CN113680368A - 一种用于去除卤代有机物的双活性位异核金属原子分散型电催化材料及其制备方法和应用 - Google Patents
一种用于去除卤代有机物的双活性位异核金属原子分散型电催化材料及其制备方法和应用 Download PDFInfo
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- 125000004429 atom Chemical group 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 18
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
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- 229910002555 FeNi Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
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- 239000007832 Na2SO4 Substances 0.000 description 1
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
本发明涉及一种具备双活性位异核金属原子络合结构催化材料的制备方法及应用。该催化材料以非金属原子修饰的天然材料(膨润土、黏土和硅藻土)和工业材料(石墨烯、炭黑、活性炭、乙炔黑和碳纳米管)为载体，非金属可以为氨基酸类、尿素、单氰胺、二氰二胺、三聚氰胺、吡咯和吡啶中的一种或两种提供的氮原子，双金属原子(Fe、Ni、Cu、Mn、Zn、Co、Sn、Rh、Ru和Pb中任意两种)与非金属原子形成配位分布在载体上。本发明的有益效果是：利用加入氮源就能制备出金属配位稳定的双活性位异核金属原子结构催化剂，可提供优异的催化性能用作卤代有机物的选择性加氢还原。本发明制备方法简单、成本低，可完全去除污染物，有在工业上大规模应用的前景。
Description
技术领域
本发明涉及一种高性能双活性位异核金属原子催化材料的制备方法，具体是氮掺杂载体负载双活性位异核金属(Fe、Ni、Cu、Mn、Zn、Co、Sn、Rh、Ru、Pb中任意两种金属)原子复合材料的制备方法，以及采用该催化剂电催化还原去除卤代有机物的研究，属于电催化材料应用领域。
背景技术
原子分散型催化剂在实际应用中具有重要的研究意义。高活性阴极催化剂可以大幅度提高处理效果，通过催化剂表面不饱和配位金属与吸附基团的相互作用，在电极表面添加各种金属催化剂，吸附目标污染物和中间体。由于大多数催化反应发生在催化剂表面，污染物难以进入金属进行反应，催化剂中金属的利用率低。因此，为了充分发挥催化剂的催化效率，开发高性能的催化剂具有重要的应用前景。目前大多数研究都是将金属减小到原子形式，通过减小催化剂中金属的几何尺寸，充分利用每个金属原子，而单金属原子催化剂(专利号CN113258084A)由于在制备和催化过程中的聚集，催化活性位点的降低和催化剂负荷相对较低，严重制约了单原子催化材料的发展和应用为了打破其单一活性组分的限制，双原子催化剂可以进一步提高活性中心和原子负载，有更多的机会通过电子轨道的相互作用来调整d带中心，具备一种以上的吸附位点而打破线性比例关系并优化多种中间体的吸附能，从而优化中间体在活性位点上的吸附能将金属的物理化学性质与原子分散材料的特殊性质结合起来，提高整体催化性能，促进双原子催化剂未来实际应用的发展。
目前对于金属原子形态催化剂的制备方法中，由于金属粒子减小到原子水平，比表面积增大，金属表面自由能增加，在制备和反应时极易发生团聚形成大的团簇，从而导致催化剂失活。因此开发一种良好载体材料能够分散稳定金属原子是制备单分散金属双原子催化剂的前提条件。氮掺杂载体材料由于其独特的表面化学结构，通过金属与氮原子形成配位结构从而稳定金属原子，不易形成团聚结构，因此在作为催化剂载体时不仅可有效的提高催化剂的反应活性，还能提高催化剂的稳定性。
因此本研究采用氮掺杂载体材料负载双活性位异核金属原子分散型阴极催化剂，采用阴极还原去除污染物的电化学处理方法，对卤代有机污染物进行处理，完全去除带有该污染物的毒性。采用简单的方法制备该催化剂，负载金属原子的种类和组分可根据需要进行调控，该方法成本低，催化效果好，在实际应用中具有普适性。
发明内容
本发明的目的在于提供一种工艺简单、易于推广的双活性位异核金属原子络合结构催化剂的制备方法及应用，使金属催化剂的利用率提高到极限，所述的催化材料具有高催化活性，可以实现对卤代有机物的去除，为实现废水资源化、解决水资源短缺的问题提供新的材料选择。
为了实现上述目的，本发明的技术方案是：该催化材料以天然材料和工业材料为载体，双金属原子(Fe、Ni、Cu、Mn、Zn、Co、Sn、Rh、Ru和Pb中任意两种金属)与氮形成配位均匀分布在载体上。
所述的非金属氮原子改性载体负载的单分散异核双金属原子催化材料的制备方法及应用，其特征在于：
S1将载体材料粉末和氮源溶于水中，通过超声分散技术制成溶液A，将两种金属前驱体溶于溶剂中，通过超声分散技术制成溶液B；
S2将溶液B分散在溶液A中，搅拌后烘干并将混合物研磨成粉末至70目以下；
S3将混合物在保护气中退火，得到以非金属氮原子修饰载体负载异核双金属原子催化材料；
S4用所制备的催化材料对卤代有机污染物进行电催化去除研究。
按上述方案，非金属氮原子改性载体负载的双活性位异核金属原子催化材料，其特征在于：所述的天然载体材料为膨润土、黏土和硅藻土中的一种，所述的工业载体材料为石墨烯、炭黑、活性炭、乙炔黑和碳纳米管中的一种。所述金属前驱体可以为铁、镍、铜、锰、锌、钴、锡、钌、铑和铅的硝酸盐、硫酸盐、碳酸盐、醋酸盐中的任意两种。所述氮源为氨基酸类、尿素、单氰胺、二氰二胺、三聚氰胺、吡咯和吡啶中的一种或者两种混合体。所述溶解金属前驱体的溶剂为N,N-二甲基甲酰胺、丙酮、水、乙醚、盐酸、甲醇、乙酸乙酯和乙醇中的一种。
本发明所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料的制备方法中，所述的A溶液中载体与氮原子比例为1:5～1:10，A溶液中混合物浓度为1～80g/L，所述的B溶液中混合物浓度为1～50mg/L，所述的保护气可以为惰性气体氩气和氮气中的一种，煅烧温度为450～750℃，升温速率为3～5℃/min，退火时间为2～4h。
所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，该催化材料中金属以异核双原子形式与非金属原子形成配位从而均匀稳定的分布在载体上，制备的氮改性载体材料具有较大的比表面积从而负载金属原子，比表面积可达到300～400m2/g，孔半径5～6nm，双金属理论负载量比值为1:1～1:4，双金属原子的粒径在0.1～0.4nm之间。
所述的方法制备的用于电催化还原去除卤代有机物的一种双活性位异核金属原子络合结构催化材料的应用，其特征在于：所述的有机污染物包括所有卤代有机物，可达到完全去除的效果。
本发明具有以下特点：
(1)本发明通过将混合物在惰性气氛下进行简单的烧结方法，就可以得到异核双原子催化剂，催化剂中金属与非金属原子形成配位，催化活性稳定。本发明制备成本低，工艺简单、易于推广，催化效果好，在工业上有大规模应用前景。
(2)所述的双活性位异核金属原子络合结构催化材料具有高催化活性，可用作卤代化合物的选择性加氢还原，不仅对污染物的去除种类广泛，而且去除效率高，可达到100％。
具体实施方式
实施例1
一种非金属氮原子改性载体材料负载的双活性位异核金属FeNi原子催化剂的制备，具体步骤如下：
将200～800mg活性炭和1～2g双氰胺溶于水中超声分散好，加入3～5ml浓度为1mg/L的硝酸铁和硝酸镍前驱液，继续超声30min后放入烘箱于60℃烘干；将混合物研磨后在氮气气氛下烧结，煅烧温度为450～750℃，升温速率为3℃/min，退火时间为2～4h，得到非金属氮原子改性活性炭负载双金属FeNi催化剂。催化材料孔径为5.7nm，比表面积为387m2/g，双金属FeNi原子粒径为0.22±0.03nm。
实施例2
一种非金属氮原子改性载体材料负载的双活性位异核金属FeCo原子催化剂的制备，具体步骤如下：
将200～800mg活性炭和1～2g双氰胺溶于水中超声分散好，加入3～5ml浓度为1mg/L的硝酸铁和碳酸钴前驱液，继续超声30min后放入烘箱于60℃烘干；将混合物研磨后在氮气气氛下烧结，煅烧温度为450～750℃，升温速率为3℃/min，退火时间为2～4h，得到非金属氮原子改性活性炭负载双金属FeCo催化剂。催化材料孔径为5.5nm，比表面积为366m2/g，双金属FeCo原子粒径为0.25±0.03nm。
实施例3
用于电催化还原去除卤代有机污染物的非金属氮原子改性载体材料负载双活性位异核金属FeNi原子催化材料的应用，其特征为所述的电催化实验采用双电极装置，阳极采用Ti/RuO2/IrO2电极板，阴极使用催化剂制备成催化阴极，在pH为8、污染物浓度为50mg/L、电流密度5mA/cm-2、电解质Na2SO4浓度为0.1mol/L条件下进行电催化实验。去除的目标污染物包括氯苯、溴苯、对氯苯酚、对溴苯酚、2,4-二氯苯酚和2,4-二溴苯酚，选取的六种污染物大量存在于药物废水和染料废水中，并涵盖了氯代和溴代有机物的苯基与苯酚基类污染物，六种污染物在60min内去除率都达到100％(如表1)。其中氯苯和溴苯在体系中去除速率最快，在40min内就可完全去除，2,4-二氯苯酚和2,4-二溴苯酚去除速率较慢，可能由于这两种有机物中存在两个卤素原子，并且存在一个羟基临位上的卤素原子，脱氯或脱溴受到羟基的作用而不能被快速脱卤，但在60min内也可完全去除。
表1不同污染物去除率与电解时间
Claims (8)
1.一种用于电催化去除卤代有机污染物的非金属氮原子改性天然材料或工业材料为载体负载双活性位异核金属原子络合结构催化材料的制备方法及应用，其特征在于：
S1将载体材料粉末和氮源溶于水中，利用超声分散技术制成溶液A，将两种金属前驱体溶于溶剂中，通过超声分散技术制成溶液B；
S2将溶液B分散在溶液A中，搅拌后烘干并将混合固体研磨成粉末；
S3将混合物在保护气中退火，得到以非金属氮原子修饰载体负载双活性位异核金属原子催化材料；
S4用所制备的催化材料对卤代有机污染物进行电催化去除研究。
2.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，其特征在于：所述的天然载体材料为膨润土、黏土和硅藻土中的一种，所述的工业载体材料为石墨烯、炭黑、活性炭、乙炔黑和碳纳米管中的一种。
3.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，其特征在于：所述S1金属前驱体可以为铁、镍、铜、锰、锌、钴、锡、钌、铑和铅的硝酸盐、硫酸盐、碳酸盐、醋酸盐中的任意两种。
4.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，其特征在于：所述S1氮源为氨基酸类、尿素、单氰胺、二氰二胺、三聚氰胺、吡咯和吡啶中的一种或者两种混合体。
5.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，其特征在于：所述S1溶解金属前驱体的溶剂为甲醇、丙酮、水、乙醚、盐酸、N,N-二甲基甲酰胺、乙酸乙酯和乙醇中的一种。
6.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，其特征在于：所述S3保护气为惰性气体氩气和氮气中的一种，煅烧温度为450～750℃，升温速率为3～5℃/min，退火时间为2～4h。
7.如权利要求1所述的非金属氮原子改性载体负载的双活性位异核金属原子络合结构催化材料，该催化材料中金属以异核双原子形式与非金属原子形成配位从而均匀稳定的分布在载体上，制备的催化材料具有较大的比表面积从而负载金属原子，比表面积可达到300～400m2/g，孔半径5～6nm，双金属理论负载量比值为1:1～1:4，双金属原子的粒径在0.1～0.4nm之间。
8.如权利要求1所述的方法制备的用于电催化还原去除卤代有机物的一种氮改性载体负载的双活性位异核金属原子催化材料的应用，其特征在于：S4所述的有机物污染物包括所有卤代有机物类，去除率可达到100％。
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