CN112939854B - 铁羟基吡啶羧酸配合物及其合成方法与光催化还原二氧化碳制一氧化碳应用 - Google Patents
铁羟基吡啶羧酸配合物及其合成方法与光催化还原二氧化碳制一氧化碳应用 Download PDFInfo
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- -1 Iron hydroxypyridine carboxylic acid Chemical compound 0.000 title claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 35
- VRCWSYYXUCKEED-UHFFFAOYSA-N 6-Hydroxypicolinic acid Chemical compound OC(=O)C1=CC=CC(=O)N1 VRCWSYYXUCKEED-UHFFFAOYSA-N 0.000 claims abstract description 19
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000004729 solvothermal method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
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- 238000007789 sealing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
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- 239000008204 material by function Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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Abstract
本发明涉及金属配位化合物功能材料技术领域,公开了铁羟基吡啶羧酸配合物及其合成方法与光催化还原二氧化碳制一氧化碳应用。该铁羟基吡啶羧酸配合物,其分子式为C12H12FeN2O8,合成方法为:6‑羟基吡啶‑2‑羧酸与六水合三氯化铁在溶剂热条件下合成,得到黄色块状晶体。本发明所得配合物可作为一种廉价光催化剂,把二氧化碳催化转变为一氧化碳且催化效果较好。本发明制备工艺简单,方便易实施,产物纯度和产率均较高,在光催化还原二氧化碳方面具有良好的应用前景。
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,更具体地,涉及铁羟基吡啶羧酸配合物及其合成方法与光催化还原二氧化碳制一氧化碳应用。
背景技术
当前,工业极速发展、化石能源消耗量急剧增加导致CO2排放量日益增加,最终导致大气中CO2含量增多,进而造成引起全球关注的温室效应、全球气候变暖、沙漠化及海洋酸化等一系列现象。因此,如何有效收集利用CO2,减少大气中CO2含量已成为全球经济发展的重要战略目标之一。光催化将二氧化碳还原为有价值的燃料是一种有希望减少全球变暖和增加能源供应的途径。可通过光催化将CO2还原为CO、HCOOH、CH4等燃料。寻找光催化还原CO2的催化剂是关键,已报道的传统的光催化系统中催化剂材料大多为价格昂贵的贵金属配合物,但利用非贵金属配合物应用于光催化还原二氧化碳的研究是目前致力研究的热点,因此,制备的该类新型的铁羟基配合物作为催化剂具有很大的潜在价值。金属铁廉价易得再加上6-羟基吡啶-2-羧酸的良好配位能力有利于合成结构新颖的铁配位化合物。
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,提供价格低廉的金属配位化合物——铁羟基吡啶羧酸配合物。
为了解决上述存在的技术问题,本发明采用下述技术方案:
本发明第一方面提供铁羟基吡啶羧酸配合物,其分子式为C12H12FeN2O8,结构式为
本发明第二方面提供第一方面所述铁羟基吡啶羧酸配合物的合成方法:使6-羟基吡啶-2-羧酸与六水合三氯化铁在溶剂热条件下合成,得到黄色块状晶体。
上述合成方法具体包括如下步骤:
S1.将6-羟基吡啶-2-羧酸与六水合三氯化铁,超声震荡20min溶于溶剂中得到混合液;
S2.将步骤S1所得混合液置于反应容器密封后进行溶剂热反应,反应结束后缓慢冷却到室温析出黄色块状晶体;
S3.洗涤步骤S2所得黄色块状晶体,自然晾干,即制得该配合物的单晶样品。
以下是上述合成方法的优选方案:
步骤S1中,6-羟基吡啶-2-羧酸与六水合三氯化铁的摩尔比为1:1,所述溶剂为乙醇与蒸馏水的混合溶剂。
步骤S2中,所述溶剂热反应的反应温度为120~140℃,反应时间为72~96小时,更优选为84~96小时;冷却的速度为10℃/h。
步骤S3中,用乙醚洗涤步骤S2所得黄色块状晶体。
本发明第三方面提供第一方面所述铁羟基吡啶羧酸配合物或第二方面所述方法合成的铁羟基吡啶羧酸配合物的应用,该配合物作为催化剂应用于光催化还原二氧化碳,将二氧化碳还原成一氧化碳。
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6-羟基吡啶-2-羧酸多配位点的特点,达到与铁离子形成配位化合物的目的。
其次,本发明采用廉价的铁盐为原料,降低了催化剂的制备成本。
再者,本发明所合成的催化剂稳定性好,能有效地把二氧化碳还原为一氧化碳,避免使用昂贵的贵金属配位化合物作为催化剂。
最后,本发明采用溶剂热的方法,简单易行,而且产品纯度高。
附图说明
图1是铁羟基吡啶羧酸配合物的晶体结构单元示意图。
图2是铁羟基吡啶羧酸配合物的XRD图。
图3是铁羟基吡啶羧酸配合物作为催化剂催化还原二氧化碳过程中产物一氧化碳的转化数随光照时间变化图。
图4是铁羟基吡啶羧酸配合物作为催化剂将二氧化碳还原为一氧化碳的气相色谱图。
具体实施方式
首先,本发明采用廉价的铁盐为原料,同时利用6-羟基吡啶-2-羧酸多配位点的特点与铁离子配位,合成结构新颖、价格低廉的配位化合物——铁羟基吡啶羧酸配合物,其分子式为C12H12FeN2O8,结构式为
其次,该配合物由6-羟基吡啶-2-羧酸与六水合三氯化铁在溶剂热条件下合成。在溶剂热条件下,两分子6-羟基吡啶-2-羧酸同时进攻一分子铁离子,配位生产黄色块状晶体。具体步骤如下:
S1.将摩尔比为1:1的6-羟基吡啶-2-羧酸与六水合三氯化铁,超声震荡20min溶于乙醇与蒸馏水的混合溶剂中得到混合液;
S2.将步骤S1所得混合液置于反应容器密封后进行溶剂热反应,反应温度为120~140℃,反应时间为72~96小时、更优选为84~96小时;反应结束后以10℃/h的速度缓慢冷却到室温析出黄色块状晶体;
S3.用乙醚洗涤步骤S2所得黄色块状晶体,自然晾干,即制得该配合物的单晶样品。
最后,该配合物在光催化方面的应用上有潜在的应用价值,尤其作为二氧化碳还原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0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在120℃下进行溶剂热反应,反应72小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例2
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在130℃下进行溶剂热反应,反应72小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例3
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在120℃下进行溶剂热反应,反应96小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例4
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在130℃下进行溶剂热反应,反应96小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例5
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在140℃下进行溶剂热反应,反应84小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例6
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在135℃下进行溶剂热反应,反应84小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
实施例7
将0.0139g(0.1mmol)6-羟基吡啶-2-羧酸与0.0270g(0.1mmol)六水合三氯化铁加入到3mL乙醇中,然后加入1mL水,超声震荡溶解。所得混合液密封后,在125℃下进行溶剂热反应,反应96小时之后,以每小时10℃的速度冷却到室温,得到黄色透明晶体,用乙醚洗涤,自然晾干,即制得铁羟基吡啶羧酸配合物的单晶样品。
测试方法:
将得到的晶体在Agilent Gemini E仪器上完成单晶X射线衍射测试,得到结构如图1。
将合成的铁羟基吡啶羧酸配合物在Rigaku R-AXIS SPIDER衍射仪上完成单晶衍射测试,测试结果如图2所示。由图可知,本发明合成的配合物,结构新颖。
将合成的铁羟基吡啶羧酸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3和图4所示。图3示出了铁羟基吡啶羧酸配合物催化还原二氧化碳过程中一氧化碳的转化数随光照时间变化的情况,表明随着光照时间的延长,一氧化碳的转化数增加。
可见,本发明合成的铁羟基吡啶羧酸配合物,不仅结构新颖,而且具有一定的光催化效果,可以在光催化系统中作为催化剂,将二氧化碳还原为一氧化碳。而且,本发明操作简单,在光催化方面有潜在的应用价值。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,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式予以穷举。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 (10)
3.如权利要求1或2任一项所述铁羟基吡啶羧酸配合物的合成方法,其特征在于,6-羟基吡啶-2-羧酸与六水合三氯化铁在溶剂热条件下合成,得到黄色块状晶体。
4.根据权利要求3所述的铁羟基吡啶羧酸配合物合成方法,其特征在于,包括如下步骤:
S1.将6-羟基吡啶-2-羧酸与六水合三氯化铁溶于溶剂中得到混合液;
S2.将步骤S1所得混合液置于反应容器密封后进行溶剂热反应,反应结束后缓慢冷却到室温析出黄色块状晶体;
S3.洗涤步骤S2所得黄色块状晶体,自然晾干,即制得该配合物的单晶样品。
5.根据权利要求4所述的铁羟基吡啶羧酸配合物合成方法,其特征在于,步骤S1中,6-羟基吡啶-2-羧酸与六水合三氯化铁的摩尔比为1:1,和/或所述溶剂为乙醇与蒸馏水的混合溶剂。
6.根据权利要求4所述的铁羟基吡啶羧酸配合物合成方法,其特征在于,步骤S2中,所述溶剂热反应的反应温度为120~140℃,反应时间为72~96小时。
7.根据权利要求4所述的铁羟基吡啶羧酸配合物合成方法,其特征在于,步骤S2中,冷却的速度为10℃/h。
8.根据权利要求4所述的铁羟基吡啶羧酸配合物合成方法,其特征在于,步骤S3中,用乙醚洗涤步骤S2所得黄色块状晶体。
9.如权利要求1或2所述铁羟基吡啶羧酸配合物或权利要求3~8任一项所述方法合成的铁羟基吡啶羧酸配合物的应用,其特征在于,该配合物作为催化剂应用于光催化还原二氧化碳。
10.根据权利要求9所述铁羟基吡啶羧酸配合物的应用,其特征在于,将二氧化碳还原成一氧化碳。
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