CN113322474A - Full-conjugated COF (chip on film) supported single-metal cobalt-site catalyst and preparation method and application thereof - Google Patents
Full-conjugated COF (chip on film) supported single-metal cobalt-site catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of monatomic catalysts, and particularly relates to a full-conjugated COF (chip on film) supported monometallic cobalt site catalyst and a preparation method and application thereof. The catalyst comprises a two-dimensional flaky sp2 carbon fully-conjugated COF material and monodisperse cobalt metal supported on the COF material; the sp2 carbon fully-conjugated COF material is prepared from 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene containing aldehyde groups and 2,2' - ([2,2' -bipyridyl ] -5,5' -diyl) diacetonitrile precursor containing cyano groups through a Knoevenagel condensation reaction. The preparation method comprises the following steps: preparing a COF material; supporting cobalt element on the COF material by liquid phase impregnation; the single metal site catalyst prepared by the invention has the characteristics of stable structure, controllable structure and coordination mode of the active site, mild preparation condition, low cost, simple process, high yield and the like.
Description
Technical Field
The invention belongs to the technical field of monatomic catalysts, and particularly relates to a full-conjugated COF material loaded single-metal cobalt site catalyst, and a preparation method and application thereof.
Background
The high performance and low cost electrocatalytic oxygen evolution catalyst is one of the key factors for realizing sustainable/clean electrochemical energy conversion technology. The monodisperse metal site catalysts (SACs) have uniformly dispersed metal active sites, and thus can achieve high activity and high selectivity of catalytic reaction, high efficiency of atom utilization, and low manufacturing cost. Most of the existing preparation methods are direct high-temperature carbonization after coordination of various materials containing metal, nitrogen and carbon sources, however, the high-temperature pyrolysis process has more influence factors, unpredictable structural changes and even reconstruction are difficult to avoid, the structure and the number of active sites of a final product are difficult to control, the research on mechanisms such as a reaction mechanism and an inactivation mechanism of a catalytic process is not facilitated, and important tests are brought to large-scale and repeatable preparation of catalyst materials. Therefore, constructing a high-efficiency single metal site catalyst with a definite coordination structure and easily controlled chemical/electronic environment at an atom/molecule level still faces a great challenge.
Covalent organic framework materials (COFs) are used as an emerging porous crystalline polymer in two-dimensional conjugated network materials, have size-adjustable nano pores, high specific surface area and good chemical stability, and the characteristics are very beneficial to creating SACs (layered organic frameworks) electrocatalysts. Most importantly, the high accuracy of atomic/molecular structure and good designability and tunability in COF materials make it an ideal platform for reasonably adjusting the electronic state environment of catalytic sites. Researchers can construct a conjugate network structure with certain conductivity through a pre-designed construction unit and a pre-designed link structure, and the requirement of rapid electronic transmission in electrochemical application is met; and various preparation monomers can be selected to enable the chemical structure to be adjustable, a proper chemical environment is provided for the load of metal atoms, the design and the manipulation of substances on the molecular or atomic level are realized, and the advantages enable the preparation method to have great application potential in the fields of electrocatalysis and the like. The definite structures of the compounds provide a wide prospect for explaining how the electronic state environment modulation influences the final catalytic performance.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a full-conjugated COF material loaded single-metal cobalt site catalyst which is simple in synthesis process, low in cost and environment-friendly, and a preparation method and application thereof.
According to the invention, the COF skeleton with an sp2 carbon conjugated structure is utilized, so that the electronic transmission performance of the COF skeleton is favorably improved, besides, bipyridine rings are uniformly distributed in the COF skeleton, uniformly distributed nucleation sites are provided, the anchoring and loading of monodisperse metal sites are favorably realized, and the active center coordination mode of a cobalt monoatomic atom can be effectively regulated and controlled by regulating and controlling different precursor metal salts. The catalyst prepared by the method has controllable active site structure and concentration and high yield. The catalyst shows excellent performance in the field of electrocatalysis and has good application prospect.
The invention provides a full-conjugated COF supported single-metal cobalt-site catalyst, which comprises a two-dimensional flaky sp2 carbon full-conjugated COF material and monodisperse cobalt metal supported on the COF material; the sp2 carbon fully-conjugated COF material is prepared from 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene containing aldehyde groups and 2,2' - ([2,2' -bipyridyl ] -5,5' -diyl) diacetonitrile precursor containing cyano groups through a Knoevenagel condensation reaction.
The preparation method of the full-conjugated COF supported single-metal cobalt-site catalyst provided by the invention comprises the following specific steps:
(1) dissolving an aldehyde precursor and a cyano precursor in an organic mixed solvent, fully dispersing, and then dropwise adding a catalyst to obtain a mixed solution.
(2) Sequentially carrying out liquid nitrogen freezing, vacuumizing and unfreezing cyclic operation on the mixed solution in the step (1), carrying out vacuum sealing, unfreezing to room temperature, and then placing the mixed solution in an oven for constant-temperature reaction for a period of time to obtain a crude product;
(3) deblocking the reaction system in the step (2), quenching the reaction system, performing solid-liquid separation, washing the solid, performing soxhlet extraction by adopting tetrahydrofuran, and then performing vacuum drying to obtain sp2 carbon fully-conjugated COF material solid powder;
(4) and (3) mixing the COF material prepared in the step (3), a soluble metal Co salt and a proper solvent, carrying out ultrasonic stripping while carrying out liquid phase loading, and separating and purifying the product to obtain the sp2 carbon fully-conjugated COF loaded monodisperse metal Co catalyst.
In the step (1), the aldehyde group precursor is 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene, and the cyano group precursor is 2,2' - ([2,2' -bipyridine ] -5,5' -diyl) diacetonitrile; in the mixed solution, the concentration of the aldehyde group precursor is 0.012 mol/L-0.024 mol/L, and the concentration of the cyano group precursor is 0.024 mol/L-0.048 mol/L.
Preferably, in the step (1), the mixed organic solvent comprises o-dichlorobenzene and n-butanol, and the volume ratio of the o-dichlorobenzene to the n-butanol is 1: 0.8-1: 1.
Preferably, in the step (1), the catalyst is one of 5M DBU (1, 8-diazabicycloundecen-7-ene) or 4M KOH aqueous solution, and the volume ratio of the catalyst solution to the organic solvent is 1: 10-1: 15.
Preferably, in the step (2), the temperature of the isothermal reaction is 120-150 ℃, and the reaction time is 72-96 hours.
Preferably, in the step (3), the solvent for washing the solid is acetone, tetrahydrofuran and methanol sequentially, the soxhlet extraction time is 12-36 h, the vacuum drying temperature is 100-120 ℃, and the vacuum drying time is 12-24 h.
Preferably, in the step (4), the soluble cobalt salt is one of cobalt chloride, cobalt bromide, cobalt sulfate, cobalt nitrate and cobalt acetate;
preferably, in step (4), the solvent is acetonitrile, methanol, a mixed solution of 10% HCl aqueous solution and ethanol, a mixed solution of 10% HBr aqueous solution and ethanol, and 10% H2SO4Aqueous solution and 10% HNO3One of the solutions;
preferably, the mass ratio of the COF material to the soluble cobalt salt in the step (4) is 1: 0.5-1: 1, and the ultrasonic stripping time is 6-10 h.
Further, considering that the solubility of metal cobalt salts in different solvents is different, and different cobalt salts can influence the coordination mode of cobalt atoms, particularly, the combination of cobalt salts and solvents is optimized, specifically, the combination of cobalt chloride and acetonitrile solution, and the combination of cobalt chloride and 10 percentA mixture of HCl aqueous solution and ethanol, a mixture of cobalt bromide and 10% HBr aqueous solution and ethanol, and a mixture of cobalt sulfate and 10% H2SO4Aqueous solution combination, cobalt nitrate and 10% HNO3Solution combination, cobalt acetate and methanol solution combination; the catalyst can obtain the monodisperse cobalt metal site catalyst containing N coordination, Cl coordination, Br coordination, hydrated proton coordination and acetic acid group coordination.
The invention provides the full-conjugated COF material supported single-metal cobalt site catalyst which can be used for electrochemical oxygen evolution reaction; the method comprises the following specific steps: mixing the fully-conjugated COF supported monodisperse metal cobalt catalyst with conductive carbon black and an ethanol Nafion binder, then performing ultrasonic dispersion uniformly to obtain catalyst ink, taking a certain amount of the ink by a liquid transfer device, uniformly coating the ink on the surface of carbon paper, and drying to obtain a working electrode; the electrochemical oxygen evolution performance was then tested under a three-electrode system, with a carbon rod as the counter electrode, an Hg/HgO electrode as the reference electrode, and 1M KOH solution as the electrolyte.
The invention has the beneficial effects that:
(1) according to the strategy for preparing the monatomic catalyst by loading the monodisperse metal Co on the surface of the sp2 carbon fully-conjugated COF material, the metal active sites are fixed on the COF material skeleton through the preset bipyridyl sites, so that the controllable preparation of the active center structure and the concentration is realized, and the loading capacity of the monatomic catalyst can be greatly improved. In addition, the sp2 carbon full-conjugated structure can provide a fast electron transfer channel, and guarantee is provided for the electrochemical application of the catalyst.
(2) The preparation method of the monatomic catalyst integrating liquid phase loading and ultrasonic stripping has obvious advantages, the composite material with two-dimensional sheets can be prepared, the two-dimensional nanosheet structure can further expose the active center of the catalyst, the contact area of the active site and an electrolyte is enlarged, and a larger specific surface area can be provided. In addition, the liquid phase loading method can regulate and control the coordination mode of the metal sites by controlling the species of the precursor metal salt, so as to regulate and control the intrinsic activity of the catalyst. Furthermore, the method has expansibility and universality, can be widely applied to different transition metal species, can prepare various catalysts with different functions according to requirements, and can realize more excellent catalytic performance than the traditional noble metal catalyst by using a small amount of cheap metal.
(3) Different from the traditional method for preparing the monatomic catalyst by high-temperature calcination and pyrolysis, the preparation method provided by the invention has the advantages of mild conditions, high yield, cheap and easily available raw materials, environment-friendly production process, low energy consumption, environmental friendliness and the like, can be used for large-scale production and application, and has good economic benefit and application prospect.
Drawings
Fig. 1 is a diagram of the synthesis of fully conjugated COF materials in example 1.
Fig. 2 is a PXRD pattern for the fully conjugated COF material of example 1.
Fig. 3 is a schematic structural diagram of a fully conjugated COF material in example 1.
Fig. 4 is an AFM image of the fully conjugated COF material supporting a monodisperse metallic cobalt catalyst in example 2.
Fig. 5 is a TEM image of the fully conjugated COF material supporting monodisperse metallic cobalt catalyst in example 2.
Fig. 6 is a graph of electrochemical oxygen evolution performance of the fully conjugated COF material supported monodisperse metallic cobalt catalyst in example 1.
Fig. 7 is a graph of electrochemical oxygen evolution performance of the fully conjugated COF material supported monodisperse metallic cobalt catalyst in example 2.
Fig. 8 is a graph of electrochemical oxygen evolution performance of the fully conjugated COF material supported monodisperse metallic cobalt catalyst in example 3.
Detailed Description
The invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
(1) 29.2mg of aldehyde group-containing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene precursor and 23mg of cyano group-containing 2,2' - ([2,2' -bipyridine ] -5,5' -diyl) diacetonitrile precursor are accurately weighed, added into a reaction tube, 1mL of o-dichlorobenzene and 1mL of n-butanol are added, after ultrasonic dispersion of a solvent, 200 μ L of 5M DBU aqueous solution is added, and mixed uniformly again.
(2) Sequentially carrying out liquid nitrogen freezing-vacuumizing-unfreezing cyclic operation on the mixed solution, sealing the reaction tube by a flame gun in a vacuum state, unfreezing to room temperature, and then placing the reaction tube in an oven to keep constant temperature of 120 ℃ for reaction for 72 hours to obtain a crude product;
(3) deblocking a reaction system after reaction explanation, quenching reaction, carrying out solid-liquid separation, washing the solid by sequentially adopting acetone, tetrahydrofuran and methanol, carrying out suction filtration and separation on the solid, wrapping the solid by using filter paper, carrying out soxhlet extraction on the solid by adopting tetrahydrofuran for 24 hours, and then carrying out vacuum drying at 120 ℃ for 12 hours to obtain sp2 carbon fully-conjugated COF material solid powder;
(4) weighing 40mg of prepared COF material, 20mg of cobalt chloride, mixing with 20mL of acetonitrile, carrying out ultrasonic stripping while carrying out liquid phase loading for 6h, then carrying out suction filtration on a product, washing with acetonitrile, and carrying out vacuum drying to obtain the full-conjugated COF material loaded monodisperse metal cobalt catalyst.
The synthetic diagram of the fully-conjugated COF material in the embodiment is shown in fig. 1, and as can be seen from fig. 1, the COF has an sp2 carbon conjugated structure, which is beneficial to improving the electronic transmission performance of the COF, and besides, bipyridyl rings are uniformly distributed in a COF framework, which is beneficial to realizing the anchoring and loading of monodisperse Co metal sites;
a PXRD pattern of the fully conjugated COF material in this embodiment is shown in fig. 2, from which it can be seen that the COF has good crystallinity, and a schematic structure diagram of the COF obtained through structural simulation is shown in fig. 3, and it is proved that the COF exhibits an AA stacked structure.
5mg of the fully-conjugated COF material supported monodisperse metallic cobalt catalyst prepared in the embodiment, 2mg of conductive carbon black, 490 mu L of ethanol and 10 mu L of a LNafion binder are ultrasonically and uniformly mixed to obtain catalyst ink, 10 mu L of the ink is taken by a pipette and uniformly coated on the surface of carbon paper, and the working electrode is obtained after drying. The electrochemical oxygen evolution performance was then tested under a three-electrode system, with a carbon rod as the counter electrode, an Hg/HgO electrode as the reference electrode, and 1M KOH solution as the electrolyte. The obtained linear sweep voltammogram is shown in FIG. 6, and can reach 10 mA cm only by 407mV overpotential-2Has good catalytic performance on the surface.
Example 2
(1) 58.4mg of aldehyde group-containing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene precursor and 46mg of cyano group-containing 2,2' - ([2,2' -bipyridine ] -5,5' -diyl) diacetonitrile precursor are accurately weighed, added into a reaction tube, 2mL of o-dichlorobenzene and 2mL of n-butanol are added, after ultrasonic dispersion of a solvent, 300 μ L of 5M DBU aqueous solution is added, and mixed uniformly again.
(2) Sequentially carrying out liquid nitrogen freezing-vacuumizing-unfreezing cyclic operation on the mixed solution, sealing the reaction tube by a flame gun in a vacuum state, unfreezing to room temperature, and then placing the reaction tube in an oven to keep the constant temperature of 130 ℃ for reaction for 96 hours to obtain a crude product;
(3) deblocking a reaction system after reaction explanation, quenching reaction, carrying out solid-liquid separation, washing the solid by sequentially adopting acetone, tetrahydrofuran and methanol, carrying out suction filtration and separation on the solid, wrapping the solid by using filter paper, carrying out soxhlet extraction on the solid by adopting tetrahydrofuran for 12 hours, and then carrying out vacuum drying at 100 ℃ for 24 hours to obtain sp2 carbon fully-conjugated COF material solid powder;
(4) weighing 40mg of prepared COF material, 20mg of cobalt acetate, mixing with 20mL of methanol, carrying out ultrasonic stripping while carrying out liquid phase loading for 8h, then carrying out suction filtration on a product, washing with acetonitrile, and carrying out vacuum drying to obtain the fully-conjugated COF material loaded monodisperse metal cobalt catalyst.
In the embodiment, an AFM image of the fully-conjugated COF material loaded monodisperse metallic cobalt catalyst is shown in fig. 4, and a TEM image of the fully-conjugated COF material loaded monodisperse metallic cobalt catalyst is shown in fig. 5, the fully-conjugated COF material loaded monodisperse metallic cobalt catalyst has a two-dimensional ultrathin lamellar structure, no obvious metal particles exist on a nano-sheet, and the situation that Co is distributed in a monoatomic form and in a COF can be inferred;
5mg of the fully-conjugated COF material supported monodisperse metallic cobalt catalyst prepared in the embodiment, 2mg of conductive carbon black, 490 mu L of ethanol and 10 mu L of a LNafion binder are ultrasonically and uniformly mixed to obtain catalyst ink, 10 mu L of the ink is taken by a pipette and uniformly coated on the surface of carbon paper, and the working electrode is obtained after drying. The electrochemical oxygen evolution performance was then tested under a three-electrode system, with a carbon rod as the counter electrode, an Hg/HgO electrode as the reference electrode, and 1M KOH solution as the electrolyte. Resulting linear sweep voltageThe ampere curve is shown in FIG. 7, and only 404mV of overpotential is needed to reach 10 mA cm-2Has good catalytic performance on the surface.
Example 3
(1) 29.2mg of aldehyde group-containing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene precursor and 23mg of cyano group-containing 2,2' - ([2,2' -bipyridine ] -5,5' -diyl) diacetonitrile precursor are accurately weighed, added into a reaction tube, 1mL of o-dichlorobenzene and 1mL of n-butanol are added, after ultrasonic dispersion of a solvent, 200 μ L of 5M DBU aqueous solution is added, and mixed uniformly again.
(2) Sequentially carrying out liquid nitrogen freezing-vacuumizing-unfreezing cyclic operation on the mixed solution, sealing the reaction tube by a flame gun in a vacuum state, unfreezing to room temperature, and then placing the reaction tube in an oven to keep constant temperature of 120 ℃ for reaction for 72 hours to obtain a crude product;
(3) deblocking a reaction system after reaction explanation, quenching reaction, carrying out solid-liquid separation, washing the solid by sequentially adopting acetone, tetrahydrofuran and methanol, carrying out suction filtration and separation on the solid, wrapping the solid by using filter paper, carrying out soxhlet extraction on the solid by adopting tetrahydrofuran for 24 hours, and then carrying out vacuum drying at 120 ℃ for 12 hours to obtain sp2 carbon fully-conjugated COF material solid powder;
(4) weighing 40mg of prepared COF material, 40mg of cobalt chloride, mixing with a mixed solution of 10% HCl and ethanol, carrying out ultrasonic stripping while carrying out liquid phase loading for 6 hours, then carrying out suction filtration on a product, washing with acetonitrile, and carrying out vacuum drying to obtain the full-conjugated COF material loaded monodisperse metal cobalt catalyst.
5mg of the fully-conjugated COF material supported monodisperse metallic cobalt catalyst prepared in the embodiment, 2mg of conductive carbon black, 490 mu L of ethanol and 10 mu L of a LNafion binder are ultrasonically and uniformly mixed to obtain catalyst ink, 10 mu L of the ink is taken by a pipette and uniformly coated on the surface of carbon paper, and the working electrode is obtained after drying. The electrochemical oxygen evolution performance was then tested under a three-electrode system, with a carbon rod as the counter electrode, an Hg/HgO electrode as the reference electrode, and 1M KOH solution as the electrolyte. The obtained linear sweep voltammogram is shown in FIG. 8, and only an overpotential of 436 mV is needed to reach 10 mA cm-2Has good catalytic performance on the surface.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a full-conjugated COF supported single-metal cobalt site catalyst is characterized by comprising the following specific steps:
(1) dissolving an aldehyde precursor and a cyano precursor in an organic mixed solvent, fully dispersing, and then dropwise adding a catalyst to obtain a mixed solution;
(2) sequentially carrying out liquid nitrogen freezing, vacuumizing and unfreezing cyclic operation on the mixed solution in the step (1), carrying out vacuum sealing, unfreezing to room temperature, and then placing the mixed solution in an oven for constant-temperature reaction for a period of time to obtain a crude product;
(3) deblocking the reaction system in the step (2), quenching the reaction system, performing solid-liquid separation, washing the solid, performing soxhlet extraction by adopting tetrahydrofuran, and then performing vacuum drying to obtain sp2 carbon fully-conjugated COF material solid powder;
(4) mixing the COF material prepared in the step (3), a soluble metal Co salt and a proper solvent, carrying out ultrasonic stripping while carrying out liquid phase loading, and then separating and purifying a product to obtain an sp2 carbon fully-conjugated COF loaded monodisperse metal Co catalyst;
in the step (1), the aldehyde group precursor is 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene, and the cyano group precursor is 2,2' - ([2,2' -bipyridine ] -5,5' -diyl) diacetonitrile; in the mixed solution, the concentration of the aldehyde group precursor is 0.012 mol/L-0.024 mol/L, and the concentration of the cyano group precursor is 0.024 mol/L-0.048 mol/L.
2. The preparation method according to claim 1, wherein the mixed organic solvent in the step (1) is composed of ortho-dichlorobenzene and n-butanol, and the volume ratio of the ortho-dichlorobenzene to the n-butanol is 1: 0.8-1: 1.
3. The preparation method of claim 2, wherein the catalyst in step (1) is one of 5M DBU or 4M KOH aqueous solution, and the volume ratio of the catalyst solution to the organic solvent is 1: 10-1: 15.
4. The preparation method according to claim 3, wherein the isothermal reaction in the step (2) is carried out at a temperature of 120-150 ℃ for 72-96 hours.
5. The preparation method according to claim 4, wherein the solvent for washing the solid in step (3) is acetone, tetrahydrofuran and methanol sequentially, the Soxhlet extraction time is 12-36 h, the vacuum drying temperature is 100-120 ℃, and the vacuum drying time is 12-24 h.
6. The method according to claim 5, wherein the soluble cobalt salt in the step (4) is one of cobalt chloride, cobalt bromide, cobalt sulfate, cobalt nitrate and cobalt acetate; the solvent is acetonitrile, methanol, a mixed solution of 10% HCl aqueous solution and ethanol, a mixed solution of 10% HBr aqueous solution and ethanol, and 10% H2SO4Aqueous solution and 10% HNO3One of the solutions.
7. The method according to claim 6, wherein in the step (4), the combination of the cobalt salt and the solvent is optimized as follows: cobalt chloride and acetonitrile solution, cobalt chloride and 10% HCl aqueous solution and ethanol mixed solution, cobalt bromide and 10% HBr aqueous solution and ethanol mixed solution, cobalt sulfate and 10% H2SO4Aqueous solution combination, cobalt nitrate and 10% HNO3Solution combination, cobalt acetate and methanol solution combination; obtaining the monodisperse cobalt metal site catalyst containing N coordination, Cl coordination, Br coordination, hydrated proton coordination or acetate group coordination.
8. The method according to any one of claims 1 to 7, wherein the mass ratio of the COF material to the soluble cobalt salt in the step (4) is 1:0.5 to 1:1, and the ultrasonic peeling time is 6 to 10 hours.
9. A mono-metallic cobalt-supported-all-conjugated COF catalyst obtained by the production method according to any one of claims 1 to 8, which comprises a two-dimensional sheet-like sp2 carbon-all-conjugated COF material and mono-dispersed cobalt metal supported on the COF material; the sp2 carbon fully-conjugated COF material is prepared from 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene containing aldehyde groups and 2,2' - ([2,2' -bipyridyl ] -5,5' -diyl) diacetonitrile precursor containing cyano groups through a Knoevenagel condensation reaction.
10. The use of a fully conjugated COF supported monometallic cobalt-site catalyst of claim 9 in electrochemically catalyzing an oxygen evolution reaction.
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| CN114164459A (en) * | 2021-12-02 | 2022-03-11 | 哈尔滨理工大学 | Two-dimensional covalent organic framework cobalt metal modified material for efficiently decomposing water to produce oxygen through electrocatalysis |
| CN114316510A (en) * | 2021-11-22 | 2022-04-12 | 江西师范大学 | Method for preparing sulfonic group-containing bimetallic composite polymer nano material |
| CN115417960A (en) * | 2022-08-16 | 2022-12-02 | 西北师范大学 | Method for stripping porphyrin-based covalent organic framework material driven by ligand |
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