CN115466366A - 一种结合金属的噻吩基有机多孔聚合物材料及其制备方法和应用 - Google Patents
一种结合金属的噻吩基有机多孔聚合物材料及其制备方法和应用 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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Abstract
本发明公开了一种结合金属的噻吩基有机多孔聚合物材料及其制备方法和应用,所述结合金属的噻吩基有机多孔聚合物材料的制备方法为:负载金属的四氨基卟啉(金属为Fe、Co、Ni、Cu或Zn)与2,2,‑联噻吩‑5,5,‑二甲醛(以下称为BD)、2,5‑噻吩二甲醛或苯并[1,2‑b:4,5‑b’]二噻吩‑2,6‑二甲醛以溶剂热的方法制备得到一种新型的网状多孔聚合物材料,由于金属卟啉基团与噻吩基团组成D‑A结构,加快电子传输速率,通过实验证明此噻吩基有机多孔聚合物材料(CoTAPP‑BD)具有电催化CO2还原为CO的性能,CO产量在‑0.8V(vs.RHE)达到最高,为0.64mol/mg。
Description
技术领域
本发明属于材料制备与催化化学交叉技术领域,具体为一种结合金属的噻吩基有机多孔聚合物材料及其制备方法和在电催化CO2还原上的应用。
技术背景
CO2气体作为一种温室气体,其大量排放严重影响了生态环境,造成冰川融化、海平面上升、厄尔尼诺现象等环境问题,故将CO2封存转化迫在眉睫。而CO2是一种结构对称的非极性分子,其稳定的结构导致CO2转化为其他化工产品存在一定难度。现阶段用于电催化CO2还原的材料多为金属、无机化合物、及其复合物,有机物在此领域应用较少。电催化过程:CO2分子靠近并吸附在催化剂表面,完成电子转移催化,得到CO2还原产物后,产物脱吸附。此过程要求催化剂具有一定CO2吸附能力以及具备一定导电特性。有机多孔聚合物材料(POFs)是一类通过共价键连接的多孔材料,具有良好的化学稳定性和热稳定性,具有密度低、比表面积大、孔径可调节性等特点,这些特点表明有机多孔材料对CO2具有一定的吸附性能。但是一般的有机多孔聚合物不存在电催化CO2还原活性位点,需要另外加入催化活性位点才能发生催化过程,而外加催化位点往往存在活性位点团聚,分散不均匀的难点,导致催化活性很低。
发明内容
针对上述问题,本发明提供了一种结合金属的噻吩基有机多孔聚合物材料,有机多孔聚合物的多级结构和较大的比表面积,使材料具有较强的CO2吸附能力;卟啉中的M-N-C结构被大量的实验和理论证明是电催化CO2还原的活性位点,将其引入材料中保证了活性位点分布均匀,解决了活性位点团聚的问题;卟啉的达共轭结构以及带金属的卟啉基与噻吩基构成D-A结构,促进电子的传输,解决了一般有机物的导电性差问题。
为实现以上目的,本发明采取如下的技术解决方案:
一种结合金属的噻吩基有机多孔聚合物材料,以MTAPP与BD、TD或BDT(2,2-联噻吩-5,5-二甲醛、2,5-噻吩二甲醛或苯并[1,2-b:4,5-b’]二噻吩-2,6-二甲醛)为原料,利用溶剂热的方法制备而成,得到固体产物后,用低沸点溶剂活化,干燥得到结合金属的噻吩基有机多孔聚合物材料,其结构式如下任意一种:
其制备方法具体包括以下步骤:
(1)合成MTAPP:在氮气气氛下,氨基卟啉(5,10,15,20-四(4-氨基苯)-21H,23H-卟啉)溶于DMF中,加入溶于甲醇的六水合三氯化铁、四水合醋酸钴、四水合醋酸镍、一水合醋酸铜或二水乙酸锌,100℃冷凝回流反应10h后,以去离子水沉淀。烘干得到MTAPP产物。
其结构式如下:
(2)合成结合金属的噻吩基有机多孔聚合物材料:将步骤(1)制得的MTAPP和BD(TD或BDT)溶于正丁醇和1,4-二氧六环的混合溶剂中,以醋酸溶液为催化剂,在液氮中快速冷冻、抽真空,如此循环数次后,达到无水无氧的环境,并在120℃下反应3天,得到结合金属的噻吩基有机多孔聚合物材料。
进一步地,所述MTAPP与BD(TD或BDT)的摩尔比为1:1;所述混合溶剂中正丁醇和1,4-二氧六环体积比为1:1。
本发明还提供了上述结合金属的噻吩基有机多孔聚合物材料的在电催化CO2还原上的应用:在电化学池的阴极和阳极槽中各加入80mL饱和KHCO3溶液,将负载结合金属的噻吩基有机多孔聚合物材料的电极、Ag/AgCl电极和石墨电极装入电化学池中,高纯CO2气体鼓泡30min。
进一步地,负载结合金属的噻吩基有机多孔聚合物材料的电极的制备方法为:向5mg结合金属的噻吩基有机多孔聚合物材料和1.7mg乙炔黑中加入1mL无水乙醇和40μL 5%Nafion溶液,超声1h得到悬浮液,将悬浮液均匀滴在碳纸上,烘干,得到负载结合金属的噻吩基有机多孔聚合物材料的电极。
本发明的有益效果
1、采用有机多孔聚合物为催化剂,其多级孔道结构和高比表面积增大了底物分子CO2与催化剂的接触面积,促进电催化CO2还原。
2、金属卟啉结构中的M-N-C是电催化活性位点,以卟啉为有机多孔聚合物的结构单元大大增加了活性位点的数量,同时促进活性位点分布的均匀性。
3、噻吩结构作为富电子单元,金属卟啉作为缺电子单元,二者通过共价键连接构成了D-A结构,解决了有机物的电子传输性能差的问题,使催化剂在较低的电位下就能发生电催化CO2还原,且具有较大的电流密度。
附图说明
图1为CoTAPP的红外光谱图;
图2为CoTAPP-PH、CoTAPP-TD、CoTAPP-BD、CoTAPP-BDT的红外光谱图;
图3为CoTAPP-BD的X射线衍射谱图
图4为CoTAPP-PH、CoTAPP-TD、CoTAPP-BD、CoTAPP-BDT的CO产量图;
图5为CuTAPP-TD、CuTAPP-BD的红外光谱图;
图6为CuTAPP-TD、CuTAPP-BD的CO产量图。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
CoTAPP合成:
在氮气气氛下,向schlenk管中加入N,N-二甲基甲酰胺(DMF),再加入TAPP(10mg),将溶有四水合醋酸钴(18.68mg)的甲醇溶液逐滴加入schlenk管中,100℃下冷凝回流10h,冷却后,以去离子水沉淀,离心,在100℃的真空烘箱中烘干,得到产物。图1的红外光谱中1000cm-1处有峰,表明Co-N键的形成。
实施例2
结合金属的噻吩基有机多孔聚合物材料的制备:
取10mL的耐热管,向其中加入CoTAPP(13.8mg,0.037mmol)和 2,2-联噻吩-5,5-二甲醛(BD)(8.214mg,0.037mmol),加入正丁醇和1,4-二氧六环的混合溶剂、 6M醋酸(其中正丁醇、1,4-二氧六环、6M醋酸体积比为10:10:1,总体积为2.1mL),超声30min,得到悬浮液。将耐热管置于液氮中闪冻,后抽真空,如此循环三次后,达到无水无氧的环境,放入烘箱中120℃反应3天,得到粗产物,将粗产物用四氢呋喃、丙酮、甲醇洗涤至上清液无色后,将固体移至真空干燥箱中150℃过夜,得到CoTAPP-BD。从图2的CoTAPP-BD的红外光谱图可以看到在1600cm-1出峰,表明键形成。从图3的X射线衍射图可知,CoTAPP-BD呈微晶态。
为证明D-A结构有利于电催化CO2还原,我们将对苯二甲醛作为连接板块,按照上述方法合成了CoTAPP-PH,将其作为对照组。同时也合成了以2,5-噻吩二甲醛或2,5-噻吩二甲醛或苯并[1,2-b:4,5-b’]二噻吩-2,6-二甲醛为连接板块的有机多孔聚合物,此配体的给电子能力介于对苯二甲醛和2,2-联噻吩-5,5-二甲醛之间。从图2的CoTAPP-PH、CoTAPP-TD、CoTAPP-BDT的红外光谱图可以看到在1600cm-1出峰,表明键形成。
实施例3
电催化CO2还原性能测试:
电极的制备:称取研磨后的5mgCoTAPP-BD、CoTAPP-TD、CoTAPP-BDT、CoTAPP-PH和1.7mg乙炔黑于离心管中,加入1mL无水甲醇溶液和50μL5%Nafion溶液,超声1h后制得ink溶液,将其逐滴滴在碳纸上,制得工作电极。向电化学池的两个电极槽中加入80ml的饱和KHCO3溶液,以石墨棒为对电极,Ag/AgCl为参比电极和玻碳电极夹为工作电极构成三电极的反应池,两电极之间以Nafion117膜为离子交换膜。反应池装好后,高纯CO2鼓泡30min排除空气。在电化学工作站(辰华CHI660E)的i-t模式下,以气相色谱(GC2060)测-0.5V、-0.6V、-0.7V、-0.8V、-0.9V(vs.RHE)的电催CO2还原产物。图4可知,CoTAPP-BD的CO产量在-0.8V(vs.RHE)达到最高,为0.64mol/mg,CoTAPP-BDT的CO产量在-0.8V(vs.RHE)达到最高,为1.47mol/mg,均高于以对苯二甲醛为连接板块的CoTAPP-PH。
实施例4
CuTAPP合成:
在氮气气氛下,向schlenk管中加入N,N-二甲基甲酰胺(DMF),再加入TAPP(10mg),将溶有一水合醋酸铜(14.97mg)的甲醇溶液逐滴加入schlenk管中,100℃下冷凝回流10h,冷却后,以去离子水沉淀,离心,在100℃的真空烘箱中烘干,得到产物。
实施例5
结合金属的噻吩基有机多孔聚合物材料的制备:
取10mL的耐热管,向其中加入CuTAPP(13.8mg,0.037mmol)和 2,2-联噻吩-5,5-二甲醛(BD)(8.214mg,0.037mmol)或2,5-噻吩二甲醛(TD)(5.18mg,0.037mmol)加入加入正丁醇和1,4-二氧六环的混合溶剂、 6M醋酸(其中正丁醇、1,4-二氧六环、6M醋酸体积比为10:10:1,总体积为2.1mL),超声30min,得到悬浮液。将耐热管置于液氮中闪冻,后抽真空,如此循环三次后,达到无水无氧的环境,放入烘箱中120℃反应3天,得到粗产物,将粗产物用四氢呋喃、丙酮、甲醇洗涤至上清液无色后,将固体移至真空干燥箱中150℃过夜,得到CuTAPP-BD和CuTAPP-TD。从图5的CuTAPP-TD、CuTAPP-BD的红外光谱图可以看到在1600cm-1出峰,表明键形成。
实施例6
电催化CO2还原性能测试:
电极的制备:称取研磨后的5mgCuTAPP-TD、CuTAPP-BD和1.7mg乙炔黑于离心管中,加入1mL无水甲醇溶液和50μL5%Nafion溶液,超声1h后制得ink溶液,将其逐滴滴在碳纸上,制得工作电极。向电化学池的两个电极槽中加入80ml的饱和KHCO3溶液,以石墨棒为对电极,Ag/AgCl为参比电极和玻碳电极夹为工作电极构成三电极的反应池,两电极之间以Nafion117膜为离子交换膜。反应池装好后,高纯CO2鼓泡30min排除空气。在电化学工作站(辰华CHI660E)的i-t模式下,以气相色谱(GC2060)测-0.5V、-0.6V、-0.7V、-0.8V、-0.9V(vs.RHE)的电催CO2还原产物。图6可知,CuTAPP-BD的CO产量在-0.9V(vs.RHE)达到最高,为0.62mol/mg。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (8)
2.一种如权利要求1所述的结合金属的噻吩基有机多孔聚合物材料的制备方法,其特征在于:包括以下步骤
(1)MTAPP合成
在氮气气氛下,氨基卟啉溶于N,N-二甲基甲酰胺中,加入溶有水合醋酸金属盐的甲醇溶液,100℃冷凝回流反应10h后,经离心、干燥后得到MTAPP产物;
(2)有机多孔聚合物材料合成
将步骤(1)制得的MTAPP和2,2-联噻吩-5,5-二甲醛、2,5-噻吩二甲醛或苯并[1,2-b:4,5-b’]二噻吩-2,6-二甲醛溶于正丁醇和1,4-二氧六环的混合溶剂中,以醋酸溶液为催化剂,在液氮中快速冷冻、抽真空,如此循环数次后,达到无水无氧的环境,并在120℃下反应3天,得到结合金属的噻吩基有机多孔聚合物材料。
3.根据权利要求2所述的制备方法,其特征在于:所述水合醋酸金属盐为水合醋酸铁、水合醋酸钴、水合醋酸镍、水合醋酸铜、水合醋酸锌中的一种。
4.根据权利要求2所述的制备方法,其特征在于:所述MTAPP与、2,5-噻吩二甲醛或苯并[1,2-b:4,5-b’]二噻吩-2,6-二甲醛的摩尔比均为1:1。
5.根据权利要求2所述的制备方法,其特征在于:所述混合溶剂中正丁醇和1,4-二氧六环体积比为1:1。
6.一种如权利要求1所述的结合金属的噻吩基有机多孔聚合物材料的在电催化CO2还原上的应用。
7.根据权利要求6所述的应用,其特征在于:在电化学池的阴极和阳极槽中各加入80mL饱和KHCO3溶液,将结合金属的噻吩基有机多孔聚合物材料的电极、Ag/AgCl电极和石墨电极装入电化学池中,高纯CO2气体鼓泡30min。
8.根据权利要求7所述的应用,其特征在于:结合金属的噻吩基有机多孔聚合物材料的电极的制备方法为:向5mg结合金属的噻吩基有机多孔聚合物材料和1.7mg乙炔黑中加入1mL无水乙醇和40μL 5% Nafion溶液,超声1h得到悬浮液,将悬浮液均匀滴在碳纸上,烘干,得到负载结合金属的噻吩基有机多孔聚合物材料的电极。
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