CN108339522B - Amino acid @ Cu-BTC composite adsorbent and preparation method thereof - Google Patents
Amino acid @ Cu-BTC composite adsorbent and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001413 amino acids Chemical class 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012265 solid product Substances 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 3
- 229940000635 beta-alanine Drugs 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 34
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000013148 Cu-BTC MOF Substances 0.000 description 33
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 30
- 239000012621 metal-organic framework Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 238000003795 desorption Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 238000007084 catalytic combustion reaction Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
本发明属于吸附材料技术领域，公开了一种氨基酸@Cu‑BTC复合吸附剂及其制备方法。将纳米ZnO加入到去离子水中，超声分散后加入DMF，得到ZnO纳米浆溶液；将Cu(NO3)2·3H2O和氨基酸溶解于去离子水中，得到Cu(NO3)2和氨基酸混合液；将均苯三甲酸溶解于乙醇中，得到均苯三甲酸溶液；将Cu(NO3)2和氨基酸混合液加入到ZnO纳米浆溶液中，搅拌混合均匀，再加入均苯三甲酸溶液反应，所得固体产物经真空活化，得到氨基酸@Cu‑BTC复合吸附剂。本发明制备的氨基酸@Cu‑BTC复合吸附剂具有优良的水汽稳定性，并同时具有高的CO2吸附能力。
The invention belongs to the technical field of adsorption materials, and discloses an amino acid@Cu-BTC composite adsorbent and a preparation method thereof. Adding nano-ZnO into deionized water, adding DMF after ultrasonic dispersion, to obtain a ZnO nanopulp solution; dissolving Cu(NO 3 ) 2 ·3H 2 O and amino acid in deionized water to obtain a mixture of Cu(NO 3 ) 2 and amino acid solution; dissolving trimesic acid in ethanol to obtain trimesic acid solution; adding Cu(NO 3 ) 2 and amino acid mixed solution into ZnO nano-pulp solution, stirring and mixing evenly, then adding trimesic acid solution to react , the obtained solid product was activated by vacuum to obtain the amino acid@Cu-BTC composite adsorbent. The amino acid@Cu‑BTC composite adsorbent prepared by the present invention has excellent water vapor stability and high CO adsorption capacity at the same time.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to an amino acid @ Cu-BTC composite adsorbent and a preparation method thereof.
Background
With the development of global industrialization, a large amount of CO is generated2Is discharged into the atmosphere, causes environmental problems such as greenhouse effect, global climate abnormity, sea level rise, frequent natural disasters, land desertification and the like, and has serious influence on the survival of human beings and the development of society all around the world. Thus, for CO2The effective capture and emission reduction become one of the hot topics researched by the scholars today. Currently capturing CO2The adopted technologies mainly comprise a low-temperature distillation method, a membrane separation method, a chemical absorption method, a physical adsorption method, a catalytic combustion method and the like. The physical adsorption method can be used for separation under the conditions of normal temperature and normal pressure, is more energy-saving and efficient, and is considered to be a novel separation method with the greatest industrial application prospect.
The adsorbent is critical in the adsorptive separation process and its performance will determine the efficiency and energy consumption of the separation process. Can be applied to CO at present2Trapped adsorbentThere are mainly traditional adsorbents such as zeolites and activated carbon, and emerging porous materials such as metal organic framework Materials (MOFs) and the like. Compared with the traditional adsorbent, the metal organic framework Materials (MOFs) have good application prospect in the adsorption separation of gas due to the characteristics of larger specific surface area, higher porosity, adjustable pore channels, easy surface functionalization modification and the like. Among them, Cu-BTC (also called HKUST-1) is one of MOFs material having excellent adsorption property to gas under normal temperature and pressure. Aprea et al reported that Cu-BTC was responsible for CO at 283K and 1bar2The Adsorption capacity of the adsorbent is up to 7.0mmol/g (P Aprea, D Caputo, N Gargiulo, et al]J Chem Eng Data,2010,55(9):3655-3661), is currently recognized as adsorbing CO at low pressure2One of the best performing MOF materials; in addition, Cu-BTC also has good adsorption performance for VOCs and ethylene/ethane. The adsorption performance of Cu-BTC is far higher than that of the traditional activated carbon, molecular sieve and silica gel adsorption material. However, in practical applications, water vapor is ubiquitous, and the moisture stability of Cu-BTC is very poor. Upon exposure to moisture, the Cu-O bond in Cu-BTC is broken due to attack by Water molecules, resulting in structural collapse (n.c. burtch, h.jasuja, k.s. walton, Water stability and association in metal-organic frameworks J]Chem Rev,114(2014) 10575-10612). Therefore, how to enhance the moisture stability of Cu-BTC has become one of the hot topics studied by many scholars. Sheets et al coated the surface of Cu-BTC with hydrophobic silane (W.Zhang, Y.Hu, J.Ge, H.L.Jiang, S.H.Yu, A surface and general coating to mole/water-resist metal-organic structures with interaction porosity, Journal of the American Chemical Society,136(2014) 16926) at 235 deg.C by vapor deposition technique, and the PDMS-modified material maintained good stability after 1 day contact with 55% relative humidity air, but no adsorption was reported. Al-Janabi et Al, applied post-synthesis modification method, grafting glycine onto Cu-BTC, and as a result, found that the material produced was at atmospheric pressureLower pair of CO2The adsorption capacity of the catalyst is reduced To only 2.2mmol/g, and is also lower than that of a common carbon material and molecular sieve (N.Al-Janabi, H.Deng, J.Borges, X.Liu, A.Garforth, F.R.Siperstein, X.Fan, A surface Post-synthetic modification Method To improved Hydrothermal Stability and CO2 selection of Cu metallic-Organic Framework, Industrial grade&Engineering Chemistry Research,55(2016)7941- > 7949.). The Liyujie and the like use a mechanical method to prepare a Cu-BTC @ GO composite material of Cu-BTC and graphite oxide, and the composite material still has the thickness of 1000m after being soaked in water for 10 hours2BET specific surface area/g, water stability is greatly improved (Y.Li, J.Miao, X.Sun, J.Xiao, Y.Li, H.Wang, Q.Xia, Z.Li, Michaochemical synthesis of Cu-BTC @ GO with enhanced water stability and tolumene addition [ J.]Chemical Engineering journal.2016,298: 191-7). Therefore, a method for improving the stability of water vapor and enhancing the stability to CO is developed2The adsorbing material with the adsorption performance has better application prospect in the aspect of adsorption and separation.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an amino acid @ Cu-BTC composite adsorbent.
The invention also aims to provide the amino acid @ Cu-BTC composite adsorbent prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an amino acid @ Cu-BTC composite adsorbent comprises the following preparation steps:
(1) adding nano ZnO into deionized water, performing ultrasonic dispersion, and adding N, N-Dimethylformamide (DMF) to obtain a ZnO nano slurry solution; adding Cu (NO)3)2·3H2Dissolving O and amino acid in deionized water to obtain Cu (NO)3)2And an amino acid mixture; dissolving trimesic acid in ethanol to obtain a trimesic acid solution;
(2) cu (NO) obtained in the step (1)3)2Adding the mixed solution of the amino acid and the ZnO nano-slurry solution into the mixed solution, and stirring the mixed solutionUniformly mixing, adding a trimesic acid solution, stirring and reacting for 5-10 min to obtain a reaction product, filtering the reaction solution, and sequentially soaking, centrifuging and drying the solid product by using methanol to obtain blue solid powder;
(3) and (3) carrying out vacuum activation on the solid powder obtained in the step (2) to obtain the amino acid @ Cu-BTC composite adsorbent.
Preferably, the ZnO and Cu (NO) in step (1)3)2·3H2The molar ratio of O is 1 (1.25-2).
Preferably, the amino acid in step (1) is glycine (Gly), β -alanine (β -Ala) or gamma-aminobutyric acid (GABA).
Preferably, the volume ratio of the total amount of the deionized water in the step (1) to the DMF to the ethanol is (1-1.1) to (1-1.2) to (1-1.3).
Preferably, the Cu (NO) in step (1)3)2·3H2The molar ratio of O to amino acid is 1 (0.2-0.5).
Preferably, the filtration in step (2) is filtration with an organic filter membrane having an average pore size of 0.45. mu.m.
Preferably, the drying in the step (2) is drying at 60-80 ℃ for 4-8 h.
Preferably, the vacuum activation in the step (3) is vacuum activation at 120-150 ℃ for 8-16 h.
An amino acid @ Cu-BTC composite adsorbent is prepared by the method.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the preparation method is simple to operate, easy to realize and good in repeatability; the synthesis reaction can be carried out at normal temperature, the reaction time is short, the completion of the whole synthesis reaction only needs 5-10 min, and the traditional hydrothermal method for synthesizing Cu-BTC needs the reaction time of 1-2 days at 160 ℃.
(2) Compared with the existing Cu-BTC adsorption material, the amino acid @ Cu-BTC composite adsorbent prepared by the invention has excellent water vapor stability and high CO2Adsorption capacity.
Drawings
FIG. 1 shows N of Cu-BTC and the amino acid @ Cu-BTC material obtained in each example2Adsorption and desorption isotherm diagram.
FIG. 2 is an XRD spectrum of Cu-BTC and the amino acid @ Cu-BTC material obtained in each example.
FIG. 3 is an SEM image of Cu-BTC and the amino acid @ Cu-BTC material obtained in each example.
FIG. 4 shows CO of Cu-BTC and the amino acid @ Cu-BTC material obtained in each example2Adsorption isotherm plot.
Fig. 5 is an XRD pattern of Cu-BTC and Gly @ Cu-BTC obtained in example 1 after 20 days of standing at RH 50%.
FIG. 6 shows CO measured at 298K and 1bar for Cu-BTC and Gly @ Cu-BTC obtained in example 1 in an environment of RH 50% for different days2Adsorption amount change chart.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Nano ZnO (3.6mmol, n)1) Dissolved in deionized water (8ml, n)2) Adding DMF (16ml, n) after ultrasonic dispersion for 10min3) Obtaining ZnO nano-slurry solution; adding Cu (NO)3)2·3H2O(7.2mmol,n4) And Gly (2.16mmol, n)5) Dissolved in deionized water (8ml, n)6) Obtaining Cu (NO)3)2And a Gly mixture; trimesic acid (3.2mmol, n)7) Dissolved in ethanol (16ml, n)8) Obtaining a trimesic acid solution; wherein the dosage ratio of each substance is (n)2+n6):n3:n8＝1:1:1；n1:n4＝1:2。
(2) Cu (NO) obtained in the step (1)3)2Adding the mixed solution of the organic acid and the Gly into a ZnO nano slurry solution, stirring and mixing uniformly, adding a trimesic acid solution, stirring and reacting for 5-10 min to obtain a blue solution containing a reaction product, filtering the solution by using an organic filter membrane with the average pore diameter of 0.45 mu m, and sequentially soaking solid products in methanolCentrifugation and drying gave a blue solid powder.
(3) And (3) placing the solid powder obtained in the step (2) at 120 ℃ for vacuum activation for 12h to obtain glycine @ Cu-BTC solid powder which is marked as Gly @ Cu-BTC material.
Example 2
(1) Nano ZnO (5.76mmol, n)1) Dissolved in deionized water (8ml, n)2) Adding DMF (19ml, n) after ultrasonic dispersion for 10min3) Obtaining ZnO nano-slurry solution; adding Cu (NO)3)2·3H2O(7.2mmol,n4) And β -Ala (2.88mmol, n)5) Dissolved in deionized water (8ml. n)6) Obtaining Cu (NO)3)2Mixing with β -Ala, adding 3.2mmol of trimesic acid7) Dissolved in ethanol (16ml, n)8) Obtaining a trimesic acid solution; wherein the dosage ratio of each substance is (n)2+n6):n3:n8＝1:1.2:1；n1:n4＝1:1.25。
(2) Cu (NO) obtained in the step (1)3)2And β -Ala mixed solution is added into the ZnO nano-slurry solution, the mixture is stirred and mixed evenly, the trimesic acid solution is added, the mixture is stirred and reacts for 5-10 min to obtain blue solution containing reaction products, the solution is filtered by an organic filter membrane with the average aperture of 0.45 mu m, and the solid products are sequentially soaked in methanol, centrifuged and dried to obtain blue solid powder.
(3) And (3) placing the solid powder obtained in the step (2) at 120 ℃ for vacuum activation for 16h to obtain β -alanine @ Cu-BTC solid powder which is marked as Ala @ Cu-BTC material.
Example 3
Nano ZnO (3.6mmol, n)1) Dissolved in deionized water (8ml, n)2) Adding DMF (16ml, n) after ultrasonic dispersion for 10min3) Obtaining ZnO nano-slurry solution; adding Cu (NO)3)2·3H2O(7.2mmol,n4) And GABA (2.88mmol, n)5) Dissolved in deionized water (8ml, n)6) Obtaining Cu (NO)3)2And a GABA mixture; trimesic acid (3.2mmol, n)7) Dissolved in ethanol (21ml, n)8) Obtaining a trimesic acid solution; wherein each one ofThe dosage ratio of the substances is (n)2+n6):n3:n8＝1:1:1.3；n1:n4＝1:2。
(2) Cu (NO) obtained in the step (1)3)2And adding the GABA mixed solution into the nano-slurry ZnO solution, stirring and mixing uniformly, adding a trimesic acid solution, stirring and reacting for 5-10 min to obtain a blue solution containing a reaction product, filtering the solution by using an organic filter membrane with the average pore diameter of 0.45 mu m, and sequentially soaking, centrifuging and drying the solid product by using methanol to obtain blue solid powder.
(3) And (3) placing the solid powder obtained in the step (2) at 150 ℃ for vacuum activation for 8h to obtain gamma-aminobutyric acid @ Cu-BTC solid powder which is marked as GABA @ Cu-BTC material.
The pore structure of the amino acid @ Cu-BTC material prepared in the above example was characterized using an ASAP2460 specific surface pore size distributor, manufactured by Micromeritics, USA. FIG. 1 shows the materials prepared in all examples and the N of Cu-BTC at 77K2And (3) an adsorption and desorption isotherm, wherein information such as the specific surface area, the pore volume and the like of the material can be calculated according to the isotherm, and the obtained structural information is listed in table 1. As can be seen from the results shown in FIG. 1 and Table 1, the BET specific surface area of the amino acid @ Cu-BTC material prepared by the invention is about 1715-1820 m2The total pore volume is 0.75-0.80 cm3(ii) in terms of/g. This shows that the material prepared by the invention has higher specific surface area and larger pore volume.
TABLE 1
FIG. 2 is an XRD pattern of all the materials prepared in examples and Cu-BTC, and it can be seen from the figure that all the materials show three characteristic diffraction peaks at 2 theta 6.8 degrees, 9.6 degrees and 11.8 degrees, which are substantially identical to the characteristic diffraction peaks reported in the literature for Cu-BTC (C.Petit, B.Mendoza, T.J.Bandosz, Reactive adsorption of amonia on Cu-based MOF/graphene composites [ J ], Langmuir,26(2010)15302-15309), indicating that the amino acid @ Cu-BTC prepared by the present invention has a similar crystal structure to the original Cu-BTC.
FIG. 3 is an SEM image of the materials prepared in all the examples and the Cu-BTC material, and it can be seen that these materials have a regular octahedral structure.
FIG. 4 is the CO at 298K for all the materials prepared in the examples and Cu-BTC2Adsorption isotherm plot. As can be seen from the figure, the example material is paired with CO compared to the original Cu-BTC2The adsorption capacity of (a) is higher.
Fig. 5 is an XRD pattern of Cu-BTC and Gly @ Cu-BTC obtained in example 1 after being left in an environment of 50% RH for 20 days. As can be seen from the figure, after being placed for 20 days, the XRD characteristic peak of the original Cu-BTC has basically disappeared, which indicates that the structure of the Cu-BTC has collapsed; the Gly @ Cu-BTC material prepared in example 1 is kept unchanged after being placed for 20 days, which indicates that the material still has a good crystal structure.
FIG. 6 shows the CO measured at 298K and 1bar for Cu-BTC and Gly @ Cu-BTC obtained in example 1 in an environment of 50% RH for different days2Adsorption amount change chart. As can be seen from the figure, the CO of Cu-BTC is observed after 20 days of standing2The adsorption amount is greatly reduced, and is only 9.12 percent of that of fresh Cu-BTC, which indicates that the water vapor stability of the Cu-BTC is poor; the Gly @ Cu-BTC material prepared in example 1 had CO content after being placed in an RH 50% environment for 20 days2The adsorption capacity is still 81.48 percent of the original adsorption capacity, which shows that the water vapor stability of the Gly @ Cu-BTC material is greatly enhanced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
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