CN106902744A - The method that one kind prepares MIL 100 (Fe) at room temperature - Google Patents

The method that one kind prepares MIL 100 (Fe) at room temperature Download PDF

Info

Publication number
CN106902744A
CN106902744A CN201710095155.1A CN201710095155A CN106902744A CN 106902744 A CN106902744 A CN 106902744A CN 201710095155 A CN201710095155 A CN 201710095155A CN 106902744 A CN106902744 A CN 106902744A
Authority
CN
China
Prior art keywords
liquid
accelerator
mil
distilled water
solution
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.)
Granted
Application number
CN201710095155.1A
Other languages
Chinese (zh)
Other versions
CN106902744B (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 a kind of method for preparing MIL 100 (Fe) at room temperature, the method comprises the following steps：Iron powder is placed in distilled water and is stirred, add concentrated nitric acid, 1 is added after stirring, 3,5 trimesic acids and the mixed solution of accelerator, then carry out 10 ~ 12h of synthetic reaction at ambient temperature, yellowish-brown crude product N, the N dimethylformamide and alcohol flushing for obtaining several times after, be soaked in NH4Purifying is stirred in F solution, is finally dried, obtain MIL 100 (Fe) sorbing material for having purified.The method of the present invention is capable of achieving to operate at normal temperatures compared with conventional method, without HF, has the advantages that energy-conserving and environment-protective, with good prospects for commercial application.

Description

The method that one kind prepares MIL-100 (Fe) at room temperature
Technical field
The invention belongs to chemical adsorbing separation Material Field, a kind of metal that can at ambient temperature prepare iron content is relate to The method of organic framework material, and in particular to the method that one kind prepares MIL-100 (Fe) at room temperature.
Background technology
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 part is constituted, it has larger specific surface area, constitutes various, and pore structure can Adjust and the advantages of can be chemically modified to it as needed, in energy stores, gas absorption and separate, be catalyzed, sense Multiple fields have shown good advantage, have great application prospect.
MIL series materials are the classes in MOFs materials.Wherein, MIL-100 (Fe) is a kind of Thermodynamically stable, environment friend Good porous material, not only there is adsorption capacity high to VOCs, has good performance to alkene-alkane separation, and be current tide To CO under the conditions of wet2One of the maximum sorbing material of adsorption capacity, with good industrial application value.At present, MIL-100 (Fe) preparation is mainly and is synthesized by high temperature hydro-thermal reaction.The deficiency that presently, there are is：, it is necessary to use hydrogen in building-up process 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, with very strong corrosivity, meeting etching apparatus, and has serious harm to people；Additionally, Reaction needs high temperature, huge [Peng J, Xian S, Xiao J, Huang Y, Xia Q, Wang H, the et al.A of energy ezpenditure supported Cu(I)@MIL-100(Fe)adsorbent with high CO adsorption capacity and CO/ N2selectivity.Chemical Engineering Journal.2015；270:282-9].
For problem above, the present invention proposes a kind of new synthesis technique, and compared with original synthesis technique, it is not only not Hydrofluoric acid is needed, but also can realize synthesizing MIL-100 (Fe) under normal temperature condition, so that the cost of commercial synthesis is reduced, It is pushed further into the industrial applications of MOFs materials.
The content of the invention
There is high temperature it is an object of the invention to be directed in the existing method for preparing MIL-100 (Fe) material, and use The shortcoming of hydrofluoric acid, there is provided the method that one kind prepares MIL-100 (Fe) at room temperature.
The purpose of the present invention is achieved through the following technical solutions.
The method that one kind prepares MIL-100 (Fe) at room temperature, comprises the following steps：
(1) mixed liquor of configuration iron powder and water, is subsequently adding concentrated nitric acid, stirs, and A liquid is obtained；
(2) 1 is configured, the aqueous solution of 3,5- trimesic acids/accelerator is obtained B liquid；
(3) in the B liquid obtained by step (2) being poured into A liquid obtained in step (1), react at ambient temperature, obtain rough MIL-100 (Fe)；
(4) the rough MIL-100 (Fe) of step (3) gained is centrifuged, N, N- dimethyl methyls is then used successively After acid amides and alcohol flushing, centrifugation, the solid matter that will be obtained is soaked in NH4Stirred in F solution, by gained after filtering Solid is dried and activated, and finally gives the MIL-100 (Fe) of purifying.
Preferably, in the A liquid that step (1) is configured, iron powder, concentrated nitric acid, the molar ratio of water are 1:(0.37~1.2): (167~170).
Preferably, step (2) described accelerator is that quinones, peroxide or piperidines nitroxide radical promote Agent.
It is further preferred that the accelerator 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, accelerator, the molar ratio of distilled water For：
(1) when accelerator is quinones, 1,3,5- trimesic acids：Accelerator：Distilled water=(0.66~0.68): (0.01~0.1):(111~115)；
(2) when accelerator is peroxide, 1,3,5- trimesic acids：Accelerator：Distilled water=(0.66~ 0.68):(1.11~5.55):(111~115)；
(3) when accelerator is piperidines nitroxide radical, 1,3,5- trimesic acids：Accelerator：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, 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 invention has the advantages that：
The present invention need not add hydrofluoric acid, it is not necessary to heat, and can synthesize MIL-100 at ambient temperature (Fe) crystal, the advantage with energy-conserving and environment-protective.
Brief description of the drawings
Fig. 1 is that the XRD of the MIL-100 (Fe) that embodiment 1-3 is prepared with hydro-thermal method characterizes comparison diagram.
Fig. 2 is the XRD spectra of MIL-100 (Fe) prepared by embodiment 4~7.
Fig. 3 is embodiment 8, the XRD spectra of the MIL-100 (Fe) of the preparation of embodiment 9.
Fig. 4 is the flow chart that the method for the present 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 the method for the present invention prepares MIL-100 (Fe) is shown in Fig. 4.
Embodiment 1
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.13ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.7g 1,3,5- and 5.4mg benzoquinones is weighed, 10ml distilled water is added, shaken Rolling, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, stir 12h.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 30mmol/L4In F solution, 10h is stirred, filtered, last 90 DEG C of drying, and in 150 DEG C of vacuum drying Lower activation 2h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -1#.
Embodiment 2
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.2ml concentrated nitric acids, stir, obtain A liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.72g 1,3,5- and 6.1mg methylbenzoquinones is weighed, 12ml distillations are added Water, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, stir 10h.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 30mmol/L4In F solution, 8h is stirred, filtered, last 90 DEG C of drying, and in 150 DEG C of vacuum drying Lower activation 5h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -2#.
Embodiment 3
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.42ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.7g 1,3,5- and 5.4mg benzoquinones is weighed, 12ml distilled water is added, shaken Rolling, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, stir 7h.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 28mmol/L4In F solution, 9h is stirred, filtered, last 90 DEG C of drying, and in 135 DEG C of vacuum drying Lower activation 10h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -3#.
As shown in figure 1, compared with the MIL-100 (Fe) that traditional hydro-thermal method is synthesized, sample 1#, 2#, 3# shows Good X-ray diffraction peak is gone out, has shown sample 1#, 2#, 3# crystallinity very well, proved that quinones substance ought be used as accelerator When, MIL-100 (Fe) successfully synthesizes.
Embodiment 4
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.42ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.71g 1,3,5- are weighed, 10ml distilled water is added, and add 10 μ L H2O2, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, 9.5h is stirred under the irradiation of visible ray.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 32mmol/L4In F solution, 10h is stirred, filtered, last 90 DEG C of drying, and in 120 DEG C of vacuum drying Lower activation 10h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -4#.
Embodiment 5
Prepare A liquid：Weigh 0.28g iron powders to be placed in 16ml distilled water, add 0.42ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.7g 1,3,5- are weighed, 10ml distilled water is added, and add 25 μ L H2O2, Rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, 12h is stirred under the irradiation of visible ray.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 35mmol/L4In F solution, 8h is stirred, filtered, last 90 DEG C of drying, and in 140 DEG C of vacuum drying Lower activation 8h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -5#.
Embodiment 6
Prepare A liquid：Weigh 0.28g iron powders to be placed in 14ml distilled water, add 0.42ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.72g 1,3,5- are weighed, 10ml distilled water is added, and add 10 μ L peroxides Change hydrogen isopropylbenzene, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, continue to stir 12h under the irradiation of visible ray.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 30mmol/L4In F solution, 10h is stirred, filtered, last 90 DEG C of drying, and in 130 DEG C of vacuum drying Lower activation 8h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -6#.
Embodiment 7
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.42ml concentrated nitric acids, stir, obtain A Liquid；
B liquid is prepared, the trimesic acids (BTC) of 0.7g 1,3,5- are weighed, 13ml distilled water is added, and add 25 μ L peroxides Change hydrogen isopropylbenzene, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, continue to stir 9.5h under the irradiation of visible ray.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 25mmol/L4In F solution, 9h is stirred, filtered, last 90 DEG C of drying, and in 150 DEG C of vacuum drying Lower activation 10h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -7#.
As shown in Figure 2, sample 4#, 5#, 6#, 7# show good X-ray diffraction peak, show sample 4#, 5#, Very well, the XRD spectra to the MIL-100 (Fe) that hydro-thermal method in Fig. 1 synthesizes is similar, proves to use peroxide for 6#, 7# crystallinity When class material is as accelerator, MIL-100 (Fe) successfully synthesizes.
Embodiment 8
Prepare A liquid：Weigh 0.28g iron powders to be placed in 17ml distilled water, add 0.13ml concentrated nitric acids, stir, obtain A Liquid；
Preparation B liquid, the weighing trimesic acids (BTC) of 0.7g 1,3,5- and 11.7mg 2,2,6,6- tetramethyl piperidines-nitrogen- Oxide (TEMPO), add 11ml distilled water, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, stir 7h.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 28mmol/L4In F solution, 10h is stirred, filtered, last 90 DEG C of drying, and in 150 DEG C of vacuum drying Lower activation 6h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -8#.
Embodiment 9
Prepare A liquid：Weigh 0.28g iron powders to be placed in 15ml distilled water, add 0.13ml concentrated nitric acids, stir, obtain A Liquid；
Preparation B liquid, the weighing trimesic acids (BTC) of 0.7g 1,3,5- and 7.8mg 2,2,6,6- tetramethyl piperidines-nitrogen- Oxide (TEMPO), add 10ml distilled water, rock, ultrasound, make its fully dispersed, obtain B liquid；
Synthetic reaction：B liquid is poured onto in A liquid, is covered, stir 12h.
Purifying：Add DMF to rinse, be centrifuged 3 times, be then again then transferred to solid with alcohol flushing, centrifugation 2 times 40ml, concentration is the NH of 30mmol/L4In F solution, 8h is stirred, filtered, last 90 DEG C of drying, and in 150 DEG C of vacuum drying Lower activation 7h, that is, obtain the MIL-100 (Fe) of the inventive method preparation, is labeled as MIL-100 (Fe) -9#.
As shown in Figure 3, sample 8#, 9# show good X-ray diffraction peak, show sample 8#, 9# crystallinity very Good, the XRD spectra to the MIL-100 (Fe) that hydro-thermal method in Fig. 1 synthesizes is similar, proves using piperidines nitroxide radical thing When matter is as accelerator, MIL-100 (Fe) successfully synthesizes.
Table 1
The parameter of pore structure of the MIL-100 (Fe) that MIL-100 (Fe) prepared by embodiment 1~9 is prepared with hydro-thermal method is shown in Table 1.

Claims (9)

1. the method that one kind prepares MIL-100 (Fe) at room temperature, it is characterised in that comprise the following steps：
（1）The mixed liquor of configuration iron powder and water, is subsequently adding concentrated nitric acid, stirs, and A liquid is obtained；
（2）The aqueous solution of 1,3,5- of configuration trimesic acids/accelerator, is obtained B liquid；
（3）By step（2）The B liquid of gained pours into step（1）In obtained A liquid, react at ambient temperature, obtain rough MIL-100（Fe）；
（4）By step（3）The rough MIL-100 of gained（Fe）It is centrifuged, DMF is then used successively After alcohol flushing, centrifugation, the solid matter that will be obtained is soaked in NH4Stirred in F solution, by the solid of gained after filtering Dry and activate, finally give the MIL-100 (Fe) of purifying.
2. method according to claim 1, it is characterised in that step（1）In the A liquid for being configured, iron powder, concentrated nitric acid, water Molar ratio be 1:（0.37~1.2）:（167~170）.
3. method according to claim 1, it is characterised in that step（2）The accelerator be quinones, peroxide or Piperidines nitroxide radical accelerator.
4. method according to claim 3, it is characterised in that the accelerator is benzoquinones, methylbenzoquinone, H2O2, peroxidating Hydrogen isopropylbenzene or 2,2,6,6- tetramethyl piperidines-nitrogen-oxide.
5. method according to claim 1, it is characterised in that step（2）In the B liquid for being configured, 1,3,5- equal benzene front three Acid, accelerator, the molar ratio of distilled water are：
（1）When accelerator is quinones, 1,3,5- trimesic acids：Accelerator：Distilled water=（0.66~0.68）:（0.01~ 0.1）:（111~115）；
（2）When accelerator is peroxide, 1,3,5- trimesic acids：Accelerator：Distilled water=（0.66~0.68）: （1.11~5.55）:（111~115）；
（3）When accelerator is piperidines nitroxide radical, 1,3,5- trimesic acids：Accelerator：Distilled water= （0.66~0.68）:（0.045~0.075）:（111~115）.
6. method according to claim 1, it is characterised in that step（3）The volume ratio of the B liquid and A liquid is 1:1~1: 1.5, the time of the reaction is 7-12 hours.
7. method according to claim 1, it is characterised in that step（4）The NH4The concentration of F solution be 25 ~ 35mmol/L。
8. method according to claim 1, it is characterised in that step（4）The time of the stirring is 8h ~ 10h.
9. method according to claim 1, it is characterised in that step（4）The activation is the vacuum at 120 DEG C ~ 150 DEG C 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 true CN106902744A (en) 2017-06-30
CN106902744B 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)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445820A (en) * 2017-08-10 2017-12-08 哈尔滨工业大学 Floride-free, the solvent-free and Fast back-projection algorithm high yield metal-organic framework materials MIL 100 of one kind（Fe）Method
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
CN109876776A (en) * 2019-02-02 2019-06-14 北京建筑大学 Indium base MOF micro-nano powder and its room temperature preparation method and application
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
CN111410749A (en) * 2020-03-17 2020-07-14 广西民族大学 Application of nano carrier MI L-100 (Fe) in loading of nitidine chloride
CN111675684A (en) * 2020-06-29 2020-09-18 广西壮族自治区农业科学院 Method for extracting procyanidine from mulberry fruits
CN114247431A (en) * 2022-01-14 2022-03-29 中南大学 Method for preparing MIL-100(Fe) material at normal temperature and normal pressure and application thereof
TWI792222B (en) * 2021-03-15 2023-02-11 國立中興大學 Heterogeneous composite catalyst and its preparation method

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
GERARDO MAJANO ET AL.: ""Room-temperature synthesis of Fe-BTC from layered iron hydroxides：the influence of precursor organisation"", 《CRYSTENGCOMM》 *
刘忠范: ""加速沸石分子筛水热晶化的羟基自由基"", 《物理化学学报》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445820A (en) * 2017-08-10 2017-12-08 哈尔滨工业大学 Floride-free, the solvent-free and Fast back-projection algorithm high yield metal-organic framework materials MIL 100 of one kind（Fe）Method
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
CN109876776A (en) * 2019-02-02 2019-06-14 北京建筑大学 Indium base MOF micro-nano powder and its room temperature preparation method and application
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
CN111410749A (en) * 2020-03-17 2020-07-14 广西民族大学 Application of nano carrier MI L-100 (Fe) in loading of nitidine chloride
CN111675684A (en) * 2020-06-29 2020-09-18 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
CN114247431A (en) * 2022-01-14 2022-03-29 中南大学 Method for preparing MIL-100(Fe) material at normal temperature and normal pressure and application thereof
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

Also Published As

Publication number Publication date
CN106902744B (en) 2019-05-14

Similar Documents

Publication Publication Date Title
CN106902744A (en) The method that one kind prepares MIL 100 (Fe) at room temperature
CN105170097B (en) A kind of TiO2Nuclear-shell structured nano-composite materials of/ZIF 8 and preparation method thereof
CN108034263B (en) Two-dimensional MOF/carbon oxide material composite film and preparation method and application thereof
Chen et al. Catalytic activities of two different morphological nano-MnO2 on the thermal decomposition of ammonium perchlorate
Fang et al. Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications
Yu et al. Cobalt-based metal organic framework as precursor to achieve superior catalytic activity for aerobic epoxidation of styrene
CN104998623B (en) A kind of composite magnetic nano particle adsorbent and its preparation method and application
Huang et al. 2-Methylol-12-crown-4 ether immobilized PolyHIPEs toward recovery of lithium (i)
CN104801244A (en) Method for preparing three-dimensional graphene-copper nanowire composite aerogel
CN108751189A (en) The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area
CN110586041B (en) Perfluoroalkyl compound extraction and analysis method based on MOFs stripping graphite phase nitrogen carbide adsorbent
CN113751076B (en) Bis-imidazolium palladium-supported porous organic polymer catalyst and preparation method and application thereof
Liu et al. Gas promotes the crystallization of nano-sized metal–organic frameworks in ionic liquid
CN111889066B (en) PH response controlled release hollow mesoporous silica nanoparticle and preparation method thereof
CN105713017A (en) High selectivity metal organic skeleton material and preparation method thereof
CN109201113A (en) A kind of functional metal organic framework composite material and preparation method thereof
CN105457602A (en) Novel nano composite material with micro-pore structure as well as preparation and application thereof
CN106975453A (en) A kind of vermiculite sorbing material of phosphate glycine betaine intercalation modifying and preparation method and application
CN112979985A (en) Composite metal organic framework material and preparation method thereof
Xiao et al. One-step synthesis of aluminum magnesium oxide nanocomposites for simultaneous removal of arsenic and lead ions in water
CN106607079A (en) Methanol-to-aromatic hydrocarbon catalyst and uses tehreof
CN109607563A (en) Zinc modification multi-stage porous ZSM-5 nano zeolite and preparation method thereof
CN106540663B (en) A kind of preparation method of the crown ether modified carbon nano tube tube material for adsorption uranium
CN105921113A (en) Adsorbent used for removing phthalic acid in water and preparation method thereof
CN104069811B (en) A kind of otide containing lighium Graphene three-dimensional framework hydrogen storage material 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