CN107096571B - 一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 - Google Patents
一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN107096571B CN107096571B CN201710471183.9A CN201710471183A CN107096571B CN 107096571 B CN107096571 B CN 107096571B CN 201710471183 A CN201710471183 A CN 201710471183A CN 107096571 B CN107096571 B CN 107096571B
- Authority
- CN
- China
- Prior art keywords
- btp
- organic framework
- polyacid
- ligand
- gemo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 10
- 239000010941 cobalt Substances 0.000 title claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- ZTOVUOVWUQVXIM-UHFFFAOYSA-N 5-[3-(1H-1,2,4-triazol-5-yl)propyl]-1H-1,2,4-triazole Chemical compound C(CCC1=NNC=N1)C1=NNC=N1 ZTOVUOVWUQVXIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 15
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 4
- 238000002050 diffraction method Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 25
- 238000012512 characterization method Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种多酸基钴金属有机框架复合光催化剂及制备方法和应用，化学式为[Co2(btp)3(GeMo12O40)]，式中btp为1，3‑双‑(1，2，4‑三氮唑基)丙烷。采用X‑射线单晶衍射仪、X‑射线粉末衍射仪、红外光谱仪、热重分析仪等测试手段对所制备的[Co2(btp)3(GeMo12O40)]单晶进行表征。本发明方法简单、环保、低成本；反应迅速、可重复性高；可按比例扩大批量生产。优点：1）此方法在金属有机框架合成技术方面具有很大的意义；2）该产品在作为光催化降解亚甲基蓝方面具有良好的潜在应用价值。
Description
技术领域
本发明属于多酸基金属有机框架制备的技术领域，特别涉及了一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用。
背景技术
穿插结构作为缠结结构的一个分支由于迷人的美学和拓扑结构引起了人们极大的兴趣。Robson和Batten两人为这种有趣的穿插结构写过两篇综述。尽管许多有趣的穿插结构被发现，它迷人的魅力仍然吸引着化学家们。另一方面，由于金属有机框架材料的多孔结构、大的比表面积和潜在的应用引起了人们广泛的研究兴趣。模板方法在设计和构造这些材料上作为一个重要的合成方法已经成为合成化学的发展趋势。在这一领域，许多不同形状和大小的中性、阴离子和阳离子客体作为模板被用来构造独特的金属有机框架。其中，多金属氧酸盐不仅因为他们拥有种类多样的多酸阴离子，也由于他们在催化、吸附、电化学和磁性材料的潜在应用，吸引了人们浓厚的兴趣。使用多金属氧酸盐作为模板来构造金属有机框架可以结合他们的优点来构造具有特殊性质的金属有机框架。然而，以非共价的多金属氧酸盐作为模板的金属有机框架的数量很少，并且大部分都不是穿插结构。穿插是极其罕见的例子，因为尺寸大并且具有高价态的多酸阴离子被认为是能够有效地阻止穿插。据我们所知，2007年王恩波和苏忠民首先合成了两个分别具有二重穿插和五重穿插的多酸基三维金属有机框架。之后，2010年杨国昱报道了第一例多酸模板四重穿插三维金属有机框架。而多酸模板二重穿插三维金属有机框架至今没有报道。
发明内容
本发明要解决的技术问题是，公开一种水热法自组装[Co2(btp)3(GeMo12O40)]金属有机框架的方法；此方法简单易行，可重复性高，并且该金属有机框架是一种潜在的光催化剂。
本发明的技术方案是：
多酸基钴金属有机框架复合光催化剂，化学式为[Co2(btp)3(GeMo12O40)]，式中btp为1，3-双-(1，2，4-三氮唑基)丙烷。该化合物为三方晶系，空间群为R -3，晶胞参数为a =16.4707(12) Å，b = 16.4707(12) Å，c = 25.6723(18) Å，α = 90.000°，β = 90.000 °，γ= 120.000 °，V = 6031.4(8) Å3， X射线单晶衍射分析表明该化合物的不对称单元包含三分之一个Co( )离子，六分之一个(GeMo12O40)4-阴离子和一个btp配体，Co()中心是六配位的，分别和来自六个btp配体上的六个端氮原子配位，形成八面体配位几何，每个btp配体作为双齿配体桥连相邻两个Co()离子，形成一个六连接三维网络，如果将Co()简化为6-连接点，btp配体充当连接体，则该三维网络的拓扑符号是412.63，为经典的pcu网络。两个完全相同的六连接三维网络互相穿插，得到二重穿插的三维pcu网络，(GeMo12O40)4-阴离子作为抗衡离子，填充在两个三维pcu网络互穿所形成的孔道内。
多酸基钴金属有机框架复合光催化剂的制备方法，以一水合醋酸钴为金属盐，1，3-双-(1，2，4-三氮唑基)丙烷作为有机配体，合成步骤如下：将一水合醋酸钴、两水合钼酸钠、1，3-双-(1，2，4-三氮唑基)丙烷、氧化锗溶于水溶液中，用2M盐酸溶液调节pH为5，装入内衬聚四氟乙烯不锈钢反应釜中，充填度为70 %，在170°C下加热5天后，冷却至室温，得到棕红色块状晶体。
所述混合物中一水合醋酸钴、两水合钼酸钠、1，3-双-(1，2，4-三氮唑基)丙烷、氧化锗的摩尔比为2:10:1:1。
多酸基钴金属有机框架复合光催化剂在紫外光和可见光下降解亚甲基蓝的应用。
本发明的有益效果：
1、本发明的方法简单、环保、低成本，可重复性高，可按比例扩大批量生产。此方法在金属有机框架合成技术方面具有很大的意义，在金属有机框架的制备及应用方面有广阔的前景。
2、光催化性质：该金属有机框架在紫外光和可见光下对降解亚甲基蓝都有很好的光催化性质。
3、本发明的合成方法具有重复性强、产品性能稳定、合成方法简单等特点。金属有机框架表现了较好的光催化性质。
附图说明
图1是[Co2(btp)3(GeMo12O40)]的单胞图；
图2是六连接pcu网络框架结构；
图3是多酸模板二重穿插三维金属有机框架；
图4是[Co2(btp)3(GeMo12O40)]在可见光和紫外光下降解亚甲基蓝的吸收光谱和浓度与照射时间曲线。
具体实施方式
将Co(CH3COO)2·H2O (0.2mmol), btp(0.1mmol), GeO2 (0.1mmol)， Na2MoO4·2H2O (1mmol)，溶解于水(10 mL)溶液中，在170°C下加热5天后，冷却至室温，得到棕红色块状晶体，产率42%。
主要的红外吸收峰为：3398(m), 3129(s), 2363(m), 1627(s), 1527(s), 1447(m), 1393(w), 1283(s), 1214(m), 1132(s), 1000(w), 950(s), 874(s), 776(m), 768(s), 673(m), 505(m)。
金属有机框架的相关表征
（1）金属有机框架的晶体结构测定
金属有机框架的衍射数据是在Bruker SMART APEX II衍射仪上收集，Mo Kα射线(λ = 0.71073 Å)，293 K。使用技术扫描进行校正。晶体结构是通过SHELEXL-97程序以直接法解出，用全矩阵最小二乘法使用SHELEXL-97进行精修。详细的晶体测定数据见表1；重要的键长和键角数据见表2；晶体结构见图1-图3。
发明的金属有机框架，所述该化合物属于三方晶系，空间群为R-3，晶胞参数为a =16.4707(12) Å，b = 16.4707(12) Å，c = 25.6723(18) Å，α = 90°，β = 90°，γ = 120°，V= 6031.4(8) Å3。X射线单晶衍射分析表明该化合物的不对称单元包含三分之一个Co()离子，六分之一个(GeMo12O40)4-阴离子和一个btp配体。Co()中心是六配位的，分别和来自六个btp配体上的六个端氮原子配位，形成八面体配位几何。每个btp配体作为双齿配体桥连相邻两个Co()离子，形成一个六连接三维网络。如果将Co()简化为6-连接点，btp配体充当连接体，则该三维网络的拓扑符号是412.63，为经典的pcu网络。两个完全相同的六连接三维网络互相穿插，得到二重穿插的三维pcu网络。(GeMo12O40)4-阴离子作为抗衡离子，填充在两个三维pcu网络互穿所形成的孔道内。
（2）金属有机框架的光催化性质
亚甲基蓝(MB)-染料污染物的一种，可以被用在污水纯化中光催化活性的评估标准。我们通过常规方法，研究了该金属有机框架对MB的光降解性质。将该金属有机框架作为光催化剂在可见光和紫外光照射下光降解亚甲基蓝。我们对它的紫外-可见光谱进行了研究。一个典型的实验过程，70mg的样品在200ml亚甲基蓝溶液(5.0×10-5mol L-1)中避光搅拌30分钟，达到化合物粒子的表面吸附平衡。然后分别将悬浊液在可见光和紫外光照射下继续搅拌，每30分钟取出3ml溶液进行分析。为了对比实验效果，没有光催化剂的亚甲基蓝溶液也分别在可见光和紫外光照射下每30分钟取出3ml溶液进行分析。实验结果表明，溶液的吸光度随着照射时间的增加而降低。这说明，亚甲基蓝逐渐被光降解。在可见光照射下6个小时后，光催化降解亚甲基蓝的效率由没有光催化剂的15%提高到有光催化剂存在的27%。在紫外光照射下6个小时后，光催化降解亚甲基蓝的效率由没有光催化剂的11%提高到有光催化剂存在的41%。我们通过对光催化实验后的光催化剂进行XRD表征，发现其没有发生变化。因此，该金属有机框架在可见光和紫外光照射下降解亚甲基蓝的实验中是一个有效且稳定的光催化剂。
表1为配合物的主要晶体学数据
表2为配合物的主要键长(Å)和键角[°]
对称代码: #1 -y+1, x-y+1, z; #2 -x+y, -x+1, z; #3 x-2/3, y-1/3, z-1/3; #4 -x+y+1/3, -x+5/3, z-1/3; #5 -y+4/3, x-y+2/3, z-1/3。
Claims (4)
1.一种多酸基钴金属有机框架复合光催化剂，其特征在于：化学式为[Co2(btp)3(GeMo12O40)]，式中btp为1，3-双-(1，2，4-三氮唑基)丙烷，该化合物为三方晶系，空间群为R-3，晶胞参数为 α＝90.000°，β＝90.000°，γ＝120.000°，X射线单晶衍射分析表明该化合物的不对称单元包含三分之一个Co(II)离子，六分之一个(GeMo12O40)4-阴离子和一个btp配体，Co(II)中心是六配位的，分别和来自六个btp配体上的六个端氮原子配位，形成八面体配位几何，每个btp配体作为双齿配体桥连相邻两个Co(II)离子，形成一个六连接三维网络，如果将Co(II)简化为6-连接点，btp配体充当连接体，则该三维网络的拓扑符号是412.63，为经典的pcu网络，两个完全相同的六连接三维网络互相穿插，得到二重穿插的三维pcu网络，(GeMo12O40)4-阴离子作为抗衡离子，填充在两个三维pcu网络互穿所形成的孔道内。
2.一种权利要求1所述的多酸基钴金属有机框架复合光催化剂的制备方法，其特征在于：以一水合醋酸钴为金属盐，1，3-双-(1，2，4-三氮唑基)丙烷作为有机配体，合成步骤如下：将一水合醋酸钴、两水合钼酸钠、1，3-双-(1，2，4-三氮唑基)丙烷、氧化锗溶于水溶液中，用2M盐酸溶液调节pH为5，装入内衬聚四氟乙烯不锈钢反应釜中，充填度为70％，在170℃下加热5天后，冷却至室温，得到棕红色块状晶体。
3.根据权利要求2所述的制备方法，其特征在于：一水合醋酸钴、两水合钼酸钠、1，3-双-(1，2，4-三氮唑基)丙烷、氧化锗的摩尔比为2:10:1:1。
4.一种如权利要求1所述的多酸基钴金属有机框架复合光催化剂在紫外光和可见光下降解亚甲基蓝的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710471183.9A CN107096571B (zh) | 2017-06-20 | 2017-06-20 | 一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710471183.9A CN107096571B (zh) | 2017-06-20 | 2017-06-20 | 一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107096571A CN107096571A (zh) | 2017-08-29 |
| CN107096571B true CN107096571B (zh) | 2019-12-13 |
Family
ID=59663096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710471183.9A Active CN107096571B (zh) | 2017-06-20 | 2017-06-20 | 一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107096571B (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092365B (zh) * | 2018-08-30 | 2022-10-18 | 哈尔滨理工大学 | 一种具有三维插层结构的多酸基晶体材料及其制备方法 |
| CN109876865B (zh) * | 2019-04-02 | 2022-03-08 | 哈尔滨理工大学 | 一种插层结构的多酸基金属有机框架的制备及催化性能 |
| CN110882727A (zh) * | 2019-12-12 | 2020-03-17 | 吉林师范大学 | 一种三重穿插金属有机框架非均相co2环加成催化剂及其制备方法与应用 |
| CN112058281B (zh) * | 2020-05-14 | 2023-02-17 | 哈尔滨理工大学 | 锗钼多酸钴配合物衍生的双金属硫化物晶体的制备和应用 |
| CN111518282B (zh) * | 2020-06-24 | 2022-03-04 | 江苏理工学院 | 可见光催化降解有机染料的羟基吡唑羧酸镉配位聚合物及其制备和应用 |
| CN113999401B (zh) * | 2021-11-25 | 2022-05-20 | 常州大学 | 一种含钴同多钼酸金属有机框架材料及其制备方法和应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130838A (zh) * | 2013-01-11 | 2013-06-05 | 天津师范大学 | 基于三氮唑配体的金属–有机框架多孔材料及其制备方法和应用 |
-
2017
- 2017-06-20 CN CN201710471183.9A patent/CN107096571B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130838A (zh) * | 2013-01-11 | 2013-06-05 | 天津师范大学 | 基于三氮唑配体的金属–有机框架多孔材料及其制备方法和应用 |
Non-Patent Citations (3)
| Title |
|---|
| "一个二重穿插的三维配位聚合物[Zn(bpdc)(H2O)2]n的合成与表征";刘宏文等;《江西师范大学学报(自然科学版)》;20091030;第33卷(第5期);第518-522页 * |
| "基于双三氮唑配体和多钼酸盐的杂化化合物的合成与性质研究";刘博;《中国博士学位论文全文数据库 工程科技I辑》;20150515;B014-91 * |
| "多酸基金属－ 有机框架的构筑及其催化性能";黄远等;《化学研究》;20160131;第27卷(第1期);第62-68页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107096571A (zh) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107096571B (zh) | 一种多酸基钴金属有机框架复合光催化剂及其制备方法和应用 | |
| Hu et al. | Iodine-templated assembly of unprecedented 3d–4f metal–organic frameworks as photocatalysts for hydrogen generation | |
| Jiang et al. | Syntheses and photoluminescent properties of two uranyl-containing compounds with extended structures | |
| Chen et al. | A novel 2-D coordination polymer constructed from high-nuclearity waist drum-like pure Ho 48 clusters | |
| Hou et al. | Two Ti 13-oxo-clusters showing non-compact structures, film electrode preparation and photocurrent properties | |
| Gong et al. | Functionalized polyoxometalate-based metal–organic cuboctahedra for selective adsorption toward cationic dyes in aqueous solution | |
| Wu et al. | A series of POM-based hybrid materials with different copper/aminotriazole motifs | |
| Liang et al. | Ethylene polyamine influence on the transition metal thiogermanates: Solvothermal syntheses and characterizations of [Ni (trien) 2] 2Ge4S10 and [{Ni (tepa)} 2 (μ-Ge2S6)] | |
| Weakley | Heteropolyanions containing two different heteroatoms. Part III. Cobalto (II) undecatungstophosphate and related anions | |
| Lai et al. | All-inorganic POM cages and their assembly: A review | |
| Wang et al. | Solvent dependent Zinc (II) coordination polymers with 1, 3, 5-benzenetricarboxylic acid and the selective photocatalytic degradation for organic dyes | |
| CN107417928A (zh) | 一种含混合配体的金属银配位聚合物及其制备方法 | |
| Fachinetti et al. | Isolation of the ion pair NaCo (CO) 4 promoted by an inorganic ligand: structure and properties of [(Co (salen)) 2NaCo (CO) 4THF] | |
| CN106432749A (zh) | 一种混合配体的二维金属镍配位聚合物及其制备方法 | |
| CN108997591B (zh) | 一种可见光响应铪基金属有机骨架材料及其制备方法 | |
| Calatayud et al. | Synthesis, spectroscopic and structural characterization of [Cu (phen)(C5O5)(H2O)]· H2O,[Ni (terpy)(C5O5)(H2O)]· H2O and [Ni (terpy) 2](NO3) 2· 0.5 H2O | |
| CN108997386B (zh) | 一种双配体构筑的锌金属有机配合物及其制备方法 | |
| Huang et al. | Anionic effects on the formation of tridentate 4′-chloro-2, 2′: 6′, 2 ″-terpyridine copper (II) complexes having 1: 1 or 1: 2 ratio of metal and ligand and their crystal symmetry | |
| Ellsworth et al. | Metal and mixed-metal coordination polymers synthesized with Pyrazine-2-carboxylate | |
| Rekik et al. | New transition metal sulfates templated by 1, 4-butanediamine,(C4H14N2)[MII (H2O) 6](SO4) 2· 4H2O (MII: Co, Ni): Structure, reactivity and thermal decomposition | |
| CN106700090B (zh) | 一种具有三重穿插多聚索结构的配位聚合物及其制备方法 | |
| CN109956981A (zh) | 一种同多酸前躯体组装锰和铜为杂原子的多酸材料 | |
| Zhang et al. | Three Cd (II) coordination polymers based on rigid 2, 6-bis (3-(pyrid-3-yl)-1, 2, 4-triazolyl) pyridine ligand: Syntheses, crystal structures, and photocatalytic properties | |
| Singh et al. | Construction and structural diversity of Cd-MOFs with pyrazole based flexible ligands and positional isomer of naphthalenedisulfonate | |
| CN110204737B (zh) | 双金属双配体型光敏性mof材料及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |