CN110818908B - Preparation method of metal organic framework material for detecting oxidizing gas - Google Patents
Preparation method of metal organic framework material for detecting oxidizing gas Download PDFInfo
- Publication number
- CN110818908B CN110818908B CN201910808027.6A CN201910808027A CN110818908B CN 110818908 B CN110818908 B CN 110818908B CN 201910808027 A CN201910808027 A CN 201910808027A CN 110818908 B CN110818908 B CN 110818908B
- Authority
- CN
- China
- Prior art keywords
- tetrazine
- dihydro
- pyridyl
- organic framework
- framework material
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Abstract
The invention relates to the technical field of gas sensing, and discloses a preparation method of a metal organic framework material for detecting oxidizing gas.
Description
Technical Field
The invention relates to the technical field of gas sensing, in particular to a preparation method of a metal organic framework material for detecting oxidizing gas.
Background
Gas sensors are widely used to monitor the concentration of various gases, such as methane or carbon monoxide in coal mines, for personal protection using portable equipment. An ideal sensor should be sensitive and stable enough to operate under ambient conditions and yet produce a signal with a short response time that can be easily sensed without the need for other equipment, a so-called wireless gas sensor. One of the simplest and most powerful means of sensing a signal is through a visible change in the color of the material. In addition, it is required to be independently usable without depending on a power source.
NOx(nitrous gas) is Nitric Oxide (NO) and nitrogen dioxide (NO)2) Are toxic gases that are commonly released into the atmosphere by automotive and industrial and domestic combustion processes. Thus, for NOxDetection and monitoring of gases is of great interest, many NOxGas sensors such as metal oxide semiconductors, solid electrolytes, conductive polymers (e.g., polypyrrole and polyaniline), and the like have been widely studied. However, the existing nitrous gas detection method depends on a power supply, cannot be used independently, and cannot achieve the visual effect through simple color change.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a metal organic framework material for detecting oxidizing gas, and in order to detect the oxidizing gas, the invention selects a dihydro-1, 2,4, 5-tetrazine unit compounded in the metal organic framework material, and the dihydro-1, 2,4, 5-tetrazine unit can be easily oxidized into 1,2,4, 5-tetrazine. A notable feature of the redox reaction is that a sharp color change occurs, the redox is reversible and can respond rapidly to minute amounts of oxidizing gases (such as nitrous gases).
The specific technical scheme of the invention is as follows: a preparation method of a metal organic framework material for detecting oxidizing gas comprises the following steps:
1) respectively weighing 4-cyanopyridine and hydrazine hydrate according to the mol ratio of 1.5:1-3:1, mixing in a reaction container, and stirring and refluxing for reaction for 4-8h at the temperature of 30-80 ℃; carrying out suction filtration to obtain an orange solid, recrystallizing in a mixed solvent of ethanol and water in a volume ratio of 0.5-1.5:1, and washing to obtain orange powder dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine for later use.
2) Dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine is dissolved in methanol according to the proportion of 40-50mg/30-40 mL.
3) Slowly dripping the obtained reactant into a hexafluoro copper silicate aqueous solution under the stirring condition; the obtained mixed solution reacts for 8-24h at 25-85 ℃, and is filtered to obtain orange yellow powder.
4) And washing with methanol to obtain the tetrazine functionalized metal organic framework material.
The dihydro-1, 2,4, 5-tetrazine units can be readily oxidized to 1,2,4, 5-tetrazine, a reaction which is distinguished by a sharp color change, since the 1,2,4, 5-tetrazine units are pink and the dihydro-1, 2,4, 5-tetrazine units are orange-yellow. Therefore, the tetrazine functionalized metal organic framework material obtained by compounding the dihydro-1, 2,4, 5-tetrazine and the metal organic framework material not only has high porosity, but also shows the reversible color change of the orange yellow to pink metal organic framework material in the oxidation-reduction reaction, and can quickly respond to trace nitrous gases.
The invention selects a brand-new self-made ligand to compound with a metal framework, so that the metal organic framework material has an pcu network structure, has good stability, has the characteristics of rapidness, high efficiency, short response time, visualization, no need of power supply, and the like, still has a stable framework structure and good sensing performance after reversible reduction treatment, and can be repeatedly utilized for many times.
The material obtained by the invention is stored in nitrogen or argon atmosphere, the powder can not generate color change within half a year, and the stability is good.
Preferably, in step 1), the molar ratio of the 4-cyanopyridine to the hydrazine hydrate is 2: 1; the reaction time was 4h and the reaction temperature was 80 ℃.
Preferably, in step 2), the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate is from 1:1 to 2: 1.
Preferably, in step 2), ultrasonic oscillation is performed while dissolving dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine.
Preferably, in step 3), the concentration of the aqueous solution of copper hexafluorosilicate ranges from 0.9 to 1.1 mol/L.
Preferably, in step 3), the dropping rate of the aqueous solution of copper hexafluorosilicate is 0.05 to 0.2 mL/s.
Preferably, in the step 3), the reaction temperature is 25-30 ℃ and the reaction time is 18-22 h.
Preferably, the dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine has a purity of greater than 98%.
Preferably, the oxidizing gas is nitrous gas.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method has low requirement on equipment and is easy for mass synthesis.
(2) The metal organic framework material for detecting the oxidizing gas prepared by the invention is based on inorganic metal ions Cu2+Inorganic anion SiF6 2-And organic ligand dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to obtain tetrazine functional metal organic framework material, which can be applied according to actual needsThe framework structure is designed, and the pore volume, the functional group modified in the framework and the like are included.
(3) The metal organic framework material for detecting the oxidizing gas has pcu network structure, has good stability, has the characteristics of rapidness, high efficiency, short response time, visualization, no need of power supply for working and the like, still has stable framework structure and good sensing performance after reversible reduction treatment, and can be repeatedly used for many times.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a tetrazine functionalized metal organic framework material having dihydro-1, 2,4, 5-tetrazine units and a metal organic framework material oxidized to form 1,2,4, 5-tetrazine units prepared in example 1 of the present invention.
FIG. 2 shows the nuclear magnetic spectrum of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine as the organic ligand prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for preparing a metal organic framework material for detecting oxidizing gases (e.g. nitrous gases), comprising the steps of:
1) respectively weighing 4-cyanopyridine and hydrazine hydrate according to the mol ratio of 1.5:1-3:1 (preferably 2: 1), mixing in a reaction vessel, and stirring and refluxing for reaction for 4-8h (preferably 4h) at 30-80 ℃ (preferably 80 ℃); carrying out suction filtration to obtain an orange solid, recrystallizing in a mixed solvent with the volume ratio of ethanol to water being 0.5-1.5:1, and washing to obtain the orange solid dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine with the purity of more than 98% for later use.
2) Dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine is dissolved in methanol according to the proportion of 40-50mg/30-40mL, and ultrasonic oscillation is carried out during the dissolving.
3) The obtained reactant is slowly dropped into a copper hexafluorosilicate aqueous solution (the concentration is 0.9 to 1.1 mol/L) under the stirring condition (the dropping speed is 0.05 to 0.2 mL/s), and the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate is 1:1 to 2: 1. The obtained mixed solution is reacted at 25-85 deg.C (preferably 25-30 deg.C) for 8-24h (preferably 18-22 h), and filtered to obtain orange yellow powder.
4) And washing with methanol to obtain the tetrazine functionalized metal organic framework material.
Example 1
Preparation of dihydro-3, 6-di-4-pyridinyl-1, 2,4, 5-tetrazine:
5.2g of 4-cyanopyridine and 5mL of hydrazine hydrate were weighed respectively and mixed in a 100mL round-bottom flask in a molar ratio of 4-cyanopyridine to hydrazine hydrate of 2:1, and the mixture was stirred under reflux at 80 ℃ for 4 hours. And (3) carrying out suction filtration by using a Buchner funnel to obtain an orange solid, recrystallizing in a mixed solvent with the volume ratio of ethanol to water being 1:1, and washing to obtain orange powder for later use.
The raw material prepared in example 1 was prepared under optimal conditions, and had high purity up to 98% (as shown in fig. 2, its nuclear magnetic spectrum:1h NMR (500 MHz, DMSO) δ 9.45 (s, 2H), 8.69 (dd, J = 4.6, 1.5 Hz, 4H), 7.77 (dd, J = 4.6, 1.6 Hz, 4H), dihydro-3, 6-di-4-pyridinyl-1, 2,4, 5-tetrazine (H) in subsequent examples2dpt) were synthesized by this example.
Preparation and application of the metal organic framework material are as follows:
dissolving 46mg of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine ligand in 30mL of methanol (ultrasonic oscillation is carried out for more than half an hour, the ligand can not be completely dissolved by frequent manual shaking in the period), then putting the reactant on a stirrer, and slowly dropping (dropping speed is 0.1 mL/s) 2mL of CuSiF in the stirring process6(ii) 1 mol/L. The molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate was 1:1 (ligand slightly excessive), and the mixed solution was reacted at room temperature overnight for 20 hours, after which it was filtered with a buchner funnel to give an orange-yellow powder, and the sample was washed several times with methanol.
Upon exposure of the sample suspended in methanol to nitrous gases, a color change of the powder was observed, and an immediate change of the orange-yellow powder to pink powder was observed, mainly because the dihydro-1, 2,4, 5-tetrazine units in the framework of the metal organic framework material were oxidized to 1,2,4, 5-tetrazine units, resulting in a rapid color change, as shown in fig. 1.
Example 2
46mg of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine ligand was dissolved in 30mL of methanol, and then the reaction mixture was put on a stirrer and slowly dropped (dropping speed was 0.1 mL/s) 2mL of CuSiF while stirring6In an aqueous solution (1 mol/L), the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate was 1:1 (slight excess of ligand). After mixing, the solution was reacted at 50 ℃ for 20 hours, and then filtered with a buchner funnel to obtain orange-yellow powder, and the sample was washed several times with methanol.
Example 3
46mg of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine ligand was dissolved in 30mL of methanol, and then the reaction mixture was put on a stirrer and slowly dropped (dropping speed was 0.1 mL/s) 2mL of CuSiF while stirring6In an aqueous solution (1 mol/L), the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate was 1:1 (slight excess of ligand). The mixed solution was reacted at 85 ℃ for 20 hours, and then filtered with a buchner funnel to obtain an orange-yellow powder, and the sample was washed several times with methanol.
Example 4
The difference from example 1 is that: the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate is 2: 1.
Example 5
The difference from example 2 is that: the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate is 2: 1.
Example 6
The difference from example 3 is that: the molar ratio of dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to copper hexafluorosilicate is 2: 1.
The metal organic framework material as one of porous materials has a relatively large specific surface area, can be used for adsorbing various gases, and has a great application prospect in gas sensing. The tetrazine functionalized metal organic framework material obtained by the invention has the outstanding advantages of easily obtained raw materials, simple preparation method, high hydrothermal stability, sensitive detection, visualization and the like, is easy to regenerate and can be repeatedly utilized.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. The application of the metal-organic framework material in the detection of the oxidizing gas is characterized by comprising the following steps:
1) respectively weighing 4-cyanopyridine and hydrazine hydrate according to the mol ratio of 1.5:1-3:1, mixing in a reaction container, and stirring and refluxing for reaction for 4-8h at the temperature of 30-80 ℃; carrying out suction filtration to obtain an orange solid, recrystallizing in a mixed solvent with the volume ratio of ethanol to water being 0.5-1.5:1, and washing to obtain orange powder dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine for later use;
2) dissolving dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine in methanol according to the proportion of 40-50mg/30-40 mL;
3) slowly dripping the obtained reactant into the hexafluoro copper silicate aqueous solution at the dripping speed of 0.05-0.2mL/s under the stirring condition; reacting the obtained mixed solution at 25-85 ℃ for 8-24h, and filtering to obtain orange yellow powder; the molar ratio of the dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine to the copper hexafluorosilicate is 1:1-2: 1;
4) and washing with methanol to obtain the tetrazine functionalized metal organic framework material.
2. The use of claim 1, wherein in step 1), the molar ratio of 4-cyanopyridine to hydrazine hydrate is 2: 1; the reaction time was 4h and the reaction temperature was 80 ℃.
3. The use of claim 1, wherein in step 2), the dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine is sonicated while dissolved.
4. The use according to claim 1, wherein in step 3), the concentration of the aqueous solution of copper hexafluorosilicate is 0.9 to 1.1 mol/L.
5. The use according to claim 1, wherein in step 3), the reaction temperature is 25-30 ℃ and the reaction time is 18-22 h.
6. The use of claim 1, wherein said dihydro-3, 6-di-4-pyridyl-1, 2,4, 5-tetrazine has a purity greater than 98%.
7. Use according to claim 1, wherein the oxidizing gas is nitrous gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910808027.6A CN110818908B (en) | 2019-08-29 | 2019-08-29 | Preparation method of metal organic framework material for detecting oxidizing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910808027.6A CN110818908B (en) | 2019-08-29 | 2019-08-29 | Preparation method of metal organic framework material for detecting oxidizing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110818908A CN110818908A (en) | 2020-02-21 |
| CN110818908B true CN110818908B (en) | 2021-12-17 |
Family
ID=69547846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910808027.6A Active CN110818908B (en) | 2019-08-29 | 2019-08-29 | Preparation method of metal organic framework material for detecting oxidizing gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110818908B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473625B (en) * | 2019-09-11 | 2022-05-20 | 杭州市富阳区浙工大银湖创新创业研究院 | Preparation method of ultra-microporous metal organic framework material for separating acetylene and ethylene |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2231706C (en) * | 1998-03-05 | 2004-10-05 | Saint Mary's University | Supramolecular laminates |
| CN1544442A (en) * | 2003-11-18 | 2004-11-10 | 浙江工业大学 | 3,6-double(3-methyl pyridine-2yl)-S-tetrazine and transition metal complex, and its preparation and uses |
| CN1563023A (en) * | 2004-03-31 | 2005-01-12 | 浙江工业大学 | 3,6-bi(2'-hydroxy-5'-chlorphenyl)-S-tetrazine and accessory ingredient of transition metal, preparation and application |
| CN101855221A (en) * | 2007-11-15 | 2010-10-06 | P.安杰莱蒂分子生物学研究所 | Pyridazinone derivatives as PARP inhibitors |
| WO2013112823A1 (en) * | 2012-01-25 | 2013-08-01 | Dow Corning Corporation | Heterophase synthesis of metal-coordinated framework materials for particle size control |
| CN103826741A (en) * | 2011-09-05 | 2014-05-28 | 株式会社可乐丽 | Adsorbent |
| CN105111225A (en) * | 2015-09-24 | 2015-12-02 | 盐城工学院 | Cu(I) coordination polymer based on 3-abpt ligand and method for preparing Cu(I) coordination polymer |
| CN107281204A (en) * | 2017-05-04 | 2017-10-24 | 北京大学 | A kind of application of asymmetrical 1,2,4,5 tetrazine molecule |
| CN108137483A (en) * | 2015-08-24 | 2018-06-08 | 科迪实验室公司 | The synthesis of Laevomethanone Hydrochloride or the right methadone of hydrochloric acid and its application method |
| CN109420480A (en) * | 2017-08-22 | 2019-03-05 | 浙江大学 | A kind of separation method of C 4 olefin mixture |
| CN109641070A (en) * | 2015-12-15 | 2019-04-16 | 特拉华大学 | Trans--cycloolefin for the limitation of radiolabeled conformation |
| CN110064436A (en) * | 2019-05-29 | 2019-07-30 | 湘潭大学 | A kind of catalyst and preparation method and purposes based on pyridyl group tetrazine ring Base Metal coordination polymer |
| CN110483794A (en) * | 2019-08-20 | 2019-11-22 | 南昌大学 | A kind of metal-organic framework material and its preparation method and application |
-
2019
- 2019-08-29 CN CN201910808027.6A patent/CN110818908B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2231706C (en) * | 1998-03-05 | 2004-10-05 | Saint Mary's University | Supramolecular laminates |
| CN1544442A (en) * | 2003-11-18 | 2004-11-10 | 浙江工业大学 | 3,6-double(3-methyl pyridine-2yl)-S-tetrazine and transition metal complex, and its preparation and uses |
| CN1563023A (en) * | 2004-03-31 | 2005-01-12 | 浙江工业大学 | 3,6-bi(2'-hydroxy-5'-chlorphenyl)-S-tetrazine and accessory ingredient of transition metal, preparation and application |
| CN101855221A (en) * | 2007-11-15 | 2010-10-06 | P.安杰莱蒂分子生物学研究所 | Pyridazinone derivatives as PARP inhibitors |
| CN103826741A (en) * | 2011-09-05 | 2014-05-28 | 株式会社可乐丽 | Adsorbent |
| WO2013112823A1 (en) * | 2012-01-25 | 2013-08-01 | Dow Corning Corporation | Heterophase synthesis of metal-coordinated framework materials for particle size control |
| CN108137483A (en) * | 2015-08-24 | 2018-06-08 | 科迪实验室公司 | The synthesis of Laevomethanone Hydrochloride or the right methadone of hydrochloric acid and its application method |
| CN105111225A (en) * | 2015-09-24 | 2015-12-02 | 盐城工学院 | Cu(I) coordination polymer based on 3-abpt ligand and method for preparing Cu(I) coordination polymer |
| CN109641070A (en) * | 2015-12-15 | 2019-04-16 | 特拉华大学 | Trans--cycloolefin for the limitation of radiolabeled conformation |
| CN107281204A (en) * | 2017-05-04 | 2017-10-24 | 北京大学 | A kind of application of asymmetrical 1,2,4,5 tetrazine molecule |
| CN109420480A (en) * | 2017-08-22 | 2019-03-05 | 浙江大学 | A kind of separation method of C 4 olefin mixture |
| CN110064436A (en) * | 2019-05-29 | 2019-07-30 | 湘潭大学 | A kind of catalyst and preparation method and purposes based on pyridyl group tetrazine ring Base Metal coordination polymer |
| CN110483794A (en) * | 2019-08-20 | 2019-11-22 | 南昌大学 | A kind of metal-organic framework material and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| A metal-organic framework with suitable pore size and dual functionalities for highly efficient postcombustion CO2 capture;Hui-Min Wen等;《JOURNAL OF MATERIALS CHEMISTRY A》;20190114;第7卷(第7期);第3128-3134页 * |
| A multidimensional overpressured layer chromatographic method for the characterization of tetrazine libraries;Gombosuren, Naran等;《JOURNAL OF BIOCHEMICAL AND BIOPHYSICAL METHODS》;20070110;第69卷(第3期);第239-249页 * |
| Metal-Organic Framework with Trifluoromethyl Groups for Selective C2H2 and CO2 Adsorption;Alduhaish, Osamah等;《CRYSTAL GROWTH & DESIGN》;20180831;第18卷(第8期);第4522-4527页 * |
| 一种用于高效C2H2/C2H4分离的二维铜金属有机框架;张秀荣等;《中国化学会2019年中西部地区无机化学化工学术研讨会会议论文集》;20190430;第223-224页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110818908A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Logan et al. | Systematic variation of the optical bandgap in titanium based isoreticular metal–organic frameworks for photocatalytic reduction of CO 2 under blue light | |
| Abednatanzi et al. | Mixed-metal metal–organic frameworks | |
| Zhang et al. | Lanthanide-MOFs constructed from mixed dicarboxylate ligands as selective multi-responsive luminescent sensors | |
| Chen et al. | Fast response and highly selective sensing of amine vapors using a luminescent coordination polymer | |
| Jaroschik et al. | Dinitrogen reduction and C–H activation by the divalent organoneodymium complex [(C5H2tBu3) 2Nd (μ-I) K ([18] crown-6)] | |
| CN106345527A (en) | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention | |
| CN110818908B (en) | Preparation method of metal organic framework material for detecting oxidizing gas | |
| Yang et al. | Metal–organic frameworks constructed from tib and carboxylate acid ligands: selective sensing of nitro explosives and magnetic properties | |
| Ye et al. | Crystal structures, luminescent and thermal properties of a new series of lanthanide complexes with 4-ethylbenzoic acid | |
| Zhou et al. | Eu (III)-based metal-organic-frameworks luminescent probe and its sensing properties for nitrobenzene and Cu (II) | |
| Wu et al. | Designing functional metal-organic frameworks from a new tripodal carboxylate ligand: Fluorescence sensing and photocatalytic properties | |
| Collison et al. | Synthesis, crystallographic and spectroscopic characterization, and magnetic properties of mixed-ligand oxovanadium (IV) hydrotris (3, 5-dimethylpyrazolyl) borate complexes | |
| Vairam et al. | Preparation and thermal behaviour of divalent transition metal complexes of pyromellitic acid with hydrazine | |
| You et al. | Designed synthesis of an sp 2 carbon-conjugated fluorescent covalent organic framework for selective detection of Fe 3+ | |
| CN110551291B (en) | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof | |
| CN111848655A (en) | Synthesis of three-dimensional cadmium complex and application of three-dimensional cadmium complex as fluorescent probe | |
| Liu et al. | A novel hexanuclear Zn6 metallacycle as a luminescent sensor for the Fe3+ ion and CCl4 molecule | |
| Luo et al. | Three bismuth (III) complexes constructed by N-containing heterocyclic carboxylic acids: Synthesis, crystal structure and photocatalytic activity | |
| CN113336955B (en) | Hollow rare earth-based MOFs material based on solvothermal method | |
| CN111909390B (en) | Light-emitting metal-organic framework material based on TPB and polycarboxylic acid ligand and preparation method and application thereof | |
| Vansant et al. | Preparation, structural characterization and properties of malonamato (− 1) complexes | |
| Kilic et al. | Synthesis, spectral characterization, electrochemical studies and catalytic properties in Suzuki–Miyaura coupling reactions of the mononuclear PdII, trinuclear PdII (BPh2) 2 and RuII PdII RuII type complexes containing 4‐amino‐1‐benzyl piperidine and phenyl groups | |
| CN108191896B (en) | Dinuclear dysprosium cluster compound using 2-aldehyde-8-hydroxyquinoline ethanolamine Schiff base as ligand and synthetic method and application thereof | |
| Ye et al. | Synthesis, crystal structure, and thermal decomposition kinetics of complex [Nd (BA) 3 bipy] 2 | |
| CN113461965A (en) | Novel metal organic framework compound and preparation method and application thereof |
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 |