴/六方氮化硼复合核壳结构纳米催化剂在催化还原硝基化合物中的应用,其特征在于:以六方氮化硼包裹钴纳米颗粒形成所述核壳结构纳米催化剂;
所述钴/六方氮化硼复合核壳结构纳米催化剂采用氨气一次常压高温焙烧法进行制备;其制备方法具体是将氧化硼、尿素和硝酸钴按比例混合,研磨成粉末,然后置于刚玉瓷舟里,再放入卧式高温管式炉中,在氨气气氛的保护下,以5℃/min的速度升温到1250℃,保持5h,所得产物取出后经研磨,即得所述钴/六方氮化硼复合核壳结构纳米催化剂;
所用氧化硼、尿素和硝酸钴的质量比为10:20:12。
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