CN103613068B - A kind of Ammonia borane composite hydrogen storage material and preparation method thereof - Google Patents

A kind of Ammonia borane composite hydrogen storage material and preparation method thereof Download PDF

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CN103613068B
CN103613068B CN201310610374.0A CN201310610374A CN103613068B CN 103613068 B CN103613068 B CN 103613068B CN 201310610374 A CN201310610374 A CN 201310610374A CN 103613068 B CN103613068 B CN 103613068B
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ammonia borane
hydrogen
preparation
hydrogen storage
storage material
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CN103613068A (en
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李忠月
刘伟
杨磊
刘昆
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Henan University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the storage technical field of transportation of new forms of energy Hydrogen Energy, particularly a kind of Ammonia borane composite hydrogen storage material and preparation method thereof.Ammonia borane loads in Porous coordination polymer for adopting pickling process by described material.Matrix material of the present invention reduces the thermolysis hydrogen discharging temperature of ammonia borane, accelerate hydrogen desorption kinetics, avoid the generation of volatile byproducts, solve the technology barrier of ammonia borane as hydrogen source material, provide possibility for hydrogen energy source is applied to vehicle-mounted and industrial aspect.Preparation method is simple simultaneously, and cost is low, effective.

Description

A kind of Ammonia borane composite hydrogen storage material and preparation method thereof
Technical field
The invention belongs to the storage technical field of transportation of new forms of energy Hydrogen Energy, particularly a kind of Ammonia borane composite hydrogen storage material and preparation method thereof.
Background technology
The energy is the important substance basis and the prime mover that promote human social development and progress.Along with the continuous exhaustion of global traditional energy, the new energy development of high-efficiency environment friendly is extremely urgent, and hydrogen is simple to prepare, and the advantages such as products of combustion is pollution-free, are considered to a kind of good substitute energy.But hydrogen applications remains in some technical bottlenecks in industry and transport, namely how safe, efficient, economic transport.
Traditional storage hydrogen mode has high-pressure hydrogen storing and liquefaction hydrogen storage two kinds.High-pressure hydrogen storing be under high pressure by hydrogen storage in special steel cylinder, the pressure that usual common steel cylinder can bear is 200 ~ 300bar, the pressure that special carbon fibre material steel cylinder can bear is 450 ~ 600bar, and this mode needs the container of high strength, and cost is high, poor stability; Liquefaction hydrogen storage, to be stored in special storage tank after liquefaction of hydrogen, although this mode reduces the volume of storage tank, but the critical temperature of hydrogen arrives at-241 DEG C, liquefaction also needs to consume a large amount of energy, and also need special insulating container, cost is very high simultaneously, be only applicable to some specific occasion, as the launch vehicle of aerospace.In view of the various deficiencies of tradition storage hydrogen mode, solid-state storage hydrogen has attracted more concern gradually, large quantifier elimination is in the news, mainly contain two kinds of approach: (1) physical adsorption: rely on the physisorption between hydrogen and material, hydrogen is fixed on duct or the surface of material, thus reaching the object of storage, this just requires that material has high-specific surface area, low-density feature.(2) chemistry storage hydrogen: form chemical bond between hydrogen and hydrogen storage material, be fixed, then discharged by suitable condition, become the available energy.Relative to physics storage hydrogen, the chemical bond formed between chemistry hydrogen storage material and hydrogen is better than the reactive force of physisorption far away, hydrogen release is out needed general higher temperature, therefore, as chemistry storage hydrogen, prior link is not inhale but put, and how under the condition of gentleness safety, fast hydrogen release is changed into the key problem in technology that the available energy is chemistry storage hydrogen.Chemical hydrogen storage material main at present has metal hydride, metal alloy and hydrogen-containing compound etc., compared with other chemical hydrogen storage materials, the research of hydrogen-containing compound storage hydrogen is started late, and belong to emerging field, wherein ammonia borine is the novel hydrogen storage material comparatively received publicity in recent years.
Ammonia borane (NH 3bH 3, AmmoniaBorane, is called for short AB) and be a kind of colourless solid material, its dehydrogenation is easy to BH 3and NH 3, and NH 3bH 3low (the 30.7gmol of molecular weight -1), hydrogen content high (19.7wt%), meanwhile, it also has the features such as room-temperature stable, decomposition temperature be moderate, and therefore the dehydrogenation of ammonia borane is considered to desirable storage hydrogen scheme gradually.
The mode of ammonia borane decomposing hydrogen mainly contains two kinds, and one is hydrolysis or alcoholysis, and two is decomposes.Obviously, if using ammonia borane as vehicle-mounted energy, so the former can bring huge volume and weight to system, be unsuitable for application, because of this latter be more suitable for apply put hydrogen mode.
Ammonia borane decomposes reaction point three steps are carried out, and the first step occurs in the fusing point neighbouring (112-114 DEG C) of ammonia borane, and second step reaction occurs in about 150 DEG C, if by NH 3bH 3whole hydrogen in molecule all discharge, and the reaction of Part III solution occurs, and temperature at least will more than 500 DEG C.Therefore as hydrogen storage material, first two steps that what ammonia borane was of greatest concern is are decomposed, and theoretical hydrogen desorption capacity is about 13wt%, considerably beyond USDOE to the hydrogen storage material target of 2015 (9wt%).But the practical application of ammonia borane is also faced with some difficult problems to be had to be solved: 1) hydrogen discharging temperature of ammonia borane to be reduced to the service temperature less than 85 DEG C that USDOE specifies; 2) hydrogen discharging rate of ammonia borane is improved; 3) avoid the generation of volatile byproducts as borazine, ammonia, diborane etc.Recently, various method is attempted improving at a lower temperature the hydrogen discharging rate of ammonia borane in succession.Such as, the compound for catalysis and uhp treatment etc. of nanometer control, metal catalytic, ionic liquid, metal (Li, Ca etc.) or methyl substituted, Ir or Ru.Although also make the hydrogen discharging performance of ammonia borane improve to some extent, really realize application and need perfect.
Summary of the invention
The object of this invention is to provide a kind of new Ammonia borane composite hydrogen storage material and preparation method thereof, optimize the thermolysis hydrogen discharging performance of ammonia borane, make it have more actual application prospect.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of Ammonia borane composite hydrogen storage material, to load to ammonia borane in Porous coordination polymer by adopting pickling process and obtains.
The preparation method of described Ammonia borane composite hydrogen storage material is as follows: first prepare Porous coordination polymer, then the solution A that ammonia borane is dissolved in methyl alcohol or tetrahydrofuran (THF) is prepared under inert conditions, Porous coordination polymer be impregnated in solution A, Porous coordination polymer concentration is 0.01-0.05g/mL, 20-30 DEG C vacuumizes 24-48 hour, except desolventizing obtains Ammonia borane composite hydrogen storage material to drying.
In solution A, the concentration of ammonia borane is 0.005-0.02g/mL.
Vacuum tightness is 0.1-1Pa.
Further, when preparing Porous coordination polymer, first by Zn (NO 3) 26H 2o and terephthalic acid are dissolved in N, obtain solution B in the mixed solvent of N '-dimethyl methane amide and water, filter after solution B drying, and solids vacuum-drying obtains described Porous coordination polymer.
Zn (NO in solution B 3) 26H 2the concentration of O is 0.01-0.1mol/L, Zn (NO 3) 26H 2the mol ratio of O and terephthalic acid is 0.5-8:1 preferred 4:1, N, and the volume ratio of N '-dimethyl methane amide and water is the preferred 49:1 of 40-100:1.
Solution B is in 80-100 DEG C of dry 12-24 hour.
Solids vacuumizes 12-24 hour under 180-220 DEG C of condition, and vacuum tightness is 0.1-1Pa.
Concrete, step is as follows:
Step 1: the Zn (NO by mol ratio being 4:1 3) 26H 2o and terephthalic acid are dissolved in N, and in the mixed solvent of N '-dimethyl methane amide and water, the volume ratio of mixed solvent is 49:1.Zn (NO 3) 26H 2the concentration of O is 0.01-0.1mol/L.
Step 2: by mixing solutions as in 80-100 DEG C of loft drier, 12-24 hour.
Step 3: filtered by the suspension liquid obtained, solid part vacuumizes 12-24 hour under 200 DEG C of conditions, and vacuum tightness is 0.1-1Pa, obtains spacious Porous coordination polymer.
Step 4: at room temperature in glove box, ammonia borane is dissolved in (methyl alcohol or tetrahydrofuran (THF)) in anhydrous solvent, concentration is 0.005-0.02g/mL, is high-purity argon atmosphere in glove box.
Step 5: the porous coordination polymer material that above-mentioned steps 3 obtains be impregnated in the ammonia borane solution that step 4 obtains, concentration is 0.01-0.05g/mL, 24-48 hour is vacuumized at 20-30 DEG C of temperature, except desolventizing is to dry, vacuum tightness is 0.1-1Pa, obtains ammonia borane Porous coordination polymer matrix material.
The matrix material obtained will seal preservation at room temperature.
The present invention utilizes Porous coordination polymer to have large specific surface area and metal catalytic center is feature all over the body, ammonia borane is loaded in Porous coordination polymer and makes matrix material, ammonia borane is introduced in Porous coordination polymer duct, the channel of new improvement ammonia borane thermolysis hydrogen discharging performance is provided, to improving its applied research further, realizing Hydrogen Energy accumulating and being significant.
Advantage of the present invention and beneficial effect as follows:
1) described matrix material is made up of Porous coordination polymer and ammonia borane, maintains the skeleton structure of this Porous coordination polymer, and ammonia borane is well distributed in title complex duct.
2) the thermolysis hydrogen discharging temperature of described matrix material is reduced to 85 DEG C by 114 DEG C, reaches gentle safe hydrogen discharging temperature.
3) described matrix material heats at constant temperature 85 DEG C, and hydrogen discharging rate is significantly accelerated, and when the theoretical hydrogen desorption capacity that ammonia borane first two steps are decomposed is about 13wt%, within about 10 minutes, just can release the hydrogen of about 6%.
4) described matrix material is putting the generation avoiding gaseous by-product borazine in hydrogen process.
To sum up, described matrix material reduces the thermolysis hydrogen discharging temperature of ammonia borane, accelerates hydrogen desorption kinetics, avoids the generation of volatile byproducts, solve the technology barrier of ammonia borane as hydrogen source material, provide possibility for hydrogen energy source is applied to vehicle-mounted and industrial aspect.Preparation method is simple simultaneously, and cost is low, effective.
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption desorption curve contrast of porous coordination and ammonia borane matrix material, and the BET specific surface area of porous coordination is 288m 2/ g, total pore volume is 0.14cc/g, and the ammonia borane matrix material BET specific surface area after load ammonia borane is 1m 2/ g, total pore volume is 0.01cc/g.
Fig. 2 is the carbon dioxide adsorption curve comparison of porous coordination and ammonia borane matrix material, and the micro pore volume of porous coordination is 0.143cc/g, and the ammonia borane composite microporous volume after load ammonia borane is 0.024cc/g.
Fig. 3 is temperature programmed control desorption-mass spectrum (hydrogen signal), and the hydrogen fignal center of pure ammonia borane is at 114 DEG C, and the hydrogen fignal center of matrix material is at 85 DEG C.
Fig. 4 is temperature programmed control desorption-mass spectrum (borazine signal), and pure ammonia borane has occurred borazine fignal center 155 DEG C time, and matrix material does not find borazine fignal center.
Fig. 5 is temperature programmed control desorption-mass spectrum (diborane signal), and pure ammonia borane has occurred diborane fignal center 162 DEG C time, and matrix material does not find diborane fignal center.
Fig. 6 is the rate curve that hydrogen is put in 85 DEG C of thermolysiss.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
A kind of Ammonia borane composite hydrogen storage material, preparation process is as follows:
Step 1, in glass beaker, by 3.6gZn (NO 3) 26H 2o and 0.66g terephthalic acid is placed in 196mLN, in N '-dimethyl methane amide, is stirred to and dissolves completely, then add 4mLH 2o, stirs.Zn (NO 3) 26H 2the concentration of O is 0.012mol/L.
Step 2, mixing solutions step 1 obtained is transferred in high temperature resistant glass reaction bottle with cover, is placed in 80 DEG C of thermostatic drying chambers 12 hours.
Step 3, suspension liquid step 2 obtained filters, and solid part vacuumizes 24 hours under 200 DEG C of conditions, and vacuum tightness is 1Pa, obtains spacious Porous coordination polymer.
Step 4, is at room temperature dissolved in 10mL anhydrous methanol by 0.05g ammonia borane in glove box, is high-purity argon atmosphere in glove box.
Step 5, get porous coordination polymer material 0.2g that above-mentioned steps 3 obtains and impregnated in the ammonia borane solution that step 4 obtains, vacuumize 48 hours at 20 DEG C of temperature, vacuum tightness is 1Pa, except desolventizing is to dry, obtains ammonia borane Porous coordination polymer matrix material.
Fig. 1,2 is respectively the contrast of nitrogen adsorption desorption curve and the carbon dioxide adsorption curve comparison of porous coordination and ammonia borane matrix material.As seen from the figure, the duct of Porous coordination polymer is occupied by ammonia borane.
Fig. 3-Fig. 5 is temperature programmed control desorption-mass spectrum, as can be seen from the figure, compared with pure ammonia borane, the temperature that hydrogen is put in the thermolysis of ammonia borane matrix material obviously reduces, be reduced to 85 DEG C by 114 DEG C, and avoid main noxious volatile by product borazine and the generation of diborane in the temperature range of whole decomposing hydrogen.
The thermolysis hydrogen discharging rate of described matrix material at 85 DEG C and pure ammonia borane are compared (Fig. 6), can find, pure ammonia borane is decomposed at this temperature hardly, and the hydrogen (the theoretical hydrogen desorption capacity of ammonia borane first two steps decomposition is about 13wt%) of 6% just released by described matrix material in 10 minutes
Embodiment 2
A kind of Ammonia borane composite hydrogen storage material, preparation process is as follows:
Step 1, in glass beaker, by 7.2gZn (NO 3) 26H 2o and 1.32g terephthalic acid is placed in 196mLN, in N '-dimethyl methane amide, is stirred to and dissolves completely, then add 4mLH 2o, stirs.Zn (NO 3) 26H 2the concentration of O is 0.024mol/L.
Step 2, mixing solutions step 1 obtained is transferred in high temperature resistant glass reaction bottle with cover, is placed in 100 DEG C of thermostatic drying chambers 12 hours.
Step 3, suspension liquid step 2 obtained filters, and solid part vacuumizes 12 hours under 200 DEG C of conditions, and vacuum tightness is 0.1Pa, obtains spacious Porous coordination polymer.
Step 4, is at room temperature dissolved in 10mL anhydrous tetrahydro furan by 0.1g ammonia borane in glove box, is high-purity argon atmosphere in glove box.
Step 5, get porous coordination polymer material 0.2g that above-mentioned steps 3 obtains and impregnated in the ammonia borane solution that step 4 obtains, vacuumize 48 hours at 20 DEG C of temperature, vacuum tightness is 1Pa, except desolventizing is to dry, obtains ammonia borane Porous coordination polymer matrix material.
Embodiment 3
A kind of Ammonia borane composite hydrogen storage material, preparation process is as follows:
Step 1, in glass beaker, by 3.6gZn (NO 3) 26H 2o and 0.66g terephthalic acid is placed in 196mLN, in N '-dimethyl methane amide, is stirred to and dissolves completely, then add 4mLH 2o, stirs.Zn (NO 3) 26H 2the concentration of O is 0.012mol/L.
Step 2, mixing solutions step 1 obtained is transferred in high temperature resistant glass reaction bottle with cover, is placed in 90 DEG C of thermostatic drying chambers 12 hours.
Step 3, suspension liquid step 2 obtained filters, and solid part vacuumizes 12 hours under 200 DEG C of conditions, and vacuum tightness is 0.1Pa, obtains spacious Porous coordination polymer.
Step 4, is at room temperature dissolved in 10mL anhydrous tetrahydro furan by 0.05g ammonia borane in glove box, is high-purity argon atmosphere in glove box.
Step 5, get porous coordination polymer material 0.45g that above-mentioned steps 3 obtains to impregnated in the ammonia borane solution that step 4 obtains, vacuumize 24 hours at 30 DEG C of temperature, vacuum tightness is 0.1Pa, except desolventizing is to dry, obtain ammonia borane Porous coordination polymer matrix material.

Claims (6)

1. a preparation method for Ammonia borane composite hydrogen storage material, is characterized in that, adopts pickling process to load in Porous coordination polymer by ammonia borane; Wherein, first prepare Porous coordination polymer, then the solution A that ammonia borane is dissolved in methyl alcohol or tetrahydrofuran (THF) is prepared under inert conditions, Porous coordination polymer be impregnated in solution A, Porous coordination polymer concentration is 0.01-0.05g/mL, 20-30 DEG C vacuumizes 24-48 hour, except desolventizing obtains Ammonia borane composite hydrogen storage material to drying; When preparing Porous coordination polymer, first by Zn (NO 3) 26H 2o and terephthalic acid are dissolved in N, obtain solution B in the mixed solvent of N '-dimethyl methane amide and water, filter after solution B drying, and solids vacuum-drying obtains described Porous coordination polymer; Zn (NO in solution B 3) 26H 2the concentration of O is 0.01-0.1mol/L, Zn (NO 3) 26H 2the mol ratio of O and terephthalic acid is 0.5-8:1, N, and the volume ratio of N '-dimethyl methane amide and water is 40-100:1.
2. the preparation method of Ammonia borane composite hydrogen storage material as claimed in claim 1, it is characterized in that, in solution A, the concentration of ammonia borane is 0.005-0.02g/mL.
3. the preparation method of Ammonia borane composite hydrogen storage material as claimed in claim 2, it is characterized in that, vacuum tightness is 0.1-1Pa.
4. the preparation method of Ammonia borane composite hydrogen storage material as claimed in claim 1, it is characterized in that, solution B is in 80-100 DEG C of dry 12-24 hour.
5. the preparation method of Ammonia borane composite hydrogen storage material as claimed in claim 1, it is characterized in that, solids vacuumizes 12-24 hour under 180-220 DEG C of condition, and vacuum tightness is 0.1-1Pa.
6. the Ammonia borane composite hydrogen storage material of the arbitrary described preparation method's acquisition of claim 1-5.
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