CN106563451A - Co-B amorphous-state alloy porous microspherical catalyst used for hydrogen release through ammonia borane alcoholysis and preparation method for Co-B amorphous-state alloy porous microspherical catalyst - Google Patents
Co-B amorphous-state alloy porous microspherical catalyst used for hydrogen release through ammonia borane alcoholysis and preparation method for Co-B amorphous-state alloy porous microspherical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910020674 Co—B Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 title abstract description 12
- 239000000956 alloy Substances 0.000 title abstract description 12
- 238000006136 alcoholysis reaction Methods 0.000 title abstract description 6
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000004005 microsphere Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- 229910000085 borane Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 23
- 150000001868 cobalt Chemical class 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940097267 cobaltous chloride Drugs 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000011232 storage material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 4
- 238000001311 chemical methods and process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000006140 methanolysis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 229910003207 NH4BO2 Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a binary amorphous-state alloy porous microspherical type efficient catalyst used for hydrogen release through catalytic alcoholysis of a hydrogen storage material ammonia borane and a preparation method for the binary amorphous-state alloy porous microspherical type efficient catalyst. A chemical formula of the catalyst can be abbreviated as CoxB(1-x), wherein a molar ratio of Co to B is x to (1-x), and x ranges from 0.15 to 0.85. The catalyst has an unformed amorphous-state phase structure, has an uniformly dispersed microspheric appearance, has a microsphere size ranging from 200 nm to 300 nm, is distributed with micropores in surface, and has a specific surface area ranging from 45 m<2>.g<-1> to 60 m<2>.g<-1>; a liquid-phase chemical process is adopted, the process is relatively simple and convenient, a high-temperature high-pressure reaction and treatment process is involved, time is relatively short, control is easy, and environmental pollution is avoided in a preparation process; and through liquid-phase chemical technological treatment, a Co-B amorphous-state alloy product still keeps certain magnetic characteristics, and therefore, the catalyst is quickly separated and recycled, regenerated and reused conveniently, and operation cost in a catalytic reaction process is favorably reduced.
Description
Technical field
The present invention relates to catalyst preparation technical field, specifically a kind of to be applied to hydrogen storage material ammonia borine catalytic alcohol
Explain Binary Amorphous Alloys porous microsphere type effective catalyst of hydrogen and preparation method thereof.
Background technology
The theoretical hydrogen of ammonia borine (Ammonia Borane, abbreviation AB) is up to 19.6wt.%, is to be found so far
Hydrogen content highest hydride type hydrogen storage material.AB is at normal temperatures and pressures stable white crystal, non-volatile, avirulence,
Heat stability is stronger, water soluble and some organic solvents.Under suitable catalyst and reaction condition auxiliary, AB can be by warm
The modes such as solution, hydrolysis or alcoholysis controllably discharge hydrogen.The pyrolysis of AB is released hydrogen point multistep and is carried out, and induction period is longer, releases completely
Hydrogen needs more than 500 DEG C of temperature, and with the generation of the toxic gas such as boron azine.Liquid phase releases hydrogen to be included hydrolyzing and alcoholysis, and two
Person is that current main flow releases hydrogen research direction.By appropriate catalyst, it is gentleer that hydrogen process is released in the hydrolysis of AB, releases hydrogen speed
Rate is very fast, but by-product NH4BO2Feasible Regeneration Ways are there is no, thus application cost is higher.The alcohol of AB explains that hydrogen process is most
Carry out in methanol system, by the auxiliary of appropriate catalysts, equally can realize at a lower temperature quickly controllably discharging hydrogen
Gas, releases hydrogen amount with hydrolysis substantially quite, and harmful side product is relatively fewer, and existing technological approaches relatively more feasible in theory,
Realize alcoholysis by-product NH4B(OCH3)4Regeneration, be conducive to recycling for AB, reduce the application cost of AB.
Research in recent years finds, it is non-that the nonmetalloid such as the non-noble metal j element such as Co and Ni and B, P is combined and generated
Crystal alloy, with preferable catalytic hydrogenation or dehydrogenation activity.Amorphous alloy has isotropic space atomic arrangement, place
In shortrange order, " glassy state " metastable structure of longrange disorder, surface has the stronger unsaturated coordination field of force, active sites
Point is more, it is easy to adsorption reaction thing molecule, thus the micro structure of uniqueness cause the catalysis activity of amorphous alloy and selectivity compared with
General crystalline material is more excellent.Experimental fact proves, the atom combination of amorphous alloy, mixing ratio and its microcosmic shape
Looks have very important impact to its catalytic performance.Therefore, base metal is sought（Such as Co, Ni）Based on active component
New amorphous state alloy catalyst, carries out it and prepares, evaluates and applied research, with very important theory significance and applies valency
Value.
The content of the invention
It is an object of the present invention to the characteristics of being directed to AB alcohol explanation hydrogen course of reaction, there is provided one kind is applied to hydrogen storage material
Ammonia borine catalytic alcohol explains Binary Amorphous Alloys porous microsphere type effective catalyst of hydrogen and preparation method thereof.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of Co-B amorphous alloy porous microsphere catalyst that hydrogen is explained for ammonia borine alcohol, the chemical formula of the catalyst can letter
It is written as CoxB1-x, the mol ratio of Co and B is x:(1-x), x values 0.15 ~ 0.85, the catalyst has unformed amorphous state
Phase structure, outward appearance is in homodisperse microspheroidal, and microspherulite diameter is 200 ~ 300nm, and surface distributed has micropore, and specific surface area is 45
~60 m2·g-1。
A kind of preparation of the Co-B amorphous alloy porous microsphere catalyst for being used for ammonia borine alcohol explanation hydrogen as above
Method, the preparation method is comprised the following steps：
Step one：The scattered cobalt salt solution of polyvinylpyrrolidone is prepared：Under room temperature condition, polyvinylpyrrolidone is dissolved in into water
In, ultrasonic disperse processes 30min, and fully dissolving obtains concentration for 10 ~ 20gL-1Polyvinylpyrrolidone homogeneous phase aqueous solution,
Soluble cobalt is subsequently adding, continues supersound process to complete molten, obtain Co2+Ion concentration is 0.5 ~ 1.0 molL -1And disperse
There is the transparent cobalt salt solution of polyvinylpyrrolidone；
Step 2：Sodium borohydride solution containing surfactant is prepared：Under the conditions of ice-water bath, to concentration be 0.05 ~
0.15mol·L-1Solubility diamine solution in add quaternary ammonium salt cationic surfactant, ultrasonic disperse processes 30min,
Fully dissolving, obtains surface-active contents for 0.01 ~ 0.03 molL-1Solution, then add sodium borohydride solids, after
Continuous supersound process obtains BH to complete molten4 -Concentration is 0.5 ~ 1.0 molL -1Alkaline sodium borohydride solution, keep in dark place standby；
Step 3：The preparation of Co-B amorphous alloy porous microsphere catalyst：According to cobalt boron mol ratio [n (Co2+)/n(BH4 -)]
Equal to x/(1-x), the wherein material proportion relation of x=0.15 ~ 0.85, for given x values, pipettes respectively amount of budget
Cobalt salt solution and sodium borohydride solution, are protected, at room temperature by the alkaline sodium borohydride solution of amount of budget lentamente by nitrogen
In being added drop-wise to cobalt salt solution, while being stirred, completion of dropping, continue to react to no longer bubble is produced in solution, obtain
It is dispersed with the suspension of black particle；
Step 4：The leaching and separation of Co-B amorphous alloy catalyst products：Prepare after reaction terminates, suspension is carried out from
The heart, isolates black solid, is quickly dissolved in black solid in dehydrated alcohol with the ratio of solid-to-liquid ratio 1 (g)/20 (mL), ultrasound
30 ~ 60min of decentralized processing, then 10 ~ 15h of reflow treatment at 60 ~ 80 DEG C, is then centrifuged, and distilled water is used successively
Wash respectively 3 ~ 5 times with dehydrated alcohol, collect solidss, under the conditions of 50 DEG C 10h is vacuum dried, obtain final product black micropowder shape
Co-B amorphous alloy porous microsphere catalyst.
Soluble cobalt is cobaltous acetate, cobaltous chloride or cobaltous sulfate in the step one.
Model K30 of polyvinylpyrrolidone in the step one, molecular weight Mw=1 × 104。
Quaternary ammonium salt cationic surfactant is cetyl trimethylammonium bromide, myristyl three in the step 2
Methyl bromide ammonium or Dodecyl trimethyl ammonium chloride.
Solubility diamidogen refers to ethylenediamine or 1,2- propane diamine in the step 2.
Described ultrasonic disperse is processed from the supersonic generator that power is 240w, frequency is 40kHz.
Beneficial effects of the present invention：
What the present invention was provided explains that the Binary Amorphous Alloys porous microsphere type of hydrogen is high suitable for hydrogen storage material ammonia borine catalytic alcohol
Effect catalyst, its active component is collectively constituted by Co and B, with certain magnetic, is easy to magnetic separation recovery and is recycled, and
Alcoholysis reaction can be used to controllably adjusting releases hydrogen speed；From base metal Co as catalyst main active,
Replace the noble metals such as dehydrogenation conventional Pt and Pd so that the preparation cost of catalyst is greatly reduced；
What the present invention was provided explains that the Binary Amorphous Alloys porous microsphere type of hydrogen is high suitable for hydrogen storage material ammonia borine catalytic alcohol
The preparation method of effect catalyst, using liquid phase chemical technique, process relative ease, is not related to the reaction of High Temperature High Pressure and processed
Journey, the time is shorter, it is easy to control, and preparation process does not have environmental pollution；Through liquid phase chemical PROCESS FOR TREATMENT so that Co-B is non-
Crystal alloy product still keeps certain magnetic characteristic, thus is easy to the sharp separation of catalyst to reclaim, regenerate and be multiplexed, and helps
In the operating cost for reducing catalytic reaction process；
Catalyst obtained by the present invention, is the amorphous alloy constituted with base metal Co and nonmetallic B, and it has raw material valency
It is honest and clean, process is simple, it is easy to control, lower-cost feature；This catalyst has certain magnetic, is easy to sharp separation and returns
Receive, contribute to reducing the use cost of catalytic reaction process；Co-B amorphous alloy products have microcellular structure, present more equal
Even is spherical, is conducive to expanding specific surface area, increases avtive spot, improves catalysis activity；According to surveying and determination, present invention gained catalyst
The mean diameter of microsphere is 250nm, and average specific surface area is 52.5 m2·g-1, catalyst is used for into 0.5wt.%'s at 25 DEG C
Ammonia borine（AB）Methanolysis release hydrogen, it averagely releases hydrogen speed for 8265.2 mlmin-1·g-1, release the average of hydrogen reaction
Apparent activation energy is 48.27 kJmol-1。
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated.
A kind of Co-B amorphous alloy porous microsphere catalyst that hydrogen is explained for ammonia borine alcohol, the chemical formula of the catalyst
Co can be abbreviated asxB1-x, the mol ratio of Co and B is x:(1-x), x values 0.15 ~ 0.85, the catalyst has unformed non-
Crystalline state phase structure, outward appearance is in homodisperse microspheroidal, and microspherulite diameter is 200 ~ 300nm, and surface distributed has micropore, specific surface area
For 45 ~ 60 m2·g-1。
Embodiment 1
A kind of preparation method of the Co-B amorphous alloy porous microsphere catalyst that hydrogen is explained for ammonia borine alcohol, including following step
Suddenly：
Step one：Under room temperature, by 10g polyvinylpyrrolidones（PVP）In dissolving in 100mL water, supersound process 30min is fully molten
Solution, adds cobaltous acetate 0.05mol, continues supersound process to complete molten, obtains transparent cobalt salt solution；
Step 2：It is 0.05 molL to 100mL, concentration under the conditions of ice-water bath-1Ethylenediamine solution in add
The cetyl trimethylammonium bromide of 0.001mol, ultrasonic disperse processes 30min, and then fully dissolving adds 0.05mol's
NaBH4Solid, continues supersound process to complete molten, obtains NaBH4Alkaline solution, keeps in dark place；
Step 3：According to n (Co2+)/n(BH4 -)=0.18, pipettes respectively the alkaline NaBH of 15mL cobalt salt solutions and 85mL4It is molten
Liquid, is protected, at room temperature by NaBH by nitrogen4Solution is lentamente added drop-wise in cobalt salt solution, while constantly magnetic agitation, drop
Plus follow-up continuous reaction is finished, till no longer producing bubble, obtain black suspension；
Step 4：Black solid is isolated after centrifugal treating suspension, in the ratio of solid-to-liquid ratio 1 (g)/20 (mL), black is consolidated
Body quickly dissolves in dehydrated alcohol, ultrasonic disperse 30min, and then reflow treatment 10h at 60 DEG C, is then centrifuged, and uses
Distilled water and dehydrated alcohol are washed respectively 3 times, collect solidss, and at 50 DEG C 10h is vacuum dried, and obtain final product black micropowder shape
Co-B amorphous alloy porous microsphere catalyst.
Jing measurings, the mean diameter of the catalyst is 280nm, and specific surface area is 46.5m2·g-1；At for 25 DEG C,
The ammonia borine of 0.5wt.%（AB）Methanolysis release hydrogen, release hydrogen speed for 7866.5 mLmin-1·g-1, release the table of hydrogen reaction
Sight activation energy is 50.63 kJmol-1。
Embodiment 2
A kind of preparation method of the Co-B amorphous alloy porous microsphere catalyst that hydrogen is explained for ammonia borine alcohol, including following step
Suddenly：
Step one：Under room temperature, 20g PVP are dissolved in 100mL water, supersound process 30min, fully dissolving, add cobaltous chloride
0.1mol, continues supersound process to complete molten, obtains transparent cobalt salt solution；
Step 2：It is 0.15 molL to 100mL, concentration under the conditions of ice-water bath-11,2- propane diamine aqueous solutions in add
The Tetradecyl Trimethyl Ammonium Bromide of 0.003mol, ultrasonic disperse processes 30min, and then fully dissolving adds 0.1mol's
NaBH4Solid, continues supersound process to complete molten, obtains NaBH4Alkaline solution, keeps in dark place；
Step 3：According to n (Co2+)/n(BH4 -)=5.70, pipette respectively the alkaline NaBH of 85mL cobalt salt solutions and 15mL4It is molten
Liquid, is protected, at room temperature by NaBH by nitrogen4Solution is lentamente added drop-wise in cobalt salt solution, while constantly magnetic agitation, drop
Plus follow-up continuous reaction is finished, till no longer producing bubble, obtain black suspension；
Step 4：Black solid is isolated after centrifugal treating suspension, in the ratio of solid-to-liquid ratio 1 (g)/20 (mL), black is consolidated
Body quickly dissolves in dehydrated alcohol, ultrasonic disperse 60min, then reflow treatment 15h at 80 DEG C, centrifugation, with distilled water and anhydrous
Ethanol is washed respectively 5 times, collects solidss, and 10 h are vacuum dried at 50 DEG C, and the Co-B amorphous states for obtaining final product black micropowder shape are closed
Golden porous microsphere catalyst.
Jing measurings, the mean diameter of the catalyst is 220nm, and specific surface area is 53.7m2·g-1；At for 25 DEG C,
The ammonia borine of 0.5wt.%（AB）Methanolysis release hydrogen, release hydrogen speed for 8433.62 mLmin-1·g-1, release hydrogen reaction
Apparent activation energy is 45.06 kJmol-1。
Embodiment 3
A kind of preparation method of the Co-B amorphous alloy porous microsphere catalyst that hydrogen is explained for ammonia borine alcohol, including following step
Suddenly：
Step one：Under room temperature, 15g PVP are dissolved in 100mL water, supersound process 30min, fully dissolving, add cobaltous sulfate
0.075mol, continues supersound process to complete molten, obtains transparent cobalt salt solution；
Step 2：It is 0.10 molL to 100mL, concentration under the conditions of ice-water bath-1Ethylenediamine solution in add
The Dodecyl trimethyl ammonium chloride of 0.002mol, ultrasonic disperse processes 30min, and then fully dissolving adds 0.075mol
NaBH4Solid, continues supersound process to complete molten, obtains NaBH4Alkaline solution, keeps in dark place；
Step 3：According to n (Co2+)/n(BH4 -)=2.90, pipette respectively the alkalescence of 74.5mL cobalt salt solutions and 25.5mL
NaBH4Solution, is protected, at room temperature by NaBH by nitrogen4Solution is lentamente added drop-wise in cobalt salt solution, while constantly magnetic force
Stirring, completion of dropping continues to react, and till no longer producing bubble, obtains black suspension；
Step 4：Black solid is isolated after centrifugal treating suspension, in the ratio of solid-to-liquid ratio 1 (g)/20 (mL), black is consolidated
Body quickly dissolves in dehydrated alcohol, ultrasonic disperse 45min, then reflow treatment 12h at 70 DEG C, with distilled water and anhydrous after centrifugation
Ethanol is alternately washed each 4 times, collects solidss, and at 50 DEG C 10h is vacuum dried, and the Co-B amorphous states for obtaining final product black micropowder shape are closed
Golden porous microsphere catalyst.
Jing measurings, the mean diameter of the catalyst is 230nm, and specific surface area is 49.8m2·g-1；At for 25 DEG C,
The ammonia borine of 0.5wt.%（AB）Methanolysis release hydrogen, release hydrogen speed for 8061.26 mLmin-1·g-1, release hydrogen reaction
Apparent activation energy is 48.73 kJmol-1。
Claims (7)
1. the Co-B amorphous alloy porous microsphere catalyst that ammonia borine alcohol explains hydrogen is used for, it is characterised in that：The catalyst
Chemical formula can be abbreviated as CoxB1-x, the mol ratio of Co and B is x:(1-x), x values 0.15 ~ 0.85, the catalyst has without fixed
The Amorphous Phase structure of type, outward appearance is in homodisperse microspheroidal, and microspherulite diameter is 200 ~ 300nm, and surface distributed has micropore, than
Surface area is 45 ~ 60 m2·g-1。
2. it is a kind of as claimed in claim 1 to be used for the Co-B amorphous alloy porous microsphere catalyst that ammonia borine alcohol explains hydrogen
Preparation method, it is characterised in that the preparation method is comprised the following steps：
Step one：The scattered cobalt salt solution of polyvinylpyrrolidone is prepared：Under room temperature condition, polyvinylpyrrolidone is dissolved in into water
In, ultrasonic disperse processes 30min, and fully dissolving obtains concentration for 10 ~ 20gL-1Polyvinylpyrrolidone homogeneous phase aqueous solution,
Soluble cobalt is subsequently adding, continues supersound process to complete molten, obtain Co2+Ion concentration is 0.5 ~ 1.0 molL -1And disperse
There is the transparent cobalt salt solution of polyvinylpyrrolidone；
Step 2：Sodium borohydride solution containing surfactant is prepared：Under the conditions of ice-water bath, to concentration be 0.05 ~
0.15mol·L-1Solubility diamine solution in add quaternary ammonium salt cationic surfactant, ultrasonic disperse processes 30min,
Fully dissolving, obtains surface-active contents for 0.01 ~ 0.03 molL-1Solution, then add sodium borohydride solids, after
Continuous supersound process obtains BH to complete molten4 -Concentration is 0.5 ~ 1.0 molL -1Alkaline sodium borohydride solution, keep in dark place standby；
Step 3：The preparation of Co-B amorphous alloy porous microsphere catalyst：According to cobalt boron mol ratio [n (Co2+)/n(BH4 -)]
Equal to x/(1-x), the wherein material proportion relation of x=0.15 ~ 0.85, for given x values, pipettes respectively amount of budget
Cobalt salt solution and sodium borohydride solution, are protected, at room temperature by the alkaline sodium borohydride solution of amount of budget lentamente by nitrogen
In being added drop-wise to cobalt salt solution, while being stirred, completion of dropping, continue to react to no longer bubble is produced in solution, obtain
It is dispersed with the suspension of black particle；
Step 4：The leaching and separation of Co-B amorphous alloy catalyst products：Prepare after reaction terminates, suspension is carried out from
The heart, isolates black solid, is quickly dissolved in black solid in dehydrated alcohol with the ratio of solid-to-liquid ratio 1 (g)/20 (mL), ultrasound
30 ~ 60min of decentralized processing, then 10 ~ 15h of reflow treatment at 60 ~ 80 DEG C, is then centrifuged, and distilled water is used successively
Wash respectively 3 ~ 5 times with dehydrated alcohol, collect solidss, under the conditions of 50 DEG C 10h is vacuum dried, obtain final product black micropowder shape
Co-B amorphous alloy porous microsphere catalyst.
3. it is as claimed in claim 2 to be used for the preparation that ammonia borine alcohol explains the Co-B amorphous alloy porous microsphere catalyst of hydrogen
Method, it is characterised in that：Soluble cobalt is cobaltous acetate, cobaltous chloride or cobaltous sulfate in the step one.
4. it is as claimed in claim 2 to be used for the system that ammonia borine alcohol explains the Co-B amorphous alloy porous microsphere catalyst of hydrogen
Preparation Method, it is characterised in that：Model K30 of polyvinylpyrrolidone in the step one, molecular weight Mw=1 × 104。
5. it is as claimed in claim 2 to be used for the preparation that ammonia borine alcohol explains the Co-B amorphous alloy porous microsphere catalyst of hydrogen
Method, it is characterised in that：In the step 2 quaternary ammonium salt cationic surfactant be cetyl trimethylammonium bromide, ten
Tetraalkyl trimethylammonium bromide or Dodecyl trimethyl ammonium chloride.
6. it is as claimed in claim 2 to be used for the preparation that ammonia borine alcohol explains the Co-B amorphous alloy porous microsphere catalyst of hydrogen
Method, it is characterised in that：Solubility diamidogen refers to ethylenediamine or 1,2- propane diamine in the step 2.
7. it is as claimed in claim 2 to be used for the preparation that ammonia borine alcohol explains the Co-B amorphous alloy porous microsphere catalyst of hydrogen
Method, it is characterised in that：Described ultrasonic disperse is processed from the supersonic generator that power is 240w, frequency is 40kHz.
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| CN108246332A (en) * | 2018-01-16 | 2018-07-06 | 浙江大学 | A kind of non-noble metal supported catalyst of two dimension and its preparation method and application |
| CN110284146A (en) * | 2019-06-21 | 2019-09-27 | 青岛科技大学 | Load selenium in situ adulterates molybdenum disulfide/transition metal boride nano material preparation and application |
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| CN101157034A (en) * | 2007-11-13 | 2008-04-09 | 上海师范大学 | A non-crystal alloy catalyst as well as its preparing method and purpose |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108246332A (en) * | 2018-01-16 | 2018-07-06 | 浙江大学 | A kind of non-noble metal supported catalyst of two dimension and its preparation method and application |
| CN110284146A (en) * | 2019-06-21 | 2019-09-27 | 青岛科技大学 | Load selenium in situ adulterates molybdenum disulfide/transition metal boride nano material preparation and application |
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