CN114621453B - 一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料的制备及应用 - Google Patents
一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料的制备及应用 Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 51
- 239000003446 ligand Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 28
- -1 pyridine carboxylic acid porphyrin Chemical compound 0.000 title claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims abstract description 15
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
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- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 11
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
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Abstract
一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料的制备及应用,属于晶态材料的技术领域。化学分子式为[Zr3(DPTC)],DPTC为有机配体5',5””‑(10,20‑二(吡啶‑4‑基)‑5,15‑二基)双([1,1':3',1”‑三苯基]‑4,4'‑二羧酸)卟啉。该金属‑有机框架的合成为封闭条件下,有机配体5',5””‑(10,20‑二(吡啶‑4‑基)‑5,15‑二基)双([1,1':3',1”‑三苯基]‑4,4'‑二羧酸)卟啉(DPTC)与氯化锆在N,N‑二甲基甲酰胺和苯甲酸的混合溶液中,经由溶剂热反应得到金属有机框架材料的晶体;此金属有机框架材料显示出光催化二氧化碳选择性还原成一氧化碳方面的应用。
Description
技术领域
本发明属于晶态材料的技术领域,技术涉及金属-有机配位聚合物材料,特征是一种锆的金属-有机框架材料的合成方法及其应用研究。
背景技术
金属-有机框架材料(Metal-Organic Frameworks,MOFs)是一种由金属离子或金属簇与有机配体通过配位键连接而形成的一种有机无机杂化多孔晶态材料,具有较大的比表面积和孔道,同时结构也易于实现剪裁。近十几年MOFs材料在催化、吸附、分离、传感等领域得到了较大发展。
MOFs材料的多孔性与大比表面积的特点决定了其在吸附及光催化二氧化碳还原领域具有良好的应用前景,其中卟啉MOFs的表现尤为突出。金属卟啉化合物在自然界的生命体中起着非常重要的作用,比如光的捕获、氧气的传输以及催化。将卟啉作为有机配体固定在MOFs框架中,不仅使MOFs具备了卟啉的固有特性,有效拓宽MOFs的可见光吸收光谱,而且将卟啉嵌入MOFs中具有易分离、可循环使用、不会发生卟啉自聚的优点。同时,稳定的双功能卟啉MOFs可以在不同领域有应用,这将大大拓宽MOFs的应用范围。因此基于卟啉配体构筑的MOFs越来越多的受到人们广泛的研究。
发明内容
本发明的目的在于提供一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料的制备及其应用。
本发明的一种三维卟啉基金属-有机框架材料,其特征在于,是由金属锆和双功能卟啉配体构成的金属-有机框架材料,化学分子式为[Zr3(DPTC)],H4DPTC为有机配体5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉,其结构式如下所示:
在该金属-有机框架中,DPTC配体呈现的是四面体构型,所连的金属簇为Zr6簇,具有D4h对称性,该金属簇是由六个锆原子通过氧原子连接而形成的Zr6八面体,其中三角面由8个μ3-O基团覆盖,Zr6簇与来自八个不同DPTC配体上的氧配位,但是吡啶基团上的N并没有参与配位;在该金属-有机框架中,Zr-O键的键长都是卟啉配体与Zr6簇相互连接,在a轴方向形成的六边形和菱形通道对应的对角线长度大约是/>和/>
从拓扑学角度看,每个DPTC配体都可以看作具有四面体构型的4-连接的节点,与此同时Zr6簇可以看作是8-连接的顶点,这两种类型的结构单元交替连接形成了一个经典的(4,8)-连接的flu拓扑网络。
该配体包含一个卟啉环,两个吡啶基团和四个羧酸基团;吡啶基团与卟啉环直接相连,配体中相邻的两个羧基夹角为119°。
本发明新型的有机配体5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉配体的合成方法,包括以下步骤:
(a)二(1H-吡咯-2-基)甲烷(3)的形成:多聚甲醛和新蒸吡咯,加入三氟乙酸,密封、惰性气体保护,加热反应完成后,加入氢氧化钠,纯化后得到二(1H-吡咯-2-基)甲烷(3);
(b)5'-甲酰基-[1,1':3',1”-三苯基]-4,4'-二羧酸二甲酯(6)的制备:将3,5-二溴苯甲醛,4-甲氧羰基苯硼酸,碳酸钠,Pd(PPh3)4放入甲醇溶液中,惰性气体保护,加热反应后抽滤即可得到所需的醛;
(c)5',5”'-(5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)的合成:将二(1H-吡咯-2-基)甲烷(3)和5'-甲酰基-[1,1':3',1”-三苯基]-4,4'-二羧酸二甲酯(6)溶解在二氯甲烷中,惰性气体保护下加入三氟乙酸,黑暗条件下反应,加入二氯二氰基苯醌,继续反应后,纯化即可得到产物;
优选每13.68mmol5'-甲酰基-[1,1':3',1”-三苯基]-4,4'-二羧酸二甲酯(6)对应二(1H-吡咯-2-基)甲烷(3)13.68mmol、三氟乙酸10.00mmol、二氯二氰基苯醌13.22mmol。
(d)5',5””-(10,20-二溴-5,15-二基)双([1,1':3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)的合成:将5',5”'-(5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)和N-溴代丁二酰亚胺溶于三氯甲烷,室温反应四天。
(e)卟啉环上上吡啶(9):将5',5””-(10,20-二溴-5,15-二基)双([1,1':3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)和4-吡啶硼酸,碳酸钾,Pd(PPh3)4溶于二氧六环和水的混合溶液中,惰性气体保护下,100℃加热反应12小时;
(f)5”'-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(9)的制备:将卟啉环上上吡啶(9):将5',5””-(10,20-二溴-5,15-二基)双([1,1':3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)和氢氧化钠在四氢呋喃/甲醇/水的混合溶液中加热回流得到最终产物。
本发明金属-有机框架材料的合成方法,包括以下步骤:
密封条件下,5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉(H4DPTC)与氯化锆(ZrCl4)在N,N-二甲基甲酰胺(DMF)和苯甲酸的混合溶液中,经由溶剂热反应得到该金属-有机框架的晶体。
进一步优选有机配体5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉(H4DPTC)与氯化锆(ZrCl4)的摩尔比为1:(1~5),每0.05mmol的氯化锆对应1mL~4mL的DMF,0.05g~4g的苯甲酸,热反应的温度为80-160℃,反应时间为12-168小时。
本发明所得一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料,既可以用于吸附二氧化碳,也可以用于二氧化碳光催化还原制备一氧化碳。
本发明所合成的有机配体属于新型的双功能吡啶羧酸卟啉羧酸配体。本发明构筑的金属-有机框架具有较大的一维通道和未配位的吡啶基团,使得该MOFs在二氧化碳光催化还原方面具有潜在应用。
附图说明
图1为合成该金属-有机框架的双功能吡啶羧酸卟啉配体的合成路线图。
图2为该金属-有机框架的次级构筑单元图,(a)对应锆的配位环境图,(b)对应的配体。
图3为该金属-有机框架的三维结构示意图。
图4为该金属-有机框架材料的(a)二氧化碳吸附等温线图及(b)二氧化碳光催化还原产生一氧化碳图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1:
在氮气保护下将多聚甲醛(100.00mmol),三氟乙酸(5mL)以及吡咯(1000mL)加入到2L圆底烧瓶中,将该反应体系在80℃条件下搅拌8小时。反应完成后,加入氢氧化钠(50mmol),将过量的吡咯旋出。粗产物通过柱层析法纯化,浓缩后得到5.9g白色固体二(1H-吡咯-2-基)甲烷(3)(产率为62%)。
实施例2:
将3,5-二溴苯甲醛(22.36mmol),4-甲氧羰基苯硼酸(38.53mmol),碳酸钠(24.36mmol),Pd(PPh3)4(0.75mmol)及600mL甲醇加入到1L圆底烧瓶中,将该混合物在氮气保护下80℃反应12小时。反应完成后将反应体系抽滤,用乙醇洗涤(200mL×2),将抽滤得到的固体溶解在三氯甲烷(500mL)中,依次用水(500mL×2)和饱和食盐水(500mL)洗涤,旋干后即可得到7.6g白色产物5'-甲酰基-[1,1':3',1”-三苯基]-4,4'-二羧酸二甲酯(6)(产率为91%)。
实施例3:
将二(1H-吡咯-2-基)甲烷(3)(13.68mmol),5'-甲酰基-[1,1':3',1”-三苯基]-4,4'-二羧酸二甲酯(6)(13.68mmol)溶解在2L二氯甲烷中,氮气保护下加入三氟乙酸(10.00mmol),黑暗条件下反应10小时后,加入二氯二氰基苯醌(13.22mmol),4小时后将反应体系旋干,残余物溶解在三氯甲烷(500mL)中,依次用水(500mL×3)和饱和食盐水(500mL)洗涤,经无水Na2SO4干燥后过滤、浓缩。粗产物通过柱层析法(SiO2,二氯甲烷/乙酸乙酯=40:1~20:1)纯化,浓缩后得到1.8g紫色固体5',5”'-(5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)(产率为13%)。1H NMR(CDCl3,400MHz):δ=10.38(s,2H),9.46(d,J=4.64Hz,4H),9.21(d,J=4.64Hz,4H),8.60(d,J=1.64Hz,4H),8.34(m,2H),8.21(d,J=8.52Hz,8H),8.01(d,J=8.52Hz,8H),3.96(s,12H),-3.06(s,2H).
实施例4:
将5',5”'-(5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)(1.5mmol)溶解在500mL三氯甲烷中,向该反应体系中逐滴加入N-溴代丁二酰亚胺(3.65mmol)溶液,室温反应四天后,依次用水(500mL×2)和饱和食盐水(500mL)洗涤,浓缩后得到1.6g紫色固体5',5””-(10,20-二溴-5,15-二基)双([1,1':3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)(产率为92%)。1H NMR(CDCl3,400MHz):δ=9.68(d,J=4.84Hz,4H),8.98(d,J=4.32Hz,4H),8.48(d,J=1.64Hz,4H),8.33(m,2H),8.21(d,J=8.52Hz,8H),7.98(d,J=8.52Hz,8H),3.96(s,12H),-2.64(s,2H)
实施例5:
在氮气保护下将5',5””-(10,20-二溴-5,15-二基)双([1,1':3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)(1.30mmol),4-吡啶硼酸(2.85mmol),K2CO3(5.06mmol),Pd(PPh3)4(0.62mmol)以及二氧六环(250mL)和水(50mL)加入到500mL圆底烧瓶中,将该反应体系在100℃下搅拌24小时。待反应完成后,旋蒸除去有机溶剂,剩余液体依次用水(300mL×2)和丙酮(300mL)洗涤得到1.4g紫色固体5',5”'-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(9)(产率为93.63%)
实施例6:
将上一步所得紫色固体5',5”'-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(9)(0.87mmol)和氢氧化钠(25mmol)在四氢呋喃(50mL)/甲醇(50mL)/水(50mL)溶液中,在回流状态下70℃搅拌12小时,反应结束后,旋蒸去除有机溶剂。剩余的固体分散200mL水中,然后滴加2M盐酸水溶液将pH调整到3。所得悬浮液过滤,固体用水洗涤(100mL×3)后,在60℃真空干燥,即可得0.86g紫色固体5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉(10)(产率为90%)。
实施例7:
称量配体H4DPTC(0.06mmol)和ZrCl4(0.12mmoL)放入4mL玻璃小瓶中,加入1mL的DMF溶液和100mg的苯甲酸,然后将该小瓶密封后放入超声仪,在室温下超声5分钟。密封后将小瓶置于100℃烘箱中反应48小时。反应结束后关闭烘箱,待冷却至室温后,将小瓶中得到的固体颗粒过滤收集,然后依次用DMF、H2O和EtOH洗涤(5mL×3),显微镜下观察得到紫色块状晶体[Zr3(DPTC)],(产率:64%,基于H4DPTC配体)。
实施例8:
称量配体H4DPTC(0.05mmol)和ZrCl4(0.20mmoL)放入4mL玻璃小瓶中,加入2mL的DMF溶液和400mg的苯甲酸,然后将该小瓶密封后放入超声仪,在室温下超声5分钟。密封后将小瓶置于120℃烘箱中反应72小时。反应结束后关闭烘箱,待冷却至室温后,将小瓶中得到的固体颗粒过滤收集,然后依次用DMF、H2O和EtOH洗涤(5mL×3),显微镜下观察得到紫色块状晶体[Zr3(DPTC)],(产率:72%,基于H4DPTC配体)。
上述实施例所得的产品的测试结果相同,具体见下述:
(1)晶体结构的确定:
选取大小合适的粉末,在200K下,利用PANalytical X’Pert PRO高分辨粉末衍射仪收集数据。数据收集使用经石墨单色器单色化的Cu-Kα靶射线。数据的吸收校正使用SCALE3 ABSPACK软件完成。晶体结构使用SHELXTL-97程序通过直接法解析得到。先用差值函数法和最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置,然后用SHELXTL-97对晶体结构进行精修。结构图见图2至图3。晶体学数据见表1。
表1金属有机框架材料的晶体学数据
图1的吡啶羧酸卟啉配体合成路线图表明:多聚甲醛和新蒸吡咯,加入三氟乙酸,密封、惰性气体保护,加热反应完成后,加入氢氧化钠,纯化后得到联吡咯(3)。将3,5-二溴苯甲醛,4-甲氧羰基苯硼酸,碳酸钠,Pd(PPh3)4放入甲醇溶液中,惰性气体保护,加热反应后抽滤即可得到所需的醛;(6)将联吡咯(3)和醛(6)溶解在二氯甲烷中,惰性气体保护下加入三氟乙酸,黑暗条件下反应10小时后,加入二氯二氰基苯醌继续反应4小时后即可得到粗产物(7)。将卟啉化合物(7)和N-溴代丁二酰亚胺溶于三氯甲烷,室温反应四天得到溴卟啉(8)。将溴卟啉(8)和4-吡啶硼酸,碳酸钾,Pd(PPh3)4溶于二氧六环和水的混合溶液中,惰性气体保护下,在100℃下反应24小时得到吡啶卟啉(9)。将吡啶卟啉化合物(9)和氢氧化钠在四氢呋喃/甲醇/水(优选体积比为1:1:1)的混合溶液中加热回流12小时得到最终吡啶羧酸卟啉配体(10)。
图2的结构图表明:框架结构中包含的无机节点为Zr6锆,有机配体为5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉。
图3的结构图表明:在该金属-有机框架中的三维堆积图。
(2)二氧化碳及二氧化碳的光催化还原
图4(a)为本发明材料对二氧化碳的吸附等温线,可以看出该材料能吸附二氧化碳。图4(b)是本发明材料光催化二氧化碳产生一氧化碳图(对应的光为可见光,温度为常温),可以看出该材料可以将二氧化碳光催化还原为一氧化碳,并且选择性为100%。
Claims (5)
1.一种双功能吡啶羧酸卟啉配体的锆的金属-有机框架材料,其特征在于,化学分子式为[Zr3(DPTC)],H4DPTC为有机配体5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1',3',1”-三苯基]-4,4'-二羧酸)卟啉;
3.按照权利要求2所述的一种基于双功能吡啶羧酸卟啉配体的锆的金属-有机框架材料,其特征在于,H4DPTC配体的合成方法,包括以下六个步骤:
(a)二(1H-吡咯-2-基)甲烷(3)的形成:多聚甲醛和新蒸吡咯,加入三氟乙酸,密封、惰性气体保护,加热反应完成后,加入氢氧化钠,纯化后得到二(1H-吡咯-2-基)甲烷(3);
(b)5'-甲酰基-[1,1',3',1”-三苯基]-4,4'-二羧酸二甲酯(6)的制备:将3,5-二溴苯甲醛,4-甲氧羰基苯硼酸,碳酸钠,Pd(PPh3)4放入甲醇溶液中,惰性气体保护,加热反应后抽滤即可得到所需的醛;
(c)5',5”'-(5,15-二基)双([1,1',3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)的合成:将二(1H-吡咯-2-基)甲烷(3)和5'-甲酰基-[1,1',3',1”-三苯基]-4,4'-二羧酸二甲酯(6)溶解在二氯甲烷中,惰性气体保护下加入三氟乙酸,黑暗条件下反应,加入二氯二氰基苯醌,继续反应后,纯化即可得到产物;
每13.68mmol5'-甲酰基-[1,1',3',1”-三苯基]-4,4'-二羧酸二甲酯(6)对应二(1H-吡咯-2-基)甲烷(3)13.68mmol、三氟乙酸10.00mmol、二氯二氰基苯醌13.22mmol;
(d)5',5””-(10,20-二溴-5,15-二基)双([1,1',3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)的合成:将5',5”'-(5,15-二基)双([1,1',3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(7)和N-溴代丁二酰亚胺溶于三氯甲烷,室温反应四天;
(e)5',5”'-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(9):将5',5””-(10,20-二溴-5,15-二基)双([1,1',3',1”-三苯基]-4,4”-二羧酸)四甲酯卟啉(8)和4-吡啶硼酸,碳酸钾,Pd(PPh3)4溶于二氧六环和水的混合溶液中,惰性气体保护下,100℃加热反应12小时;
(f)5',5””-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)卟啉(10)的制备:将5',5”'-(10,20-二(吡啶-4-基)-5,15-二基)双([1,1':3',1”-三苯基]-4,4'-二羧酸)四甲酯卟啉(9)和氢氧化钠在四氢呋喃/甲醇/水的混合溶液中加热回流得到最终产物;
4.权利要求1-2任一项所述的基于双功能吡啶羧酸卟啉配体的锆的金属-有机框架材料的制备方法,其特征在于,包括以下步骤:
密封条件下,H4DPTC与氯化锆在N,N-二甲基甲酰胺DMF和苯甲酸的混合溶液中,经由溶剂热反应得到该金属-有机框架的晶体;有机配体H4DPTC与氯化锆的摩尔比为1:(1~5),每0.05mmol的氯化锆对应1mL~4mL的DMF,0.05g~4g的苯甲酸,热反应的温度为80-160℃,反应时间为12-168小时。
5.权利要求1-2任一项所述的基于双功能吡啶羧酸卟啉配体的锆的金属-有机框架材料的应用,用于吸附二氧化碳,或用于二氧化碳光催化还原制备一氧化碳。
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