CN116355212A - 一种具有电催化产双氧水性能的三维共价有机聚合物的制备及应用 - Google Patents
一种具有电催化产双氧水性能的三维共价有机聚合物的制备及应用 Download PDFInfo
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Abstract
一种具有电催化产双氧水性能的三维共价有机聚合物的制备及应用,属于废水处理等环境相关领域。通过将具有三维马鞍状结构、全π‑共轭特点的环辛四烯四噻吩衍生物配体与芘‑4,5,9,10‑四酮和醋酸胺进行多组分的Debus‑Radziszewski缩合反应,一步法得到咪唑连接的全共轭三维COPs。本发明的咪唑连接的三维COPs具有良好的化学稳定性,多孔性和本征半导体特性,该材料具备优异的电催化合成双氧水(H2O2)的性能,其电催化生成的H2O2能有效降解亚甲基蓝染料。
Description
技术领域
本发明属于多孔有机聚合物材料领域,具体涉及一种新型的咪唑连接的三维全共轭共价有机聚合物材料的制备,该共价有机聚合物可用于2电子氧还原电催化合成双氧水,并有效降解亚甲基蓝染料。
背景技术
共价有机聚合物(Covalent Organic Polymers,COPs)是一类通过共价键将不同几何构型和长度的有机配体组装成多维度多功能的有机多孔材料。因其优良的稳定性、高的比表面积、大的孔体积、可控的孔结构和孔道易修饰的特点,COPs近年来受到人们的广泛关注,在包括了多相催化、气体吸附与存储、药物缓释、水处理等领域具有较好的应用前景(Chem.Mater.2019,31,3313-3323)。
此外,COPs是由有机结构单元通过共价键连接而成,该领域最重要的一个关键科学问题是如何构建稳定的连接(Acc.Chem.Res.2015,48,3053)。当前基于环三嗪、吩嗪、苯并噻唑、喹啉和苯并咪唑等杂环作为连接单元的COPs已被巧妙构建,这类杂环的引入,不仅增加了材料的稳定性,还引入了杂原子,有利于改善和提高材料的电催化等半导体性能。基于此,2019年Wang等人报道了一种通过多组分反应合成的咪唑连接的二维结构的共价有机框架(Covalent Organic frameworks,COFs)(J.Am.Chem.Soc.2019,141,18004-18008),由于咪唑连接点的形成,使得这类材料具有良好的结晶性和超高的稳定性。
然而,相比于目前报道广泛的二维共价有机聚合物,构建新的三维拓扑结构和发展新的三维共价有机聚合物材料,对于推动其在如废水处理环境相关等领域的实际应具有重要意义。为此,我们将咪唑环作为连接单元,利用环辛四烯四噻吩衍生物三维共轭马鞍结构特点,构筑了一种新型的咪唑连接的全共轭三维COP材料。该材料具有优异的2电子氧还原电催化性能,能高选择性、高产率的合成双氧水(H2O2)。并且所合成的H2O2可有效的用于降解亚甲基蓝染料。该发明为COPs材料在环境等方面的发展提供新的思路。
目前,关于将咪唑单元作为连接的三维共价有机聚合物材料的制备方法及其氧还原产生H2O2,并利用Fenton反应有效降解亚甲基蓝染料的应用,国内外未见研究报道或专利公开。
发明内容
本发明的目的在于提供一种高稳定性的咪唑连接的全共轭三维共价有机聚合物材料的制备方法,该材料具备电催化产H2O2的性能,能用于降解亚甲基蓝染料。
为实现上述目的,本发明采用的技术方案具体包括如下内容:
本发明第一方面提供一种咪唑连接的三维共价有机聚合物材料的制备方法,包括以下步骤:
(1)将芳杂环取代的马鞍状环辛四烯四噻吩衍生物配体COThP-CHO、芘-4,5,9,10-四酮(Pyrene-4,5,9,10-tetraone,PyT)和既作为反应组分又作为催化剂的醋酸铵(NH4OAc)加入溶剂中分散溶解;其中COThP-CHO为共轭马鞍状构型的环辛四烯四噻吩衍生物配体,其中取代的芳香环选自苯环、呋喃、噻吩、硒吩以及其他芳杂环。
(2)反应体系经短暂超声溶解分散后,再冷冻-真空-解冻循环,然后密封条件下升温反应至完全;
(3)产物经过滤、洗涤,再经索提纯化,即得咪唑连接的全共轭结构的三维共价有机聚合物(命名为BUCT-COP-7)。
进一步,所述步骤(1)中,COThP-CHO、芘-4,5,9,10-四酮和NH4OAc的摩尔比为:1:2:2~20(NH4OAc的摩尔比相对于COThP-CHO优选为12)。
进一步,所述步骤(1)中,溶剂为N,N-二甲基乙酰胺-均三甲苯混合溶剂。
进一步,所述步骤(1)中,所述溶剂为N,N-二甲基乙酰胺与均三甲苯体积比1~9:9~1(优选为2:8)的混合溶剂。
进一步,所述步骤(2)中,超声时间为1~30min,冷冻-真空-解冻循环的方法为:将反应物用液氮冷冻、抽真空、通氮气解冻。
进一步,所述步骤(2)中,升温反应的温度为50~200℃之间,反应时间为1~10天。
进一步,所述步骤(3)中,分别以二氯甲烷、乙醇洗涤、四氢呋喃等有机溶剂索氏提取,最后真空干燥即得咪唑连接的全共轭三维共价有机聚合物。
本发明采用Debus-Radziszewski缩合反应将COThP-CHO、芘-4,5,9,10-四酮和NH4OAc一步合成制备咪唑连接的全共轭的三维COP材料,其合成路线如下:
其中取代的芳环可以是苯环、呋喃、噻吩、硒吩等芳环或芳杂环。PyT上的取代基R可以是氢原子、C1-20等烷基或其它取代基团。
本发明第二方面提供上述三维共价有机聚合物材料的制备方法制得的产物在2电子氧还原产生H2O2中的电化学测试,包括以下步骤:将本发明制备的共价有机聚合物和单壁碳纳米管以一定的质量比(优选1:1)配成墨水滴于旋转环盘电极(RRDE),以其作为阴极,碳棒为阳极,甘汞电极为参比电极,组成三电极体系,通入氧气饱和一定时间后测试其电催化性能。
进一步,所述墨水在RRDE上的质量负载为0.1~0.3mg/cm2。
进一步,材料在0.1M KOH溶液中测试电化学LSV曲线和过氧化氢选择性曲线。
本发明第三方面提供第二方面所述的3D COP的应用方法,包括以下步骤:将所述的共价有机聚合物材料和导电剂(可以是单壁或多壁碳纳米管、乙炔黑、科琴黑等)以一定质量比(优选1:1)配成墨水滴于气体扩散电极上,以其作为阴极催化剂,碳棒为阳极,以Nafion115将两极隔开,组装气体扩散电池。利用空气中的O2进行电解,一定时间后,取适量含有H2O2的阴极电解液,利用Fenton反应,滴定一定量的亚甲基蓝溶液,观察其染料降解情况。
进一步,所述墨水在气体扩散电极上的质量负载为0.2-1mg/cm2。
进一步,所取电解液体积为3mL,亚甲基蓝溶液为6mL。
进一步,通过Fenton反应原理,所用亚甲基蓝为pH=1,浓度为200ppm,其中含有0.1mmol Fe2+的溶液。
本发明的优点在于:
1)本发明通过Debus-Radziszewski反应,一步法合成了具有高稳定性的咪唑单元连接的新型全共轭三维共价有机聚合物材料。
2)本发明所制备的三维共价有机聚合物可用于2电子氧还原电催化产H2O2,平均电子转移数n为2.49,H2O2选择性达82.1%。
3)本发明所制备的三维共价有机聚合物通过气体扩散电解池器件,利用空气中的O2进行电解,在较小的电流密度10mA/cm2放电3小时后,可产生相对较高的H2O2产量1090mmol/g,平均产率为363.3mmol/g/h,法拉第效率为80%左右。
4)本发明所制备的三维共价有机聚合物在气体扩散电解池中以10mA/cm2电解3h后,取3mL阴极电解液加入6mL,pH=1,含有0.1mmol Fe2+的亚甲基蓝溶液中,短暂摇晃后,可以明显观察到颜色褪色,即染料被有效降解。
附图说明
图1为本发明制备的共价有机聚合物材料(BUCT-COP-7)的X射线光电子能谱(XPS)谱图;
图2为本发明制备的共价有机聚合物材料(BUCT-COP-7)的红外(FTIR)谱图;
图3为本发明制备的共价有机聚合物材料(BUCT-COP-7)的固体核磁图;
图4为本发明制备的共价有机聚合物材料在0.1M KOH溶液中测试的旋转环盘电极(RRDE)下的LSV曲线。
图5为本发明制备的共价有机聚合物材料在0.1M KOH溶液中测试的旋转环盘电极(RRDE)下的过氧化氢选择性曲线。
图6为本发明进行气体扩散电池测试时组装的实物图。
图7为本发明在进行气体扩散电池测试时,在不同电流密度下进行放电所得到的H2O2产率和相应的法拉第效率。
图8为本发明在进行气体扩散电池测试时,在电流密度为10mA/cm2时放电3小时的稳定性和不同时间的H2O2产量。
图9为本发明在进行气体扩散电池测试时,取10mA/cm2放电3小时后的适量阴极电解液加入200ppm的亚甲基蓝溶液中降解后的浓度测试。
图10为本发明在对200ppm的亚甲基蓝溶液降解前后的颜色对比。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图和实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。
实施例1
采用上述共价有机聚合物材料的合成路径合成三维COP产物标记为BUCT-COP-7。
步骤如下:
将苯基取代的马鞍状配体COThP-CHO(0.02mmol)、芘-4,5,9,10-四酮(0.04mmol)和既作为反应组分又作为催化剂的NH4OAc(0.24mmol)置于Pyrex管中,加入N,N-二甲基乙酰胺/均三甲苯(v/v=2:8,总体积为1mL),超声处理10分钟。然后把Pyrex管在液氮浴中快速冷冻,再抽真空到0mbar的内部压力,经三次冷冻-真空-解冻循环后进行真空密封,升温至室温后,将Pyrex管置于150℃~180℃的烘箱中3-7天。反应后,溶液用滤纸过滤,再用二氯甲烷和乙醇洗涤过滤,最后用四氢呋喃索氏提取24-48小时,以去除反应溶剂及小分子寡聚物。
图1用XPS的C1s谱图以验证在该溶剂体系下两单体形成较好键型的共价有机聚合物。图2给出了BUCT-COP-7的红外光谱,图3则是BUCT-COP-7的固态核磁共振谱,通过FT-IR和固态核磁共振谱证实了咪唑单元的形成。FT-IR光谱显示了咪唑基团在约1639cm-1和3412cm-1处的典型条带,与咪唑化合物模型相似。
通过测试在0.1M KOH碱性溶液中的旋转环盘电极(RRDE)下的LSV曲线确定COP的ORR活性(附图4),可以看出有一定的H2O2产生。通过计算,可以得出在0.6-0.7V(vs.RHE)之间,H2O2产率可达82.1%(附图5)。
实施例2:三维全共轭共价有机聚合物BUCT-COP-7电催化合成H2O2,并有效降解亚甲基蓝染料的应用按照以下步骤。
通过将BUCT-COP-7共价有机聚合物和单壁碳纳米管以一定质量比(如1:1),与加入无水乙醇:水:Nafion(溶液的浓度为5wt%)=10:10:1(体积比)配成墨水,将其滴于气体扩散电极上,质量负载为0.5mg cm-2,以其作为阴极催化剂,碳棒为阳极,以Nafion 115将两极隔开,电解液为0.1M KOH,组装气体扩散电池(附图6)。
利用空气中的O2进行电解,通过不同电流密度分别电解10分钟,得到H2O2产率与电流密度相关的曲线(附图7),其中在50mA cm-2下电解,其H2O2产率可达1680.39mmol g-1h-1。在较小的电流密度10mA/cm2放电3小时后,可产生相对较高的H2O2产量1090mmol/g,平均产率为363.3mmol/g/h,法拉第效率为80%左右(附图8)。取10mA/cm2放电3小时后含有H2O2的阴极电解液3ml,利用Fenton反应,滴于6mL,pH=1,含有0.1mmol Fe2+的200ppm亚甲基蓝溶液中,通过液态紫外测试,反应后亚甲基蓝含量几乎为0(附图9),同时观察到降解前后深蓝色染料变为无色(附图10)。实验证明,咪唑连接的三维COP有较好的电催化氧还原产生H2O2的能力。其产生的H2O2同时能够有效的应用于降解有机染料废水领域。
上述实施例仅仅是为清楚地说明本发明所作的举例,但不能理解为是对权利要求的限制。本发明不仅局限于以上实施例,其具体结构允许有变化。凡在本发明独立权利要求的保护范围内所作的各种变化均在本发明保护范围内。
附图1说明,在284.2eV和285.4eV处,分峰得到咪唑单元特有的C=C及C=N的峰,证明3D-COP的成功合成。
附图2说明,BUCT-COP-7中咪唑基团在约1648cm-1处出现典型条带,与咪唑模型化合物模型相似,证明其中咪唑单元的合成。
附图3说明,固态核磁共振谱中出现咪唑单元的特征峰,进一步证明了COP的合成。
附图4为BUCT-COP-7进行旋转环盘电极(RRDE)测试时的盘电流和环电流,可以看出材料是进行2电子的氧还原反应,产生一定的H2O2。
附图5为不同电压下产生的H2O2产率,在0.6-0.7V(vs.RHE)之间,H2O2产率达80%左右。
附图6为进行气体扩散电池测试时组装的实物图。
附图7为气体扩散电池测试过程中,不同电流密度下的H2O2产率以及法拉第效率曲线。可以看出,在电流密度30mA cm-2以上时,其H2O2产率可达1000mmol gcat -1h-1以上,同时法拉第效率维持在80%左右。
附图8为气体扩散电池测试过程中,在电流密度为10mA/cm2时放电3小时的稳定性以及H2O2产量。可以看出在较小的电流密度10mA/cm2放电3小时后,可产生相对较高的H2O2产量1090mmol/g。
附图9为气体扩散电池稳定性测试后,取含有H2O2的阴极电解液3mL,利用Fenton反应,滴于6mL,pH=1,含有0.1mmol Fe2+的200ppm亚甲基蓝溶液中,通过液态紫外测试,反应后亚甲基蓝含量几乎为0。
附图10为进行亚甲基蓝染料降解前后染料颜色变化,可以看出,深蓝色的染料被明显的降解。
Claims (10)
1.一种三维共价有机聚合物的制备方法,其特征在于,包括以下几个步骤:
(1)将芳环取代的马鞍状环辛四烯四噻吩衍生物配体COThP-CHO、芘-4,5,9,10-四酮(Pyrene-4,5,9,10-tetraone,PyT)衍生物和既作为反应组分又作为固体催化剂的醋酸铵(NH4OAc)三组分试剂加入溶剂中分散均匀;
(2)反应体系经短暂超声分散后,再经过冷冻-真空-解冻循环,然后密封条件下升温反应至完全;
(3)产物经过滤、洗涤、索提纯化,即得咪唑连接的三维共价有机聚合物。
3.根据权利要求1所述的方法,其特征在于:COThP-CHO、芘-4,5,9,10-四酮和NH4OAc的摩尔比为:1:2:2~20,优选1:2:12。
4.根据权利要求1所述的方法,其特征在于:所述步骤(1)中,溶剂为N,N-二甲基乙酰胺与均三甲苯混合溶剂,N,N-二甲基乙酰胺与均三甲苯体积比1~9:9~1(优选为2:8)。
5.根据权利要求1所述的方法,其特征在于:所述步骤(2)中,超声时间为1~30min,冷冻-真空-解冻循环的方法为:将反应物用液氮冷冻、抽真空、通氮气解冻;密封反应的条件是在氮气氛围或真空条件下;
所述步骤(2)中,升温反应温度为50~200℃,反应时间为1~10天。
6.根据权利要求1所述的方法,其特征在于:所述步骤(3)中,以二氯甲烷、乙醇洗涤,并用四氢呋喃等有机溶剂索氏提取1~5天,最后真空干燥即得咪唑连接的三维共价有机聚合物。
7.一种咪唑连接的三维共价有机聚合物材料,其特征在于:采用权利要求1-6任一项所述的方法制备,其结构为COThP-CHO与芘-4,5,9,10-四酮通过咪唑单元链接,形成完全π-共轭结构的三维共价有机聚合物。
8.按照权利要求7所述的咪唑连接的三维共价有机聚合物材料的应用,用于在2电子氧还原产生H2O2并降解亚甲基蓝染料。
9.按照权利要求8所述的应用,其特征在于:将所述的共价有机聚合物材料和导电剂以一定质量比(优选1:1)配成墨水滴于气体扩散电极上,以其作为阴极催化剂,碳棒为阳极,以Nafion膜将两极隔开,组装气体扩散电池;导电剂选自单壁或多壁碳纳米管、乙炔黑、科琴黑。
10.按照权利要求9所述的应用,利用空气中的O2进行电解,一定时间后,取适量含有H2O2的阴极电解液,利用Fenton反应,滴定亚甲基蓝溶液,进行染料降解情况。
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