CN106000351A - Preparation and adsorption application of novel micro-porous ball based on ZIF (Co<2+>) metal organic framework material - Google Patents

Preparation and adsorption application of novel micro-porous ball based on ZIF (Co<2+>) metal organic framework material Download PDF

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CN106000351A
CN106000351A CN201610350526.1A CN201610350526A CN106000351A CN 106000351 A CN106000351 A CN 106000351A CN 201610350526 A CN201610350526 A CN 201610350526A CN 106000351 A CN106000351 A CN 106000351A
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zif
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porous
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王璐莹
代娟
雷建都
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Beijing Forestry University
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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
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/28—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
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a preparation and an adsorption application of a novel micro-porous ball based on a ZIF (Co<2+>) metal organic framework material. In the preparation process of micro-ball, a carboxyl functionalized polymer macro-porous ball is taken as a substrate and the ZIF (Co<2+>) metal organic framework material is compounded on the surface of the micro-ball according to an in-situ growth method, thus obtaining the novel micro-porous ball with micro-porous structure. The preparation method comprises the following steps: dispersing a defined amount of carboxylation macro-porous micro-balls into a divalent cobalt salt solution for a period of time; adding imidazole solution into the dispersing solution, fully reacting for a period of time and then centrifuging at a low speed to collect the modified micro-balls; repeatedly soaking and washing, and then drying in vacuum, thus obtaining the novel micro-porous ball. As an adsorbent, the novel micro-porous ball can quickly and efficiently absorb dye in water. According to the preparation method of the novel micro-porous ball provided by the invention, the micro-ball based on other metal organic framework material can be further designed and prepared and the micro-porous structures of different organic framework materials can be combined for optimizing the absorbing property.

Description

Based on ZIF(Co2+) type metal-organic framework materials novel microporous ball preparation and Adsorption applications
Technical field
The present invention relates to a class based on ZIF(Co2+) preparation method of novel microporous ball of type organic framework material, belong to suction Enclosure material technical field.
Background technology
Metallic organic framework (Metal-organic frameworks, MOFs) is a kind of novel organic inorganic hybridization material Material, is typically independently filled by strong coordinate bond form by specific metal ion or metal cluster and corresponding organic ligand and is formed, And there is the network structure of some cycles.Its gas absorption and separation, store, be catalyzed, the neck such as medicine carrying, photoelectric magnetic property material The good application prospect of domain views.As a kind of novel porous solid-state material, due to the using value that it is special, receive wide General concern and research.
Zeolite imidazole ester frame structure material (ZIFs) belongs to the one of MOFs, and wherein, the crosslinking of organic imidazate is connected to In transition metal, form a kind of tetrahedral framework.This material structure is similar to zeolite structured, and has organic solvent-resistant, relatively The advantages such as high heat stability and chemical stability so that it is store at gas, separate and the aspect such as catalysis has a wide range of applications. But owing to the duct of ZIFs is micropore (diameter≤2nm) mostly, and the structure comparison in duct is single, poor selectivity etc. lacks Point so that molecule diffusion in its duct is hindered, is additionally also restricted the adsorption of macromole.
Apply further to expand metal-organic framework materials, researcher attempt metal-organic framework materials and other Material cladding gets up.Such as, in many analyzes test experience chromatograph packing material, owing to metal-organic framework materials crystal needs to depend on Invest other materials such as silica spheres, thus be used for analyzing detection as chromatograph packing material.Guo-qiang Liu et al. (Guo-qiang Liu, Ming-xi Wan, Zheng-hong Huang, Fei-yu Kang, Preparation of graphene/metal-organic composites and their adsorption performance for Benzene and ethanol, New. Carbon. Mater, 2015,30 (6), 566-571.) utilize Graphene conduct Substrate, is combined metal-organic framework materials MOF-5, has obtained having different Graphene mass percent Graphene/MOF-5 complex, and this composite is used for doing adsorption test, and explore duct and reference area pass System, experimental result shows the specific surface area when Graphene mass percent is 5.25% with maximum, and records this material to benzene Phenol and ethanol have good adsorption effect.Except silicon dioxide, metal and metallic compound, carbon are as substrate, polyphosphazene polymer Compound is also commonly utilized in composite metal organic framework material.Shaozhou Li(S. Z. Li, W. N. Zhang, F. W. Huo, The structural and catalytic properties of nanoparticles@MOF composites: A case study of Au@ZIF-8 hybrid crystals, Physica. E, 2015, 69, 56-60.) use metal-organic framework materials coating noble metal gold grain, successfully synthesize the Au@ZIF-8 with catalytic effect Granule, experimental result shows that it has good catalytic effect.
If in ZIFs crystal is grafted onto the internal gutter of carboxy-functionalized macroporous polymer microsphere and the surface of ball Synthesize a kind of novel microporous ball based on metal-organic framework materials, it is likely that improve the adsorptivity of metallic framework organic material Energy.
Summary of the invention
It is an object of the invention to provide a kind of based on ZIF(Co2+) the novel microporous ball of type metal-organic framework materials Preparation method, by introducing carboxy-functionalized macroporous polymer microsphere, fully by ZIFs crystal in the synthetic system of ZIFs In being grafted onto the internal gutter of macroporous microsphere and the surface of ball.On the one hand the composite of the method gained, so that microsphere Specific surface area is greatly improved.On the other hand, the application overcoming ZIFs crystalline nanometric level size limits, and expands metal The further application of organic framework material.
For reaching above-mentioned purpose, present invention firstly provides a kind of based on ZIF(Co2+) type metal-organic framework materials new The preparation method of type micropore ball, it comprises the following steps:
The macroporous polymer microsphere of a certain amount of carboxyl functional is added the ligand solution of divalent cobalt, through ultrasonic disperse extremely Stir certain time in isothermal vibration case again after Jun Yun, make macroporous microsphere be uniformly dispersed and abundant with cobalt salt effect；To contain again There is glyoxaline ligand solution to add macroporous microsphere dispersion liquid, and react certain time under stirring in isothermal vibration case.Reaction knot Shu Hou, low-speed centrifugal is collected the modified microsphere in reactant liquor, is repeatedly soaked with solvent and obtain solid product with centrifugation, through vacuum It is dried to obtain ZIF(Co2+) type micropore ball.
At above-mentioned novel ZIF(Co2+)In the preparation method of type micropore ball, it is preferable that the polymerization of described carboxyl functional Thing macroporous microsphere is one prepared by the polymeric materials such as polystyrene, polyacrylate, poly (glycidyl methacrylate).
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that the divalent cobalt used can be Cobalt nitrate, cobaltous acetate, cobaltous sulfate, the one of cobaltous chloride.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that solvent is DMF, Methanol, the one of deionized water or mixture.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that imidazoles is 2-methylimidazole, benzo The one of imidazoles.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that the mass ratio of microsphere and cobalt salt is 1:1 ~1:4；The mol ratio of cobalt salt and imidazoles is: 1:0.05 ~ 1:4.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that cobalt salt solution concentration is: 0.05 ~ 0.6mol/L；Imidazole solution concentration is: 0.5 ~ 2mol/L.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in, it is preferable that concussion case temperature be that room temperature is to 50 DEG C, shaking speed is 130 ~ 160r/min, and the time is 20 ~ 24h.
At above-mentioned novel ZIF(Co2+) type micropore ball preparation method in centrifugal speed be 200 ~ 1000r/min, product is clear Washing solvent is dehydrated alcohol or absolute methanol or deionized water, and baking temperature is 60 ~ 80 DEG C.
Beneficial effect: novel ZIF(Co prepared by the present invention2+) type micropore ball has a higher specific surface area, the most also gram The application having taken ZIFs crystalline nanometric level size limits, and expands the further application of metal-organic framework materials.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of carboxyl functional's polyacrylate macroporous microsphere.
Fig. 2 be embodiment 1 preparation ZIF-9 micropore ball material sweep Electronic Speculum figure.
Fig. 3 is the scanning electron microscope (SEM) photograph of the ZIF-67 micropore ball material of embodiment 2 preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but it is not intended that to the present invention can practical range Restriction.
Comparative example 1.
Unmodified carboxyl functional's polyacrylic acid ester microsphere is used for static adsorption test as adsorbent, evaluates and tests it The performance of absorbing dye in water, dyestuff used is Congo red or light blue.Prepare certain density aqueous dye solutions, weigh respectively 0.01g adsorbent adds dye solution, and being placed in constant temperature oscillator and keeping frequency of oscillation is 150 r/min.Inhale at 30 DEG C After attached 12h, centrifugation adsorbent and solution, take the dye solution after the mensuration absorption of upper solution ultraviolet spectrophotometer dense Degree, is calculated adsorbent fuel adsorbance under this adsorption conditions by formula defined below.The surveyed absorption result of this example is shown in Table 1.q= (C0-Ct)V/m
In formula, q is adsorbance, mg/g；C0With CtSolution concentration before being respectively absorption and after absorption, mg/L；V absorption used is molten Liquid amasss, L；M is sorbent used quality, g.
Comparative example 2.
1.91g Co(NO3)2·6H2O is dissolved in 100mLN, obtains cobalt salt solution, 8.5g benzo miaow in dinethylformamide Azoles is dissolved in 100mLN, is made into benzimidazole solution in dinethylformamide, and cobalt salt solution is at 30 DEG C, and the constant temperature of 150r/min shakes Swing stirring 24h in device, add benzimidazole solution continuation stirring 24h and obtain ZIF-9 dispersion liquid.High speed centrifugation collects gained ZIF- 9 particles, the most overnight soak with dehydrated alcohol and centrifugal obtain purification ZIF-9, the available powder of vacuum drying 24h under 80 ° of C Shape ZIF-9.The static adsorption of ZIF-9 nanoparticle is tested with comparative example 1, and dye solution used is Congo red solution, absorption knot Fruit is shown in Table 1.
Embodiment 1.
1.91g Co(NO3)2·6H2O is dissolved in 100mL DMF and obtains cobalt salt solution, 8.5g benzo Imidazoles is dissolved in 100mL DMF and is made into benzimidazole solution, and 1.0g polyacrylate carboxyl microsphere adds N, In dinethylformamide so that it is be uniformly dispersed.Microsphere dispersion liquid is mixed with cobalt salt solution, at 30 DEG C, the perseverance of 150r/min Stirring 24h in temperature agitator, adds benzimidazole solution continuation stirring 24h and obtains novel ZIF-9 type micropore ball dispersion liquid.Low speed Centrifugal collect gained ZIF-9 type micropore ball material, the most overnight soak with dehydrated alcohol again and centrifugal obtain purification ZIF-9 type micropore Ball, vacuum drying 24h available powder ZIF-9 type micropore ball under 80 ° of C.The static adsorption test of ZIF-9 type micropore ball is same Comparative example 1, dye solution used is Congo red solution, and absorption result is shown in Table 1.
Table 1 comparative example and the sorbent used adsorbance under different solutions concentration of embodiment.
Can be seen that the different adsorbent adsorbances to same concentration Congo red solution in above-mentioned three examples by table 1 absorption property Difference, wherein embodiment 1 is all higher than comparative example 1 and the adsorbance of comparative example 2, and this is owing to ZIF-9 is wrapped in the surface of microsphere Its specific surface area is made to be far longer than self, beneficially the absorption of Congo red.
Comparative example 3.
1.91g Co(NO3)2·6H2O is dissolved in 100mLDMF and obtains cobalt salt solution, and 4.9g 2-methylimidazole is dissolved in 100mLN, obtains 2-methylimidazole solution in dinethylformamide, cobalt salt solution at 30 DEG C, the constant temperature oscillator of 150r/min Middle stirring 24h, adds 2-methylimidazole solution continuation stirring 24h and obtains ZIF-67 dispersion liquid.High speed centrifugation collects gained ZIF- 67 particles, the most overnight soak with dehydrated alcohol and centrifugal obtain purification ZIF-67, the available powder of vacuum drying 24h under 80 ° of C Powder ZIF-67.The static adsorption of ZIF-67 nanoparticle is tested with comparative example 1, and dye solution used is malachite green solution, Absorption result is shown in Table 2.
Embodiment 2.
1.91g Co(NO3)2·6H2O is dissolved in 100mLN, obtains cobalt salt solution, 4.9g 2-first in dinethylformamide Base imidazoles is dissolved in 100mLN, obtains 2-methylimidazole solution in dinethylformamide, and 1.0g polyacrylate carboxyl microsphere adds Enter in DMF so that it is be uniformly dispersed.Microsphere dispersion liquid is added in cobalt salt solution at 30 DEG C, 150r/min Constant temperature oscillator in stirring 24h, add 2-methylimidazole solution continue stirring 24h obtain novel ZIF-67 type micropore ball dispersion Liquid.Low-speed centrifugal collects gained ZIF-67 type micropore ball material, the most overnight soaks with dehydrated alcohol and centrifugal obtains purification ZIF-67 type micropore ball, vacuum drying 24h available powder ZIF-67 type micropore ball under 80 ° of C.ZIF-67 micropore ball quiet State adsorption test is with comparative example 1, and dye solution used is malachite green solution, and absorption result is shown in Table 2.
Table 2 comparative example and the sorbent used adsorbance under different solutions concentration of embodiment.
Be can be seen that in above-mentioned three examples that different adsorbents are to the adsorbance of same concentration light blue solution not by table 2 absorption property With, wherein embodiment 2 is all higher than comparative example 1 and the adsorbance of comparative example 3, and this is to make owing to ZIF-67 is wrapped in the surface of microsphere Its specific surface area is far longer than self, beneficially the absorption of light blue.

Claims (8)

1. a class is based on ZIF(Co2+) the micropore ball of type metal-organic framework materials and preparation thereof, its preparation method includes walking as follows Rapid: the macroporous polymer microsphere of a certain amount of carboxyl functional to be added the ligand solution of divalent cobalt, through ultrasonic disperse extremely Stir certain time in isothermal vibration case again after Jun Yun, make macroporous microsphere be uniformly dispersed and abundant with cobalt salt effect；To contain again There is glyoxaline ligand solution to add macroporous microsphere dispersion liquid, and react certain time under stirring in isothermal vibration case；Reaction knot Shu Hou, low-speed centrifugal is collected the modified microsphere in reactant liquor, is repeatedly soaked with solvent and obtain solid product with centrifugation, through vacuum It is dried to obtain ZIF(Co2+) type micropore ball.
Preparation method the most according to claim 1, it is characterised in that the macroporous polymer microsphere of described carboxyl functional Prepare for polymeric materials such as polystyrene, polyacrylate, poly (glycidyl methacrylate)s.
Preparation method the most according to claim 1, it is characterised in that described divalent cobalt part is cobalt nitrate, cobaltous acetate, Cobaltous sulfate, the one of cobaltous chloride；Described glyoxaline ligand is 2-methylimidazole, the one of benzimidazole.
Preparation method the most according to claim 1, it is characterised in that the solvent of described ligand solution is N, N-dimethyl methyl Amide, methanol, the one of deionized water or mixture.
Preparation method the most according to claim 1, it is characterised in that described microsphere is 1 with the mass ratio of divalent cobalt: 0.5~1:8；The mol ratio of divalent cobalt and imidazoles is: 1:0.05 ~ 1:0.8.
Preparation method the most according to claim 1, it is characterised in that described divalent cobalt solution concentration is: 0.05 ~ 0.6mol/L；Imidazole solution concentration is: 0.5 ~ 6mol/L.
Preparation method the most according to claim 1, it is characterised in that in described isothermal vibration case, condition is that room temperature is to 60 DEG C, 100 ~ 300r/min, 2 ~ 24h.
Preparation method the most according to claim 1, it is characterised in that centrifugal speed is 200-1200r/min；Baking temperature For 60-110 DEG C；Drying time is 12 ~ 24h.
CN201610350526.1A 2016-05-25 2016-05-25 Preparation and adsorption application of novel micro-porous ball based on ZIF (Co<2+>) metal organic framework material Pending CN106000351A (en)

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CN106948087A (en) * 2017-02-28 2017-07-14 青岛大学 A kind of zeolite imidazole ester framework Nanocomposites tunica fibrosa and preparation method thereof
CN107224968A (en) * 2017-08-08 2017-10-03 北京林业大学 A kind of preparation method and application of new solid extracting agent
CN107552017A (en) * 2017-08-30 2018-01-09 河南师范大学 The preparation method of the@CC composite adsorbing materials of ZIF 67 and its adsorption cleaning processing containing the application in Methyl Orange in Wastewater
CN108586652A (en) * 2018-02-11 2018-09-28 中国科学院化学研究所 A kind of chirality organometallic skeletal hollow nano-sphere and the preparation method and application thereof
CN109206630A (en) * 2018-11-07 2019-01-15 中国科学院生态环境研究中心 Three-dimensional level hollow structure Co-ZIF material and preparation method thereof
CN109728311A (en) * 2019-01-09 2019-05-07 长江大学 The metal organic framework compound hollow microsphere of load iron cobalt sulfide
WO2019175717A1 (en) * 2018-03-14 2019-09-19 Desiccant Rotors International Private Limited Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof
CN110681358A (en) * 2019-11-19 2020-01-14 北京林业大学 ZIFs material-based high-performance adsorption film
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition
CN111892791A (en) * 2020-07-31 2020-11-06 北京化工大学 Preparation method of composite material, composite material and application thereof
CN112958040A (en) * 2021-02-08 2021-06-15 浙江科技学院 Co-MOF-D113-6 nano composite resin, preparation method and application
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CN112958041A (en) * 2021-02-08 2021-06-15 浙江科技学院 Core-shell structure nano composite resin, preparation method and application in electroplating wastewater treatment
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CN106948087A (en) * 2017-02-28 2017-07-14 青岛大学 A kind of zeolite imidazole ester framework Nanocomposites tunica fibrosa and preparation method thereof
CN107224968A (en) * 2017-08-08 2017-10-03 北京林业大学 A kind of preparation method and application of new solid extracting agent
CN107552017A (en) * 2017-08-30 2018-01-09 河南师范大学 The preparation method of the@CC composite adsorbing materials of ZIF 67 and its adsorption cleaning processing containing the application in Methyl Orange in Wastewater
CN108586652A (en) * 2018-02-11 2018-09-28 中国科学院化学研究所 A kind of chirality organometallic skeletal hollow nano-sphere and the preparation method and application thereof
CN108586652B (en) * 2018-02-11 2019-07-16 中国科学院化学研究所 A kind of chirality organometallic skeletal hollow nano-sphere and the preparation method and application thereof
JP2021518253A (en) * 2018-03-14 2021-08-02 デシカント・ローターズ・インターナショナル・プライヴェート・リミテッド Methods for In situ Synthesis of Organic Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs), and Zeolite Imidazole Structures (ZIFs), and Their Applications
WO2019175717A1 (en) * 2018-03-14 2019-09-19 Desiccant Rotors International Private Limited Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof
CN109206630A (en) * 2018-11-07 2019-01-15 中国科学院生态环境研究中心 Three-dimensional level hollow structure Co-ZIF material and preparation method thereof
CN109728311A (en) * 2019-01-09 2019-05-07 长江大学 The metal organic framework compound hollow microsphere of load iron cobalt sulfide
CN110681358A (en) * 2019-11-19 2020-01-14 北京林业大学 ZIFs material-based high-performance adsorption film
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition
CN111892791A (en) * 2020-07-31 2020-11-06 北京化工大学 Preparation method of composite material, composite material and application thereof
CN112958039A (en) * 2021-02-08 2021-06-15 浙江科技学院 Multilayer nano composite resin, preparation method and application in dye wastewater
CN112958041A (en) * 2021-02-08 2021-06-15 浙江科技学院 Core-shell structure nano composite resin, preparation method and application in electroplating wastewater treatment
CN112958040A (en) * 2021-02-08 2021-06-15 浙江科技学院 Co-MOF-D113-6 nano composite resin, preparation method and application
CN112958040B (en) * 2021-02-08 2022-08-02 浙江科技学院 Co-MOF-D113-6 nano composite resin, preparation method and application
CN112958039B (en) * 2021-02-08 2022-08-12 浙江科技学院 Multilayer nano composite resin, preparation method and application in dye wastewater
CN114106352A (en) * 2021-11-25 2022-03-01 浙江理工大学 Cobalt-based metal-hydrogen bond-organic framework material and preparation method and application thereof
CN115212846A (en) * 2022-08-11 2022-10-21 中国矿业大学 Carbon dioxide capture material and preparation method thereof
CN115212846B (en) * 2022-08-11 2023-05-09 中国矿业大学 Carbon dioxide trapping material and preparation method thereof
CN115920863A (en) * 2022-12-30 2023-04-07 武汉汇碳科技有限公司 Composite material for gas adsorption separation and preparation method thereof

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Application publication date: 20161012