CN115888656A - Hydrothermal synthesis method of metal organic framework Cys-MIL-101 adsorbent - Google Patents
Hydrothermal synthesis method of metal organic framework Cys-MIL-101 adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 77
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 24
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 235000018417 cysteine Nutrition 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
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- 229960002433 cysteine Drugs 0.000 claims description 21
- 239000008213 purified water Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 9
- 239000004201 L-cysteine Substances 0.000 claims description 9
- 235000013878 L-cysteine Nutrition 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 5
- IFQSXNOEEPCSLW-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride Chemical compound Cl.SCC(N)C(O)=O IFQSXNOEEPCSLW-UHFFFAOYSA-N 0.000 claims description 4
- IFQSXNOEEPCSLW-HSHFZTNMSA-N (2s)-2-amino-3-sulfanylpropanoic acid;hydron;chloride Chemical compound Cl.SC[C@@H](N)C(O)=O IFQSXNOEEPCSLW-HSHFZTNMSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-UWTATZPHSA-N D-Cysteine Chemical compound SC[C@@H](N)C(O)=O XUJNEKJLAYXESH-UWTATZPHSA-N 0.000 claims description 4
- 229930195710 D‐cysteine Natural products 0.000 claims description 4
- VLSOAXRVHARBEQ-UHFFFAOYSA-N [4-fluoro-2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(F)C=C1CO VLSOAXRVHARBEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940078469 dl- cysteine Drugs 0.000 claims description 4
- QIJRTFXNRTXDIP-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride;hydrate Chemical compound O.Cl.SCC(N)C(O)=O QIJRTFXNRTXDIP-UHFFFAOYSA-N 0.000 claims description 3
- QIJRTFXNRTXDIP-YBBRRFGFSA-N (2s)-2-amino-3-sulfanylpropanoic acid;hydrate;hydrochloride Chemical compound O.Cl.SC[C@@H](N)C(O)=O QIJRTFXNRTXDIP-YBBRRFGFSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- LJPYJRMMPVFEKR-UHFFFAOYSA-N prop-2-ynylurea Chemical compound NC(=O)NCC#C LJPYJRMMPVFEKR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000415 L-cysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])S[H] 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 125000004354 sulfur functional group Chemical group 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
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- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000013255 MILs Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000013256 coordination polymer Substances 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention belongs to the technical field of new materials in porous material science and chemical industry, and relates to a hydrothermal synthesis method of a metal organic framework Cys-MIL-101 adsorbent. Taking water as a solvent, cysteine and terephthalic acid as double ligands, chromium nitrate nonahydrate as metal salt, hydrofluoric acid or hydrochloric acid as a mineralizer, growing at 170-200 ℃ for 10-12 hours, purifying by water, N-dimethylformamide and 95% ethanol, and then drying in vacuum at 130 ℃ for 10 hours to obtain the activated double-ligand metal organic framework Cys-MIL-101 adsorbent. The Cys-MIL-101 adsorbent synthesized by the method has the advantages of higher specific surface area and micropore capacity, rich nitrogen and sulfur functional groups and excellent gas adsorption performance.
Description
Technical Field
The invention belongs to the technical field of new materials in porous material science and chemical industry, and particularly relates to a hydrothermal synthesis method of a metal organic framework Cys-MIL-101 adsorbent.
Background
Metal-organic frameworks (MOFs), also known as coordination polymers, are popular artificial porous crystal materials and widely used in the fields of gas adsorption separation, catalysis, magnetism, fluorescence, probes, targeting preparations, water purification, new energy and the like. MOFs are periodic, porous, and space topological network crystals formed by self-assembly of multidentate small molecular ligands and metal ions or metal ion clusters (Secondary Building blocks, SBUs). Most MOFs have a typical three-dimensional frame structure, regular microscopic geometry, uniform pore channels and pore diameters.
The few MILs-101 known as MILs are MOFs which have a large specific surface area, a high pore volume, good water vapor, acid and base and thermal stability (cf. Ferey, et al, science,2005, 309. Gas adsorption separation is an important application area of MIL-101. However, the gas adsorption performance of the MIL-101 with a single-phase structure is poor: 1atm and 298K, CO 2 、CF 4 The adsorption capacity of the gas is only between 0.3 and 0.4mmol/g, and CO 2 /N 2 、CF 4 /N 2 The gas selectivity is as low as 1.8 to 2.0 (see Senkovska, et al, microporousand Mesoporous Materials,2012,156 (1): 115-120, motkuri, et al, nature Communications,2014, 5.
The application of the MIL-101 framework adsorbent in the field of gas adsorption and separation is limited to a greater extent due to the lower gas adsorption capacity and the poorer gas selectivity. At medium and low pressure, the adsorption quantity and selectivity of MOFs gas mainly come from the contribution of metal active sites and functional groups. Although MIL-101 with single-phase structure has high specific surface area and large pore volume, the key defect is that the frame lacks functional groups (such as-NH) with strong adsorbability to gas 2 、-OH、-NO 2 and-SH, etc.), and the source of the defect is the synthesis of MIL-101 The ligand being terephthalic acid (H) only 2 BDC). The functional groups with the framework structure are enriched, and the method is an effective way for improving the adsorption quantity and selectivity of MOFs.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, namely, the essential defect of deficient functional groups of a single MIL-101 crystal structure is overcome, a novel MIL-101 rich in functional groups is developed, and the CO content of an MIL-101 adsorbent is improved 2 、CF 4 The adsorption quantity of the gases is equal, and the CO is promoted 2 /N 2 、CF 4 /N 2 And the selectivity of the gases.
The purpose of the invention is realized by the following technical scheme:
a hydrothermal synthesis method of a metal organic framework Cys-MIL-101 adsorbent is characterized in that cysteine and terephthalic acid are used as double ligands to be fed together when the Cys-MIL-101 adsorbent is synthesized.
Further, the ratio of the amount of the cysteine to the amount of the terephthalic acid material is 3.
Furthermore, the ratio of the cysteine to the terephthalic acid is 10-15.
Further, the cysteine comprises one or more of L-cysteine, D-cysteine, DL-cysteine, L-cysteine hydrochloride, D-cysteine hydrochloride, DL-cysteine hydrochloride, L-cysteine hydrochloride monohydrate, D-cysteine hydrochloride monohydrate and DL-cysteine hydrochloride monohydrate.
Further, the cysteine is L-cysteine.
A hydrothermal synthesis method of a metal organic framework Cys-MIL-101 adsorbent specifically comprises the following steps:
s1, putting the cysteine, the terephthalic acid, sufficient metal salt, a mineralizer and water into a hydrothermal kettle;
s2, preserving heat for 10-12 hours at 170-200 ℃, cooling, filtering and centrifuging to obtain crystals;
s3, fully cleaning the crystal by adopting purified water, N-dimethylformamide and 95% ethanol;
s4, drying the washed crystal at 130 ℃ for 10 hours in vacuum to obtain the Cys-MIL-101 adsorbent.
Further, in step S1, the metal salt includes chromium nitrate nonahydrate.
Further, in step S1, the mineralizer includes one of hydrofluoric acid and hydrochloric acid.
Further, in general, in hydrothermal synthesis of a metal-organic framework, the mass ratio of ligand, metal salt, mineralizer and water is 1:1:1:278.
Further, an application of the metal organic framework Cys-MIL-101 adsorbent in gas adsorption separation.
The beneficial effects of the invention are:
1. the BET specific surface area of the synthesized double-ligand type Cys-MIL-101 adsorbent reaches 3239.94m 2 The specific surface area of Langmuir is up to 4216.41m 2 G, DFT micropore volume 1.39cm 3 Per g, pore diameter
Cys-MIL-101 adsorbent at 1atm and 298K for pure component CO 2 、CF 4 、CH 4 、SF 6 、NF 3 、C 2 F 6 、N 2 The adsorption capacity of the adsorbent reaches 2.38, 1.13, 0.59, 2.54, 0.85, 2.49 and 0.10mmol/g, and the equivalent component of CO is equal to that of the adsorbent 2 /N 2 、CF 4 /N 2 、CH 4 /N 2 、SF 6 /N 2 、NF 3 /N 2 、C 2 F 6 /N 2 The selectivity of the compound reaches 23.8, 11.3, 5.9, 25.4, 8.5 and 24.9.
2. The double-ligand Cys-MIL-101 adsorbent synthesized by the method is rich in nitrogen and sulfur functional groups, and the gas adsorption capacity of the adsorbent is improved.
Drawings
FIG. 1 shows the 10% L-Cys-MIL-101 adsorbent Infrared Spectrum (IR) synthesized in example 4;
FIG. 2 depicts the 10% L-Cys-MIL-101 adsorbent phase Structure (PXRD) synthesized in example 4;
FIG. 3 is a Scanning Electron Microscope (SEM) analysis of the 10% L-Cys-MIL-101 adsorbent synthesized in example 4;
FIG. 4 is a 10% L-Cys-MIL-101 adsorbent simultaneous thermogravimetric analysis (TG-DSC) of the synthesis of example 4;
FIG. 5 is the nitrogen adsorption and desorption isotherm (BET) of 10% L-Cys-MIL-101 adsorbent 77K synthesized in example 4;
FIG. 6 (a, b) is the gas adsorption isotherm (ADS) of 10% L-Cys-MIL-101 adsorbent synthesized in example 4;
FIG. 7 is the 10% L-Cys-MIL-101 adsorbent gas Selectivity isotherm (Selectivity) of the synthesis of example 4.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1:3% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 3.
Taking 0.36mmol of L-cysteine, 11.64mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle together, preserving the heat for 10 hours at 200 ℃, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum for 10 hours at 130 ℃ to obtain the activated double ligand type 3-Cys-MIL-101 adsorbent. The adsorbent yield was 60% based on the amount of ligand.
Example 2:5% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 5.
Taking 0.6mmol of L-cysteine, 11.4mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle together, preserving the heat for 10 hours at 200 ℃, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum for 10 hours at 130 ℃ to obtain the activated double ligand type 5-Cys-MIL-101 adsorbent. The adsorbent yield was 65% based on the amount of ligand.
Example 3:7% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 7.
Taking 0.84mmol of L-cysteine, 11.16mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml of polytetrafluoroethylene lined hydrothermal kettle, preserving the heat at 200 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals with purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double ligand type 7L-Cys-MIL-101 adsorbent. The adsorbent yield was 69% based on the amount of ligand.
Example 4:10% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 10.
Taking 1.2mmol of L-cysteine, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle, keeping the temperature at 200 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double-ligand type 10L-Cys-MIL-101 adsorbent. The adsorbent yield was 78% with respect to the amount of ligand.
Example 5:15% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 15.
1.8mmol of L-cysteine, 10.2mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water are taken and put into a 100ml of polytetrafluoroethylene lined hydrothermal kettle together, the temperature is kept at 200 ℃ for 10 hours, the mixture is cooled, filtered and centrifuged, crystals are fully washed by purified water, N-Dimethylformamide (DMF) and 95 percent ethanol, and the crystals are dried in vacuum at 130 ℃ for 10 hours, thus obtaining the activated double ligand type 15-percent L-Cys-MIL-101 adsorbent. The adsorbent yield was 73% based on the amount of ligand.
Example 6:20% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 20.
2.4mmol of L-cysteine, 9.6mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water are jointly added into a 100ml polytetrafluoroethylene lined hydrothermal kettle, the temperature is kept at 200 ℃ for 10 hours, the mixture is cooled, filtered and centrifuged, crystals are fully washed by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and the crystals are dried in vacuum at 130 ℃ for 10 hours, thus obtaining the activated double-ligand type 20L-Cys-MIL-101 adsorbent. The adsorbent yield was 70% based on the amount of ligand.
Example 7:30% Synthesis of L-Cys-MIL-101 adsorbent
In this example, the mass ratio of L-cysteine to terephthalic acid was 30.
Taking 3.6mmol of L-cysteine, 8.4mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle, keeping the temperature at 200 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double-ligand type 30L-Cys-MIL-101 adsorbent. The adsorbent yield was 74% with respect to the amount of ligand.
Example 8:10% Synthesis of D-Cys-MIL-101 adsorbent
In this example, the mass ratio of D-cysteine to terephthalic acid was 10.
Taking 1.2mmol of D-cysteine, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml of polytetrafluoroethylene lined hydrothermal kettle, preserving the heat at 200 ℃ for 10 hours, cooling, filtering and centrifuging, fully cleaning crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double ligand type 10-D-Cys-MIL-101 adsorbent.
Example 9:10% Synthesis of DL-Cys-MIL-101 adsorbent
In this example, the mass ratio of DL-cysteine to terephthalic acid was 10.
Taking 1.2mmol of DL-cysteine, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrofluoric acid and 3336mmol of water, putting the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle, keeping the temperature at 200 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double ligand type 10 DL-Cys-MIL-101 adsorbent.
Example 10:10% Synthesis of L-Cys-MIL-101-Cl adsorbent
In this example, the mass ratio of L-cysteine hydrochloride to terephthalic acid was 10.
1.2mmol of L-cysteine hydrochloride, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrochloric acid and 3336mmol of water are taken and put into a 100ml of polytetrafluoroethylene lined hydrothermal kettle together, the temperature is kept at 195 ℃ for 10 hours, the mixture is cooled, filtered and centrifuged, crystals are fully washed by purified water, N-Dimethylformamide (DMF) and 95 percent ethanol, and the crystals are dried in vacuum at 130 ℃ for 10 hours, thus obtaining the activated double ligand type 10L-Cys-MIL-101-Cl adsorbent.
Example 11:10% Synthesis of D-Cys-MIL-101-Cl adsorbent
In this example, the mass ratio of D-cysteine hydrochloride to terephthalic acid was 10.
Taking 1.2mmol of D-cysteine hydrochloride, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrochloric acid and 3336mmol of water, feeding the materials into a 100ml polytetrafluoroethylene lined hydrothermal kettle together, preserving the temperature at 195 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying in vacuum at 130 ℃ for 10 hours to obtain the activated double-ligand type 10D-Cys-MIL-101-Cl adsorbent.
Example 12:10% Synthesis of DL-Cys-MIL-101-Cl adsorbent
In this example, the mass ratio of DL-cysteine hydrochloride to terephthalic acid was 10.
Taking 1.2mmol of DL-cysteine hydrochloride, 10.8mmol of terephthalic acid, 12mmol of chromium nitrate nonahydrate, 12mmol of hydrochloric acid and 3336mmol of water, feeding the materials into a 100ml of polytetrafluoroethylene lined hydrothermal kettle together, preserving the heat at 195 ℃ for 10 hours, cooling, filtering and centrifuging, fully washing crystals by purified water, N-Dimethylformamide (DMF) and 95% ethanol, and drying the crystals in vacuum at 130 ℃ for 10 hours to obtain the activated double ligand type 10-percent DL-Cys-MIL-101-Cl adsorbent.
In addition, L-cysteine hydrochloride monohydrate, D-cysteine hydrochloride monohydrate and DL-cysteine hydrochloride monohydrate can be jointly fed with terephthalic acid as a dual ligand to carry out dual ligand in-situ self-assembly to synthesize the Cys-MIL-101 adsorbent.
10% L-Cys-MIL-101 adsorbent synthesized in example 4 was tested using a Micromeritics Instrument Corp. ASAP 2460 gas analyzer (V3.01) and the results are shown in Table 1:
TABLE 1% of the BET specific surface area and pore size and pore volume of the L-Cys-MIL-101 adsorbent
As is clear from Table 1, 10% of the L-Cys-MIL-101 adsorbent synthesized in example 4 had a BET specific surface area as high as 3239.94m 2 The specific surface area of Langmuir is up to 4216.41m 2 G, DFT micropore volume 1.39cm 3 Per g, pore diameter
Cys-MIL-101 adsorbent at 1atm and 298K for pure component CO 2 、CF 4 、CH 4 、SF 6 、NF 3 、C 2 F 6 、N 2 The adsorption capacity of the adsorbent reaches 2.38, 1.13, 0.59, 2.54, 0.85, 2.49 and 0.10mmol/g, and the equivalent component of CO is equal to that of the adsorbent 2 /N 2 、CF 4 /N 2 、CH 4 /N 2 、SF 6 /N 2 、NF 3 /N 2 、C 2 F 6 /N 2 The selectivity of the catalyst reaches 23.8, 11.3, 5.9, 25.4, 8.5 and 24.9, and the performance is good.
Table 2 Synthesis of example 410% of the adsorbent of L-Cys-MIL-101, it can be seen that the adsorbent contains N, S and other elements, and further described as being rich in-NH 2 And functional groups such as-SH and the like, and can effectively improve the adsorption quantity and selectivity of the gas.
TABLE 2% L-Cys-MIL-101 adsorbent organic element composition
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and is not to be construed as limited to the exclusion of other embodiments, and that various other combinations, modifications, and environments may be used and modifications may be made within the scope of the concepts described herein, either by the above teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A hydrothermal synthesis method of a metal organic framework Cys-MIL-101 adsorbent is characterized in that when the Cys-MIL-101 adsorbent is synthesized, cysteine and terephthalic acid are used as double ligands to be fed together.
2. The hydrothermal synthesis method of metal-organic framework Cys-MIL-101 adsorbent as claimed in claim 1, wherein the ratio of the amount of cysteine to the amount of terephthalic acid material is 3.
3. The hydrothermal synthesis method of the metal-organic framework Cys-MIL-101 adsorbent as claimed in claim 1, wherein the amount ratio of the cysteine to the terephthalic acid is 10.
4. The hydrothermal synthesis method of the metal-organic framework Cys-MIL-101 adsorbent as claimed in claim 1, wherein the cysteine comprises one or more of L-cysteine, D-cysteine, DL-cysteine, L-cysteine hydrochloride, D-cysteine hydrochloride, DL-cysteine hydrochloride, L-cysteine hydrochloride monohydrate, D-cysteine hydrochloride monohydrate, and DL-cysteine hydrochloride monohydrate.
5. The hydrothermal synthesis method of a metal-organic framework Cys-MIL-101 adsorbent as claimed in claim 1, wherein the cysteine is L-cysteine.
6. The hydrothermal synthesis method of metal organic framework Cys-MIL-101 adsorbent according to any one of claims 1-5, characterized by comprising the following steps:
s1, putting the cysteine, the terephthalic acid, sufficient metal salt, a mineralizer and water into a hydrothermal kettle;
s2, preserving heat for 10-12 hours at 170-200 ℃, cooling, filtering and centrifuging to obtain crystals;
s3, fully cleaning the crystal by adopting purified water, N-dimethylformamide and 95% ethanol;
s4, drying the cleaned crystals at 130 ℃ for 10 hours in vacuum to obtain the Cys-MIL-101 adsorbent.
7. The method for hydrothermal synthesis of a metal-organic framework Cys-MIL-101 adsorbent as claimed in claim 6, wherein in step S1, the metal salt comprises chromium nitrate nonahydrate.
8. The method as claimed in claim 6, wherein in step S1, the mineralizer comprises one of hydrofluoric acid and hydrochloric acid.
9. Use of a metal organic framework Cys-MIL-101 adsorbent according to any one of claims 1 to 8 in adsorptive separation of gases.
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