CN105817268B - The Ni-B catalyst of terpolymer nanosphere load - Google Patents
The Ni-B catalyst of terpolymer nanosphere load Download PDFInfo
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- CN105817268B CN105817268B CN201610317780.1A CN201610317780A CN105817268B CN 105817268 B CN105817268 B CN 105817268B CN 201610317780 A CN201610317780 A CN 201610317780A CN 105817268 B CN105817268 B CN 105817268B
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- catalyst
- nickel
- terpolymer
- nanosphere
- sodium borohydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides the Ni B catalyst of terpolymer nanosphere load, the catalyst is with N N-isopropylacrylamides, 2 acrylamide, 2 methyl propane sulfonic acid, N N-tert-butyl acrylamides are comonomer, N, N ' methylene-bisacrylamides are crosslinking agent, and potassium peroxydisulfate is initiator, passes through surfactant- free emulsion polymerization synthesis of ternary copolymer nano ball；Nanosphere, which is distributed in nickel sulfate solution, adsorbs nickel ion, and the nickel ion of absorption is reduced to nickel metal after centrifugation；Terpolymer nanosphere containing a small amount of nickel metal is distributed in nickel plating solution and carries out chemical nickel plating, obtains the Ni B catalyst of terpolymer nanosphere load.Catalyst raw material provided by the invention is easy to get, synthetic method is simple, high catalytic efficiency, operation are simple, can be repeated as many times use, is suitble to catalysis preparing hydrogen by sodium borohydride hydrolysis reaction.
Description
Present patent application is the applying date on May 30th, 2014, application No. is 201410240494.0, entitled three
The divisional application of the Chinese patent application of the Ni-B catalyst of membered copolymer nanosphere load and its preparation method and application.
Technical field
The invention belongs to materials science field, more particularly to a kind of polymer composite, in particular to one kind three
Ni-B catalyst, preparation method and its application in catalysis preparing hydrogen by sodium borohydride hydrolysis reaction of membered copolymer load.
Background technology
In order to future source of energy is overcome to lack and the problems such as environmental pollution, find reproducible green energy resource be Present Global urgently
The important topic that need to be solved.At present, Hydrogen Energy is considered as one of optimal clean energy resource in future source of energy structure, the energy of hydrogen
Metric density is high, and combustion product is water, is a kind of green energy resource.Hydrogen source is also extremely wide, can not only pass through natural gas weight
The approach such as whole, biomass cracking produce, and can be obtained by solar energy electrolysis or photocatalytic water, therefore hydrogen is a kind of potential
Instead of the novel energy of the traditional energies such as gasoline or diesel oil.But Hydrogen Energy is in actual application, also by preparation Hydrogen Energy and
Two big key factor of Hydrogen Energy is storeed to restrict.Due to the theoretical hydrogen storage amount 10.6wt% of sodium borohydride, using sodium borohydride into
Row storage hydrogen is paid close attention to by more and more people.
But sodium borohydride hydrolytic hydrogen production under no catalysts conditions is slower, it is therefore desirable to add in catalyst to add
Its fast reaction.At present, common catalyst has noble metal Ru, Pt, Pd and transition group non-noble metal Ni, Co etc., these catalysis
Agent has the high catalytic activity of comparison so that the hydrogen of high-purity can realize controlled release from sodium borohydride solution.
Chinese patent application 201010134982.5 reports the Ru/C catalyst by the use of porous carbon materials as carrier, this
Catalyst surface area is big, and activity is high, long lifespan, but noble metal Ru reserves are limited, and expensive, practical application is not extensive.
Chinese patent application 201310068396.9 reports a kind of Co-B catalyst, by with CeO2Wait rare earth oxides
Mixing, to be catalyzed preparing hydrogen by sodium borohydride hydrolysis, this method is simple, and hydrogen yield is higher.But this DNAcarrier free catalyst is easily sent out
It is raw to reunite, catalytic activity is caused drastically to decline, it is poor to reuse ability.
For sodium borohydride hydrolyst there are higher price or catalytic activity are low, performance is bad at present, and catalyst repeats profit
With with regenerability it is poor the defects of.
Invention content
In order to overcome the shortcomings of the metallic catalyst of current support type, first aspect present invention purpose is to provide a kind of raw material
It is easy to get, synthetic method is simple, high catalytic efficiency, operation are simple, can be repeated as many times the Ni-B of macromolecule loading used
Nanocatalyst, it is suitble to be catalyzed preparing hydrogen by sodium borohydride hydrolysis reaction.
To achieve the above object, the present invention takes following technical proposals to realize：
A kind of Ni-B catalyst of terpolymer nanosphere load, is prepared using following raw material and method：With N- isopropyls
Base acrylamide (NIPAM), 2- acrylamide-2-methyl propane sulfonics (AMPS), N tert butyl acrylamide (NtBAM) are copolymerization
Monomer, N, N '-methylene-bisacrylamide (MBAM) are crosslinking agent, and potassium peroxydisulfate (KPS) is initiator, is gathered by soap-free emulsion
Legal synthesis of ternary copolymer p (NIPAM-co-AMPS-co-NtBAM).It is molten that terpolymer nanosphere is distributed to nickel sulfate
In liquid, absorption a period of time, centrifugation restores the nickel ion in absorption；By the terpolymer nanometer containing a small amount of nickel metal
Ball, which is distributed in nickel plating solution, carries out chemical nickel plating, obtains the Ni-B catalyst of terpolymer load.
In the present invention：
NIPAM refers to n-isopropyl acrylamide, and AMPS refers to 2- acrylamide-2-methyl propane sulfonics, and NtBAM refers to N-
N-tert-butyl acrylamide, MBAM refer to N, and N '-methylene-bisacrylamide, KPS refer to potassium peroxydisulfate.Wherein terpolymer is born
The Ni-B catalyst of load is made using following preparation method：
A. the preparation of terpolymer nanosphere：Weigh 1.13g n-isopropyl acrylamide, 0.104g 2- acryloyls
Amine -2- methyl propane sulfonic acids, 0.254g N tert butyl acrylamides, 0.046g N, N '-methylene-bisacrylamide are in 100mL tri-
In mouth flask, 45mL distilled water is added in, under nitrogen atmosphere 70 DEG C of stirring and dissolvings, then add in 5mL and contain 0.053g persulfuric acid
Aqueous solutions of potassium is closed after continuing logical 10min nitrogen, and sealing reaction 5h obtains terpolymer nanosphere lotion；
B. the pretreatment of terpolymer nanosphere：15mL terpolymer nanosphere lotions are taken in 35mL nickel sulfate solutions
In, the wherein a concentration of 0.04g/mL of nickel sulfate solution stirs 15h, and centrifugation is centrifuged repeatedly with water, until by physical absorption
Until nickel ion is all washed off, then by solid be redispersed in 50mL contain come in 0.1g sodium borohydride aqueous solutions reduced nickel from
Son is stirred to react, and as storing solution, is reacted for next step；
The preparation of c.Ni-B catalyst：Terpolymer nanospheres of the 1mL by pretreatment is measured in containing potassium tartrate
Sodium, sodium hydroxide, nickel sulfate, sodium borohydride nickel plating solution in, mechanical agitation 2h at 90 DEG C, after reaction, centrifugation, repeatedly
It is centrifuged with water, obtained catalyst is dried, obtains Ni-B finished catalysts.
Further, a concentration of 108g/L of the step c mesotartaric acid potassium sodium, a concentration of 50g/L of sodium hydroxide, sulfuric acid
A concentration of 39.8g/L of nickel, a concentration of 1.6-6.7g/L of sodium borohydride.
Further, in the step c sodium borohydride a concentration of 5g/L.
In the preparation method：
The initiator be potassium peroxydisulfate, crosslinking agent N, N '-methylene-bisacrylamide.
The Ni-B nanocatalysts that the third aspect of the present invention purpose is to provide the load of terpolymer nanosphere are being catalyzed
Application in preparing hydrogen by sodium borohydride hydrolysis reaction, the method applied in specific catalysis reaction are as follows：Ni-B catalyst is disperseed
Yu Shuizhong is poured into single port bottle, is placed in water bath with thermostatic control, then pours into sodium borohydride aqueous solution, clogs bottleneck with plug rapidly, is treated
When having the continuous air bubbles to emerge, the hydrogen of generation is collected in timing.
The catalyzed side reaction formula being related to is as follows：
Beneficial effects of the present invention are as follows：
(1) macromolecule loading Ni-B nanocatalysts prepared by the present invention are terpolymer
P (NIPAM-co-AMPS-co-NtBAM) loads Ni-B catalyst, wherein, for loading the terpolymer of Ni-B
Nanosphere molecular structure is as shown in Equation 1, and the above-mentioned Ni-B catalyst loaded using terpolymer nanosphere can be repeated several times back
It receives and uses, and catalyst is easily separated and stable in the air from reaction system.
Formula 1：For the molecular structure of the terpolymer nanosphere of carried metal.
(2) reactivity of the Ni-B catalyst produced by the present invention when being catalyzed sodium borohydride is higher, hydrogen yield also phase
To higher.
(3) Ni-B nanocatalysts catalysis NaBH4The activation energy of hydrolytic hydrogen production reaction is than other existing many containing only Ni
The activation energy of the catalyst system and catalyzing of metal is low.
Description of the drawings
Fig. 1 is the influence that different temperatures hydrolyzes sodium borohydride initial hydrogen-producing speed；
Fig. 2 is ln k~1/T relational graphs.
Fig. 3 is the TEM photos of the Ni-B catalyst of the preferable embodiment terpolymer load of the present invention one.
Fig. 4 is the TEM photos of the Ni-B catalyst of another preferable embodiment terpolymer load of the invention.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
Embodiment 1：
The preparation of Ni-B nanocatalysts
(1) preparation of terpolymer nanosphere：
Weigh 1.13g n-isopropyl acrylamide, 0.104g 2- acrylamide-2-methyl propane sulfonics, 0.254g uncles N-
Butylacrylamide, 0.046g N, N '-methylene-bisacrylamide add in 45mL distilled water in 100mL three-necked flasks,
Then the lower 70 DEG C of stirring and dissolvings of nitrogen atmosphere add in 5mL and contain 0.053g persulfate aqueous solutions, after continuing logical 10min nitrogen
It closes, sealing reaction 5h.
(2) pretreatment of terpolymer nanosphere：
Copolymer emulsion made from 15mL above-mentioned steps is taken to be scattered in 35mL to contain in 1.39g nickel sulfate solutions, is stirred
15h is mixed, is centrifuged, is centrifuged with water, solid is dispersed in 40mL water repeatedly then, it is water-soluble that addition 10mL contains 0.1g sodium borohydrides
Liquid is stirred to react, as storing solution.
(3) preparation of Ni-B catalyst：
Copolymer emulsions of the 1mL by pretreatment is measured in 60mL nickel plating aqueous solutions, which contains 6.5g
Sodium potassium tartrate tetrahydrate, 3.0g sodium hydroxides, 2.39g nickel sulfates, 0.3g sodium borohydrides nickel plating solution, mixed solution is poured into
In the three-necked flask of 250mL, the speed mechanical stirring 2h of 410r/min at 90 DEG C, after reaction, centrifugation is washed with water repeatedly
It washs, centrifuges, obtained catalyst is dried.
Embodiment 2：
The preparation method is the same as that of Example 1, difference lies in：In the preparation of Ni-B catalyst, sodium borohydride makes in nickel plating solution
Amount is 0.1g.
Embodiment 3：
The preparation method is the same as that of Example 1, difference lies in：In the preparation of Ni-B catalyst, sodium borohydride makes in nickel plating solution
Amount is 0.2g.
Embodiment 4：
The preparation method is the same as that of Example 1, difference lies in：In the preparation of Ni-B catalyst, change hydroboration in nickel plating solution
The amount that sodium uses is 0.4g.
Embodiment 5：
Different catalysts prepared by above-mentioned 1-4 embodiments are respectively applied to catalysis preparing hydrogen by sodium borohydride hydrolysis reaction, and
Detect catalytic effect.
It is specific as follows：Take 4mg catalyst and 0.095g NaBH4It in there-necked flask, is placed in water bath with thermostatic control (45 DEG C), uses
Glass ground joint plug clogs bottleneck, checks air-tightness, adds in 50mL distilled water in there-necked flask rapidly, and continuous air bubbles to be had are emerged
When, timing collects the hydrogen of generation, measures its volume.
Interpretation of result：
1. the different catalysts of above-described embodiment 1~4, that catalysis preparing hydrogen by sodium borohydride hydrolysis reacts as a result, statistics is as follows
Shown in table 1.
Table 1, different catalysts are catalyzed the result of above-mentioned preparing hydrogen by sodium borohydride hydrolysis reaction (45 DEG C)：
| Serial number | It is collected into hydrogen total volume/mL | Ultimate yield/% |
| Embodiment 1 | 210 | 93.3 |
| Embodiment 2 | 197 | 87.6 |
| Embodiment 3 | 207 | 92.0 |
| Embodiment 4 | 206 | 91.6 |
As can be seen from Table 1：These catalyst can effectively be catalyzed preparing hydrogen by sodium borohydride hydrolysis reaction, and yield is good.
In catalyst preparation process, as sodium borohydride dosage increases, the obtained nickel content on catalyst also accordingly increases, yield
It is corresponding to improve.
2. the influence for hydrolyzing initial rate to sodium borohydride in different temperatures is tested, as shown in Table 2 and Figure 1.
The influence of table 2, temperature to hydrolysis
It can be seen that according to table 2, Fig. 1：Different temperatures to sodium borohydride hydrolysis initial rate influence, with temperature by
Step raising, sodium borohydride hydrolysis initial rate improve a lot, and influence the yield of final hydrogen at different temperatures.
Fig. 2 is lnk~1/T curve graphs, wherein, k is the slope (data for being shown in Table 2) of each straight line in Fig. 1, and T is absolutely temperature
Degree.The activation energy of preparing hydrogen by sodium borohydride hydrolysis reaction is calculated according to slopeaFor 47.81kJmol-1.Document report its
Comparison such as 3 institute of table of the activation energy numerical value and the activation energy numerical value of the present invention of catalyst this hydrogen manufacture reaction of his type
Show.
Table 3, catalyst of the present invention are compared with the activation energy of other catalyst.
As can be seen from Table 3：The activation energy of the Ni-B catalyst of terpolymer load prepared by the present invention is low, used in water
NaBH in phase4Production hydrogen is very efficient.The doctoral thesis that East China University of Science Zou Yue in 2012 surpasses can also be referred to be reported
Ru/C catalysts NaBH4The activation energy of hydrolytic hydrogen production reaction is 50.74kJ/mol.Another aspect, relative to adopting
With pure Pd, pure Ru catalyst for, the present invention have more preferably cost advantage, that is, in terms of the cost performance of catalytic effect more
With advantage.
Product testing：
The Ni-B nanocatalysts that terpolymer nanosphere produced by the present invention loads are made into transmission electron microscope
(TEM) it analyzes, the typical photo of shooting is as shown in Figure 3 and Figure 4.Fig. 3 and Fig. 4 is the Ni-B catalyst of terpolymer load
TEM photos.It can be seen in terpolymer nanosphere in each width figure, nickel metal forms cluster particle and is dispersed in copolymer
In ball.
Ni-B nanocatalysts prepared by the present invention, nickel metal form metal cluster, nickel in terpolymer nanosphere
There is no the mutual reunions of bigger between metal, and comparatively surface area is big for many clusters, and activity is high.Catalyzing manufacturing of hydrogen reaction knot
Shu Hou, and can be detached catalyst with reaction solution by the modes such as simply filtering, centrifuging, reach the effect repeatedly used
Fruit.
Although the invention has been described by way of example and in terms of the preferred embodiments, but it is not for limiting the present invention, any this field
Technical staff without departing from the spirit and scope of the present invention, may be by the methods and technical content of the disclosure above to this hair
Bright technical solution makes possible variation and modification, therefore, every content without departing from technical solution of the present invention, and according to the present invention
Technical spirit any simple modifications, equivalents, and modifications made to the above embodiment, belong to technical solution of the present invention
Protection domain.
Claims (2)
1. a kind of Ni-B catalyst of terpolymer nanosphere load, which is characterized in that the catalyst is with N- isopropyls third
Acrylamide, 2- acrylamide-2-methyl propane sulfonics, N tert butyl acrylamide are comonomer, N, N '-methylene bisacrylamide acyl
Amine is crosslinking agent, and potassium peroxydisulfate is initiator, passes through surfactant- free emulsion polymerization synthesis of ternary copolymer nano ball；Nanosphere disperses
Nickel ion is adsorbed into nickel sulfate solution, the nickel ion of absorption is reduced to nickel metal after centrifugation；A small amount of nickel metal will be contained
Terpolymer nanosphere, which is distributed in nickel plating solution, carries out chemical nickel plating, and the Ni-B for obtaining the load of terpolymer nanosphere is urged
Agent；
The preparation method of the Ni-B catalyst of wherein described terpolymer nanosphere load, includes the following steps：
A. the preparation of terpolymer nanosphere：Weigh 1.13g n-isopropyl acrylamide, 0.104g 2- acrylamides -2-
Methyl propane sulfonic acid, 0.254g N tert butyl acrylamides, 0.046g N, N '-methylene-bisacrylamide are in tri- mouthfuls of burnings of 100mL
In bottle, 45mL distilled water is added in, under nitrogen atmosphere 70 DEG C of stirring and dissolvings, then add in 5mL and contain 0.053g potassium peroxydisulfate water
Solution is closed after continuing logical 10min nitrogen, and sealing reaction 5h obtains terpolymer nanosphere lotion；
B. the pretreatment of terpolymer nanosphere：15mL terpolymer nanosphere lotions are taken in 35mL nickel sulfate solutions,
The wherein a concentration of 0.04g/mL of nickel sulfate solution, stir 15h, centrifugation, centrifuged repeatedly with water, until by the nickel of physical absorption from
It is sub all wash off until, solid be then redispersed in 50mL contain and restore nickel ion in 0.1g sodium borohydride aqueous solutions, stir
Reaction is mixed, as storing solution, is reacted for next step；
The preparation of c.Ni-B catalyst：Terpolymer nanospheres of the 1mL by pretreatment is measured in containing sodium potassium tartrate tetrahydrate, hydrogen
Sodium oxide molybdena, nickel sulfate, sodium borohydride nickel plating solution in, mechanical agitation 2h at 90 DEG C, after reaction, centrifugation, use water repeatedly
Obtained catalyst is dried, obtains Ni-B finished catalysts by centrifugation；
A concentration of 108g/L of the step c mesotartaric acid potassium sodium, a concentration of 50g/L of sodium hydroxide, nickel sulfate it is a concentration of
39.8g/L, a concentration of 1.6-6.7g/L of sodium borohydride.
2. Ni-B catalyst according to claim 1, which is characterized in that a concentration of 5g/ of sodium borohydride in the step c
L。
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| JP2531588B2 (en) * | 1987-07-13 | 1996-09-04 | 出光興産株式会社 | Method for producing metal-supported particles having ferromagnetism |
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