CN112844486B - For CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 Composite material and method for producing the same - Google Patents

For CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 Composite material and method for producing the same Download PDF

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CN112844486B
CN112844486B CN202110128413.8A CN202110128413A CN112844486B CN 112844486 B CN112844486 B CN 112844486B CN 202110128413 A CN202110128413 A CN 202110128413A CN 112844486 B CN112844486 B CN 112844486B
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CN112844486A (en
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胡丽华
徐威
渠吉发
丁良辉
王晓
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Nanjing Institute of Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention discloses a catalyst for catalyzing CO 2 ZIF-8/CeO for cycloaddition reaction 2 A composite material and a method for preparing the same. The preparation method comprises the following steps: 1) Preparation of spindle-shaped CeO 2 (ii) a 2) Preparation of ZIF-8/CeO 2 The composite material comprises the following components: adding CeO 2 Dispersing the powder in a methanol solution, adding inorganic zinc salt, and stirring at room temperature to obtain a dispersion liquid; mixing the dispersion liquid with a methanol solution of 2-methylimidazole, and performing post-treatment after the reaction is finished to obtain ZIF-8/CeO 2 A composite material. ZIF-8/CeO obtained by the preparation method 2 The material has high specific surface area and porosity and catalyzes CO 2 The yield of the product of the cycloaddition reaction can reach more than 90 percent, the catalytic activity is not obviously reduced when the catalyst is used for the fifth time, the reusability of the catalyst is obviously higher than that of a ZIF-8 material, and the catalyst is a catalytic material with high stability.

Description

For CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 Composite material and method for producing the same
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a catalyst for CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 Composite materials and methods for making the same.
Background
Zeolite-like imidazolate framework materials (ZIFs) are a common class of Metal Organic Frameworks (MOFs), are formed by coordination of transition metal ions and imidazole-like organic compounds, and have a zeolite framework structure. ZIFs not only have the advantages of large specific surface area, high porosity, high crystallinity and the like, but also have the characteristics of adjustable pore diameter and structural and functional diversity. Therefore, the ZIFs material has huge development potential in the fields of adsorption, separation, catalysis, drug delivery and the like, and is a research hotspot of the current novel nano porous material.
The ZIFs have Lewis acid sites derived from metal ions and basic sites derived from nitrogen on the skeleton, and thus can be used as the materialAs heterogeneous catalysts for various types of catalytic reactions, e.g. CO 2 Cycloaddition reaction, knoevenagel condensation reaction, friedel-Crafts acylation reaction, ester exchange reaction of vegetable oil and the like. CO 2 2 Conversion of cycloaddition to cyclic carbonate is CO 2 One of the important methods for chemical fixation has important significance for reducing carbon emission and reasonably utilizing carbon resources. ZIFs are useful for catalyzing CO 2 The conversion to cyclic carbonates is due to the catalytic CO of Lewis acid sites in the backbone 2 Reaction with epoxide to produce propylene carbonate and other precursors of polycarbonate. In addition, ZIFs have very high CO due to the basic sites of their imidazole ligands 2 Adsorption capacity and therefore ability to adsorb CO 2 The reaction to convert to cyclic carbonates shows higher CO 2 Absorption rate. And the polar nature of ZIFs favors CO 2 Binding and preferential adsorption of polar carbon-oxygen bonds.
But are currently mostly used for CO 2 ZIFs catalysts for cycloaddition reaction still have the problems of low catalytic activity or selectivity, low recycling capability and the like. In addition, the thermal stability of ZIFs materials has certain limitations and is easily decomposed in strong acid and strong base environments, which greatly limits their applications in the field of catalysis. Therefore, heterogeneous catalyst systems with high efficiency and high stability were developed for chemically fixing CO under mild conditions 2 It remains challenging.
Disclosure of Invention
The invention aims to solve the technical problem of providing ZIF-8/CeO aiming at the defects in the prior art 2 A micro-nano structure material and a preparation method thereof. The ZIF-8/CeO 2 The material has high specific surface area and porosity, high stability, and can catalyze CO 2 The cycloaddition reaction has good catalytic activity and reusability.
In order to solve the technical problem, the invention provides a method for CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 Composite material, ZIF-8/CeO 2 CeO in composite material 2 Is in a spindle shape, and ZIF-8 particles are uniformly loaded on CeO 2 An outer surface of (a); ZIF-8/CeO 2 The composite material is of a micro-nano structure and has a hierarchical pore structure; wherein the ZIF-8 particles have a microporous structure of CeO 2 Has a mesoporous structure.
Wherein the particle size of the ZIF-8 particles is 200-300nm and is uniform; in which spindle-shaped CeO 2 The diameter of (A) is 1-2um, and the length of (B) is 8-12um.
The invention provides a method for catalyzing CO 2 ZIF-8/CeO for cycloaddition reaction 2 The preparation method of the micro-nano structure material comprises the following steps:
1) Preparation of spindle-shaped CeO 2 : ce (NO) 3 ) 3 ·6H 2 Dissolving O and urea in deionized water, and stirring for 30-60 min to form homogeneous mixed solution; then transferring the mixed solution into a polytetrafluoroethylene lining of a stainless steel reaction kettle, and crystallizing under a hydrothermal condition; self-heating and cooling the reaction kettle to room temperature, and then centrifuging, ultrasonically washing and drying to obtain white powder; calcining the white powder in a muffle furnace at a certain temperature to obtain light yellow powder, namely CeO 2 。
2) Preparation of ZIF-8/CeO 2 The composite material is as follows: subjecting the CeO obtained in the step 1) 2 Dispersing the powder in a certain amount of methanol solution, then adding inorganic zinc salt, and stirring at room temperature for 1-2 h to obtain dispersion liquid; slowly adding the methanol solution of 2-methylimidazole (2-Mim) into the dispersion liquid, continuously stirring for 5-90 min, centrifuging, ultrasonically washing and drying the reaction liquid after the reaction is finished to obtain ZIF-8/CeO 2 A composite material.
Further, ce (NO) in step 1) 3 ) 3 ·6H 2 The concentrations of the O and urea aqueous solutions are respectively 30mmol/L and 80mmol/L, the crystallization temperature is 120 ℃, and the time is 8h;
preferably, the drying temperature in the step 1) is 60-80 ℃, and preferably 70 ℃; the drying time is 12-36 h, preferably 24h.
Further, the calcining temperature in the step 1) is 600 ℃, and the calcining time is 5h.
Further, ceO in the dispersion liquid in the step 2) 2 The concentration of (2) is 1-2 wt%, and the dosage of methanol is 2-10 mL.
Further, the inorganic zinc salt in the step 2) is zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), zinc acetate dihydrate (Zn (OAc) 2 ·2H 2 O) or zinc chloride.
Further, the inorganic zinc salt and CeO in the step 2) 2 In a molar ratio of (0.1-3): 1; the molar ratio of the inorganic zinc salt to the 2-Mim is 1: (4-8); the dosage of the methanol in the methanol solution of the 2-methylimidazole is 2-10 mL.
Preferably, the drying temperature in the step 2) is 80-110 ℃, and preferably 110 ℃; the drying time is 12h to 18h, preferably 12h.
The invention also protects the high-stability catalyst ZIF-8/CeO prepared by the method 2 A composite material.
The invention also protects the high-stability catalyst ZIF-8/CeO 2 Use of composite materials for CO 2 Use of chemical fixation in the cycloaddition reaction of carbon dioxide and an epoxide. .
The obtained ZIF-8/CeO 2 The composite material was tested for catalytic performance as follows:
mixing a certain amount of ZIF-8/CeO 2 Catalyst and styrene oxide are put into a reaction kettle; using 0.2MPa CO for the reaction kettle 2 Purging 5 times to remove air, then adding 0.7MPa CO in one portion 2 Filling into a reaction kettle; the mixture reacts under the magnetic stirring of 300 r/min; after the reaction was complete, the reactor was cooled to ambient temperature and excess CO was vented 2 (ii) a Centrifuging the residual liquid and performing qualitative and quantitative analysis by GC-MS; the catalyst was washed three times with ethanol and dried.
Wherein the liquid-solid ratio of the catalyst to the styrene oxide is (0.1-1.5): 20.5 (g: mL), preferably 1:20.5 (g: mL).
Wherein the reaction temperature is 80-140 ℃, and preferably 120 ℃; the reaction time is 4h to 10h, preferably 6h.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention synthesizes ZIF-8/CeO with a micro-nano structure by adopting a simpler method 2 The ZIF-8/CeO composite material is prepared by controlling the raw material ratio and the synthesis conditions 2 The composite material is uniformly and stably synthesized;
2. ZIF-8/CeO synthesized by the invention 2 The composite material has higher specific surface area and porosity and a hierarchical pore structure, so that the stability of the ZIF-8 is improved;
3、ZIF-8/CeO 2 composite material catalysis of CO 2 The cyclic carbonate is prepared by cycloaddition reaction, the yield can reach more than 90 percent, the catalytic activity is not obviously reduced when the cyclic carbonate is repeatedly used for the fifth time, the apparent structure is not obviously changed, the repeated use performance of the cyclic carbonate is obviously higher than that of a ZIF-8 material, and the cyclic carbonate is a catalytic material with high stability.
Drawings
FIG. 1 is a scanning electron micrograph of materials prepared in examples 1 to 9.
FIG. 2 is an X-ray diffraction pattern of the materials prepared in examples 1, 4 and 9.
FIG. 3 is a thermogravimetric plot of the materials prepared in examples 1, 4 and 9.
Fig. 4 shows the catalytic performance and the results of recycling of the catalysts prepared in examples 1, 4 and 9.
Detailed Description
The foregoing aspects of the present invention are described in further detail below by way of examples, but it should not be construed that the scope of the subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above aspects of the present invention are within the scope of the present invention.
The experimental procedures used in the following examples are conventional procedures unless otherwise specified, and reagents, methods and equipment used therein are conventional in the art unless otherwise specified.
1. For CO 2 Synthesis of catalytic materials for cycloaddition reactions
Example 1
Spindle shaped CeO 2 Preparation method ofThe method comprises the following steps:
(1) 1.04g Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.38g of urea in 80mL of deionized water, and stirring for 60min at room temperature to form a homogeneous mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene lining of a 100mL stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and performing hydrothermal treatment for 8 hours at 120 ℃;
(3) Cooling the reaction kettle to room temperature by self-heating, taking out the lower-layer precipitate, centrifuging, ultrasonically washing with water and ethanol for several times, and then drying in an oven at 70 ℃ for 24 hours to obtain white powder;
(4) Placing the white powder in a muffle furnace, calcining for 5 hours at 600 ℃ to obtain light yellow powder, namely spindle-shaped CeO 2 。
CeO prepared in example 1 2 The scanning electron micrograph of (A) is shown in figure 1, the X-ray diffraction micrograph is shown in figure 2, the thermogravimetric curve is shown in figure 3, and the structural characterization test data is shown in table 1.
Example 2
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1: 10 2 Composite material
(1) 1.0479g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3825g of urea in 80mL of deionized water, and stirring at room temperature for 60min to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, and calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1034g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.0223g of Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.0245g of 2-Mim into 10mL of methanol, slowly adding the methanol solution of 2-Mim into the dispersion liquid, continuously stirring for 1h, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain faint yellow powder ZIF-8/CeO 2 A composite material.
EXAMPLE 2 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 3
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1:4 2 Composite material
(1) 1.0476g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3829g of urea in 80mL of deionized water, and stirring at room temperature for 60min to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, and calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1025g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.0516g of Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.0572g of 2-Mim in 10mL of methanol, slowly adding the methanol solution of 2-Mim into the dispersion liquid, continuously stirring for 1h, centrifuging, ultrasonically washing and drying the reaction liquid after the reaction is finished to obtain faint yellow powder ZIF-8/CeO 2 A composite material.
Example 3 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 4
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1 2 Composite material
(1) 1.0465g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3834g of urea in 80mL of deionized water, and stirring for 60min at room temperature to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1054g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol,followed by the addition of 0.1088g Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.1200g of 2-Mim into 10mL of methanol, slowly adding the methanol solution of 2-Mim into the dispersion liquid, continuously stirring for 1h, centrifuging, ultrasonically washing and drying the reaction liquid after the reaction is finished to obtain faint yellow powder ZIF-8/CeO 2 A composite material.
EXAMPLE 4 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in figure 1, the X-ray diffraction map is shown in figure 2, the thermogravimetric curve is shown in figure 3, and the structural characterization test data is shown in table 1.
Example 5
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1 2 Composite material
(1) 1.0436g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3843g of urea in 80mL of deionized water, and stirring at room temperature for 60min to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1001g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.2040g Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.2289g of 2-Mim in 10mL of methanol, slowly adding the methanol solution of 2-Mim into the dispersion liquid, continuously stirring for 1h, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain a light yellow powder ZIF-8/CeO 2 A composite material.
Example 5 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 6
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1 2 Composite material
(1) 1 is added.0447g Ce(NO 3 ) 3 ·6H 2 Dissolving O and 0.3831g of urea in 80mL of deionized water, and stirring for 60min at room temperature to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, and calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.0876g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.3719g of Zn (OAc) 2 ·2H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.5562g of 2-Mim in 10mL of methanol, slowly adding the methanol solution of 2-Mim into the dispersion liquid, continuously stirring for 1h, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain a light yellow powder ZIF-8/CeO 2 A composite material.
Example 6 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 7
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1 2 Composite material
(1) 1.0420g of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3834g of urea in 80mL of deionized water, and stirring at room temperature for 60min to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, and calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1004g of the obtained CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.0512g of Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.0568g of 2-Mim in 10mL of methanol, slowly adding the 2-Mim methanol solution into the dispersion liquid, continuously stirring for 20min, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain light yellow powder ZIF-8/CeO 2 A composite material.
Example 7 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 8
According to the mol ratio of Zn (NO) 3 ) 2 ·6H 2 O:2-Mim:CeO 2 Methanol =1:4 2 Composite material
(1) 1.0429g Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 0.3853g of urea in 80mL of deionized water, and stirring at room temperature for 60min to form a homogeneous mixed solution; then transferring the mixed solution into a 100mL stainless steel reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8h; taking out the lower layer precipitate, centrifuging, washing and drying for 24h to obtain white powder, and calcining at 600 deg.C for 5h to obtain yellowish CeO 2 And (3) powder.
(2) 0.1013g of the resulting CeO was taken 2 The powder was dispersed in 10mL of methanol, followed by the addition of 0.0524g of Zn (NO) 3 ) 2 ·6H 2 O, stirring for 1 hour at room temperature to obtain a dispersion liquid; dissolving 0.0585g of 2-Mim in 10mL of methanol, slowly adding the 2-Mim methanol solution into the dispersion liquid, continuously stirring for 90min, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain faint yellow powder ZIF-8/CeO 2 A composite material.
Example 8 preparation of ZIF-8/CeO 2 The scanning electron micrograph of the composite material is shown in FIG. 1.
Example 9
Synthesis of ZIF-8 material, comprising the steps of:
4.13g of Zn (NO) are added separately 3 ) 2 ·6H 2 O and 4.67g of 2-Mim are added to 200mL of methanol and stirred until completely dissolved. Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-Mim to methanol is 1. Then, the two clear solutions were mixed and stirred at room temperature for 1h. The white precipitate obtained was collected by centrifugation and washed three times with methanol. Finally, the sample was dried at 70 ℃ for 24 hours to obtain ZIF-8 as a white powder.
ZIF-8/CeO prepared in example 9 2 The scanning electron micrograph of the composite material is shown in figure 1, the X-ray diffraction diagram is shown in figure 2, and the thermogravimetric curve is shown in figure 3As shown, the structural characterization test data is shown in table 1.
2. The materials prepared in examples 1, 4 and 9 were evaluated for their catalytic performance by the following method:
0.10g of catalyst and 18mmol of styrene oxide are put into a reaction kettle; using 0.2MPa CO for the reaction kettle 2 Purging 5 times to remove air, then 0.7MPa CO in one portion 2 Filling into a reaction kettle; the mixture is reacted for 6 hours at 120 ℃ under the magnetic stirring of 300 r/min; after the reaction was complete, the reactor was cooled to ambient temperature and excess CO was vented 2 (ii) a 0.1mL of toluene and 6mL of acetone were added to the reaction vessel, and the liquid in the reaction vessel was washed into a centrifuge tube, centrifuged, and the supernatant was removed, followed by qualitative and quantitative analysis by GC-MS, and the results are shown in Table 1. The catalyst was washed with ethanol three times, dried and reused, and the catalytic results are shown in fig. 4.
Table 1 performance test data for materials prepared in examples 1, 4 and 9
Figure BDA0002924283420000071
As can be seen from Table 1, the ZIF-8/CeO of the present invention 2 The composite material has large specific surface area and porosity, and has a hierarchical pore structure for CO 2 The cycloaddition reaction has higher catalytic activity, and the product yield can reach more than 90 percent. FIG. 4 shows the results of catalyst reuse, and it can be seen that ZIF-8/CeO 2 The cycle performance of the composite material is obviously higher than that of a ZIF-8 material, and the composite material is a catalytic material with high stability.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any simple modifications, equivalents and improvements made by those skilled in the art without departing from the technical scope of the present invention are all within the scope of the present invention.

Claims (9)

1. Is used forCO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 A composite material characterized by: ZIF-8/CeO 2 CeO in composite material 2 Is in a spindle shape, and ZIF-8 particles are uniformly loaded on CeO 2 An outer surface of (a); ZIF-8/CeO 2 The composite material is of a micro-nano structure and has a hierarchical pore structure; wherein the ZIF-8 particles have a microporous structure of CeO 2 Then has a mesoporous structure; wherein the particle size of the ZIF-8 particles is 200-300nm, and the particle size is uniform; in which CeO is in the form of a spindle 2 The diameter of (2) is 1-2um, and the length is 8-12um.
2. Use according to claim 1 for CO 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Preparation of spindle-shaped CeO 2 : adding Ce (NO) 3 ) 3 ·6H 2 Dissolving O and urea in deionized water, and stirring for 30-60min to form a homogeneous mixed solution; then transferring the mixed solution into a polytetrafluoroethylene lining of a stainless steel reaction kettle, and crystallizing under a hydrothermal condition; cooling the reaction kettle to room temperature by self-heating, and then performing centrifugation, ultrasonic washing and drying treatment to obtain white powder; calcining the white powder in a muffle furnace at a certain temperature to obtain light yellow powder which is CeO 2 ；
2) Preparation of ZIF-8/CeO 2 The composite material comprises the following components: subjecting the CeO obtained in the step 1) 2 Dispersing the powder in a certain amount of methanol solution, then adding inorganic zinc salt, and stirring at room temperature for 1 to 2h to obtain a dispersion liquid; slowly adding the methanol solution of the 2-methylimidazole into the dispersion liquid, continuously stirring for 5-90min, centrifuging the reaction liquid after the reaction is finished, ultrasonically washing and drying to obtain ZIF-8/CeO 2 A composite material.
3. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: ce (NO) in step 1) 3 ) 3 ·6H 2 The concentrations of the aqueous solutions of O and urea were 30mm, respectivelyol/L and 80mmol/L, the crystallization temperature is 120 ℃, and the time is 8h.
4. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: the drying temperature in the step 1) is 60 to 80 ℃; drying time is 12h to 36h; the calcining temperature in the step 1) is 600 ℃, and the calcining time is 5h.
5. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: ceO in the dispersion liquid in the step 2) 2 The concentration of the methanol is 1 to 2wt percent, and the dosage of the methanol is 2 to 10mL.
6. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: the inorganic zinc salt in the step 2) is zinc nitrate hexahydrate Zn (NO) 3 ) 2 •6H 2 O, zinc acetate dihydrate Zn (OAc) 2 •2H 2 At least one of O or zinc chloride.
7. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: the inorganic zinc salt and CeO in the step 2) 2 The molar ratio of (1) to (3) is: 1; the dosage of methanol in the methanol solution of the 2-methylimidazole is 2-10mL.
8. Use for CO according to claim 2 2 Chemically fixed high-stability catalyst ZIF-8/CeO 2 The preparation method of the composite material is characterized by comprising the following steps: the drying temperature in the step 2) is 80-110 ℃; the drying time is 12h to 18h.
9. The high stability catalyst as claimed in any one of claims 1 and 2ZIF-8/CeO 2 Composite material in CO 2 Use in chemical fixation, characterized in that: used in the cycloaddition reaction of carbon dioxide and epoxide.
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