CN108484646A - 一种变色有机无机杂化材料及其制备方法和应用 - Google Patents
一种变色有机无机杂化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种变色有机无机杂化材料及其制备方法和应用,该材料的化学式为[Cd3(CPBPY)2(BDC)3],其中CPBPY为3‑苯甲酸‑4,4'‑联吡啶,BDC为对苯二羧酸。其制备方法是在溶剂热的条件下,将硝酸镉、对苯二甲酸和一氯化‑3‑苯甲酸基‑4,4'‑联吡啶溶于由乙醇、水和N,N’‑二甲基甲酰胺按比例配制的混合溶剂中,100℃下加热5~10天,然后按照5~10℃/h的速率冷却,过滤洗涤后得到黄色块状晶体并置于史莱克管中,抽真空至含氧量不超过0.06ppm,使用高压汞灯光照射样品,管中样品由黄色变成淡蓝色,即得到本发明的目标产物。本发明的晶体在真空条件下结构稳定,合成简单,条件温和,操作方便,在常温条件下快速探测低浓度氧气,灵敏度高,测试成本低,在氧分子探测方面具有美好的应用前景。
Description
技术领域
本发明涉及化学化工技术领域,具体为一种变色有机无机杂化材料及其制备方法和应用。
背景技术
随着我国科技的快速发展,探测分子氧受到了人们的广泛关注,在生命科学、生物学、气象学、海洋学、医学以及环境下等众多科学领域中也发挥着越来越重要的作用。在探测分子氧技术中,氧含量是一个重要的控制指标,根据实际选择适合的氧含量分析测试方法和设备是保证准确测定氧含量的重要前提。目前氧含量分析的主要方法有:1、化学法,包括化学比色法和化学容量法,即根据气体中氧与无色的一价铜氨离子定量反应来进行氧含量的探测;2、电化学法;3、氧化锆浓差电池法,即以氧化锆陶瓷材料为传感器进行探测;4、黄磷发光法,黄磷与氧反应发出一定强度的光,在一定范围内光强度与氧的浓度成一定的函数关系。将光强度转化成电流信号加以测量;5、库仑分析法,利用氧在电池电极上发生的电解反应计算氧含量;6、磁式氧分析法;7、气相色谱法,即利用各种物质在色谱柱内的保留时间来定性,利用响应值来定量,此方法也可测定气体中氧含量;8、气-质联用法,利用各种物质在色谱柱内的保留时间和分子及碎片的m/e来定性,利用响应值来定量,此方法也可测定气体中氧含量。
上述分析探测氧含量的方法都需要相关的仪器进行辅助,目前一些传统的探测氧气的传感器包括克拉克类型电极和光学器件,但是克拉克类型氧气传感器探测氧气的灵敏度不够,而且光学氧气传感器需要借助荧光仪,探测过程中依据材料的发光性能会随氧气的浓度加强或者猝灭进行判断,此类荧光仪价格昂贵,检测成本较高,操作比较复杂。因此,设计和发展此类新型氧气探测材料非常必要。
发明内容
本发明的目的是为了解决上述技术的不足,依据紫精基光致变色材料由于光诱导产生紫精自由基从而表现出明显的颜色变化,氧气分子可以猝灭自由基,且随着自由基的消失,颜色恢复,进而能够快速的肉眼探测氧气存在的原理,提供一种能够快速探测低浓度氧气的变色有机无机杂化材料及其制备方法。
为实现上述目的,本发明采用的技术方案是:
一种变色有机无机杂化材料,化学式为[Cd3(CPBPY)2(BDC)3],其中CPBPY为3-苯甲酸-4,4'-联吡啶,BDC为对苯二羧酸,该变色有机无机杂化材料属于单斜晶系,空间群为P21/c,晶胞参数为: α=90°,β=94.576(2)°,γ=90°,晶体颜色为淡蓝色,在真空条件下非常稳定。
上述变色有机无机杂化材料的制备方法,包括如下步骤:
S1、按照一定的摩尔比称量硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶并混合,将混合物中加入到溶剂中,于空气氛围下搅拌30min后进行溶剂热反应,所述反应温度为100℃,反应时间为5~10天,反应结束后按照5~10℃/h的速率冷却,过滤洗涤后得到黄色块状晶体;
S2、将S1得到的晶体材料放入到史莱克管中,抽真空至含氧量不超过0.06ppm,然后使用高压汞灯光照射样品,管中样品由黄色变成浅蓝色,即得到变色有机无机杂化材料。
进一步,一氯化-3-苯甲酸基-4,4'-联吡啶的制备过程为:
步骤1、将2,4-二硝基氯苯和4,4’-联吡啶按照1:1的摩尔比称量并混合,接着向混合物中加入丙酮,在75℃下加热,并且搅拌回流24h。然后真空抽滤,并用丙酮洗涤产物直至滤出液变为无色,在真空烘箱中将产物于室温下固体烘干,得到浅灰色的产物,即为一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶;
步骤2、向步骤1得到的一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶中加入乙醇,再加入少量三乙胺,搅拌30分钟后加入间氨基苯甲酸,在93℃下反应48h;
步骤3、反应结束后通过旋蒸法将溶剂除去,再加入适量的水并搅拌1h,然后真空抽滤,加水溶解,再加入丙酮直至固体粉末完全溶解,真空抽滤,抽滤后得到的固体粉末即为一氯化-3-苯甲酸基-4,4'-联吡啶。
进一步,S1中硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶的摩尔比为5:5:2。
进一步,S1中的溶剂为乙醇、水和N,N’-二甲基甲酰胺的混合溶液,乙醇、水和N,N’-二甲基甲酰胺的体积比为2:1:4。
进一步,步骤1中丙酮与4,4’-联吡啶摩尔比为1000:1,步骤2中三乙胺与一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为8:1,间氨基苯甲酸和一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为1:1。
上述变色有机无机杂化材料在低浓度氧气的快速探测中的应用。
与现有技术相比,本发明的有益效果如下:
1、本发明的变色有机无机杂化材料制备过程简单,条件温和,原料简单易得,成本低廉;
2、本发明的变色有机无机杂化材料能够在常温条件下快速探测低浓度氧气,灵敏度高;
3、本发明的变色有机无机杂化材料在探测低浓度氧气过程中操作简单,且能够实时观测,测试成本低廉。
附图说明
图1为本发明一种变色有机无机杂化材料中金属镉离子的配位环境图;
图2为本发明一种变色有机无机杂化材料的简化拓扑图;
图3为本发明一种变色有机无机杂化材料的制备原料一氯化-3-苯甲酸基-4,4'-联吡啶的合成路线图;
图4为本发明一种变色有机无机杂化材料在惰性气氛下刺激响应的变色情况;
图5为本发明一种变色有机无机杂化材料在晶体变色前后的EPR信号;
图6为本发明一种变色有机无机杂化材料中的吡啶上α-碳上氢原子到羧基氧的距离;
图7为本发明一种变色有机无机杂化材料中的相邻吡啶环上的二面角。
具体实施方式
以下结合附图和具体实施方式对本发明进行详细的描述。
一种变色有机无机杂化材料,化学式为[Cd3(CPBPY)2(BDC)3],其中CPBPY为3-苯甲酸-4,4'-联吡啶,BDC为对苯二羧酸,该变色有机无机杂化材料属于单斜晶系,空间群为P21/c,晶胞参数为: α=90°,β=94.576(2)°,γ=90°,晶体颜色为淡蓝色,在真空条件下非常稳定。
通过X-ray衍射分析该变色有机无机杂化材料,该晶体的不对称结构单元中含有3个镉离子,2个CPBPY配体和3个BDC配体,如图1所示,Cd(1)与Cd(2)通过羧酸氧原子O(2)桥连,O(2)来自于CPBPY配体,又由于Cd(2)恰好处于倒反中心,进而形成了对称的Cd3簇。每个Cd3簇通过有机连接子与周围的6个Cd3簇紧密相连,四个方向上的连接子是由BDC和CPBPY共同构成,而其他两个方向上仅是BDC配体,如图2所示,从而形成pcu简单立方拓扑。
本发明的变色有机无机杂化材料的制备方法,包括以下步骤:
S1、按照一定的摩尔比称量硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶并混合,将混合物中加入到溶剂中,于空气氛围下搅拌30min后进行溶剂热反应,所述反应温度为100℃,反应时间为5~10天,反应结束后按照5~10℃/h的速率冷却,过滤洗涤后得到黄色块状晶体;
S2、将S1得到的晶体材料放入到史莱克管中,抽真空至含氧量不超过0.06ppm,然后使用高压汞灯光照射样品,管中样品由黄色变成浅蓝色,即得到变色有机无机杂化材料。
进一步,S1中一氯化-3-苯甲酸基-4,4'-联吡啶的合成路线图如图3所示,具体制备过程为。
步骤1、将2,4-二硝基氯苯和4,4’-联吡啶按照1:1的摩尔比称量并混合,然后向混合物中加入丙酮,在75℃下加热,并且搅拌回流24h,然后真空抽滤,并用丙酮洗涤产物直至滤出液变为无色,在真空烘箱中将产物于室温下固体烘干,得到浅灰色的产物,即为一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶;
步骤2、向步骤1中得到的一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶中加入乙醇,再加入少量三乙胺,搅拌30分钟后加入间氨基苯甲酸,在93℃下反应48h;
步骤3、反应结束后通过旋蒸法将溶剂除去,加入适量的水并搅拌1h,然后真空抽滤,再加水溶解,再加入丙酮直至固体粉末完全溶解,真空抽滤,抽滤后得到的固体粉末即为一氯化-3-苯甲酸基-4,4'-联吡啶。
进一步,S1中硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶的摩尔比为5:5:2。
进一步,S1中的溶剂为乙醇、水和N,N’-二甲基甲酰胺的混合溶液,乙醇、水和N,N’-二甲基甲酰胺的体积比为2:1:4。
进一步,步骤1中丙酮与4,4’-联吡啶摩尔比为1000:1,步骤2中三乙胺与一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为8:1,间氨基苯甲酸和一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为1:1。
上述变色有机无机杂化材料在低浓度氧气的快速探测中的应用。
实施例1
首先将2,4-二硝基氯苯(16.16g,78mmol)和4,4’-联吡啶(12.40g,78mmol)溶于80ml丙酮,在75℃下边加热边搅拌24h,得到浅灰色的产物一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶;紧接着在5.0g一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶中加入200ml乙醇,再加入2.8ml三乙胺,搅拌30分钟,再加入1.50g间氨基苯甲酸,在93℃下反应48h。通过旋蒸法除去溶剂,再加水,搅拌1h,并真空抽滤,抽滤后再加水溶解,滴入丙酮至固体粉末,真空抽滤,得到的固体粉末就是一氯化-3-苯甲酸基-4,4'-联吡啶。
然后将硝酸镉(0.155g,0.5mmol)、对苯二甲酸(0.082g,0.5mmol)和一氯化-3-苯甲酸基-4,4'-联吡啶(0.056g,0.2mmol)溶于由乙醇(2mL)、水(1mL)和N,N’-二甲基甲酰胺(4mL)混合配制的溶剂中,于空气氛围下搅拌30min,加热到100℃并保持7天,然后以每小时5℃/h的速度冷却到室温。过滤并洗涤得到黄色块状晶体。将合成的上述晶体材料放入到史莱克管中,抽真空,含氧量不能超过0.06ppm,抽真空后用高压汞灯光照样品,样品会由黄色变成浅蓝色,即得到该变色有机无机杂化材料。
实施例2
制备方法与实施例1的相同,不同的是硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶在溶剂中的反应时间为10天,降温速率为10℃/h。
实施例3
制备方法与实施例1的相同,不同的是硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶在溶剂中的反应时间为5天,降温速率为5℃/h。
以实施例1为例,取制得的有机无机杂化材料进行紫外线照射,如图4和图5所示,在真空条件或者惰性气氛下,浅蓝色晶体具有EPR信号(Electron ParamagneticResonance电子顺磁共振谱),信号的位置在g=2.0043,产生了紫精自由基。如图6和图7所示,吡啶的α-碳原子上氢原子到羧基氧的距离为这可能是电子由供体上转移到缺电子紫精的通道。另外,具有N+离子的吡啶环和相邻的吡啶之间的夹角仅为10.8°,接近于0°,这种几何构型非常有利于稳定光诱导产生的紫精自由基。当浅蓝色晶体处于低浓度氧气氛围时,自由基遇O2后猝灭,晶体会褪色。如果晶体接触到纯氧气,其颜色在5秒内恢复到原来的状态(图4);如果晶体接触到空气,其褪色时间需要15秒;当氧气含量为总体积的0.1%时,其响应时间需要40秒;当氧气含量为0.01%时,其响应时间需要150秒。
以上所述仅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,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种变色有机无机杂化材料,其特征在于,所述变色有机无机杂化材料的化学式为[Cd3(CPBPY)2(BDC)3],其中CPBPY为3-苯甲酸-4,4'-联吡啶,BDC为对苯二羧酸,所述的变色有机无机杂化材料属于单斜晶系,空间群为P21/c,晶胞参数为:α=90°,β=94.576(2)°,γ=90°,晶体颜色为淡蓝色,在真空条件下非常稳定。
2.一种变色有机无机杂化材料的制备方法,其特征在于,包括如下步骤:
S1、按照一定的摩尔比称量硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶并混合,将混合物中加入到溶剂中,于空气氛围下搅拌30min后进行溶剂热反应,所述反应温度为100℃,反应时间为5~10天,反应结束后按照5~10℃/h的速率冷却,过滤洗涤后得到黄色块状晶体;
S2、将S1得到的晶体材料放入到史莱克管中,抽真空至含氧量不超过0.06ppm,然后使用高压汞灯光照射样品,管中样品由黄色变成淡蓝色,即得到变色有机无机杂化材料。
3.根据权利要求2所述的一种变色有机无机杂化材料的制备方法,其特征在于,所述一氯化-3-苯甲酸基-4,4'-联吡啶的制备过程为:
步骤1、将2,4-二硝基氯苯和4,4’-联吡啶按照1:1的摩尔比称量并混合,然后向混合物加入丙酮,在75℃下加热,并且搅拌回流24h,然后真空抽滤,并用丙酮洗涤产物直至滤出液变为无色,在真空烘箱中将产物于室温下固体烘干,得到浅灰色的产物,即为一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶;
步骤2、向步骤1得到的一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶中加入乙醇,再加入三乙胺,搅拌30分钟后加入间氨基苯甲酸,在93℃下反应48h;
步骤3、反应结束后通过旋蒸法将溶剂除去,加入适量的水并搅拌1h,然后真空抽滤,加水溶解,再加入丙酮直至固体粉末完全溶解,真空抽滤,抽滤后得到的固体粉末即为一氯化-3-苯甲酸基-4,4'-联吡啶。
4.根据权利要求2所述的一种变色有机无机杂化材料的制备方法,其特征在于,所述S1中硝酸镉、对苯二甲酸和一氯化-3-苯甲酸基-4,4'-联吡啶的摩尔比为5:5:2。
5.根据权利要求2所述的一种变色有机无机杂化材料的制备方法,其特征在于,所述S1中的溶剂为乙醇、水和N,N’-二甲基甲酰胺的混合溶液,乙醇、水和N,N’-二甲基甲酰胺的体积比为2:1:4。
6.根据权利要求3所述的一种变色有机无机杂化材料的制备方法,其特征在于,所述步骤1中丙酮与4,4’-联吡啶的摩尔比为1000:1,步骤2三乙胺与一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为8:1,间氨基苯甲酸和一氯化-1-(2,4-二硝基苯基)-4,4'-联吡啶的摩尔比为1:1。
7.根据权利要求1所述的一种变色有机无机杂化材料的应用,其特征在于,用于低浓度氧气的快速探测。
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