CN104261347A - Method for producing hydrogen by hydrolyzing ammonia borane - Google Patents
Method for producing hydrogen by hydrolyzing ammonia borane Download PDFInfo
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- CN104261347A CN104261347A CN201410408826.1A CN201410408826A CN104261347A CN 104261347 A CN104261347 A CN 104261347A CN 201410408826 A CN201410408826 A CN 201410408826A CN 104261347 A CN104261347 A CN 104261347A
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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
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Abstract
The invention discloses a method for producing hydrogen by hydrolyzing ammonia borane. The hydrogen is made by mixing an ammonia borane aqueous solution with a catalyst, and the catalyst is a reduced-state polyoxometallate anion-modified metal or alloy catalyst. Meanwhile, the invention discloses a preparation method and an application of the reduced-state polyoxometallate anion-modified catalyst.
Description
Technical field
The present invention relates to the energy and petrochemical complex catalytic material technical field, particularly relate to the method for a kind of ammonia borane hydrolysis hydrogen manufacturing.
Background technology
Hydrogen is a kind of clean, efficient ideal capacity carrier.With H
2for the Proton Exchange Membrane Fuel Cells (PEMFCs) of fuel is considered to the Alternative routes that the rare-view set-up mankind solve current energy source problem.Because the construction of hydrogen fuel filling network system is also not within the foreseeable future, the H that current PEMFCs uses
2obtain primarily of storage hydrogen and hydrogen manufacturing two schemes.Existing storage hydrogen scheme, the have 5.5wt% of use value (target in 2015) and 7.5wt% (ultimate aim) hydrogen-storage amount from u.s. department of energy setting also have very large distance.Thus, research and develop the research and development of the removable hydrogen generating system based on the chemical conversion of high-energy-density storage hydrogen material, become one of hot subject of current fuel cell field most challenge and seemed particularly important.
In known chemical hydrogen storage material system, ammonia borine has the storage hydrogen massfraction up to 19.6wt%, and under normal temperature, normal pressure, nonflammable or blast, is a kind of excellent hydrogen storage media having application prospect.Ammonia borine prepares hydrogen by pyrolysis dehydrogenation and hydrolysis/dehydrogenation two kinds of modes.Compared to the pyrolysis dehydrogenation reaction of ammonia borine, it is better that ammonia borane hydrolysis dehydrogenation reaction has reaction controllability, and reaction conditions gentleness, hydrogen discharging rate is very fast, the selectivity comparatively advantages of higher of hydrogen, and causes the extensive concern of investigators.For ammonia borane hydrolysis dehydrogenation systems, precious metals pt catalyzer, compared to other metal catalysts, demonstrates excellent catalytic performance (Q.Xu, M.Chandra.J.Power Sources, 2006,163,364-370;
metin, V.Mazumder, S.
et al.J.Am.Chem.Soc., 2010,132,1468-1469).But consider that the cost of precious metals pt nanocatalyst is higher, the activity thus improving Pt seems particularly important with the usage quantity reducing Pt.In addition, base metal and alloy catalyst (patent CN 102500377A, CN 102513125A) thereof also have better catalyze ammonia borane hydrolysis dehydrogenation.Although its performance is lower than noble metal catalyst, consider the cost factor of catalyzer, base metal and alloy catalyst thereof have larger competitive edge.
For ammonia borane hydrolysis dehydrogenation systems catalyzer, catalyst nano-particles is not only easily reunited, and more easily by the dioxygen oxidation in air atmosphere, thus reduce the ammonia borane hydrolysis performance of catalyzer.Therefore, how to design and the microtexture of optimization of catalysts and characteristic electron to improve its ammonia borane hydrolysis dehydrogenation, thus reducing the cost of noble metal catalyst or improve the performance of non-precious metal catalyst, is one of current problem demanding prompt solution.
Summary of the invention
The catalyzer aiming to provide a kind of new ammonia borane hydrolysis dehydrogenation of the present invention.
In a first aspect of the present invention, provide the method for a kind of ammonia borane hydrolysis hydrogen manufacturing, the ammonia borine aqueous solution and catalyst mix are obtained hydrogen, described catalyzer is the anion modified metal or alloy catalyzer of reduction-state polyoxometallate.
In another preference, described polyoxometallate is X
my
nz
xo
y, wherein X is H
+, metallic cation or organic cation, ligating atom centered by Y, Z is polyacid atom; Described reduction-state polyoxometallic acid salt anionic is Y
nz
xo
y (m+l)-; More preferably, described reduction-state polyoxometallic acid salt anionic is selected from SiW
12o
40 5-, PW
12o
40 4-or PMo
12o
40 4-; Be SiW best
12o
40 5-.
In another preference, described metal or alloy catalyzer comprises loading type and non-loading type; Described metal catalyst is Pt catalyzer; Described alloy catalyst is Ni-B catalyzer.
In another preference, the mol ratio of described polyoxometallic acid salt anionic and metal catalyst or alloy catalyst is 0-0.6; More preferably 0.1-0.5.
In another preference, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
(1) reductive agent is utilized to make the reduction of polyoxometallic acid salt anionic obtain the polyoxometallate anion solutions 1 of reduction-state; With
(2) reduction-state polyoxometallate anion solutions 1 is joined as-reduced metal or alloy catalyst surface, obtain the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; More preferably ammonia borine.
In another preference, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
A polyoxometallate anion solutions joins and reduces or unreduced metal or alloy catalyst surface by (); With
B () uses reductive agent to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; More preferably ammonia borine.
In another preference, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
I () will not to be reduced or as-reduced polyoxometallate anion solutions is impregnated into the surperficial back loading catalyst activity component of carrier; With
(ii) reductive agent is used to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; More preferably ammonia borine.
In a second aspect of the present invention, provide the preparation method of the anion modified metal or alloy catalyzer of a kind of reduction-state polyoxometallate, described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; Preferred ammonia borine; Described method comprises step:
(1) reductive agent makes the reduction of polyoxometallic acid salt anionic obtain the polyoxometallate anion solutions 1 of reduction-state; With
(2) reduction-state polyoxometallate anion solutions 1 is joined the metal or alloy catalyst surface of reduction, obtain the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified;
Or described method comprises step:
A polyoxometallate anion solutions joins and reduces or unreduced metal or alloy catalyst surface by (); With
B () uses reductive agent to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Or described method comprises step:
I () will not to be reduced or as-reduced polyoxometallate anion solutions is impregnated into the surperficial back loading catalyst activity component of carrier; With
(ii) reductive agent is used to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate.
In a third aspect of the present invention, provide the purposes of the anion modified metal or alloy catalyzer of a kind of reduction-state polyoxometallate, for the hydrogen manufacturing of ammonia borane hydrolysis.
Accordingly, present invention optimizes microtexture and the characteristic electron of catalyzer, improve ammonia borane hydrolysis dehydrogenation, thus reduce the cost of noble metal catalyst or improve the performance of non-precious metal catalyst.
Accompanying drawing explanation
Fig. 1 shows the color of the color of silicotungstic acid solution and the silicotungstic acid solution of ammonia borane reduction; Wherein A does not reduce silicon tungsten acid solution; B is the silicon tungsten acid solution after reduction.
Fig. 2 is the hydrogen discharging performance test pattern of ammonia borane hydrolysis on the anion modified Pt/CNTs catalyzer of the silicotungstic sodium of the anion modified Pt/CNTs catalyzer of Pt/CNTs catalyzer, silicotungstic sodium or silicotungstic acid and reduction-state or silicotungstic acid.
Fig. 3 is the hydrogen discharging performance test pattern with silicotungstic sodium or the anion modified Ni-B catalyst ammonia borane hydrolysis of silicotungstic acid.
Fig. 4 is the hydrogen discharging performance test pattern with silicotungstic sodium or the anion modified Ni-B/MCM-41 catalyst ammonia borane hydrolysis of silicotungstic acid.
Fig. 5 is the TEM figure with silicotungstic sodium or anion modified Ni-B catalyzer continuous catalysis ammonia borane hydrolysis 5 rear catalysts of silicotungstic acid.
Fig. 6 is the TEM figure with Ni-B catalyzer continuous catalysis ammonia borane hydrolysis 5 rear catalysts.
Fig. 7 is the hydrogen discharging performance test pattern with the anion modified Ni-B/MCM-41 catalyst ammonia borane hydrolysis of loading type polyoxometallate.
Embodiment
Contriver, through extensive and deep research, finds that the anion modified catalyzer of a kind of reduction-state polyoxometallate significantly can improve the activity of catalyze ammonia borane hydrolysis, selectivity and stability.On this basis, the present invention is completed.
The catalyzer used in the method for ammonia borane hydrolysis provided by the invention hydrogen manufacturing is the anion modified metal or alloy catalyzer of reduction-state polyoxometallate; Described polyoxometallate is X
my
nz
xo
y, wherein X is H
+, metallic cation or organic cation, ligating atom centered by Y, Z is polyacid atom; Described reduction-state polyoxometallic acid salt anionic is Y
nz
xo
y (m+l)-; Preferably from SiW
12o
40 5-, PW
12o
40 4-or PMo
12o
40 4-; More preferably SiW
12o
40 5-.The metal or alloy catalyzer of this area routine can be used, such as but not limited to, loading type and non-loading type; Preferred metal catalyst is Pt catalyzer; Preferred alloy catalyst is Ni-B catalyzer.The mol ratio of described polyoxometallic acid salt anionic and metal or alloy catalyzer is that 0-0.6 (finds in experimentation, the polyoxometallate adding minute quantity just can promote the hydrolysis reaction of ammonia borine, and the lower limit of the polyoxometallate that we can weigh is 1mg, i.e. corresponding 0.002:1, that is, the consumption reducing polyoxometallate more also can play promoter action, but cannot weigh now again.); Preferred 0.1-0.5.
For noble metal catalyst, Pt/CNTs catalyzer as anion modified in reduction-state polyoxometallate can be placed separately; For non-precious metal catalyst, NiB catalyzer as anion modified in reduction-state polyoxometallate then can not be placed separately, must use in ammonia borane hydrolysis hydrogen production reaction immediately.
The anion modified metal or alloy catalyzer of reduction-state polyoxometallate provided by the invention can be obtained by three kinds of methods, preferred method one.Be described below respectively:
Method one
(1) utilize reductive agent to be reduced by polyoxometallic acid salt anionic, obtain the solution 1 of the polyoxometallic acid salt anionic containing reduction-state;
(2) by reduction-state polyoxometallate anion solutions 1, as-reduced metal or alloy catalyst surface is joined.
The reductive agent related in step (1) can be that this area routine uses, such as but not limited to, ammonia borine, sodium borohydride, hydrazine and formaldehyde, a kind of preferred scheme uses ammonia borine.When using ammonia borine as reductive agent, complete the reaction of ammonia borane hydrolysis hydrogen manufacturing simultaneously.The reductive agent used in the method is the ammonia borine aqueous solution.When using ammonia borine as reductive agent, because ammonia borine is reaction solution simultaneously, ammonia borine will will keep certain ratio with the amount of used catalyst substance, so the concentration of the ammonia borine aqueous solution is a definite value here.
The metal or alloy catalyzer that step (2) relates to includes but not limited to, Au, Pd, Pt, Ag, Ru, Fe, Co, Ni, Cu, Fe-Co, Au-Ni, Ni-Pt, Ni-Pd, Au-Co, Fe-Ni, Ni-B, Co-B etc.; The as-reduced metal or alloy catalyzer that step (2) relates to can be obtained by the method for this area routine, such as but not limited to, use the reducing solutions such as sodium borohydride, hydrazine hydrate and ammonia borine, and the reducing gas such as hydrogen comes reducing metal or alloy catalyst presoma, thus obtain the metal or alloy catalyzer of reduction.
Step (2) can be mutually mixed with the solution of containing metal or alloy catalyst by reduction-state polyoxometallate anion solutions 1, stirs for some time, makes reduction-state polyoxometallate Anion-adsorption to metal or alloy catalyst surface; Or the metal or alloy catalyzer of reduction is immersed in solution 1, stir for some time, make reduction-state polyoxometallate Anion-adsorption to metal or alloy catalyst surface.
The mol ratio of polyoxometallic acid salt anionic and metal catalyst or alloy catalyst described in method one is 0-0.6, preferred 0.1-0.5.
Method two
A (), by the solution 2 containing polyoxometallic acid salt anionic, joins and reduces or unreduced metal or alloy catalyst surface;
B () utilizes reductive agent to reduce.
The metal or alloy catalyzer that step (a) relates to includes but not limited to, Au, Pd, Pt, Ag, Ru, Fe, Co, Ni, Cu, Fe-Co, Au-Ni, Ni-Pt, Ni-Pd, Au-Co, Fe-Ni, Ni-B, Co-B etc.; The metal or alloy catalyzer of the reduction that step (a) relates to can be obtained by the method for this area routine, such as but not limited to, use the reducing solutions such as sodium borohydride, hydrazine hydrate and ammonia borine, and the reducing gas such as hydrogen comes reducing metal or alloy catalyst presoma, thus obtain the metal or alloy catalyzer of reduction.
Step (a) can be to have been reduced or the solution of unreduced metal or alloy catalyzer mixes mutually with containing by the solution 2 containing polyoxometallic acid salt anionic, stir for some time, make polyoxometallate Anion-adsorption to reducing or unreduced metal or alloy catalyst surface, or will to reduce or unreduced metal or alloy catalyzer is immersed in solution 2, stirring for some time, making polyoxometallate Anion-adsorption to reducing or unreduced metal or alloy catalyst surface.
The reductive agent related in step (b) can be that this area routine uses, such as but not limited to, ammonia borine, sodium borohydride, hydrazine and formaldehyde, a kind of preferred scheme uses ammonia borine.When using ammonia borine as reductive agent, complete the reaction of ammonia borane hydrolysis hydrogen manufacturing simultaneously.The reductive agent used in the method is the ammonia borine aqueous solution.When using ammonia borine as reductive agent, because ammonia borine is reaction solution simultaneously, ammonia borine will will keep certain ratio with the amount of used catalyst substance, so the concentration of the ammonia borine aqueous solution is a definite value here.
When using the solution 2 of polyoxometallic acid salt anionic, " utilizing reductive agent to reduce " refers to, when metal or alloy catalyzer reduces, uses reductive agent, as polyoxometallate reduces by ammonia borine, sodium borohydride, hydrazine or formaldehyde.When metal or alloy catalyzer does not reduce, when adopting hydrogen reducing metal or alloy catalyzer, reductive agent such as ammonia borine, sodium borohydride, hydrazine or formaldehyde should be used to be reduced by polyoxometallate.When adopt reductive agent be the reducing metals such as ammonia borine, sodium borohydride, hydrazine or formaldehyde or alloy catalyst time, reductive agent such as ammonia borine, sodium borohydride, hydrazine or formaldehyde can simultaneously by polyoxometallate and metal or alloy catalyst reductions.
When reductive agent is ammonia borine, sodium borohydride, hydrazine or formaldehyde, can simultaneously by polyoxometallate and metal or alloy catalyst reduction.
The mol ratio of the salt anionic of polyoxometallic acid described in method two and metal catalyst or alloy catalyst is 0-0.6, preferred 0.1-0.5.
Method three
I () will contain the solution 2 of polyoxometallic acid salt anionic or be impregnated into the surface of carrier containing the solution 1 of the polyoxometallic acid salt anionic of reduction-state, then supported catalyst active ingredient;
(ii) reductive agent is utilized to reduce.
The carrier related in step (i) can be the support of the catalyst that this area is commonly used, such as but not limited to, silicon-dioxide, aluminum oxide, gac, carbon nanotube, carbon fiber, Graphene, molecular sieve (SBA-15, MCM-41, KIT-6, MCM-48, TS-1, TS-2D etc.), preferred carbon nanotube and MCM-41.
The catalyst activity component related in step (i) is metal or alloy, and described metal or alloy can be that this area is commonly used, such as but not limited to, Au, Pd, Pt, Ag, Ru, Fe, Co, Ni, Cu, Fe-Co, Au-Ni, Ni-Pt, Ni-Pd, Au-Co, Fe-Ni, Ni-B, Co-B etc., preferred metal is Pt (platinum), and preferred alloy is Ni-B (nickel-boron).
The mode supported catalyst active ingredient of this area routine can be used in step (i).Such as but not limited to, adopt equi-volume impregnating to impregnated on carrier by metal or alloy, standing high temperature drying is reduced after obtaining catalyst precursor 1.
Preferably, Pt/CNTs catalyzer can be obtained by following step:
(1) adopt equi-volume impregnating to impregnated on CNTs by platinum acid chloride solution, standing high temperature drying obtains catalyst precursor 1;
(2) catalyst precursor 1 is reduced in a hydrogen atmosphere, obtain Pt/CNTs catalyzer.
Preferably, Ni-B/MCM-41 catalyzer can be obtained by following step:
(1) adopt pickling process to impregnated on MCM-41 by nickel nitrate solution, standing high temperature drying obtains catalyst precursor 1;
(2) by the aqueous solution of catalyst precursor 1 and sodium borohydride, stir and obtain Ni-B/MCM-41 catalyzer.
The reductive agent related in step (ii) can be that this area routine uses, such as but not limited to, ammonia borine, sodium borohydride, hydrazine and formaldehyde, a kind of preferred scheme uses ammonia borine.When using ammonia borine as reductive agent, complete the reaction of ammonia borane hydrolysis hydrogen manufacturing simultaneously.The reductive agent used in the method is the ammonia borine aqueous solution.When using ammonia borine as reductive agent, because ammonia borine is reaction solution simultaneously, ammonia borine will will keep certain ratio with the amount of used catalyst substance, so the concentration of the ammonia borine aqueous solution is a definite value here.
When using the solution 2 of polyoxometallic acid salt anionic, " utilizing reductive agent to reduce " refers to, when adopting hydrogen reducing metal or alloy catalyzer, reductive agent such as ammonia borine, sodium borohydride, hydrazine or formaldehyde should be used to be reduced by polyoxometallate.When adopt reductive agent be the reducing metals such as ammonia borine, sodium borohydride, hydrazine or formaldehyde or alloy catalyst time, reductive agent such as ammonia borine, sodium borohydride, hydrazine or formaldehyde can simultaneously by polyoxometallate and metal or alloy catalyst reductions.
The mol ratio of polyoxometallic acid salt anionic and metal catalyst or alloy catalyst described in method three is 0-0.6, preferred 0.1-0.5.
The reduction-state polyoxometallic acid salt anionic that the present invention relates to obtains by reductive agent and polyoxometallate solution reaction.In one embodiment of the invention, with ammonia borane reduction silicotungstic sodium or silicotungstic acid, the 10wt% ammonia borine aqueous solution is mixed with silicotungstic acid or silicotungstic sodium solution, ultrasonic, obtain the solution of the polyoxometallic acid salt anionic of reduction-state.The molar weight of ammonia borine is far longer than the molar weight (>=60:1) of polyoxometallic acid salt anionic, reactant (i.e. the 10wt% ammonia borine aqueous solution) is utilized to reduce many metal-salts hydrochlorate, reaction process can be simplified, avoid introducing other impurity, thus preferably it prepares reduction-state polyoxometallic acid salt anionic as reductive agent.
Fig. 1 gives and does not reduce and the picture of as-reduced silicotungstic sodium or silicon tungsten acid solution.Result shows: silicotungstic sodium or silicon tungsten acid solution are colourless, and after adding the agent of ammonia borane reduction, solution shows atropurpureus, illustrates that silicotungstic acid root negatively charged ion is reduced.When reductive agent is sodium borohydride, hydrazine and formaldehyde, polyoxometallic acid salt anionic is PW
12o
40 3-and PMo
12o
40 3-time, do not reduce and the colour-change of as-reduced polyoxometallic acid salts solution similar.
In the present invention, catalyst precursor can be prepared by equi-volume impregnating, such as but not limited to the disclosed method of document (G.Ertl etc. compile " Handbook of Heterogeneous Catalysis ", Wiley, 2008).
In the present invention, the catalytic performance of the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified puts hydrogen test sign by ammonia borane hydrolysis, hydrogen desorption capacity is measured by drainage, specific practice is placed in bottom 25mL there-necked flask by the catalyzer prepared, this there-necked flask is connected with a 500mL wash bottle, under water-bath 30 DEG C of conditions, the aqueous solution containing ammonia borine is added fast with 25mL syringe, control certain stir speed (S.S.), catalyze ammonia borane hydrolysis puts hydrogen, measures hydrogen desorption capacity by measuring the quality of discharging water.
Advantage of the present invention is mainly:
1, the polyoxometallic acid salt anionic of reduction-state can promote the electron transmission of metallic catalyst surfaces, is conducive to the absorption of ammonia borine molecule at metallic catalyst surfaces, thus considerably improves the performance of ammonia borane hydrolysis dehydrogenation.
2, the polyoxometallic acid salt anionic of reduction-state not only can suppress the reunion of catalyst nano-particles, and can consume the oxygen that may exist in reaction system, thus improves the stability of catalyzer.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the same meaning be familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
The reagent used in following embodiment and material are respectively:
Ammonia borine is purchased from SIGMA-ALDRICH, and molecular formula is NH
3bH
3, molecular weight is 30.87, and purity is greater than 97%.
Sodium borohydride is purchased from Shanghai Tian Lian Chemical Industry Science Co., Ltd, and molecular formula is NaBH
4, molecular weight is 37.85, and purity is greater than 96%.
MCM-41, purchased from Nanjing Ji Cang nanometer company limited, amasss≤900m than table face
2/ g, aperture: 3.5nm, pore volume: 0.8cm
3/ g.
Nickelous nitrate is purchased from Shanghai Tian Lian Fine Chemical Co., Ltd, and molecular weight is 290.81, and molecular formula is Ni (NO
3)
2﹒ 6H
2o.
Silicotungstic acid is purchased from SIGMA-ALDRICH, and molecular formula is H
4siW
12o
40﹒ xH
2o, molecular weight is 2878.17.
Phospho-wolframic acid is purchased from aladdin, and molecular formula is H
3pW
12o
40﹒ xH
2o, molecular weight is 2880.05.
Phospho-molybdic acid is purchased from aladdin, and molecular formula is H
3pMo
12o
40﹒ xH
2o, molecular weight is 1825.25.
The 3.0wt%Pt/CNTs catalyzer related in following embodiment is prepared by following step:
(1) adopt equi-volume impregnating to impregnated on CNTs by platinum acid chloride solution, leave standstill 12h, dry 12h at 80 DEG C, obtains catalyst precursor 1;
(2) catalyst precursor 1 is reduced under the hydrogen atmosphere of 250 DEG C, obtain Pt/CNTs catalyzer.
The Ni-B/MCM-41 catalyzer related in following embodiment is prepared by following step:
(1) adopt pickling process to impregnated on MCM-41 by nickel nitrate solution, the charge capacity of Ni is 10%, and leave standstill 12h, dry 8h at 120 DEG C, obtains catalyst precursor 1;
(2) aqueous solution of 0.1225g catalyst precursor 1 and 2g0.7wt% sodium borohydride is added drop-wise in round-bottomed flask, stirs for some time, obtain Ni-B/MCM-41 catalyzer.
The loading type Ni-B/STA-MCM-41 catalyzer related in following embodiment is prepared by following step:
(1) adopt equi-volume impregnating by silicotungstic acid (H
4siW
12o
40sTA) load is on MCM-41, mix with carrier by a certain amount of many metallized metals salt, water and the dehydrated alcohol of quality such as then to add, supersound process 1h, then stirs 12h, dry 3h at 120 DEG C, roasting 3h at 180 DEG C again, then wash the unnecessary silicotungstic acid of removing with water, finally roasting 3h at 180 DEG C.The charge capacity of silicotungstic acid is 20wt%.
(2) with equi-volume impregnating by nickel impregnation in load on the MCM-41 of silicotungstic acid, the charge capacity of Ni is 10%, leaves standstill 12h, dry 8h at 120 DEG C, obtains the presoma 2 of loading type Ni-B/STA-MCM-41 catalyzer.
(3) aqueous solution of 0.1225g catalyst precursor 2 and 2g0.7wt% sodium borohydride is added drop-wise in round-bottomed flask, stirs for some time, obtain Ni-B/STA-MCM-41 catalyzer.Wherein, wherein, SiW
12o
40 4-siW is become by sodium borohydride reduction
12o
40 5-.
Adopt same method, load (charge capacity 20wt%) phospho-wolframic acid (H can be obtained
3pW
12o
40, PTA) or phospho-molybdic acid (H
3pMo
12o
40, PMA) Ni-B/PTA-MCM-41 or Ni-B/PMA-MCM-41 catalyzer.
Embodiment 1
Employing method one, SiW
12o
40 5-be 1:1 with the mol ratio of Pt.First the 5g10wt% ammonia borine aqueous solution and 2g silicotungstic sodium or silicon tungsten acid solution are joined in there-necked flask, ultrasonic 5min, then adds the as-reduced 3.0wt%Pt/CNTs catalyzer of 0.025g, fully stirs, and the speed of putting hydrogen is measured by drainage, result of study is as shown in Figure 2.
Embodiment 2
Adopt method two, SiW
12o
40 4-be 1:1 with the mol ratio of Pt, and SiW
12o
40 4-siW is reduced into while the reaction of ammonia borine
12o
40 5-.First as-reduced for 0.025g Pt catalyzer and 2g silicotungstic sodium or silicon tungsten acid solution are joined in there-necked flask and stir for some time, then add the 5g10wt% ammonia borine aqueous solution, and measured the speed of putting hydrogen by drainage, result of study as shown in Figure 2.
Result shows: 1-2 and comparative example 1 (i.e. Pt/CNTs catalyzer) in conjunction with the embodiments, can discover method one prepare catalyzer (the i.e. silicotungstic acid negatively charged ion (SiW of pre-reduction
12o
40 5-) the Pt catalyzer modified) and activity have raising by a relatively large margin, and the activity inhibited of catalyzer prepared by method two.
Employing method for the moment, namely first by oxidation state polyoxometallic acid salt anionic (SiW
12o
40 4-, SiW
12o
40 4-: Pt=1) be reduced to reduction-state polyoxometallic acid salt anionic (SiW
12o
40 5-), then when being adsorbed onto catalyst surface, the catalyzer that the activity of catalyzer is prepared apparently higher than the Pt/CNTs Catalyst And Method two do not modified with polyoxometallate; When adopting method two, namely first by the polyoxometallic acid salt anionic (SiW of oxidation state
12o
40 4-, SiW
12o
40 4-: Pt=1) be adsorbed on catalyst surface, then with reductive agent, the oxidation state polyoxometallic acid salt anionic being adsorbed on catalyst surface is reduced to reduction-state polyoxometallic acid salt anionic (SiW
12o
40 5-), the activity of the catalyzer prepared in this case is higher than not with the Pt/CNTs catalyzer that polyoxometallate is modified.
Two kinds of methods are all finally that the polyoxometallate Anion-adsorption of reduction-state plays modification at catalyst surface, the only method of pre-reduction, and namely comparatively method two is good for method one effect, but method two equally also has promoter action.
Embodiment 3
Employing method one, SiW
12o
40 5-be 0.03:1 with the mol ratio of Ni.First 1.42mL1.2mol/L nickel nitrate solution and 2g0.7wt% sodium borohydride solution are added in there-necked flask, stir for some time.Then add silicotungstic sodium or the silicotungstic acid solution of the reduction of the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage, result of study as shown in Figure 3.
Embodiment 4
Adopt method two, SiW
12o
40 4-be 0.03:1 with the mol ratio of Ni, and SiW
12o
40 4-siW is reduced into while the reaction of ammonia borine
12o
40 5-.First the nickel nitrate solution of 1.42mL1.2mol/L and 2g0.7wt% sodium borohydride solution are added drop-wise in there-necked flask, stir for some time, then 2g silicotungstic sodium/silicotungstic acid solution is added, stir for some time, add the 5g10wt% ammonia borine aqueous solution again, measured the speed of putting hydrogen by drainage, result of study as shown in Figure 3.
Result shows: 3-4 and comparative example 2 (i.e. Ni-B catalyzer) in conjunction with the embodiments, can discover method one prepare catalyzer (the i.e. silicotungstic acid root negatively charged ion (SiW of pre-reduction
12o
40 5-) the Ni-B catalyzer modified) and activity and selectivity all higher than catalyzer prepared by method two, and far above Ni-B catalyzer.
Embodiment 5
Adopt method two, SiW
12o
40 4-be 0.002:1 to 0.6:1 with the mol ratio of Ni, and SiW
12o
40 4-siW is reduced into while the reaction of ammonia borine
12o
40 5-.First 2g silicotungstic sodium or silicotungstic acid solution and as-reduced Ni-B/MCM-41 catalyzer are added in there-necked flask and stir for some time, then add the 5g10wt% ammonia borine aqueous solution, and measured the speed of putting hydrogen by drainage, result of study as shown in Figure 4.
Result shows: relative to Ni-B/MCM-41 catalyzer (comparative example 3), the SiW prepared with method two
12o
40 5-activity and the selectivity of the Ni-B/MCM-41 catalyzer modified all are improved.
Embodiment 6
Adopt method two, SiW
12o
40 4-be 0.1:1 and SiW with the mol ratio of Ni
12o
40 4-siW is reduced into while the reaction of ammonia borine
12o
40 5-.The nickel nitrate solution of 1.42mL1.2mol/L and 2g0.7wt% sodium borohydride solution are added drop-wise in there-necked flask, stir for some time, then 2g silicotungstic sodium or silicon tungsten acid solution is added, stir for some time, add the 5g10wt% ammonia borine aqueous solution again, measured the speed of putting hydrogen by drainage.When no longer including water and discharging, illustrate that reaction terminates, and then add the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage.After operation like this 4 times, the pattern of catalyzer as shown in Figure 5.
Result shows: relative to comparative example 4, reunite hardly after successive reaction 5 times with the anion modified Ni-B catalyzer of reduction-state silicotungstic acid root, and Ni-B catalyzer agglomeration after successive reaction 5 times is very serious, this illustrates that reduction-state silicotungstic acid root negatively charged ion can prevent the gathering of Ni-B catalyst particle.
Embodiment 7
Employing method three, adds as-reduced Ni-B/STA-MCM-41 catalyzer in there-necked flask and stirs for some time, then adds the 5g10wt% ammonia borine aqueous solution, and is measured the speed of putting hydrogen by drainage, and result of study as shown in Figure 7.Adopt and use the same method, record the hydrogen discharging rate of Ni-B/PTA-MCM-41 catalyzer and Ni-B/PMA-MCM-41 catalyze ammonia borane hydrolysis, result of study as shown in Figure 7.
Result shows: relative to Ni-B/MCM-41 catalyzer (comparative example 3), catalyzer prepared by method three, i.e. reduction-state silicotungstic acid root negatively charged ion (SiW
12o
40 5-), phospho-wolframic acid root negatively charged ion (PW
12o
40 4-) or phospho-molybdic acid root negatively charged ion (PMo
12o
40 4-) activity of catalyzer of modifying and selectivity have raising by a relatively large margin.
Embodiment 8
Employing method one, SiW
12o
40 5-be 0.1:1 with the mol ratio of Ni.First 1.42mL1.2mol/L nickel nitrate solution and 2g0.7wt% sodium borohydride solution are added in there-necked flask, stir for some time.Then add silicotungstic sodium or the silicotungstic acid solution of the reduction of the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage, shown in result of study table 1.Adopt and use the same method, record the phospho-wolframic acid root negatively charged ion (PW of reduction-state
12o
40 4-) or phospho-molybdic acid root negatively charged ion (PMo
12o
40 4-) hydrogen discharging rate of Ni-B catalyst ammonia borane hydrolysis modified, shown in result of study table 1.
Embodiment 9
Adopt method two, SiW
12o
40 4-be 0.1:1 with the mol ratio of Ni, and SiW
12o
40 4-siW is reduced into while the reaction of ammonia borine
12o
40 5-.The nickel nitrate solution of 1.42mL1.2mol/L and 2g0.7wt% sodium borohydride solution are added drop-wise in there-necked flask, stir for some time, then 2g silicotungstic sodium/silicotungstic acid solution is added, stir for some time, add the 5g10wt% ammonia borine aqueous solution again, measured the speed of putting hydrogen by drainage, result of study is as shown in table 1.Adopt and use the same method, record the phospho-wolframic acid root negatively charged ion (PW of reduction-state
12o
40 4-) or phospho-molybdic acid root negatively charged ion (PMo
12o
40 4-) hydrogen discharging rate of Ni-B catalyst ammonia borane hydrolysis modified, result of study is as shown in table 1.
The hydrogen discharging rate of the Ni-B catalyzer that table 1 reduction-state polyoxometallate root is anion modified
Result shows: 8-9 in conjunction with the embodiments, the hydrogen discharging rate of the catalyzer that the hydrogen discharging rate of catalyzer (the Ni-B catalyzer that namely the polyoxometallate root of pre-reduction is anion modified) prepared by method one is all prepared higher than method two; The hydrogen discharging rate of the Ni-B catalyzer that reduction-state silicotungstic acid root is anion modified is higher than the hydrogen discharging rate of reduction-state phospho-wolframic acid root negatively charged ion or the anion modified Ni-B catalyzer of phospho-molybdic acid root.
Comparative example 1
Join in there-necked flask by as-reduced for 0.025g Pt catalyzer and 2g water, stir for some time, then add the 5g10wt% ammonia borine aqueous solution, and measured the speed of putting hydrogen by drainage, result of study as shown in Figure 2.
Result shows: relative to embodiment 1-2 and comparative example 1 (i.e. Pt/CNTs catalyzer), can discover method one prepare catalyzer (the i.e. silicotungstic acid negatively charged ion (SiW of pre-reduction
12o
40 5-) the Pt catalyzer modified) and activity have raising by a relatively large margin, and the activity inhibited of catalyzer prepared by method two.
Comparative example 2
The nickel nitrate solution of 1.42mL1.2mol/L is placed in there-necked flask, then the aqueous solution of 2g0.7wt% sodium borohydride is added drop-wise in round-bottomed flask, stirs for some time, then add the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage, result of study as shown in Figure 3.
Result shows: Ni-B catalyst ammonia borane hydrolysis puts the activity and selectivity of hydrogen all lower than catalyzer (the i.e. silicotungstic acid root negatively charged ion (SiW of pre-reduction prepared by method one
12o
40 5-) the Ni-B catalyzer modified) and the catalyzer prepared of method two.
Comparative example 3
As-reduced Ni-B/MCM-41 catalyzer is placed in there-necked flask, then adds the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage, result of study as shown in Figure 4.
Result shows: the SiW prepared with method two
12o
40 5-the activity of the Ni-B/MCM-41 catalyzer (embodiment 5) modified and selectivity are higher than Ni-B/MCM-41 catalyzer.
Comparative example 4
The nickel nitrate solution of 1.42mL1.2mol/L and 2g0.7wt% sodium borohydride solution are added drop-wise in there-necked flask, stir for some time, add the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage.When no longer including water and discharging, illustrate that reaction terminates, and then add the 5g10wt% ammonia borine aqueous solution, measured the speed of putting hydrogen by drainage.After operation like this 4 times, the pattern of catalyzer as shown in Figure 6.
Result shows: reunite hardly after successive reaction 5 times with the anion modified Ni-B catalyzer (embodiment 6) of reduction-state silicotungstic acid root, and Ni-B catalyzer agglomeration after successive reaction 5 times is very serious, this illustrates that reduction-state silicotungstic acid root negatively charged ion can prevent the gathering of Ni-B catalyst particle.
Above result shows, the method for preparing catalyst that reduction-state polyoxometallate provided by the invention is modified, easy, efficient.The method for preparing catalyst that reduction-state polyoxometallate provided by the invention is modified not only significantly can optimize the activity of noble metal catalyst, reduce the cost of noble metal catalyst, and be a kind ofly prepare very promising method that is efficient, low cost non-precious metal catalyst.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
Claims (10)
1. a method for ammonia borane hydrolysis hydrogen manufacturing, obtains hydrogen by the ammonia borine aqueous solution and catalyst mix, it is characterized in that, described catalyzer is the anion modified metal or alloy catalyzer of reduction-state polyoxometallate.
2. the method for claim 1, is characterized in that, described polyoxometallate is X
my
nz
xo
y, wherein X is H
+, metallic cation or organic cation, ligating atom centered by Y, Z is polyacid atom; Described reduction-state polyoxometallic acid salt anionic is Y
nz
xo
y (m+l)-.
3. method as claimed in claim 2, it is characterized in that, described reduction-state polyoxometallic acid salt anionic is selected from SiW
12o
40 5-, PW
12o
40 4-or PMo
12o
40 4-; Preferred SiW
12o
40 5-.
4. the method for claim 1, is characterized in that, described metal or alloy catalyzer comprises loading type and non-loading type; Described metal catalyst is Pt catalyzer; Described alloy catalyst is Ni-B catalyzer.
5. the method for claim 1, is characterized in that, the mol ratio of described polyoxometallic acid salt anionic and metal catalyst or alloy catalyst is 0-0.6; Preferred 0.1-0.5.
6. the method as described in any one of claim 1-5, is characterized in that, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
(1) reductive agent is utilized to make the reduction of polyoxometallic acid salt anionic obtain the polyoxometallate anion solutions 1 of reduction-state;
(2) reduction-state polyoxometallate anion solutions 1 is joined as-reduced metal or alloy catalyst surface, obtain the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; Preferred ammonia borine.
7. the method as described in any one of claim 1-5, is characterized in that, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
A polyoxometallate anion solutions joins and reduces or unreduced metal or alloy catalyst surface by ();
B () uses reductive agent to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; Preferred ammonia borine.
8. the method as described in any one of claim 1-5, is characterized in that, the preparation method of the metal or alloy catalyzer that described reduction-state polyoxometallate is anion modified comprises step:
I () will not to be reduced or as-reduced polyoxometallate anion solutions is impregnated into the surperficial back loading catalyst activity component of carrier;
(ii) reductive agent is used to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; Preferred ammonia borine.
9. a preparation method for the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified, is characterized in that, described reductive agent is selected from ammonia borine, sodium borohydride, hydrazine or formaldehyde; Preferred ammonia borine; Described method comprises step:
(1) reductive agent makes the reduction of polyoxometallic acid salt anionic obtain the polyoxometallate anion solutions 1 of reduction-state;
(2) reduction-state polyoxometallate anion solutions 1 is joined the metal or alloy catalyst surface of reduction, obtain the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified;
Or described method comprises step:
A polyoxometallate anion solutions joins and reduces or unreduced metal or alloy catalyst surface by ();
B () uses reductive agent to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate;
Or described method comprises step:
I () will not to be reduced or as-reduced polyoxometallate anion solutions is impregnated into the surperficial back loading catalyst activity component of carrier;
(ii) reductive agent is used to obtain the anion modified metal or alloy catalyzer of reduction-state polyoxometallate.
10. a purposes for the metal or alloy catalyzer that reduction-state polyoxometallate is anion modified, is characterized in that, for the hydrogen manufacturing of ammonia borane hydrolysis.
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