CN113683784A - Preparation method and application of carbon dioxide adsorbing material with metal organic framework - Google Patents
Preparation method and application of carbon dioxide adsorbing material with metal organic framework Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 121
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
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- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000003213 activating effect Effects 0.000 claims abstract description 9
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- 238000000034 method Methods 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000013118 MOF-74-type framework Substances 0.000 abstract description 75
- 238000001179 sorption measurement Methods 0.000 description 26
- 239000013078 crystal Substances 0.000 description 20
- 239000011701 zinc Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
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- 239000003463 adsorbent Substances 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
The invention discloses a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps: step 1, dissolving metal salt in water to form a solution A; step 2, dissolving 2, 5-dihydroxy terephthalic acid in a solution containing ethanol and N, N-dimethylformamide to form a solution B; and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material. The invention also discloses an application of the carbon dioxide adsorbing material with the metal organic framework. The invention solves the problems of high equipment requirement and high operation difficulty in the preparation of MOF-74 materials in the prior art.
Description
Technical Field
The invention belongs to CO2The invention belongs to the technical field of adsorption material preparation, and particularly relates to a preparation method of a carbon dioxide adsorption material with a metal organic framework.
Background
In recent years, human beings have burned various kinds of fossil gas minerals having strong radioactivity such as petroleum and natural gas, or burned and produced CO such as CO by cutting trees2、CH4And the various radioactive fossil gases directly enter and radiate into the earth's atmosphere, directly contributing to the rapid warming of the climate in today's world. Carbon dioxide capture and sequestration (CCS) technology is one of the most important technologies to cope with global climate change in the short term. CO capture in coal-fired power plants2For the post-combustion trapping, there are low-temperature distillation, solvent absorption, membrane separation, adsorption and the like. Wherein the adsorption method has the characteristics of simple operation, low requirement on environmental protection, low regeneration energy consumption and the like, which become CO in recent years2The research on the trapping technology is hot and widely applied.
The porous solid physical adsorption material comprises activated carbon, molecular sieves, Metal Organic Frameworks (MOFs) and the like, wherein the MOFs is a novel porous material discovered in the last ten years, and has developed pores, huge specific surface area and pore volume, adjustable pore size, good thermal stability and chemical stability, multiple unsaturated coordination bonds and excellent adsorption performance, and the like, and in addition, many MOFs have respiratory characteristics, so that CO adsorbed in the pores can be adsorbed2The physicochemical structural property of the adsorption and desorption circulation is kept stable by changing the external environmental conditions. MOFs materials are the current focus of research. Recent studies have shown that MOF-74 is directed to CO2The adsorption studies of (A) are most frequent because a 6-coordinate three-dimensional framework structure is formed during the synthesis of MOF-74, wherein the framework structure is located inside the pore channelsThe coordination bond with small molecule (water, ethanol) is easy to break to obtain 5-coordinate unsaturated framework structure, and in addition, MOF-74 contains abundant microporous pore canal.
MOF-74 Material as CO2The adsorbent has the advantages of large adsorption capacity, low regeneration energy consumption and the like, and has good application prospect. However, the existing preparation methods of MOF-74 materials are hydrothermal methods, microwave methods and the like, the requirements on instruments and equipment are high, and the technology for industrially preparing MOF-74 materials in large quantities is not mature. The MOF-74 material is prepared by adopting a condensation reflux method, and the method is simple and cheap in instrument construction and provides theoretical support for low energy consumption, large-scale production and application of the MOF-74 adsorbent material.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework carbon dioxide adsorbing material, which solves the problems of high equipment requirement and high operation difficulty in the preparation of MOF-74 materials in the prior art.
The invention also aims to provide application of the carbon dioxide adsorbing material with the metal organic framework.
The first technical scheme adopted by the invention is that the preparation method of the carbon dioxide adsorbing material with the metal organic framework is implemented according to the following steps:
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The first technical aspect of the present invention is also characterized in that,
In the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of the ethanol to the N, N-dimethylformamide (1-1.5): 1.
the molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is (2-4): 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 130-150 ℃, and the heating time is 16-24 hours.
And in the step 3, the drying temperature is 60-100 ℃.
The temperature of the activation treatment in the step 3 is 200-250 ℃, and the time is 4-6 h.
The second technical scheme adopted by the invention is that the application of the carbon dioxide adsorbing material with the metal organic framework is to adsorb industrial CO at room temperature and normal pressure based on the prepared carbon dioxide adsorbing material with the metal organic framework2The use of (1).
The preparation method has the beneficial effects that the metal organic framework is prepared by adopting a condensation reflux method, the device requirement is low, the synthesis process is simple and feasible, and the industrial preparation can be realized. MOF-74 formed with 2, 5-dihydroxyterephthalic acid as the organic chain and transition metal ions has abundant micropores and unsaturated coordination bonds. The MOF-74 crystals with different morphologies can be obtained by adding different metal salts, and the results show that the morphologies of the five synthesized samples are almost hexagonal needle-shaped crystals, but compared with the crystals of MOF materials synthesized by other metal salts, the MOF materials synthesized by nickel nitrate are longer and shorter, and have more moderate and uniform thickness. Wherein the specific surface area of the MOF-74(Ni) material synthesized by nickel nitrate is up to 1128.61m2The volume of the/g, t-Plot (adsorption) micropores was 0.46cm3G, Langmuir adsorption specific surface area 1097.67m2(ii) in terms of/g. CO at 0 ℃ and 25 ℃ at 1bar2The adsorption capacity was 8.3mmol/g and 6.6mmol/g, respectively, while N was present under the corresponding conditions2The amounts of adsorption of (A) were 1.28mmol/g and 0.87 mmol/g. The material has the advantages of simple preparation process, large adsorption capacity, good selectivity, reusability and capability of treating novel high-efficiency industrial CO2The development of the adsorption material has higher reference and research values. A series of MOFs prepared by the invention-74 materials nickel nitrate synthesized metal organic frameworks were found to have regular, uniform crystal morphology, large specific surface area, high micropore volume and extremely high CO2Adsorption capacity. Further, it was found that Ni2+Has the most suitable ion size, so that the synthesized metal organic framework material MOF-74(Ni) is the most suitable CO prepared by a condensation reflux method2Adsorbing the material.
Drawings
FIG. 1 is a field emission electron microscope (FE-SEM) photograph of a material synthesized from different metal salts according to the present invention; wherein (a) is MOF-74(Co), (b) is MOF-74(Ni), (c) is MOF-74(Ce), (d) is MOF-74(Zn), (e) is MOF-74 (Zn);
FIG. 2 is N of a series of MOF-74 materials2Adsorption and desorption curves;
FIG. 3 is an X-ray diffraction (XRD) spectrum of a series of MOF-74 materials;
FIG. 4 is a Thermogravimetric (TG) spectrum of a series of MOF-74 materials; wherein, diagram (a) is MOF-74(Co), diagram (b) is MOF-74(Ni), diagram (c) is MOF-74(Ce), diagram (d) is MOF-74(Zn), and diagram (e) is MOF-74 (Cu);
FIG. 5 CO of a series of MOF-74 materials2Static adsorption and desorption curves.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of the ethanol to the N, N-dimethylformamide (1-1.5): 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is (2-4): 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 130-150 ℃, and the heating time is 16-24 hours.
And in the step 3, the drying temperature is 60-100 ℃.
The temperature of the activation treatment in the step 3 is 200-250 ℃, and the time is 4-6 h.
Application of carbon dioxide adsorbing material with metal organic framework, namely adsorbing industrial CO at room temperature and normal pressure based on carbon dioxide adsorbing material with metal organic framework prepared by preparation method of carbon dioxide adsorbing material with metal organic framework2The use of (1).
Example 1
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of ethanol to N, N-dimethylformamide is 1: 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is 4: 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 150 ℃, and the heating time is 16 h.
The drying temperature in step 3 is 100 ℃.
The temperature of the activation treatment in the step 3 is 250 ℃, and the time is 4 h.
Example 2
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of ethanol to N, N-dimethylformamide is 1: 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is 2: 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 140 ℃, and the heating time is 24 hours.
The drying temperature in step 3 is 80 ℃.
The temperature of the activation treatment in the step 3 is 220 ℃, and the time is 5 h.
Example 3
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in step 2, the volume ratio of ethanol to N, N-dimethylformamide is 1.2: 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is 2: 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 140 ℃, and the heating time is 20 hours.
The drying temperature in step 3 is 80 ℃.
The temperature of the activation treatment in the step 3 is 220 ℃, and the time is 5 h.
Example 4
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in step 2, the volume ratio of ethanol to N, N-dimethylformamide is 1.2: 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is 3: 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 130 ℃, and the heating time is 16 h.
The drying temperature in step 3 is 60 ℃.
The temperature of the activation treatment in the step 3 is 200 ℃, and the time is 6 h.
Example 5
The invention relates to a preparation method of a carbon dioxide adsorbing material with a metal organic framework, which is implemented according to the following steps:
in the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of ethanol to N, N-dimethylformamide is 1.5: 1.
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
The molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxy terephthalic acid in the solution B in the step 3 is 4: 1.
in the step 3, the temperature for heating the mixed solution of the solution A and the solution B is controlled to be 130 ℃, and the heating time is 16 h.
The drying temperature in step 3 is 60 ℃.
The temperature of the activation treatment in the step 3 is 200 ℃, and the time is 6 h.
As shown in FIG. 1, the MOF-74 materials synthesized by Co, Ni, Ce, Zn and Cu metal ions have approximately the same morphology and are hexagonal needle-shaped crystals, but the specific performances are slightly different. As can be seen from FIG. a, MOF-74(Co) exhibits uniform and dense crystals with lengths concentrated in the range of 2-3 μm; the MOF-74 material synthesized from Ni2+ has a shorter crystal length of only about 0.8 μm compared to that of the material in the graph b, and the crystals are gathered together to form a 'seaweed' -shaped crystal cramped; compared with the former two, the morphology of MOF-74(Ce) is greatly different, thin and long, the crystal distribution is relatively dispersed, and the crystals can be approximately in a bird nest shape; FIG. d is a crystal morphology of MOF-74(Zn), the sample appearing to consist of larger particles about 5 μm in diameter, actually smaller inter-grown crystals, which aggregate into larger "columnar" crystals; MOF-74(Cu) is based on hexagonal needle crystals ranging from very fine crystallites to larger, coarser, longer needles, and it contains not only some hexagonal needle crystals but also a few small blocky particles doped. Through observation and comparison, the following results are found: the MOF-74 materials synthesized by different metal central ions have relatively similar morphologies and are all in the form of hexagonal needle crystals.
As can be seen from FIG. 2, all the curves of the MOF-74 material in the graph are basically the superposition of the adsorption-desorption isotherms of the type I and the type IV, which shows that the MOF-74 material has both mesoporous and microporous structures. As can be understood from the graph a, when N is2In the low pressure region (P/P0)<0.05), the MOF-74 crystal is quickly adsorbed and reaches saturation; while in the medium-pressure region (P/P0 ═ 0.05-0.9), the MOF-74 crystals adsorb N2The amount of (c) tends to be smooth as the pressure increases; but in the high-pressure region (P/P0 ═ 0.9-1.0), N2The adsorption capacity of (a) is increased to a certain extent with the increase of the pressure, indicating that the macropores contribute to the filling of air between the particles.
As can be seen from Table 1, the specific surface area of MOF-74(Ni) reached 1128.61m2The pore volume of the micropores is also greatly up to 0.46cm3(ii) in terms of/g. However, the specific surface areas of MOF-74(Ce), MOF-74(Zn) and MOF-74(Cu) were 100m2(ii) below,/g, illustrating possible Ce2+、Zn2+、Cu2+It is not feasible to prepare MOF-74 materials using a condensation reflux process,when the MOF-74 material is prepared by a condensation reflux method, the material is stirred for a long time at a high temperature, and the formation of metal organic framework micro-mesopores is damaged, so that the expected adsorption effect cannot be achieved; and the micro-pore volumes of MOF-74(Ce), MOF-74(Zn) and MOF-74(Cu) in the table are almost 0, further indicating that the three materials do not have CO2 adsorption capacity. The equivalent specific surface area of MOF-74(Co) is in the central position and has certain adsorption capacity.
TABLE 1 pore Structure parameters of MOF-74 series of materials
The specific surface area of MOF-74(Ni) from Table 1 was 1128.61m2In terms of a volume of micropores, 0.46cm3The concentration is higher than that of MOF-74 materials synthesized by other metal salts.
From FIG. 3, it can be seen that a series of metal organic frameworks synthesized by the present invention are consistent with the XRD results of MOF-74 reported in the literature, and the condensation reflux method successfully synthesizes MOF-74.
Fig. 4 is a thermal stability curve, and it can be seen that the weight loss curves of different materials are approximately the same, so that their weight loss processes are also substantially consistent. The thermal degradation process can be roughly divided into three stages. Wherein, the weight loss before 196 ℃ is because the solvent molecules in the adsorbent, namely water and ethanol, are removed, and the weight loss rate is about 20 percent; the weight loss in the second stage is mainly about 250 ℃, and DMF in the solvent is mainly removed, which shows that ethanol is easier to remove than DMF, which is the reason why the sample is soaked by ethanol for a long time and is kept still after the reaction is finished, and the DMF adsorbed on the MOF-74 adsorbent is mainly replaced by ethanol, so that the desolvation treatment before the adsorbent is used is easier and more thorough, more metal sites are exposed, and the adsorption force is increased; the third stage of thermal weight loss is obvious in weight loss at 400 ℃, the weight loss rate is accelerated, and the stage is a MOF-74 framework structure collapse stage and a sample complete cracking stage. In FIG. 4(d), the MOF-74(Zn) is the most thermally stable, with the framework collapsing only at 351 ℃ and the sample completely breaking away at 550 ℃; whereas the MOF-74(Co) in FIG. 4(a) has the lowest thermal stability, with the framework structure collapsing at 231 ℃ and the material being completely decomposed at 341 ℃. The good thermal stability of MOF-74(Zn) may be due to its not forming much three-dimensional channel structure, while the thermal stability of MOF-74(Co) and MOF-74(Ni) in FIG. 4(b) should be weaker because of the larger specific surface area of the formed more abundant three-dimensional channel structure. The thermal stability of the MOF-74(Ce) in the remaining FIG. 4(c) and MOF-74(Cu) adsorbents in FIG. 4(e) is at an intermediate level.
FIG. 5 is a static pressure swing adsorption curve of CO2 at 25 deg.C, the MOF-74(Co) and MOF-74(Ni) adsorbents have excellent CO2 removal capacity, and the CO2 captured at 298K and 1.0bar exceeds 4.5 mmol/g. Of these, MOF-74(Ni) had the highest CO2 capture capacity (6.8 mmol/g at 298K and 1.0 bar) which was about 7.6 times that of commercial activated carbon (0.89 mmol/g). Scientists studied the adsorption capacity of MOF-74 materials prepared by solvothermal method to CO2 and found that MOF-74(Co)>MOF-74(Zn)>MOF-74(Ni)>MOF-74(Cu), the MOF-74(Zn) material prepared by the condensation reflux method has extremely low adsorption capacity because Zn and 2, 5-dihydroxyterephthalic acid form the crystal structure of the MOF-74 under the normal pressure heating state (from an XRD spectrogram, the MOF-74 prepared by the same method with other elements has the same diffraction peak) but are difficult to form rich three-dimensional honeycomb structures, so that the number of micropores is low, and the MOF-74(Zn) does not have enough unsaturated metal sites to CO2The molecules are adsorbed.
Claims (8)
1. The preparation method of the carbon dioxide adsorbing material with the metal organic framework is characterized by comprising the following steps:
step 1, dissolving metal salt in water to form a solution A;
step 2, dissolving 2, 5-dihydroxy terephthalic acid in a solution containing ethanol and N, N-dimethylformamide to form a solution B;
and 3, uniformly mixing the solution A and the solution B to obtain a mixed solution, heating and stirring the mixed solution, filtering and washing the solution and then drying the solution when precipitates appear in the solution, and then activating the solution under a vacuum condition to obtain the metal organic framework material.
2. The method for preparing the carbon dioxide adsorbing material with the metal-organic framework according to claim 1, wherein the metal salt in the step 1 is one of cobalt nitrate, nickel nitrate, cerium nitrate, copper nitrate and zinc nitrate; the molar mass ratio of the metal salt to the water is 1: (10-15).
3. The method for preparing a carbon dioxide adsorbing material with a metal-organic framework according to claim 2, wherein in the solution containing ethanol and N, N-dimethylformamide in the step 2, the volume ratio of ethanol to N, N-dimethylformamide is (1-1.5): 1.
4. the method for preparing the carbon dioxide adsorbing material with the metal-organic framework according to claim 3, wherein the molar mass ratio of the metal salt in the solution A to the 2, 5-dihydroxyterephthalic acid in the solution B in the step 3 is (2-4): 1.
5. the preparation method of the carbon dioxide adsorbing material with the metal organic framework as claimed in claim 4, wherein the temperature for heating the mixed solution of the solution A and the solution B in the step 3 is controlled to be 130-150 ℃, and the heating time is 16-24 h.
6. The preparation method of the carbon dioxide adsorbing material with the metal organic framework as claimed in claim 4, wherein the drying temperature in the step 3 is 60-100 ℃.
7. The preparation method of the carbon dioxide adsorbing material with the metal organic framework as claimed in claim 4, wherein the temperature of the activation treatment in the step 3 is 200-250 ℃ and the time is 4-6 h.
8. Application of carbon dioxide adsorbing material with metal organic frameworkCharacterized in that the carbon dioxide adsorbing material with metal organic framework prepared by the preparation method of the carbon dioxide adsorbing material with metal organic framework of any one of claims 1 to 7 adsorbs industrial CO at room temperature and normal pressure2The use of (1).
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