CN102274715A - Modified metal organic framework porous adsorption material and working substance pair adsorbed by same - Google Patents
Modified metal organic framework porous adsorption material and working substance pair adsorbed by same Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 title abstract description 17
- 238000001179 sorption measurement Methods 0.000 title abstract description 13
- 239000000126 substance Substances 0.000 title description 2
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 benzoic ethers Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- LMAQRGNIWKAAFR-UHFFFAOYSA-N benzene;dicarboxy carbonate Chemical compound C1=CC=CC=C1.OC(=O)OC(=O)OC(O)=O LMAQRGNIWKAAFR-UHFFFAOYSA-N 0.000 claims description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 239000013384 organic framework Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 235000013847 iso-butane Nutrition 0.000 claims description 3
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 10
- 230000000536 complexating effect Effects 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000005381 potential energy Methods 0.000 abstract description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000011160 research Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- SEAZNTDWFMFOKA-UHFFFAOYSA-N 4-ethyl-1,2,4-triazole Chemical compound CCN1C=NN=C1 SEAZNTDWFMFOKA-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000013352 DUT-6 Substances 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000013236 Zn4O(BTB)2 Substances 0.000 description 1
- MKKVKFWHNPAATH-UHFFFAOYSA-N [C].N Chemical compound [C].N MKKVKFWHNPAATH-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 239000013259 porous coordination polymer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
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- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 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
- 239000002594 sorbent Substances 0.000 description 1
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- Sorption Type Refrigeration Machines (AREA)
Abstract
The invention relates to a modified metal organic framework porous material in an adsorption refrigeration system and an adsorption working medium pair thereof; the modified metal organic framework porous material is prepared by dissolving metal ion nitrate and organic ligand in a molar ratio of 1: 1-10 in N, N-dialkyl formamide, stirring for 10-60 minutes, controlling the reaction temperature to be 25-250 ℃ and the reaction time to be 24-72 hours, and complexing by a hydrothermal synthesis method. The material has the advantages of large specific surface area, ordered pore structure height, controllable pore size, controllable functional groups on the pore surface and surface potential energy, and obviously improved adsorption performance. The modified metal organic framework porous material adsorption working medium pair has wide prospect in a refrigeration system, in particular to a low-temperature heat source driven adsorption refrigeration system.
Description
Technical field
It is right to the present invention relates to a kind of modified metal organic backbone porous adsorbing material and absorption working pair thereof, is used to reduce system's desorption temperature, increases the systemic circulation adsorbance, and then improves unit mass adsorbent refrigerating capacity.Metallic organic framework porous material absorption working pair is to adsorbing application of cold temperature waste heat or solar energy in the air conditioning condition, 50～150 ℃ of regeneration temperatures in typical enclosed.Belong to novel porous material application in the chemical field.
Background technology
Adsorptive refrigeration technology adopts the shock-free cold-producing medium of environment, can utilize low grade heat energies such as solar energy and industrial exhaust heat to drive, and has environmental protection and power savings advantages concurrently, and the boundary that is subjected in recent years freezing pays close attention to widely.In mainly concentrating on both at home and abroad for the research field of absorption refrigeration, aspects such as low temperature exhaust heat and solar energy utilization.Adsorptive refrigeration technology has been obtained significant progress through the development of nearly decades, has had a spot of absorption refrigeration product to throw the people to market.Aspect practicability, the U.S., Germany, Japan, Britain etc. have on a small scale that commodity occur, and domestic is that the research institution of representative has also released the silica gel-water refrigeration unit that low-temperature heat source drives with king of Shanghai Communications University such as bamboo.Though the absorption refrigeration technology has had the product market of having advanced the people of part, on the whole, changes technology and does not reach the heavy industrialization level as yet.The restriction of adsorbent mass-and heat-transfer and whole system endless form, the key that influences absorption refrigeration is the performance of sorbing material itself: the desorbed of adsorbed materials temperature is higher, and sorbing material energy storage density is lower in being subjected to system.Therefore, can develop the adsorbent of superior performance under the low temperature, and right with the superior absorption working pair of cold-producing medium component property, be the key of adsorptive refrigeration technology development.
Metallic organic framework complex (MOFs, be also referred to as Coordination Polymers or heterozygosis compound) be the novel porous material that a class has broad prospect of application, the Coordination Polymers that transition metal ions or metal cluster and organic ligand utilize the method for molecule assembling and crystal engineering to obtain with certain size and shape band cavity.In recent years, the design of Coordination Polymers porous material, synthetic, structure and performance study are very active.This stephanoporate framework crystalline material can be connected with the machine part by different metal ion and various rigid bridge and carry out complexing, designs and the metallic organic framework that synthesizes different apertures, thereby makes that the structural change of MOFs is infinite.Metal ion and the organic ligand of preparation MOFs are rich and varied, can be according to the performance of material, and wait as the size and dimension in functional group, duct and to be selected.Central metallic ions has almost contained the ion that all transition metals form, even comprise the metal ion of tetravalence, this appearance for new MOFs provides countless possibilities, part in the change metal-organic framework materials structure can be regulated and control the flexibility of pore structure, can obtain different adsorption properties.This just makes that the MOFs material can be right with cold-producing medium composition absorption working pair with numerous absorption type refrigeratings, reaches the absorption refrigeration purpose.In addition, MOFs compares with traditional porous material (as zeolite molecular sieve, active carbon) has characteristics such as structure is plastic, specific area is big, porosity is high, synthesize convenience, pore size distribution is even, and these characteristics also meet the definition of absorption type refrigerating, adsorption type heat pump usefulness superior adsorbent.Show great application prospect in the absorption type refrigerating field.
On the other hand, in recent years along with to the increasing sharply of porous Coordination Polymers research, the poromerics with specific function also occurs in succession.Domestic and international many scholars study MOFs material absorption property: Singapore scholar A.Nalaparaju has carried out the research that two kinds of MOFs material ZMOFs and ZIFs are used to adsorb alcohols, water; American scholar Andrew R. has carried out MOF-177 and MOF-5 is used for CO absorption
2Research; German scholar Nicole Klein has carried out the research of DUT-6 absorption normal butane.Domestic research for MOFs material absorption refrigeration agent gas is also fewer, is the research of MOFs absorption hydrogen, alkane mostly.Along with more and more cold-producing mediums in MOF material Study on adsorption property, also in adsorption refrigeration system, quote and lay a good groundwork for the MOF material.
At present, the absorption refrigeration working medium of better performances that is generally used for the absorption refrigeration process study is to being: silica gel-water, molecular sieve-water, methyl alcohol-active carbon, active carbon-ammonia.Wherein water, ammonia, methyl alcohol are respectively the refrigerant gas of evaporation latent heat maximum.Molecular sieve-aqueous systems generally needs higher desorption temperature, and other three kinds of working medium can well be utilized solar energy and low grade residual heat to all carrying out desorb at low temperatures.But methyl alcohol has severe toxicity, and ammonia has penetrating odor, and incompatible with copper product, and this has also restricted their industrialized prospect.Silica gel is a kind of have amorphous chain and cancellated silicon polymer, it is a kind of hydrophilic polar adsorbent, very easy adsorbed water steam, absorption property is stable, can under lower heat source temperature, drive, and the latent heat of vaporization of water is big, thereby, it is right that silica gel-water just is used as absorption type refrigerating working medium by people very naturally, and silica gel also is the adsorption refrigeration adsorbent of industrial prospect maximum.But silica gel adsorption isotherm on the water belongs to the II type of Brunauer classification, and adsorbance increases with pressure and rises.Therefore, be under low pressure, the adsorbance of water on silica gel is less, has limited the evaporating temperature of silica gel-water absorption type refrigerating, and this also is to cause the bigger reason of most of silica gel-water refrigeration unit volumes on the market.
In sum, can develop and want the adsorbent that mates with cold-producing medium and form absorption working pair being the key of absorption refrigeration technical development.
Summary of the invention
The object of the invention be in existing, low temperature drives absorption type refrigerating adsorbent shortcoming, proposes a kind of cooling modified metal organic backbone porous material; Another object of the present invention also provides the absorption working pair that contains above-mentioned modified metal organic backbone porous material right.
Technical scheme of the present invention is: a kind of modified metal organic backbone porous adsorbing material, it is characterized in that being made by following steps: with metal ion nitrate and organic ligand is 1 in molar ratio: 1-10, be dissolved in N, in the N-dialkylformamide, stirred 10-60 minute, the control reaction temperature is 25-250 ℃, and the reaction time is 24-72 hour, makes modified metal organic backbone porous adsorbing material; Wherein metal ion is selected from a kind of in IIIB, IV B, V B, VI B, VIII B, VIII, I B or the IIB family in the IUPAC periodic table of elements, or a kind of in I A, II A, IIIA, IVA or the VII A family; Organic ligand is selected from phthalic acid, benzene tricarbonic acid's ester, benzene three benzoic ethers, naphthalene dicarboxylic acids ester, imidazole-2-carboxylic acid or 1, any one in two (1,2, the 4-triazole-4-yl) ethane of 2-or two kinds.
Preferred described metal ion is a kind of among Zn, Cu, Ni, In or the Na.The mol ratio of preferred described metal ion nitrate and organic ligand is 1: 2-4.
The present invention also provides a kind of absorption working pair that contains above-mentioned modified metal organic backbone porous adsorbing material right, this absorption working pair is to being made up of modified metal organic backbone porous material and cold-producing medium, and wherein cold-producing medium is chosen a kind of in water, alcohol, ammonia or the alkane.Preferred described cold-producing medium is selected from a kind of in water, ammonia, methyl alcohol, ethanol, normal butane or the iso-butane.
The present invention forms the modified metal organic backbone porous adsorbing material of one-dimensional chain skeleton, two-dimensional rectangle skeleton, α cage three-dimensional framework or three-dimensional netted skeleton structure by the hydrothermal synthesis method complexing.
The present invention chooses modified metal organic backbone porous material and makes absorption type refrigerating system adsorbent, make that it can to form absorption working pair right with cold-producing medium, reduced the absorbing refrigeration system desorption temperature, improve the circulation adsorbance under adsorbent low temperature, the low pressure, increased the refrigerating capacity of unit adsorbent in the adsorption process.
The present invention utilizes metallic organic framework porous material big characteristics of circulation adsorbance under low temperature, low pressure, is used for typical air conditioner refrigerating operating mode, has increased unit mass adsorbent refrigerating capacity in the refrigeration system, the consolidation system refrigeration performance.
The present invention utilizes the characteristics of metallic organic framework porous material Heat stability is good, has strengthened absorption refrigeration unit running stability and adsorbent service life.
Beneficial effect:
(1) with respect to present existing adsorbent, specific area of the present invention is big, the pore structure high-sequential, hole dimension is controlled and the functional group of hole surface and the controlled system of surperficial potential energy, and absorption property obviously improves.
(2) with respect at present existing adsorbent shortcoming, the present invention's circulation adsorbance under low-temp low-pressure is bigger, and under lower temperature, lower pressure, refrigeration performance is higher than silica gel and 13X, and its refrigeration performance obviously improves.
(3) regeneration temperature of the present invention can be 50～150 ℃, can utilize in industrial waste heat and the solar energy etc., low temperature exhaust heat, wide material sources.
Description of drawings
Fig. 1 is the shape of adsorbent cage described in the case study on implementation 1 skeleton structure: a) dodecahedron MBB (InN
4(CO2)
4) constitute: each phosphide atom and four H
3Four nitrogen-atoms are connected with four oxygen atoms in the ImDC ligand; B) four connected TBU (InN
4); C) angle of ligand ImDC; D) allow maximum atom in the sorbent structure cage.
Fig. 2 is the three-dimensional netted skeleton structure diagram of adsorbent in the case study on implementation 3: a) a benzene triphen formic acid unit is connected to 3 Zn
4On the O unit; B) structure chart on 001 direction; C) Zn
4Structure fragment on the O, structure comprise six annulus and zinc atom.Adsorbent has the network structure of (6,3) coordination, and octahedron has 6 coordination sites among the figure, and the center is the benzenetricarboxylic acid unit with three coordination sites.
Fig. 3 is the XRD figure of case study on implementation 3 adsorbents.
Fig. 4 is the three-dimensional netted skeleton structure diagrams of case study on implementation 4 adsorbents: basket structure a) meso-hole structure b); C) the three-dimensional netted benefit structure of opening up of case study on implementation 4 adsorbents; D) network structure of Jian Huaing.
Fig. 5 is unit cell configuration (A) and secondary structure unit figure (B) in the case study on implementation 5 adsorbent three-dimensional orthogonal skeletons.
The specific embodiment
The invention will be further described below in conjunction with instantiation, so that the understanding of the present invention is not thereby limiting the invention.
In each case study on implementation, choosing after adsorbate not of the same race and the modification organometallic skeletal porous material, to form absorption working pair right, investigates its refrigeration performance.
Case study on implementation 1
Two nitric hydrate indiums and 4, the 5-dicarboxylic acid imidazole is dissolved in N in the ratio of (1: 2), in the dinethylformamide, mix and pour in the polytetrafluoroethylene (PTFE) reactor, 85 ℃ of reaction temperatures, the reaction time is 24h, forms three-dimensional cage shape mesh skeleton structure adsorbent by the hydrothermal synthesis method complexing.To form absorption working pair right with water, and under 25 ℃, 0.1MPa, its unit mass adsorbent refrigerating capacity can reach 1187.74KJ/kg; To form absorption working pair right with methyl alcohol, and under 25 ℃, 0.1MPa, its unit mass adsorbent refrigerating capacity can reach 423.17KJ/kg; To form absorption working pair right with ethanol, and under 25 ℃, 0.1MPa, its unit mass adsorbent refrigerating capacity can reach 323.33KJ/kg.The shape of adsorbent cage described in the case study on implementation 1 skeleton is by dodecahedron MBB (InN
4(CO
2)
4) constitute each phosphide atom and four H
3Four nitrogen-atoms are connected with four oxygen atoms in the ImDC ligand.The three-dimensional cage shape of adsorbent skeleton structure as shown in Figure 1.
Case study on implementation 2
Nickel nitrate, benzene tricarbonic acid's ester and 1,2-two (1,2,4-triazole-4-yl) ethane is dissolved in N in the ratio of (1: 1: 3), and in the dinethylformamide, 25 ℃ were stirred 60 minutes, 250 ℃ of reaction temperatures in 24 hours reaction time, form the 3 D stereo skeleton structure by the hydrothermal synthesis method complexing.Right with water composition working medium, under typical air conditioning condition (10 ℃ of evaporating temperatures), its unit mass adsorbent refrigerating capacity reaches 518.28KJ/kg.The network structure of adsorbent 3 D stereo described in the example 2 is by benzene tricarbonic acid, 1,2-pair (1,2, formations such as 4-triazole-4-base, nickle atom, oxygen atom.
Case study on implementation 3
Zinc nitrate and benzene three benzoic ethers are dissolved in N in the ratio of (4: 5), and in the N-DEF, 25 ℃ were stirred 10 minutes, and 80 ℃ of reaction temperatures in 72 hours reaction time, form the three-dimensional framework structure by the hydrothermal synthesis method complexing.To form absorption working pair right with ammonia, and under 25 ℃, 0.1MPa, its unit mass adsorbent refrigerating capacity can reach 283.72KJ/kg.Adsorbent mesh skeleton structure is by a benzene triphen formic acid unit and 3 Zn in the case study on implementation 3
4O is connected, Zn
4Structure fragment on the O comprises six annulus and zinc atom.Adsorbent has the network structure of (6,3) coordination, and octahedron has 6 coordination sites among the figure, and the center is the benzenetricarboxylic acid unit with three coordination sites.Three-dimensional netted skeleton structure of adsorbent and XRD figure are seen Fig. 2 and Fig. 3 respectively.As can be seen from Figure 3: highest peak appears at 2 υ=5.2 °, and two other peak appears at 2 υ=10.8 ° respectively, 2 υ=7.0 °.
Case study on implementation 4
Zinc nitrate, naphthalene dicarboxylic acids ester and benzene three benzoic ethers are dissolved in N in the ratio of (1: 1: 1), and in the dinethylformamide, 25 ℃ were stirred 60 minutes, and 25 ℃ of reaction temperatures in 48 hours reaction time, form the three-dimensional netted benefit structure of opening up by the hydrothermal synthesis method complexing.It is right that adsorbent after the improvement and normal butane are formed absorption working pair, and under 25 ℃, 0.1MPa, adsorbance can reach 5 times of traditional MOF-5, and its unit mass adsorbent refrigerating capacity can reach 421.3KJ/kg.The three-dimensional netted skeleton of case study on implementation 4 described adsorbents mainly is made of group variety and benzene three benzoic acid.The three-dimensional netted skeleton structure of described adsorbent is seen accompanying drawing 4.
Case study on implementation 5
Copper nitrate and benzene tricarbonic acid's ester are dissolved in N in the ratio of (1: 2), and in the dinethylformamide, 25 ℃ were stirred 60 minutes, and 30 ℃ of reaction temperatures in 72 hours reaction time, form the three-dimensional orthogonal skeleton structure by the hydrothermal synthesis method complexing.To form absorption working pair right with iso-butane, and under 25 ℃, 0.1MPa, its unit mass adsorbent refrigerating capacity can reach 47.58KJ/kg.Case study on implementation 5 adsorbents are octahedral structure, has good symmetry, be formed by connecting by 6 dimerization copper unit by 4 benzene tricarbonic acid's fat unit, its structure is referred to as Pocket owing to being similar to the string bag, and this Pocket unit is connected to each other and has constituted the copper-crystal that comprises cavity.Interconnect the main aperture road that has formed three-dimensional orthogonal between the cavity, and Pocket is communicated with the cavity in main aperture road, has formed a kind of special inferior duct.Adsorbent three-dimensional orthogonal skeleton structure as shown in Figure 5.From the figure as can be seen: adsorbent is octahedral structure, has good symmetry, be formed by connecting by 6 dimerization copper unit by 4 benzene tricarbonic acid unit, its structure is referred to as Pocket owing to being similar to the string bag, and this Pocket unit is connected to each other and has constituted the copper-benzene tricarbonic acid's crystal that comprises cavity.Interconnect the main aperture road that has formed three-dimensional orthogonal between the cavity, and Pocket is communicated with the cavity in main aperture road, has formed a kind of special inferior duct.
Claims (5)
1. modified metal organic backbone porous adsorbing material, it is characterized in that being made by following steps: with metal ion nitrate and organic ligand is 1 in molar ratio: 1-10, be dissolved in N, in the N-dialkylformamide, stirred 10-60 minute, the control reaction temperature is 25-250 ℃, and the reaction time is 24-72 hour, makes the metallic organic framework porous adsorbing material; Wherein metal ion is selected from a kind of in IIIB, IVB, VB, VI B, VIII B, VIII, I B or the IIB family in the IUPAC periodic table of elements, or a kind of in I A, II A, IIIA, IVA or the VII A family; Organic ligand is phthalic acid, benzene tricarbonic acid's ester, benzene three benzoic ethers, naphthalene dicarboxylic acids ester, imidazole-2-carboxylic acid or 1, any one in two (1,2, the 4-triazole-4-yl) ethane of 2-or two kinds.
2. modified metal organic backbone porous adsorbing material according to claim 1 is characterized in that described metal ion is a kind of among Zn, Cu, Ni, In or the Na.
3. modified metal organic backbone porous adsorbing material according to claim 1, the mol ratio that it is characterized in that described metal ion nitrate and organic ligand is 1: 2-4.
4. the absorption working pair of a modified metal organic backbone porous adsorbing material as claimed in claim 1 is right, it is characterized in that absorption working pair to being made up of modified metal organic backbone porous material and cold-producing medium, wherein cold-producing medium is chosen a kind of in water, alcohol, ammonia or the alkane.
5. working medium according to claim 4 is right, and its speciality is that described cold-producing medium is selected from a kind of in water, ammonia, methyl alcohol, ethanol, normal butane or the iso-butane.
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