CN110606938B - 一种含4-乙烯基吡啶合镉的聚合配合物及其制备方法与用途 - Google Patents
一种含4-乙烯基吡啶合镉的聚合配合物及其制备方法与用途 Download PDFInfo
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Abstract
本发明涉及一种以4‑乙烯基吡啶合镉配合物作辅助电子受体A的D‑A‑π‑A型聚合配合物(如下式)及其制备方法,其用途为在染料敏化太阳能电池中作染料敏化剂,该聚合配合物是以大π共轭结构的苯并二噻吩联二噻吩衍生物(BDTT)为电子给体D,以4‑乙烯基吡啶合镉配合物作辅助电子受体A,以与镉配位的另一个配体8‑羟基喹啉作π桥,氰基丙烯酸为电子受体A和锚定基团,将镉配合物与给体BDTT通过Heck聚合反应制备的一种新型聚合配合物染料敏化剂PBDTT‑PY‑Cd,该染料敏化剂表现出良好的光伏性能和高的热稳定性,其光电转化效率PCE达到8.01%,热分解温度为301℃,对染料敏化太阳能电池的研发具有一定的应用价值。
Description
技术领域
本发明涉及一种以4-乙烯基吡啶合镉配合物为辅助电子受体A的D-A-π-A型聚合配合物及其制备方法,并应用于染料敏化太阳能电池中作染料敏化剂,属于新材料中的光电材料领域。
背景技术
染料敏化太阳能电池(DSSC)是目前最具研究和发展应用潜力的有机太阳能电池之一,吸引了全世界范围内的深入研究,而染料敏化剂在吸收太阳光后能产生光生电子,是染料敏化太阳能电池(DSSC)的关键光敏材料,染料敏化剂的合成和性能研究起始于钌基配合物染料,但因钌的高成本以及来源受限而逐渐转向了纯有机和普通过渡金属配合物染料敏化剂的研究,目前的有机染料敏化剂面临稳定性差和光电效率有限等缺陷,普通金属配合物的吸光性能也有局限,为解决这些问题,本发明研究了将有机和配合物染料通过聚合得到的聚合配合物染料敏化剂,其吸光性能、电子传输性能和光电转化效率都得到了提升。发明内容
本发明的目的:在于提供一种以4-乙烯基吡啶合镉配合物为辅助电子受体的D-A-π-A型聚合配合物染料敏化剂PBDTT-PY-Cd及其制备方法。通过Heck聚合反应将电子受体部分4-乙烯基吡啶合镉配合物与电子给体部分二噻吩-苯并二噻吩衍生物(BDTT)聚合,形成D-A-π-A结构的聚合配合物功能染料,并应用于染料敏化太阳能电池中作染料敏化剂。
本发明的技术方案是:一种含4-乙烯基吡啶合镉的聚合配合物,其特征在于该化合物是以4-乙烯基吡啶合镉配合物作辅助电子受体A,具有D-A-π-A型的分子结构,其通式如式1:
式1 一种含4-乙烯基吡啶合镉的聚合配合物PBDTT-PY-Cd的结构通式。
一种含4-乙烯基吡啶合镉的聚合配合物PBDTT-PY-Cd的制备方法:
(1). 4-乙烯基吡啶(1)的合成:向三口反应瓶中加入摩尔比为0.040:0.080:0.005:1.000的4-甲基吡啶,多聚甲醛,苯甲酸和蒸馏水,在常压下加热回流10~20 h后,减压下蒸出未少量反应的4-甲基吡啶,可得粗吡啶乙醇,将适量的氢氧化钠水溶液放入三口反瓶中,加入少量亚甲基蓝,升温到130~150℃,减压滴加粗吡啶乙醇,乙烯吡啶与水立即被蒸馏出来,迅速冷却到室温,同时加入亚甲基蓝和少量固体氢氧化钠,静置24~36 h,溶液即分为两层,上层为乙烯吡啶,加入亚甲基蓝50 ℃以下进行减压精馏,得无色液体,沸点120~121 ℃,向纯4-乙烯基吡啶中加入亚甲基蓝进行保存,以防聚合;
(2). 含镉配合物(PY-Cd)(2)的合成:将摩尔比为1:1的辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸和配体4-乙烯基吡啶溶解在适量的四氢呋喃溶液中,再慢慢滴加一定含过量醋酸镉(Cd(CH3COO)2·2H2O)的甲醇溶液,滴加后测量体系pH值,必要时用冰乙酸或氨水调节,使其保持在弱酸性。因配体4-乙烯基吡啶稳定性有限,体系只升温至50~60 ℃,继续反应6~10 h后停止反应,将得到的混合物冷却到室温过滤,并用无水乙醇洗涤过滤得到的固体,产物在真空干燥箱干燥后,为黄色固体产物;
(3). 聚合金属配合物(PBDTT-PY-Cd)(3)的合成:聚合金属配合物PBDTT-PY-Cd通过Heck聚合反应获得,按1.000:1.000:0.041:0.229的摩尔比依次称取配合物单体PY-Cd ,给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT),以及催化剂醋酸钯(Pd(CH3COO)2和三(2-甲苯基)膦,然后加入精制的DMF溶剂,以及少量干燥过的三乙胺,氮气保护下升温到90~100 ℃,继续反应48~72 h,反应停止后将体系静置到室温,再过滤混合物中的固体,并用无水甲醇洗涤数次,真空干燥后得到棕黄色固体产物;
一种含4-乙烯基吡啶合镉的聚合配合物的用途:在染料敏化太阳能电池中用作染料敏化剂。
发明的主要优势在于:一种含4-乙烯基吡啶合镉的聚合配合物,以4-乙烯基吡啶合镉的配合物作辅助电子受体,并且将有机金属配合物聚合化,以扩大配合物分子的共轭π体系,提高其吸光性能和载流子传输能力,因而提高其作为染料敏化剂的光伏性能。
附图说明
图1 本发明实施例合成的4-乙烯基吡啶的核磁共振氢谱(1HNMR)(400MHz,CDCl3,TMS);
图2 本发明实施例合成的化合物PY-Cd和PBDTT-PY-Cd的红外光谱(IR)(KBr晶体压片,4000~500 cm-1);
图3 本发明实施例合成的化合物PY-Cd和PBDTT-PY-Cd的紫外-可见吸收光谱(UV-vis);
图4 本发明实施例合成的化合物PBDTT-PY-Cd的热重分析(TGA)曲线(TGA);
图5 本发明实施例合成的化合物PBDTT-PY-Cd作染料敏化剂的染料敏化太阳能电池的电流密度-电压(J-V)曲线;
图6 本发明实施例合成的化合物PBDTT-PY-Cd作染料敏化剂的染料敏化太阳能电池的外量子效率(IPCE)曲线。
具体实施方式
本发明的化合物的制备合成反应路线为:
下面结合具体实施例对本发明做进一步的说明。
实施例1:
一种含4-乙烯基吡啶合镉的聚合配合物PBDTT-PY-Cd。
其分子结构式为:
上述聚合镉的配合物PBDTT-PY-Cd的制备方法:
A. 4-乙烯基吡啶(1)的合成:向三口反应瓶中加入4-甲基吡啶3.72 g (40.00mmol),多聚甲醛2.40 g (80.00 mmol),苯甲酸0.06 g (5.00 mmol),蒸馏水18 mL,在常压下加热回流10 h后,减压下蒸出未少量反应的4-甲基吡啶,可得粗吡啶乙醇约3.5 g,将40%的氢氧化钠水溶液50 mL放入三口反瓶中,加入50 mg亚甲基蓝,升温到140 ℃,减压滴加粗吡啶乙醇,乙烯吡啶与水立即被蒸馏出来,迅速冷却到室温,同时加入0.1%亚甲基蓝和1.5g固体氢氧化钠,静置24 h,溶液即分为两层,上层为乙烯吡啶,加入0.1%亚甲基50 ℃以下进行减压精馏,得无色液体2.8 g,产率66.0%,沸点120~121 ℃。向纯4-乙烯基吡啶中加入0.1%亚甲基蓝进行保存,以防聚合,1H-NMR (CDCl3, ppm): 8.56 (d, 2H, Ar−H), 7.27(d, 2H, Ar−H), 6.62-6.69 (q, 1H, −CH=), 5.95-6.00 (d, 1H, =CH2), 5.47-5.51(d, 1H, =CH2),13C-NMR (CDCl3, ppm): 150.05, 144.52, 134.62, 124.55, 120.65,118.58(其核磁共振氢谱表征如图1所示);
B. 含镉配合物(PY-Cd)(2)的合成:将辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸(0.48 g, 2.00 mmol)和配体4-乙烯基吡啶(0.42 g, 2.00 mmol)溶解在30 mL四氢呋喃溶液中,再慢慢滴加20 mL含0.56 g (2.10 mmol)的醋酸镉(Cd(CH3COO)2·2H2O)的甲醇溶液,滴加后测量体系pH值,必要时用冰乙酸或氨水调节,使其保持在弱酸性,因配体4-乙烯基吡啶稳定性有限,体系只升温至50 ℃,继续反应8 h后停止反应,将得到的混合物冷却到室温过滤,并用无水乙醇洗涤过滤得到的固体,产物在真空干燥箱干燥后,为黄色固体产物0.79 g,产率为64.0%,FTIR (KBr, cm-1): 3442(O−H), 2212(C≡N), 1676(C=O), 1601(C=N), 1564(C=N), 1101(C−O−Cd), 496(N−Cd). Anal. Calcd. for [C29H24N4O5Cd]: C,56.09; H, 3.90; N, 9.02. Found: C, 56.15; H, 3.91; N, 9.04%(其红外光谱表征如图2所示,紫外-可见吸收光谱(UV-Vis)如图3所示);
C. 聚合金属配合物(PBDTT-PY-Cd)(3)的合成:聚合金属配合物PBDTT-PY-Cd通过Heck聚合反应获得。依次称取配合物单体PY-Cd (0.20 g, 0.32 mmol),给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT)(0.24 g, 0.32mmol),以及催化剂醋酸钯(Pd(CH3COO)2, 0.0029 g, 0.0130 mmol)和三(2-甲苯基)膦(0.0220 g, 0.0720 mmol),然后加入精制的DMF溶剂8 mL,以及干燥过的三乙胺(3 mL),氮气保护下升温到90 ℃,继续反应48 h。反应停止后将体系静置到室温,再过滤混合物中的固体,并用无水甲醇洗涤数次,真空干燥后得到棕黄色固体产物0.21 g,产率为53.0%,FTIR(KBr, cm-1): 3431(O−H), 2922, 2850(C-H), 2208(C≡N), 1660(C=O), 1599(C=N),1562(C=N), 1099(C−O−Cd), 494(N−Cd). Anal. Calcd. for [C65H68N4O5S4Cd]: C,63.68; H, 5.59; N, 4.57; S, 10.46. Found: C, 63.73; H, 5.58; N, 4.56; S,10.45%. Mn=9.74 Kg/mol, PDI=2.34(其红外光谱表征如图2所示,紫外-可见吸收光谱(UV-Vis)如图3所示)。
实施例2:
测定聚合金属配合物染料PBDTT-PY-Cd的热重分析(TGA)曲线,方法:SDTQ600的热重分析仪,N2保护下以20℃/min的升温速度进行测试,测试结果如图4。
实施例3:
J-V曲线测试光源为氙灯模拟的光强100 mW/cm2的AM 1.5 G的太阳光,通过Keithley 2400 数字源表改变电压并记录电流随电压的变化值;IPCE测试由OrielCornerstone单色仪提供光源,在短路条件下测得,波长的测试间隔为10 nm。DSSC的有效工作面积为0.25 cm2;测定以聚合金属配合物PBDTT-PY-Cd为染料敏化剂的染料敏化太阳能电池的性能参数和光电转换效率,其电池电流密度-电压(J-V)曲线如图5,电池外量子效率(IPCE)曲线如图6;表一是它们的光伏性能和光电转换效率测试结果。
表1 基于聚合金属配合物染料敏化剂的DSSC的光伏性能数据
polymer | solvent | <i>J</i><sub>sc</sub>(mA/cm<sup>-2</sup>) | <i>V</i><sub>oc</sub>(V) | <i>FF</i>(%) | PCE (%) |
PBDTT-PY-Cd | DMF | 14.95 | 0.75 | 71.63 | 8.01 |
注, solvent:溶解染料敏化剂以制膜的溶剂,Jsc:短路电流密度,Voc:开路电压,FF:填充因子,PCE:太阳能电池的光电转换效率。
Claims (3)
2.根据权利要求1所述的一种含4-乙烯基吡啶合镉聚合配合物PBDTT-PY-Cd的制备方法:
(1) 4-乙烯基吡啶(1)的合成:向三口反应瓶中加入摩尔比为0.040:0.080:0.005:1.000的4-甲基吡啶,多聚甲醛,苯甲酸和蒸馏水,在常压下加热回流10~20 h后,减压下蒸出未少量反应的4-甲基吡啶,可得粗吡啶乙醇,将适量的氢氧化钠水溶液放入三口反应 瓶中,加入少量亚甲基蓝,升温到130~150℃,减压滴加粗吡啶乙醇,乙烯吡啶与水立即被蒸馏出来,迅速冷却到室温,同时加入亚甲基蓝和少量固体氢氧化钠,静置24~36 h,溶液即分为两层,上层为乙烯吡啶,加入亚甲基蓝50 ℃以下进行减压精馏,得无色液体,沸点120~121℃,向纯4-乙烯基吡啶中加入亚甲基蓝进行保存,以防聚合;
(2) 含镉配合物PY-Cd(2)的合成:将摩尔比为1:1的辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸和配体4-乙烯基吡啶溶解在适量的四氢呋喃溶液中,再慢慢滴加一定含过量醋酸镉(Cd(CH3COO)2·2H2O)的甲醇溶液,滴加后测量体系pH值,必要时用冰乙酸或氨水调节,使其保持在弱酸性;因配体4-乙烯基吡啶稳定性有限,体系只升温至50~60 ℃,继续反应6~10 h后停止反应,将得到的混合物冷却到室温过滤,并用无水乙醇洗涤过滤得到的固体,产物在真空干燥箱干燥后,为黄色固体产物;
(3) 聚合金属配合物PBDTT-PY-Cd(3)的合成:聚合金属配合物PBDTT-PY-Cd通过Heck聚合反应获得,按1.000:1.000:0.041:0.229的摩尔比依次称取配合物单体PY-Cd ,给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT),以及催化剂醋酸钯Pd(CH3COO)2和三(2-甲苯基)膦,然后加入精制的DMF溶剂,以及少量干燥过的三乙胺,氮气保护下升温到90~100 ℃,继续反应48~72 h,反应停止后将体系静置到室温,再过滤混合物中的固体,并用无水甲醇洗涤数次,真空干燥后得到棕黄色固体产物。
3.根据权利要求1所述的一种含4-乙烯基吡啶合镉的聚合配合物PBDTT-PY-Cd的用途,在染料敏化太阳能电池中用作染料敏化剂。
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