CN109382128B - Method and catalyst for catalytic synthesis of cyclic carbonate - Google Patents
Method and catalyst for catalytic synthesis of cyclic carbonate Download PDFInfo
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- CN109382128B CN109382128B CN201811271719.3A CN201811271719A CN109382128B CN 109382128 B CN109382128 B CN 109382128B CN 201811271719 A CN201811271719 A CN 201811271719A CN 109382128 B CN109382128 B CN 109382128B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- B01J31/0239—Quaternary ammonium compounds
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- 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- 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
- C07D317/42—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
Abstract
The invention discloses a catalyst and application thereof, in particular to a catalyst for catalyzing CO2A catalyst for synthesizing cyclic carbonate. The catalyst of the invention is Fe with a stacked pore structure4 Ⅲ(Fe(CN)6)3Or KM4(FeⅢ(CN)6)3Wherein M is Co or Ni or Zn. The catalyst of the invention can synthesize cyclic carbonate by the reaction substrate of epoxide under normal pressure and without solvent.
Description
Technical Field
The invention relates to a method for catalytically synthesizing cyclic carbonate and a catalyst thereof.
Background
Carbon dioxide (CO)2) Is a colorless, tasteless and nontoxic gas. In recent years, the problem of global warming caused by an increase in the content of carbon dioxide in the atmosphere has attracted researchers' extensive attention [1,2 ]]. Although carbon dioxide readily causes greenhouse effect, it has the advantage of being inexpensive and readily available (see: X.Wang, Y.ZHou, Z.Guo, G.Chen, J.Li, Y.Shi, Y.Liu, J.Wang, chem.Sci.6(2015) 6916-.
M.A.Subhani,T.E.Müller,W.Leitner,C.Gürtler, Green Chem.16(2014)1865-1870.)。]Carbon dioxide can be synthesized as a carbon 1 starting material such as formamide (see S.W.
Klankermayer, kastem Beydoun, and, w.leitner, angelw.chem.int.ed.55 (2016) 7296-: s.g. jadhav, p.d. vaidya, b.m. Bhanage, j.b. joshi, chem.eng.res.des.92(2014) 2557-2567), formic acid (see: c.a. Huff, m.s.sanford, ACS catal.3(2013) 2412-: J.W.Comerford, I.D.V.Ingram, M.North, X.Wu, Green chem.17(2015) 1966-.7 (2017)5478-5482.). The cyclic carbonate can be used as an aprotic polar solvent, and also has wide application in the aspects of synthetic plastics, medicines and the like (see: C.J.Whiteoak, N.Kiellad, V.Laserna, E.C. Escudero-Ad & ltn, E.Martin, A.W.Kleij, J.Am.chem.Soc.135(2013) 1228-phase 1231, B).
F.
S.P.Verevkin,A.
Chem.Rev.110(2010) 4554-4581.，C.M.Alder,J.D.Hayler,R.K.Henderson,A.M.Redman,L.Shukla, L.E.Shuster,H.F.Sneddon,Green Chem.18(2016)3879-3890.)。
The direct synthesis of cyclic carbonates from CO2 and epoxides is a highly efficient green route with one hundred percent of atom utilization (c. marti i, g. fireani, a.w.kleij, ACS catal.5(2015) 1353-. At present, heterogeneous catalytic systems for synthesizing cyclic carbonates are mainly ionic liquids, onium salts, etc. (see: X.Wang, Y.ZHou, Z.Guo, G.Chen, J.Li, Y.Shi, Y.Liu, J.Wang, chem.Sci.6 (2015)) 6916-.
B.Rieger,T.Repo,Appl.Catal.A-Gen. 365(2009)194-198.，A.-L.Girard,N.Simon,M.Zanatta,S.Marmitt,P.
J. Dupont, Green chem.16(2014)2815-2825, s.zhang, y.chen, f.li, x.lu, w.dai, r.mori, cat.today 115(2006)61-69. In addition, a large number of heterogeneous catalysts such as metal salts, metal oxides and metal-organic frameworks (MOFs) catalyze the reaction (see: A. Decorts, M. Martinez Belmonte, J. Benet-Buchholz, A. W. Kleij, chem. Commun.46(2010) 4580-4582, J. -Q. Wang, W. -G. Cheng, J. Sun, T. -Y.Shi, X. -P.Zhang, S. -J. Zhang, RSCAdv.4 (2014)) 2360-. Compared with homogeneous catalysts, heterogeneous catalysts have the advantages of easy separation, low catalytic cost and the like. Heterogeneous catalysts have relatively low catalytic efficiency, and thus increasing the catalytic activity of heterogeneous catalysts is one of the challenges facing catalytic researchers.
Disclosure of Invention
The invention provides a catalyst for catalytically synthesizing cyclic carbonate, a preparation method of the catalyst, and a method for synthesizing and preparing the cyclic carbonate by using the catalyst.
The catalyst for catalytically synthesizing the cyclic carbonate is Fe with a stacked pore structure4 Ⅲ(Fe(CN)6)3Or KM of stacked pore structure4(FeⅢ(CN)6)3Wherein M is Co or Ni or Zn.
The catalyst of the invention is Fe4 Ⅲ(Fe(CN)6)3The preparation method comprises the following steps: FeCl is added2·4H2O and K3[Fe(CN)6]·6H2Dissolving O in distilled water respectively, mixing the two solutions under stirring, heating the mixture at 80 ℃ for 12 hours, centrifugally separating the obtained solid, fully washing the obtained solid with high-purity water, and drying at 80 ℃ to obtain the catalyst.
Catalyst KM of the invention4(FeⅢ(CN)6)3The preparation method comprises the following steps: FeCl is added2·4H2O (Co(NO3)2·6H2O,Ni(NO3)26H2O, ZnCl2) and K3[Fe(CN)6]·6H2Dissolving O in distilled water, mixing the above two solutions under stirring, heating at 80 deg.C for 12 hr, centrifuging to obtain solid, washing with high purity water, and drying at 80 deg.CThe catalyst is described.
The method for catalytically synthesizing the cyclic carbonate comprises the following steps: adding a reaction substrate of an epoxide to a reaction vessel, using said catalyst Fe4 Ⅲ(Fe(CN)6)3Or KM4(FeⅢ(CN)6)3And co-catalyst, stirring the reaction system in oil bath at 60-100 ℃ under normal pressure for reaction, and filtering and collecting a product, namely cyclic carbonate after the reaction is finished, wherein the co-catalyst is any quaternary ammonium salt.
Preferably, the method for catalytically synthesizing the cyclic carbonate ester of the present invention is such that the co-catalyst used is TBAB.
Preferably, the method for catalytically synthesizing the cyclic carbonate ester of the present invention is such that the co-catalyst used is TBAC.
Preferably, the method for catalytically synthesizing the cyclic carbonate ester according to the present invention is such that the co-catalyst used is TBAI.
In the method for catalytically synthesizing the cyclic carbonate, the substrate used can be any one of styrene oxide, epichlorohydrin, methyl propyl glycidyl ester, n-butyl glycidyl ether, cyclohexene oxide or phenyl glycidyl ether.
Relevant experiments show that the catalyst has high catalytic activity for catalyzing the cyclic reaction of carbon dioxide and epoxide under the conditions of normal pressure and no solvent, can be recycled, has a very simple preparation method, and is an efficient and green iron complex catalyst. The method can obtain the product with high conversion rate and selectivity under mild conditions (no solvent and 100 ℃). In addition, the catalyst can be well separated from a substrate after the reaction is finished, so that the catalyst is convenient to recycle; the method does not need a solvent in the reaction process, avoids the step of separating the solvent after the reaction is finished, and does not need additional pressurizing equipment because the pressure of carbon dioxide is normal pressure in the reaction process.
Drawings
FIG. 1 is Fe according to the invention4 Ⅲ(Fe(CN)6)3CatalysisElectron microscope and energy spectrum of the preparation. Wherein: (a) is a transmission electron micrograph, (b) is an energy dispersive x-ray spectrum thereof, and (c) is a comparative catalyst FeⅢ 4(Fe(CN)6)3Transmission electron microscopy of cube, (d) wide angle annular dark field scanning transmission electron microscopy, and (e-h) FeⅢ 4(Fe(CN)6)3And (4) element distribution diagram.
FIG. 2 is FeⅢ 4(Fe(CN)6)3Nitrogen desorption and pore volume curve, wherein: (a) feⅢ 4(Fe(CN)6)3And FeⅢ 4(Fe(CN)6)3-cube nitrogen sorption and desorption curve, (b) FeⅢ 4(Fe(CN)6)3And FeⅢ 4(Fe(CN)6)3Pore volume of cube.
FIG. 3 is FeⅢ 4(Fe(CN)6)3An X-ray diffraction pattern and a fine diffraction pattern, wherein: (a) all elements FeⅢ 4(Fe(CN)6)3XPS full spectrum of (a), (b) XPS fine spectrum of Fe element.
FIG. 4 is FeⅢ 4(Fe(CN)6)3An X-ray diffraction pattern and a raman spectrum, wherein: (a) is X diffraction pattern, and (b) is Raman spectrum.
FIG. 5 is FeⅢ 4(Fe(CN)6)3The conversion rate and the selectivity after recycling are shown in the figure.
Detailed Description
The present invention is illustrated below with reference to examples.
Preparation of catalyst
1. Preparation of the catalyst
1.1 FeⅢ 4(Fe(CN)6)3Preparation of
FeCl is added2·4H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) was dissolved in 20mL distilled water, respectively. Mixing the two solutions under magnetic stirring, transferring the mixture to a polytetrafluoroethylene liningStainless steel autoclave and heated at 80 ℃ for 12 hours. Finally, the solid obtained by centrifugal separation was washed 3 times with high-purity water and dried at 80 ℃ for 12 hours to obtain FeⅢ 4(Fe(CN)6)3。
1.2 KM4(FeⅢ(CN)6)3(Fe(CN)6)3Preparation of cube
Mixing Co (NO)3)2·6H2O,. 6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) was dissolved in 20mL of distilled water, respectively. The two solutions were mixed under magnetic stirring and the mixture was transferred to a polytetrafluoroethylene lined stainless steel autoclave and heated at 80 ℃ for 12 hours. Finally, the solid obtained by centrifugal separation was washed 3 times with high-purity water and dried at 80 ℃ for 12 hours to obtain KCo4(FeⅢ(CN)6)3。
Reacting ZnCl2·6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) was dissolved in 20mL distilled water, respectively. The two solutions were mixed under magnetic stirring, and the mixture was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and heated at 80 ℃ for 12 hours. Finally, the solid obtained by centrifugal separation was washed 3 times with high-purity water and dried at 80 ℃ for 12 hours to obtain KZn4(FeⅢ(CN)6)3。
Mixing Ni (NO)3)2·6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) was dissolved in 20mL of distilled water, respectively. The two solutions were mixed under magnetic stirring, and the mixture was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and heated at 80 ℃ for 12 hours. Finally, the solid obtained by centrifugal separation was washed 3 times with high-purity water and dried at 80 ℃ for 12 hours to obtain (KNi)4(FeⅢ(CN)6。
1.3 Fe(CN)6)3Preparation of cube
(Fe (CN))6)3The preparation of-cube can be found in l.zhang, h.b.wu, x.w.lou, J.Am, chem, Soc, 135(2013)10664-]Under constant magnetic stirring, 0.5mmol of K4Fe(CN)6·3H2After adding O to HCl solution (0.1M, 50mL) and stirring for 10 minutes, a clear solution was obtained. The mixture was then transferred to a polytetrafluoroethylene lined stainless steel autoclave and heated at 80 ℃ for 12 hours. Finally, the resulting solid was collected by centrifugation and washed 3 times with ultrapure water, and then dried at 80 ℃ for 12 hours.
2. Catalyst characterization
The morphology and microstructure of the catalyst prepared before were characterized by Transmission Electron Microscopy (TEM), see figure 1.
FeⅢ4(Fe(CN)6)3The TEM image of (fig. 1a) shows that the catalyst is in a cluster morphology. To study FeⅢ 4(Fe(CN)6)3The catalyst was subjected to a large angle annular dark field scanning transmission electron microscope (HAADF-STEM), see fig. 1d, and the catalyst contained elements of carbon, nitrogen, and iron, respectively. Analysis of element profile 1b in the catalyst showed a uniform distribution of C, N, K and Fe in the catalyst, and in addition provided the mole fractions of the elements in the catalyst (C83.55%, N10.50%, K0.33% and Fe 3.39%). FIG. 1c shows FeⅢ 4(Fe(CN)6)3Cube structure. FIGS. 1 e-1 h of the mapping plot show that the elements of the catalyst are distributed more uniformly.
In order to characterize the specific surface area of the catalyst, the present invention performed BET tests on the catalyst, see fig. 2.
As can be seen from FIG. 2a, the adsorption-desorption curve conforms to the type IV adsorption isotherm, indicating that the catalyst has a stacking pore structure [24 ]]。FeⅢ 4(Fe CN)6)3Has a specific surface area and a pore volume of 296.3m, respectively2G and 0.23cm3(ii) in terms of/g. The large surface area and pore volume may provide more exposed active sites for the catalyst [25,26]。 FeⅢ 4(Fe(CN)6)3The adsorption and desorption curves of the cube show that the catalyst does not have a mesoporous structure. FeⅢ 4(Fe(CN)6)3Surface area of cube andpore volumes were each 10.0m2G and 0.018cm3(ii) in terms of/g. The small specific surface area and the pore volume indicate FeⅢ 4(Fe(CN)6)3The cube catalyst is a solid cubic structure, the structural properties of which are detrimental to the contact of the active site with the substrate.
To characterize the valence distribution of the elements of the catalyst, the catalyst was subjected to XPS testing, see fig. 3 and 4.
From the XPS survey (FIG. 3a) it is clear that there are elements C1s (284.6eV), N1s (397.9 eV) and Fe 2p (708.5 and 721.8eV) on the catalyst surface. The fine spectrum of Fe 2p (fig. 3b) consists of four main peaks with binding energies of 708.5,711.5,721.4 and 724.3eV, respectively. Peaks at 708.5 and 724.3eV correspond to [ Fe ]II(CN)6]Fe 2p of3/2And Fe 2p1/2Binding energies of 711.5 and 721.4eV correspond to FeⅢ4(Fe(CN)6)3Fe in (1)Ⅲ2p3/2And Fe III 2p1/2。
As can be seen from fig. 4a, the XRD pattern of the catalyst of the lattice plane shows 8 characteristic peaks at 17.3 °, 24.6 °, 35.2 °, 39.4 °, 43.4 °, 50.5 °, 53.9 ° and 57.0 ° as the (200), (220), (400), (420), (422), (440), (600) and (620) crystal planes of the catalyst. FIG. 4b shows Raman spectra at 2091 and 2130 cm-1Two strong peaks are stretching vibration of carbon-nitrogen triple bonds. Furthermore, at 264 and 534cm-1The spectral band is the stretching and bending vibration peak of Fe-C ≡ N-Fe.
Second, evaluation of catalyst
Catalyst performance was tested in a 25mL three necked round bottom flask at atmospheric pressure. A three-necked round bottom flask was charged with epoxide (5mmol), catalyst (10mg) and cocatalyst (Bu)4NBr or others) 2.5 mol%, and the reaction system was stirred in an oil bath at 600rpm/min for 0.25-5 hours. After the reaction, the product was collected by filtration and purified by gas chromatography mass spectrometry (GC-MS, Agilent 6,890N/5,937N) and1HNMR (Using CDCl)3Varian Inova 400,400MHz) as solvent to examine conversion, selectivity and product yield.
Calculation of the Activity of the catalystComprises the following steps: conversion [% 100 × ([ C ]0-C1]/[C0]) Selectivity: × [ C "] /[C’]And yield% (% 100 × [ C ] "]/[C0]，[C0]As initial substrate concentration, [ C ]1]Is substrate concentration at the end of the reaction, [ C']Product concentration [ C ] "]Is the concentration of the target product.
By oxidation of styrene with CO2The catalysts were evaluated as model reactions with cycloaddition to produce styrene carbonate, and the catalytic results are shown in table 1.
When the reaction is carried out without a cocatalyst (Table 1, item 1) or at 100 ℃ and 1atm CO2When only TBAB (table 1, entry 2) was used under pressure, there was only a small amount of product. This process indicates that a catalyst and a cocatalyst are essential for the cycloaddition reaction. Items 3-9 show that different types of catalysts have different catalytic activities. FeⅢ 4(Fe(CN)6)3The catalyst has good catalytic effect that the conversion rate and the selectivity are both 99 percent in the presence of a cocatalyst (TBAB). Fe when TBAC (item 8) or TBAI (item 9) is used as a cocatalystⅢ 4(Fe(CN)6)3The catalytic effect of (a) cannot achieve the good effect of the former. From the above studies, it can be concluded that Lewis acids and nucleophilic reagents in the reaction are the necessary conditions for the reaction. The three co-catalysts differ in the halogen ion, so that the co-catalyst has a major influence on the cycloaddition reaction, mainly the halogen ion. From Table 1, the activity is as TBAB>TBAI>TBAC decreases in order due to the nucleophilic nature (Cl) of the halide anion->Br->I-) And leaving ability (I)->Br->Cl-). From 3,10-13, it was found that the temperature also had a large influence on the cycloaddition reaction. As the temperature decreases, the conversion and selectivity also decrease. Lower reaction temperatures will produce more by-products, and therefore higher temperatures are beneficial for achieving better yields.
TABLE 1 results of styrene oxide and CO2 reaction with different catalysts
Reaction conditions are as follows: styrene oxide (5mmol), 2.5 mol% cocatalyst, catalyst (10mg), CO2Pressure (1atm), reaction time (3h), GC-MS to determine conversion and selectivity.
In order to investigate the broad spectrum of catalysts, the present invention performed cycloaddition reactions on other types of epoxides at 1atm pressure and 100 ℃. The conversion of different types of epoxides into related products and the conversion, selectivity are shown in table 2. As can be seen from Table 2, the conversion and selectivity were good for most of the substrates. In the presence of TBAB and catalyst, the conversion and selectivity of epichlorohydrin are 99%, mainly the electron-withdrawing ability of chlorine atom. The conversion of cyclohexene oxide was not effective, probably due to steric hindrance.
TABLE 2 epoxide and CO2Cycloaddition reaction of
a reaction condition: epoxide (5mmol), 2.5 mol% catalyst, catalyst (10mg), CO2 pressure (1atm), reaction time (3h), conversion and selectivity were determined by GC-MS. b reaction time (5 hours)
Third, catalyst recycling
Third, catalyst recycling
A good catalyst should not only have good catalytic activity but also have good recyclability and recyclability. The invention carries out the circulation of the catalyst under the condition of one atmosphere of carbon dioxide and styrene oxide at 100 ℃ without solvent by taking TBAB as a co-catalyst, centrifugally collects the catalyst after the reaction is finished, washes the catalyst with ethanol for three times, and then dries the catalyst in vacuum so as to be reused for the next reaction. The catalyst repetition performance is shown in fig. 5, and it can be seen that the catalytic performance of the catalyst is slightly reduced after five cycles. This result indicates that the catalyst has good recyclability and recyclability. Finally, we examined the catalyst with ICP after five cycles and found that the Fe content dropped from 37.39% to 33.92%.
Claims (2)
1. A method for catalytically synthesizing cyclic carbonate is characterized in that a reaction substrate, a catalyst and a cocatalyst of epoxide are added into a reaction container under normal pressure, the used cocatalyst is any quaternary ammonium salt, a reaction system is stirred and reacted in an oil bath at the temperature of 60-100 ℃ under normal pressure, products are collected by filtration after the reaction is finished, and the cyclic carbonate is obtained, wherein the catalyst is Fe with a stacking hole structure4 Ⅲ(Fe(CN)6) The preparation method is to mix FeCl2·4H2O and K3[Fe(CN)6]·6H2Dissolving O in distilled water respectively, mixing the two solutions under stirring, heating the mixture at 80 ℃ for 12 hours, centrifugally separating the obtained solid, fully washing the obtained solid with high-purity water, and drying at 80 ℃ to obtain the catalyst.
2. A method for catalytically synthesizing cyclic carbonate is characterized in that a reaction substrate, a catalyst and a co-catalyst of epoxide are added into a reaction container under normal pressure, the used co-catalyst is any quaternary ammonium salt, a reaction system is stirred and reacted in an oil bath at the temperature of 60-100 ℃ under normal pressure, and after the reaction is finished, a product is collected by filtration to obtain the cyclic carbonate, wherein the catalyst is KM with a stacking hole structure4(FeⅢ(CN)6)3Wherein M is Co, Ni or Zn, and the catalyst is prepared by mixing Co (NO3)2·6H2O、Ni(NO3)26H2O or ZnCl2 and K3[Fe(CN)6]·6H2Dissolving O in distilled water respectively, mixing the above two solutions under stirring, heating the mixture at 80 deg.C for 12 hr, centrifuging to obtain solid, and washing with high-purity waterDrying treatment at 80 ℃ after the solid to obtain the catalyst.
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