CN106902744B - A method of preparing MIL-100 (Fe) at room temperature - Google Patents

A method of preparing MIL-100 (Fe) at room temperature Download PDF

Info

Publication number
CN106902744B
CN106902744B CN201710095155.1A CN201710095155A CN106902744B CN 106902744 B CN106902744 B CN 106902744B CN 201710095155 A CN201710095155 A CN 201710095155A CN 106902744 B CN106902744 B CN 106902744B
Authority
CN
China
Prior art keywords
liquid
promotor
mil
distilled water
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710095155.1A
Other languages
Chinese (zh)
Other versions
CN106902744A (en
Inventor
李忠
王勋
夏启斌
肖静
张宇帆
苗广
王兴杰
梁菀纹
皮云红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201710095155.1A priority Critical patent/CN106902744B/en
Publication of CN106902744A publication Critical patent/CN106902744A/en
Application granted granted Critical
Publication of CN106902744B publication Critical patent/CN106902744B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses the methods that one kind prepares MIL-100 (Fe) at room temperature, this method comprises the following steps: iron powder being placed in distilled water and is stirred, concentrated nitric acid is added, the mixed solution of 1,3,5- trimesic acids and promotor is added after stirring, then 10 ~ 12h of synthetic reaction is carried out at room temperature, after obtained yellowish-brown crude product n,N-Dimethylformamide and ethyl alcohol is rinsed several times, it is soaked in NH4Purifying is stirred in F solution, is finally dried, is obtained purified MIL-100 (Fe) adsorbent material.Method of the invention is compared with the traditional method, it can be achieved that operate at normal temperature, does not add HF, has the advantages that energy conservation and environmental protection, has good prospects for commercial application.

Description

A method of preparing MIL-100 (Fe) at room temperature
Technical field
The invention belongs to chemical adsorbing separation Material Field, relate to a kind of to prepare iron-containing metal at room temperature The method of organic framework material, and in particular to a method of MIL-100 (Fe) is prepared at room temperature.
Background technique
Metal organic framework (Metal-Organic Frameworks, MOFs), be by metal ion or metal cluster with have The porous material with three-dimensional structure that machine ligand is constituted, with biggish specific surface area, composition multiplicity, pore structure can It adjusts and the advantages that can be chemically modified as needed to it, in energy stores, gas absorption and separates, is catalyzed, senses Multiple fields have shown good advantage, have great application prospect.
MIL series material is one kind in MOFs material.Wherein, MIL-100 (Fe) is a kind of Thermodynamically stable, environment friend Good porous material, not only has high adsorption capacity to VOCs, has good performance to alkene-alkane separation, and be current tide To CO under the conditions of wet2One of the maximum adsorbent material of adsorption capacity, there is good industrial application value.Currently, MIL-100 (Fe) preparation mainly passes through high temperature hydro-thermal reaction and synthesizes.Presently, there are deficiency be: in the synthesis process, need to use hydrogen Fluoric acid [Horcajada PS, S.Serre, C.Hong, D.Y.Seo, Y.K.Chang, J.S.Greneche, J.M.Margiolaki,I.Ferey,G.Synthesis and catalytic properties of MIL-100(Fe),an iron(III)carboxylate with large pores.Chemical communications.2007(27):2820- 2], it is a kind of severe poisonous chemicals, there is very strong corrosivity, equipment can be corroded, and have serious harm to people；In addition, Reaction needs high temperature, huge [Peng J, Xian S, Xiao J, Huang Y, Xia Q, Wang H, the et al.A of energy consumption supported Cu(I)@MIL-100(Fe)adsorbent with high CO adsorption capacity and CO/ N2selectivity.Chemical Engineering Journal.2015；270:282-9].
In view of the above problems, the present invention proposes a kind of new synthesis technology, compared with original synthesis technology, it is not only not Hydrofluoric acid is needed, but also may be implemented to synthesize MIL-100 (Fe) under normal temperature conditions, so that the cost of commercial synthesis is reduced, It is pushed further into the industrial applications of MOFs material.
Summary of the invention
It is an object of the invention to for there are high temperature in the existing method for preparing MIL-100 (Fe) material, and use The shortcomings that hydrofluoric acid, provides a kind of method for preparing MIL-100 (Fe) at room temperature.
The purpose of the present invention is achieved through the following technical solutions.
A method of it preparing MIL-100 (Fe) at room temperature, includes the following steps:
(1) mixed liquor for configuring iron powder and water, is then added concentrated nitric acid, stirs evenly, and A liquid is made；
(2) 1 is configured, B liquid is made in 3,5- trimesic acids/promotor aqueous solution；
(3) the resulting B liquid of step (2) is poured into A liquid made from step (1), reacts, obtains crude at room temperature MIL-100 (Fe)；
(4) crude MIL-100 (Fe) obtained by step (3) is centrifuged, then successively uses N, N- dimethyl methyl Amide and ethyl alcohol rinse, after centrifuge separation, and obtained solid matter is soaked in NH4It is stirred in F solution, it will be resulting after filtering Solid is dried and is activated, and the MIL-100 (Fe) of purifying is finally obtained.
Preferably, in the A liquid that step (1) is configured, iron powder, concentrated nitric acid, water molar ratio be 1:(0.37~1.2): (167~170).
Preferably, step (2) promotor is that quinones, peroxide or piperidines nitroxide radical promote Agent.
It is further preferred that the promotor is benzoquinones, methylbenzoquinone, H2O2, cumyl hydroperoxide or 2,2,6,6- tetra- Methyl piperidine-nitrogen-oxide.
Preferably, in the B liquid that step (2) is configured, 1,3,5- trimesic acid, promotor, distilled water molar ratio Are as follows:
(1) when promotor is quinones, 1,3,5- trimesic acid: promotor: distilled water=(0.66~0.68): (0.01~0.1): (111~115)；
(2) when promotor is peroxide, 1,3,5- trimesic acid: promotor: distilled water=(0.66~ 0.68): (1.11~5.55): (111~115)；
(3) when promotor is piperidines nitroxide radical, 1,3,5- trimesic acid: promotor: distilled water= (0.66~0.68): (0.045~0.075): (111~115).
Preferably, the volume ratio of step (3) the B liquid and A liquid is 1:1.5~1:1, and the time of the reaction is that 7-12 is small When.
Preferably, step (4) NH4The concentration of F solution is 25~35mmol/L.
Preferably, the time of step (4) described stirring is 8h~10h.
Preferably, step (4) activation is activation 2h~10h under 120 DEG C~150 DEG C of vacuum drying.
Compared with prior art, the present invention has the advantage that
The present invention does not need addition hydrofluoric acid, does not need to heat, and can synthesize MIL-100 at room temperature (Fe) crystal has energy-saving and environment-friendly advantage.
Detailed description of the invention
Fig. 1 is the XRD characterization comparison diagram of the MIL-100 (Fe) of embodiment 1-3 and hydro-thermal method preparation.
Fig. 2 is the XRD spectra of MIL-100 (Fe) prepared by embodiment 4~7.
Fig. 3 be embodiment 8, embodiment 9 prepare MIL-100 (Fe) XRD spectra.
Fig. 4 is the flow chart that method of the invention prepares MIL-100 (Fe).
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not It is confined to this.
The flow chart that method of the invention prepares MIL-100 (Fe) is shown in Fig. 4.
Embodiment 1
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.13ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g and 5.4mg benzoquinones are weighed, 10ml distilled water is added, shakes It shakes, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 12h.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 30mmol/L4In F solution, 10h is stirred, filtering, last 90 DEG C dry, and in 150 DEG C of vacuum drying Lower activation 2h is labeled as MIL-100 (Fe) -1# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 2
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.2ml concentrated nitric acid is added, stirs evenly, obtains A liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.72g and 6.1mg methylbenzoquinone are weighed, 12ml distillation is added Water rocks, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 10h.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 30mmol/L4In F solution, 8h is stirred, filtering, last 90 DEG C dry, and in 150 DEG C of vacuum drying Lower activation 5h is labeled as MIL-100 (Fe) -2# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 3
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.42ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g and 5.4mg benzoquinones are weighed, 12ml distilled water is added, shakes It shakes, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 7h.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 28mmol/L4In F solution, 9h is stirred, filtering, last 90 DEG C dry, and in 135 DEG C of vacuum drying Lower activation 10h is labeled as MIL-100 (Fe) -3# to get to the MIL-100 (Fe) of the method for the present invention preparation.
As shown in Figure 1, sample 1#, 2#, 3# are shown compared with the MIL-100 (Fe) that traditional hydro-thermal method is synthesized Good X-ray diffraction peak is gone out, has shown sample 1#, 2#, 3# crystallinity is fine, proves quinones substance ought be used as promotor When, MIL-100 (Fe) is successfully synthesized.
Embodiment 4
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.42ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.71g is weighed, 10ml distilled water is added, and 10 μ L are added H2O2, rock, ultrasound, keep its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 9.5h under the irradiation of visible light.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 32mmol/L4In F solution, 10h is stirred, filtering, last 90 DEG C dry, and in 120 DEG C of vacuum drying Lower activation 10h is labeled as MIL-100 (Fe) -4# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 5
Preparation A liquid: it weighs 0.28g iron powder and is placed in 16ml distilled water, 0.42ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g is weighed, 10ml distilled water is added, and 25 μ L H are added2O2, It rocks, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 12h under the irradiation of visible light.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 35mmol/L4In F solution, 8h is stirred, filtering, last 90 DEG C dry, and in 140 DEG C of vacuum drying Lower activation 8h is labeled as MIL-100 (Fe) -5# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 6
Preparation A liquid: it weighs 0.28g iron powder and is placed in 14ml distilled water, 0.42ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.72g is weighed, 10ml distilled water is added, and 10 μ L peroxides are added Change hydrogen isopropylbenzene, rocks, ultrasound, keep its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and continues to stir 12h under the irradiation of visible light.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 30mmol/L4In F solution, 10h is stirred, filtering, last 90 DEG C dry, and in 130 DEG C of vacuum drying Lower activation 8h is labeled as MIL-100 (Fe) -6# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 7
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.42ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g is weighed, 13ml distilled water is added, and 25 μ L peroxides are added Change hydrogen isopropylbenzene, rocks, ultrasound, keep its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and continues to stir 9.5h under the irradiation of visible light.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 25mmol/L4In F solution, 9h is stirred, filtering, last 90 DEG C dry, and in 150 DEG C of vacuum drying Lower activation 10h is labeled as MIL-100 (Fe) -7# to get to the MIL-100 (Fe) of the method for the present invention preparation.
As shown in Figure 2, sample 4#, 5#, 6#, 7# show good X-ray diffraction peak, show sample 4#, 5#, 6#, 7# crystallinity are fine, and the XRD spectra of the MIL-100 (Fe) synthesized with hydro-thermal method in Fig. 1 is similar, prove to use peroxide When substance is as promotor, MIL-100 (Fe) is successfully synthesized.
Embodiment 8
Preparation A liquid: it weighs 0.28g iron powder and is placed in 17ml distilled water, 0.13ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g and 11.7mg 2,2,6,6- tetramethyl piperidines-nitrogen-are weighed 11ml distilled water is added in oxide (TEMPO), rocks, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 7h.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 28mmol/L4In F solution, 10h is stirred, filtering, last 90 DEG C dry, and in 150 DEG C of vacuum drying Lower activation 6h is labeled as MIL-100 (Fe) -8# to get to the MIL-100 (Fe) of the method for the present invention preparation.
Embodiment 9
Preparation A liquid: it weighs 0.28g iron powder and is placed in 15ml distilled water, 0.13ml concentrated nitric acid is added, stirs evenly, obtains A Liquid；
B liquid is prepared, 1,3,5- trimesic acid (BTC) of 0.7g and 7.8mg 2,2,6,6- tetramethyl piperidines-nitrogen-are weighed 10ml distilled water is added in oxide (TEMPO), rocks, ultrasound, keeps its fully dispersed, obtain B liquid；
Synthetic reaction: being poured onto B liquid in A liquid, cover, and stirs 12h.
Purifying: DMF is added and rinses, be centrifuged 3 times, is then rinsed with ethyl alcohol, centrifugation 2 times, is then transferred to solid again 40ml, concentration are the NH of 30mmol/L4In F solution, 8h is stirred, filtering, last 90 DEG C dry, and in 150 DEG C of vacuum drying Lower activation 7h is labeled as MIL-100 (Fe) -9# to get to the MIL-100 (Fe) of the method for the present invention preparation.
As shown in Figure 3, sample 8#, 9# show good X-ray diffraction peak, show sample 8#, 9# crystallinity is very Good, the XRD spectra of the MIL-100 (Fe) synthesized with hydro-thermal method in Fig. 1 is similar, proves to use piperidines nitroxide radical object When matter is as promotor, MIL-100 (Fe) is successfully synthesized.
Table 1
The parameter of pore structure for the MIL-100 (Fe) that the MIL-100 (Fe) of Examples 1 to 9 preparation is prepared with hydro-thermal method is shown in Table 1.

Claims (8)

1. the method that one kind prepares MIL-100 (Fe) at room temperature, which comprises the steps of:
(1) mixed liquor for configuring iron powder and water, is then added concentrated nitric acid, stirs evenly, and A liquid is made；
(2) 1 is configured, B liquid is made in 3,5- trimesic acids/promotor aqueous solution；
(3) the resulting B liquid of step (2) is poured into A liquid made from step (1), reacts, obtains crude at room temperature MIL-100(Fe)；
(4) crude MIL-100(Fe obtained by step (3)) is centrifuged, then successively uses n,N-Dimethylformamide It is rinsed with ethyl alcohol, after centrifuge separation, obtained solid matter is soaked in NH4It is stirred in F solution, by resulting solid after filtering It dries and activates, finally obtain the MIL-100 (Fe) of purifying；
Step (2) promotor is quinones, peroxide or piperidines nitroxide radical promotor.
2. the method according to claim 1, wherein in the A liquid that step (1) is configured, iron powder, concentrated nitric acid, water Molar ratio be 1:(0.37 ~ 1.2): (167 ~ 170).
3. the method according to claim 1, wherein the promotor is benzoquinones, methylbenzoquinone, H2O2, peroxidating Hydrogen isopropylbenzene or 2,2,6,6- tetramethyl piperidine-nitrogen-oxide.
4. the method according to claim 1, wherein in the B liquid that step (2) is configured, 1,3,5- equal benzene front three Acid, promotor, distilled water molar ratio are as follows:
(1) when promotor is quinones, 1,3,5- trimesic acid: promotor: distilled water=(0.66 ~ 0.68): (0.01 ~ 0.1): (111 ~ 115)；
(2) when promotor is peroxide, 1,3,5- trimesic acid: promotor: distilled water=(0.66 ~ 0.68): (1.11 ~ 5.55): (111 ~ 115)；
(3) when promotor is piperidines nitroxide radical, 1,3,5- trimesic acid: promotor: distilled water= (0.66 ~ 0.68): (0.045 ~ 0.075): (111 ~ 115).
5. the method according to claim 1, wherein the volume ratio of step (3) the B liquid and A liquid is 1:1 ~ 1: 1.5, the time of the reaction is 7-12 hours.
6. the method according to claim 1, wherein step (4) described NH4The concentration of F solution be 25 ~ 35mmol/L。
7. the method according to claim 1, wherein the time of step (4) described stirring is 8h ~ 10h.
8. the method according to claim 1, wherein step (4) activation is in 120 DEG C ~ 150 DEG C of vacuum Dry lower activation 2h ~ 10h.
CN201710095155.1A 2017-02-22 2017-02-22 A method of preparing MIL-100 (Fe) at room temperature Active CN106902744B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710095155.1A CN106902744B (en) 2017-02-22 2017-02-22 A method of preparing MIL-100 (Fe) at room temperature

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710095155.1A CN106902744B (en) 2017-02-22 2017-02-22 A method of preparing MIL-100 (Fe) at room temperature

Publications (2)

Publication Number Publication Date
CN106902744A CN106902744A (en) 2017-06-30
CN106902744B true CN106902744B (en) 2019-05-14

Family

ID=59208079

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710095155.1A Active CN106902744B (en) 2017-02-22 2017-02-22 A method of preparing MIL-100 (Fe) at room temperature

Country Status (1)

Country Link
CN (1) CN106902744B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445820B (en) * 2017-08-10 2020-08-25 哈尔滨工业大学 Method for rapidly synthesizing high-yield metal organic framework material MIL-100(Fe) without fluorine and solvent
CN107715916A (en) * 2017-10-09 2018-02-23 贵州师范大学 A kind of MIL 100（Fe）The preparation method and applications of nanocatalyst
CN109876776B (en) * 2019-02-02 2022-04-15 北京建筑大学 Indium-based MOF micro-nano powder and room-temperature preparation method and application thereof
CN110639618A (en) * 2019-10-14 2020-01-03 山东科技大学 Freeze-drying type porous MIL-100 catalyst for benzene hydroxylation reaction and preparation method and application thereof
CN111410749B (en) * 2020-03-17 2022-04-08 广西民族大学 Application of nano-carrier MIL-100(Fe) in loading nitidine chloride
CN111675684B (en) * 2020-06-29 2023-05-16 广西壮族自治区农业科学院 Method for extracting procyanidine from mulberry fruits
TWI792222B (en) * 2021-03-15 2023-02-11 國立中興大學 Heterogeneous composite catalyst and its preparation method
CN114247431B (en) * 2022-01-14 2023-02-03 中南大学 Method for preparing MIL-100 (Fe) material at normal temperature and normal pressure and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102336774A (en) * 2011-07-20 2012-02-01 中国科学院化学研究所 Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material
CN103242374A (en) * 2013-05-24 2013-08-14 浙江师范大学 Preparation method of metal organic framework material MIL-100 (Fe)
CN104190364A (en) * 2014-08-25 2014-12-10 云南中烟工业有限责任公司 Low-toxicity preparation method of MIL-100(Fe) crystal with high capacity of adsorbing CO
CN105622445A (en) * 2015-12-28 2016-06-01 北京林业大学 Method for synthesizing nanoscale metal-organic framework materials at room temperature
CN105771907A (en) * 2016-04-11 2016-07-20 华南理工大学 MOPs bi-ligand adsorbing material Fe-btc(dobdc) and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102336774A (en) * 2011-07-20 2012-02-01 中国科学院化学研究所 Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material
CN103242374A (en) * 2013-05-24 2013-08-14 浙江师范大学 Preparation method of metal organic framework material MIL-100 (Fe)
CN104190364A (en) * 2014-08-25 2014-12-10 云南中烟工业有限责任公司 Low-toxicity preparation method of MIL-100(Fe) crystal with high capacity of adsorbing CO
CN105622445A (en) * 2015-12-28 2016-06-01 北京林业大学 Method for synthesizing nanoscale metal-organic framework materials at room temperature
CN105771907A (en) * 2016-04-11 2016-07-20 华南理工大学 MOPs bi-ligand adsorbing material Fe-btc(dobdc) and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Room-temperature synthesis of Fe-BTC from layered iron hydroxides：the influence of precursor organisation";Gerardo Majano et al.;《CrystEngComm》;23131214;第15卷(第46期);第9823-10144页
"加速沸石分子筛水热晶化的羟基自由基";刘忠范;《物理化学学报》;20160415;第32卷(第4期);第805-806

Also Published As

Publication number Publication date
CN106902744A (en) 2017-06-30

Similar Documents

Publication Publication Date Title
CN106902744B (en) A method of preparing MIL-100 (Fe) at room temperature
CN106582887B (en) Catalyst based on metal organic framework material and preparation method and application thereof
CN103432997B (en) Cu base organic backbone-graphene oxide composite porous material and preparation method thereof
CN107175125B (en) Activation method of MOFs base oxygen reduction electrocatalyst
CN106582880B (en) A kind of molybdenum disulfide/MIL-101 composite photocatalyst material and the preparation method and application thereof
CN108751189A (en) The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area
Huang et al. 2-Methylol-12-crown-4 ether immobilized PolyHIPEs toward recovery of lithium (i)
CN105170095A (en) In-based organic framework-graphene oxide composite material as well as preparation method and application thereof
CN105713017A (en) High selectivity metal organic skeleton material and preparation method thereof
CN105384762B (en) A kind of synthetic method of metal-organic framework materials MIL 53 (Al)
CN110064372A (en) A kind of metal organic framework magnetic composite and its preparation method and application
CN109201113A (en) A kind of functional metal organic framework composite material and preparation method thereof
CN110756203A (en) Ni2P/Mn0.3Cd0.7S photocatalytic water splitting composite catalyst and preparation method and application thereof
CN108948368B (en) Method for rapidly preparing nickel-based metal organic framework material
CN105709692A (en) Copper based metal organic skeleton material and preparation method thereof
CN105713018A (en) Metal organic skeleton material and preparation method thereof
CN105921113A (en) Adsorbent used for removing phthalic acid in water and preparation method thereof
CN102643185A (en) Green and simple preparation method for 2,3,5-trimethylbenzoquinone (TMBQ)
CN110270312B (en) Metal organic framework material-activated carbon composite fiber membrane and preparation method thereof
CN104447452B (en) A kind of synthetic method of mercapto-functionalized polyaryl carboxylic acids compound
CN106984289B (en) A kind of preparation method of porous ceramic surface perfluoro caprylic acid molecular imprinting adsorbing agent
CN107088401B (en) Rapid CO production using ionic liquid additives2Method for producing adsorbent
CN109970985A (en) A kind of method of room temperature synthesis metal-organic framework material PCN-224
CN107096567B (en) The composite catalyst and preparation method of synthesis of propylene glycol
CN106693958A (en) Alkyl anthraquinone hydrogenation catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant