CN108671961B - 一种钌配合物光催化剂,制备方法及其应用 - Google Patents
一种钌配合物光催化剂,制备方法及其应用 Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 11
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012954 diazonium Chemical group 0.000 claims abstract description 14
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001345 alkine derivatives Chemical group 0.000 claims abstract description 8
- 150000001989 diazonium salts Chemical group 0.000 claims abstract description 8
- 229910017673 NH4PF6 Inorganic materials 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 12
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- 238000006731 degradation reaction Methods 0.000 claims description 7
- -1 tetrafluoroborate diazonium benzene salt Chemical class 0.000 claims description 7
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- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 claims description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 2
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 claims description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- IFPWCRBNZXUWGC-UHFFFAOYSA-M gold(1+);triphenylphosphane;chloride Chemical compound [Cl-].[Au+].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IFPWCRBNZXUWGC-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
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- 125000005620 boronic acid group Chemical group 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- GANAQXGHGKBVKP-UHFFFAOYSA-N 1-benzyl-4-phenyltriazole Chemical compound C1=C(C=2C=CC=CC=2)N=NN1CC1=CC=CC=C1 GANAQXGHGKBVKP-UHFFFAOYSA-N 0.000 abstract description 6
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- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- YJCNOXTTXJASGR-UHFFFAOYSA-N 5-diazo-2-methoxycyclohexa-1,3-diene Chemical class COC1=CCC(=[N+]=[N-])C=C1 YJCNOXTTXJASGR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- LPNBBFKOUUSUDB-UHFFFAOYSA-M p-toluate Chemical compound CC1=CC=C(C([O-])=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-M 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
本发明提供了一种新型光催化剂,化学结构式如下图:其化学式为C34H28N8RuP2F16,分子量为940.07。合成方法为以Ru(2,2'‑bipyridine)2Cl2和1‑苄基‑4‑苯基‑1H‑1,2,3‑三唑为原料,且摩尔比为1:1.05,然后在通过与NH4PF6进行阴离子交换,得到一种新型光催化剂。光催化性能测表明该光催化剂在白光照射条件下具有较好的降解苯基硼酸的性能,此外该钌配合物和Ph3AuCl组成的双金属光催化剂在蓝光照射条件下具有较好的催化末端炔与重氮盐的偶联反应。本发明所采用的工艺方法简单、效率高;所得新型光催化剂纯度高,单晶形貌规则、尺寸均匀,C34H28N8RuP2F16的发现和研究有助于进一步拓宽钌系列光催化材料的研究领域,也将为设计和合成新型可见光催化剂提供一些新思路。
Description
技术领域
本发明属于功能材料领域,特别涉及一种新型钌配合物光催化材料的制备方法及其应用。
背景技术
[Ru(bpy)3]2+,三[2,2’联吡啶]钌离子,作为一种商业化的光敏剂,具有水溶性好,化学、电化学和光化学性能稳定,氧化还原可逆,发光效率高,应用pH范围宽,可电化学再生,激发态寿命长等特点,在有机光催化反应中得到了广泛的应用。[Ru(bpy)3]2+价格昂贵,在有机反应中被大量消耗,导致环境污染和生产成本高,而新型钌配合物催化剂C34H28N8RuP2F16的发现和研究有助于进一步拓宽钌系列光催化材料的研究领域,也将为设计和合成新型可见光催化剂提供一些新思路。比如下关于可循环的磁性氧化铁的支持的钌配合物光催化剂的设计。
从文献报道来看,C34H28N8RuP2F16作为光催化剂的报道尚未见报道。它具有与商业化昂贵的[Ru(bpy)3]2+不可比拟的优点,如反应速度快、合成时间短、反应效率高、产品具有较高的纯度、可负载性等优点,在合成光催化有机反应等领域里显示了良好的发展态势和广阔的应用前景。
发明内容
以Ru(2,2'-bipyridine)2Cl2和1-苄基-4-苯基-1H-1,2,3-三唑为原料,通过与NH4PF6进行阴离子交换,得到一种新型光催化剂。光催化性能测表明该光催化剂在白光照射条件下具有较好的降解苯基硼酸的性能,此外该钌配合物和Ph3AuCl组成的双金属光催化剂在蓝光照射条件下具有较好的催化末端炔与重氮盐的偶联反应。
本发明的所述的钌配合物光催化剂,其化学式为C34H28N8RuP2F16,分子量为940.07,该化合物的结构式如下:
所述的钌配合物光催化剂的制备方法,包括以下制备步骤:
步骤1:将Ru(2,2'-bipyridine)2Cl2溶解于N,N-二甲基甲酰胺溶液(或者N,N-二甲基乙酰胺,二甲基亚砜等高沸点溶剂)中,搅拌至溶解;
步骤2:将1-苄基-4-苯基-1H-1,2,3-三唑加入步骤1的溶液中,搅拌至溶解;步骤3:步骤2所得溶液加热到120-180℃,反应18-30小时;
步骤4:待反应结束冷却到室温,将饱和NH4PF6水溶液缓慢加入步骤3的溶液中,再搅拌反应1-3小时;
步骤5:反应完毕后,抽滤,剩余物经干燥即得到化合物C34H28N8RuP2F16,即可完成钌配合物光催化剂的合成。
1.所述的Ru(2,2'-bipyridine)2Cl2、1-苄基-4-苯基-1H-1,2,3-三唑的摩尔比为1:0.5-1.5。 Ru(2,2'-bipyridine)2Cl2、NH4PF6的摩尔比为1:3.0-5.0。
本发明的技术方案将所述的钌配合物光催化剂在降解苯基硼酸中的应用。
所述的钌配合物光催化剂在降解苯基硼酸的步骤如下:
步骤1:将苯基硼酸溶解于N,N-二甲基甲酰胺溶液中,搅拌至溶解;
步骤2:将钌配合物光催化剂加入反应体系中,同时加入三乙胺反应;
步骤3:可见光下搅拌反应12-24h时间即可完成苯基硼酸的降解。
所述的钌配合物光催化剂相对于苯基硼酸的添加量关系为摩尔比0.01-0.04:1。
本发明的技术方案将所述钌配合物光催化剂在催化末端炔与重氮盐的偶联反应上的应用。
所述的末端炔烃包括苯乙炔,对甲基苯乙炔,对甲氧基苯乙炔,对氯苯乙炔,对溴苯乙炔,正已炔;所述的重氮盐包括四氟硼酸重氮苯盐,四氟硼酸重氮对甲氧基苯盐,四氟硼酸重氮对甲基苯盐等。
钌配合物在光照条件下催化苯基硼酸的反应机理如图4所示,RuII在光照条件下被三乙胺还原成RuI,随后RuI又被氧气氧化成RuII完成循环,随即苯基硼酸就被降解为苯酚。
钌配合物在光照条件下催化末端炔和重氮盐的反应机理如图5所示,该反应涉及一价金和光催化剂双金属催化反应。
附图说明
图1是本发明制备的新型光催化剂的1H-NMR谱图。
图2是本发明制备的新型光催化剂的13C-NMR谱图.
图3是本发明中降解苯基硼酸后苯酚1H-NMR谱图。
图4是本发明中氧化偶联反应的产物的1H-NMR谱图。
图5是本发明中钌配合物在光照条件下催化苯基硼酸的反应机理。
图6是本发明中一价金和光催化剂双金属光催化偶联反应的机理。
具体实施方式
实施例1
本发明采用的制备方案包括以下步骤
步骤1:将1.00×10-4mol的Ru(2,2'-bipyridine)2Cl2溶解于N,N-二甲基甲酰胺溶液(5ml) 中,搅拌至溶解;
步骤2:将1.05×10-4mol的1-苄基-4-苯基-1H-1,2,3-三唑加入步骤1的溶液中,搅拌至溶解,其中Ru(2,2'-bipyridine)2Cl2、1-苄基-4-苯基-1H-1,2,3-三唑的摩尔比为1:1.05;
步骤3:步骤2所得溶液加热到160℃,反应24小时.
步骤4:待反应结束冷却到室温,将提前配好的饱和NH4PF6水溶液(5ml)缓慢加入步骤3 的溶液中,再搅拌2小时。此时体系中会出现大量固体。
步骤5:反应完毕后,抽滤,剩余物经干燥即得到化合物C34H28N8RuP2F16,即可完成新型钌配合物光催化剂的合成。
图1是本发明制备的新型光催化剂的1H-NMR谱图。
1H NMR(300MHz,CD2Cl2):δ:10.75(s,1H),9.05-9.10(m,2H),8.85-8.90(m,3H),8.00-8.20(m,4H),7.80-7.90(m,1H),7.70-7.76(m,3H),7.60(s,1H),7.45-7.50(m,2H),7.40-7.45 (m,2H),7.30-7.38(m,6H),7.25-7.30(m,1H),5.63(q,2H).
图2是本发明制备的新型光催化剂的13C-NMR谱图.
实施例2
利用本发明实施例1所得新型钌配合物光催化剂在降解苯基硼酸中的应用。
包括如下步骤:
步骤1:将5.00×10-4mol的苯基硼酸溶解于N,N-二甲基甲酰胺溶液(2ml)中,搅拌至溶解;
步骤2:将1.00×10-5mol的新型光催化剂加入反应体系中,同时将1.00×10-3mol的三乙胺加入反应体系中;
步骤3:打开光化学反应仪中的可见光源(36W荧光灯照射),让苯基硼酸开始在新型光催化剂1的作用下被光催化降解成苯酚;
步骤4:光催化反应开始后,每隔30min从反应中取样做核磁谱图,检测苯基硼酸的降解。最终产率80%。
图3是本发明中降解苯基硼酸后苯酚1H-NMR谱图。
1H NMR(300MHz,CD2Cl2):δ:7.25-7.30(m,2H),6.90-7.00(m,1H),6.80-6.89(m,2H), 5.07(s,1H).
实施例3
利用本发明实施例1所得新型钌配合物光催化剂在催化催化末端炔与重氮盐的偶联反应的应用。包括如下步骤:
步骤1:将2.00×10-3mol的苯乙炔(2)溶解于N,N-二甲基甲酰胺溶液(2ml)中,搅拌至溶解;
步骤2:将1.00×10-5mol的新型光催化剂和5.00×10-5三苯基磷氯化金加入反应体系中,同时将5.00×10-4mol的苯乙炔(2)加入反应体系中;
步骤3:打开光化学反应仪中的蓝光光源(23W荧光灯照射),让苯乙炔(2)和四氟硼酸重氮对甲氧基苯盐(3)开始在新型光催化剂1和三苯基磷氯化金的作用下发生氧化偶联反应。
步骤4:光催化反应开始后,每隔30min从反应中取样做核磁谱图,检测氧化偶联反应。最终产率80%。
图4是本发明中氧化偶联反应的产物的1H-NMR谱图。
1H NMR(300MHz,CD2Cl2):δ:7.50-7.67(m,4H),7.30-7.47(m,3H),6.80-7.90(m,2H), 3.87(s,3H)。
Claims (7)
4.根据权利要求2所述的应用,其特征在于,步骤1中所述的溶剂包括N,N-二甲基甲酰胺溶液、N,N-二甲基乙酰胺、二甲基亚砜中的任意一种。
5.根据权利要求1所述的应用,其特征在于,钌配合物光催化剂在降解苯基硼酸的步骤如下:
步骤1:将苯基硼酸溶解于N,N-二甲基甲酰胺溶液中,搅拌至溶解;
步骤2:将钌配合物光催化剂加入反应体系中,同时加入三乙胺反应;
步骤3:可见光下搅拌反应18-24小时即可完成苯基硼酸的降解。
6.根据权利要求5所述的应用,其特征在于,钌配合物光催化剂苯相对于基硼酸的添加量关系为摩尔比0.01-0.04:1。
7.权利要求1所述的钌配合物光催化剂与三苯基磷氯化金在催化末端炔与重氮盐的偶联反应上的应用,所述的末端炔烃包括苯乙炔、对甲基苯乙炔、对甲氧基苯乙炔、对氯苯乙炔、对溴苯乙炔、正已炔中的任意一种;所述的重氮盐包括四氟硼酸重氮苯盐、四氟硼酸重氮对甲氧基苯盐、四氟硼酸重氮对甲基苯盐中的任意一种。
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