CN105642346A - 银纳米晶负载型催化剂及其制备方法和用途 - Google Patents
银纳米晶负载型催化剂及其制备方法和用途 Download PDFInfo
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
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- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 4
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/60—
Abstract
本发明涉及一种多孔有机聚合物及其制备方法和应用于原位制备超小银纳米晶复合催化剂的策略。这类多孔有机聚合物催化剂由苯二3-氨基丙腈和对苯二醛类似物通过缩合合反应制备而成，其制备过程简单，材料骨架具有大尺寸孔道结构、较高热稳定和化学稳定性；通过原位光还原反应吸附和还原银离子制备超小银纳米晶负载型催化剂。
Description
技术领域
本发明属于银纳米晶负载型催化剂制备技术领域，具体涉及一种由小分子聚合生成多孔有机聚合物材料的合成方法，和利用其作为底物原位制备超小银纳米晶负载型催化剂的应用。
背景技术
金属银由于具有特殊的物理化学性质，在光、电、磁、催化等领域都发挥着重要的作用。纳米银目前所具备的广泛用途，在很大程度上取决于其粒径大小、比表面积、形貌等。其中粒径小的纳米银具有一些普通大颗粒银所不具备的特殊效应，如小尺寸效应、表面效应和催化性能等，银纳米粒子的特殊性质在很大程度上取决于这些效应。多孔有机聚合物具有高比表面积、优良的化学稳定性、合成简单、空间拓扑结构丰富和组成结构可设计性等优点，是过渡金属催化有机反应的良好载体。实现多孔有机聚合物负载纳米粒子结构和性能的可控合成，对于发展新型的高效异相催化体系、拓宽多孔有机聚合物的应用范围具有重要意义，由于其在催化等领域具有潜在的应用价值，成为近年来研究的热点。
发明内容
本发明的目的是提出了一种基于多孔有机聚合物制备超小银(小于5纳米)纳米晶负载型催化剂的方法和用途。
本发明提出多孔有机聚合物的制备方法：以苯二3-氨基丙腈和对苯二醛类似物的有机缩合反应合成多孔有机聚合物[C(13+3n)H(4+2n)N3]。
本发明提出的超小银纳米晶负载型催化剂的制备步骤如下：将制备的多孔有机聚合物[C(13+3n)H(4+2n)N3]加入硝酸银溶液，搅拌过夜，在[C(13+3n)H(4+2n)N3]上负载银，然后使用光还原法得到超小银纳米晶负载型催化剂Ag[C(13+3n)H(4+2n)N3]。
附图说明
图1为所得多孔有机聚合物材料[C(13+3n)H(4+2n)N3]的扫描电镜图。
图2为所得多孔有机聚合物材料[C(13+3n)H(4+2n)N3]的结构图。
图3为所得超小银纳米晶负载型催化剂Ag[C(13+3n)H(4+2n)N3]的透射电镜图。
具体实施方式
实施例1：苯二3-氨基丙腈的制备
以优选比例对苯二腈、乙腈和叔丁醇钾1：4：6为例：在圆底烧瓶中加入40ml甲苯，并顺序加入乙腈4.0mmol、苯二腈1.0mmol、缓慢加入叔丁醇钾6.0mmol。上述混合物常温搅拌反应12小时后，加入50ml饱和碳酸氢钠溶液。过滤得到固体产物，分别用蒸馏水和乙醇清洗三次，烘箱70℃干燥。
实施例2：多孔有机聚合物材料的合成
以优选比例苯二3-氨基丙腈和对苯二醛类似物2：1为例：在配备有蛇形冷凝管的双颈瓶中加入实施例1中制得的苯二3-氨基丙腈0.4mmol、对苯二醛类似物0.2mmol和冰醋酸10ml。在反应体系中通30分钟氮气，之后升温至125℃，氮气氛围回流反应48小时。反应完成后，冷却过滤，固体用少量热醋酸清洗，然后分别用去离子水和乙醇清洗三次，真空干燥箱干燥，得到氰基修饰的多孔有机聚合物材料[C(13+3n)H(4+2n)N3]。合成材料的扫描电镜图见图1，分子结构示意图见图2。
实施例3：多孔有机聚合物材料[C(13+3n)H(4+2n)N3]作为底物负载银的实验
以优选剂量10mg为例：将10mg实施例2中新制的[C(13+3n)H(4+2n)N3]加入不同浓度的硝酸银溶液10ml，搅拌过夜(12h)后离心分离，固体用去离子水清洗三次，真空干燥箱干燥，得到负载银的多孔有机聚合物材料。
实施例4：超小银纳米晶负载型催化剂的制备
以优选剂量10mg为例：将10mg上述负载银的多孔有机聚合物加入10mL去离子水中，在全波段可见光光源下搅拌(1h)后离心分离，固体用去离子水清洗三次，真空干燥箱70℃干燥，得到超小银纳米晶负载型催化剂Ag[C(13+3n)H(4+2n)N3]。
Claims (7)
1.一种银纳米晶负载型催化剂，命名为Ag0[C(13+3n)H(4+2n)N3]，负载底物[C(13+3n)H(4+2n)N3]为多孔有机聚合物，其孔道大小可以通过缩合单体的苯环数目控制；银的负载量可以通过多孔有机聚合物的孔道尺寸调控；银纳米粒子的平均粒径小于5纳米。
2.一种权利要求1所述的催化剂的制备方法，包括如下步骤：
(1)对苯二腈、乙腈和叔丁醇钾按照一定量和比例，以甲苯为溶剂，室温下搅拌反应1小时以上，其后加入过量饱和碳酸氢钠溶液淬灭反应，产生的固体过滤后清洗、干燥箱干燥得到对苯二3-氨基丙腈；
(2)将步骤(1)得到的对苯二3-氨基丙腈和对苯二醛类似物按照一定的量和比例，以冰醋酸为溶剂，在氮气氛围中回流反应12小时以上，产生的固体过滤后清洗、干燥箱干燥得到多孔有机聚合物[C(13+3n)H(4+2n)N3]；
(3)配置不同浓度的硝酸银溶液，分别在溶液中加入步骤(2)得到的一定量的负载底物[C(13+3n)H(4+2n)N3]，搅拌2小时以上，固体物离心分离后清洗、干燥箱干燥得到负载银的多孔有机聚合物材料；
(4)将步骤(3)得到的负载银的多孔有机聚合物材料加入去离子水中，在全波段可见光光源下搅拌2小时后离心分离、清洗、干燥箱干燥得到超小银纳米晶负载型催化剂Ag0[C(13+3n)H(4+2n)N3]。
3.如权利要求2所述的制备方法，其特征在于：所述步骤(1)中，对苯二腈和乙腈的用量控制为1：2～1：6，优选1：3～1：5，叔丁醇钾为乙腈用量1.5倍以上，实际操作中以优选比例对苯二腈和乙腈1：4：称取乙腈4.0mmol加入40ml甲苯中，搅拌下继续加入苯二腈1.0mmol、缓慢加入叔丁醇钾6.0mmol，常温搅拌反应2小时以上，加入50ml饱和碳酸氢钠溶液淬灭反应，过滤得到固体产物，分别用蒸馏水和乙醇清洗三次，烘箱70℃干燥。
4.如权利要求2所述的制备方法，其特征在于：所述步骤(2)中，对苯二3-氨基丙腈和对苯二醛类似物的用量控制为3：2～4：1，反应温度100～140℃，实际操作中以优选比例对苯二3-氨基丙腈和对苯二醛类似物2：1：称取对苯二3-氨基丙腈0.4mmol，对苯二醛类似物0.2mmol加入5～20ml冰醋酸中，搅拌下继续加入苯二腈1.0mmol、缓慢加入过量叔丁醇钾6.0mmol，在氮气氛围中120℃回流反应48小时以上，产生的固体过滤后过滤得到固体产物，分别用热的冰醋酸、蒸馏水和乙醇清洗三次，烘箱70℃干燥到多孔有机聚合物[C(13+3n)H(4+2n)N3]；化学式中n为对苯二醛类似物中苯环数目。
5.如权利要求2所述的制备方法，其特征在于：所述步骤(3)中，多孔有机聚合物[C(13+3n)H(4+2n)N3]的用量为5～50mg，优选10mg；硝酸银溶液的用量为5～50ml，优选10ml；硝酸银溶液的浓度范围5-50mg·l-1，优选10mg·l-1。
6.如权利要求2所述的制备方法，其特征在于：所述步骤(4)中，负载银的多孔有机聚合物[C(13+3n)H(4+2n)N3]的用量为5～50mg，优选10mg；去离子水用量为5～50ml，优选10ml，所用光源为全波段可见光源。
7.权利要求1所述的催化剂用于硝基苯衍生物的催化还原反应。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7652132B2 (en) * | 2003-05-09 | 2010-01-26 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals |
| CN104117390A (zh) * | 2014-06-20 | 2014-10-29 | 南开大学 | 负载银纳米颗粒的金属有机框架配合物催化剂的制备方法 |
| CN104324760A (zh) * | 2014-10-09 | 2015-02-04 | 济南大学 | 一种功能性配位聚合物的制备方法和应用 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7652132B2 (en) * | 2003-05-09 | 2010-01-26 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals |
| CN104117390A (zh) * | 2014-06-20 | 2014-10-29 | 南开大学 | 负载银纳米颗粒的金属有机框架配合物催化剂的制备方法 |
| CN104324760A (zh) * | 2014-10-09 | 2015-02-04 | 济南大学 | 一种功能性配位聚合物的制备方法和应用 |
Non-Patent Citations (1)
| Title |
|---|
| 吕健 等: "银纳米粒子复合材料及其抗菌性能研究", 《中国化学会第九届全国无机化学学术会议》 * |
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