CN113578382A - 高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法 - Google Patents
高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一类高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法,该光催化剂采用简单的三元共聚合的Suzuki偶联反应进行制备,其构建单元包括:芘、噻吩或噻吩衍生物和二苯并噻吩砜。用于聚合的芘基单体和二苯并噻吩砜基单体带有相同的可聚合官能团,可同时与噻吩或噻吩衍生物单体发生Suzuki偶联反应,以保证聚合物结构中芘单元与二苯并噻吩砜单元之间通过噻吩或噻吩衍生物单元相连接。本发明聚合物光催化剂具有光催化产氢活性高、表观量子效率高、光学带隙窄、结构和组成连续可调的特点,且其制备过程简单、产率高、性能稳定,在太阳光下就可以释放氢气,可用于光催化产氢领域。
Description
技术领域
本发明属于光催化分解水制氢材料技术领域,具体涉及一类具有高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法。
背景技术
利用太阳能分解水产氢是一种将太阳能转化为化学能的简单经济且高效的技术手段,一直备受全球科学家的高度关注。近几十年以来,国内***绕提高半导体光催化剂的光催化效率开展了大量的科学研究,已经开发了上千种半导体光催化剂用于光催化分解水产氢/产氧。
半导体光催化剂是利用太阳能光催化分解水产氢的关键材料,而提高半导体光催化剂的光催化活性主要是通过调控半导体的结构、组成来实现。其中,有机聚合物光催化剂由于合成方法多样、结构易设计及理化性质易调控等优势,在光催化分解水制氢领域具有巨大的发展潜力,近年来受到了广泛的研究关注。其中,D-A型聚合物光催化剂由于受体单元的强拉电子效应,可以有效地促进光生电荷的分离效率,进而提高聚合物光催化剂的光催化活性。例如,1,4-苯二硼酸和4,7-二溴-2,1,3-苯并噻二唑通过Suzuki偶联反应可制备一种具有D-A结构的有机聚合物光催化剂B-BT-1,4,以三乙醇胺(TEOA)为牺牲剂,并在使用Pt助催化剂以及可见光照射的条件下获得了2.32mmol h-1g-1的光催化产氢速率(Angew.Chem.Int.Ed.,2016,55,9202-9206)。当以芘单元作为电子供体,苯并噻二唑为电子受体,通过Suzuki偶联反应得到的D-A型聚合物L-PyBT,以TEOA为牺牲剂,以Pt作为助催化剂,在可见光下获得了1.67mmol h-1g-1的光催化产氢速率(Polym.Chem.,2018,9,4468-4475)。当以二苯并噻吩砜作为电子受体,芘基作为电子供体时,通过改变二苯并噻吩砜与芘单元的连接位点所得的聚合物PySO(Small,2018,14,1801839),P16PySO(Appl.Surf.Sci.,2019,495,143537)和PyDOBT-1(Macromolecules,2018,51,9502-9508),以TEOA为牺牲剂未负载Pt时,在可见光下分别获得了4.74mmol h-1g-1、6.38mmol h-1g-1和5.70mmol h-1g-1的光催化产氢活性。氟取代的二苯并噻吩砜与芘基通过Suzuki偶联反应所得的聚合物PyDF,以TEOA为牺牲剂未负载Pt时,在可见光下获得了4.09mmol h-1g-1的光催化产氢速率(J.Mater.Chem.A,2020,8,2404-2411)。当以噻蒽-5,5,10,10-四氧化物作为电子受体与电子给体芘基通过Suzuki偶联反应时,所得聚合物PySEO-1在以TEOA为牺牲剂未负载Pt时,在可见光下获得了4.51mmol h-1g-1的光催化产氢活性(ChemSusChem,2020,13,369-375)。当以9,9-螺二芴作为电子给体时,其与二苯并噻吩砜通过Suzuki偶联反应所得聚合物S-CMP3在以三乙胺(TEA)为牺牲剂未负载Pt时获得了3.11mmol h-1g-1的可见光催化产氢活性(Chem.Mater.,2019,31,305-313)。苯基与二苯并噻吩砜通过Suzuki偶联反应所得聚合物P7(Angew.Chem.Int.Ed.,2016,55,1792-1796)和DBTD-CMP1(ACS Catal.,2018,8,8590-8596),在可见光下,分别以TEA和TEOA为牺牲剂,未负载Pt时,分别获得了3.68mmolh-1g-1和2.46mmol h-1g-1的光催化产氢速率。当以苯并三噻吩作为电子给体时,其与二苯并噻吩砜通过Suzuki偶联反应所得聚合物BTT-CPP,在以抗坏血酸(AA)作为牺牲剂未负载Pt时,在可见光下获得了12.63mmol h-1g-1的光催化产氢速率(Macromolecules,2021,54,2661-2666)。当以苯基作为电子给体,噻吩基和吡嗪基作为电子受体时,通过Suzuki偶联反应所得的聚合物P13(J.Mater.Chem.A,2018,6,11994-12003)和P28(Chem.Mater.,2018,30,5733-5742)在以TEA为牺牲剂未负载Pt时,分别获得了0.25mmol h-1g-1和0.96mmol h- 1g-1的可见光催化产氢速率。
以上所列举的有机聚合物带隙都较宽,对可见光部分吸收较弱,很难充分利用太阳光中的可见光,因此可见光下光催化分解水制氢性能较低。当作为电子供体的1,4-二乙炔基苯和作为电子受体的氟和甲氧基取代的苯并噻二唑通过Sonogashira偶联得到的B-FOBT-1,4-E,在可见光下以TEOA为牺牲剂,未负载Pt助催化剂的条件下,获得了13.3mmolh-1g-1的光催化产氢速率(ACS Energy Lett.,2018,3,2544-2549)。1,3,6,8-四溴芘与2,5-二溴二噻吩并[3,2-b:2',3'-d]噻吩砜通过直接C-H芳基化偶联反应所得聚合物PyDTDO-3,在可见光下、未负载Pt和以AA作为牺牲剂时,获得了16.32mmol h-1g-1的光催化产氢活性(Chem.Sci.,2021,12,1796-1802)。1,3,6,8-四溴芘与2,2-二并噻吩通过直接C-H芳基化偶联反应所得聚合物CP1(J.Mater.Chem.A,2019,7,24222-24230),在可见光条件下,以AA作为牺牲剂时,光催化产氢速率为15.97mmol h-1g-1。当以1,3,6,8-四溴芘分别与2,5-双(三甲基甲锡基)噻吩、2,5-二(三甲基甲锡烷基)噻吩并[3,2-b]噻吩和2,5-二(三甲基甲锡烷基)二噻吩并[3,2-b:2',3'-d]噻吩通过Stille偶联反应聚合时,得到了聚合物Py-T、Py-Tt、Py-Ttt(J.Mater.Chem.A,2021,9,5787-5795),在以AA作为牺牲剂未负载Pt的条件下分别获得了38.1mmol h-1g-1、45.8mmol h-1g-1和38.9mmol h-1g-1的可见光催化产氢速率。相比于CP1,Py-Tt性能提升的主要原因可能是因为Py-Tt具有更好的共平面性,有利于光生电子的传输。以上几种聚合物催化剂的光催化性能得到提升,主要是因为他们具有较窄的带隙,提高了对可见光的吸收。虽然Py-T、Py-Tt、Py-Ttt具有较低的带隙,但是它们不具有强吸电子单元,导致光生电子和空穴无法有效分离,这也限制了其光催化性能的进一步提高。
以上列举的有机聚合物光催化剂都是由两种功能化的单体通过偶联反应聚合得到。研究表明,通过三元或者多元共聚的方式可以调控聚合物的光学性质、电学性质和调控有机聚合物的光催化活性。例如,Cooper等人采用三元共聚的方式得到了一系列有机聚合物光催化剂CP-CMP1-15,通过调节三种单元的投料比实现了对有机聚合物光学带隙、比表面积和光催化性能的调控(J.Am.Chem.Soc.2015,137,3265-3270)。通过调节四苯乙烯基、苯基和9-芴酮的投料比,所得三元共聚物F0.5CMP在以Na2S/Na2SO4为牺牲剂未负载Pt时获得了0.66mmol h-1g-1的可见光产氢活性(Chem.Eur.J.,2019,25,3867-3874)。当在聚合物骨架中引入苯单元作为桥键连接芘单元和二苯并噻吩砜单元时,通过调节供体单元和受体单元的投料比,所得D-π-A聚合物PyBS-3(Adv.Mater.,2021,2008498)在以TEOA为牺牲剂未负载Pt时,获得了14mmol h-1g-1的可见光分解水产氢活性。当以AA作为牺牲剂时,获得了36mmol h-1g-1的可见光分解水产氢活性,相比于PyDOBT-1、PyBS-3性能得到了大幅度提升,这主要是由于苯桥键的引入降低了分子之间的扭曲程度,有利于电子的传输,但是其能带结构依旧较宽,因此,在可见光照射下则表现出较低的催化产氢活性。
发明内容
本发明的目的是提供一类在可见光照射下具有高光催化分解水制氢活性的含噻吩基聚合物光催化剂,并为该类聚合物光催化剂提供一种工艺步骤简单、收率高的制备方法。
针对上述目的,本发明所采用的含噻吩基聚合物光催化剂的结构如式A或式B所示:
式A中n:m的摩尔比=1:3~10,式B中x:y的摩尔比=1:2~10。
本发明含噻吩基聚合物光催化剂的制备方法为:在氮气保护下,将碳酸钾水溶液、1,3,6,8-四溴芘、噻吩-2,5-二硼酸二频哪醇酯或2,5-双(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)噻吩并[3,2-b]噻吩、3,7-二溴二苯并噻吩砜、四(三苯基膦)钯加入到有机溶剂中,加热至回流反应24~72小时,反应结束后冷却到室温,用二氯甲烷、甲醇和水洗涤,真空干燥,得到式A所示的含噻吩基聚合物光催化剂(记为Py-TP-BTDO)或式B所示的含噻吩基聚合物光催化剂(记为Py-TTP-BTDO),反应方程式如下:
上述制备方法中,优选1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜的摩尔比为1:3~10,1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜的摩尔比为1:2~10,而噻吩-2,5-二硼酸二频哪醇酯或2,5-双(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)噻吩并[3,2-b]噻吩的用量为1,3,6,8-四溴芘摩尔量的两倍与3,7-二溴二苯并噻吩砜摩尔量之和。
上述制备方法中,优选四(三苯基膦)钯的加入量为1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜中总的溴官能团摩尔量的0.8%~2%,碳酸钾的加入量为1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜中总的溴官能团摩尔量的2~5倍。
上述制备方法中,进一步优选加热至回流反应36~48小时。
上述制备方法中,所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃中任意一种。
本发明的有益效果如下:
1、本发明在芘单元和二苯并噻吩砜单元之间引入具有窄带隙结构的噻吩或噻吩并[3,2-b]噻吩,可以有效降低聚合物的带隙,也可以提高聚合物分子链的共平面性,同时也保证了强拉电子单元二苯并噻吩砜的存在,获得了具有高可见光催化分解水制氢活性的窄带隙聚合物光催化剂。
2、本发明聚合物光催化剂采用三元共聚法制备,所得光催化剂重复性好、比表面积大、带隙窄、可见光活性高、光催化产氢稳定性高,在可见光照射下仍具有高的光催化产氢活性,光生电子和空穴分离效果好,制备过程简单,成本较低,毒害小,有利于环境保护和大规模应用。与大多数报道的有机聚合物光催化剂相比,本发明所制备的光催化剂用于催化分解水产氢表现出更加优异的光催化性能,处于国内外领先水平。
附图说明
图1是实施例1和2制备的聚合物光催化剂的红外光谱图。
图2是实施例1和2制备的聚合物光催化剂固体核磁共振碳谱图。
图3是实施例1和2制备的聚合物光催化剂的扫描电子显微镜照片。
图4是实施例1和2制备的聚合物光催化剂的XRD图谱。
图5是实施例1和2制备的聚合物光催化剂的紫外可见吸收光谱图。
图6是实施例1和2制备的聚合物光催化剂在波长大于300nm的光照下光催化产氢速率与光照时间的关系图。
图7是实施例1和2制备的聚合物光催化剂在波长大于420nm的光照下光催化产氢速率与光照时间的关系图。
图8是实施例1制备的聚合物光催化剂在模拟太阳光下(λ>300nm)的光催化产氢测试照片。
图9是实施例2制备的聚合物光催化剂在模拟太阳光下(λ>300nm)的光催化产氢测试照片。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
在氮气保护下,将20mL N,N-二甲基甲酰胺、2mL 2mol/L碳酸钾水溶液加入到装有68.9m(0.13mmol)1,3,6,8-四溴芘、262.1mg(0.78mmol)噻吩-2,5-二硼酸二频哪醇酯、194.5mg(0.52mmol)3,7-二溴二苯并噻吩砜和25.0mg(21.6μmol)四(三苯基膦)钯的反应瓶中,加热至150℃回流反应48小时,反应结束后冷却到室温,用二氯甲烷、甲醇和水多次洗涤,在100℃真空条件下干燥24小时,得到橙黄色固体粉末Py-TP-BTDO,其中n:m的摩尔比为1:4。
实施例2
在氮气保护下,将20mL N,N-二甲基甲酰胺、2mL碳酸钾溶液(2mol L-1)加入到装有68.9m(0.13mmol)1,3,6,8-四溴芘、305.8mg(0.78mmol)2,5-双(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)噻吩并[3,2-b]噻吩、194.5mg(0.52mmol)3,7-二溴二苯并噻吩砜和25.0mg(21.6μmol)四(三苯基膦)钯的反应瓶中,加热至150℃回流反应48小时,反应结束后冷却到室温,用二氯甲烷、甲醇和水多次洗涤,在100℃真空条件下干燥24小时,得到红色粉末Py-TTP-BTDO,其中x:y的摩尔比为1:4。
采用红外光谱和固体核磁碳谱对实施例1和实施例2制备产物的化学结构进行表征,结果见图1~2。图1中,1596cm-1和1591cm-1处的峰归结为芳香骨架的振动,1306cm-1和1154cm-1处的峰为砜基的振动峰。图2中,110~150ppm为芳香环上碳原子的出峰信号区域,其中,138ppm为与砜基上的硫原子相连接的碳原子的信号峰。由图3可知,实施例1制备产物呈现纳米片堆积形貌,实施例2制备产物呈纳米颗粒形态。图4的XRD结果表明实施例1和实施例2产物均为无定型结构。
为了证明本发明的有益效果,发明人采用实施例1~2制备的聚合物光催化剂分别进行了光催化分解水产氢测试,具体方法如下:
将10mg聚合物光催化剂超声分散在100mL含1mol/L AA的水和DMF体积比为9:1的混合液中,AA作为牺牲剂,DMF作为分散剂,待聚合物催化剂分散后倒入反应器,接入光催化***,光源为300W氙灯,420nm滤光片用来模拟可见光,分别在可见光和紫外-可见光下对实施例1~2制备的聚合物光催化剂进行光催化分解水产氢测试,采用气相色谱进行光催化分解水产氢在线分析,结果见表1。
表1光学带隙、所用牺牲剂和产氢速率(λ>420nm)
由表1可见,本发明聚合物光催化剂在可见光下具有非常高的光催化活性,可见光下产氢速率最高可达80.65mmol h-1g-1,与文献(Macromolecules 2018,51,9502-9508)中的有机聚合物PyDOBT-1相比,可见光下的光催化产氢速率提高了141~215倍;与文献(Adv.Mater.,2021,2008498)中的有机聚合物PyBS-3相比,可见光下聚合物的光催化产氢速率提高了21~23倍。
为了进一步证明本发明聚合物光催化剂的有益效果,发明人采用实施例1和实施例2制备的聚合物光催化剂分别进行了光催化分解水释放氢气的观察实验,具体方法如下:
将5mg聚合物光催化剂均匀涂敷在粘有双面胶的玻璃板上,双面胶为普通双面胶,仅用于固定聚合物光催化剂,然后将粘有聚合物光催化剂的玻璃板缓慢倾斜放入装有AA的石英容器中,用300W氙灯模拟太阳光垂直照射石英容器。在光催化反应过程中,肉眼可见大量明显的气泡(氢气)产生(见图8和图9)。
Claims (6)
3.根据权利要求2所述的含噻吩基聚合物光催化剂的制备方法,其特征在于:所述1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜的摩尔比为1:3~10,1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜的摩尔比为1:2~10,噻吩-2,5-二硼酸二频哪醇酯或2,5-双(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)噻吩并[3,2-b]噻吩的用量为1,3,6,8-四溴芘摩尔量的两倍与3,7-二溴二苯并噻吩砜摩尔量之和。
4.根据权利要求2所述的含噻吩基聚合物光催化剂的制备方法,其特征在于:所述四(三苯基膦)钯的加入量为1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜中总的溴官能团摩尔量的0.8%~2%,碳酸钾的加入量为1,3,6,8-四溴芘与3,7-二溴二苯并噻吩砜中总的溴官能团摩尔量的2~5倍。
5.根据权利要求2所述的含噻吩基聚合物光催化剂的制备方法,其特征在于:加热至回流反应36~48小时。
6.根据权利要求2所述的含噻吩基聚合物光催化剂的制备方法,其特征在于:所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃中任意一种。
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