CN110833864A - 用于高效光催化分解水产氧的新型组合物及其应用 - Google Patents
用于高效光催化分解水产氧的新型组合物及其应用 Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 7
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 23
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- -1 perylene imide Chemical class 0.000 claims description 25
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- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- HLFSDGLLUJUHTE-SNVBAGLBSA-N Levamisole Chemical compound C1([C@H]2CN3CCSC3=N2)=CC=CC=C1 HLFSDGLLUJUHTE-SNVBAGLBSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229940063013 borate ion Drugs 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
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- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 2
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- 229960001614 levamisole Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000003384 small molecules Chemical class 0.000 description 11
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- 238000000034 method Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
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- 238000010521 absorption reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于高效光催化分解水产氧的新型组合物及其应用。本发明所述的光催化分解水的组合物包括苝酰亚胺类共轭小分子/聚合物光催化材料及金属纳米助催化剂。所述的共轭小分子/聚合物光催化材料具有良好的水溶性及和合适的能级,并且与金属纳米助催化剂能够较好结合在一起,发挥较好的催化性能。本发明所述材料及其组合物能够高效催化水分解产氧。与现有技术相比,本发明提供的材料及组合物能够极大地提高产氧效率。
Description
技术领域
本发明涉及光催化领域,具体涉及基于一类苝酰亚胺类共轭小分子/聚合物光催化材料以及金属及金属氧化物、硫化物、磷化物的组合物及其制备方法在有机光催化产氧中的应用。
背景技术
目前,世界能源需求在很大程度上依赖石油、煤炭和天然气等正在迅速枯竭的化石燃料,这不仅使得能源短缺问题越来越严重,同时也带来了环境污染、温室效应等一系列恶劣影响。在这种情况下,开发新型的清洁可持续能源成为了必要。利用太阳光照将水分解为氧气和氢气的光催化过程,可以持续生产和储存化学燃料并进行绿色能源循环,受到了广泛的关注。在水分解过程中,产氧反应是热力学吸能反应,需要巨大的活化能,反应动力学缓慢,需要同时转移4个电子和4个质子,因而被认为是一种更具挑战性的反应。因此,活性产氧光催化剂的研究在光解水研究中占有重要地位。
光催化材料应在较宽的光谱范围内具有较宽的吸收光谱,以吸收更多的阳光、提供足够深的HOMO能级以提供足够的产氧驱动力,并具有良好的光稳定性以维持长期的应用。此外,该系统中的每一组分应很好地结合在一起,以促进电荷转移和光催化产氧。然而,要达到上述所有条件具有很大的挑战性,设计良好的光催化材料并调节其与其他组分之间的相互作用是一个关键问题。
本专利着眼于解决目前产氧催化剂面临的难题,加入金属及其氧化物、硫化物、磷化物的纳米颗粒能有效促进空穴向水的传输,从而减少载流子复合,提高光催化制氢效率,提出采用苝酰亚胺类共轭小分子/聚合物,增强光催化材料与助催化剂的相互作用与电荷传输与分离,提高光催化产氧效率。
发明内容
本发明的目的在于设计并合成苝酰亚胺类共轭小分子/聚合物及金属及金属氧化物、硫化物、磷化物的组合物用于高效光催化产氧。
本发明技术方案如下。
用于高效光催化分解水产氧的新型组合物,包括苝酰亚胺类光催化材料以及金属纳米助催化剂;所述苝酰亚胺类光催化材料包括苝酰亚胺类共轭小分子光催化材料、苝酰亚胺类共轭聚合物光催化材料中的一种以上;所述苝酰亚胺类共轭小分子光催化材料和苝酰亚胺类共轭聚合物光催化材料,具有以下结构:
其中,n为小于100万的正整数;m>1;R1、R2为中性胺基团或四级季铵盐基团,所述四级季铵盐中阴离子为氟、氯、溴、碘或三氟甲磺酸根、四氟硼酸根离子;R3、R4、R5、R6为烷基链,其中至少一条烷基链末端为中性胺基团或四级季铵盐基团,四级季铵盐中阴离子为卤素离子或碘酸根、硝酸根、三氟甲磺酸根、四氟硼酸根、四咪唑硼酸根离子;所述卤素离子包括氟离子、氯离子、溴离子或碘离子;A为共轭单元结构;X1~X8为氢、氟、氯、溴、碘原子。
进一步地,所述R3、R4、R5、R6为具有1~40个碳原子的直链、支链或者环状烷基链,其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基,甲基,乙基,甲氧基、硝基取代,氢原子被氟原子或上述官能团取代;R3、R4、R5、R6相同或不同。
进一步地,所述的A为共轭单元结构,具有如下结构的一种或一种以上:
进一步地,所述金属纳米助催化剂为尺寸为10nm~500nm的钴、镍金属及其氧化物、硫化物、磷化物纳米颗粒中的一种以上。
进一步地,所述金属纳米助催化剂与苝酰亚胺类光催化材料的质量比为(0.01~0.05):1。
一种用于新型组合物作为高效光催化分解水产氧催化剂的应用。
与现有技术相比,本发明具有以下优点:
(1)本发明设计了苝酰亚胺类共轭小分子/聚合物光催化材料,通过调节其侧链,能够极大地提高聚合物与金属及其氧化物、硫化物之间的相互作用,促进电荷分离和电子传输,能够极大地提高光催化产氧效率;
(2)本发明设计了苝酰亚胺类共轭小分子/聚合物,具有较深的最高占据分子轨道,可以产生较大的光催化产氧驱动力,提高产氧效率;
(3)本发明设计了苝酰亚胺类共轭小分子/聚合物,其侧链的阳离子基团可以增强光催化剂在水中的分散性有利与提高电荷分离效率和产氧效率。
附图说明
图1代表性所述的苝酰亚胺类共轭小分子/聚合物紫外-可见光-近红外吸收谱图;
图2代表所述的苝酰亚胺类共轭小分子/聚合物和金属纳米颗粒组合物光催化产氧效率图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明,其目的在于帮助更好的理解本发明的内容,具体包括合成、表征与器件制备,但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
代表性合成路线如下:
(1)共轭小分子SM-1,SM-2按照文献[Advanced Materials,2014,26(21):3473-3477.]公开的方法合成。
(2)共轭小分子SM-3的合成
将小分子SM-2(0.4mmol)和于250mL水中并加入到500mL两口烧瓶中,通入氮气保护,加入溴化钾(14mmol),在70℃条件下反应48h。将溶液浓缩,装入透析袋(MWCO 500D)中,在水溶液中透析2天,用乙酸乙酯将小分子沉淀出来。将上述操作重复一次。将沉淀烘干,得到红色小分子SM-3,产率96%。
实施例2
代表性合成路线如下:
(1)单体M1按照文献[European Journal of Organic Chemistry,2015,3296–3302.]公开的方法合成。
(2)单体M2按照文献[高分子通报,2019,(02):52-62.]公开的方法合成。
(3)聚合物P1的合成:
将单体M1(0.2mmol)和单体M2(0.2mmol)加入到25mL两口圆底烧瓶中,然后加入5mL氯苯和1.5ml二异丙胺。将混合溶液脱气三次以除去氧气,加入7mgPd(PPh3)2Cl2、4mgCuI,再次将反应液脱气,然后加热至60℃,反应2h后用甲醇将聚合物沉淀出来,分别用甲醇、正己烷、氯仿抽提,然后将氯仿相浓缩并再次沉淀在甲醇中。收集固体并干燥,得到183mg深绿色聚合物P1,产率80%。
实施例3
代表性合成路线如下:
(1)单体M3按照文献[Solar RRL 2017,1,1700055.]公开的方法合成。
(2)单体M4按照文献[Journal of Polymer Science Part A:PolymerChemistry,2014,52(8):1200-1215.]公开的方法合成。
(3)聚合物P2的合成:
将单体M3(0.25mmol)和单体M4(0.25mmol)加入到25mL两口圆底烧瓶中,然后加入5mL甲苯和2ml三甲胺。将混合溶液脱气三次以除去氧气,加入2mgPd(PPh3)2Cl2、1mgCuI,再次将反应液脱气,然后加热至70℃,反应10h后用甲醇将聚合物沉淀出来,分别用甲醇、正己烷、氯仿抽提,然后将氯仿相浓缩并再次沉淀在甲醇中。收集固体并干燥,得到207mg深绿色聚合物P2,产率92%。
(4)聚合物P3的合成:
将聚合物P2(100mg)加入到100mL两口圆底烧瓶中,然后加入25mL甲苯,再加入1mL溴乙烷,加热到50℃,搅拌48h。在此过程中,每8h加入5mL甲醇,将溶液浓缩,用正己烷和乙酸乙酯沉淀。将沉淀溶解在甲醇中,再次用正己烷和乙酸乙酯沉淀。收集固体并干燥,得到109mg红色聚合物P3,产率91%。
实施例4
以实施例1所合成的共轭小分子SM-2作为光催化剂与四氧化三钴纳米颗粒组合,在光催化产氧中应用
将10mg共轭小分子SM-2加入到50毫升0.01M的硝酸银去离子水溶液中,搅拌溶解,加入0.3mg四氧化三钴纳米颗粒和100mg三氧化二镧纳米颗粒,超声10分钟分散均匀,随后进行光催化产氧。
实施例5
以实施例1所合成的共轭聚合物P1作为光催化剂与四氧化三钴纳米颗粒组合,在光催化产氧中应用
将10mg共轭聚合物P1加入到50毫升0.01M的硝酸银去离子水溶液中,超声10分钟分散均匀。加入0.5mg四氧化三钴纳米颗粒和100mg三氧化二镧纳米颗粒,超声10分钟分散均匀,随后进行光催化产氧。
对上述实施例1、2、3、4、5所述的苝酰亚胺类共轭小分子/聚合物和金属纳米颗粒组合物表征如下:图1为实施例1-3中苝酰亚胺类共轭小分子/聚合物SM-1、SM-2、SM-3、P-1、P-2、P-3的紫外-可见吸收(UV-vis)光谱图,由图1可知,所述的苝酰亚胺类共轭小分子/聚合物在可见光范围内均具有良好的吸收。
图2为实施例1-5所述的苝酰亚胺类共轭小分子/聚合物和金属纳米颗粒组合物的光催化水分解产氧效率。由图2可知,所述的组合物具有较高的产氧效率,其中SM-3具有最高的产氧效率。
Claims (6)
1.用于高效光催化分解水产氧的新型组合物,其特征在于,包括苝酰亚胺类光催化材料以及金属纳米助催化剂;所述苝酰亚胺类光催化材料包括苝酰亚胺类共轭小分子光催化材料、苝酰亚胺类共轭聚合物光催化材料中的一种以上;所述苝酰亚胺类共轭小分子光催化材料和苝酰亚胺类共轭聚合物光催化材料,具有以下结构:
其中,n为小于100万的正整数;m>1;R1、R2为中性胺基团或四级季铵盐基团,所述四级季铵盐中阴离子为氟、氯、溴、碘或三氟甲磺酸根、四氟硼酸根离子;R3、R4、R5、R6为烷基链,其中至少一条烷基链末端为中性胺基团或四级季铵盐基团,四级季铵盐中阴离子为卤素离子或碘酸根、硝酸根、三氟甲磺酸根、四氟硼酸根、四咪唑硼酸根离子;所述卤素离子包括氟离子、氯离子、溴离子或碘离子;A为共轭单元结构;X1~X8为氢、氟、氯、溴或碘原子。
2.根据权利要求1所述用于高效光催化分解水产氧的新型组合物,其特征在于,所述R3、R4、R5、R6为具有1~40个碳原子的直链、支链或者环状烷基链,其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基,甲基,乙基,甲氧基、硝基取代,氢原子被氟原子或上述官能团取代;R3、R4、R5、R6相同或不同。
4.根据权利要求1所述用于高效光催化分解水产氧的新型组合物,其特征在于,所述金属纳米助催化剂为尺寸为10nm~500nm的钴、镍金属及其氧化物、硫化物、磷化物纳米颗粒中的一种以上。
5.权利要求1所述用于高效光催化分解水产氧的新型组合物,其特征在于,所述金属纳米助催化剂与苝酰亚胺类光催化材料的质量比为(0.01~0.05):1。
6.权利要求1所述用于新型组合物作为高效光催化分解水产氧催化剂的应用。
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