CN111686732A - 一种碳包覆铁基催化剂及其制备方法和催化苯羟基化制苯酚的应用 - Google Patents
一种碳包覆铁基催化剂及其制备方法和催化苯羟基化制苯酚的应用 Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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Abstract
本发明公开了一种碳包覆铁基催化剂及其制备方法和催化苯羟基化制苯酚的应用,其以碳包覆铁基催化剂为催化剂,苯为原料,过氧化氢为氧化剂,在一定的温度下进行苯的羟基化反应。本发明方法操作简单,反应条件温和,反应周期短,可重复性高,催化剂易合成,不需要复杂昂贵的设备,具有一定的工业化应用前景。本发明通过在铁基催化剂表面构筑石墨碳层制备了具有核壳结构的Fe@C和FeM@C等纳米材料,这既可以防止反应过程中金属物种的溶出,提高催化剂的稳定性,又可以充分利用石墨碳层来调控底物分子苯的吸附及活化、产物分子苯酚的脱附,从而提高苯酚的产率及选择性。本发明提供了一种开发廉价、稳定、高效的铁基纳米催化剂的实用方法,具有潜在的应用前景。
Description
技术领域
本发明属于多相催化和有机合成技术领域,具体涉及一种碳包覆铁基催化剂及其制备方法和催化苯羟基化制苯酚的应用。
背景技术
苯酚作为一种重要的有机化工原料,主要用于制备酚醛树脂和双酚以及医药中间体。目前,工业上合成苯酚最常用的三步异丙苯法,其存在着能耗高、污染严重和原子利用率低等问题。人们需要寻找一种新的合成方法来代替传统的工业合成方法。利用H2O2为氧化剂将苯直接氧化制苯酚的合成方法引起人们的重视,因为其符合21世纪绿色、可持续发展的需求。可是苯环具有高稳定性,使苯环的C-H难以被活化,且产物苯酚更活泼,使其容易更进一步氧化,则需要引入多相催化剂来更有效地合成苯酚。由于铁基催化剂低成本,环境友好型且无毒,这引起了研究者的兴趣,并将其应用于苯羟基化制苯酚,拥有良好的苯酚产率。但其自身还存在一定的问题限制其发展,例如,亲水性的铁基催化剂不利于非极性苯在其表面的吸附,但对苯酚分子有较强的亲和力,降低了其对苯酚的选择性,还有在非均相芬顿催化过程中,铁物种不可避免地溶出,会使催化剂失活,增加铁污泥的生成,降低了其稳定性。因此,我们有必要对这些铁基材料进行适当的改性,以实现苯酚的高效合成。
发明内容
针对上述问题,本发明提供了一种碳包覆铁基催化剂及其制备方法和催化苯羟基化制苯酚的应用,该方法合成技术简单、易于操作,表现出良好的苯酚产率,循环稳定性和高选择性,具有潜在的应用前景。
为实现上述目的,本发明采用如下技术方案:
一种碳包覆铁基催化剂的制备方法,具体包括以下步骤:
当碳包覆铁基催化剂只包含了金属Fe时:在40~80 ℃水浴条件下,将碳前驱物溶于水,加入一定量铁前驱物,待铁源与碳源充分的配位后,加入一定量二氧化硅(SiO2)溶胶,所加入的SiO2质量与总前驱物(铁与碳的前驱物)的质量比为0~10,搅拌时间为2~8 h。接着在管式炉氩气气氛中程序退火处理,第一阶段的退火温度为400~550 ℃,保持时间为0.5~2.5 h,第二阶段的退火温度为650~900 ℃,保持时间为1~6 h,得到Fe@C与SiO2混合物。将其浸泡在1~6 mol/L氟化氢铵溶液中12~36 h,离心,真空烘箱烘干,得到碳包覆铁基催化剂(Fe@C)
当碳包覆铁基催化剂包含了金属Fe和M时:在40~80 ℃水浴条件下,将碳前驱物溶于水,加入一定量铁和M混合前驱物,待其与碳源充分的配位后,加入一定量二氧化硅(SiO2)溶胶,所加入的SiO2质量与总前驱物(金属与碳的前驱物)的质量比为0~10,搅拌时间为2~8 h。接着在管式炉氩气气氛中程序退火处理,第一阶段的退火温度为400~550 ℃,保持时间为0.5~2.5 h,第二阶段的退火温度为650~900 ℃,保持时间为1~6 h,得到FeM@C与SiO2混合物。将其浸泡在1~6 mol/L氟化氢铵溶液中12~36 h,离心,真空烘箱烘干,得到碳包覆铁基催化剂(FeM@C)。
进一步地,所述金属Fe与M的物质量比为:0~3,M为Co,Ni,Mo,Cu,Mg中的一种。
所述金属(Fe,M)的前驱物为氯化盐、硝酸盐或硫酸盐;碳的前驱物为氰胺、二聚氰胺、三聚氰胺和葡萄糖等。
本发明还公开了上述碳包覆铁基催化剂的应用:以碳包覆铁基催化剂为催化剂,苯为原料,过氧化氢为氧化剂,在有机物-水体系中苯羟基化反应制备苯酚,反应结束后,待混合物自然冷却至室温,加入乙醇,以淬灭反应并将两相体系转化为单相,接着加入内标物。通过离心分离催化剂和产物,获得的产物采用液相色谱来进行定量分析。
进一步地,有机物-水体系中水和有机物溶剂的体积比为0~5,最佳体积比为1:1;所述有机物溶剂为乙腈,乙酸,乙酸乙酯,丙酮,二氯甲烷,二甲基酰胺,辛烷中的一种。
进一步地,所述苯羟基化反应温度在40℃~100℃,苯羟基化反应时间为1 h~24h。
进一步地,反应结束后加入的乙醇为2 mL~10 mL,内标物为甲苯。
本发明与现有技术相比,具有以下优点:
(1)本发明通过在铁基催化剂表面构筑碳层制备了具有核壳纳米结构Fe@C,这既可以防止在芬顿反应过程中铁物种的流失和团聚,又可以促进苯分子的吸附和活化,减弱苯酚分子的吸附能力,从而提高催化剂的循环稳定性和选择性。研究结果表明,碳包覆铁纳米材料在苯羟基化制备苯酚中的产率为18%,选择性为95%,经10次循环反应,其产率仍然保持稳定。
(2)本发明将变价过渡金属钴引入碳包覆铁中,合成了碳包覆铁钴合金。变价金属钴的引入可以促进芬顿反应过程中Fe3+还原为Fe2+,加快过氧化氢的活化,产生更多的羟基自由基,从而提高了催化活性,其产率提升到27%。
(3)本发明方法工艺简单,原料价格低廉,反应条件温和,生产成本低,绿色环保,适合大规模生产。
附图说明
图1为实施例1制备的碳包覆铁基催化剂(Fe@C)的SEM,TEM,HR-TEM谱图;
图2为实施例1制备的碳包覆铁基催化剂(Fe@C)和对比例1制备的碳载铁(Fe/C)催化剂的反应前后的XRD谱图;
图3为实施例1制备的碳包覆铁基催化剂(Fe@C)和对比例1制备的碳载铁(Fe/C)催化剂的苯羟基化循环活性图;
图4为实施例1制备碳包覆铁基催化剂(FeCo@C)的TEM图;
图5为实施例1制备碳包覆铁基催化剂(FeCo@C)的元素分布图;
图6为实施例1制备碳包覆铁基催化剂(FeCo@C)的苯羟基化循环活性图。
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 碳包覆铁基催化剂(Fe@C)及碳包覆铁基催化剂(FeCo@C)的制备及苯羟基化性能测试
(1)碳包覆铁基催化剂(Fe@C)的合成方法:
将 1 g FeCl3·6H2O 与2 g二聚氰胺分散在去离子水中,80 ℃油浴搅拌2 h,随后加入 12 g SiO2溶胶,持续加热搅拌2 h。再将其置于液氮中进行降温,进行冷冻干燥处理,待样品干燥,在管式炉氩气气氛中程序退火处理,第一阶段的退火温度为 500 ℃,时间为 1h,第二阶段的退火温度为 750℃,时间为 2 h,得到Fe@C与SiO2混合物。续用 4 mol/L氟化氢铵洗涤样品24 h,离心处理,真空烘箱烘干,得到Fe@C。
(2)碳包覆铁基催化剂(FeCo@C)的合成方法
将2 g二聚氰胺分散在去离子水中,再加入FeCl3·6H2O和CoCl2·6H2O的混合溶液(nFe:nCo=1:1,金属的总物质的量与Fe@C中铁的投放量保持一致),80 ℃油浴搅拌2 h,随后加入12 g SiO2溶胶,持续加热搅拌2 h。再将其置于液氮中进行降温,进行冷冻干燥处理,待样品干燥,在管式炉氩气气氛中程序退火处理,第一阶段的退火温度为 500 ℃,时间为 1 h,第二阶段的退火温度为 750℃,时间为 2 h,得到FeCo@C与SiO2混合物。续用 4 mol/L氟化氢铵洗涤样品24 h,离心处理,真空烘箱烘干,得到FeCo@C。
(3)Fe@C和FeCo@C苯羟基化性能测试:将 30 mg 催化剂加入到盛有3 mL水和3 mL乙腈的圆底烧瓶中,再加入0.25 mL苯和2 mL H2O2,60℃水浴,反应时间为4 h。在反应结束后,待混合物冷却,将3 mL乙醇注入混合物中以淬灭反应并将两相体系转化为单相,接着加入甲苯作为内标物,通过液相色谱来分析反应产物。
对比例1碳载铁(Fe/C)催化剂的制备及苯羟基化性能测试
(1)碳载铁(Fe/C)的合成方法:
a.将2 g 葡萄糖与1 g二聚氰胺分散在去离子水中,80 ℃油浴搅拌 1 h,加入1 gSiO2模板,持续加热搅拌2 h。随后放入液氮进行降温,冷冻干燥,待样品水分抽干。接着在管式炉氩气气氛中程序退火处理,第一阶段的煅烧温度为 500 ℃,时间为 1 h,第二阶段退火温度为 750℃,时间为 2 h,续用4 mol/L的氟化氢铵洗涤样品24 h,离心,真空烘箱烘干,得到碳(C)。
b. 将 0.1 g C与一定量的FeCl3·6H2O(Fe/C的含铁量与Fe@C一致)分散在去离子水中,90℃油浴搅干,接着在管式炉氩气气氛中退火处理,温度为 750℃,时间为 2 h,再在氢气气氛中450℃下退火4 h,得到碳载铁(Fe/C)。
(2)碳载铁(Fe/C)苯羟基化催化反应:分别将 30 mg碳载铁加入到 盛有3 mL水和3 mL乙腈的圆底烧瓶中,再加入0.25 mL的苯和2 mL的H2O2,60℃水浴,反应时间为4 h。在反应结束后,待混合物冷却,将3 mL乙醇注入混合物中以淬灭反应并将两相体系转化为单相,接着加入甲苯作为内标物。通过液相色谱来分析反应产物。
图1a是Fe@C的SEM图,可以清晰的看到图中Fe@C是以颗粒状的形式存在,单个颗粒的直径为30 nm左右。图1b是Fe@C的TEM图,可以观察到金属铁核完全地被碳壳包裹住,它们的尺寸约为5-10 nm,用高分辨率TEM图像进一步研究了Fe@C纳米粒子的局部结构,图1c明显地呈现出两种清晰的晶格条纹。其中一种晶格间距d=0.202 nm,对应于Fe的(110)晶面,表明Fe@C中金属铁芯的产生;另一种晶格间距d=0.34 nm,对应于碳的(002)晶面,表明碳壳层石墨化良好。这些结果说明我们成功合成了具有核壳纳米结构Fe@C。图2是Fe@C和Fe/C反应前后的X射线衍射图谱(XRD),从图中可看出Fe@C样品在反应前后无明显变化,但是反应后的Fe/C样品在2θ=44.6oand 65.2o处的金属铁的衍射峰消失,说明金属铁在反应中严重流失。图3是Fe@C和Fe/C样品的苯羟基化循环活性图,由图可知,Fe@C样品第二轮的活性比第一轮高了一倍多,这是由于第一轮活化之后,Fe@C样品接近碳层的金属铁被氧化生成Fe2+/Fe3+,促进其更有效地活化过氧化氢,产生更多的羟基自由基。同时也能观察到Fe@C样品从第二轮到十轮的苯酚产率保持稳定,而Fe/C样品,反应4次,其产率呈急剧下降的趋势,说明Fe@C催化剂有着良好的循环稳定性。图4为FeCo@C的TEM图,从图中我们可以观察到其为核壳结构,且金属核大小为5-10 nm,再从其元素分布图(图5)观察到二元金属元素(Fe-Co)共存在同样的位置,二元金属分布不存在偏析的情况,说明我们成功制备了碳包覆铁钴合金。图6为碳包覆铁钴合金(FeCo@C)的苯羟基化循环活性图,与Fe@C(图3)相比,FeCo@C的活性整体得到了明显的提升,经过第一轮活化后,其苯酚产率为27%,且表现出良好的稳定性。
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 (10)
1.一种碳包覆铁基催化剂的制备方法,其特征在于: 包括以下步骤:在水浴条件下,先将碳前驱物溶于水,加入铁基前驱物,待充分配位后,加入二氧化硅溶胶,搅拌2~8 h;然后进行退火处理,得到碳包覆铁基与SiO2混合物,最后浸泡在氟化氢铵溶液中,经离心烘干得到碳包覆铁基催化剂。
2.根据权利要求1所述的碳包覆铁基催化剂的制备方法,其特征在于:所述碳前驱物包括氰胺、二聚氰胺、三聚氰胺、葡萄糖中的一种。
3.根据权利要求1所述的碳包覆铁基催化剂的制备方法,其特征在于:所述铁基前驱物为金属Fe前驱物或金属Fe与M前驱物,M为Co,Ni,Mo,Cu和Mg中的一种,所述铁基前驱物为金属Fe与M的氯化盐、硝酸盐或硫酸盐。
4.根据权利要求1所述的碳包覆铁基催化剂的制备方法,其特征在于:所述二氧化硅溶胶的质量与铁基前驱物和碳前驱物总质量比为0~10。
5.根据权利要求1所述的碳包覆铁基催化剂的制备方法,其特征在于:所述水浴温度为40~80 ℃。
6.根据权利要求1所述的碳包覆铁基催化剂的制备方法,其特征在于:所述退火处理分为两个阶段,第一阶段的退火温度为400~550 ℃,时间为0.5~2.5 h,第二阶段的退火温度为650~900 ℃,时间为1~6 h。
7.一种如权利要求1-6任一项所述的制备方法制得的碳包覆铁基催化剂。
8.一种如权利要求7所述的碳包覆铁基催化剂的应用,其特征在于:以碳包覆铁基催化剂为催化剂,苯为原料,过氧化氢为氧化剂,在有机物-水体系中苯羟基化反应制备苯酚。
9.根据权利要求8所述的应用,其特征在于:有机物-水体系中水和有机物溶剂的体积比为0~5,所述有机物溶剂为乙腈,乙酸,乙酸乙酯,丙酮,二氯甲烷,二甲基酰胺,辛烷中的一种。
10.根据权利要求8所述的应用,其特征在于:所述苯羟基化反应温度在40℃~100℃,苯羟基化反应时间为1 h~24 h。
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