CN112194687B - 一种以醚键桥联型双吡啶羧酸为配体的金属镍配合物及其合成方法与光催化应用 - Google Patents
一种以醚键桥联型双吡啶羧酸为配体的金属镍配合物及其合成方法与光催化应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 49
- 239000003446 ligand Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- OQVVVVYHNKQXHR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1C1=CC=CC=N1 OQVVVVYHNKQXHR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- DIEMCUFYSOEIDU-UHFFFAOYSA-N 6-fluoropyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(F)=N1 DIEMCUFYSOEIDU-UHFFFAOYSA-N 0.000 claims abstract description 24
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- -1 bipyridine carboxylic acid Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004729 solvothermal method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明涉及金属有机配合物光功能材料技术领域，公开了一种以醚键桥联型双吡啶羧酸为配体的金属镍配合物及其合成方法与应用。该以醚键桥联型双吡啶羧酸为配体的金属镍配合物的分子式为C12H10N2NiO7·2(H2O)，其合成方法为：将2‑氟吡啶‑6‑甲酸与六水合氯化镍(NiCl2·6H2O)在溶剂热条件下由二分子配体2‑氟吡啶‑6‑甲酸转化合成醚键型配体，再与镍配位反应得到深蓝色的块状晶体。本发明所得以醚键桥联型双吡啶羧酸为配体的金属镍配合物合成方法创新、结构新颖，而且具有一定的光催化效果，可作为一种廉价光催化剂，将二氧化碳催化还原为一氧化碳。本发明操作方法简单，在光催化还原二氧化碳方面具有潜在的应用价值。
Description
技术领域
本发明涉及金属配位化合物功能材料技术领域，尤其涉及一种以醚键桥联型双吡啶羧酸为配体的金属镍配合物及其合成方法与光催化应用。
背景技术
一方面，随着工业技术的发展，化石燃料的燃烧，CO2排放量日益增长，另一方面，绿色植被的减少，致使CO2的吸收量减小， CO2气体增多，进而引起了温室效应、全球气候变暖等一系列问题。如何有效收集并利用CO2，已成为各科研人员研究的主题。将CO2还原为有机化合物这一构想，在某种程度上解决CO2的排放所带来问题。为完成这一构想，可以利用可见光催化还原CO2，获得如CO、HCOOH、CH3OH等化合物。光催化体系中最重要的是光催化剂，传统的光催化剂是价格昂贵的贵金属配合物，而非贵金属配合物应用于光催化还原二氧化碳的研究目前还鲜有报道。因此，合成新型的镍醚键配合物作为光催化剂具有一定的应用价值。2-氟吡啶-6-甲酸结构独特，有3个配位点，配位能力较强，能与镍离子配位生成结构稳定的配合物。此外，金属镍及化合物非常廉价，应用于光催化在经济上是可行的。
发明内容
有鉴于此，本发明为克服上述现有技术所述的至少一种不足，提供一种结构新颖、价格低廉的金属配位化合物——以醚键桥联型双吡啶羧酸为配体的金属镍配合物以醚键桥联型双吡啶羧酸为配体的金属镍配合物，可作为催化剂应用于光催化还原二氧化碳。
本发明采用下述技术方案：
本发明首先提供以醚键桥联型双吡啶羧酸为配体的金属镍配合物，其分子式为C12H10N2NiO7·2(H2O)。
进一步地，其结构式为
。
进一步地，其形态为固态晶体，属于正交晶系，空间群为Pbca，晶胞参数为：a=19.2026 (9) Å、b=7.0859 (4) Å、c=21.9775 (11) Å，α=β=γ=90°，V=2990.4 (3) Å3。
所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物由2-氟吡啶-6-甲酸与六水合氯化镍（NiCl2·6H2O）通过溶剂热反应合成得到。
本发明其次提供上述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法：将2-氟吡啶-6-甲酸与六水合氯化镍（NiCl2·6H2O）在溶剂热反应下由二分子配体2-氟吡啶-6-甲酸转化合成醚键型配体，再与镍配位反应得到深蓝色的块状晶体。
上述合成方法包括如下步骤：
S1. 用溶剂将2-氟吡啶-6-甲酸和六水合氯化镍溶解得到透明的混合液；
S2. 将步骤S1所得混合液密封后进行溶剂热反应，反应结束后缓慢冷却到室温，得到深蓝色的块状晶体；
S3. 洗涤步骤S2所得晶体，自然晾干，即得所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
以下是上述合成方法的优选方案：
步骤S1中，2-氟吡啶-6-甲酸和六水合氯化镍的摩尔比为1:1；溶剂为乙醇和水。
步骤S2中，溶剂热反应在120℃~140℃下进行，反应时间为48~96h；冷却的速度为5℃/h。
步骤S3中，用乙醚洗涤干燥步骤S2所得晶体。
本发明最后提供上述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的应用，具体将该以醚键桥联型双吡啶羧酸为配体的金属镍配合物应用作为光催化剂，尤其作为二氧化碳还原成一氧化碳的光催化剂。
本发明与现有技术相比较有如下有益效果：
首先，本发明利用了2-氟吡啶-6-甲酸多配位点的特点，与镍离子形成稳定的配位化合物。
其次，本发明采用廉价的镍为原料，降低了催化剂的制备成本。
第三，本发明所选用的催化剂能有效地把二氧化碳还原为一氧化碳，避免使用贵金属配位化合物作为催化剂。
第四，本发明所选用的催化剂稳定性好。
最后，本发明的合成方法上：采用溶剂热反应法，操作简单。
附图说明
图1是以醚键桥联型双吡啶羧酸为配体的金属镍配合物的晶体结构单元示意图。
图2是以醚键桥联型双吡啶羧酸为配体的金属镍配合物作为光催化剂还原二氧化碳的产物的气相色谱图。该图表明在使用以醚键桥联型双吡啶羧酸为配体的金属镍配合物为催化剂时，二氧化碳还原为一氧化碳随光照时间变化的转换数图。
图3是以以醚键桥联型双吡啶羧酸为配体的金属镍配合物为催化剂还原二氧化碳为一氧化碳的气相色谱图。
具体实施方式
首先，本发明采用廉价的镍为原料，利用2-氟吡啶-6-甲酸多配位点、能与镍离子
形成稳定配位的特点，提出一种晶体结构新颖的化合物——以醚键桥联型双吡啶羧酸为配
体的金属镍配合物，其分子式为C12H10N2NiO7·2(H2O)；结构式为
；
其形态为固态晶体，属于正交晶系，空间群为Pbca，晶胞参数为：a=19.2026 (9)Å、b=7.0859 (4) Å、c=21.9775 (11) Å，α=β=γ=90°，V=2990.4 (3) Å3。
该以醚键桥联型双吡啶羧酸为配体的金属镍配合物由2-氟吡啶-6-甲酸与六水合氯化镍（NiCl2·6H2O）通过溶剂热反应合成得到。
其次，本发明采用溶剂热反应法合成上述以醚键桥联型双吡啶羧酸为配体的金属镍配合物：将2-氟吡啶-6-甲酸与六水合氯化镍（NiCl2·6H2O）在溶剂热反应下由二分子配体2-氟吡啶-6-甲酸转化合成醚键型配体，再与镍配位反应得到深蓝色的块状晶体。具体步骤包括：
S1. 用溶剂将2-氟吡啶-6-甲酸和六水合氯化镍溶解得到透明的混合液；
S2. 将步骤S1所得混合液密封后进行溶剂热反应，反应结束后缓慢冷却到室温，得到深蓝色的块状晶体；
S3. 洗涤步骤S2所得晶体，自然晾干，即得所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
优选地，步骤S1中，2-氟吡啶-6-甲酸和六水合氯化镍的摩尔比为1:1；溶剂为乙醇和水。步骤S2中，溶剂热反应在120~140℃下进行，反应时间为48~96h；冷却的速度为5℃/h。步骤S3中，用乙醚洗涤步骤S2所得晶体。
最后，本发明给出将上述以醚键桥联型双吡啶羧酸为配体的金属镍配合物作为光催化剂的应用，尤其作为二氧化碳还原成一氧化碳的光催化剂。
为了让本领域的技术人员更好地理解本发明的技术方案，下面结合具体实施例对本发明做进一步阐述。
实施例1
将14.2mg(0.1mmol) 2-氟吡啶-6-甲酸溶于4ml乙醇中，之后加入23.8mg(0.1mmol) 六水合氯化镍混合，再加入2ml水，并超声震荡溶解。所得混合液密封后，于120℃下进行溶剂热反应，反应48h之后，以每小时5℃的速度冷却到室温，得到深蓝色块状透明晶体，用乙醚洗涤，即制得以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
实施例2
将14.2mg(0.1mmol) 2-氟吡啶-6-甲酸溶于4ml乙醇中，之后加入23.8mg(0.1mmol) 六水合氯化镍混合，再加入2ml水，并超声震荡溶解。所得混合液密封后，于120℃下进行溶剂热反应，反应72h之后，以每小时5℃的速度冷却到室温，得到深蓝色块状透明晶体，用乙醚洗涤，即制得以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
实施例3
将14.2mg(0.1mmol) 2-氟吡啶-6-甲酸溶于4ml乙醇中，之后加入23.8mg(0.1mmol) 六水合氯化镍混合，再加入2ml水，并超声震荡均匀。所得混合液密封后，于120℃下进行溶剂热反应，反应96h之后，以每小时5℃的速度冷却到室温，得到深蓝色块状透明晶体，用乙醚洗涤，即制得以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
实施例4
将14.2mg(0.1mmol) 2-氟吡啶-6-甲酸溶于4ml乙醇中，之后加入23.8mg(0.1mmol) 六水合氯化镍混合，再加入2ml水，并超声震荡均匀。所得混合液密封后，于130℃下进行溶剂热反应，反应96h之后，以每小时5℃的速度冷却到室温，得到深蓝色块状透明晶体，用乙醚洗涤，即制得以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
实施例5
将14.2mg(0.1mmol) 2-氟吡啶-6-甲酸溶于4ml乙醇中，之后加入23.8mg(0.1mmol) 六水合氯化镍混合，再加入2ml水，并超声震荡均匀。所得混合液密封后，于140℃下进行溶剂热反应，反应96h之后，以每小时5℃的速度冷却到室温，得到深蓝色块状透明晶体，用乙醚洗涤，，即制得以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
测试方法：
将制得的以醚键桥联型双吡啶羧酸为配体的金属镍配合物在Rigaku R-AXISSPIDER 衍射仪上完成单晶衍射测试，测试结果如图1。可见，本发明合成得到一种新的化合物，其结构新颖。
将制得的以醚键桥联型双吡啶羧酸为配体的金属镍配合物作为光催化剂应用于二氧化碳的还原反应，反应产物在SHIMADZU GC-2014C进行气相色谱测试，结果如图2和图3所示。
可见，本发明合成得到一种新的化合物，不仅结构新颖，而且具有一定的光催化效果，可作为一种廉价光催化剂，将二氧化碳催化还原为一氧化碳。本发明操作方法简单，在光催化还原二氧化碳方面具有潜在的应用价值。
显然，本发明的上述实施例仅是为了详细说明本发明所作的举例，并非是对本发明的实施方式的限定。对于所属领域的研究人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方案予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (8)
1.以醚键桥联型双吡啶羧酸为配体的金属镍配合物，其分子式为C12H10N2NiO7·2(H2O)，其结构式为：
2.根据权利要求1所述的以醚键桥联型双吡啶羧酸为配体的金属镍配合物，其特征在于，形态为固态晶体，属于正交晶系，空间群为Pbca，晶胞参数为：a=19.2026 (9) Å、b=7.0859 (4) Å、c=21.9775 (11) Å，α=β=γ=90°，V=2990.4 (3) Å3。
3.一种如权利要求1~2任一项所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法，其特征在于，将2-氟吡啶-6-甲酸与六水合氯化镍在溶剂热反应下由二分子配体2-氟吡啶-6-甲酸转化合成醚键型配体，再与镍配位反应得到深蓝色的块状晶体。
4.根据权利要求3所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法，其特征在于，包括如下步骤：
S1. 用溶剂将2-氟吡啶-6-甲酸和六水合氯化镍溶解得到透明的混合液；
S2. 将步骤S1所得混合液密封后进行溶剂热反应，反应结束后缓慢冷却到室温，得到深蓝色的块状晶体；
S3. 洗涤步骤S2所得晶体，即得所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的单晶样品。
5.根据权利要求4所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法，其特征在于，步骤S1中，2-氟吡啶-6-甲酸和六水合氯化镍的摩尔比为1:1；溶剂为乙醇和水。
6.根据权利要求4所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法，其特征在于，步骤S2中，在120℃~140℃下进行溶剂热反应，反应时间为48h~96h；冷却的速度为5℃/h。
7.根据权利要求4所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物的合成方法，其特征在于，步骤S3中，用乙醚洗涤步骤S2所得晶体。
8.一种如权利要求1~2任一项所述以醚键桥联型双吡啶羧酸为配体的金属镍配合物作为光催化剂的应用，其特征在于，以醚键桥联型双吡啶羧酸为配体的金属镍配合物作为二氧化碳还原成一氧化碳的光催化剂。
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