CN106311326B - A kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst - Google Patents
A kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst Download PDFInfo
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- CN106311326B CN106311326B CN201610591289.8A CN201610591289A CN106311326B CN 106311326 B CN106311326 B CN 106311326B CN 201610591289 A CN201610591289 A CN 201610591289A CN 106311326 B CN106311326 B CN 106311326B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
- B01J31/067—Molecularly imprinted polymers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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Abstract
The present invention provides a kind of preparation methods of " selectivity/non-selective " adjustable Ni base catalyst.Function monomer used in the preparation method is the function monomer of the segment containing long molecule, for constructing molecule segment mobility mechanism.Substrate and active constituent presoma are dissolved in dimethyl sulfoxide by this method, after ultrasonic disperse and cooperation, function monomer, crosslinking agent and initiator is added, nitrogen deoxidation is then led into solution, sealing is placed on irradiation under ultraviolet lamp and causes polymerization, forms catalyst precursor.Ni ion is through sodium borohydride reduction in catalyst precursor, products therefrom is after ethyl alcohol, acetic acid elute the substrate of trace, it is cleaned repeatedly with water, vacuum drying, " selectivity/non-selective " adjustable Ni base catalyst is obtained, and can be used for the preparation of the step-by-step reduction and o-phenylenediamine of nitro isomer.The features such as simple, raw material is easy to get, is easy to operate the preparation method with technical principle, easily prepared.
Description
Technical field
The invention belongs to be catalyzed new technical field, and in particular to a kind of " selectivity/non-selective " adjustable Ni base catalysis
The preparation method of agent.
Background technique
Catalysis is the foundation stone of modern chemical industry, realizes that highly selective and specific catalytic action is that current industry is badly in need of
The great matter of science and technology solved.Based on molecular recognition, imprinted polymer be carrier, metal nanoparticle is active group
The appearance of the high-selectivity catalyst preparation method of part creates condition for the realization of this target.The reason is that the system
Preparation Method has combined the molecule distinguishability of carrier material and the catalytic action ability of metal-based catalyst, thus to realize
The effect of highly selective and specific catalytic is paved the way.
It is known that the preparation of above-mentioned high-selectivity catalyst is usually subjected to: (1) making active component presoma metal ion
Cooperated with specific substrates, forms template molecule；(2) function monomer is added, keeps template molecule complementary with function monomer generation
Interaction, carry out self assembly；(3) crosslinking agent is added, bulk polymerization is generated around self-assembled composite；(4) living
Property metal precursor metal ion is reduced to metal nanoparticle through reducing agent, is fixed in cross-linked polymer carrier；(5) it removes
Substrate molecule (non-covalent bond is generally eluted by solvent, and covalent bond then passes through hydrolysis) in polymer support, formation and substrate
Molecular structure is complementary, the arrangement of function base determines, the catalyst with molecular recognition function.Due to this feature, catalyst is prepared
Than more " man-made antibody ", the molecule distinguishability high to substrate molecule is shown, and taken into account metal-based catalyst
Catalytic action ability, to make it possible highly selective and specific catalytic action.
However, in practical applications, most catalytic action processes are related to multi-step chemical reaction and multi-component reaction object, often need
Control catalytic reaction process, fill selective reaction perhaps and carried out in particular step, rather than selective reaction in other steps into
Row, such as nitro isomer step-by-step reduction and o-phenylenediamine preparation, to avoid unnecessary side reaction.Therefore, catalysis row
The preparation for being directly realized by " selectivity/non-selective " adjustable catalyst is expected always in the development of industry.However, being based on existing catalysis
The technology of preparing and method of agent, people can not be directly realized by the adjustable catalytic action process of selectivity, and domestic and foreign literature and specially
Benefit is without related technology reports, to force new technology, the new method of people's development catalyst preparation.
In the development process of science and technology, the emergence of new branch of science invariably accompanies new technology, new material chemical anti-
Application in answering.The progress of catalytic field is even more so, various challenges is faced constantly in complications, and eventually led to catalyst
Prepare the appearance of new principle, new method.The preparation for realizing " selectivity/non-selective " adjustable catalyst, must fundamentally solve
Certainly reactant leads to the key technology of metal nanoparticle selectivity adjustable inlet.Knowledge is derived from naturally, derived to natural phenomena
Understanding and cognition.After 1 years Natural Selection and Evolutions, natural biology and its tissue and the perfect compatibility of environment and ring
Answering mechanism is that the realization of this target creates condition.Natural biology such as sea cucumber etc. during evolution, gel body group
It knits and forms " soft/hard " dormancy mechanism capable of reversing.When temperature is below about 20 DEG C, sea cucumber enters dormant state, machine
Body tissue becomes hard such as huge rock, to escape predator's predation and reduce energy consumption；Conversely, when temperature is higher than 20 DEG C, sea cucumber
Revival, body tissue activation, becomes soft gelatinous polymer, to create conditions for activity and search of food.Although extra large
Join exact dormancy mechanism still up for research, but the glass of people's gelatin polymer is reminded in the commutation behavior of its spawn
Change transformation behavior, it may be assumed that (be lower than transition temperature) under the conditions of lower temperature, the movement of gelatin polymer molecule segment " is frozen
The characteristic firmly such as huge rock is presented in knot ", polymer；Conversely, molecule segment mobility sharply increases when being higher than transition temperature,
The property of soft hydrogel is presented in polymer.By it is this it is unique in a manner of, gelatin polymer and its molecule segment mobility induce
Polymeric inner phase transition behavior.Although natural biology and environment compatibility and response mechanism are its nature, developed with catalyst
It is unrelated, but the compatibility and response mechanism of itself and environment are paved the way for the realization of selective adjustable inlet, are catalyst preparation
The formation of new technology, new method lays the foundation.
Summary of the invention
The purpose of the present invention is being directed to current industry great matter of science and technology urgently to be solved, provide it is a kind of " selectivity/
It is non-selective " preparation method of adjustable Ni base catalyst.This method introduces the concept of natural biology and environmental compatible, by molecule
The mechanism of segment mobility is introduced to the preparation of Ni base catalyst, induces imprinted polymer carrier inside phase by the variation of temperature
Transformation behavior causes the adjustable reactant entrance of selectivity, to realize " selectivity/non-selective " adjustable Ni base catalyst
Preparation.Monomer used by the preparation method and active component presoma Ni ion are common monomer and metal ion, tool
There is raw material to be easy to get, the features such as convenient, principle is simple, easily prepared of drawing materials.
The preparation method of " selectivity/non-selective " adjustable Ni base catalyst of the invention a kind of, by the following method into
Row: substrate to be measured and active component presoma are dissolved in dimethyl sulfoxide, and after ultrasonic disperse and sufficiently cooperation, function is added
Monomer, crosslinking agent and initiator, then lead to nitrogen deoxidation into solution, and sealing is placed on irradiation under ultraviolet lamp and causes polymerization, shape
At catalyst precursor.Ni ion is through sodium borohydride reduction in catalyst precursor, and products therefrom is through Ethanol-Acetic Acid mixed solution
It after the substrate for eluting trace, is cleaned repeatedly with water, vacuum drying is catalyzed to get to " selectivity/non-selective " adjustable Ni base
Agent.
The active component presoma is Ni ionic compound, it is therefore preferable to nickel nitrate.
The substrate to be measured is nitro compound, it is therefore preferable to nitroaniline.
The function monomer is the function monomer of the segment containing long molecule, for constructing molecule segment mobility concept, preferably
Ground is 6- heptenoic acid or 7- octenoic acid.
The crosslinking agent is that there are two the polymerisable monomers of activity double key for tool, it is therefore preferable to N, N- methylene bisacrylamide acyl
Amine.
The initiator is that can carry out light-initiated initiator, it is therefore preferable to azodiisobutyronitrile.
The ultrasonic disperse and cooperation time are 20-30 minutes；
The time of the logical nitrogen deoxidation is 5-10 minutes；Ultraviolet lamp irradiation time is 20-30 hours.
The dosage of the dimethyl sulfoxide is can be completely dissolved substrate, active constituent presoma, function monomer, crosslinking agent and draw
It sends out subject to agent；
The molar ratio of the substrate to be measured and active component presoma dosage is less than or equal to the maximum coordination number 4 of Ni ion；
Dosage of crosslinking agent is 2-4 times of function monomer mole；Initiator amount be subject to can initiated polymerization, be function monomer matter
The 2~15% of amount.
In the Ethanol-Acetic Acid mixed solution, the volume ratio of ethyl alcohol and acetic acid is 9:1.
The present invention caters to current industry great matter of science and technology urgently to be solved, and the Ni base catalyst of preparation can be directly real
Existing " selectivity/non-selective " adjustable catalytic action, and can be used for the step-by-step reduction of nitro isomer and the system of o-phenylenediamine
It is standby, it has the following prominent advantages:
(1) compared with the preparation of traditional imprinted polymer/catalyst with metal nanoparticles, invention introduces natural biologies
With the concept of environmental compatible, the adjustable reactant entrance of selectivity is caused, realizes " selectivity/non-selective " adjustable catalyst
Preparation；
(2) compared with non-response metal-based catalyst, the present invention introduces the mechanism of molecule segment mobility to catalyst
Preparation, imprinted polymer carrier inside is induced by the variation of temperature and compares change, authorizes metal-based catalyst intelligent response
Ability.
(3) the technology of the present invention principle is simple, easy to operate, easily prepared, and required equipment requirement is not high, it is easy to accomplish big rule
Mould industrialized production.
Detailed description of the invention
Fig. 1 is the technical principle of prepared Ni base catalyst in the embodiment of the present invention 1.
Fig. 2 is the FT-IR spectrum of prepared Ni base catalyst in the embodiment of the present invention 1.
Fig. 3 is the TEM photo of prepared Ni base catalyst in the embodiment of the present invention 1.
Fig. 4 is the SEM photograph of prepared Ni base catalyst in the embodiment of the present invention 1.
Fig. 5 is that volt-ampere DCV figure is desorbed in the dynamic of prepared Ni base catalyst and substrate interaction in the embodiment of the present invention 1
Fig. 6 is prepared Ni base catalyst dynamic light scattering DLS transformation curve in the embodiment of the present invention 1.
Fig. 7 is " selectivity/non-selective " adjustable catalytic action of prepared Ni base catalyst in the embodiment of the present invention 1,
A-32 DEG C, B-42 DEG C.
Fig. 8 is " selectivity/non-selective " adjustable catalytic action of prepared Ni base catalyst in the embodiment of the present invention 2,
A-35 DEG C, B-45 DEG C.
Fig. 9 is " selectivity/non-selective " adjustable catalytic action of prepared Ni base catalyst in the embodiment of the present invention 3,
A-25 DEG C, B-40 DEG C.
Figure 10 is " selectivity/non-selective " adjustable catalytic action of prepared Ni base catalyst in the embodiment of the present invention 4,
A-30 DEG C, B-41 DEG C.
Specific embodiment
It is for a more detailed description to the present invention with embodiment below.These embodiments are only the preferred embodiment for the present invention
Description, rather than the limitative examples of the scope of the invention.Without departing from the essence of the present invention, art technology
Conspicuous improvement that personnel make, replacement or modification belong to the range of embodiment of the present invention description.
Embodiment 1:
Substrate paranitroanilinum (0.5mmol) and active constituent presoma nickel nitrate (0.25mmol) are dissolved in diformazan Asia
In sulfone (10mL), through ultrasonic disperse and after cooperation 25 minutes, function monomer 7- octenoic acid (1.0mmol), the Asia crosslinking agent N, N is added
Bisacrylamide (3.5mmol) and initiator azodiisobutyronitrile (0.1g) are then led to nitrogen deoxidation 8 into solution and are divided
Clock, sealing are placed on irradiation under ultraviolet lamp and cause polymerization (24 hours), form catalyst precursor.In catalyst precursor Ni from
Son is restored through excess sodium borohydrate (2.5mmol), and products therefrom is through ethyl alcohol (90vol-%)-acetic acid (10vol-%) mixed solution
It after the paranitroanilinum for eluting trace, is cleaned, is dried in vacuo to get adjustable Ni base catalyst (its of selectivity is arrived repeatedly with water
Technical principle is shown in Fig. 1；Labeled as " MIP-Ni-NA-L ", wherein MIP is imprinted polymer carrier, Ni is nickel nano particle, NA is
Paranitroanilinum, L are long-chain function monomer 7- octenoic acid).
For the sake of comparison, and consider the effect of long-chain function chain, the present embodiment is under similarity condition except without using NA
And outside NA and Ni preparation NIP-Ni-L and NIP-L, also it is prepared for the MIP-Ni-NA of no long-chain function chain.With MIP-Ni-NA-
The preparation of L, NIP-Ni-L do not use substrate NA, and the preparation of NIP-L is simultaneously without using substrate NA and active constituent Ni.MIP-
Ni-NA is free of long-chain function chain, in addition to replacing 7- octenoic acid with the acrylic acid of same mole in preparation process, remaining with
MIP-Ni-NA-L prepares identical (NIP label preparation process does not use substrate, is the polymer support of non-substrate trace).
The FTIR spectrum of these types of catalyst, TEM photo and SEM photograph is set forth in Fig. 2, Fig. 3 and Fig. 4, to its group
It is characterized at, structure and form, shows that MIP-Ni-NA-L catalyst has composition, structure and shape designed by the present invention
State, wherein the nickel nano particle of the size containing about 20nm.
The interaction for preparing catalyst and substrate is measured by the desorption of catalyst surface immunoabsorbent substrate, passes through substrate dynamic
The current potential size of volt-ampere DCV figure is desorbed, obtains catalyst to the affinity of substrate.By compare substrate trace catalyst with it is non-
Substrate trace catalyst obtains catalyst to the molecule distinguishability of substrate, and the result is shown in Fig. 5.By the MIP-Ni- of substrate trace
NA-L and MIP-Ni-NA is rendered obvious by out the higher affinity of NIP-Ni-L and NIP-L of more non-substrate trace, shows preparation
MIP-Ni-NA-L catalyst is the Ni base catalyst with molecule distinguishability designed by the present invention.
The temperature sensitive transformation behavior of catalyst is detected by dynamic light scattering DLS, and the temperature by changing system obtains catalyst
The variation (Rc) of volume.By comparing the catalyst that long-chain includes and the catalyst for being free of long-chain, long-chain function chain is obtained to system
The contribution of standby catalyst transformation behavior, the result is shown in Fig. 6.Long-chain function chain is introduced to the preparation of MIP-Ni-NA-L catalyst, is awarded
MIP-Ni-NA-L Thermo-sensitive phase transformation ability is given, transformation temperature appears in about 37 DEG C.
Based on the measurement to transformation behavior, it is selected above 32 and 42 DEG C the bottom of in transformation temperature respectively and compares measurement.
Catalytic performance test uses following system: being reduced to probe with specific substrate paranitroanilinum and the like meta nitro aniline
It is water-soluble to be added to the sodium borohydride that 2mL concentration is 2.0 μm of oL/mL for reaction, the solution for being 0.06 μm of ol/mL by 1mL concentration of substrate
In liquid.MIP-Ni-NA-L obtained by the present embodiment and reference catalyst are added on above-mentioned system respectively, make the concentration of catalyst
It for 1.0mg/mL, is measured, the result is shown in Fig. 7.Under the conditions of 32 DEG C, the MIP-Ni-NA-L catalyst of preparation is to specificity
Substrate paranitroanilinum shows the feature of highly selective catalytic action；In contrast, under the conditions of 42 DEG C, MIP-Ni-NA-L
Selectivity is not showed substantially to paranitroanilinum and the like meta nitro aniline.The MIP-Ni-NA-L catalyst of preparation is aobvious
The feature of " selectivity/non-selective " adjustable catalysis is shown.
Embodiment 2:
It is operated with embodiment 1, long-chain function monomer is changed into 6- heptenoic acid (1.0mmol) by 7- octenoic acid, it is other complete
It is operated with embodiment 1, the Ni base catalyst MIP-Ni-NA-L that obtained transformation temperature is about 39 DEG C.It is identical in same embodiment 1
It is catalyzed under test condition, is selected above and compares measurement lower than 35 and 45 DEG C of transformation temperature, the result is shown in Fig. 8.At 35 DEG C
Under the conditions of, the MIP-Ni-NA-L catalyst of preparation shows the spy of selective catalysis effect to specific substrate paranitroanilinum
Point；In contrast, under the conditions of 45 DEG C, MIP-Ni-NA-L is to specific substrate paranitroanilinum and the like meta nitro aniline
Do not show selectivity.The MIP-Ni-NA-L catalyst of preparation equally shows " selectivity/non-selective " adjustable catalysis
Feature.
Embodiment 3:
It is operated with embodiment 1, specific substrate is changed to ortho-nitraniline, it is other to be prepared completely with embodiment 1, phase is made
The Ni base catalyst MIP-Ni-NA-L that height is about 37 DEG C.Under the identical catalysis test condition of same embodiment 1, catalysis is surveyed
Examination substrate is changed to specific substrate ortho-nitraniline and the like meta nitro aniline, is selected above and lower than the 25 of transformation temperature and 40
DEG C measurement is compared, the result is shown in Fig. 9.Under the conditions of 25 DEG C, the MIP-Ni-NA-L catalyst of preparation is to specific substrate neighbour
Nitroaniline shows the characteristics of selective catalysis effect；In contrast, under the conditions of 40 DEG C, MIP-Ni-NA-L is to specificity
Substrate o-nitrophenyl amine and the like meta nitro aniline does not show selectivity.The MIP-Ni-NA-L catalyst of preparation is same
Show the feature of " selectivity/non-selective " adjustable catalysis.
Embodiment 4:
It is operated with embodiment 1, specific substrate is changed to meta nitro aniline, it is other to be prepared completely with embodiment 1, phase is made
The Ni base catalyst MIP-Ni-NA-L that height is about 37 DEG C.Under the identical catalysis test condition of same embodiment 1, catalysis is surveyed
Examination substrate is changed to specific substrate meta nitro aniline and the like ortho-nitraniline, is selected above and lower than the 30 of transformation temperature and 41
DEG C measurement is compared, the result is shown in Figure 10.Under the conditions of 30 DEG C, the MIP-Ni-NA-L catalyst of preparation is to specific substrate
Meta nitro aniline shows the characteristics of selective catalysis effect；In contrast, under the conditions of 41 DEG C, MIP-Ni-NA-L is to special
Property substrate meta nitro aniline and the like ortho-nitraniline does not show selectivity.The MIP-Ni-NA-L catalyst of preparation is again
The secondary feature for showing " selectivity/non-selective " adjustable catalysis, shows the preparation method of Ni base catalyst of the present invention in nitro
There is certain applicability in the catalyst system of compound and the like.
Claims (6)
1. a kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst, which is characterized in that by the following method
It carries out: substrate to be measured and active component presoma is dissolved in dimethyl sulfoxide, after ultrasonic disperse and sufficiently cooperation, function is added
Then energy monomer, crosslinking agent and initiator lead to nitrogen deoxidation into solution, sealing is placed on irradiation initiation under ultraviolet lamp and polymerize,
Catalyst precursor is formed, Ni ion mixes molten through sodium borohydride reduction, products therefrom through Ethanol-Acetic Acid in catalyst precursor
It after liquid elutes the substrate of trace, is cleaned repeatedly with water, vacuum drying is urged to get to " selectivity/non-selective " adjustable Ni base
Agent；
The active component presoma is Ni ionic compound, and the substrate to be measured is nitro compound；
The function monomer is 6- heptenoic acid or 7- octenoic acid, and the crosslinking agent is N, and N- methylene-bisacrylamide is described to draw
Hair agent is azodiisobutyronitrile.
2. a kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst according to claim 1, special
Sign is that the active component presoma is nickel nitrate, and the substrate to be measured is nitroaniline.
3. a kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst according to claim 1, special
Sign is that the ultrasonic disperse and cooperation time are 20-30 minutes；The time of the logical nitrogen deoxidation is 5-10min；Ultraviolet lamp
Irradiation time is 20-30h.
4. a kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst according to claim 1, special
Sign is that the molar ratio of the substrate to be measured and active component presoma dosage is less than or equal to the maximum coordination number 4 of Ni ion；It hands over
Join 2-4 times that agent dosage is function monomer mole；Initiator is the 2~15% of function monomer quality.
5. a kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst according to claim 1, special
Sign is, in the Ethanol-Acetic Acid mixed solution, the volume ratio of ethyl alcohol and acetic acid is 9:1.
6. a kind of preparation method preparation of " selectivity/non-selective " adjustable Ni base catalyst according to claim 1
Ni base catalyst, which is characterized in that the Ni base catalyst can be directly used for the step-by-step reduction and adjacent benzene of nitro isomer
The preparation of diamines.
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| CN104162451A (en) * | 2014-07-16 | 2014-11-26 | 江苏大学 | Preparation method of high selectivity and specificity nickel-based catalyst |
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| CN104959163A (en) * | 2015-05-19 | 2015-10-07 | 江苏大学 | Controllable and adjustable metal nanoparticle-loaded polymer catalyst and preparation method thereof |
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| JP2015182010A (en) * | 2014-03-24 | 2015-10-22 | 東英産業株式会社 | Decomposition catalyst body for organic compound, production method thereof, and adsorption and decomposition method for organic compound |
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| CN104353494A (en) * | 2014-07-16 | 2015-02-18 | 江苏大学 | Preparation method of intelligent nickel-based catalyst with automatic on/off control function |
| CN104190467A (en) * | 2014-07-23 | 2014-12-10 | 江苏大学 | Preparation method of intelligent non-PNIPAm-based temperature-sensitive nickel catalyst |
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