CN104069883B - A kind of cobalt-base catalyst for alcohol oxidation generation ester and preparation method thereof and application - Google Patents
A kind of cobalt-base catalyst for alcohol oxidation generation ester and preparation method thereof and application Download PDFInfo
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Abstract
The invention belongs to liquid phase oxidation technical field, disclose a kind of cobalt-base catalyst for alcohol oxidation generation ester and preparation method thereof and application, described cobalt-base catalyst is mainly elementary composition by cobalt and carbon, nitrogen, wherein each element wt ratio is: cobalt 27.0～50.0wt%, carbon 45.0～60.0wt%, nitrogen 0.5～20.0wt%；In described cobalt-base catalyst, the particle diameter of cobalt nano-particle is 5～40nm.Described cobalt-base catalyst, with ZIF-67 for precursor, is prepared by the mode of pyrolysis in an inert atmosphere.Under described cobalt-base catalyst exists, in normal temperature and pressure atmospheric environment, without alkaline assistant, two kinds of alcohol react can prepare ester type compound.Cobalt-base catalyst of the present invention is prone to a large amount of synthesis, and has magnetic recoverable；The method utilizing the oxidation of described cobalt-base catalyst catalytic alcohol to generate ester, has the advantages such as cost is low, simple to operate, environmental protection, reaction condition is gentle, product is easily separated.
Description
Technical field
The invention belongs to liquid phase oxidation technical field, relate to a kind of cobalt-base catalyst, be specifically related to a kind of cobalt-base catalyst for alcohol oxidation generation ester and preparation method thereof and application.
Background technology
Ester group, as one of most important functional group of organic chemistry filed, is widely present in various fine chemicals, natural chemicals, polymer, can be used as food additive or cosmetics additive, and some esters can be used for medicine and other fields.Such as methyl ester is widely used as flavoring agent, solvent, diluent and extractant etc., has very high commercial value.Aromatic ester has multifunctionality to be commonly used as organic synthesis intermediate due to it, is widely used as micro-liquid crystal polymer, cosmetics, pharmaceuticals etc..
At present, research worker is mainly through four approach synthesizing ester compounds.Last century Mo mainly derivant such as acyl chlorides or the anhydride etc. of employing acid react with alcohol and synthesize, but this reaction path can generate some unwanted by-products, and cause the wasting of resources and environmental pollution (LarockRC, " Comprehensiveorganictransformations:aguidetofunctionalgr ouppreparations ", NewYork:Wiley-VCH.1999).About 2005, it is found that more direct synthesis path is to react generation ester type compound with transition-metal catalyst catalysis halogenated aryl hydrocarbon and alcohol, but this wherein to relate to halogenated aryl hydrocarbon carbonylation, reaction condition comparatively harshness is desirable that high temperature and at CO atmosphere and high pressure, and reaction system is (halogenated aryl hydrocarbon contaminated environment) not environmentally.Research worker is it is found that reacted generation ester by aldehyde and alcohol subsequently, but to add the slaine of equivalent or metal-oxide (such as potassium acid sulfate or manganese dioxide) in reaction system as oxidant.Additionally, the aldehyde in reactant is also required to be generated by alcohol oxidation, compares and take time and effort (XuB, LiuX, HaubrichJ, " Vapour-phasegold-surface-mediatedcouplingofaldehydeswith methanol ", NatureChemistry, 2010,2,61).More by-product occur in the synthesis path of three of the above ester simplicity all not and reaction, raw material availability is not high.As can obtain one of most basic chemicals in a large number from nature, directly being generated ester by alcohol is the simplest, economy, environmentally friendly synthesis approach.
Current substantial amounts of catalyst is developed and is applied to generate ester reaction with alcohol for monoreactant oxidation, including homogeneous catalysis and heterogeneous catalysis two individual system.
Homogeneous catalysis system aspect, mainly Lei in 2011 etc. are with the double; two acetonitrile palladium chloride of noble metal for catalyst, and the sodium tert-butoxide of two equivalents is alkali, and fluorine boronation silver is additive, under oxygen atmosphere, efficient catalytic alcohol generates ester (LiuC, WangJ, MengL, " Palladium CatalyzedAerobicOxidativeDirectEsterificationofAlcohols ", Angew.Chem.Int.Ed., 2011,123,5250).
Based on the viewpoint of sustainable development, research heterogeneous catalysis system has attracted the sight of more researcher.Mainly introducing catalytic oxidation alcohol in recent years below and generate the inhomogeneous reaction catalyst system and catalyzing of ester, main use is all noble metal catalyst, such as Au, Pd etc..The catalyst the most widely that heterogeneous catalysis alcohol oxidation in recent years generates used in ester is Au catalyst, and gold is nearly all dispersed on carrier and reduces golden size to improve the dispersibility of gold by research worker, and this is owing to the golden catalysis activity of smaller particle is higher.When making catalyst with this noble metal of Au, major part document all also needs to add alkali and promotes alcohol dehydrogenase process, and nearly all requires to carry out under oxygen atmosphere, and reaction temperature is also of a relatively high.Kobayashi in 2010 etc. are by synthesizing Au/Pt bimetallic catalyst, and the potassium carbonate at three equivalents is alkali, achieve alcohol oxidation and generate the reaction of ester under oxygen atmosphere.After alcohol is oxidized to aldehyde, aldehyde is preferential through hydration generation glycol, still hemiacetal is preferentially formed, and author thinks that its Au/Pt bimetallic catalyst exists coordinating effect and promoted that aldehyde generates hemiacetal, thus having promoted that this reaction carries out (KaizukaK, MiyamuraH, KobayashiS, " RemarkableEffectofBimetallicNanoclusterCatalystsforAerob icOxidationofAlcohols:CombiningMetalsChangestheActivitie sandtheReactionPathwaystoAldehydes/CarboxylicAcidsorEste rs ", JournaloftheAmericanChemicalSociety, 2010, 132, 15096).
Additionally, Stahl in 2013 etc. utilize Pd/charcoal (5wt%) catalyst, at Bi (NO3)3, Te metal coordinative role under, first with palladium for catalyst alcohol oxidation reaction in inhomogeneous reaction.Bi and Te can accelerate the productivity of reaction rate, selectivity and target product, this catalyst system and catalyzing substrate applicability is good, the esterification of the fatty alcohol of the energy most of aromatic alcohol of catalysis and more difficult reaction, but this reaction is also required to add the Feldalat KM of monovalent and need pure oxygen atmosphere (PowellAB, StahlSS, " AerobicOxidationofDiversePrimaryAlcoholstoMethylEsterswi thaReadilyAccessibleHeterogeneousPd/Bi/TeCatalyst ", OrganicLetters, 2013,15,5072).
Although increasing bibliographical information confirms that being directly synthesized ester by alcohol oxidation is a up-and-coming direction, but remain a need for catalytic efficiency and Practical Performance to catalyst further and improve.Homogeneous catalysis alcohol oxidative esterification reaction generally requires interpolation inorganic base or mineral acid, catalytic alcohol could generate ester under noble metal or visible ray, and the activity of reaction system need to promote, and separates after having reacted complex.Heterogeneous catalysis alcohol oxidative esterification reaction is required for greatly precious metal and makees catalyst, it is necessary to adding alkali and promote alcohol dehydrogenase process, and be desirable that greatly and carry out under pure oxygen atmosphere, requisite oxygen atmospheric pressure is sometimes even up to 1MPa, and reaction temperature is also of a relatively high.Due to the price of the finiteness of Precious Metals Resources and costliness thereof, finding economic and environment-friendly cheap catalyst is the key promoting alcohol direct oxidation to generate ester commercial Application.For reaction substrate, aromatic alcohol with this active group of phenyl ring existence thus activity is higher, fatty alcohol and heterocyclic alcohol reaction response activity are undesirable, are required for greatly just carrying out than the more stringent conditioned response of aromatic alcohol.
Summary of the invention
In order to overcome shortcoming and the deficiency of prior art, preparation has highly active cheap metal catalyst, and be applied under mild reaction conditions alcohol oxidation directly generate ester, the primary and foremost purpose of the present invention be in that provide a kind of for alcohol oxidation generate ester cobalt-base catalyst；
Another object of the present invention is to the preparation method that above-mentioned cobalt-base catalyst is provided；
It is still another object of the present invention to provide the application of cobalt-base catalyst.
The purpose of the present invention is achieved through the following technical solutions:
A kind of cobalt-base catalyst generating ester for alcohol oxidation, described cobalt-base catalyst is mainly elementary composition by transition metals cobalt and carbon, nitrogen, and wherein each element wt ratio is: cobalt 27.0～50.0wt%, carbon 45.0～60.0wt%, nitrogen 0.5～20.0wt%；In described cobalt-base catalyst, the particle diameter of cobalt nano-particle is 5～40nm.
A kind of preparation method according to the above-mentioned cobalt-base catalyst generating ester for alcohol oxidation, comprises the steps:
(1) preparation of metallo-organic framework material ZIF-67 and activation: weigh cabaltous nitrate hexahydrate respectively, 2-methylimidazole (writing a Chinese character in simplified form: Im) is added in water, is stirred at room temperature, obtains mixed solution；By described mixed solution centrifugation, being filtrated to get precipitation, wash unreacted part in precipitation with water, again with methanol solution rinses described precipitation；Finally described precipitation is carried out evacuation process, namely obtain metallo-organic framework material ZIF-67；
(2) preparation of catalyst: with step (1) gained metallo-organic framework material ZIF-67 for precursor, inert atmosphere heats to target temperature, isothermal pyrolysis, it is cooled to room temperature, obtain powdery product, be the described cobalt-base catalyst generating ester for alcohol oxidation.
Preferably, the molar ratio of cabaltous nitrate hexahydrate described in step (1), 2-methylimidazole and water is Co2+:Im:H2O=1:58:1100.
Preferably, the time being stirred at room temperature described in step (1) is 6～8 hours.
Preferably, step (1) described application of vacuum is for be deposited in 80～200 DEG C of evacuation 12～36h by described.
Preferably, step (2) described target temperature is 400～1200 DEG C.
Preferably, the time of step (2) described isothermal pyrolysis is 0.5～12h.
The above-mentioned application being not added with in alkali air atmosphere in catalytic alcohol oxidation generation ester at normal temperature and pressure for the cobalt-base catalyst of alcohol oxidation generation ester.
The preferred version of above-mentioned application comprises the steps: described cobalt-base catalyst and alcohol are put into reactor, is stirred reaction at normal temperatures and pressures, can produce the ester of correspondence.
Preferably, described alcohol is fragrance primary alconol, fatty alcohol or glycol；The control condition being stirred reaction under described normal temperature and pressure is reaction temperature 15～35 DEG C, and reaction pressure is normal pressure, and the stirring reaction time is 3～5 days；The mol ratio of described alcohol and cobalt-base catalyst (calculating with cobalt) is 1～10；
Preferably, described cobalt-base catalyst after 300～450 DEG C of hydrogen reducing 0.5～4h, recycling capable of circulation.
Principles of the invention:
Cobalt-base catalyst provided by the present invention is with metallo-organic framework for precursor, adopts a step pyrolysismethod to be prepared from.The advantage that catalyst precarsor ZIF-67 selected by the present invention possesses is: one, and the ZIF-67 of synthesis is smaller, and after pyrolysis, material granule is little has bigger active surface；Its two, the phosphorus content of ZIF-67 is high, can effectively hinder the reunion of cobalt nano-particle in pyrolytic process；And the nitrogen content of ZIF-67 is high, the nitrogen element in the catalyst that adulterates after pyrolysis can promote the carrying out of reaction.
The present invention has such advantages as relative to prior art and effect:
(1) cobalt-base catalyst of the present invention is prone to a large amount of synthesis, and has magnetic, utilizes Magnetic Isolation catalyst and reaction mixture after reaction, and operation is very simple.
(2) cobalt-base catalyst provided by the present invention, adopt heterogeneous catalysis system, under normal temperature and pressure conditions, it is added without alkaline assistant, alcohol oxidation can be realized efficiently and generate ester, solve the low problem needing alkaline assistant with alcohol oxidation generation ester of catalyst activity under temperate condition, avoid using traditional noble metal (gold, palladium etc.), harsh reaction condition (temperature and pressure as higher), there is the advantages such as cost is low, simple to operate, environmental protection, reaction condition is gentle, product separation is simple.
(3) cobalt-base catalyst of the present invention recycle functional.By the cobalt-base catalyst of recovery at 300～450 DEG C of hydrogen reducing 0.5～4h, the cobalt-base catalyst after reduction is reused catalysis activity and selectivity after repeatedly and is not all changed.
(4) cobalt-base catalyst catalytic alcohol of the present invention is utilized to produce the catalyst system and catalyzing of ester, reaction condition is gentle, efficient, selectivity is high and good stability, and by-product is few, it is not necessary to alkaline assistant, environmental protection, is the catalyst system and catalyzing of eco-friendly catalytic alcohol oxidation generation ester.
(5) cobalt-base catalyst of the present invention has good substrate applicability, it is possible to the various alcohol reaction of efficient catalytic generates corresponding ester, and the yield of ester reaches as high as more than 99%.
Accompanying drawing explanation
Fig. 1 is the high power transmission electron microscope picture of cobalt-base catalyst of the present invention.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Metallo-organic framework material ZIF-67 used in the present invention, can prepare according to below embodiment 1 or 2:
Embodiment 1
Weigh cabaltous nitrate hexahydrate respectively, 2-methylimidazole is added in deionized water, and molar ratio is Co2+:Im:H2O=1:58:1100, is stirred at room temperature 6 hours, obtains the mixed solution in purple；By the mixed solution centrifugation in purple, being filtrated to get the precipitation of purple, wash away unreacted part with a large amount of deionized waters, again with methanol solution rinses purple and precipitates 3 times；Finally the purple of collection is deposited in 80 DEG C of evacuation 24h, obtains metallo-organic framework material ZIF-67.
Embodiment 2
Weigh cabaltous nitrate hexahydrate respectively, 2-methylimidazole is added in deionized water, and molar ratio is Co2+:Im:H2O=1:58:1100, is stirred at room temperature 6 hours, obtains the mixed solution in purple；By the mixed solution centrifugation in purple, being filtrated to get the precipitation of purple, wash away unreacted part with a large amount of deionized waters, again with methanol solution rinses purple and precipitates 3 times；Finally the purple of collection is deposited in 200 DEG C of evacuation 24h, obtains metallo-organic framework material ZIF-67.
Cobalt-base catalyst for alcohol oxidation generation ester of the present invention can be prepared by the method described in any one of embodiment 3～10:
Embodiment 3
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 400 DEG C, isothermal pyrolysis 0.5h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 4
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 400 DEG C, isothermal pyrolysis 12h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 5
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 1200 DEG C, isothermal pyrolysis 0.5h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 6
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 1200 DEG C, isothermal pyrolysis 12h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 7
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 600 DEG C, isothermal pyrolysis 8h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 8
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 700 DEG C, isothermal pyrolysis 8h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
Embodiment 9
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 800 DEG C, isothermal pyrolysis 8h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.The high power transmission electron microscope picture of the cobalt-base catalyst for alcohol oxidation generation ester of the present embodiment gained is as it is shown in figure 1, B is the partial enlarged drawing in A square frame.
Embodiment 10
With ZIF-67 for precursor, heat in inert atmosphere to target temperature 900 DEG C, isothermal pyrolysis 8h, be cooled to room temperature；The black powder collected is the described cobalt-base catalyst generating ester for alcohol oxidation.
The scheme that the catalytic applications of the cobalt-base catalyst generating ester for alcohol oxidation of the present invention can be passed through in embodiment 11～14 realizes:
Embodiment 11
Raw alcohol that reactant shown in table 1 is arranged, described in be used for that alcohol oxidation generates the cobalt-base catalyst of ester, methanol and normal hexane (solvent) join and carry out oxidation in test tube and generate the reaction of ester, concrete reaction condition is as follows: reaction temperature 25 DEG C, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (calculates) mol ratio for 6 with cobalt, reaction atmosphere is air atmosphere, and the response time is 4 days；Having reacted rear natural cooling, Magnetic Isolation cobalt-base catalyst and reaction mixture, GC-MS detects product, and result is as shown in table 1.
The raw material of ester, product and the productivity that table 1. cobalt-base catalyst catalytic oxidation alcohol is corresponding with methanol generation
The cobalt-base catalyst reclaimed methanol washs, reduction 0.5h in 400 DEG C of atmosphere of hydrogen；Cobalt-base catalyst repeat the above steps after reduction.The productivity that described cobalt-base catalyst recycles is as shown in table 2, from table 2 it can be seen that this cobalt-base catalyst reuses 5 secondary response effects also without reduction, illustrates that this cobalt-base catalyst is very stable, can repeatedly reuse.
Cobalt-base catalyst described in table 2. recycle performance measurement result
Embodiment 12
Raw alcohol that reactant shown in table 1 is arranged, described in be used for that alcohol oxidation generates the cobalt-base catalyst of ester, methanol and normal hexane (solvent) join and carry out oxidation in test tube and generate the reaction of ester, concrete reaction condition is as follows: reaction temperature 15 DEG C, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (calculates) mol ratio for 1 with cobalt, reaction atmosphere is air atmosphere, and the response time is 3 days.Product and the result of productivity and table 1 that reaction measures after terminating are close.
Embodiment 13
Raw alcohol that reactant shown in table 1 is arranged, described in be used for that alcohol oxidation generates the cobalt-base catalyst of ester, methanol and normal hexane (solvent) join and carry out oxidation in test tube and generate the reaction of ester, concrete reaction condition is as follows: reaction temperature 35 DEG C, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (calculates) mol ratio for 1 with cobalt, reaction atmosphere is air atmosphere, and the response time is 5 days.Product and the result of productivity and table 1 that reaction measures after terminating are close.
Embodiment 14
Raw alcohol that reactant shown in table 1 is arranged, described in be used for that alcohol oxidation generates the cobalt-base catalyst of ester, methanol and normal hexane (solvent) join and carry out oxidation in test tube and generate the reaction of ester, concrete reaction condition is as follows: reaction temperature 35 DEG C, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (calculates) mol ratio for 10 with cobalt, reaction atmosphere is air atmosphere, and the response time is 4 days.Product and the result of productivity and table 1 that reaction measures after terminating are close.
The Surface Physical Chemistry property analysis of precursor ZIF-67 and cobalt-base catalyst of the present invention:
Respectively the cobalt-base catalyst of the ZIF-67 of embodiment 1 gained and embodiment 7～10 gained is carried out Surface Physical Chemistry property analysis.First carry out specific surface area and pore volume measures: ZIF-67 and cobalt-base catalyst are after 150 DEG C of vacuum drying 12h, on MicromeriticsASAP2020 analyser, carry out nitrogen adsorption desorption test when 77K thus obtaining specific surface area and the pore volume of material.Analysis result is as shown in table 3.
The pore structure data of the cobalt-base catalyst that the different carbonization temperature of table 3. prepares
From table 3, the specific surface area of cobalt-base catalyst of the present invention is about 300m2g-1, there is the aperture of Relatively centralized.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the cobalt-base catalyst generating ester for alcohol oxidation, it is characterized in that: described cobalt-base catalyst is mainly elementary composition by transition metals cobalt and carbon, nitrogen, wherein each element wt ratio is: cobalt 27.0～50.0wt%, carbon 45.0～60.0wt%, nitrogen 0.5～20.0wt%；In described cobalt-base catalyst, the particle diameter of cobalt nano-particle is 5～40nm；
The preparation method of the described cobalt-base catalyst generating ester for alcohol oxidation, comprises the steps:
(1) preparation of metallo-organic framework material ZIF-67 and activation: weigh cabaltous nitrate hexahydrate respectively, 2-methylimidazole is added in water, is stirred at room temperature, obtains mixed solution；By described mixed solution centrifugation, being filtrated to get precipitation, wash unreacted part in precipitation with water, again with methanol solution rinses described precipitation；Finally described precipitation is carried out evacuation process, namely obtain metallo-organic framework material ZIF-67；The molar ratio of cabaltous nitrate hexahydrate described in step (1), 2-methylimidazole and water is Co2+: 2-methylimidazole: H2O=1:58:1100；The time being stirred at room temperature described in step (1) is 6～8 hours；
(2) preparation of catalyst: with step (1) gained metallo-organic framework material ZIF-67 for precursor, inert atmosphere heats to target temperature, isothermal pyrolysis, it is cooled to room temperature, obtain powdery product, be the described cobalt-base catalyst generating ester for alcohol oxidation；Step (2) described target temperature is 400～1200 DEG C；The time of step (2) described isothermal pyrolysis is 0.5～12h.
2. the cobalt-base catalyst generating ester for alcohol oxidation according to claim 1, it is characterised in that: step (1) described application of vacuum is for be deposited in 80～200 DEG C of evacuation 12～36h by described.
3. the application being not added with in alkali air atmosphere in catalytic alcohol oxidation generation ester at normal temperature and pressure for the cobalt-base catalyst of alcohol oxidation generation ester according to claim 1.
4. application according to claim 3, it is characterised in that: comprise the steps: described cobalt-base catalyst and alcohol are put into reactor, be stirred reaction at normal temperatures and pressures, the ester of correspondence can be produced.
5. application according to claim 3, it is characterised in that: described alcohol is fragrance primary alconol, fatty alcohol or glycol；The control condition being stirred reaction under described normal temperature and pressure is reaction temperature 15～35 DEG C, and reaction pressure is normal pressure, and the stirring reaction time is 3～5 days；The mol ratio that described alcohol and cobalt-base catalyst calculate with cobalt is for 1～10.
6. application according to claim 3, it is characterised in that: described cobalt-base catalyst after 300～450 DEG C of hydrogen reducing 0.5～4h, recycling capable of circulation.
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| CN105552392A (en) * | 2016-01-06 | 2016-05-04 | 复旦大学 | Cobalt diselenide/graphite carbon composite material, namely oxygen reduction catalyst, and preparation method thereof |
| CN106549163B (en) * | 2016-11-03 | 2019-07-30 | 大连理工大学 | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate |
| CN108144612B (en) * | 2016-12-02 | 2020-12-29 | 中国科学院大连化学物理研究所 | Cobalt-based catalyst for synthesizing carboxylic ester by one-pot method and preparation and application thereof |
| CN106902879B (en) * | 2017-01-19 | 2019-09-10 | 湖北大学 | A kind of preparation method and applications of Co@C@MOF magnetic catalyst |
| CN108654685B (en) * | 2017-03-31 | 2021-08-24 | 南京工业大学 | Method for improving catalytic selectivity of organic matter sites |
| CN109651456B (en) * | 2018-12-31 | 2020-07-28 | 京山瑞生制药有限公司 | Preparation method of sucrose oleate with high monoester content |
| CN110575842B (en) * | 2019-10-12 | 2020-08-11 | 福州大学 | Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst |
| CN112876355B (en) * | 2019-11-29 | 2022-03-08 | 中国科学院大连化学物理研究所 | Method for preparing carboxylic ester compound by breaking carbon-carbon bond through oxidation of secondary alcohol compound |
| CN113385171A (en) * | 2021-07-14 | 2021-09-14 | 大连理工大学 | Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation |
| CN114733548A (en) * | 2022-04-09 | 2022-07-12 | 润泰化学（泰兴）有限公司 | Method for preparing methyl methacrylate by dehydrogenating and esterifying isobutyric acid |
| CN114904535B (en) * | 2022-04-26 | 2023-12-22 | 天津师范大学 | Preparation method of nano enzyme with activity superior to that of natural laccase |
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