CN104001551B - The Ni-B Catalysts and its preparation method of poly-N-tert-butyl acrylamide nanosphere load and application - Google Patents
The Ni-B Catalysts and its preparation method of poly-N-tert-butyl acrylamide nanosphere load and application Download PDFInfo
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- CN104001551B CN104001551B CN201410239496.8A CN201410239496A CN104001551B CN 104001551 B CN104001551 B CN 104001551B CN 201410239496 A CN201410239496 A CN 201410239496A CN 104001551 B CN104001551 B CN 104001551B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides Ni-B Catalysts and its preparation method and the application of the load of poly-N-tert-butyl acrylamide nanosphere, N-tert-butyl acrylamide initiated polymerization is poly-N-tert-butyl acrylamide nanosphere by described catalyst precipitation polymerization method; Nanosphere is distributed to absorbed Ni ion in nickel sulfate solution, after filtration, the nickel ion of absorption is reduced to nickel metal; Poly-N-tert-butyl acrylamide nanosphere containing a small amount of nickel metal is distributed in nickel plating solution and carries out chemical nickel plating, obtain the Ni-B catalyst of poly-N-tert-butyl acrylamide nanosphere load.Catalyst raw material provided by the invention is easy to get, synthetic method is simple, catalytic efficiency is high, operation is simple, can repeatedly use, and is applicable to the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis.
Description
Technical field
The invention belongs to materials science field, particularly a kind of polymer composite, specifically refer to a kind of Ni-B catalyst of poly-N-tert-butyl acrylamide load, preparation method and the application in the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis thereof.
Background technology
Hydrogen is a kind of clean secondary energy sources, and it can pass through the methods such as gas renormalizing, electrolysis photocatalytic water, chemical hydride and obtain.But due to the non-renewable of natural gas and the problem such as electrolysis photocatalytic water efficiency is not high, gradually limit their application.
At present, sodium borohydride is because having higher hydrogen density and storing the concern that stabilized hydrogen more and more receives people.But under normal temperature, preparing hydrogen by sodium borohydride hydrolysis speed is very slow, and the speed therefore improving preparing hydrogen by sodium borohydride hydrolysis is very necessary.For this reason, people have developed diversified catalyst, noble metal and the Ni such as such as Ru, Pt, Pd, the light transition metal such as Co.The noble metal that, reserves expensive compared to these are limited, the common metal broader applications such as Ni, Co are in preparing hydrogen by sodium borohydride hydrolysis reaction.
Chinese patent application 201210388720.0 reports with TiO
2co-B catalyst for carrier carrys out the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis, the features such as this catalyst is with low cost, catalytic activity is high, property stable in the air is good, easy to use.
It is Ni and the Ni-B nano-particle catalyst of carrier that Chinese patent application 201010527837.3 reports with silica, and this catalyst preparing is easy, and stability is good.
But the defects such as at present sodium borohydride hydrolyst exists that price is higher or catalytic activity is low, performance is not good, catalyst recycling and regenerability difference.
Summary of the invention
In order to overcome the deficiency of the metallic catalyst of current support type, first aspect present invention object is to provide the Ni-B nanocatalyst of the macromolecule loading that a kind of raw material is easy to get, synthetic method is simple, catalytic efficiency is high, operation is simple, can repeatedly use, and it is applicable to the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis.
For achieving the above object, the present invention takes following technical proposals to realize:
The Ni-B catalyst of poly-N-tert-butyl acrylamide nanosphere load, adopts following raw material and method to prepare: be poly-N-tert-butyl acrylamide nanosphere with precipitation polymerization method by N-tert-butyl acrylamide initiated polymerization; Poly-N-tert-butyl acrylamide nanosphere is distributed in nickel sulfate solution, absorption a period of time, filters, by the nickel ion reduction in absorption; Poly-N-tert-butyl acrylamide nanosphere containing a small amount of nickel metal is distributed in nickel plating solution and carries out chemical nickel plating, obtain the Ni-B catalyst of poly-N-tert-butyl acrylamide load.
Second aspect present invention object is to provide the preparation method of the Ni-B nanocatalyst of poly-N-tert-butyl acrylamide load, comprises the following steps:
A. the preparation of poly-N-tert-butyl acrylamide nanosphere: by N tert butyl acrylamide, potassium peroxydisulfate, distilled water with mol ratio for 1.2 × 10
3: 5.6:8.3 × 10
5ratio put in reaction vessel, 70 DEG C of stirring and dissolving under nitrogen atmosphere, nitrogen is led in rear stopping, sealed reaction 12h, obtains poly-N-tert-butyl acrylamide nanosphere emulsion;
B. the pretreatment of poly-N-tert-butyl acrylamide nanosphere: get a certain amount of poly-N-tert-butyl acrylamide emulsion in nickel sulfate solution, stir 10min, filter, repeatedly wash with water, then solid is redispersed in sodium borohydride aqueous solution, stirring reaction 10min, filter, repeatedly wash with water, dry.
The preparation of c.Ni-B catalyst: by be scattered in containing mol ratio through pretreated poly-N-tert-butyl acrylamide nanosphere be the sodium potassium tartrate tetrahydrate of 23:75:9:8, NaOH, nickelous sulfate, sodium borohydride nickel plating solution in, mechanical agitation 2h at 90 DEG C, after reaction terminates, filter, repeatedly wash with water, until washed away by nickel ion, by dry for the catalyst obtained, obtain Ni-B finished catalyst.
Further, the concentration of described step c mesotartaric acid potassium sodium is 108g/L, and the concentration of NaOH is 50g/L, and the concentration of nickelous sulfate is 39.8g/L, and the concentration of sodium borohydride is 1.6-6.7g/L.
Further, in described step c, the concentration of sodium borohydride is 5g/L.
In described preparation method:
Described initator is potassium peroxydisulfate.
A third aspect of the present invention object is to provide the application of Ni-B nanocatalyst in the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis of poly-N-tert-butyl acrylamide load, the method applied in concrete catalytic reaction is as follows: be scattered in water by Ni-B catalyst, pour in single port bottle, be placed in water bath with thermostatic control, pour sodium borohydride aqueous solution into again, clog bottleneck with stopper rapidly, in time having continuous air bubbles to emerge, timing, collects the hydrogen produced.
The catalytic reaction equation related to is as follows:
Beneficial effect of the present invention is as follows:
(1) the macromolecule loading Ni-B catalyst prepared of the present invention is poly-N-tert-butyl acrylamide load Ni-B catalyst, wherein, for load Ni-B poly-N-tert-butyl acrylamide nanosphere forming process as shown in Equation 1.Compare with the metallic catalyst of the inorganic material such as TiO2 and silica load, using macromolecule as the catalyst of carrier, there is unique advantage: a. macromolecular material is easily processed into various shape, such as pull into film or make microballoon, can relatively easily make catalytic reaction device; B. macromolecule ligand can not only direct fixing metal, controls catalytic performance, and its rational structure also can show corresponding smaller ligand can not " polymer effect " of catalysis; C. macromolecular compound can protect metal, forms stable nanocluster increasing specific surface area; D. select the macromolecular material containing certain functional group as carrier, the solvent polarity of reaction system or hydrophilic or hydrophobicity requirement can be applicable to; E. utilize the space multistory effect of macromolecule carrier, regioselective synthesis or three-dimensional selection can be realized and be separated.
The post processing of macromolecule loading heterogeneous catalysis is simpler: after completion of the reaction can easily by solid-liquid separating method by other Component seperation in polymer catalyst and reaction system, regenerate and reuse, reduce costs, reduce environmental pollution.
Above-mentioned employing gathers the Ni-B catalyst of N-tert-butyl acrylamide nanosphere load, can repeatedly repeat to reclaim to use, and catalyst is easily separated and stable in the air from reaction system.
Formula 1: for the forming process of the poly-N-tert-butyl acrylamide nanosphere of carried metal.
(2) reactivity of Ni-B catalyst when catalysis sodium borohydride that obtain of the present invention is higher, and hydrogen yield is also relatively high.
(3) Ni-B nanocatalyst catalyzing N aBH
4the activation energy of hydrolytic hydrogen production reaction is lower than existing other many activation energy containing the catalyst system and catalyzing of Ni metal.
Accompanying drawing explanation
Fig. 1 is that different temperatures is hydrolyzed the impact of initial hydrogen-producing speed to sodium borohydride;
Fig. 2 is lnk ~ 1/T graph of a relation.
Fig. 3 is the TEM photo that the present invention's better embodiment gathers the Ni-B catalyst of N-tert-butyl acrylamide load.
Fig. 4 is the TEM photo that another better embodiment of the present invention gathers the Ni-B catalyst of N-tert-butyl acrylamide load.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1:
The preparation of Ni-B nanocatalyst:
1. the preparation of poly-N-tert-butyl acrylamide nanosphere:
Take 1.5g N-tert-butyl acrylamide in 250mL there-necked flask, add 140mL distilled water, under nitrogen atmosphere 70 DEG C of stirring and dissolving, then add 10mL and contain 0.015g persulfate aqueous solution, close after continuing logical 10min nitrogen, sealed reaction 12h.
2. the pretreatment of poly-N-tert-butyl acrylamide nanosphere:
Getting poly-N-tert-butyl acrylamide emulsion dispersion prepared by 15mL said method contains in 1.39g nickel sulfate solution in 35mL, stir 10min, filter, repeatedly wash with water, then by solid dispersal in 40mL water, add 10mL and contain 0.1g sodium borohydride aqueous solution, stirring reaction 10min, filter, repeatedly wash with water, dry.
The preparation of 3.Ni-B catalyst:
Taking 0.02g is dispersed in 10mL water through pretreated poly-N-tert-butyl acrylamide nanosphere, pour in the 60mL nickel plating aqueous solution, this nickel plating solution contains 6.5g sodium potassium tartrate tetrahydrate, 3.0g NaOH, 2.39g nickelous sulfate and 0.3g sodium borohydride, mixed solution is poured in the there-necked flask of 250mL, at 90 DEG C, the speed mechanical of 410r/min stirs 2h, after reaction terminates, filters, repeatedly wash with water, by dry for the catalyst obtained.
Embodiment 2:
Preparation method is with embodiment 1, and difference is: in the preparation of Ni-B catalyst, and changing the amount that in nickel plating solution, sodium borohydride uses is 0.1g.
Embodiment 3:
Preparation method is with embodiment 1, and difference is: in the preparation of Ni-B catalyst, and changing the amount that in nickel plating solution, sodium borohydride uses is 0.2g.
Embodiment 4:
Preparation method is with embodiment 1, and difference is: in the preparation of Ni-B catalyst, and changing the amount that in nickel plating solution, sodium borohydride uses is 0.4g.
Embodiment 5:
The application experiment of catalyst
By different catalysts prepared by above-mentioned 1-4 embodiment, be applied to the reaction of catalysis preparing hydrogen by sodium borohydride hydrolysis respectively, and detect catalytic effect respectively.
Specific as follows: to get 8mg catalyst and 0.095gNaBH4 in there-necked flask, be placed on (45 DEG C) in water bath with thermostatic control, bottleneck is clogged with glass ground joint plug, check air-tightness, be rapidly in there-necked flask and add 50mL distilled water, in time having continuous air bubbles to emerge, timing, collect the hydrogen produced, measure its volume.
Interpretation of result:
1. the different catalysts of above-described embodiment 1 ~ 4, the result of catalysis preparing hydrogen by sodium borohydride hydrolysis reaction, adds up as shown in table 1 below.
The result of table 1, above-mentioned preparing hydrogen by sodium borohydride hydrolysis reaction (45 DEG C) of different catalysts catalysis:
| Sequence number | Collect hydrogen cumulative volume/mL | Ultimate yield/% |
| Embodiment 1 | 202 | 89.8 |
| Embodiment 2 | 198 | 88.0 |
| Embodiment 3 | 200 | 88.9 |
| Embodiment 4 | 194 | 86.2 |
As can be seen from Table 1: these catalyst all can effectively react by catalysis preparing hydrogen by sodium borohydride hydrolysis, and yield is good.
2. test is in the impact of different temperatures on sodium borohydride hydrolysis initial rate, as shown in Table 2 and Figure 1.
Table 2, temperature are on the impact of hydrolysis
Can find out according to table 2, Fig. 1: different temperatures is on the impact of sodium borohydride hydrolysis initial rate, and along with the progressively rising of temperature, sodium borohydride hydrolysis initial rate improves a lot, and affects final hydrogen productive rate at different temperatures.
Fig. 2 is lnk ~ 1/T curve map, and wherein, k is the slope (data see table 2) of each straight line in Fig. 1, and T is that absolute temperature calculates the activation energy of preparing hydrogen by sodium borohydride hydrolysis reaction according to slope
afor 45.43kJmol
-1.The activation energy numerical value of this hydrogen of Ni catalyst manufacture reaction and the more as shown in table 3 of activation energy numerical value of the present invention of the other types of bibliographical information.
Table 3, catalyst of the present invention compare with the activation energy of other catalyst.
| Catalyst | Activation energy a(kJ mol -1) |
| P(AMPS)-Ni | 42.28 |
| PVP-Ni | 48 |
| Bulk Ni | 71 |
| Raney Ni | 63 |
| The present invention | 45.43 |
As can be seen from Table 3: the activation energy of the Ni-B catalyst of poly-N-tert-butyl acrylamide load prepared by the present invention is low, is used in NaBH in aqueous phase
4it is very efficient for producing hydrogen.The Ru/C catalyst NaBH that the thesis for the doctorate that can also surpass with reference to East China University of Science Zou Yue in 2012 is reported
4the activation energy of hydrolytic hydrogen production reaction is 50.74kJ/mol.Another one aspect, relative to the catalyst adopting pure Pd, pure Ru, the present invention has better cost advantage, that is has more advantage in the cost performance of catalytic effect.
Product checking:
The Ni-B catalyst of poly-N-tert-butyl acrylamide load the present invention obtained does transmission electron microscope (TEM) analysis, and the typical photo of shooting as shown in Figure 3 and Figure 4.Fig. 3 and Fig. 4 is the TEM photo (in figure, scale is 200nm) of the Ni-B catalyst of poly-N-tert-butyl acrylamide load.Can see nickel Metal Supported in each width figure in poly-N-tert-butyl acrylamide nanosphere, ball does not produce bulk nickel agglomerate or bulky grain Ni outward.
Ni-B nanocatalyst prepared by the present invention, nickel Metal Supported is in poly-N-tert-butyl acrylamide nanosphere, and prevent the mutual reunion caking between nickel metal, surface area is large, active high.After catalyzing manufacturing of hydrogen reaction terminates, by simple filtration, the mode such as centrifugal, catalyst can be separated with reactant liquor again, reach the effect repeatedly used.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all belong to the protection domain of technical solution of the present invention.
Claims (5)
1. a Ni-B catalyst for poly-N-tert-butyl acrylamide nanosphere load, is characterized in that, is poly-N-tert-butyl acrylamide nanosphere with precipitation polymerization method by N-tert-butyl acrylamide initiated polymerization; Nanosphere is distributed to absorbed Ni ion in nickel sulfate solution, after filtration, the nickel ion of absorption is reduced to nickel metal; Poly-N-tert-butyl acrylamide nanosphere containing a small amount of nickel metal is distributed in nickel plating solution and carries out chemical nickel plating, obtain the Ni-B catalyst of poly-N-tert-butyl acrylamide nanosphere load.
2. the preparation method of the Ni-B catalyst of poly-N-tert-butyl acrylamide nanosphere load as claimed in claim 1, is characterized in that, comprise the following steps:
A. the preparation of poly-N-tert-butyl acrylamide nanosphere: by N tert butyl acrylamide, potassium peroxydisulfate, distilled water with mol ratio for 1.2 × 10
3: 5.6:8.3 × 10
5ratio put in reaction vessel, 70 DEG C of stirring and dissolving under nitrogen atmosphere, nitrogen is led in rear stopping, sealed reaction 12h, obtains poly-N-tert-butyl acrylamide nanosphere emulsion;
B. the pretreatment of poly-N-tert-butyl acrylamide nanosphere: get 15mL and gather N-tert-butyl acrylamide nanosphere emulsion in 35mL nickel sulfate solution, stir 10min, filter, repeatedly wash, until the nickel ion of physical absorption is all washed off, then solid is redispersed in 50mL and contains in 0.1g sodium borohydride aqueous solution and carry out reduced nickel ion, stirring reaction 10min, filter, repeatedly wash with water, dry;
The preparation of c.Ni-B catalyst: take and be scattered in the nickel plating solution containing sodium potassium tartrate tetrahydrate, NaOH, nickelous sulfate, sodium borohydride through pretreated poly-N-tert-butyl acrylamide nanosphere, mechanical agitation 2h at 90 DEG C, after reaction terminates, filter, repeatedly wash with water, until washed away by nickel ion, by dry for the catalyst obtained, obtain Ni-B finished catalyst.
3. the preparation method of Ni-B catalyst according to claim 2, it is characterized in that, the concentration of described step c mesotartaric acid potassium sodium is 108g/L, and the concentration of NaOH is 50g/L, the concentration of nickelous sulfate is 39.8g/L, and the concentration of sodium borohydride is 1.6-6.7g/L.
4. the preparation method of Ni-B catalyst according to claim 3, is characterized in that, in described step c, the concentration of sodium borohydride is 5g/L.
5. the application of Ni-B catalyst in catalysis sodium borohydride and hydrolytic hydrogen production reaction of poly-N-tert-butyl acrylamide nanosphere load as claimed in claim 1.
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| CN102029159A (en) * | 2010-11-02 | 2011-04-27 | 天津工业大学 | Catalyst for catalytically hydrolyzing sodium borohydride to prepare hydrogen and preparation method thereof |
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| CN102923651A (en) * | 2011-08-10 | 2013-02-13 | 武盖斯·布鲁斯托尔公司 | Device for the generation of hydrogen, apparatuses that contain the device, and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090196821A1 (en) * | 2008-02-06 | 2009-08-06 | University Of Delaware | Plated cobalt-boron catalyst on high surface area templates for hydrogen generation from sodium borohydride |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59162206A (en) * | 1983-03-08 | 1984-09-13 | Mitsui Mining & Smelting Co Ltd | Manufacture of fine nickel and cobalt powder |
| CN101347736A (en) * | 2007-07-20 | 2009-01-21 | 中国科学院金属研究所 | Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof |
| CN102029159A (en) * | 2010-11-02 | 2011-04-27 | 天津工业大学 | Catalyst for catalytically hydrolyzing sodium borohydride to prepare hydrogen and preparation method thereof |
| CN102350356A (en) * | 2011-07-28 | 2012-02-15 | 北京理工大学 | Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method |
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| CN102950009A (en) * | 2012-10-12 | 2013-03-06 | 南京大学 | Load type CoB catalyst for process of preparing hydrogen through hydrolysis of sodium borohydride and preparation method of load type CoB catalyst |
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