CN113929105B - Preparation method of metal organic framework derived nickel silicate - Google Patents

Preparation method of metal organic framework derived nickel silicate Download PDF

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CN113929105B
CN113929105B CN202111024421.4A CN202111024421A CN113929105B CN 113929105 B CN113929105 B CN 113929105B CN 202111024421 A CN202111024421 A CN 202111024421A CN 113929105 B CN113929105 B CN 113929105B
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organic framework
metal organic
preparation
silicate
suspension
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CN113929105A (en
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聂士斌
徐煜轩
杨继年
戴广龙
冯雪松
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Anhui University of Science and Technology
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Anhui University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/20Silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

A preparation method of metal organic framework derived nickel silicate, belonging to the technical field of inorganic material preparation. Firstly, sodium silicate is subjected to ultrasonic treatment to be completely dissolved in deionized water, then a proper amount of absolute ethyl alcohol and a nickel-metal organic framework (Ni-MOF) are added, after the sodium silicate is uniformly dispersed, a proper amount of sodium hydroxide solution is added, the pH value of the suspension is regulated, then the suspension is subjected to ultrasonic dispersion treatment to obtain a green suspension, the green suspension is transferred into a polytetrafluoroethylene high-pressure reaction kettle to react at 160 ℃, after the reaction is completed, the reaction is naturally cooled to room temperature, and after centrifugation, cleaning and drying, the obtained light green powder is the metal organic framework derived nickel silicate. The preparation method has the advantages that the prepared metal organic framework derived nickel silicate has obvious lamellar structure, the lamellar distribution is uniform, the preparation method is simple to operate, the preparation period is short, and the preparation method is suitable for large-scale preparation.

Description

Preparation method of metal organic framework derived nickel silicate
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of metal organic framework derived nickel silicate.
Background
According to the description of chemical progress (chemical progress, 38:2835-2846, 2019), nickel silicate is a two-dimensional mineral material, has the advantages of larger specific surface area, low raw material price, easy availability, adjustable interlayer groups and the like, and therefore has wide application prospect in the aspects of electrode anode materials, catalysis, sewage treatment, flame retardance and the like.
To date, researchers have developed a variety of techniques for preparing nickel silicate, of which the hydrothermal, ammonia evaporation and sol-gel processes are the main ones that are widely used. According to the description of catalyst Today (2010,157 (1-4): 397-403), a hydrothermal method is mainly to uniformly mix a certain amount of silicon source and nickel source and adjust the pH value, and then introduce the mixture into a reaction kettle to react under high temperature and high pressure conditions to generate nickel silicate. According to the description of catalytic science and Technology (Catalysis Science & Technology,5:5095-5099,2015.), the ammonia evaporation method usually uses silica sol as a main raw material and ammonia water as a precipitant, and the reaction is continued at a certain temperature. As the reaction proceeds, the pH of the solution decreases due to the continuous volatilization of the aqueous ammonia, and nickel silicate is finally obtained. According to the description of J Material chemistry (Journal of Materials Chemistry,10:789-795,2000), the sol-gel rule is to use a silane coupling agent as a silicon source, to prepare a solution with a nickel source and a mineralizer and to mix them thoroughly, and to age them for several days to obtain nickel silicate. Although the nickel silicate can be prepared by the method, the obtained nickel silicate has irregular morphology and serious lamellar stacking, even lamellar structure cannot be observed, and the application of the nickel silicate is limited.
According to the description of sustainable chemistry and Engineering (ACS Sustainable Chemistry & Engineering,7:9272-9280,2019), a class of emerging materials consisting of nickel metal ions or metal clusters and organic linkers for nickel metal organic frameworks (Ni-MOFs) has been used in the fields of drug delivery, gas storage or separation, catalysis, flame retardance of polymer composites, and the like.
Disclosure of Invention
The invention aims to provide a preparation method of metal organic framework derived nickel silicate, which takes a metal organic framework (Ni-MOF) as a template to prepare nickel silicate with obvious lamellar structure and uniform distribution, and overcomes the defects that the nickel silicate prepared by the traditional method is irregular in appearance, serious in lamellar stacking and even has no lamellar structure observed.
The invention relates to a preparation method of metal organic framework derived nickel silicate, which comprises the following steps:
firstly, sodium silicate is subjected to ultrasonic treatment to be completely dissolved in deionized water, then a proper amount of absolute ethyl alcohol and a nickel-metal organic framework (Ni-MOF) are added, after the sodium silicate is uniformly dispersed, a proper amount of sodium hydroxide solution is added, the pH value of the suspension is regulated, then the suspension is subjected to ultrasonic dispersion treatment to obtain a green suspension, the green suspension is transferred into a polytetrafluoroethylene high-pressure reaction kettle to react at 160 ℃, after the reaction is completed, the reaction is naturally cooled to room temperature, and after centrifugation, cleaning and drying, the obtained light green powder is the metal organic framework derived nickel silicate.
Further, the mass ratio of the nickel-metal organic framework (Ni-MOF), sodium silicate and deionized water is 1: 1-2: 40-100;
further, the volume ratio of absolute ethyl alcohol to deionized water is 1:1, a step of;
further, the pH value of the suspension is 11-12.
Compared with the existing nickel silicate preparation method, the technical progress of the invention is mainly as follows:
1. the metal organic framework derived nickel silicate prepared by the method has obvious lamellar structure, and the lamellar is uniformly distributed, so that the catalyst loading and the compatibility with a polymer matrix are improved.
2. The preparation method disclosed by the invention is simple to operate, short in preparation period and suitable for large-scale preparation.
Drawings
FIG. 1 is an X-ray diffraction pattern of metal-organic framework-derived nickel silicate prepared in example 1
FIG. 2 is a scanning electron microscope image of metal organic framework-derived nickel silicate prepared in example 1
FIG. 3 is an X-ray diffraction pattern of the metal-organic framework-derived nickel silicate prepared in example 2
FIG. 4 is an X-ray diffraction pattern of metal-organic framework-derived nickel silicate prepared in example 3
FIG. 5 is an X-ray diffraction pattern of nickel silicate prepared in comparative example 1
FIG. 6 is a scanning electron microscope image of the nickel silicate prepared in comparative example 1
Detailed Description
The objects, technical solutions and advantages of the embodiments of the present invention will be more apparent, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Firstly, 1.14g of sodium silicate is subjected to ultrasonic treatment to be completely dissolved in 60ml of deionized water, then 60ml of absolute ethyl alcohol and 0.8g of nickel-metal organic framework (Ni-MOF) are added, after the sodium silicate is uniformly dispersed, a proper amount of 1mol/L sodium hydroxide solution is added, the pH value of the suspension is adjusted to 11.3, then the suspension is subjected to ultrasonic dispersion treatment to obtain green suspension, the green suspension is transferred into a polytetrafluoroethylene high-pressure reaction kettle to react for 15 hours at 160 ℃, after the reaction is completed, the solution is naturally cooled to room temperature, and after centrifugation, cleaning and drying, the obtained light green powder is the metal organic framework derived nickel silicate.
FIG. 1 is an X-ray diffraction chart of the metal organic framework-derived nickel silicate prepared in the present example, wherein characteristic peaks respectively correspond to (001), (002/011), (003), (130/200), (150/240/310) and (060/330) crystal planes, indicating successful preparation of the metal organic framework-derived nickel silicate. Fig. 2 is a scanning electron microscope picture of the present example, and it can be clearly observed that the metal-organic framework-derived nickel silicate has a distinct lamellar structure and that the lamellar distribution is uniform.
Example 2
Firstly, 0.8g of sodium silicate is subjected to ultrasonic treatment to be completely dissolved in 40ml of deionized water, then 40ml of absolute ethyl alcohol and 0.8g of nickel-metal organic framework (Ni-MOF) are added, after the sodium silicate is uniformly dispersed, a proper amount of 1mol/L sodium hydroxide solution is added, the pH value of the suspension is adjusted to 11, then the suspension is subjected to ultrasonic dispersion treatment to obtain green suspension, the green suspension is transferred into a polytetrafluoroethylene high-pressure reaction kettle to react for 15 hours at 160 ℃, after the reaction is completed, the solution is naturally cooled to room temperature, and after centrifugation, cleaning and drying, the obtained light green powder is the metal organic framework derived nickel silicate.
FIG. 3 is an X-ray diffraction chart of the metal organic framework-derived nickel silicate prepared in this example, wherein characteristic peaks respectively correspond to (001), (002/011), (003), (130/200), (150/240/310) and (060/330) crystal planes, indicating successful preparation of the metal organic framework-derived nickel silicate.
Example 3
Firstly, 1.6g of sodium silicate is subjected to ultrasonic treatment to be completely dissolved in 100ml of deionized water, then 100ml of absolute ethyl alcohol and 0.8g of nickel-metal organic framework (Ni-MOF) are added, after the sodium silicate is uniformly dispersed, a proper amount of 1mol/L sodium hydroxide solution is added, the pH value of the suspension is regulated to 12, then the suspension is subjected to ultrasonic dispersion treatment to obtain green suspension, the green suspension is transferred into a polytetrafluoroethylene high-pressure reaction kettle to react for 15 hours at 160 ℃, after the reaction is completed, the solution is naturally cooled to room temperature, and after centrifugation, cleaning and drying, the obtained light green powder is the metal organic framework derived nickel silicate.
FIG. 4 is an X-ray diffraction chart of the metal organic framework-derived nickel silicate prepared in this example, wherein characteristic peaks respectively correspond to (001), (002/011), (003), (130/200), (150/240/310) and (060/330) crystal planes, indicating successful preparation of the metal organic framework-derived nickel silicate.
Comparative example 1
The sol-gel method for preparing nickel silicate comprises the following steps: 2.21g of a silane coupling agent KH550 and 1.96g of nickel chloride were sequentially added to 50ml of absolute ethanol, and after complete dissolution, the mixture was designated as solution A. Slowly adding the solution A into 200ml of 0.05mol/L sodium hydroxide solution, uniformly stirring, aging for 72 hours at room temperature, and centrifugally collecting, cleaning and drying to obtain light green powder which is the nickel silicate prepared by the sol-gel method.
Fig. 5 and 6 are an X-ray diffraction pattern and a scanning electron microscope, respectively, of a sol-gel process for preparing nickel silicate. The characteristic peaks appearing in FIG. 5 correspond to the (001), (020/110), (130, 200) and (060/330) crystal planes respectively, and are consistent with the characteristic peak positions of the X-ray diffraction pattern of nickel silicate prepared by the sol-gel method reported in the front edge of chemical science and engineering (Frontiers of Chemical Science and Engineering, DOI:10.1007/s 11705-021-2074-6), which indicates that the sol-gel method successfully prepares nickel silicate. In addition, it is evident from FIG. 6 that the nickel silicate prepared by this method is in the form of a lump without a distinct lamellar structure.
From the above examples and comparative examples, the present invention successfully prepared metal-organic framework-derived nickel silicate with obvious lamellar structure and uniform distribution using metal-organic framework (Ni-MOF) as a template. In addition, the preparation method is simple to operate, short in preparation period and suitable for large-scale preparation.

Claims (1)

1. The preparation method of the metal organic framework derived nickel silicate comprises the following steps:
firstly, completely dissolving sodium silicate in deionized water by ultrasonic treatment, then adding a proper amount of absolute ethyl alcohol and a nickel-metal organic framework (Ni-MOF), after the sodium silicate is uniformly dispersed, adding a proper amount of sodium hydroxide solution, adjusting the pH value of the suspension, then carrying out ultrasonic dispersion treatment to obtain a green suspension, transferring the green suspension into a polytetrafluoroethylene high-pressure reaction kettle, reacting at 160 ℃, naturally cooling to room temperature after the reaction is completed, and centrifuging, cleaning and drying to obtain light green powder which is the metal organic framework-derived nickel silicate; the mass ratio of the nickel-metal organic framework (Ni-MOF), sodium silicate and deionized water is 1: 1-2: 40-100; the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1, a step of; the pH of the suspension is 11-12.
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CN114015199B (en) * 2021-11-30 2023-09-15 安徽理工大学 Wear-resistant epoxy resin composite material and preparation method thereof
CN114230978B (en) * 2022-01-17 2023-09-19 安徽理工大学 Flame-retardant epoxy resin based on phosphorus-containing nickel silicate whisker and preparation method thereof
CN115895194A (en) * 2022-12-29 2023-04-04 安徽理工大学 Hierarchical layered nickel silicate modified epoxy resin composite material and preparation method thereof

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