CN114713284A - 一种含b←n配位键的有机共轭聚合物光催化剂及制备方法、应用 - Google Patents
一种含b←n配位键的有机共轭聚合物光催化剂及制备方法、应用 Download PDFInfo
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- CN114713284A CN114713284A CN202210173445.4A CN202210173445A CN114713284A CN 114713284 A CN114713284 A CN 114713284A CN 202210173445 A CN202210173445 A CN 202210173445A CN 114713284 A CN114713284 A CN 114713284A
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Abstract
本发明提供了一种含B←N配位键的有机共轭聚合物光催化剂及制备方法、应用；所述光催化剂是由B、N的Lewis酸碱性进行重芳构化反应制备得到吡啶硼烷配合物；再通过锂化反应获得硼酸酯单体，最后硼酸酯单体自聚合形成共轭聚合物。本发明还涉及前述光催化剂的制备方法及应用。本发明所涉及的光催化剂具有强的电荷分离能力，首次将其应用于光催化裂解水析氢；该光催化剂在可见光照射下，在牺牲剂存在的条件下，可实现极高的产氢速率，达到22350μmol g‑1h‑1以上。此外其表观量子效率(AQY)在420nm波长下可达23.3％，具有极高的开发潜力。
Description
技术领域
本发明属于有机光催化裂解水领域；尤其涉及一种含B←N配位键的有机共轭聚合物光催化剂及制备方法、应用。
背景技术
现代科技的发展和人类文明与能源息息相关，而传统化石能源(如煤、石油、天然气等)燃烧时释放出大量的温室气体CO2，CH4等，会对环境造成严重的污染。另一方面，化石燃料的枯竭导致了严重的能源短缺，因此人们大力寻求可替代的清洁和可再生能源。其中，将太阳能以化学键的形式储存起来进行有效利用，是目前公认的最具发展前景的可再生能源系统之一。
氢能作为一种公认的绿色二次能源，有希望成为化石能源最理想的替代品，因而广受关注。而将太阳能与氢能进行有机的结合，即通过可见光驱动分解水制氢由于其绿色环保和可持续性，是一种理想的太阳能转换和存储技术。然而，光解水过程高度依赖于光催化剂来进行质子还原和水氧化。因此，开发高效稳定的光催化剂成为光解水领域亟待解决的问题之一。
硼是一种典型的缺电子单元，硼原子空的p轨道可以与π共轭体系形成强烈的p-π共轭，使其具有特殊的光物理和电子特性，并使它们成为有机(光)电子学的有吸引力的材料。此外，包括端基官能化聚合物和嵌段共聚物在内的更复杂的聚合物结构现在可以通过控制/活性聚合技术实现，为含硼纳米结构材料的合成及应用提供了一个新的路径。
发明内容
本发明的目的是提供了一种含B←N配位键的有机共轭聚合物光催化剂及制备方法、应用。本发明为了实现高效的光催化裂解水过程，从调节电子结构的角度出发。本发明制备得到的催化剂解决了催化剂光利用率低，催化活性差等问题。
本发明是通过以下技术方案实现的：
本发明涉及一种含B←N配位键的有机共轭聚合物光催化剂，所述光催化剂是由B、N的Lewis酸碱性进行重芳构化反应制备得到吡啶硼烷配合物；再通过锂化反应获得硼酸酯单体，最后硼酸酯单体自聚合形成共轭聚合物。
本发明还涉及一种含B←N配位键的有机共轭聚合物光催化剂的制备方法，包括如下步骤：
步骤1，中间体(2)的制备：在-78℃下，向5-溴-2-(4-溴苯基)吡啶(1)3.00g,9.58mmol和二异丙基乙基胺1.6mL，9.20mmol的50mL CH2Cl2溶液中，滴加BBr31.0M inCH2Cl2,20mL，20.00mmol；在室温条件下搅拌12h后，加入饱和的K2CO3水溶液，形成的沉淀过滤收集，用水和丙酮洗涤，得到淡黄色固体5-溴-2-(4-溴-2-(二溴硼烷基)苯基)吡啶(2)；
步骤2，中间体(3)的制备：在室温条件下向搅拌的含有5-溴-2-(4-溴-2-(二溴硼烷基)苯基)吡啶(2)2.41g,5.00mmol的50mL甲苯溶液中加入三甲基铝1.1M的正己烷溶液10mL，11.00mmol；搅拌2小时后，进行淬灭反应；分离有机层并用乙酸乙酯萃取两次，洗涤，经MgSO4干燥并浓缩，残余物通过硅胶制备薄层色谱纯化，得到5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)；
步骤3，中间体(4)的制备：在-78℃下，向含有5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)1.06g，3.00mmol的30mL Et2O溶液中逐滴加入n-BuLi 1.94mL，3.10mmol，搅拌1小时后，加入i-PrOBpin 1.12g，6.00mmol，搅拌12小时，用水猝灭后，分离有机层，用乙酸乙酯萃取水层两次，合并有机层并洗涤，经MgSO4干燥并浓缩，残余物通过硅胶制备薄层色谱纯化，得到2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)；
步骤4，催化剂(5)的制备：将2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)400mg,1.00mmol的15mL N,N-二甲基甲酰胺和K2CO3水溶液2M，3mL装入烧瓶，用N2鼓泡20分钟脱气，加入[Pd(PPh3)4]20mg，并加热至100℃反应2天；冷却至室温并倒入水中；过滤收集沉淀物并用H2O、甲醇、丙酮和二氯甲烷洗涤；处理后，得到最终产物淡绿色固体产物。
本发明利用B、N的Lewis酸碱性进行重芳构化反应制备一种吡啶硼烷配合物，然后通过锂化反应获得硼酸酯单体，最后硼酸酯单体自聚合形成共轭聚合物。本发明所涉及的一种含B←N配位键的有机共轭聚合物光催化剂，其结构的高度可调性，可将硼上甲基替换成乙基，异丙基，己基，苯基，五氟苯基和噻吩基等烷基或芳香基。本发明所涉及的一种含B←N配位键的有机共轭聚合物光催化剂，相对于C-C键连接的聚二甲基芴具有更广泛的可见光吸光能力。本发明所涉及的一种含B←N配位键的有机共轭聚合物光催化剂，给体-受体属性的增强，以及电荷分离能力的提升。本发明所涉及的含B←N配位键的有机共轭聚合物光催化剂，其结构的高度可调性，可将苯基替换成联苯，萘，蒽，芘和噻吩等。本发明所涉及的含B←N配位键的有机共轭聚合物光催化剂，其结构的高度可调性，可将吡啶替换成嘧啶，喹啉，异喹啉等。
本发明所涉及的含B←N配位键的有机共轭聚合物光催化剂的应用，在可见光照射下，在牺牲剂存在的条件下，可实现高效的水分解制氢性能。
本发明所涉及的光催化剂具有强的电荷分离能力，首次将其应用于光催化裂解水析氢。该材料在可见光照射下，在牺牲剂存在的条件下，可实现极高的产氢速率，达到22350μmol g-1h-1以上。此外其表观量子效率(AQY)在420nm波长下可达23.3％，具有极高的开发潜力。
本发明具有以下优点：
(1)本发明利用B←N键替换C-C键的策略，通过重芳构化反应、锂化反应和偶联反应方法制备一种聚二甲基芴的等电子体材料；该催化剂增强了π共轭聚合物中激子的解离，与仅含有C-C单元的聚芴相比，大大提高了光催化活性，该催化剂与三芳基硼不同，四配位结构设计进一步增加了分子的极性和亲水性。
(2)本发明制备得到的有机共轭聚合物光催化剂引入极化B←N键从根本上改变给定分子的电子特性，实现了非极性分子到极性分子的转变；B←N键的形成增强了体系的给体-受体性质；HOMO/LUMO能级和带隙的变化增强了可见光吸收能力以及催化驱动力。
(3)本发明制备得到的有机共轭聚合物光催化剂在100mW cm-2可见光下，具有优异的光催化活性(HER＝22350μmol g-1h-1，AQY420＝23.3％)，在更强的可见光照射下，析氢速率达到60,000μmol g-1h-1以上；无论是产氢速率还是AQY，在目前的线性聚合物光催化剂中都处于领先地位。此外，硼氮结构的可变性为有机光催化领域带来了无限可能和新的活力。对于水的氧化、二氧化碳的还原等领域很少涉及硼氮结构。硼氮结构的固有选择性和能级的特殊性将起到关键作用。
附图说明
图1为本发明实施例1中的含B←N配位键的有机共轭聚合物光催化剂的合成路线图；
图2为本发明实施例1制得的催化剂实验测得的13C CP/MAS NMR谱图；
图3为本发明实施例1制得的催化剂在固体状态下的紫外吸收和荧光发射光谱图；
图4为本发明实施例1制得的催化剂在固体状态下475、500和520nm进行瞬态发光衰减光谱测试得到寿命衰减曲线图；
图5为本发明实施例1制得的催化剂与水的接触角图片；
图6为本发明实施例1制得的催化剂在不同体系下的产氢时间依赖图；
图7为本发明实施例1制得的催化剂的产氢稳定性测试图；
图8为本发明实施例1制得的催化剂在光催化反应前后的FTIR光谱图；
图9为本发明实施例1制得的催化剂在不同波长下的表观量子产率(AQY)图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是，以下的实施实例只是对本发明的进一步说明，但本发明的保护范围并不限于以下实施例。
实施例1
本实施例涉及一种新型含B←N配位键的有机共轭聚合物光催化剂的制备方法，如图1所示，其按照如下步骤制备得到：
步骤1，中间体(2)的制备：在-78℃下，向5-溴-2-(4-溴苯基)吡啶(3.00g,9.58mmol)和二异丙基乙基胺i-Pr2NEt(1.6mL,9.20mmol)的CH2Cl2(50mL)溶液中，滴加BBr3(1.0M in CH2Cl2,20mL,20.00mmol)。在室温搅拌12h后，将饱和的K2CO3水溶液加入反应混合物中。形成的沉淀过滤收集，用水和丙酮洗涤，得到淡黄色固体(4.20g,8.70mmol,91％)(2)。1H NMR(400MHz,CDCl3,ppm):δ9.01(d,J＝1.5Hz,1H),8.27(dd,J＝8.4,2.1Hz,1H),7.99(s,1H),7.80(dd,J＝8.4,0.6Hz,1H),7.57-7.59(m,2H).
步骤2，中间体(3)的制备：在室温下向搅拌的含有5-溴-2-(4-溴-2-(二溴硼烷基)苯基)吡啶(2)(2.41g,5.00mmol)的甲苯(50mL)溶液中加入三甲基铝Me3Al(1.1M的正己烷溶液,10mL,11.00mmol)。在该温度下搅拌2小时后，通过加水淬灭反应。分离有机层并用乙酸乙酯萃取(两次)，用水(一次)、盐水(一次)洗涤，经MgSO4干燥并浓缩。残余物通过硅胶制备薄层色谱纯化，得到5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)(1.44g，4.08mmol，82％产率)。1H NMR(400MHz,CDCl3,ppm):δ8.49(s,1H),8.07(d,J＝8.0Hz,1H),7.79(d,J＝8.0Hz,1H),7.73(s,1H),7.65(d,J＝8.0Hz,1H),7.41(d,J＝8.0Hz,1H),0.03(s,6H).13C{1H}NMR(100MHz,CDCl3,ppm):δ155.03,143.91,142.49,132.75,132.42,128.69,128.59,126.81,123.16,118.81,117.03,8.90.
步骤3，中间体(4)的制备：在-78℃下，向含有5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)(1.06g，3.00mmol)的Et2O(30mL)溶液中逐滴加入n-BuLi(1.6M在己烷中，1.94mL，3.10mmol)。在该温度下搅拌1小时后，加入i-PrOBpin(1.12g，6.00mmol)并将反应混合物在室温下搅拌12小时。用水猝灭后，分离有机层，然后用乙酸乙酯萃取水层(两次)。合并有机层并用水(一次)、盐水(一次)洗涤，经MgSO4干燥并浓缩。残余物通过硅胶制备薄层色谱纯化，得到2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)(0.89g，2.22mmol，产率74％)。1H NMR(400MHz,CDCl3,ppm):δ8.72(s,1H),8.30(d,J＝8.0Hz,1H),7.89(d,J＝8.0Hz,1H),7.76(s,1H),7.70(d,J＝8.0Hz,1H),7.41(d,J＝8.0Hz,1H),1.39(s,12H),0.04(s,6H).13C{1H}NMR(100MHz,CDCl3,ppm):δ157.71,148.16,145.50,133.82,132.39,128.47,126.78,123.46,118.81,117.19,84.93,24.98,8.76.
步骤4，催化剂(5)的制备：将2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)(400mg,1.00mmol)、N,N-二甲基甲酰胺(15mL)和K2CO3水溶液(2M,3mL)装入烧瓶。混合物用N2鼓泡20分钟脱气，然后加入[Pd(PPh3)4](20mg)，并加热至100℃反应2天。将混合物冷却至室温并倒入水中。过滤收集沉淀物并用H2O、甲醇、丙酮和二氯甲烷洗涤。处理后，得到淡绿色固体产物(160mg，77％产率)。图2为催化剂的13C CP/MASNMR谱图。图3可以发现催化剂的吸收边带为468nm，而荧光发射峰为479nm。图4显示用360nm激发催化剂时，在475,500和520nm处的荧光寿命分别为0.81,1.47和2.15ns。图5可以发现催化剂具有较好的亲水性。
试验例
将实施例1制备得到的新型含B←N配位键的有机共轭聚合物光催化剂进行光催化分解水析氢实验，评价其催化效果。
实验过程：在烧瓶中加入10mg聚合物粉末，50ml水/甲醇/三乙胺(1:1:1)或水/甲醇/三乙醇胺(1:1:1)或0.2M抗坏血酸水溶液/甲醇(1:1:1)的混合物。将得到的悬浮液超声至光催化剂分散，然后用N2鼓泡脱气30分钟。利用配备热导检测器(TCD)的气相色谱仪(Varian 450-GC)每60分钟监测一次排出气体的累积量。光源为300w氙灯，带有截止滤波器用于产生可见光(λ>420nm)。用TCD检测器检测氢，参照已知氢浓度的标准气体。未测量反应混合物中溶解的氢，且计算中忽略了氢气析出所产生的压力增加。
在图6中可以发现，当使用三乙醇胺(TEOA)作为牺牲剂和MeOH作为分散剂时，催化剂显示出一般HER为2440μmol g-1h-1。用三乙胺(TEA)代替TEOA，HER急剧增加，达到22350μmol g-1h-1的惊人数值，表明TEA是一个高效的牺牲性空穴接受体。此外，常用的牺牲剂0.2M抗坏血酸(AA)也被用来研究光催化产氢性能，显示出较低的HER，为1983μmol g-1h-1。
如图7，为了估计催化剂的光稳定性，在可见光照明下连续反应21小时。在15小时后，光催化性能略微下降了10％，但仍显示出20000μmol g-1h-1的生产速率，表明该催化剂具有良好的光催化稳定性。如图8，在循环测试后，没有观察到FT-IR的明显变化，这表明该聚合物保持了其原始结构。在各种单色光照射下，使用300W氙气灯催化剂的表观量子产率(AQY)进行了测试。如图9，催化剂在420nm处表现出23.3％的高AQY。
本发明制备得到的有机共轭聚合物光催化剂在100mW cm-2可见光下，具有优异的光催化活性(HER＝22350μmol g-1h-1，AQY420＝23.3％)，在更强的可见光照射下，析氢速率达到60,000μmol g-1h-1以上；无论是产氢速率还是AQY，在目前的线性聚合物光催化剂中都处于领先地位。此外，硼氮结构的可变性为有机光催化领域带来了无限可能和新的活力。对于水的氧化、二氧化碳的还原等领域很少涉及硼氮结构。硼氮结构的固有选择性和能级的特殊性将起到关键作用。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质。
Claims (3)
1.一种含B←N配位键的有机共轭聚合物光催化剂，其特征在于，所述光催化剂是由以下步骤制备而得：首先由B、N的Lewis酸碱性进行重芳构化反应制备得到吡啶硼烷配合物；再通过锂化反应获得硼酸酯单体；最后硼酸酯单体自聚合形成共轭聚合物。
2.一种如权利要求1所述的含B←N配位键的有机共轭聚合物光催化剂的制备方法，其特征在于，包括如下步骤：
步骤1，中间体(2)的制备：在-78℃下，向5-溴-2-(4-溴苯基)吡啶(1)3.00g,9.58mmol和二异丙基乙基胺1.6mL，9.20mmol的50mL CH2Cl2溶液中，滴加BBr31.0M in CH2Cl2,20mL，20.00mmol；在室温条件下搅拌12h后，加入饱和的K2CO3水溶液，形成的沉淀过滤收集，用水和丙酮洗涤，得到淡黄色固体5-溴-2-(4-溴-2-(二溴硼烷基)苯基)吡啶(2)；
步骤2，中间体(3)的制备：在室温条件下向搅拌的含有5-溴-2-(4-溴-2-(二溴硼烷基)苯基)吡啶(2)2.41g,5.00mmol的50mL甲苯溶液中加入三甲基铝1.1M的正己烷溶液10mL，11.00mmol；搅拌2小时后，进行淬灭反应；分离有机层并用乙酸乙酯萃取两次，洗涤，经MgSO4干燥并浓缩，残余物通过硅胶制备薄层色谱纯化，得到5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)；
步骤3，中间体(4)的制备：在-78℃下，向含有5-溴-2-(4-溴-2-(二甲基硼烷基)苯基)吡啶(3)1.06g，3.00mmol的30mL Et2O溶液中逐滴加入n-BuLi 1.94mL，3.10mmol，搅拌1小时后，加入i-PrOBpin 1.12g，6.00mmol，搅拌12小时，用水猝灭后，分离有机层，用乙酸乙酯萃取水层两次，合并有机层并洗涤，经MgSO4干燥并浓缩，残余物通过硅胶制备薄层色谱纯化，得到2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)；
步骤4，催化剂(5)的制备：将2-(4-溴-2-(二甲基硼烷基)苯基)-5-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)吡啶(4)400mg,1.00mmol的15mL N,N-二甲基甲酰胺和K2CO3水溶液2M，3mL装入烧瓶，用N2鼓泡20分钟脱气，加入[Pd(PPh3)4]20mg，并加热至100℃反应2天；冷却至室温并倒入水中；过滤收集沉淀物并用H2O、甲醇、丙酮和二氯甲烷洗涤；处理后，得到最终产物淡绿色固体产物。
3.一种如权利要求1所述的含B←N配位键的有机共轭聚合物光催化剂的应用，其特征在于，在可见光照射下，在牺牲剂存在的条件下，用于实现高效的水分解制氢性能。
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