CN106076242A - A kind of MOFs bimetallic adsorbing material (Fe, Co) BTC and preparation method thereof - Google Patents
A kind of MOFs bimetallic adsorbing material (Fe, Co) BTC and preparation method thereof Download PDFInfo
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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
- B01J20/02—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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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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- 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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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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 adsorbing material technical field, disclose a kind of MOFs bimetallic adsorbing material (Fe, Co) BTC and preparation method thereof.Described preparation method is: reduced iron powder, cabaltous nitrate hexahydrate, Trimesic acid are mixed with water, it is uniformly mixed and obtains ternary water mixed solution, it is subsequently adding salpeter solution and Fluorinse, mix homogeneously obtains reaction mother liquor, reaction mother liquor is heated to 150～180 DEG C and carries out synthetic reaction 8～16h, product is separated, purification and vacuum activation, obtains described MOFs bimetallic adsorbing material (Fe, Co) BTC.Compared with existing Fe BTC adsorbent, bimetallic adsorbing material (Fe, Co) BTC prepared by the present invention enhances CO2Active force, can significantly improve CO2Adsorption capacity.
Description
Technical field
The invention belongs to adsorbing material technical field, be specifically related to a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC
And preparation method thereof.
Background technology
Greenhouse gases CO2Discharge in a large number the global warming caused be the mankind face up to now the most serious
Global Environmental Problems.Therefore, to CO2Carry out capturing and sealing up for safekeeping and will become minimizing and control CO2One of effective means of discharge.Closely
Nian Lai, a class emerging porous MOFs material is adjustable etc. excellent due to its superhigh specific surface area and pore volume, pore structure and surface property
Point so that it is at CO2Capture field has boundless application prospect.Millward et al.(A.R.Millward,
O.M.Yaghi,Metal-organic frameworks with exceptionally high capacity for
storage of carbon dioxide at room temperature,J Am Chem Soc 127(2005)17998-
17999.) MOF-177 is reported when 298K and 35bar to CO2Adsorption capacity be up to 33.5mmol/g；Yang et al.
(D.A.Yang,H.Y.Cho,J.Kim,S.T.Yang,W.S.Ahn,CO2capture and conversion using Mg-
MOF-74prepared by a sonochemical method,Energ Environ Sci 5(2012)6465-6473.)
Report Mg-MOF-74 when 308K and 1bar to CO2Adsorption capacity be up to 9mmol/g, be to generally acknowledge under low pressure at present
CO absorption2The MOF material that performance is best；In actual application, water vapour is ubiquitous, MOF-177 and Mg-MOF-74 its
Water stability is the most poor, and once with moisture, its structure is quickly caved in, almost without actual application value.MIL-101(Cr)
It is hydrothermal stability and the MOFs material of chemical stability that current minority has excellence with MIL-100 (Fe), and at room temperature
To CO under condition of normal pressure2All there is with VOCs good absorption property, be considered to have good actual application prospect.Especially
MIL-100 (Fe) (also referred to as Fe-(BTC)), owing to its aperture is slightly less than MIL-101 (Cr), the therefore VOCs to low concentration
And CO2All there is more preferable absorption property (F.Xu, S.K.Xian, Q.B.Xia, Y.W.Li, Z.Li, Effect of
Textural Properties on the Adsorption and Desorption of Toluene on the Metal-
Organic Frameworks HKUST-1and MIL-101,Adsorpt Sci Technol 31(2013)325-
339.S.K.Xian,J.J.Peng,Z.J.Zhang,Q.B.Xia,H.H.Wang,Z.Li,Highly enhanced and
weakened adsorption properties of two MOFs by water vapor for separation of
CO2/CH4and CO2/N-2binary mixtures,Chem Eng J 270(2015)385-392.).While it is true, people
Also it is attempt to by modification, the absorption property of this type of material of raising further, such as Bandosz et al. (C.Petit,
T.J.Bandosz,Synthesis,Characterization,and Ammonia Adsorption Properties of
Mesoporous Metal-Organic Framework(MIL(Fe))-Graphite Oxide Composites:
Exploring the Limits of Materials Fabrication,Adv Funct Mater 21(2011)2108-
2117.) attempt graphite oxide GO Yu MIL-100 (Fe) to be combined, prepare MIL-100 (Fe)@GO material, but fail.Make
Person analyzes the octahedra cage structure subglobular that reason is MIL-100 (Fe) so that GO and its surface are that different angles are intersected,
It is unfavorable for that metallic site is combined with oxygen-containing functional group.
Summary of the invention
In place of solving the shortcoming and defect of above prior art, the primary and foremost purpose of the present invention is to provide a kind of MOFs
The preparation method of bimetallic adsorbing material (Fe, Co)-BTC.Than MIL-100 (Fe), there is more preferable absorption property with acquisition one
Material.
Another object of the present invention is to provide a kind of MOFs bimetallic adsorbing material prepared by said method
(Fe,Co)-BTC。
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of MOFs bimetallic adsorbing material (Fe, Co)-BTC, including following preparation process:
Reduced iron powder, cabaltous nitrate hexahydrate, Trimesic acid are mixed with water, is uniformly mixed and obtains the mixing of ternary water
Solution, is subsequently adding salpeter solution and Fluorinse, and mix homogeneously obtains reaction mother liquor, reaction mother liquor is heated to 150～
180 DEG C carry out synthetic reaction 8～16h, and product is separated, purification and vacuum activation, obtain the absorption of described MOFs bimetallic
Material (Fe, Co)-BTC.
Preferably, described separation process is as follows: reactant liquor is cooled to room temperature, adds DMF (DMF)
Filter after stirring, remove unreacted part, after drying, obtain rough solid (Fe, Co)-BTC material.
Preferably, described purification step is: product dehydrated alcohol 80～120 DEG C (in hermetic container) soak after from
The heart, dried one or many, then the centrifugation after 50～80 DEG C of impregnation process of perfluorinated aqueous ammonium, then through water logging
Stain, centrifuging treatment one or many, add dehydrated alcohol after drying after 80～120 DEG C (in hermetic container) soaks
Centrifugal, dried one or many, obtains the most orange-yellow (Fe, Co)-BTC material.
Preferably, described vacuum activation refers to carry out vacuum drying activation 8～16h at a temperature of 100～250 DEG C.
Preferably, described reduced iron powder: cabaltous nitrate hexahydrate: the mol ratio of Trimesic acid is 10:(0.5～3): (6～
9)；The molal volume of described reduced iron powder and water is than for 10:(45～55) mmol/mL.
Preferably, described Fluorinse refers to the Fluorinse that mass concentration is 40%.
Preferably, described water: salpeter solution: the volume ratio of Fluorinse is (45～55): (0.4～0.5): (0.8～
1)。
A kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC, is prepared by said method.
Compared to existing technology, the invention have the advantages that and beneficial effect:
(1) compared with existing Fe-BTC adsorbent, bimetallic adsorbing material (Fe, Co)-BTC prepared by the present invention strengthens
To CO2Active force, can significantly improve CO2Adsorption capacity；
(2) preparation method of the present invention is simple, reproducible.
Accompanying drawing explanation
Fig. 1 is Fe-BTC and (Fe, Co)-BTC of preparing of each embodiment is to N2Adsorption isotherm line chart (77K)；
Fig. 2 is Fe-BTC (left) and the SEM figure of (Fe, Co)-BTC-3# (right) of embodiment 3 preparation；
Fig. 3 is Fe-BTC and the FTIR figure of (Fe, Co)-BTC-3# of embodiment 3 preparation；
Fig. 4 is CO2Adsorption isotherm line chart on (Fe, Co)-BTC material prepared by Fe-BTC and each embodiment
(298.15K, 0～1bar).
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
By reduced iron powder (10mmol), six water and cobalt nitrate (0.5mmol), Trimesic acid (6.7mmol) and distilled water
(45ml) it is uniformly mixed and obtains ternary water mixed solution, be subsequently adding HNO3Solution (0.4ml), 40%NaF solution
(0.8ml) be mixed to get reaction mother liquor, then reaction mother liquor is placed in reactor be heated to 150 DEG C under the conditions of react 16h, obtain
Containing the mixed liquor of product (Fe, Co)-BTC, it is cooled to room temperature (25 DEG C).(Fe, Co)-BTC reaction obtained reacts product
Thing mixed liquor, is added thereto to 25ml DMF, stirs 2h at normal temperatures, use G1Funnel filters, by most of unreacted part
Remove, be then dried to obtain rough solid (Fe, Co)-BTC material.Then by this solid material soaked in absolute ethyl alcohol, put
In 100 DEG C of heat treated 24h, it is repeated 2 times, after being centrifuged, is dried to obtain solid material.Add 0.75g ammonium fluoride and water, be placed in
60 DEG C of heat treated 12h, after centrifugation, then with water retting twice, after recentrifuge, are dried to obtain solid material.Finally add
Enter 60ml dehydrated alcohol, be placed in 100 DEG C of heat treated 24h, be repeated twice, after being centrifuged, be dried to obtain the most orange-yellow
(Fe, Co)-BTC material.Gained solid material is placed in 150 DEG C of vacuum activation 8h obtain MOFs bimetallic adsorbing material (Fe,
Co)-BTC, is designated as: (Fe, Co)-BTC-1#.
Embodiment 2
By reduced iron powder (10mmol), six water and cobalt nitrate (1mmol), Trimesic acid (7.2mmol) and distilled water
(50ml) it is uniformly mixed and obtains ternary water mixed solution, be subsequently adding HNO3Solution (0.5ml), 40%NaF solution
(0.9ml) be mixed to get reaction mother liquor, then reaction mother liquor is placed in reactor be heated to 160 DEG C under the conditions of react 12h, obtain
Containing the mixed liquor of product (Fe, Co)-BTC, it is cooled to room temperature (25 DEG C).(Fe, Co)-BTC reaction obtained reacts product
Thing mixed liquor, is added thereto to 30ml DMF, stirs 2h at normal temperatures, use G1Funnel filters, by most of unreacted part
Remove, be then dried to obtain rough solid (Fe, Co)-BTC material.Then by this solid material soaked in absolute ethyl alcohol, put
In 120 DEG C of heat treated 16h, it is repeated 2 times, after being centrifuged, is dried to obtain solid material.Add 0.8g ammonium fluoride and water, be placed in
80 DEG C of heat treated 8h, after centrifugation, then with water retting twice, after recentrifuge, are dried to obtain solid material.It is eventually adding
80ml dehydrated alcohol, is placed in 120 DEG C of heat treated 16h, is repeated twice, centrifugal after, be dried to obtain the most orange-yellow (Fe,
Co)-BTC material.Gained solid material is placed in 120 DEG C of vacuum activation 12h obtain MOFs bimetallic adsorbing material (Fe, Co)-
BTC, is designated as: (Fe, Co)-BTC-2#.
Embodiment 3
By reduced iron powder (10mmol), six water and cobalt nitrate (2mmol), Trimesic acid (8mmol) and distilled water
(55ml) it is uniformly mixed and obtains ternary water mixed solution, be subsequently adding HNO3Solution (0.5ml), 40%NaF solution (1ml)
Be mixed to get reaction mother liquor, then reaction mother liquor is placed in reactor be heated to 180 DEG C under the conditions of react 8h, obtain producing containing reaction
The mixed liquor of thing (Fe, Co)-BTC, is cooled to room temperature (25 DEG C).(Fe, Co)-BTC product mixed liquor that reaction is obtained,
It is added thereto to 20ml DMF, stirs 2h at normal temperatures, use G1Funnel filters, and is removed by most of unreacted part, then
It is dried to obtain rough solid (Fe, Co)-BTC material.Then by this solid material soaked in absolute ethyl alcohol, it is placed in 110 DEG C and adds
Heat treatment 24h, is repeated 2 times, and after being centrifuged, is dried to obtain solid material.Add 0.85g ammonium fluoride and 75ml water, be placed in 70 DEG C
Heat treated 10h, after centrifugation, then with water retting twice, after recentrifuge, is dried to obtain solid material.It is eventually adding
75ml dehydrated alcohol, is placed in 110 DEG C of heat treated 24h, is repeated twice, centrifugal after, be dried to obtain the most orange-yellow (Fe,
Co)-BTC material.Gained solid material is placed in 100 DEG C of vacuum activation 12h obtain MOFs bimetallic adsorbing material (Fe, Co)-
BTC, is designated as: (Fe, Co)-BTC-3#.
Embodiment 4
By reduced iron powder (10mmol), six water and cobalt nitrate (3mmol), Trimesic acid (9mmol) and distilled water
(50ml) it is uniformly mixed and obtains ternary water mixed solution, be subsequently adding HNO3Solution (0.5ml), 40%NaF solution (1ml)
Be mixed to get reaction mother liquor, then reaction mother liquor is placed in reactor be heated to 160 DEG C under the conditions of react 16h, obtain containing reaction
The mixed liquor of product (Fe, Co)-BTC, is cooled to room temperature (25 DEG C).(Fe, Co)-BTC product mixing that reaction is obtained
Liquid, is added thereto to 25ml DMF, stirs 2h at normal temperatures, use G1Funnel filters, and is removed by most of unreacted part, so
After be dried to obtain rough solid (Fe, Co)-BTC material.Then by this solid material soaked in absolute ethyl alcohol, it is placed in 100 DEG C
Heat treated 24h, is repeated 2 times, and after being centrifuged, is dried to obtain solid material.Add 0.75g ammonium fluoride and 70ml water, be placed in 60
DEG C heat treated 12h, after centrifugation, then with water retting twice, after recentrifuge, is dried to obtain solid material.It is eventually adding
70ml dehydrated alcohol, is placed in 100 DEG C of heat treated 24h, is repeated twice, centrifugal after, be dried to obtain the most orange-yellow (Fe,
Co)-BTC material.Gained solid material is placed in 110 DEG C of vacuum activation 12h obtain MOFs bimetallic adsorbing material (Fe, Co)-
BTC, is designated as: (Fe, Co)-BTC-4#.
The sign of above example gained MOFs bimetallic adsorbing material (Fe, Co)-BTC and performance measurement:
(1) sign of MOFs bimetallic adsorbing material (Fe, Co)-BTC:
Fig. 1 is Fe-BTC and (Fe, Co)-BTC of preparing of each embodiment is to N2Adsorption isotherm (77K), table 1 is
BET and the Langmuir specific surface area of (Fe, Co)-BTC prepared by each embodiment.As can be seen from the above results, embodiment 2
(Fe, Co)-BTC-2# specific surface area of preparation is maximum, has reached 2372m2/ g, but excess addition the second metal can cause ratio
The decline of surface area, such as embodiment 4.But can be seen that (Fe, Co)-BTC prepared by each embodiment has good porous to tie
Structure.
The specific surface area of (Fe, Co)-BTC prepared by each embodiment of table 1
Fig. 2 is Fe-BTC (left) and the SEM figure of (Fe, Co)-BTC-3# (right) of embodiment 3 preparation, it can be seen that (Fe,
Co)-BTC-3# crystal there occurs change relative to Fe-BTC shape, and has agglomeration.
Fig. 3 shows the FTIR figure of (Fe, Co)-BTC-3# of Fe-BTC and embodiment 3 preparation, it can be seen that see (Fe,
Co)-BTC-3# and Fe-BTC has similar infared spectrum, is a difference in that (Fe, Co)-BTC-3# compares Fe-BTC and exists
1536cm-1Place belongs to Vas (COO-1) peak intensity decline, it may be possible to be not coordinated with iron ion on the cobalt ion of doping and part
Carboxyl be coordinated, and it can be seen that be 480cm at wavelength-1There is a peak at place, and this is Fe-O vibration peak, but
(Fe, Co)-BTC-3# is at 662cm-1There is a new peak at place, and this is the vibration peak of Co-O.
(2) MOFs bimetallic adsorbing material (Fe, Co)-BTC CO absorption2Performance
In order to confirm that (Fe, Co)-BTC material prepared by each embodiment is at CO2Adsorption capacity is better than existing Fe-BTC
Material, the absorption property of (Fe, Co)-BTC and Fe-BTC that the present invention is prepared by we compares, and evaluation result is as follows:
Fig. 4 shows CO2Adsorption isotherm on (Fe, Co)-BTC material prepared by Fe-BTC and each embodiment
(298.15K, 0～1bar).It can be seen that (Fe, Co)-BTC-3# material of embodiment 3 preparation is to CO2Absorption hold
Measure the adsorption capacity apparently higher than Fe-BTC, improve 45.3%.
Table 2 lists different adsorbent under 1bar pressure to CO2Adsorbance.As can be seen from the table, in embodiment 3
(Fe, Co)-BTC-3# of preparation presents the highest CO2Adsorption capacity, has reached 3.27mmol/g, than traditional adsorbent with
And the adsorbance of most of MOFs material is the highest.Sole exception is Mg-MOF-74, and this is owing to it contains a large amount of to CO2Have
The magnesium ion unsatuated metal site of extremely strong effect.
The different adsorbing material CO under 1bar of table 22Absorption property
([6]Y.D.Li,H.H.Yi,X.L.Tang,F.R.Li,Q.Yuan,Adsorption separation of
CO2/CH4gas mixture on the commercial zeolites at atmospheric pressure,Chem
Eng J 229(2013)50-56.[7]J.McEwen,J.D.Hayman,A.O.Yazaydin,A comparative study
of CO2,CH4and N-2adsorption in ZIF-8,Zeolite-13X and BPL activated carbon,Chem
Phys 412(2013)72-76.[8]J.H.Zhou,H.L.Zhao,J.X.Li,Y.J.Zhu,J.Hu,H.L.Liu,Y.Hu,
CO2capture on micro/mesoporous composites of(zeolite A)/(MCM-41)with Ca2+
located:Computer simulation and experimental studies,Solid State Sci 24(2013)
107-114.[9]R.L.Tseng,F.C.Wu,R.S.Juang,Adsorption of CO2at atmospheric
pressure on activated carbons prepared from melamine-modified phenol-
formaldehyde resins,Separation and Purification Technology 140(2015)53-60.
[10]R.Banerjee,H.Furukawa,D.Britt,C.Knobler,M.O'Keeffe,O.M.Yaghi,Control of
Pore Size and Functionality in Isoreticular Zeolitic Imidazolate Frameworks
and their Carbon Dioxide Selective Capture Properties,J Am Chem Soc131(2009)
3875-+.[11]Z.G.Hu,M.Khurana,Y.H.Seah,M.Zhang,Z.G.Guo,D.Zhao,Ionized Zr-MOFs
for highly efficient post-combustion CO2capture,Chem Eng Sci 124(2015)61-69.
[12]T.M.McDonald,W.R.Lee,J.A.Mason,B.M.Wiers,C.S.Hong,J.R.Long,Capture of
Carbon Dioxide from Air and Flue Gas in the Alkylamine-Appended Metal-Organic
Framework mmen-Mg-2(dobpdc),J Am Chem Soc 134(2012)7056-7065.)
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of MOFs bimetallic adsorbing material (Fe, Co)-BTC, it is characterised in that include following preparation process:
Reduced iron powder, cabaltous nitrate hexahydrate, Trimesic acid are mixed with water, be uniformly mixed obtain ternary water mixing molten
Liquid, is subsequently adding salpeter solution and Fluorinse, and mix homogeneously obtains reaction mother liquor, and reaction mother liquor is heated to 150～180
DEG C carrying out synthetic reaction 8～16h, product is separated, purification and vacuum activation, obtains described MOFs bimetallic adsorbing material
(Fe,Co)-BTC。
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
As follows in described separation process: reactant liquor is cooled to room temperature, filter after adding DMF stirring, remove the most anti-
The part answered, obtains rough solid (Fe, Co)-BTC material after drying.
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
In described purification step it is: product dehydrated alcohol is centrifuged after soaking at 80～120 DEG C, dried one or many, then warp
Ammonium fluoride aqueous solution centrifugation after 50～80 DEG C of impregnation process, then through water retting, centrifuging treatment one or many, dry
Add centrifugal, dried one or many after dehydrated alcohol soaks at 80～120 DEG C after dry, obtain the most orange-yellow
(Fe, Co)-BTC material.
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
In: described vacuum activation refers to carry out vacuum drying activation 8～16h at a temperature of 100～250 DEG C.
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
In: described reduced iron powder: cabaltous nitrate hexahydrate: the mol ratio of Trimesic acid is 10:(0.5～3): (6～9)；Described reduction
The molal volume of iron powder and water is than for 10:(45～55) mmol/mL.
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
In: described Fluorinse refers to the Fluorinse that mass concentration is 40%.
The preparation method of a kind of MOFs bimetallic adsorbing material (Fe, Co)-BTC the most according to claim 1, its feature exists
In: described water: salpeter solution: the volume ratio of Fluorinse is (45～55): (0.4～0.5): (0.8～1).
8. MOFs bimetallic adsorbing material (Fe, Co)-BTC, it is characterised in that: described in any one of claim 1～7
Method prepare.
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| CN106669737A (en) * | 2017-01-04 | 2017-05-17 | 上海应用技术大学 | Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure |
| CN108404872A (en) * | 2018-05-29 | 2018-08-17 | 中国科学院生态环境研究中心 | Arsenic-removing adsorption agent and preparation method |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110548544A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Iron oxide doped iron metal organic framework, green macro preparation method and application |
| CN112675720A (en) * | 2020-12-10 | 2021-04-20 | 石河子大学 | Preparation method and application of mixed matrix membrane filled with bimetallic strip material |
| CN112979977A (en) * | 2021-02-04 | 2021-06-18 | 中国科学院山西煤炭化学研究所 | For CO2Trapped bimetallic MOFs material, preparation method and application |
| CN113825738A (en) * | 2019-05-14 | 2021-12-21 | 阿特密斯株式会社 | Method for producing metal organic frameworks |
| US11857945B2 (en) | 2017-08-21 | 2024-01-02 | Ecole Polytechnique Federale De Lausanne (Epfl) | Composites for extraction of metal or contaminating chemical species |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110011805A1 (en) * | 2008-01-24 | 2011-01-20 | Basf Se | Porous metal organic frameworks as desiccants |
| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN103691398A (en) * | 2013-12-13 | 2014-04-02 | 北京化工大学常州先进材料研究院 | Carbon dioxide adsorbent and preparation method thereof |
-
2016
- 2016-06-06 CN CN201610397350.5A patent/CN106076242A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110011805A1 (en) * | 2008-01-24 | 2011-01-20 | Basf Se | Porous metal organic frameworks as desiccants |
| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN103691398A (en) * | 2013-12-13 | 2014-04-02 | 北京化工大学常州先进材料研究院 | Carbon dioxide adsorbent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAO WANG, ET AL: "Preparation, characterization and bifunctional catalytic properties of MOF(Fe/Co) catalyst for oxygen reduction/evolution reactions in alkaline electrolyte", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY 》 * |
| 荆钰，等: "金属有机骨架材料MIL-100（Fe）的一氧化碳吸附性能", 《天然气化工》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106669737A (en) * | 2017-01-04 | 2017-05-17 | 上海应用技术大学 | Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure |
| CN106669737B (en) * | 2017-01-04 | 2019-05-24 | 上海应用技术大学 | A kind of carbon/palladium-cobalt heterogeneous catalyst preparation method of magnetic core-shell structure |
| US11857945B2 (en) | 2017-08-21 | 2024-01-02 | Ecole Polytechnique Federale De Lausanne (Epfl) | Composites for extraction of metal or contaminating chemical species |
| CN108404872A (en) * | 2018-05-29 | 2018-08-17 | 中国科学院生态环境研究中心 | Arsenic-removing adsorption agent and preparation method |
| CN113825738A (en) * | 2019-05-14 | 2021-12-21 | 阿特密斯株式会社 | Method for producing metal organic frameworks |
| EP3971160A4 (en) * | 2019-05-14 | 2023-08-02 | Atomis Inc. | Method for producing metal-organic structure |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110548544A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Iron oxide doped iron metal organic framework, green macro preparation method and application |
| CN110548544B (en) * | 2019-07-12 | 2021-09-21 | 华南理工大学 | Iron oxide doped iron metal organic framework, green macro preparation method and application |
| CN112675720A (en) * | 2020-12-10 | 2021-04-20 | 石河子大学 | Preparation method and application of mixed matrix membrane filled with bimetallic strip material |
| CN112979977A (en) * | 2021-02-04 | 2021-06-18 | 中国科学院山西煤炭化学研究所 | For CO2Trapped bimetallic MOFs material, preparation method and application |
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