CN106967205B - 具有优异光催化制氢性能共轭席夫碱聚合物的制备方法及其应用 - Google Patents
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Abstract
本发明公开了一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法及其应用。所述制备方法包括以下步骤:称取一定量的苯二胺和对苯二甲醛,然后溶解于有机溶剂中,并滴入冰醋酸;将溶液置于惰性气体氛围中,搅拌下升温至回流状态并持续2‑48小时;反应结束冷却至室温后,离心分离,洗涤干燥,得到所述具有优异光催化制氢性能共轭席夫碱聚合物。本发明的合成方法具有反应条件温和,工艺简单,产率高且重现性好的优点,所制备的具有优异光催化制氢性能共轭席夫碱聚合物,包括两种纳米棒状和纳米片状结构,可应用于光催化分解水制氢或光电器件等领域。
Description
技术领域
本发明属于共轭聚合物技术领域,具体涉及一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法及其应用。
背景技术
传统无机半导体光催化剂虽然来源丰富,但其带隙能较大且难以调控,这不利于太阳光的利用,从而降低了光催化制氢的效率。共轭聚合物是完全由π共轭体系构成,作为非均相光催化剂,成为了新一代的转化太阳能为化学能的催化剂。它们具有光催化过程的三个关键特征,即坚固的,无毒的和可见光反应性。有机共轭高分子具有类似于无机半导体的能带结构,展现出非常像导电金属的电子带,在能量大于其带隙能的辐射下产生光生载流子,同时其丰富、可调的能带结构,可以使光谱响应范围拓宽到整个紫外-可见区,从而得到高效的光催化活性。然而,有机共轭高分子聚合物的光催化性能不仅仅与分子结构有关,还与它们的聚集态的构成、聚合物的结晶与取向等方面有关。因为聚合物的分子链取向、结晶可以提高非定域π电子的流动。当一定能量的太阳光照射时,产生的载流子就会被快速转移到链上、重叠链间的π电子共轭体系中,这有效得减少光生空穴和电子的再复合,从而提高光催化降解或制氢性能。
发明内容
本发明的首要目的在于提供一种具有优异光催化制氢性能的共轭席夫碱聚合物的制备方法。
本发明的另一目的在于提供上述制备方法制得的共轭席夫碱聚合物。
本发明的再一目的在于提供上述共轭席夫碱聚合物的应用。
本发明目的通过以下技术方案实现:
一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,包括以下步骤:
(1)称取一定量的苯二胺和对苯二甲醛,然后溶解于有机溶剂中,并控制苯二胺和对苯二甲醛的浓度范围均为0.01-1mol/L;溶液混合溶解均匀后滴入冰醋酸;
(2)将上述溶液置于惰性气体氛围中(如氮气,氩气),搅拌下升温至回流状态并持续2-48小时;反应结束冷却至室温,离心分离,洗涤,干燥,得到所述共轭席夫碱聚合物为聚亚胺。
步骤(1)所述苯二胺和对苯二甲醛的物质的量比为1:1。
本发明所述的室温是指20-30℃。
步骤(1)所述的苯二胺为邻苯二胺、间苯二胺或对苯二胺。
步骤(1)所述的冰醋酸与有机溶剂的体积比为1:100-1:20。
步骤(1)所述的有机溶剂为乙醇、二甲基亚砜、N,N-二甲基甲酰胺等能够溶解苯二胺和对苯二醛的溶剂。
步骤(2)所述洗涤是指用无水乙醇洗涤。
所述的共轭席夫碱聚合物其形貌特征分别有纳米棒状和纳米片状两种结构。所述的纳米棒状共轭席夫碱聚合物,纳米棒相互之间缠绕成更大的纳米棒,直径不超过50nm,长度不超过3μm,内部实心。所述纳米片状共轭席夫碱聚合物,聚合物呈一维生长成片状,片层之间相互堆叠。
所述的共轭席夫碱聚合物可应用于光催化分解水制氢或光电器件等领域。
与现有技术相比,本发明具有以下优点及有益效果:
本发明的合成方法具有反应条件温和,工艺简单,产率高且重现性好的优点,所制备的共轭席夫碱聚合物可应用于光催化分解水制氢或光电器件等领域。
附图说明
图1是实施例1合成的纳米棒状共轭席夫碱聚合物的SEM图;
图2是实施例1合成的纳米棒状共轭席夫碱聚合物的HRTEM图;
图3是实施例1合成的纳米棒状共轭席夫碱聚合物的N2吸脱附等温曲线图;
图4是实施例1合成的纳米棒状共轭席夫碱聚合物的XRD图;
图5是实施例2合成的纳米片状共轭席夫碱聚合物的SEM图;
图6是实施例2合成的纳米片状共轭席夫碱聚合物的HRTEM图;
图7是实施例2合成的纳米片状共轭席夫碱聚合物的N2吸脱附等温曲线图;
图8是实施例2合成的纳米片状共轭席夫碱聚合物的XRD图;
图9是实施例3合成的纳米片状共轭席夫碱聚合物的SEM图;
图10是实施例3合成的纳米片状共轭席夫碱聚合物的HRTEM图;
图11是实施例3合成的纳米片状共轭席夫碱聚合物的N2吸脱附等温曲线图;
图12是实施例3合成的纳米片状共轭席夫碱聚合物的XRD图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。由技术常识可知,本发明也可通过其它的不脱离本发明技术特征的方案来描述,因此所有在本发明范围内或等同本发明范围内的改变均被本发明包含。
实施例1
分别称取0.58g邻苯二胺和0.67g对苯二甲醛,然后溶解于50mL的乙醇中,搅拌下加入3滴冰醋酸,在氮气氛围中升温至回流状态并保持16h。待反应结束冷却至室温,在高速离心机中离心20分钟,并用无水乙醇洗涤三次,在80℃真空干燥箱中干燥24h,得到纳米棒状的共轭席夫碱聚合物聚亚胺。
对本实施例产物使用扫描电镜观察其微观形貌,结果如图1所示,所制备出的聚亚胺为纳米棒状结构,棒与棒之间相互残绕,堆叠,纳米棒的直径均小于50nm;对本实施例产物使用透射电镜观察其微观形貌,结果如图2所示,所制备出的聚亚胺为内部实心的棒状结构;对本实施例产物进行N2吸脱附等温曲线测试,如图3所示,所制备出的聚亚胺几乎无微孔介孔结构;对本实施例产物进行XRD测试,衍射图如图4所示,所制备出的聚亚胺有良好的结晶度或有序性。
实施例2
分别称取0.58g间苯二胺和0.67g对苯二甲醛,然后溶解于50mL的乙醇中,搅拌下加入3滴冰醋酸,在氮气氛围中升温至回流状态并保持16h。待反应结束冷却至室温,在高速离心机中离心20分钟,并用无水乙醇洗涤三次,在80℃真空干燥箱中干燥24h,得到纳米片状的共轭席夫碱聚合物聚亚胺。
对本实施例产物使用扫描电镜观察其微观形貌,结果如图5所示,所制备出的聚亚胺为纳米片状结构,呈曲面生长的趋势;对本实施例产物使用透射电镜观察其微观形貌,结果如图6所示,进一步说明所述的共轭席夫碱聚合物为纳米片状结构;对本实施例产物进行N2吸脱附等温曲线测试,如图7所示,所制备出的聚亚胺几乎无微孔介孔结构;对本实施例产物进行XRD测试,衍射图如图8所示,所制备出的聚亚胺基本为无定形结构,有序性较差。
实施例3
分别称取0.58g对苯二胺和0.67g对苯二甲醛,然后溶解于50mL的乙醇中,搅拌下加入3滴冰醋酸,在氮气氛围中升温至回流状态并保持16h。待反应结束冷却至室温,在高速离心机中离心20分钟,并用无水乙醇洗涤三次,在80℃真空干燥箱中干燥24h,得到纳米片状的共轭席夫碱聚合物聚亚胺。
对本实施例产物使用扫描电镜观察其微观形貌,结果如图9所示,所制备出的聚亚胺为纳米片状结构,片层相对较厚,堆叠紧密;对本实施例产物使用透射电镜观察其微观形貌,结果如图10所示,进一步说明所述的共轭席夫碱聚合物为纳米片状结构;对本实施例产物进行N2吸脱附等温曲线测试,如图11所示,所制备出的聚亚胺几乎无微孔介孔结构;对本实施例产物进行XRD测试,衍射图如图12所示,所制备出的聚亚胺有良好的结晶度或有序性。
实施例4
对实施例1-3中所制备的产物进行光催化分解水制氢的性能测试。具体步骤如下:
将100mg所制备的产物(聚亚胺)置于含20wt%的甲醇水溶液中,在抽真空除去空气后用300W的氙灯(λ>420nm)照射8h,这个过程中整个反应体系均保持在室温。所产生的氢气用气相色谱(5A分子筛色谱柱、TCD热导检测、载气为氮气)定量分析,在没有助催化剂的情况下,实施例1-3中所制备的产物光分解水制氢的平均速率分别为242μmol/h,92μmol/h,96μmol/h。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,包括以下步骤:
(1)称取一定量的苯二胺和对苯二甲醛,然后溶解于有机溶剂中,并控制苯二胺和对苯二甲醛的浓度范围均为0.01-1mol/L;溶液混合溶解均匀后滴入冰醋酸;
(2)将步骤(1)混合的溶液置于惰性气体氛围中,搅拌下升温至回流状态并持续2-48小时;反应结束冷却至室温后,离心分离,洗涤,干燥,得到所述具有优异光催化制氢性能共轭席夫碱聚合物。
2.根据权利要求1所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,步骤(1)所述苯二胺和对苯二甲醛的物质的量比为1:1。
3.根据权利要求1所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,步骤(1)所述的苯二胺为邻苯二胺、间苯二胺或对苯二胺。
4.根据权利要求1所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,步骤(1)所述的冰醋酸与有机溶剂的体积比为1:100-1:20。
5.根据权利要求1所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,步骤(1)所述的有机溶剂为乙醇、二甲基亚砜或N,N-二甲基甲酰胺。
6.根据权利要求1所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法,其特征在于,步骤(2)所述洗涤是指用无水乙醇或甲醇洗涤。
7.一种具有优异光催化制氢性能共轭席夫碱聚合物,其特征在于,其由权利要求1至6任一项所述的一种具有优异光催化制氢性能共轭席夫碱聚合物的制备方法制得。
8.权利要求7所述的具有优异光催化制氢性能共轭席夫碱聚合物在光催化分解水制氢领域中的应用。
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