CN113061260B - 一种稀土金属卟啉框架材料及其制备方法与应用方法 - Google Patents
一种稀土金属卟啉框架材料及其制备方法与应用方法 Download PDFInfo
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- CN113061260B CN113061260B CN202110295377.4A CN202110295377A CN113061260B CN 113061260 B CN113061260 B CN 113061260B CN 202110295377 A CN202110295377 A CN 202110295377A CN 113061260 B CN113061260 B CN 113061260B
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- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 Rare earth metal porphyrin Chemical class 0.000 title claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 18
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 25
- 239000003446 ligand Substances 0.000 claims description 23
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical compound CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052693 Europium Inorganic materials 0.000 abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000013078 crystal Substances 0.000 description 54
- 238000005406 washing Methods 0.000 description 27
- 239000012621 metal-organic framework Substances 0.000 description 25
- 239000011521 glass Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000005538 encapsulation Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000010586 diagram Methods 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000982 solution X-ray diffraction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SSZGZNMFUXOAFG-UHFFFAOYSA-N 1-chloro-2-ethylsulfonylethane Chemical compound CCS(=O)(=O)CCCl SSZGZNMFUXOAFG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 1
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002575 chemical warfare agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明提供了一种稀土金属卟啉框架材料及其制备方法与应用，所述稀土金属卟啉框架材料，其通式为M‑HTCPP‑Ln；其中，M为金属铁或者金属钴或者金属镍或者金属锰或者金属锌，Ln为金属镧或者金属铕或者金属钆或者金属铈。本发明提供的稀土金属卟啉框架材料具有优异的催化性能，在一定光照条件下产生大量单线态氧，将硫芥模拟物快速地选择性氧化成绿色环保的亚砜化合物，具有很高的选择性，很好的热稳定性，可以批量放大合成，重复性好，同时合成工艺流程简单，可操作性强，具有广阔的应用前景。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种稀土金属卟啉框架材料及其制备方法与应用方法。
背景技术
芥子油双(2-氯乙基)硫化物(表示为HD)曾作为化学武器广泛用于第一次世界大战后期，HD作为战争毒剂，最显著的毒性就是使接触者皮肤起疱、糜烂并坏死。通过将HD选择性地氧化为亚砜是一种温和且环保的方法。在各种氧化剂中，单线态氧(1O2)尤为突出，是一种温和氧化剂，因此，开发能高效产生1O2以及快速降解HD的新型光催化剂是一项紧迫而又具有挑战性的工作。
金属有机框架材料(Metal-Organic Frameworks,MOFs)是由金属离子和有机配体自组装构成的配位框架材料，此类结构的物质不仅可能同时含有金属和有机配体的特性，还可能含有金属和有机配体均没有的新性能。作为一种新兴由于金属有机框架的结构的可调整性和永久孔隙率，具有广泛的化学和物理特性，在气体存储和分离，药物递送或催化有着广泛的应用。同时，许多基于卟啉的MOFs在一定条件下能产生单线态氧1O2，利用这一特点，它们被用于生物医学以及癌症治疗。对于合成MOF，卟啉的连接基团已有深入的研究。其中，4-5,10,15,20-四(4-羧基苯基)卟啉(H6TCPP)作为多羧酸配体，而稀土离子对硬供体原子和含有氧配体具有高度亲和力，所以稀土卟啉MOF能合成各种各样的结构，同时又具有许多有趣的特性。但目前还没有一种光催化CEES反应效率较好的金属有机框架材料。
发明内容
针对上述背景，本发明的目的在于提供一种稀土金属卟啉框架材料。
本发明另一目的在于提供上述稀土金属卟啉框架材料的制备方法。
本发明再一目的在于提供上述稀土金属卟啉框架材料在光催化氧化硫芥物种的应用。
为实现上述目的，本发明提供如下技术方案：
一种稀土金属卟啉框架材料，其通式为M-HTCPP-Ln，其中，M为金属铁、金属钴、金属镍、金属锰或金属锌，Ln为金属镧、金属铕、金属钆或金属铈。
优选地，当所述M为金属铁，Ln为金属镧时，所述稀土金属卟啉框架材料的分子式为C48H28LaN4FeO10。
一种制备所述稀土金属卟啉框架材料的方法，具体为：将H6TCPP配体、金属盐和镧系金属混合后，再加入DMF和盐酸水溶液，进行加热反应完成后即得到稀土金属卟啉框架材料。
所述H6TCPP、金属盐与镧系金属的摩尔比为0.012：0.01：0.008～0.02；优选为0.012:0.01:0.085～0.012。
所述金属盐为FeCl2·4H2O、CoCl2·4H2O、NiCl2·6H2O、MnCl2·4H2O、ZnCl2·4H2O。
所述镧系金属为La2(C2O4)3·10H2O、Gd2(C2O4)3·10H2O、Eu2(C2O4)3·10H2O、CeCl3·7H2O。
所述H6TCPP与DMF的摩尔体积比为0.012mmol：2～3mL；优选为0.012mmol：2mL；所述H6TCPP与盐酸水溶液的摩尔体积比为0.012mmol：2～3mL；优选为0.012mmol：3mL。
所述加热反应的温度为130～160℃，时间为24～72小时，优选地，所述加热反应的温度为150℃，时间为50小时。
所述稀土金属卟啉框架材料在光催化氧化硫芥物种中的应用。
一种使用所述稀土金属卟啉框架材料光催化氧化硫芥物种的方法，具体为将M-HTCPP-Ln与硫芥物种混合后，置于蓝色LED灯下，进行光催化降解。
与现有成果相比，本发明具有如下有益效果：
1、本发明成功合成的金属有机框架材料，其中，根据单晶衍射表明，金属有机框架材料Fe-HTCPP-La的晶体属于单斜晶系，空间群为C2/c。根据SXRD分析及Fe-HTCPP-La的单晶结构图可知，La是八配位的，与来自四个TCPP配体的羧酸基团的一个O配位，与来自1个H6TCPP配体的羧酸基团的两个O配位，还与两个水分子的O配位，配体H6TCPP金属中心为Fe。晶胞参数为：
α＝γ＝90°，β＝99.642(3)°，
2、本发明提供一套能大量合成新型稀土卟啉MOF的方法，且得到的金属有机框架材料具有很好的热稳定性，可以批量放大合成，重复性好，同时合成工艺流程简单。
3、本发明中，M-HTCPP-Ln材料在一定条件下能快速高效产生单线态氧1O2和超氧阴离子自由基O2 ·—，继而快速氧化硫芥模拟物，具有很高的选择性。
附图说明
图1为实施例1制备的M-HTCPP-Ln的粉末XRD衍射图；
图2为实施例1制备的M-HTCPP-Ln的粉末XRD衍射图；
图3为实施例1制备的M-HTCPP-Ln的粉末XRD衍射图；
图4为实施例1制备的M-HTCPP-Ln的粉末XRD衍射图；
图5为实施例1制备的TCPP-Ln的粉末XRD衍射图；
图6为实施例1制备的Fe-HTCPP-La的热分析图；
图7为实施例1制备的Fe-HTCPP-La的稳定性图；
图8为实施例1制备的Fe-HTCPP-La的框架图；
图9为实施例1制备的Fe-HTCPP-La的框架图；
图10为实施例1制备的Fe-HTCPP-La的框架图；
图11为实施例1制备的Fe-HTCPP-La的框架图；
图12为实施例1制备的Fe-HTCPP-La二氧化碳吸附等温线；
图13为实施例1制备的Fe-HTCPP-La的电子自旋共振谱捕获单线态氧图；
图14为实施例1制备的Fe-HTCPP-La的电子自旋共振谱捕获超氧阴离子自由基图；
图15为实施例1中监测Fe-HTCPP-La作为催化剂时光催化反应的1H NMR图；
图16为实施例2中光催化反应前后的Fe-HTCPP-La的粉末XRD衍射图；
图17为实施例2中光催化反应Fe-HTCPP-La可重复性测试图；
具体实施方式
下面结合具体实施例和附图，对本发明进行详细说明。本发明中H6TCPP的化学名称为4-5,10,15,20-四(4-羧基苯基)卟啉，DMF的化学名称为N，N-二甲基甲酰胺，CEES的化学名称为2-氯乙基乙基硫醚，CEESO的化学名称为1-氯-2-(乙磺酰基)乙烷。
实施例1
Fe-HTCPP-La的制备：
将配体H6TCPP(0.012mmol)、FeCl2·4H2O(0.01mmol)和La2(C2O4)3·10H2O(0.012mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Fe-HTCPP-La。
实施例2
Co-HTCPP-La的制备：
将配体H6TCPP(0.012mmol)、CoCl2·4H2O(0.01mmol)和La2(C2O4)3·10H2O(0.01mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Co-HTCPP-La。
实施例3
Ni-HTCPP-La的制备：
将配体H6TCPP(0.012mmol)、NiCl2·6H2O(0.01mmol)和La2(C2O4)3·10H2O(0.015mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(2mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Ni-HTCPP-La。
实施例4
Mn-HTCPP-La的制备：
将配体H6TCPP(0.012mmol)、MnCl2·4H2O(0.01mmol)和La2(C2O4)3·10H2O(0.015mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(2mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Mn-HTCPP-La。
实施例5
Zn-HTCPP-La的制备：
将配体H6TCPP(0.012mmol)、ZnCl2·4H2O(0.01mmol)和La2(C2O4)3·10H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Zn-HTCPP-La。
实施例6
Fe-HTCPP-Eu的制备：
将配体H6TCPP(0.012mmol)、FeCl2·4H2O(0.01mmol)和Eu2(C2O4)3·10H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Fe-HTCPP-Eu。
实施例7
Fe-HTCPP-Gd的制备：
将配体H6TCPP(0.012mmol)、FeCl2·4H2O(0.01mmol)和Gd2(C2O4)3·10H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Fe-HTCPP-Gd。
实施例8
Ni-HTCPP-Eu的制备：
将配体H6TCPP(0.012mmol)、NiCl2·6H2O(0.01mmol)和Eu2(C2O4)3·10H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Ni-HTCPP-Eu。
实施例9
Ni-HTCPP-Gd的制备：
将配体H6TCPP(0.012mmol)、NiCl2·6H2O(0.01mmol)和Gd2(C2O4)3·10H2O(0.008mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Ni-HTCPP-Gd。
实施例10
Ni-HTCPP-Ce的制备：
将配体H6TCPP(0.012mmol)、NiCl2·6H2O(0.01mmol)和CeCl3·7H2O(0.011mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mLDMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Ni-HTCPP-Ce。
实施例11
Zn-HTCPP-Eu的制备：
将配体H6TCPP(0.012mmol)、ZnCl2·4H2O(0.01mmol)和Eu2(C2O4)3·10H2O(0.0085mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Zn-HTCPP-Eu。
实施例12
Co-HTCPP-Ce的制备：
将配体H6TCPP(0.012mmol)、CoCl2·4H2O(0.01mmol)和CeCl3·7H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(2mL)和0.8N盐酸水溶液(3mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mLDMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为Co-HTCPP-Ce。
对比例1
TCPP-La的制备：
将配体H6TCPP(0.01mmol)和La2(C2O4)3·10H2O(0.009mmol)加入到硬质玻璃管中，然后添加DMF(3mL)和0.8N盐酸水溶液(2mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为TCPP-La。
对比例2
TCPP-Ce的制备：
将配体H6TCPP(0.01mmol)、CeCl3·7H2O(0.012mmol)加入到硬质玻璃管中，然后添加DMF(3mL)和0.8N盐酸水溶液(2mL)，封装后将混合物放在烘箱里加热，在150℃下放置50小时，以5℃/h的速率冷却至室温。开管后，过滤收集晶体，用20mL DMF洗涤3次、20mL甲醇洗涤3次，干燥，即得到金属有机框架材料，记为TCPP-Ce。
对上述实施例制备得到的M-HTCPP-Ln进行了如下表征：
(1)粉末X-射线衍射表征纯度
粉末衍射数据收集在bruker D8 advance衍射仪上完成，仪器的操作电压为40KV，电流为40mA，使用石墨单色化的铜靶X射线(Cu Kα，
)，在5°到50°范围内连续扫描完成。单晶结构粉末衍射谱模拟转化使用Mercury软件。图1-4为M-HTCPP-Ln的粉末衍射图，图5为TCPP-Ln的粉末衍射图，从图1-5可知，合成的M-HTCPP-Ln(M＝Fe,Co,Ni,Mn,Zn,Ln＝La,Eu,Gd,Ce)、TCPP-Ln(Ln＝La,Ce)分别与模拟的M-HTCPP-Ln、TCPP-Ln出峰位置相吻合，证明本申请已成功合成出了M-HTCPP-Ln和TCPP-Ln。
(2)热稳定性分析及化学稳定性分析
为了验证本发明制备的M-HTCPP-Ln具备很好的热稳定性和化学稳定性，在METTLER TOLEDO TGA 2上完成热重分析测试。见图6，从图中可知，M-HTCPP-Ln在400℃后骨架开始分解，表明M-HTCPP-Ln具有比较高的热稳定性。图7给出了本发明制备的Fe-HTCPP-La在各种常见溶剂和水中浸泡3d后的PXRD衍射图，从图7中可知材料有良好的溶剂稳定性和水稳定性。
(3)晶体结构的测定
在显微镜下选取合适大小的单晶，其中，选取Fe-HTCPP-La的单晶，在日本理学公司的XtaLab PRO单晶X-射线衍射仪上进行(Cu Kα，
)，射线通过石墨单色器单色。数据处理使用衍射仪的程序CrysAlisPro.1；结构使用直接法解出初始模型，然后用基于F2的最小二乘法精修结构。所有的非氢原子都进行各项异性精修，用理论加氢的方法确定氢原子的位置。客体分子处于高度无序状态，使用PLATON软件的SQEEZE程序处理。
实施例制得的Fe-HTCPP-La的晶体属于单斜晶系，空间群为C2/c。根据SXRD分析及Fe-HTCPP-La的单晶结构图如图8-11可知，La是八配位的，与来自四个TCPP配体的羧酸基团的一个O配位，与来自1个TCPP配体的羧酸基团的两个O配位，还与两个水分子的O配位，配体TCPP金属中心为Fe。晶胞参数为：
α＝γ＝90°，β＝100.428(2)°，
Fe-HTCPP-La的晶体学衍射点数据收集与结构精修的部分参数如表1所示。
表1 Fe-HTCPP-La的晶体学数据
aR1＝∑(||F0|-|Fc||)/∑|F0|；bwR2＝[∑w(F0 2-Fc 2)2/∑w(F0 2)2]1/2
图12为Fe-HTCPP-La二氧化碳吸附等温线，从图中可知，Fe-HTCPP-L具有一般的比表面积(BET＝270.4cm2 g-1)和孔隙率。
应用实施例M-HTCPP-Ln用于光催化氧化硫芥模拟物
(1)将获得的晶体用DMF和甲醇分别洗涤三次，浸泡在甲醇溶液中，每天交换溶液三次，三天后过滤M-HTCPP-Ln并将其置于真空干燥箱中80℃活化12h以除去材料中的客体分子。(2)M-HTCPP-Ln(2.0mg，0.2mmol)分散在密封玻璃反应器中加入0.5mL MeOH。用氧气吹扫15min后，添加向玻璃反应器中添加CEES(0.2mmol)和0.5mL MeOH。密封后，将其暴露在蓝色LED灯下，反应一段时间后，用注射器吸取反应液，并用有机相的滤头过滤反应液，并通过气相-质谱联用仪测试进行监测测量，测试是在德国Agilent公司7890B气相-质谱联用仪上完成的，检测器为FID，载气为氦气、流速为1mL/min，进样器温度为250℃、AUX-2温度为250℃、离子源为230℃、四极杆为150℃、柱温为300℃。测试结果显示如图15，在反应0min时，体系中只有CEES；在反应5min时，反应体系中CEES已完全选择性转化为CEESO。
表2催化剂催化CEES反应的在不同条件下的催化时间
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。
Claims (9)
1.一种稀土金属卟啉框架材料，其特征在于：所述稀土金属卟啉框架材料通式为M-HTCPP -Ln，其中，M为金属铁，Ln为金属镧，所述稀土金属卟啉框架材料的分子式为C48H28LaN4FeO10。
2.一种如权利要求1所述的稀土金属卟啉框架材料的制备方法，其特征在于，包括如下步骤：将H6TCPP配体、金属盐和镧系金属混合后，再加入DMF和盐酸水溶液，进行加热反应完成后即得到稀土金属卟啉框架材料。
3.根据权利要求2所述的方法，其特征在于：所述TCPP、金属盐与镧系金属的摩尔比为0.012：0.01：0.008~0.02。
4.根据权利要求2所述的方法，其特征在于：所述TCPP、金属盐与镧系金属的摩尔比为0.012：0.01：0.085~0.012。
5.根据权利要求2所述的方法，其特征在于：所述金属盐为FeCl2·4H2O，所述镧系金属为La2(C2O4)3·10H2O。
6.根据权利要求2所述的方法，其特征在于：所述H6TCPP与DMF的摩尔体积比为0.012mmol：2~3mL；所述H6TCPP与盐酸水溶液的摩尔体积比为0.01 2mmol：2~3 mL。
7.根据权利要求2所述的方法，其特征在于：所述加热反应的温度为130~160℃，时间为24~72小时。
8.权利要求1所述稀土金属卟啉框架材料在光催化氧化2-氯乙基乙基硫醚中的应用。
9.一种使用权利要求1所述稀土金属卟啉框架材料催化氧化2-氯乙基乙基硫醚的方法，其特征在于具体为：将M-HTCPP-Ln与2-氯乙基乙基硫醚混合后，置于蓝色LED灯下，进行光催化降解。
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