CN109400891A - A kind of cadmium Base Metal organic frame and its preparation method and application - Google Patents
A kind of cadmium Base Metal organic frame and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of cadmium Base Metal organic frames and its preparation method and application.A kind of novel porous three-dimensional cadmium Base Metal organic frame of plane aroma type ligand self assembly of the present invention by cadmium salt and containing tetracarboxylic acid acid functional group, in its structure, each cadmium ion and four carboxyl coordinations from different ligands, and four carboxyls of each ligand are coordinated with four cadmium ions respectively, the one-dimensional diamond passages along c- axis have been constructed, and then have formed three-dimensional framework.Cadmium Base Metal organic frame of the invention is the pts three-dimensional network topological structure of (4,4) connection, since it has many advantages, such as bigger serface, high porosity and big conjugation center, in CO2Its big conjugation center enhancing and CO can be passed through in adsorption process2Between interaction force, and then show to CO2High-selectivity adsorption performance and big adsorption capacity.Meanwhile such material has that synthetic method is simple, thermal stability is strong, chemical stability is strong, is expected to apply in the fields such as carbon dioxide capture and clean energy resource storage.
Description
Technical field
The present invention relates to field of functional materials more particularly to a kind of cadmium Base Metal organic frame and preparation method thereof and answer
With.
Background technique
Metal organic framework (MOFs) is the new function material bodies being self-assembly of by metal ion/cluster and organic ligand
System is widely used in attached aspiration, storage and separation the characteristics of due to its chemical stability, high surface area and high porosity
In.In recent years, due to CO2It is a large amount of discharge cause global warming to pose a serious threat the existence of the mankind, many researchers
It is devoted to study and synthesize selective CO2The MOFs of absorption property.In order to improve CO2Adsorption capacity and selectivity,
Various strategies are suggested, comprising: 1, the suitable ligand of selection；2, nitrogenous or other polar groups are introduced into carry out in hole rationally
Decoration；3, by increasing diversity, the size for changing ligand or the length of organic ligand, designing metal ion in MOFs structure
The modes such as coordination mode come reduced bore.However, existing strategy may cause the surface area and CO of MOFs2Under adsorption capacity
It drops and hinders its practical application.Therefore, it designs and synthesizes and has both big adsorption capacity and highly selective CO2The material of adsorption capacity is extremely
It closes important.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of cadmium Base Metal organic frames and its preparation method and application, should
Cadmium Base Metal organic frame is to CO2With high-selectivity adsorption ability.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of cadmium Base Metal organic frame, by cadmium salt and
Plane aroma type ligand self assembly containing tetracarboxylic acid acid functional group；The plane aroma type containing tetracarboxylic acid acid functional group is matched
Body is 1,3,6,8- tetracarboxylic pyrenes, is had the following structure:
Each cadmium ion and four carboxyl coordinations from different ligands, and four carboxyls of each ligand are respectively with four
A cadmium ion coordination.
Compared with the existing technology, the present invention passes through cadmium salt and 1,3,6,8- tetracarboxylic pyrene (H4PTC) ligand self assembly
A kind of novel porous three-dimensional cadmium Base Metal organic frame (Cd-PTC), is the pts three-dimensional network topological structure of (4,4) connection,
Its pointSymbol is (42·84), since it has many advantages, such as bigger serface, high porosity and big conjugation center,
CO2Its big conjugation center enhancing and CO can be passed through in adsorption process2Between interaction force, and then show to CO2Gao Xuan
Selecting property absorption property and big adsorption capacity.
A kind of preparation method of cadmium Base Metal organic frame, comprising the following steps:
S1: 1,3,6,8- tetrabromo pyrene and copper cyanider are dissolved in quinoline, heating stirring obtains 1,3,6,8- four cyanos
Pyrene；
S2: described 1,3,6,8- four cyano pyrene is dissolved in the in the mixed solvent of NaOH solution and dehydrated alcohol, is heated back
Stream, obtains 1,3,6,8- tetracarboxylic pyrenes；
S3: the 1,3,6,8- tetracarboxylic pyrene and cadmium salt are dissolved in the mixed solvent of nitric acid, dimethylformamide and water
In, heated sealed obtains cadmium Base Metal organic frame.
Further, in step S1, the molar ratio of described 1,3,6,8- tetrabromo pyrenes and copper cyanider is 1:(30~35).
Further, step S1 are as follows: 1,3,6,8- tetrabromo pyrene and copper cyanider are dissolved in quinoline, at 95~105 DEG C
0.5~1h is heated, then 45~50h of heating stirring at 225~235 DEG C；It is then cooled to room temperature, dehydrated alcohol is added, then
0.8~1.2h of heating stirring at 80~90 DEG C；Then it filters, successively washs filtering products therefrom with nitric acid, dehydrated alcohol, obtain
To 1,3,6,8- four cyano pyrene.
Further, in step S2, the volume ratio of the NaOH solution and dehydrated alcohol is 1:(1.5~1.8).
Further, step S2 are as follows: described 1,3,6,8- four cyano pyrene is dissolved in the mixed of NaOH solution and dehydrated alcohol
In bonding solvent, 20~28h is heated to reflux at 105~115 DEG C；It is then cooled to room temperature, is acidified to pH=1 with hydrochloric acid；Then
Filtering washs filtering products therefrom with water, dehydrated alcohol, obtains 1,3,6,8- tetracarboxylic pyrenes.
Further, in step S3, the molar ratio of described 1,3,6,8- tetracarboxylic pyrenes and cadmium salt is 1:(0.9~1.1).
Further, in step S3, the volume ratio of the nitric acid, dimethylformamide and water is 1:(65~70): (30~
35)。
Further, step S3 are as follows: described 1,3,6,8- tetracarboxylic pyrene and cadmium salt are dissolved in nitric acid, dimethylformamide
With the in the mixed solvent of water, 66~78h of heated sealed at 95~105 DEG C；It is then cooled to room temperature, is filtered, and use dimethyl
Formamide washing filtering products therefrom, obtains cadmium Base Metal organic frame.
Cadmium Base Metal organic frame of the present invention is in CO2Application in absorption and separation, the cadmium Base Metal have machine frame
Frame and CO2With strong interaction force, and can be from CO2/N2And CO2/CH4High-selectivity adsorption CO in mixture2。
In order to better understand and implement, illustrates the present invention with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is H4PTC ligand synthetic route chart.
Fig. 2 is Cd in Cd-PTC2+Central metal ion coordination mode schematic diagram.
Fig. 3 is deprotonation ligand PTC4-Coordination mode schematic diagram.
Fig. 4 is three-dimensional framework multi-panel stereogram of the Cd-PTC from [100] direction.
Fig. 5 is three-dimensional framework multi-panel stereogram of the Cd-PTC from [001] direction.
Fig. 6 is that view is filled in the space of the porous three-dimensional frame of Cd-PTC, has one-dimensional diamond passages along c- axis.
The view for the pts network topology structure that (4,4) that Fig. 7 is Cd-PTC connect.
Fig. 8 is the TGA curve of the Cd-PTC of Cd-PTC crude product and desolvation.
The PXRD figure that Fig. 9 is the Cd-PTC of Cd-PTC crude product and desolvation.
Figure 10 is nitrogen adsorption/desorption curve of the Cd-PTC of desolvation at 77K.
Figure 11 is the Cd-PTC of desolvation respectively at 273K and 298K, to CO2, CH4And N2Gas absorption isothermal
Line.
Figure 12 is the Cd-PTC of the desolvation calculated by IAST method to mixed gas CO2/N2(volume ratio 15/
And CO 85)2/CH2The selectivity of (volume ratio 50/50).
Figure 13 is at 298K, and the Cd-PTC of desolvation is to mixed gas CO2/N2The dynamic of (volume ratio 15/85) is worn
Saturating adsorption curve.
Figure 14 is at 298K, and the Cd-PTC of desolvation is to mixed gas CO2/CH4The dynamic of (volume ratio 50/50)
Penetrate adsorption curve.
Specific embodiment
The present invention provides a kind of cadmium Base Metal organic frames, and by cadmium salt and the plane containing tetracarboxylic acid acid functional group is fragrant
Type ligand self assembly；The plane aroma type ligand containing tetracarboxylic acid acid functional group is 1,3,6,8- tetracarboxylic pyrenes, tool
Just like flowering structure:
Each cadmium ion and four carboxyl coordinations from different ligands, and four carboxyls of each ligand are respectively with four
A cadmium ion coordination.The cadmium salt can be cadmium nitrate, caddy or cadmium sulfate.
The present invention also provides a kind of preparation methods of cadmium Base Metal organic frame, comprising the following steps:
(1) in molar ratio it is 1:(30~35 by 1,3,6,8- tetrabromo pyrene and copper cyanider) it is dissolved in quinoline, 95~105
0.5~1h is heated at DEG C, then 45~50h of heating stirring at 225~235 DEG C；It is then cooled to room temperature, anhydrous second is added
Alcohol, then 0.8~1.2h of heating stirring at 80~90 DEG C；Then it filters, successively washs filtering gained with nitric acid, dehydrated alcohol and produce
Object obtains 1,3,6,8- four cyano pyrenes.
(2) by the volume ratio that the 1,3,6,8- four cyano pyrene is dissolved in NaOH solution and dehydrated alcohol be 1:(1.5~
1.8) in the mixed solvent is heated to reflux 20~28h at 105~115 DEG C；It is then cooled to room temperature, is acidified to pH with hydrochloric acid
=1；Then it filters, washs filtering products therefrom with water, dehydrated alcohol, obtain 1,3,6,8- tetracarboxylic pyrenes.
(3) in molar ratio it is 1:(0.9~1.1 by the 1,3,6,8- tetracarboxylic pyrene and cadmium salt) it is dissolved in nitric acid, diformazan
The volume ratio of base formamide and water is 1:(65~70): the in the mixed solvent of (30~35), the heated sealed 66 at 95~105 DEG C
~78h；It is then cooled to room temperature, is filtered, and washs filtering products therefrom with dimethylformamide, obtaining cadmium Base Metal has machine frame
Frame (Me2NH2)2[Cd(PTC)]·2H2O。
It is further illustrated below by way of specific embodiment.
Embodiment 1
The preparation method of the cadmium Base Metal organic frame of the present embodiment, comprising the following steps:
(1) by 1,3,6,8- tetrabromo pyrene (12g, 23.4mmol) of raw material and copper cyanider Cu (CN)2(90g, 0.78mol) dissolution
In 120mL quinoline solvent, mixed solution is placed at 100 DEG C and heats 0.5h, then the heating stirring 48h at 230 DEG C；Then
It is cooled to room temperature, dehydrated alcohol, then the heating stirring 1h at 85 DEG C is added；Then it filters, obtained product is with mass fraction
30% nitric acid washing, to remove copper residue, then is washed with dehydrated alcohol repeatedly, obtains 1,3,6,8- four cyano pyrenes.
(2) by described 1,3,6,8- four cyano pyrene (2.26g, 7.5mmol) be dissolved in NaOH aqueous solution (10M, 60mL) and
The in the mixed solvent of dehydrated alcohol (EtOH, 90mL), is placed in the round-bottomed flask of 250mL, is heated to reflux for 24 hours at 105 DEG C；
It is then cooled to room temperature, pH=1 is acidified to the hydrochloric acid that mass fraction is 37%, the carboxylate formed in reflux course is matched
Body acidification, so that salt becomes carboxylic acid again again, and removes excessive NaOH in solution；Then filter, obtained product water and
Dehydrated alcohol washing, obtains 1,3,6,8- tetracarboxylic pyrene ligand (H4PTC), quality 1.84g, yield 62.5%.H4PTC
Ligand synthetic route chart is as shown in Figure 1.
(3) by the H4PTC ligand (19mg, 0.05mmol), Cd (NO3)2·4H2O (15mg, 0.05mmol) is dissolved in
The in the mixed solvent of nitric acid (5M, 60 μ L), dimethylformamide (DMF, 4mL) and water (2mL), sealing are placed in the reaction of 10mL glass
In bottle, 72h is heated at 100 DEG C；It being then cooled to room temperature, is filtered with the speed of 5 DEG C/min, obtained product is washed with DMF,
Then it air-dries, obtains cadmium Base Metal organic frame (Me2NH2)2[Cd(PTC)]·2H2O, i.e. C24H26N2O10Cd is (hereinafter abbreviated as
Cd-PTC), yield is 43% (amount based on ligand calculates).
Elemental analysis
Elemental analysis is obtained by 240 elemental analyser of Perkin-Elmer.C24H26N2O10Cd elemental analysis: it calculates
Value: C 46.88, H 4.26, N 4.56%；Measured value: C 46.69, H 4.20, N 4.58%.
Structural analysis
X-ray diffraction test uses graphite monochromatic Mo-K alpha ray by Bruker APEX II diffractometerIt is carried out at 296K.Empirical absorption correction value is used to correct for diffraction.By being used respectively in APEX2
More scan methods of SADABS and XPREP carry out absorption correction and space group determines.Using SHELXL program (SHELXTL-
2014) structure, is solved by direct method, and uses F2Complete matrix least square method refines to structure.In final circulation,
Using the isotropism displacement parameter of organic hydrogen atom by the position of organic hydrogen atom of computational theory.Due to [Me2NH2]+Sun from
Son and free solvent molecule are highly disordered in the structure, the interference of its scattering are eliminated by the SQUEEZE program of PLATON, most
The fruit that terminates is used for the determination of structure.Crystal parameter, data collection and the data of refinement are summarized in table 1；Table 2 lists selected
Bond distance, structure are as shown in Figure 2.
The refined structure crystal data of 1 Cd-PTC of table
The bond distance of 2 Cd-PTC of table
Structural analysis shows that Cd-PTC has monoclinic system C2/c space group.In the structure of Cd-PTC, each Cd2+In
Heart metal ion and the carboxylic acid functional of four bidentates chelating from four different ligands are coordinated, as shown in Figure 2；Each go matter
Sonization PTC4-Ligand connects four Cd2+Ion, four all carboxyls both participate in coordination, as shown in Figure 3；To form edge
The novel three-dimensional metal organic framework of a- axis, as shown in Figure 4.The carboxyl and Cd of each ligand2+It is coordinated the small basic unit formed
One-dimensional diamond passages are joined together to form by the pyrene ring in ligand, as it can be seen in figures 5 and 6, the frame is along [001] and [100]
Direction has one-dimensional diamond passages, having a size ofBy PLATON calculate Solvent accessibilities volume is(per unit unit cell volume is), porosity is up to 53.5%.In order to better grasp immanent structure, answer
Analysis of Topological Structure, each ligand and each Cd are carried out to Cd-PTC with 4.0 program of TOPOS2+Ion can be respectively as 4 connections
Node, therefore entire frame can be considered as the pts network topology of binode (4,4) connection,Symbol is (42·84),
As shown in Figure 7.
Thermogravimetric analysis
Thermogravimetric analysis (TGA) is on 209 F3 Tarsus of Netzsch Thermo Microbalance TG, in nitrogen
Under air-flow, carried out with the heating rate of 5 DEG C/min from room temperature to 80 DEG C.
The thermal gravimetric analysis curve of the Cd-PTC of Cd-PTC crude product and desolvation is as shown in Figure 8.Cd-PTC crude product is first
Secondary weight loss is 5.39%, the loss (calculated value 5.85%) corresponding to solvent DMF molecule；Then, when temperature is higher than 250 DEG C
When, there is weight loss sharply in entire frame, this is attributed to the decomposition of frame.
X is measured at 40kV and 40mA with Cu target pipe and graphite monochromator on Bruker D8 Advance diffractometer to penetrate
Line powder diagram (PXRD), as shown in figure 9, diffraction maximum between Cd-PTC product and analog product from single crystal analysis result
Matched well, it was confirmed that the phase purity of Cd-PTC product.
Adsorption analysis
Using Quantachrome Autosorb-iQ-MP gas absorption analysis-e/or determining adsorption isotherm.In order to measure
The hole characteristic of Cd-PTC carries out N2 adsorption experiment.The product being prepared is heated into 4h at 80 DEG C under vacuum, to remove
There is object hydrone, obtains the Cd-PTC of desolvation.It is tested by further TGA and PXRD, the results showed that desolvation
Cd-PTC after removing all hydrones, frame keeps complete and keeps its original crystallinity (as shown in FIG. 8 and 9).
At 77K, 1.0atm, N2 adsorption/desorption isotherm of the Cd-PTC of desolvation increases severely when starting, bent for typical I type
Line, as shown in Figure 10, N2Adsorbance is reached for 302.4cm3/ g shows it with pore characteristics.Its Brunauer-Emmett-
Teller (BET) specific surface area is 965m2/ g, total pore volume 0.57cm3/g。
In order to preferably measure porosity, the Cd-PTC of desolvation carries out CO at 273K and 298K respectively2、CH4And N2
Absorption measurement.As shown in figure 11, Cd-PTC is in 273K to CO2With 80cm3The good adsorption amount of/g, in 298K to CO2Tool
There is 58cm3The adsorbance of/g.However, Cd-PTC is to CH under the same conditions4And N2Adsorbance it is very small, in 273K and 298K
Under, for CH4Adsorbance be respectively 9.2cm3/ g and 6.7cm3/ g, for N2Adsorbance be respectively 2.8cm3/ g and
1.9cm3/g.Obviously, opposite CH4And N2, Cd-PTC is to CO2With higher adsorbance, this phenomenon is attributable to CO2It is biggish
Quadrupole moment (- 1.4 × 10-39cm2) specific interaction can be generated with Cd-PTC main body framework.
In order to preferably test the adsorptive selectivity and separating property of Cd-PTC, using Ideal adsorption solution theory (IAST)
It calculates when pressure is up to 100kPa, Cd-PTC is to CO2With N2Mixed gas (volume ratio 15/85), CO2With CH4Mixed gas
The separation selectivity of (volume ratio 50/50).As shown in figure 12, gradually rising with pressure, Cd-PTC is to CO2/N2(volume
Than for the selection coefficient (CO of absorption 15/85)2The N of volume and absorption2The ratio between volume) from 175 it is gradually lowered to 106.Cd-PTC
To CO2/CH4Selection coefficient (the CO of absorption of (volume ratio 50/50)2The CH of volume and absorption4The ratio between volume) it is near from 31
19.These are the result shows that relative to N2And CH4, Cd-PTC is to CO2With higher selection coefficient, thus it is to CO2With stronger
Adsorption capacity.
In order to further determine specific separation and purification performance, Kinetic penetration adsorption experiment has also been carried out.Such as Figure 13 institute
Show, at 298K, before adsorption column penetrates, by CO2/N2Gas is mixed according to 15/85 volume ratio, and Kinetic penetration adsorbs table
Bright CO2It can be successfully separated from mixture, dynamic CO2Adsorbance is 0.78mmol/g, the property with HKUST-1 and IRMOF-74
Can quite, adsorbance is respectively 0.45 and 0.8mmol/g.As shown in figure 14, for CO2/CH4(volume ratio 50/50), by
It is relatively low in the segregation ratio of mixed gas, within a short period of time it can be observed that penetration phenomenon.
Compared with the existing technology, the present invention passes through cadmium salt and 1,3,6,8- tetracarboxylic pyrene (H4PTC) ligand self assembly
One kind having the novel porous three-dimensional cadmium Base Metal organic frame (Cd-PTC) of the pts three-dimensional network topological structure of (4,4) connection,
The frame has porosity and big conjugation center, and gas absorption tests the Cd-PTC and CO for showing desolvation2With strong
Interaction force, and can be from CO2/N2And CO2/CH4High-selectivity adsorption CO in mixture2。
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (10)
1. a kind of cadmium Base Metal organic frame, it is characterised in that: pass through cadmium salt and the plane aroma type containing tetracarboxylic acid acid functional group
Ligand self assembly；The plane aroma type ligand containing tetracarboxylic acid acid functional group is 1,3,6,8- tetracarboxylic pyrenes, is had
Such as flowering structure:
Each cadmium ion and four carboxyl coordinations from different ligands, and four carboxyls of each ligand respectively with four cadmiums
Ion coordination.
2. a kind of preparation method of cadmium Base Metal organic frame, it is characterised in that: the following steps are included:
S1: 1,3,6,8- tetrabromo pyrene and copper cyanider are dissolved in quinoline, heating stirring obtains 1,3,6,8- four cyano pyrenes；
S2: described 1,3,6,8- four cyano pyrene is dissolved in the in the mixed solvent of NaOH solution and dehydrated alcohol, is heated to reflux, obtains
To 1,3,6,8- tetracarboxylic pyrene；
Described 1,3,6,8- tetracarboxylic pyrene and cadmium salt: being dissolved in the in the mixed solvent of nitric acid, dimethylformamide and water by S3, close
Envelope heating, obtains cadmium Base Metal organic frame.
3. the preparation method of cadmium Base Metal organic frame according to claim 2, it is characterised in that: described in step S1
The molar ratio of 1,3,6,8- tetrabromo pyrene and copper cyanider is 1:(30~35).
4. the preparation method of cadmium Base Metal organic frame according to claim 3, it is characterised in that: step S1 are as follows: by 1,
3,6,8- tetrabromo pyrenes and copper cyanider are dissolved in quinoline, 0.5~1h are heated at 95~105 DEG C, then at 225~235 DEG C
45~50h of heating stirring；It is then cooled to room temperature, dehydrated alcohol, then 0.8~1.2h of heating stirring at 80~90 DEG C is added；
Then it filters, successively washs filtering products therefrom with nitric acid, dehydrated alcohol, obtain 1,3,6,8- four cyano pyrenes.
5. the preparation method of cadmium Base Metal organic frame according to claim 2, it is characterised in that: described in step S2
NaOH solution and the volume ratio of dehydrated alcohol are 1:(1.5~1.8).
6. the preparation method of cadmium Base Metal organic frame according to claim 5, it is characterised in that: step S2 are as follows: by institute
The in the mixed solvent that 1,3,6,8- four cyano pyrenes are dissolved in NaOH solution and dehydrated alcohol is stated, is heated to reflux at 105~115 DEG C
20~28h；It is then cooled to room temperature, is acidified to pH=1 with hydrochloric acid；Then it filters, washs filtering gained with water, dehydrated alcohol and produce
Object obtains 1,3,6,8- tetracarboxylic pyrenes.
7. the preparation method of cadmium Base Metal organic frame according to claim 2, it is characterised in that: described in step S3
The molar ratio of 1,3,6,8- tetracarboxylic pyrene and cadmium salt is 1:(0.9~1.1).
8. the preparation method of cadmium Base Metal organic frame according to claim 7, it is characterised in that: described in step S3
The volume ratio of nitric acid, dimethylformamide and water is 1:(65~70): (30~35).
9. the preparation method of cadmium Base Metal organic frame according to claim 8, it is characterised in that: step S3 are as follows: by institute
It states 1,3,6,8- tetracarboxylic pyrenes and cadmium salt is dissolved in the in the mixed solvent of nitric acid, dimethylformamide and water, at 95~105 DEG C
66~78h of heated sealed；It is then cooled to room temperature, is filtered, and washs filtering products therefrom with dimethylformamide, obtains cadmium base
Metal organic frame.
10. cadmium Base Metal organic frame described in claim 1 is in CO2Application in absorption and separation.
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| CN201811051923.4A CN109400891B (en) | 2018-09-10 | 2018-09-10 | Cadmium-based metal organic framework and preparation method and application thereof |
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Cited By (4)
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| WO2020060873A3 (en) * | 2018-09-14 | 2020-04-23 | Rutgers, The State University Of New Jersey | Mof compositions for selective separation of hydrocarbons |
| CN114105901A (en) * | 2020-08-27 | 2022-03-01 | 江西省科学院应用化学研究所 | Metal organic framework based on Cd (II), composite catalyst, preparation method and application thereof |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
| CN116693868B (en) * | 2023-05-10 | 2024-05-10 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020060873A3 (en) * | 2018-09-14 | 2020-04-23 | Rutgers, The State University Of New Jersey | Mof compositions for selective separation of hydrocarbons |
| US11918951B2 (en) | 2018-09-14 | 2024-03-05 | Rutgers, The State University Of New Jersey | MOF compositions for selective separation of hydrocarbons |
| CN114105901A (en) * | 2020-08-27 | 2022-03-01 | 江西省科学院应用化学研究所 | Metal organic framework based on Cd (II), composite catalyst, preparation method and application thereof |
| CN114105901B (en) * | 2020-08-27 | 2022-12-02 | 江西省科学院应用化学研究所 | Metal organic framework based on Cd (II), composite catalyst, preparation method and application thereof |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
| CN116693868B (en) * | 2023-05-10 | 2024-05-10 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
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