CN108754662B - 共价类三嗪结构发光有机半导体聚合物纳米纤维的制备方法及其光催化产氢应用 - Google Patents
共价类三嗪结构发光有机半导体聚合物纳米纤维的制备方法及其光催化产氢应用 Download PDFInfo
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Abstract
本发明属于纳米材料技术领域,具体涉及一种共价类三嗪结构发光有机半导体聚合物及其制备方法,将不同有机构筑单元通过碳碳键连接。用简单的溶剂热反应,以及路易斯碱作为催化剂催化醛基与亚甲基脱水缩合反应合成制备类三嗪结构共价有机半导体聚合物。用紫外吸收光谱和荧光光谱研究了此衍生物的光物理性质,并且研究了该共价类三嗪结构发光有机半导体聚合物在光催化分解水上的应用。本发明制备得到的此化合物是一类综合性质优良的荧光有机半导体材料,在光催化分解水反应中能高效稳定的传递电子。
Description
技术领域
本发明涉及一种高效稳定的共价类三嗪结构发光有机半导体聚合物纳米纤维材料,具体地说,涉及一类含有类三嗪结构的发光有机半导体聚合物纳米纤维及其在光催化分解水产氢方面的应用。
背景技术
随着工业的发展,化石燃料的使用导致环境问题日益严重,将太阳能转化为清洁的可运输燃料如氢气或甲醇是实现可持续增长的关键。自从20世纪70年代Honda和Fujishima报道了TiO2作为光阳极产氢以来,对新型光催化剂材料的研究已经触及了元素周期表的每一个元素。
研究者将重心主要放在无机光催化剂上,特别是金属氧化物和硫化物半导体材料及其改性(如掺杂剂,固溶体的形成,组装复合材料等)(Xing J, Fang WQ, Zhao HJ, etal. Inorganic photocatalysts for overall water splitting[J]. Chem Asian J,2012, 7(4): 642-657.)。大部分无机光催化剂将高光催化活性与化学稳定性结合起来,然而它们仅仅具有有限的可变性。相反,基于有机或金属络合物的均相光催化剂可提供分子定制性,以调整其光电性质、活性和选择性(Wang M, Na Y, Gorlov M, et al. Light-driven hydrogen production catalysed by transition metal complexes inhomogeneous systems[J]. Dalton Trans, 2009, 33(33): 6458-6467.)。然而,分子光催化剂的可调性是以低稳定性、合成路线的挑战性以及难以扩展性为代价的。两者之间的折中方案是通过将功能分子结合到稳固的基质中来实现均相光催化剂的多相化(BailarjrJ. â HETEROGENIZINGâ HOMOGENEOUS CATALYSTS[J]. Catalysis Reviews, 10(1): 17-36.)。在传统(热)催化领域的最初构想中,这种策略可以提供高活性和合成可调的“单一位点”催化剂,其本质上是分子,但具有非均相催化剂的益处,包括易于分离(因此可回收)和易于改进其光物理性质,并且在许多情况下可以赋予优异的化学和热稳定性。这种聚合物或“软”材料也受益于诸如重量轻、价格低廉、易于合成以及毒性相对较低等特性。
有机二维(2D)聚合物表现出具有扩展π共轭的微孔或中孔组织结构;本发明的有机二维(2D)聚合物是无定形的,即材料结构不具有长程有序性质。二维多孔聚合物已在气体吸附、多相催化和传感等领域得到了广泛的探索(Xu Y, Jin S, Xu H, et al.Conjugated microporous polymers: design, synthesis and application[J].Chemical Society Reviews, 2013, 42(20): 8012-8031.)。然而,迄今为止这些聚合物几乎没有被作为太阳能燃料生产的光催化剂研究过。事实上,除了普遍存在的石墨相碳氮聚合物之外,只有少数体系已被报道。
发明内容
本发明的目的在于提供一种高效稳定的共价类三嗪结构发光有机半导体聚合物纳米纤维材料,具体地说,提供一类含三嗪结构的发光有机半导体聚合物纳米纤维材料的制备方法。
本发明的另一个目的在于提供上述化合物光催化分解水产氢方面的应用。
本发明提供的共价类三嗪结构发光有机半导体聚合物纳米纤维材料具有合适的价带导带位置、稳定的发光特性和优秀的电子传输能力。
本发明提供的共价类三嗪结构发光有机半导体聚合物纳米纤维材料,其结构式如下:
式中:X为碳原子或氮原子。
本发明通过简单的合成路线:采用溶剂热反应,使用路易斯碱为催化剂催化碳碳双键的形成。简单高产率地合成以sp2碳杂化连接的共价类三嗪结构发光有机半导体聚合物。
用固体核磁共振表征了化合物的化学结构,用紫外吸收光谱和荧光光谱研究了此衍生物的光物理性质。研究了该共价类三嗪结构发光有机半导体聚合物纳米纤维材料在光催化分解水上的应用。实验结果表明此化合物是一类综合性质优良的发光有机半导体聚合物纳米纤维材料,在光催化分解水反应中能高效稳定的传递电子。
所述共价类三嗪结构发光有机半导体聚合物纳米纤维材料的制备方法,具体包括以下步骤:
(1)向三颈瓶中加入0-38毫克三醛化合物2,4,6-三(4-醛基苯基)-1,3,5-三嗪,0-38毫克4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛,7-30 毫克1,4-苯二乙腈,0.2-0.6 毫升均三甲苯,0.9-3.4 毫升二氧六环超声震荡。往反应茄瓶中滴加0.1-0.4 毫升 4 M的碱溶液。
(2)将反应茄瓶用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入惰性气体,操作重复三次。体系升至室温后,放入烘箱中反应3天。
(3)取出反应茄瓶降至室温后用水洗涤三次,然后用有机溶剂洗涤。将固体放入索氏提取器中,用四氢呋喃THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到亮黄色粉末。
步骤(1)中碱溶液为氢氧化钠水溶液、氢氧化钾水溶液、碳酸铯水溶液中的任意一种。
步骤(2)中的惰性气体为氩气、氮气、氦气中的任意一种。
步骤(3)中的有机溶剂为二氯甲烷、DMF、丙酮、乙醇、四氢呋喃、三氯甲烷、乙腈中的一种或多种。
所述的共价类三嗪结构发光有机半导体聚合物在光催化产氢上的应用,是在可见光的激发下,能够光催化分解水得到氢气。所述的光催化产氢反应过程具体如下:称取10-30 毫克共价类三嗪结构有机半导体聚合物,2-5 毫克抗坏血酸,2-8 毫克助催化剂,80-160 毫升水混合,调节pH在1-7,用波长范围大于400纳米的氙灯光源光照。
本发明的优点在于:
1、合成的共价类三嗪结构发光有机半导体聚合物纳米纤维材料具有优异的荧光性质。
2、具有适宜的价带导带位置。其导带底的位置低于H+/H2 (0 V vs RHE)的还原电势,足以还原水得到氢气。价带顶位置高于O2/H2O (+1.23 V vs RHE),足以氧化水得到氧气。
3、该有机半导体聚合物纳米纤维用于光催化体系,具有稳定高效的特点。在实验条件下,光照5 h最高产氢量为87143μmol/g。并且光催化产氢活性光照25 h仍稳定,最高达到产氢量为416150μmol/g。
附图说明
图1为3C-sp2c-COP以及不同氮含量的3N-sp2c-COP合成路线;
图2为本发明实施例样品的扫描电镜图;其中a图为3C-sp2c-COP(a)样品,b图为25% 3N-sp2c-COP(b)样品,c图为50% 3N-sp2c-COP(c)样品,d图为75% 3N-sp2c-COP(d)样品,e图为3N-sp2c-COP(e)样品。
图3为发明实施例样品的固体荧光发射光谱。
图4为发明实施例样品分散在水中的液体荧光发射光谱。
图5为发明实施例样品的紫外可见漫反射吸收光谱。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
在一个5 ml反应茄瓶中加入25.0 mg 4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛(0.064 mmol),15.0 mg 1,4-苯二乙腈(0.096 mmol)后加入0.334 ml均三甲苯,1.766 ml二氧六环超声震荡。往反应茄瓶中滴加0.2 mL 4 M的氢氧化钠水溶液。加完后,将体系用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入氩气,操作重复三次。体系升至室温后,放入90℃的烘箱中反应3天。降至室温后用水洗涤三次,然后分别用二氯甲烷、DMF、丙酮洗涤。将固体放入索氏提取器中,用THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到黄色粉末3C-sp2c-COP。元素分析:理论值C(88.40%),H(4.24%),N(7.36%),实验值C(86.13%),H(4.66%),N(6.48%)。
实施例2
在一个5 ml反应茄瓶中加入6.3 mg 2,4,6-三(4-醛基苯基)-1,3,5-三嗪(0.016mmol),18.8 mg 4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛(0.048 mmol),15.0 mg 1,4-苯二乙腈(0.096 mmol)后加入0.334 ml均三甲苯,1.766 ml二氧六环超声震荡。往反应茄瓶中滴加0.2 mL 4 M的氢氧化钠水溶液。加完后,将体系用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入氩气,操作重复三次。体系升至室温后,放入90 ℃的烘箱中反应3天。降至室温后用水洗涤三次,然后分别用二氯甲烷、DMF、丙酮洗涤。将固体放入索氏提取器中,用THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到黄色粉末25%-3N-sp2c-COP。元素分析:理论值C(86.70%),H(4.10%),N(9.2%),实验值C(86.02%),H(3.84%),N(8.25%)。
实施例3
在一个5 ml反应茄瓶中加入12.6 mg 2,4,6-三(4-醛基苯基)-1,3,5-三嗪(0.032mmol),12.5 mg 4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛(0.032 mmol),15.0 mg 1,4-苯二乙腈(0.096 mmol)后加入0.334 ml均三甲苯,1.766 ml二氧六环超声震荡。往反应茄瓶中滴加0.2 mL 4 M的氢氧化钠水溶液。加完后,将体系用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入氩气,操作重复三次。体系升至室温后,放入90 ℃的烘箱中反应3天。降至室温后用水洗涤三次,然后分别用二氯甲烷、DMF、丙酮洗涤。将固体放入索氏提取器中,用THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到黄色粉末50%-3N-sp2c-COP。元素分析:理论值C(83.90%),H(3.87%),N(12.23%),实验值C(82.75%),H(3.57%),N(10.48%)。
实施例4
在一个5 ml反应茄瓶中加入18.9 mg 2,4,6-三(4-醛基苯基)-1,3,5-三嗪(0.048mmol),6.2 mg 4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛(0.016 mmol),15.0 mg 1,4-苯二乙腈(0.096 mmol)后加入0.334 ml均三甲苯,1.766 ml二氧六环超声震荡。往反应茄瓶中滴加0.2 mL 4 M的氢氧化钠水溶液。加完后,将体系用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入氩气,操作重复三次。体系升至室温后,放入90 ℃的烘箱中反应3天。降至室温后用水洗涤三次,然后分别用二氯甲烷、DMF、丙酮洗涤。将固体放入索氏提取器中,用THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到亮黄色粉末75%-3N-sp2c-COP。元素分析:理论值C(83.33%),H(3.82%),N(12.85%),实验值C(81.32%),H(4.28%),N(11.64%)。
实施例5
在一个5 ml反应茄瓶中加入25.2 mg 2,4,6-三(4-醛基苯基)-1,3,5-三嗪(0.064mmol),15.0 mg 1,4-苯二乙腈(0.096 mmol)后加入0.334 ml均三甲苯,1.766 ml二氧六环超声震荡。往反应茄瓶中滴加0.2 mL 4 M的氢氧化钠水溶液。加完后,将体系用液氮冷冻,在真空吸附线体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入氩气,操作重复三次。体系升至室温后,放入90 ℃的烘箱中反应3天。降至室温后用水洗涤三次,然后分别用二氯甲烷、DMF、丙酮洗涤。将固体放入索氏提取器中,用THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到亮黄色粉末3N-sp2c-COP。元素分析:理论值C(81.66%),H(3.69%),N(14.65%),实验值C(79.88%),H(3.96%),N(13.35%)。
实施例6
秤取1 g六水合氯铂酸,加入少量乙二醇溶解。然后将溶液移至100 ml容量瓶中,定容得到1 g/100 ml的氯铂酸乙二醇溶液。用移液枪吸取上述配制的氯铂酸乙二醇溶液(1.326 ml,0.0256 mmol H2PtCl6·6H2O,5 mg Pt)置于100 ml施兰克瓶中,加入聚乙烯吡咯烷酮(PVP,0.139 g,MW40 000, 1.25 × 10-3 mol),乙二醇(22.674 ml),0.2 M氢氧化钠的乙二醇溶液(1 ml)。密封后超声5分钟,超声完毕后抽真空,将施兰克瓶内压力降至5mbar。抽真空完毕后将施兰克瓶置于微波炉中,800 W功率下反应至溶液颜色由橙色变成棕黑色后停止微波加热。得到助催化剂PVP-Pt胶体溶液。
实施例7
在反应器中加入3C-sp2c-COP(20 mg),25 ml PVP-Pt的乙二醇溶液(5 mg Pt),抗坏血酸(0.9 g),75 ml水。将溶液超声20 min后,调节pH=4。将反应体系抽真空,用λ≥400nm的氙灯光源照射。光照5 h,光催化产氢过程中每隔1小时用气相色谱仪检测氢气的含量。
实施例8
具体制备方法和活性测试与本部分实例7基本相同,不同之处在于将3C-sp2c-COP改为25%-3N-sp2c-COP。
实施例9
具体制备方法和活性测试与本部分实例7基本相同,不同之处在于将3C-sp2c-COP改为50%-3N-sp2c-COP。
实施例10
具体制备方法和活性测试与本部分实例7基本相同,不同之处在于将3C-sp2c-COP改为75%-3N-sp2c-COP。
实施例11
具体制备方法和活性测试与本部分实例7基本相同,不同之处在于将3C-sp2c-COP改为3N-sp2c-COP。
实施例12
在反应器中加入3C-sp2c-COP(20 mg),25 ml PVP-Pt的乙二醇溶液(5 mg Pt),抗坏血酸(0.9 g),75 ml水。将溶液超声20 min后,调节pH=7。将反应体系抽真空,用λ≥ 400nm的氙灯光源照射。光照5 h,光催化产氢过程中每隔1小时用气相色谱仪检测氢气的含量。
实施例13
具体制备方法和活性测试与本部分实例12基本相同,不同之处在于将3C-sp2c-COP改为25%-3N-sp2c-COP。
实施例14
具体制备方法和活性测试与本部分实例12基本相同,不同之处在于将3C-sp2c-COP改为50%-3N-sp2c-COP。
实施例15
具体制备方法和活性测试与本部分实例12基本相同,不同之处在于将3C-sp2c-COP改为75%-3N-sp2c-COP。
实施例16
具体制备方法和活性测试与本部分实例12基本相同,不同之处在于将3C-sp2c-COP改为3N-sp2c-COP。
Claims (7)
2.一种制备如权利要求1所述的共价类三嗪结构发光有机半导体聚合物纳米纤维的方法,其特征在于:具体包括以下步骤:
(1)向三颈瓶中加入6.3-38毫克2,4,6-三(4-醛基苯基)-1,3,5-三嗪,6.2-38毫克4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛,7-30 毫克1,4-苯二乙腈,0.2-0.6 毫升均三甲苯,0.9-3.4 毫升二氧六环超声震荡;往反应茄瓶中滴加0.1-0.4 毫升 4 M的碱溶液;
(2)将反应茄瓶用液氮冷冻,在真空吸附体系下将玻璃瓶内压力降至10 mbar以下,温度提高到室温然后充入惰性气体,操作重复三次;体系升至室温后,放入烘箱中反应3天;
(3)取出反应茄瓶降至室温后用水洗涤三次,然后用有机溶剂洗涤;将固体放入索氏提取器中,用四氢呋喃THF洗涤2天后置于真空烘箱中110℃干燥12小时,得到亮黄色粉末。
3.根据权利要求2所述的共价类三嗪结构发光有机半导体聚合物纳米纤维的制备方法,其特征在于:步骤(1)中碱溶液为氢氧化钠水溶液、氢氧化钾水溶液、碳酸铯水溶液中的任意一种。
4.根据权利要求2所述的共价类三嗪结构发光有机半导体聚合物纳米纤维的制备方法,其特征在于:步骤(2)中的惰性气体为氩气、氮气、氦气中的任意一种。
5.根据权利要求2所述的共价类三嗪结构发光有机半导体聚合物纳米纤维的制备方法,其特征在于:步骤(3)中的有机溶剂为二氯甲烷、DMF、丙酮、乙醇、四氢呋喃、三氯甲烷、乙腈中的一种或几种。
6.一种如权利要求1所述的共价类三嗪结构发光有机半导体聚合物纳米纤维在光催化产氢上的应用,其特征在于:所述的共价类三嗪结构发光有机半导体聚合物在光催化分解水产氢中的应用是在可见光的激发下,能够光催化分解水得到氢气。
7.根据权利要求6所述的应用,其特征在于:所述的光催化产氢反应过程具体如下:称取10-30 毫克共价类三嗪结构有机半导体聚合物,2-5 毫克抗坏血酸,2-8 毫克助催化剂,80-160 毫升水混合,调节pH在1-7,用波长范围大于400纳米的氙灯光源光照。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102086600A (zh) * | 2010-04-10 | 2011-06-08 | 何鹰 | 新型盐剂 |
CN103232458A (zh) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | 一种具有单原子层结构的石墨相氮化碳材料的制备方法 |
CN103449360A (zh) * | 2012-05-29 | 2013-12-18 | 中国科学院理化技术研究所 | 一种光催化产氢体系及其制备氢气的方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103232458A (zh) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | 一种具有单原子层结构的石墨相氮化碳材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
三嗪类化合物的合成及其产酸性能研究;王健等;《感光科学与光科学》;20061130;第24卷(第6期);第436-443页 * |
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