CN113054207A - 金属盐辅助快速生长金属有机骨架衍生物的制备方法 - Google Patents
金属盐辅助快速生长金属有机骨架衍生物的制备方法 Download PDFInfo
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Abstract
本发明提供一种金属盐辅助快速生长金属有机骨架衍生物的制备方法，属于纳米材料制备和燃料电池催化技术领域。该方法首先将金属盐和高分子聚合物加入有机溶剂中，搅拌得到混合溶液，采用静电纺丝技术得到金属盐/高分子纳米纤维膜，然后将含有金属有机骨架MOF生长所需的有机配体溶液均匀涂覆在金属盐/高分子纳米纤维膜上，然后通过热压技术实现纳米纤维中的金属离子与配体的化学键结合，使得MOF材料在纳米纤维膜上致密均匀生长，MOF/纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。该方法在制备过程中无甲醇、乙醇、水等溶剂的使用，制备时间短、工艺简单、对环境友好、适合规模化生产，在能源催化与环保领域具有重要的应用价值。
Description
技术领域
本发明涉及纳米材料制备和燃料电池催化技术领域，特别是指一种金属盐辅助快速生长金属有机骨架衍生物的制备方法。
背景技术
开发高活性的非贵金属基催化剂替换传统昂贵铂基催化剂至关重要且一直存在众多挑战。研究表明高的比表面积、分层的孔道结构、高活性位点、均匀的杂原子掺杂以及高电导率是获得优异电催化性能的关键因素。具有超分子结构的金属有机骨架(MOF)由金属离子和有机配体组成，在惰性气氛中通过简单的碳化可转化为高比表面积、高活性位点、均匀杂原子修饰的多孔碳。基于上述因素，MOF衍生碳的电催化剂备受关注。然而，MOF衍生的碳基电催化剂结构单一、导电网络不连续、负载金属纳米颗粒团聚、机械稳定性差等问题，影响了其实际应用。
一维碳纳米纤维材料因其优异的导电性、柔韧性、可实现MOF的均匀负载等特性，将纳米纤维材料与MOF材料相结合解决了MOF本身存在的问题，在提高电催化性能和柔性器件方面具有一定优势。目前MOF和纳米纤维的结合方式已得到广泛的研究，主要通过二次生长、原位晶化、层沉积制备金属有机骨架/纳米纤维膜。其中，二次生长和原位晶化法需消耗大量的溶液并产生大量的废液，这极大地阻碍了MOF材料的大规模生产和工业应用；层沉积法设备相对昂贵，并且目前大规模商业应用受到限制。
热压法具有制备简单、易规模化生产、环境友好等优点，在热压过程中高分子聚合物中的配位基团与MOF中金属离子发生强化学键的作用，同时金属离子与有机配体自组装，实现MOF颗粒均匀地分散在PAN纳米纤维上。在惰性气氛中通过简单的碳化可转化为金属嵌入的氮掺杂多孔碳纳米纤维材料。
发明内容
本发明要解决的技术问题是提供一种金属盐辅助快速生长金属有机骨架衍生物的制备方法。在制备过程中无甲醇、乙醇、水等溶剂的使用，制备时间短、工艺简单、对环境友好、适合规模化生产，在能源储存领域具有重要的应用价值。
该方法首先将金属盐和高分子聚合物加入有机溶剂中，充分搅拌得到混合溶液，采用静电纺丝技术得到金属盐/高分子纳米纤维膜，然后将含有金属有机骨架MOF生长所需的有机配体溶液均匀涂覆在金属盐/高分子纳米纤维膜上，然后通过热压技术实现纳米纤维中的金属离子与配体的化学键结合，使得MOF材料在纳米纤维膜上致密均匀生长，MOF/纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。
具体包括步骤如下：
(1)将合成目标MOF的金属盐和高分子聚合物加入有机溶剂中，搅拌后得到均匀混合溶液，利用静电纺丝技术得到金属盐/高分子纳米纤维膜；
(2)按照有机配体与金属盐的质量比为2～10的比例，将含有目标MOF的有机配体溶液涂覆在金属盐/高分子纳米纤维膜上，通过热压技术给上述材料施加一定的温度和压力，金属离子与配体开始在纳米纤维膜表面组装，生长成均匀的MOF/高分子纳米纤维膜；
(3)MOF/高分子纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。
其中，步骤(1)中金属盐和高分子聚合物的质量比为0.5～2.0；高分子聚合物与有机溶剂的质量比为0.7～1.5。
步骤(1)中静电纺丝技术参数为外加电压为12-30kV，进料速率为0.5-1.0mL/h，接收距离为8-20cm，喷口尺寸为19-27G，环境相对湿度为22-45％之间，温度为20-45℃。
金属盐的金属离子包括锌、钴、铜、铁、锆、锰、镍；纳米纤维原材料包括聚乙烯醇、聚丙烯腈、细菌纤维素、聚酰亚胺、聚苯胺；有机溶剂为二甲基甲酰胺、二甲基乙酰胺、丙酮、苯、二氯甲烷、二甲基亚砜、碳酸乙烯酯等有机溶剂的溶液；有机配体采用咪唑类、羧酸类、卟啉类、吡啶类、酚类、对苯二甲酸、均苯三甲酸中的一种。
步骤(2)中含有目标MOF的有机配体溶液中有机配体与溶剂质量比为3～0.2。
步骤(2)中热压技术的加热温度为80℃～220℃，压力为0.1MPa～5.0MPa，时间为6～30min。
步骤(3)中煅烧条件为：升温速率1-5℃/min，在650-1100℃保温1-3h，然后自然冷却到室温。
本发明的上述技术方案的有益效果如下：
(1)本发明的方法所制备的金属有机骨架/纳米纤维膜实现结合紧密，不易脱落，且具有一定的柔性与较好的机械性，可直接作为自支撑电极；
(2)基于热压工艺制备的可规模化生产的金属有机骨架/纳米纤维膜碳化后呈现出金属嵌入的氮掺杂多孔碳纳米纤维相互交联的三维网络结构，解决了MOF衍生的电催化剂结构单一、导电网络不连续、负载金属纳米颗粒团聚、机械稳定性差等问题，且具有高的比表面积、分层的孔道结构、丰富的高活性位点、均匀的杂原子掺杂以及高电导率等优势。同时，金属和氮元素的掺杂提高材料的导电性并提供高活性位点，这些特点有效提高电催化性能；
(3)在制备过程中无需使用水、乙醇、甲醇等溶剂，对环境友好；
(4)热压制备工艺简单、在短时间和较低的温度下就可实现金属有机骨架在纳米纤维膜上的均匀生长，可有效降低生产成本和安全隐患，适合大规模生产，具有很好的应用前景。
附图说明
图1为本发明制备方法示意图；
图2为本发明中双金属有机骨架(BMZIF)/PAN纳米纤维膜的SEM图；
图3为本发明中双金属有机骨架(BMZIF)/PAN纳米纤维碳化膜SEM图；
图4为本发明中碳化后的双金属有机骨架(BMZIF)/PAN纳米纤维柔性展示图；
图5为本发明中双金属有机骨架(BMZIF)/PAN纳米纤维碳化膜作为锂空气电池自支撑阴极的倍率性能测试图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述。
本发明提供一种金属盐辅助快速生长金属有机骨架衍生物的制备方法。
本方法首先将金属盐和高分子聚合物加入有机溶剂中，充分搅拌得到混合溶液，采用静电纺丝技术得到金属盐/高分子纳米纤维膜，然后将含有金属有机骨架MOF生长所需的有机配体溶液均匀涂覆在金属盐/高分子纳米纤维膜上，然后通过热压技术实现纳米纤维中的金属离子与配体的化学键结合，使得MOF材料在纳米纤维膜上致密均匀生长，MOF/纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。
如图1所示，具体包括步骤如下：
(1)将合成目标MOF的金属盐和高分子聚合物加入有机溶剂中，搅拌后得到均匀混合溶液，利用静电纺丝技术得到金属盐/高分子纳米纤维膜；
(2)按照有机配体与金属盐的质量比为2～10的比例，将含有目标MOF的有机配体溶液涂覆在金属盐/高分子纳米纤维膜上，通过热压技术给上述材料施加一定的温度和压力，金属离子与配体开始在纳米纤维膜表面组装，生长成均匀的MOF/高分子纳米纤维膜；
(3)MOF/高分子纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。
下面结合具体实施例予以说明。
实施例1
第一步，制备金属盐/聚丙烯腈(PAN)纳米纤维膜
将1.0g聚丙烯腈(PAN)和1.0g乙酸钴加入10mL二甲基甲酰胺溶液中，常温下磁力搅拌10h形成均匀的纺丝溶液。将上述纺丝液转移到10mL注射器内并置于注射泵上，通过静电纺丝技术得到乙酸钴/聚丙烯腈(PAN)纳米纤维膜。纺丝外加电压为12-20kV，注射泵进料速度为0.6mL/h，针头与滚轮接收器的距离为20cm，注射器针头为19#。
第二步，制备ZIF-8/PAN纳米纤维膜
如图1所示，将0.35g二甲基咪唑(2-MeIm)和5mL的聚乙二醇(PEG200)置于研钵中研磨均匀，然后涂覆在乙酸钴/聚丙烯腈(PAN)纳米纤维膜上，设置热压温度为80℃-120℃，热压时间为10min。在一定的温度和压力下，锌离子与2-MeIm配体开始在PAN纳米纤维膜表面组装，生长成均匀的ZIF-8/PAN纳米纤维膜。
第三步，制备ZIF-8/PAN纳米纤维碳化膜
将样品放入管式炉内，升温速率1-5℃/min，在650-1100℃下保温1-3h，然后自然冷却到室温，最终得到金属嵌入的氮掺杂多孔碳纳米纤维材料。
实施例2
第一步，制备双金属盐/聚丙烯腈(PAN)纳米纤维膜：
将1.0g聚丙烯腈、0.47g乙酸钴、0.53g乙酸锌加入10mL二甲基甲酰胺溶液中，常温下磁力搅拌10h形成均匀的纺丝溶液。将上述纺丝液转移入10mL注射器内并置于注射泵上，通过静电纺丝技术得到乙酸钴-乙酸锌/PAN纳米纤维膜。纺丝外加电压为12-20kV，注射泵进料速度为0.6mL/h，针头与滚轮接收器的距离为20cm，注射器针头为19#。
第二步，制备双金属有机骨架(BMZIF)/PAN纳米纤维膜
将0.35g二甲基咪唑(2-MeIm)和5ml的聚乙二醇(PEG200)置于研钵中研磨均匀，然后涂覆在乙酸锌/乙酸钴/聚丙烯腈(PAN)纳米纤维膜上，设置热压温度为80℃-120℃，热压时间为10min。在一定的温度和压力下，锌离子、钴离子开始与2-MeIm配体在PAN纳米纤维膜表面结合，生长成均匀的双金属有机骨架(BMZIF)/PAN纳米纤维膜。如图2所示，BMZIF颗粒均匀且致密地生长在PAN纳米纤维膜上。
第三步，制备双金属有机骨架(BMZIF)/PAN纳米纤维碳化膜
将样品放入管式炉内，升温速率1-5℃/min，在650-1100℃下保温1-3h，然后自然冷却到室温，如图3所示，由于锌金属盐的挥发和双金属有机骨架的收缩，碳化后的样品呈现双金属嵌入的氮掺杂多孔碳纳米纤维材料。
热压法具有制备简单、易规模化生产、环境友好等优点。在热压过程中高分子聚合物中的配位基团与MOF中金属离子发生强化学键的作用，MOF材料可以强而均匀地分散在PAN纳米纤维上，在惰性气氛中通过简单的碳化可转化为高比表面积、高活性位点、高导电率、均匀杂原子修饰的多孔碳。本发明合成的金属有机骨架衍生物/纳米纤维同时具备一定的柔性(如图4)，当作为锂空电池自支撑阴极时，如图5所示，碳化后的BM/PAN纳米纤维催化剂在电流密度为0.02mA/cm2和截止容量为0.2mAh/cm2时，显示出极低的0.49V的中值充电极化电压和0.06V的中值放电极化电压，具有极低的中值放电/充电电压差为0.55V。碳化后的BM/PAN纳米纤维催化剂优异的性能可能是由于独特的大孔和介孔结构，保证了较大的比表面积、较好的氧气传输环境、暴露更多丰富的催化位点。
本发明在电催化领域以及柔性器件等领域具有重要的应用价值。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：包括步骤如下：
(1)将合成目标MOF的金属盐和高分子聚合物加入有机溶剂中，搅拌后得到均匀混合溶液，利用静电纺丝技术得到金属盐/高分子纳米纤维膜；
(2)按照有机配体与金属盐的质量比为2～10的比例，将含有目标MOF的有机配体溶液涂覆在金属盐/高分子纳米纤维膜上，通过热压技术施加一定的温度和压力，金属离子与配体开始在纳米纤维膜表面组装，生长成均匀的MOF/高分子纳米纤维膜；
(3)MOF/高分子纳米纤维膜在惰性气体下煅烧后形成金属嵌入的氮掺杂多孔碳纳米纤维。
2.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述步骤(1)中金属盐和高分子聚合物的质量比为0.5～2.0；高分子聚合物与有机溶剂的质量比为0.7～1.5。
3.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述步骤(1)中静电纺丝技术参数为外加电压为12-30kV，进料速率为0.5-1.0mL/h，接收距离为8-20cm，喷口尺寸为19-27G，环境相对湿度为22-45％之间，温度为20-45℃。
4.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述金属盐的金属离子包括锌、钴、铜、铁、锆、锰、镍；高分子聚合物包括聚乙烯醇、聚丙烯腈、细菌纤维素、聚酰亚胺、聚苯胺；有机溶剂包括二甲基甲酰胺、二甲基乙酰胺、丙酮、苯、二氯甲烷、二甲基亚砜、碳酸乙烯酯；有机配体采用咪唑类、羧酸类、卟啉类、吡啶类、酚类、对苯二甲酸、均苯三甲酸中的一种。
5.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述步骤(2)中含有目标MOF的有机配体溶液中有机配体与溶剂质量比为3～0.2。
6.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述步骤(2)中热压技术的加热温度为80℃～220℃，压力为0.1MPa～5.0MPa，时间为6～30min。
7.根据权利要求1所述的金属盐辅助快速生长金属有机骨架衍生物的制备方法，其特征在于：所述步骤(3)中煅烧条件为：升温速率1-5℃/min，在650-1100℃保温1-3h，然后自然冷却到室温。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694963A (zh) * | 2021-09-27 | 2021-11-26 | 江南大学 | 钴嵌入富氮多孔碳材料/自组装纳米卟啉复合光催化剂及其制备方法和应用 |
| CN114068872A (zh) * | 2021-10-13 | 2022-02-18 | 江苏恒力化纤股份有限公司 | 具有双重亲锂性的聚合物纳米纤维金属锂复合负极及制法 |
| CN114307693A (zh) * | 2022-01-04 | 2022-04-12 | 大连理工大学 | 一种MOFs与聚合物双连续的混合基质膜的制备方法 |
| CN114790585A (zh) * | 2022-04-21 | 2022-07-26 | 扬州大学 | 一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器 |
| CN115478364A (zh) * | 2022-09-26 | 2022-12-16 | 北京科技大学 | 一种自支撑电纺碳纳米纤维复合膜的制备方法及应用 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080305377A1 (en) * | 2007-03-15 | 2008-12-11 | University Of Rochester | Long metallic nanowires, methods of making, and use thereof in proton exchange membrane fuel cell |
| CN105348198A (zh) * | 2015-09-29 | 2016-02-24 | 中能科泰（北京）科技有限公司 | 金属有机骨架膜及其制备方法 |
| CN107875863A (zh) * | 2017-10-31 | 2018-04-06 | 华南理工大学 | 一种无溶剂自转化制备金属有机骨架膜的方法 |
| US20190020028A1 (en) * | 2016-01-14 | 2019-01-17 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| US20200220219A1 (en) * | 2017-02-07 | 2020-07-09 | Ford Cheer International Limited | Electrospun composite separator for electrochemical devices and applications of same |
| CN111785978A (zh) * | 2020-07-10 | 2020-10-16 | 广州市香港科大霍英东研究院 | 一种液流电池用多孔电极及其制备方法 |
| US20210020956A1 (en) * | 2017-12-26 | 2021-01-21 | Kolon Industries, Inc. | Catalyst, preparation method therefor, electrode comprising same, membrane-electrode assembly, and fuel cell |
-
2021
- 2021-03-02 CN CN202110228812.1A patent/CN113054207B/zh not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080305377A1 (en) * | 2007-03-15 | 2008-12-11 | University Of Rochester | Long metallic nanowires, methods of making, and use thereof in proton exchange membrane fuel cell |
| CN105348198A (zh) * | 2015-09-29 | 2016-02-24 | 中能科泰（北京）科技有限公司 | 金属有机骨架膜及其制备方法 |
| US20190020028A1 (en) * | 2016-01-14 | 2019-01-17 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| US20200220219A1 (en) * | 2017-02-07 | 2020-07-09 | Ford Cheer International Limited | Electrospun composite separator for electrochemical devices and applications of same |
| CN107875863A (zh) * | 2017-10-31 | 2018-04-06 | 华南理工大学 | 一种无溶剂自转化制备金属有机骨架膜的方法 |
| US20210020956A1 (en) * | 2017-12-26 | 2021-01-21 | Kolon Industries, Inc. | Catalyst, preparation method therefor, electrode comprising same, membrane-electrode assembly, and fuel cell |
| CN111785978A (zh) * | 2020-07-10 | 2020-10-16 | 广州市香港科大霍英东研究院 | 一种液流电池用多孔电极及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| LICHONG PENG ET AL.: ""Heavy metal elimination based on metal organic framework highly loaded on flexible nanofibers"", 《ENVIRONMENTAL RESEARCH》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694963A (zh) * | 2021-09-27 | 2021-11-26 | 江南大学 | 钴嵌入富氮多孔碳材料/自组装纳米卟啉复合光催化剂及其制备方法和应用 |
| CN113694963B (zh) * | 2021-09-27 | 2023-09-29 | 江南大学 | 钴嵌入富氮多孔碳材料/自组装纳米卟啉复合光催化剂及其制备方法和应用 |
| CN114068872A (zh) * | 2021-10-13 | 2022-02-18 | 江苏恒力化纤股份有限公司 | 具有双重亲锂性的聚合物纳米纤维金属锂复合负极及制法 |
| CN114307693A (zh) * | 2022-01-04 | 2022-04-12 | 大连理工大学 | 一种MOFs与聚合物双连续的混合基质膜的制备方法 |
| CN114790585A (zh) * | 2022-04-21 | 2022-07-26 | 扬州大学 | 一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器 |
| CN114790585B (zh) * | 2022-04-21 | 2023-11-24 | 扬州大学 | 一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器 |
| CN115478364A (zh) * | 2022-09-26 | 2022-12-16 | 北京科技大学 | 一种自支撑电纺碳纳米纤维复合膜的制备方法及应用 |
| CN115478364B (zh) * | 2022-09-26 | 2023-11-24 | 北京科技大学 | 一种自支撑电纺碳纳米纤维复合膜的制备方法及应用 |
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