WO2022038627A1 - Hybrides cof-graphène et cof-cnt tridimensionnels ayant une stabilité chimique remarquable pour le stockage de méthane - Google Patents

Hybrides cof-graphène et cof-cnt tridimensionnels ayant une stabilité chimique remarquable pour le stockage de méthane Download PDF

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WO2022038627A1
WO2022038627A1 PCT/IN2021/050726 IN2021050726W WO2022038627A1 WO 2022038627 A1 WO2022038627 A1 WO 2022038627A1 IN 2021050726 W IN2021050726 W IN 2021050726W WO 2022038627 A1 WO2022038627 A1 WO 2022038627A1
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cof
azo
cofs
graphene
cnt
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Rahul Banerjee
Jugal Kishore DAS
Nillotpal SINGHA
Himadri Sekhar Sasmal
Kaushik Dey
Deepak Vjjendra SHASTRY
Nandakumar Thenmani
Sanjeev Kumar
Parivesh Chugh
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Indian Institute Of Science Education And Research (Iiser) Kolkata
Gail (India) Limited
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0241—Imines or enamines

Definitions

  • the present invention relates to Porous Crystalline Three Dimensional Covalent Organic Frameworks with Remarkable Chemical Stability for Methane Storage. More particularly, the present invention relates to Porous Crystalline Three Dimensional Covalent Organic Frameworks Composed of Carbon Nanotube or Graphene with Exceptional Stability and High Surface Area.
  • Covalent organic frameworks are a new class of porous covalent organic structures whose pillar is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be attained.
  • COFs are made by a combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si.
  • the current gas storage target set by the Department of Energy (DOE) is 350 cc/g at 35 bars, which is comparable to the energy density of the compressed natural gas at 250 bar.
  • DOE Department of Energy
  • hybrid porous solids are one of the most amiable and interesting materials due to their tunable structures, multifunctional properties, and having their numerous applications and particularly more vital in the domain of adsorption and storage of gases molecules.
  • 3D COFs or its composites are necessary which might present many opportunities in the functional material chemistry owing to their unique porous structure and potential applications in diversified areas.
  • at least one organic linker is required to be three dimensional in nature which could connect with the other building blocks in all three-dimensional ways to form covalently linked 3D framework structure.
  • the structure of 3D COFs will be of different topology and thereby generating a 3D pore channel which will be responsible for a very high value of the surface area in these materials.
  • the current inventors had successfully synthesized the 3D COF>TpOMe-TAPM and recorded its methane storage capacity. Also, the current inventors had reported a unique strategy to enhance both the crystallinity and surface area of COF>TpOMe-TAPM which was enhanced from 558 to 1224 m 2 /g using some modified synthetic strategies. The inventors had also successfully synthesized another highly crystalline 3D COF>Tp-TAPM following the same recipe. In another report, the present inventors had shown COF>Tp_Azo, which has a better surface area than the 3D COF>Tp_TAPM. Therefore, the better performance/ surf ace area of 3D COF>Tp_Azo has driven the present inventors to a new direction in investigating the 3D COFs with higher uptake of gases, particularly, methane.
  • Fig. 1 depicts the synthetic route of the formation of COF>Tp_Azo
  • Fig. 2 depicts a sequential pictorial representation of the formation of COF>Tp_Azo in solid-state
  • Fig. 3 depicts a comparison of FT-IR spectra between synthesized COF>Tp_Azo and the starting materials (Tp and Azo)
  • Fig. 4 shows PXRD patterns of COF>Tp_Azo without CNT or graphene
  • Fig. 5 shows the synthetic route of the formation of COF>Tp_Azo@CNT
  • Fig. 6 depicts a sequential pictorial representation of the formation of COF>Tp_Azo@CNT in solid-state
  • Fig. 7 shows FTIR spectra of COF>TpAzo and COF>TpAzo@CNT composite
  • Fig. 8 shows the comparative study of PXRD patterns among Pristine Carbon nanotube, COF>Tp_Azo and COF>Tp_Azo@Graphene composite
  • Fig. 9 shows the synthetic route of the formation of COF>Tp_Azo@Graphene
  • Fig. 10 depicts a sequential pictorial representation of the formation of COF>Tp_Azo@Graphene in solid-state
  • Fig. 11 shows FTIR spectra of COF>TpAzo and COF>TpAzo@Graphene composite
  • Fig. 12 depicts the comparative study of PXRD patterns among (a) Pristine Graphene, COF>Tp_Azo, and COF>Tp_Azo@Graphene composite
  • Fig. 13 shows FESEM images of COF>Tp_Azo (a-b), COF>Tp_Azo@CNT (c), and COF>Tp_Azo@Graphene (d)
  • Fig. 14 shows TEM images of COF>Tp_Azo@CNT
  • Fig. 15 shows Line mapping (A-E) and EDX spectrum (F) of COF>Tp_Azo@CNT
  • Fig. 16 depicts the comparative study of the thermal stability by TGA curve (a) and DTG curve (b) of three different COF>Tp_Azo, COF>Tp_Azo@Graphene and COF>Tp_Azo@CNT
  • Fig. 17 shows N2 adsorption isotherm of synthesized COF>Tp_Azo at 77 K
  • Fig. 18 shows N2 adsorption isotherm of synthesized of COF>Tp_Azo@Graphene at 77 K
  • Fig. 19 shows N2 adsorption isotherm of synthesized of COF>Tp_Azo@CNT at 77 K
  • Fig. 20 shows CEL adsorption isotherm of synthesized COF>Tp_Azo at 298 K
  • Fig. 21 shows CH4 adsorption isotherm of synthesized COF>Tp_Azo@Graphene at 298 K
  • Fig. 22 shows CEL adsorption isotherm of synthesized COF>Tp_Azo@CNT at 298 K
  • Fig. 23 shows the Pellet making process: The picture of a pelletizing machine (A), the zoomed picture of the pressure gauge where the pressure has been fixed to 1 ton ⁇ 907 kg for 1 min on the COF samples to make the COF pellets (B), the images of TpAzo COF (C), TpAzo@Graphene (B), and TpAzo@CNT (C) pellets.
  • Fig. 24 shows the image of the closest packing of TpAzo@CNT COF pellets inside a standard plastic vial of 7 ml volume capacity.
  • Fig. 25 shows the PXRD patterns of TpAzo@CNT in powder (left) and pellet (right) forms.
  • Fig. 26 shows the N2 adsorption isotherms of synthesized TpAzo@CNT powder (left) and pellet (right) at 77K.
  • Fig. 27 shows the CH4 adsorption isotherms of synthesized TpAzo (powder), TpAzo@Graphene (pellet), and TpAzo@CNT pellet at 298 K. The adsorption isotherm of the pellet is calculated in V/V (STP).
  • Fig. 28 shows Variation of methane uptake by TpAzo@CNT with pressure for 5 cycles.
  • the present invention provides Porous Crystalline Three Dimensional Covalent Organic Frameworks Composed of Carbon Nanotube or Graphene with Exceptional Stability and High Surface Area.
  • the invention provides Porous Crystalline Three Dimensional Covalent Organic Frameworks 3D (COFs) hybrid composites which comprises Graphene or Carbon nanotube incorporated into a COF composed of an aldehyde and an azo amine.
  • COFs Porous Crystalline Three Dimensional Covalent Organic Frameworks 3D
  • the aldehyde is selected from the group consisting of 2,4,6-Trimethoxy-l,3,5- benzenetricarbaldehyde (TpOMe) or Triformylphloroglucinol (TP).
  • TpOMe 2,4,6-Trimethoxy-l,3,5- benzenetricarbaldehyde
  • TP Triformylphloroglucinol
  • the aldehyde is Triformylphloroglucinol (TP) and the azo amine is 4,4’- Azodianiline
  • the COFs are prepared using judicially selected 3D linkers, i.e., 2,4,6- Trimethoxy-l,3,5-benzenetricarbaldehyde (TpOMe) and Triformylphloroglucinol (TP) .
  • TpOMe 2,4,6- Trimethoxy-l,3,5-benzenetricarbaldehyde
  • TP Triformylphloroglucinol
  • the present invention provides 3D COFs hybrid composites prepared of Tp aldehyde, Azo amine, and graphene or with carbon nanotube. Incorporation of CNTs or graphene into COFs results in better crystals because of the unusual mechanical, thermo-conductive, electro-conductive, and hydrophobic properties of the CNTs & graphene. According to the present invention, the following 3D COFs with improved properties such as high surface area and methane uptake are provided:
  • the COFs thus obtained are characterized using PXRD and further by measuring the porosity in addition to TGA, FTIR, BET, FESEM, Raman & TEM.
  • the COFs provided in the present invention are excellent candidates for methane storage due to the formation of unique 3D architecture, properties like charge distribution, and higher surface area for methane uptake.
  • the present invention provides Porous Crystalline Three Dimensional Covalent Organic Frameworks Composed of Carbon Nanotube or Graphene with Exceptional Stability and High Surface Area, for Methane Storage.
  • COFs are an artistic class of functional nanostructures with the remarkable properties like the extraordinary combination of high crystallinity, tunable pore size, large surface area, and distinctive molecular architecture and thus become a pretty interesting material for numerous applications ranging from energy to environment.
  • COFs are a prominent and rapidly emerging class of lightweight materials and influence the gravimetric storage capacity which makes them excellent candidates for gas storage applications.
  • carbon-based derivatives such as graphene, fullerene, and carbon nanotubes materials have shown unique properties, such as good electrical conductivity and good thermal/chemical stability as well as good mechanical properties. These materials are more captivating because of its low cost with negligible toxicity. These outstanding properties make them attractive for various applications, such as environmental remediation, energy storage systems (i.e. batteries, supercapacitors), and catalysis application.
  • both these materials have associated and imposed with some inherent disadvantages which restrict their applications to a greater extent.
  • COFs exhibits inferior performance at poor electron mobility and the aggregated 7t-stacked layers.
  • they have difficulty in providing strong adsorptive forces to retain small molecules under certain conditions because of their open framework and which makes it difficult to post-functionalize.
  • graphene materials lacks porosity and exhibit low surface area apart from other positive properties thereby limiting its applications.
  • the present inventors have provided a feasible solution to increase the performance of COFs by introducing graphene or CNT-based composite materials into it.
  • these hybrid composites exhibit synergistic performance like high chemical and operational stability, high porosity, and thus higher storage of gases such as methane.
  • These unique composites of the present invention additionally lead to surprising improvements in electronic conductivity and stability. Therefore, the hybrid composites made from the assembly of graphene/CNT -based COFs material possess extraordinary characteristics with respect to the parent materials.
  • the COF/graphene or CNT-based composite materials not only eliminates the disadvantages of parent materials such as COFs and Graphene/CNTs but also exhibit synergistic properties, as discussed herein below. More challenging is the synthesis of graphene or CNT/COF composites without sacrificing their individual properties. Generally, graphene intercalation in COFs reduces the surface area and loses its original porosity. To circumvent the above problem, a simple and cost-effective method is provided to develop these hybrid materials without losing its comprehensive porosity.
  • the present invention provides Porous Crystalline Three Dimensional Covalent Organic Frameworks Composed of Carbon Nanotube or Graphene with Exceptional Stability and High Surface Area.
  • the present invention provides Porous Crystalline Three Dimensional Covalent Organic Frameworks 3D (COFs) hybrid composites which comprises Graphene or Carbon nanotube incorporated into a COF composed of an aldehyde and an azoamine.
  • COFs Three Dimensional Covalent Organic Frameworks 3D
  • the aldehyde is selected from the group consisting of 2,4,6-Trimethoxy-l,3,5- benzenetricarbaldehyde (TpOMe) or Triformylphloroglucinol (TP).
  • the aldehyde is Triformylphloroglucinol (TP) and the azo amine is 4,4’ -Azodianiline
  • the COFs are prepared using judicially selected 3D linkers, i.e., 2,4,6-Trimethoxy-l,3,5-benzenetricarbaldehyde (TpOMe) and Triformylphloroglucinol (Tp)
  • the present invention provides 3D COF composite materials prepared of Tp aldehyde, Azo amine, and graphene or carbon nanotube and further characterized these hybrid materials thus obtained using PXRD and by measuring the porosity, in addition to TGA, FTIR, BET, FESEM, Raman & TEM. Accordingly, the present invention provides the following 3D COFswith improved properties such as higher surface area and methane uptake: a) COF>Tp_Azo@Graphene b) COF> Tp_Azo@CNT
  • the present inventors have surprisingly found that the incorporation of conjugated 2D graphene sheets or ID carbon nanotubes inside the COF>Tp_Azo greatly improves the quality as well as the performance of the native COF>Tp_Azo. Because of the extensive conjugation through ⁇ -electrons, these types of carbon allotropes show excellent mechanical, electrical, and thermophysical properties and also high chemical stability. Most importantly, the charge separation induced polarity which can interact with the protons of a CHi molecule and thus enhances its uptake.
  • the present invention provides rapid, scalable, solid-state synthesis of porous crystalline three dimensional Covalent Organic Frameworks 3D (COFs) hybrid composite having exceptional chemical Stability and High Surface Area for Methane Storage , which process comprises;
  • step a) Adding graphene or carbon nanotubes to the mixture of step a) and heating the mass at 70 to 100 °C to obtain porous composite COFs;
  • the aldehyde is Triformylphloroglucinol and the amine is 4,4’ -Azodianiline.
  • the porous composite COF thus obtained displayed a very high surface area (up to 2400 m 2 /g) and excellent crystallinity.
  • Porous Crystalline Three Dimensional Covalent Organic Frameworks, 3D(COFs) hybrid composites thus obtained can be compressed into desired shape and size without compromising on chemical stability, crystallinity, porosity and Surface Area.
  • Three-dimensional COFs of the present invention have a very high surface area as well as porosity and hence the 3D COFs exhibit full accessibility from within the pores to all the edges and faces of the molecular units used to construct the framework, for the gas storage.
  • maximizing the number of edges arising from aromatic rings in a porous material increases the number of adsorption sites and surface area.
  • the structures of COFs contain no latent edges, and the entire framework is a surface replete with binding sites for gas adsorption.
  • COF-105 reported in the prior art has a surface area of 6450 m 2 /g (equivalent to 1.4 American football fields per gram) and COF-108 has a pore volume of 5.4 cm 3 /g with the lowest density crystalline material known (0.17 g/cm 3 ).
  • the pristine COF>Tp_Azo material is selected due to its exceptional inherent properties like fine thermal stability, upper surface area as well as better chemical stability.
  • the protocol for the synthesis of these hybrid materials is optimized and the formation mechanism is explained through different characterizations techniques like PXRD, TGA, FTIR, BET, FESEM, Raman & TEM, etc. From the XRD patterns, it shows that the synthesized materials are highly crystalline and their ⁇ hkl> values are matching well with the reported data.
  • the thermal stability of the prepared composite materials is explained by TGA which shows higher thermal stability as compared to pristine COF materials. The thermal stability is achieved due to the incorporation of CNT in the COF matrix.
  • the performance of these hybrid materials is evaluated for CO2 and CH4 adsorption study and observed that the implication of CNT and graphene to the pristine COF material gives a higher methane uptake value over the pristine materials.
  • the vial was then removed from the oven and allowed to cool down to room temperature.
  • the COF was then washed sequentially with water, N, N-dimethylacetamide, hot water, and finally acetone just before drying the sample in the oven to make it prepare for characterizations and methane uptake.
  • the washing is done and continues till the yellow color disappears in N, N-dimethylacetamide (hot condition at 90 °C), then washing it with hot water several times -8-10 h followed by acetone.
  • the synthetic route of the formation of COF>Tp_Azo@CNT is shown in Figure 5 and sequential pictorial representation of the formation of COF>Tp_Azo@CNT in solid-state is shown in Figure 6.
  • the pristine multiwalled carbon nanotube shows its characteristic sharp peak at 25.9°, which is assigned as the 29 (002) facet and that is very much close to 26.2° present in the COF>Tp_Azo@CNT, concluding the presence of carbon nanotube in the composite.
  • the vial was then removed from the oven and allowed to cool down to room temperature.
  • the COF was then washed sequentially with water, N, N-dimethylacetamide, and finally acetone just before drying the sample in the oven to make it prepare for characterizations and methane uptake.
  • the synthetic route of the formation of COF>Tp_Azo@Graphene is shown in Figure 9.
  • the sequential pictorial representation of the formation of COF>Tp_Azo@Graphene in solid-state is shown in Figure 1 .
  • the pristine graphene shows its characteristic sharp peak at 26.48°, which is assigned as the 29 (002) facet and that is very much close to 26.88° present in the COF>Tp_Azo@graphene, concluding the presence of graphene in the composite.
  • the comparative study of PXRD patterns among (a) Pristine Graphene, COF>Tp_Azo, and COF>Tp_Azo@Graphene composite is shown in Figure 12.
  • FESEM Field Emission Scanning Electron Microscope
  • TEM images were obtained using FEI Tecnai G2 F20 X-TWIN TEM at an accelerating voltage of 200 kV.
  • the TEM samples were prepared for analysis by drop-casting the samples (dispersed in isopropanol) on copper grids TEMWindow (TED PELLA, INC. 200 mesh).
  • the image (Fig. 14) is showing the nanofibers corresponding to the carbon nanotubes surrounded by the COF particles.
  • Thermogravimetric analysis was carried out on a TG50 analyzer (Mettler-Toledo) and an SDT Q600 TG-DTA analyzer under N2 atmosphere at a heating rate of 10 °C min- 1 within a temperature range of 30-900 °C. It has been observed that the native COF>Tp_Azo is stable up to 346 °C, while COF>Tp_Azo@Graphene and COF>Tp_Azo@ CNT are stable up to 358 °C and 371 °C respectively in terms of their thermal stability (Fig. 16 a). The next calculation that is useful and finalizes the characterization is the peak calculation of the 1st derivative of the weight loss curve.
  • the 1st derivative peak temperatures are 433 °C, 438 °C, and 443 °C for COF>Tp_Azo,COF>Tp_Azo@Graphene, and COF>Tp_Azo@ CNT respectively (Fig. 16 b).
  • the peak of the first derivative indicates the point of the greatest rate of change on the weight loss curve. This is also known as the inflection point. Hence, comparatively higher thermal stability is noticed in the case of hybrid materials.
  • the porosity of the COF-TpAzo was established by Quantachrome Autosorb-iQ2 N2 sorption-desorption measurements. Nitrogen adsorption analyses were performed at 77 K using a liquid nitrogen bath (77 K) on a Quantachrome Quadrasorb automatic volumetric instrument. All the COFs samples were outgassed for 12 h at 120 °C under vacuum prior to the gas adsorption studies. The surface areas were evaluated using the Brunauer-Emmett-Teller (BET) model applied between P/Po values of 0.05 and 0.3 for microporous and mesoporous COFs.
  • BET Brunauer-Emmett-Teller
  • the Tp_AzoCOF shows significantly high N2 uptake estimating to BET surface areas of 2372 m 2 /g (Fig.17).
  • the isotherm is typical of the Type II curve and shows a reversible adsorption and desorption feature indicating a reversible N2 uptake.
  • the surface area of the COF indicates the high porosity of the surface and it also indicates that there is a high probability of methane uptake at high pressure.
  • N2 adsorption isotherm of synthesized COF>Tp_Azo at 77 K is shown in Figure 17.
  • COF>Tp_Azo, COF>Tp_Azo@Graphene, and COF>Tp_Azo@CNT methane adsorption study was performed.
  • the COF>Tp_Azo material performs well at 298 K and the result is almost 180 CC/g at 65 bar (Fig.20).
  • the composite COF materials i.e., COF>Tp_Azo@Graphene (Fig.21), and COF>Tp_Azo@CNT (Fig.22) show the value nearly same to the pristine COF, 164 CC/g and 166 CC/g at 65 bar respectively.
  • the CHi adsorption plots are given here for better understanding.
  • Fig. 24 shows a close packing of 30 pellets inside a standard 7 mL screwed plastic vial representing a gas cylinder that is fully packed with the porous pellets.
  • the amount of the adsorbed gas inside such cylinders is not completely due to pellets.
  • Fig. 27 shows the CH4 adsorption isotherms of synthesized TpAzo (powder), TpAzo@Graphene (pellet), and TpAzo@CNT pellet at 298 K.
  • the adsorption isotherm of the pellet is calculated in V/V (STP).
  • STP V/V
  • the TpAzo (powder), TpAzo@Graphene (pellet), and TpAzo@CNT pellet shows the CH4 uptake of 102, 167, 164 cm 3 /cm 3 respectively. But at higher pressure at 65 bar the materials show pretty good CH4 adsorption capacity which is near to the DOE target.
  • TpAzo pellet
  • TpAzo@Graphene pellet
  • TpAzo@CNT pellet shows the CH4 uptake of 173, 260, 262 cm 3 /cm 3 respectively at 65 bar.Dynamic CH4 adsorption study for TpAzo@CNT:
  • Fig. 29 shows the comparison of the experimental (green) and simulated eclipsed- AA (pink) and Pawley refinement difference (grey) for the synthesized COF TpAzo@CNT.
  • the experimental PXRD patterns with ⁇ 100> peak at 20 ⁇ 3.588 (TpAzo@CNT) is in accordance with the simulated AA eclipsed stacking model (Fig. 29), and the error is ⁇ 3%.
  • Table 1 evidently demonstrates that the present 3D COFs exhibits higher adsorption of CH4 uptake compared known COFs; in addition to higher thermal and chemical stability.
  • Table 2 CH4 uptakes for TpAzo@CNT at 35, 40, and 65 bar pressures for each cycle at 283 K
  • Density of the bulk materials is ⁇ 1.58 g/cc
  • Methane adsorptions for TpAzo@CNT at different cycles at 35, 40, and 65 bar pressures are tabulated above (Table 2).
  • the experiment has been performed at 283 K.
  • adsorption decreases with repetition of the experiments and that is probably because of improper desorption or activation or the regeneration of the samples.
  • the material sustains its crystallinity and porosity if properly activated and made the pores free of any gas.
  • DOE target for methane adsorption DOE target for methane adsorption:
  • a sol-gel monolithic metal-organic framework HKUST-1 shows 270 cc/cc volumetric adsorption surpasses the DOE target published in Nature Materials in 2017. However, the material loses the efficiency while densified and packed.
  • the current storage target for adsorbed natural gas (ANG) set by US Department of Energy (DOE) is 263 cm 3 (STP) cm' 3 at room temperature and 65 bar, equivalent to the storage capacity of an empty tank at 250 bar.
  • Methane may be used as a transportation fuel but current gas-powered vehicles rely on high- pressure or low-temperature tanks to allow sufficient fuel to be stored on-board, which can be costly and unwieldy.
  • Research efforts have therefore focused on porous materials such as metal-organic frameworks (MOFs) or Covalent Organic Frameworks (COFs) that can adsorb, store and release methane at more reasonable pressures and temperatures. While the capacities of many MOFs in powder form are promising, these typically have low packing densities when formed into densified pellets of the type required in an on-board tank, limiting their practical storage capacity.
  • MOFs metal-organic frameworks
  • COFs Covalent Organic Frameworks
  • the present invention provides Tp_Azo/CNT and Tp Azo/Graphene and the synthesis of Tp_Azo/CNT and Tp_Azo/Graphene hybrid materials for CH4 storage application using simple, low cost, and energy-efficient techniques.
  • the materials are highly crystalline which shows the higher surface area with better thermal stability as compared to pristine COF; hence, can be successfully employed in gas storage applications.
  • the materials are highly crystalline which shows the higher surface area with better thermal stability as compared to pristine COF; hence, can be useful for gas storage applications.
  • the ratio of CNT or Graphene and pristine COF in the hybrid material can be optimized without sacrificing the surface area and other properties which are the main approach to influence the gas adsorption behavior and mainly useful for higher methane uptake.
  • hybrid composite materials provided in the present invention is useful for high methane uptake and could be a platform for other application as given below-

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Nanotechnology (AREA)
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Abstract

La présente invention concerne des structures organiques covalentes tridimensionnelles cristallines poreuses présentant une stabilité chimique remarquable pour le stockage de méthane. Plus particulièrement, la présente invention concerne des structures organiques covalentes tridimensionnelles cristallines poreuses composées de nanotubes de carbone ou de graphène ayant une stabilité exceptionnelle et une surface de contact élevée.
PCT/IN2021/050726 2020-08-17 2021-07-24 Hybrides cof-graphène et cof-cnt tridimensionnels ayant une stabilité chimique remarquable pour le stockage de méthane WO2022038627A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155526A (zh) * 2022-07-30 2022-10-11 山东交通学院 一种处理核废水的富勒烯共价有机框架材料的制备方法
CN115873193A (zh) * 2022-11-30 2023-03-31 吉林大学 一种孔道含三氟甲基的共价有机骨架材料、制备方法及其在小分子烃吸附和分离中的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180272313A1 (en) * 2014-12-19 2018-09-27 Korea Institute Of Industrial Technology Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof
IN201913002035A (fr) * 2019-01-17 2020-07-24

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180272313A1 (en) * 2014-12-19 2018-09-27 Korea Institute Of Industrial Technology Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof
IN201913002035A (fr) * 2019-01-17 2020-07-24

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155526A (zh) * 2022-07-30 2022-10-11 山东交通学院 一种处理核废水的富勒烯共价有机框架材料的制备方法
CN115155526B (zh) * 2022-07-30 2023-06-20 山东交通学院 一种处理核废水的富勒烯共价有机框架材料的制备方法
CN115873193A (zh) * 2022-11-30 2023-03-31 吉林大学 一种孔道含三氟甲基的共价有机骨架材料、制备方法及其在小分子烃吸附和分离中的应用

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