CN112007660A - 一种花簇状FeS2@C固氮催化剂的制备方法及应用 - Google Patents
一种花簇状FeS2@C固氮催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种花簇状FeS2@C固氮催化剂的制备方法及应用,其制备方法包括步骤:将六水三氯化铁、1,3,5‑均苯三甲酸和聚乙烯吡咯烷酮K30(PVP)溶于水溶液中,超声形成均匀的溶液,然后将溶液加入反应釜中于130℃反应72小时,待温度降至室温,经离心、洗涤、干燥,得到MIL‑100(Fe)@PVP前驱体;再将MIL‑100(Fe)@PVP和硫脲加入反应釜中,并在200℃下水热反应24小时,冷却至室温后,经硫酸和去离子水分别洗涤,烘干得到FeS2@C复合材料。本发明方法操作简单、成本低廉、原材料获取广泛。该催化剂用于常温常压条件下的电催化固氮,具有优异的电催化产氨活性。
Description
技术领域
本发明属于电催化技术领域,具体涉及一种FeS2@C复合材料的制备以及该复合材料在电催化固氮中的应用。
背景技术
氨是基本的化工原料,在经济生产中占有重要地位。氨可用来生产化学肥料,氮肥和复合肥料基本都是以氨为原料生产的,在农业中应用广泛。目前为止,固氮类型可分为:高能固氮、生物固氮和工业固氮。高能固氮多为大自然中闪电产生的高能量促使氨的形成,生物固氮是利用某些生物的生物作用或仿生技术进行的固氮,工业固氮主要为Haber-Bosch工艺来生产氨。Haber-Bosch工艺需要在高温高压条件(350-550℃,150-350atm)下进行反应,耗能较高且污染环境。考虑到化石燃料的短缺与全球气候的变化,探索在温和条件下发生合成氨的催化反应尤为重要。
电催化固氮近年来被证实可在温和条件下进行,是一种潜在的合成氨替代技术。目前电催化合成氨面临的主要问题是较低的产氨效率和法拉第效率,这主要是因为在常温常压下,由于氮气中的氮氮三键非常牢固,氮气和氢气的反应在反应动力学上非常难以进行,而且由于析氢电位和氮还原电位非常接近,析氢反应作为竞争反应会严重制约氮还原合成氨的效率,所以在氮气还原和析氢反应中寻找一个平衡点将有助于促进电催化固氮。在生物固氮中,固氮酶的铁蛋白和钼铁蛋白催化固氮反应的进行,所以模仿固氮酶利用铁元素与钼元素应用于电催化固氮可能会取得不错的效果。近年来,有许多研究涉及铁元素与钼元素的固氮催化剂,然而它们的产氨率与法拉第效率还亟需提升。
MOFs材料是指金属离子与有机配体自组装形成的具有网络结构的周期性晶体多孔材料。它具有高孔隙率、孔道规则和大比表面积等优点。由于MOFs材料具有这些优点,利用MOFs材料为前驱体制备的复合物可能会提升固氮性能。目前,研究人员将金属纳米颗粒负载到MOFs材料上进行光催化固氮研究,发现MOFs材料对氮气的吸附和金属纳米颗粒的热电子作用协同促进光催化固氮,将MOFs材料应用于电催化固氮有很好的应用价值。
发明内容
本发明的目的是提供一种利用水热法将MIL-100(Fe)@PVP和硫脲合成的FeS2@C复合材料,用于电催化固氮。
本发明涉及一种用于电催化固氮的FeS2@C复合材料催化剂,该电化学工作电极由碳布和碳布上包裹的复合材料FeS2@C构成,该工作电极的合成按以下步骤进行:
一、MIL-100(Fe)@PVP的制备:将六水三氯化铁,1,3,5-均苯三甲酸和聚乙烯吡咯烷酮K30(PVP)溶于水溶液中,超声形成均匀的溶液。然后将溶液加入反应釜中,在一定温度下反应一段时间,冷却至室温,离心,洗涤,真空干燥,得到MIL-100(Fe)@PVP。
二、FeS2@C复合材料的制备:将MIL-100(Fe)@PVP和硫脲以一定质量比加入去离子水中,搅拌3小时,加入反应釜中,在一定温度下反应一段时间,冷却至室温,离心,洗涤,真空干燥,得到FeS2@C。
三、工作电极的制备:将上述复合材料进行研磨,取一定量的FeS2@C复合材料,加入到含有异丙醇和nafion的水溶液中,进行超声。取适量的混合均匀的溶液滴涂在活化好的碳布上,静置。
步骤一中所述的六水三氯化铁、1,3,5-均苯三甲酸和聚乙烯吡咯烷酮K30的质量比为37.8:27.2:1;
步骤一中所述的反应温度为130℃,反应时间为72小时;
步骤一中所述的洗涤方式为:将所得产物用无水乙醇和去离子水分别离心洗涤3次;
步骤一中所述的真空干燥温度为60℃;
步骤二中所述的MIL-100(Fe)@PVP和硫脲的质量比为1:4;
步骤二中所述的反应温度为200℃,反应时间为24小时;
步骤二中所述的洗涤方式为:将获得的样品分别用0.5mol L–1硫酸和去离子水离心洗涤3次;
步骤二中所述的真空干燥温度为60℃;
步骤三中FeS2@C复合材料质量为10mg,异丙醇体积为0.75ml,nafion溶液体积为0.05ml,去离子水体积为2.2ml;
步骤三中超声时间为1.5小时,静置时间为8小时。
本发明通过X射线粉末衍射、扫描电子显微镜、安培响应法、线性扫描伏安法和紫外可见分光光度法等方法对上述FeS2@C材料进行表征与电化学性能测试。
本发明所具有的优点和效果:
本发明操作简单,通过一步水热法合成MIL-100(Fe)@PVP前驱体,再进行硫化生成由30-60nm的纳米片组成的花簇状结构FeS2@C材料。花簇状结构可以增大物质的表面积,从而提高活性位点的暴露,充分使催化剂与电解液接触,促进电子转移,增大了催化剂的催化活性。该材料基于MOFs的特殊框架结构特点,充分暴露了活性位点,大量的铁元素活性位点促进了氮气还原。FeS2@C催化剂具有优异的电催化固氮性能,在电催化固氮反应中,-0.6V的电压下,氨产量为38.02μg h-1mgcat. -1,法拉第效率为27.6%。本发明工艺简单、材料易得、成本较低,有利于工业化生产。
附图说明:
图1为复合材料FeS2@C的X射线粉末衍射图;
图2为复合材料FeS2@C的扫描电镜图片;
图3为FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同电压下,催化剂的时间-电流图;
图4为FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同电压反应后,各电解液的紫外可见光吸收光谱图;
图5为FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同电压下的氨产量图;
图6为FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同电压下的的法拉第效率图。
具体实施方式:
(1)将1.89g六水三氯化铁、1.36g 1,3,5-均苯三甲酸和0.05g聚乙烯吡咯烷酮K30溶于50mL水溶液中,超声形成均匀的溶液。然后将溶液加入反应釜中,于130℃下反应72小时,待冷却至室温,用无水乙醇和去离子水各离心洗涤3次,于60℃下真空烘干,得到MIL-100(Fe)@PVP前驱体。
(2)将0.1g MIL-100(Fe)@PVP和0.4g硫脲加入50ml去离子水中,搅拌3小时,放入反应釜中,并在200℃下水热反应24小时,待冷却至室温,经0.5mol L–1硫酸和去离子水分别离心洗涤3次,60℃下真空干燥12小时得到FeS2@C复合材料。
(3)将碳布依次放入丙酮溶液、无水乙醇和去离子水溶液中,并分别超声30分钟,再用水冲洗碳布,然后将碳布放入反应釜中,加入浓硝酸,于120℃下活化1小时。烘干活化好的碳布,裁剪成1cm×1cm大小的方块。取10mg FeS2@C加入溶有0.75ml异丙醇和0.05mlnafion溶液的2.2ml去离子水中,超声1.5小时,然后将超声均匀的材料滴涂于碳布上,形成含有0.3mg/cm2催化剂的工作电极。
图1中展示了材料FeS2@C的X射线粉末衍射图,对应FeS2的标准卡片(JCPDS,no.42-1340)。如图所示,衍射峰2θ=28.5°、33.1°、37.1°、40.8°、47.4°、56.3°和64.3°分别对应FeS2相的(111)、(200)、(210)、(211)、(220)、(311)、和(321)晶面。得到的衍射峰与标准卡片中的特征衍射峰吻合,说明材料中含有FeS2。
图2中展示了材料FeS2@C的扫描电镜图,所得材料是由30-60nm的纳米片组成的花簇状结构,多孔隙的结构具有较高的比表面积,使催化剂与电解液充分接触。
图3中为材料FeS2@C在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,分别在-0.4V、-0.5V、-0.6V和-0.7V电压下的电流-时间曲线图,图中显示该材料随着电压增加,电流密度也随之增大。
图4为材料FeS2@C在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,反应结束后,对电解液进行紫外可见分光光度法测量溶液中的吸光度。由图可知,吸光度随着电压增大先升高后降低,在-0.6V电压下对应的吸光度最高。
图5为FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同反应电压下电催化固氮的氨产量。如图可知,氨产率随着电压增大先升高后降低,在-0.6V电压下产氨量最高,可达38.02μg h-1mgcat. -1。
图6中展示了FeS2@C催化剂在pH为3.5的硫酸钾溶液(1.0mol L–1钾离子)中进行固氮反应,不同反应电压下电催化固氮的法拉第效率。由图可知,法拉第效率随着电压增大先升高后降低,在-0.6V电压下法拉第效率最高,可达27.6%。
综上所述,本发明运用水热法,利用六水三氯化铁、1,3,5-均苯三甲酸、聚乙烯吡咯烷酮K30和硫脲为反应物,成功合成由30-60nm的纳米片组成的花簇状结构FeS2@C材料。该材料在电催化固氮反应中,-0.6V的电压下,氨产量为38.02μg h-1mgcat. -1,法拉第效率为27.6%。
Claims (8)
1.一种花簇状FeS2@C固氮催化剂的制备方法,包括步骤如下:
(1)将六水三氯化铁、1,3,5-均苯三甲酸和聚乙烯吡咯烷酮K30(PVP)溶于水溶液中,超声形成均匀的溶液,然后将溶液在反应釜中于130℃反应72小时,冷却至室温后,经离心、洗涤、干燥,得到MIL-100(Fe)@PVP前驱体;
(2)将MIL-100(Fe)@PVP和硫脲加入去离子水中,搅拌均匀,加入反应釜中,并在200℃下水热反应24小时,冷却至室温后,经硫酸和去离子水分别洗涤,烘干得到FeS2@C复合材料。
2.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(1)中所述的六水三氯化铁、1,3,5-均苯三甲酸和聚乙烯吡咯烷酮K30的质量比为37.8:27.2:1。
3.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(1)中所述的反应温度为130℃,反应时间为72小时。
4.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(1)中所述的洗涤为:将产物用无水乙醇和去离子水分别离心洗涤3次;所述的干燥即在60℃下真空干燥12小时。
5.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(2)所述的MIL-100(Fe)@PVP和硫脲的质量比为1:4。
6.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(2)所述的反应温度为200℃,反应时间为24小时。
7.根据权利要求1所述的FeS2@C复合材料制备方法,其特征在于,步骤(2)所述的洗涤为:将获得的产物分别用0.5mol L–1硫酸和去离子水离心洗涤3次;所述的干燥即在60℃下真空干燥12小时。
8.权利要求1所述的FeS2@C材料的应用,应用于常温常压下电催化固氮反应。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113201758A (zh) * | 2021-04-08 | 2021-08-03 | 哈尔滨理工大学 | 一种FeS2@GO固氮催化剂的制备方法及应用 |
CN113736470A (zh) * | 2021-09-15 | 2021-12-03 | 昆明理工大学 | 一种高寒高海拔地区湿污泥制备矿区土壤调理剂的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109585183A (zh) * | 2018-11-12 | 2019-04-05 | 浙江工业大学 | 一种多孔FeS2@Fe7S8/石墨烯三维致密宏观体的制备方法及应用 |
CN110128326A (zh) * | 2019-06-05 | 2019-08-16 | 哈尔滨理工大学 | 具有双功能电催化性能的多酸基超分子材料及制备方法 |
CN111482185A (zh) * | 2019-01-29 | 2020-08-04 | 北京大学深圳研究生院 | 一种自支撑FeSx电催化剂及其制备方法与应用 |
-
2020
- 2020-09-17 CN CN202010980232.3A patent/CN112007660A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109585183A (zh) * | 2018-11-12 | 2019-04-05 | 浙江工业大学 | 一种多孔FeS2@Fe7S8/石墨烯三维致密宏观体的制备方法及应用 |
CN111482185A (zh) * | 2019-01-29 | 2020-08-04 | 北京大学深圳研究生院 | 一种自支撑FeSx电催化剂及其制备方法与应用 |
CN110128326A (zh) * | 2019-06-05 | 2019-08-16 | 哈尔滨理工大学 | 具有双功能电催化性能的多酸基超分子材料及制备方法 |
Non-Patent Citations (1)
Title |
---|
XINMING WANG ET.AL: "Polyoxometalate-based metal–organic framework-derived bimetallic hybrid materials for upgraded electrochemical reduction of nitrogen", 《GREEN CHEM.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113201758A (zh) * | 2021-04-08 | 2021-08-03 | 哈尔滨理工大学 | 一种FeS2@GO固氮催化剂的制备方法及应用 |
CN113736470A (zh) * | 2021-09-15 | 2021-12-03 | 昆明理工大学 | 一种高寒高海拔地区湿污泥制备矿区土壤调理剂的方法 |
CN113736470B (zh) * | 2021-09-15 | 2022-07-19 | 昆明理工大学 | 一种高寒高海拔地区湿污泥制备矿区土壤调理剂的方法 |
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