CN111039994A - 三联吡啶铂配合物及在光解水制氢中的应用 - Google Patents
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Abstract
本发明公开了一种三联吡啶铂配合物及在光解水制氢中的应用，本发明的三联吡啶铂配合物的合成路径为：将乙酰吡啶、二甲氨基肉桂醛在浓氨水和氢氧化钾的乙醇水溶液中反应，得到三联吡啶配体dmtpy，随后与cis－[Pt(dmso)2Cl2]前体配合物在无水甲醇中回流反应，生成三联吡啶铂配合物[Pt(dmtpy)Cl]Cl。本发明制备的三联吡啶铂配合物具有很强可见光吸收性质，能够同时作为光敏剂和催化剂，在中性pH的甲醇水溶液中能够作为单分子光解水制氢均相催化剂，在紫外—可见光区都获得了较好的催化性能。并且，在DNA的存在下，该三联吡啶铂配合物在近红外区的光吸收显著增强，并能够有效催化近红外下的光解水制氢。
Description
技术领域
本发明涉及光解水制氢技术领域，特别涉及一种三联吡啶铂配合物及在光解水制氢中的应用。
背景技术
由于煤、石油、天然气等化石能源的使用，大量新增温室气体CO2以及同时产生的烟气污染，正在严重威胁着全球生态。氢是一种清洁能源，其完全燃烧的产物——水，不会给环境带来任何污染。氢主要以化合物的形态贮存于水中，而水是地球上最广泛的物质。更重要的是，其燃烧产物水能够再次被分解为氢气和氧气，重复利用。传统的电解水虽然取得了一定的进展，但是该过程需要耗费大量由化石能源提供的电力，造成了一定的资源消耗和环境污染。太阳能，是一种取之不尽用之不竭、清洁环保的一次能源，是最大的可开发能源。因此，利用太阳能光解水制氢成为具有可再生、节能、环保等多种优势的解决方案。
当前开发的太阳能光解水催化剂主要集中在非均相半导体材料。如催化剂TiO2半导体能够吸收波长＜370nm的紫外光，通过价带—导带的电子跃迁产生“电子—空穴”，使水电离生成氢气和氧气。事实上，太阳光的光谱范围内，波长小于400nm的紫外光区仅占4％，而43％为波长400－700nm的可见光，53％为波长大于700nm的红外光。大多数半导体催化材料的吸收集中在紫外区，太阳能利用率有待提升。于是研究者将目光投向了如何提升催化体系的可见光区吸收性能。在近期报道中，研究者用邻苯二酚等烯二醇类有机配体对TiO2纳米颗粒进行了表面修饰，把TiO2的光吸收范围扩展到了可见光区，从而提高TiO2半导体的太阳光吸收利用率。
除了非均相光催化剂，过渡金属配合物可以作为均相光催化剂，催化水的还原制氢、水的氧化制氢、二氧化碳还原等一系列与能源和环境密切相关的反应。其中经典的例子有Co3+、Ni2+、Rh3+等配合物。近期研究中，一个三联吡啶铂配合物[Pt(tpy)Cl]+能在只需EDTA作为牺牲剂的条件下，同时完成吸收光和还原水制氢气两个功能。随后，进一步发现将光敏基团甲基紫精引入该Pt配合物结构中，或者加入另外一种简单的Pt配合物(如顺铂等)，可以进一步提升其催化效率。该研究组还将光敏性的Ru配合物结构与光催化活性的Pt配合物通过化学键构建了Ru－Pt异双核配合物，成功用作单分子太阳能转化器件。因此，设计基于过渡金属配合物的、具有更广的光吸收、尤其是覆盖太阳光全范围的紫外—可见—近红外区范围的光催化剂，对提高光解水制氢催化剂性能这一关键问题具有重要意义。
发明内容
本发明的第一个发明目的在于：针对当前光解水制氢的研究进展，提供一种具有良好紫外—可见光吸收的三联吡啶铂配合物，以能够同时作为光敏剂和催化剂，进而在紫外—可见光区都能获得较好的催化性能。
本发明采用的技术方案如下：一种三联吡啶铂配合物，由阳离子和阴离子组成，其特征在于，所述阳离子结构是如式I：
进一步，三联吡啶铂配合物并不限定阴离子的种类，本技术领域常规阴离子均能实现本发明的目的，作为优选，阴离子为无机盐阴离子，更优选为PF6 －、ClO4 －、Cl－、NO3 －或BPh4 －，作为一种最优选方案，本发明所述三联吡啶铂配合物的阴离子为Cl－。
本发明的第二个目的在于，提供上述三联吡啶铂配合物的制备方法。
本发明采用的技术方案如下：一种三联吡啶铂配合物的制备方法，其特征在于，包括以下步骤：
步骤1、将二甲氨基肉桂醛和乙酰吡啶在浓氨水和强碱(例如氢氧化钾、氢氧化钠等)的乙醇水溶液中混合反应，得到三联吡啶配体；
步骤2、将三联吡啶配体与cis－[Pt(dmso)2Cl2]前体配合物(顺－二(二甲基亚砜)二氯合铂)在无水有机溶剂(例如甲醇、乙醇、丙醇等)中回流反应后，即得到三联吡啶铂配合物。
进一步，为了更好地得到高得率的三联吡啶配体，所述步骤1具体为：依次将二甲氨基肉桂醛、乙酰吡啶、无水乙醇、强碱(例如氢氧化钾、氢氧化钠等)和浓氨水加入反应容器中，搅拌反应后，抽滤，得到的固体即为三联吡啶配体。
进一步，为了提高三联吡啶配体的纯度，抽滤后得到的固体用无水有机溶剂(例如无水乙醇)洗涤后，静置干燥即得三联吡啶配体。进一步，若要得到其他形式的无机阴离子，在回流反应后，加入无机阴离子即可，例如可以加入PF6 －、ClO4 －、Cl－、NO3 －或BPh4 －等。
进一步，所述步骤2具体为：将三联吡啶配体溶于无水有机溶剂(例如无水甲醇、乙醇、丙醇、丙酮等)中，加入cis－[Pt(dmso)2Cl2]前体配合物回流反应，浓缩结晶后得到三联吡啶铂配合物。
本发明的第三个目的在于，提供一种三联吡啶铂配合物在光解水制氢中的应用。
进一步，将三联吡啶铂配合物用于光解水制氢时，所述三联吡啶铂配合物作为光解水的光敏剂和催化剂使用。
进一步，在DNA存在的条件下，所述三联吡啶铂配合物与DNA构成的光解水制氢体系对近红外光吸收增强。
综上所述，由于采用了上述技术方案，本发明的有益效果是：
1、本发明提供的三联吡啶铂配合物，可作为紫外—可见光解水制氢的光催化剂，其结构稳定，具有良好的、范围广泛的光谱吸收性质，是新型的光解水制氢光催化剂；
2、本发明设计的具有良好紫外—可见光吸收的三联吡啶铂配合物，能够同时作为光敏剂和催化剂使用，在中性pH值下的甲醇水溶液中能够作为单分子光解水制氢催化剂，并在紫外—可见光区都获得了较好的催化性能；
3、通过发明人的意外发现，在DNA的存在下，该三联吡啶铂配合物在近红外区的光吸收显著增强，能够有效催化近红外光解水，因此，本发明构建了新的三联吡啶铂配合物与DNA的光解水制氢体系，该DNA辅助铂催化近红外光解水制氢体系目前并未见报道；
4、将本发明的三联吡啶铂配合物应用于光解水制氢中时，具有以下优势：(1)具有良好的水溶性；(2)具有良好的光谱性质，尤其在可见区具有优异光吸收性质；(3)所构建的DNA辅助铂催化剂光解水制氢体系能够仅在近红外光照下有效的光解水制氢。
附图说明
图1为本发明所制备的三联吡啶铂配合物的合成途径；
图2为本发明所制备的三联吡啶铂配合物在水溶液中的吸收光谱图，以及DNA对吸收光谱的影响；
图3为本发明所制备的三联吡啶铂配合物在紫外可见区光解水制氢实验数据图；
图4为本发明所制备的三联吡啶铂配合物在DNA存在的条件下在近红外区光解水制氢实验数据图。
具体实施方式
下面结合附图，对本发明作详细的说明。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，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仅用以解释本发明，并不用于限定本发明。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备，所用试剂和材料均为市购。
实施例1
三联吡啶铂配合物的制备：
步骤1、在150ml锥形瓶中，依次加入0.876g二甲氨基肉桂醛、1.21g乙酰吡啶、50ml无水乙醇、1.54g氢氧化钾固体、29ml浓度为25％的氨水，充分搅拌，反应液由黄绿色变为橘红色，室温搅拌24小时，抽滤，得到黄色固体；
步骤2、用无水乙醇洗涤，静置干燥得到黄色粉末1.18mg产物，为三联吡啶配体dmtpy，计算产率为62％；
步骤3、将94mg三联吡啶配体dmtpy溶于50ml无水甲醇，加入105.6mgcis－[Pt(dmso)2Cl2]前体配合物，在无水甲醇中回流24小时，浓缩甲醇反应液至10ml，静置析出固体，即为三联吡啶铂配合物[Pt(dmtpy)Cl]Cl，产率68.8％。
核磁共振氢谱图：1HNMR(300Hz，dmso－d6)：δ8.91(d，J＝5.4Hz，2H)，8.67(s，2H)，8.60(d，J＝7.2Hz，2H)，8.52(t，J＝7.8Hz，2H)，7.96(t，J＝6.3Hz，2H)，7.54(d，J＝8.7Hz，2H)，7.03(d，J＝16.2Hz，2H)，6.81(d，J＝9.0Hz，2H)，3.03(s，6H)。电喷雾质谱图：ESI－MS(methanol)m/z calc.for C25H22Cl2N4Pt([M+)：609.01；Found：609.16。
实施例2
三联吡啶铂配合物的吸收光谱测试：
在25℃，将三联吡啶铂配合物配置为20μM水溶液，于岛津－UV2700紫外可见光谱仪记录250－800nm范围的紫外吸收光谱。从图2可见，三联吡啶铂配合物在可见区590nm处有很强的吸收峰，而在三联吡啶铂配合物水溶液中逐渐加入DNA，配合物在700－800nm范围的吸收明显增强。
实施例3
三联吡啶铂配合物的光解水催化测试：
将三联吡啶铂配合物配置成50μM浓度的甲醇水溶液(体积比1：1)，取50ml该溶液，分别以400nm截止滤光片和700nm截止滤光片设置光催化光源PLS－SXE300UV，在Labsolar－6A全玻璃自动在线微量气体分析系统进行光解水反应，间隔10分钟自动取样，在气相色谱分析氢气产量。从图3可以看出，三联吡啶铂配合物在紫外—可见光—近红外和可见—近红外光照条件下，光解水产氢效率很高。而从图4可以看出，在仅用近红外光照情况下，光解水产氢作用比较弱，而在10μM小牛胸腺DNA或10μM鱼精DNA存在下，催化效果增强5倍。
因此，本发明制备的三联吡啶铂配合物具有很强可见光吸收性质，能够同时作为光敏剂和催化剂，在中性pH的甲醇水溶液中能够作为单分子光解水制氢均相催化剂，在紫外—可见光区都获得了较好的催化性能。另一方面，在DNA的存在下，该三联吡啶铂配合物在近红外区的光吸收显著增强，并能够有效催化近红外下的光解水制氢。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种三联吡啶铂配合物，由阳离子和阴离子组成，其特征在于，所述阳离子结构是如式I：
2.如权利要求1所述的三联吡啶铂配合物，其特征在于，所述阴离子为无机盐阴离子。
3.如权利要求1所述的三联吡啶铂配合物，其特征在于，所述阴离子为PF6 －、ClO4 －、Cl－、NO3 －或BPh4 －。
4.一种如权利要求1所述的三联吡啶铂配合物的制备方法，其特征在于，包括以下步骤：
步骤1、将二甲氨基肉桂醛和乙酰吡啶在浓氨水和强碱的乙醇水溶液中混合反应，得到三联吡啶配体；
步骤2、将三联吡啶配体与cis－[Pt(dmso)2Cl2]前体配合物在有机溶剂中回流反应后，即得到三联吡啶铂配合物。
5.如权利要求4所述的三联吡啶铂配合物的制备方法，其特征在于，所述步骤1具体为：依次将二甲氨基肉桂醛、乙酰吡啶、无水乙醇、强碱和浓氨水加入反应容器中，搅拌反应后，抽滤，得到的固体即为三联吡啶配体。
6.如权利要求5所述的三联吡啶铂配合物的制备方法，其特征在于，抽滤后得到的固体用无水有机溶剂洗涤后，静置干燥即得三联吡啶配体。
7.如权利要求4所述的三联吡啶铂配合物的制备方法，其特征在于，所述步骤2具体为：将三联吡啶配体溶于无水有机溶剂中，加入cis－[Pt(dmso)2Cl2]前体配合物进行回流反应，浓缩结晶后得到三联吡啶铂配合物。
8.一种如权利要求1所述的三联吡啶铂配合物在光解水制氢中的应用。
9.如权利要求8所述的三联吡啶铂配合物在光解水制氢中的应用，其特征在于，所述三联吡啶铂配合物作为光解水的光敏剂和催化剂使用。
10.如权利要求9所述的三联吡啶铂配合物在光解水制氢中的应用，其特征在于，在DNA存在的条件下，所述三联吡啶铂配合物与DNA构成的光解水制氢体系对近红外光吸收增强。
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