CN104069842B - Porous carbon loaded with nano metal oxide catalyst and preparation method thereof and hydrogen storage material - Google Patents
Porous carbon loaded with nano metal oxide catalyst and preparation method thereof and hydrogen storage material Download PDFInfo
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- CN104069842B CN104069842B CN201410219744.2A CN201410219744A CN104069842B CN 104069842 B CN104069842 B CN 104069842B CN 201410219744 A CN201410219744 A CN 201410219744A CN 104069842 B CN104069842 B CN 104069842B
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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
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Abstract
The invention discloses a kind of Catalysts and its preparation method of porous carbon loaded with nano metal oxide and the hydrogen storage material of this catalyst of application, preparation method comprises: metal organic frame immerses in the mixed liquor of furfuryl alcohol and ethanol and stirs 12 ~ 60 hours under air-proof condition by (1); (2) the product filtration of step (1) is obtained pressed powder, under inert atmosphere protection, be warming up to 140 ~ 165 DEG C; (3) product of step (2) is warming up to 700 ~ 1000 DEG C under inert gas protection, after insulation cooling, obtains the catalyst of porous carbon loaded with nano metal oxide.Method for preparing catalyst of the present invention is easy, and it is low that the hydrogen storage material adding this catalyst has hydrogen discharging temperature, and hydrogen discharging rate is fast, inhales that to put reversible hydrogen good, the advantage had extended cycle life.
Description
Technical field
The present invention relates to hydrogen storage material field, be specifically related to a kind of porous carbon loaded with nano metal oxide catalyst and preparation method thereof and the application in hydrogen storage material.
Background technology
The energy is one of mankind's critical elements of depending on for existence and development, is the important substance basis of national economy and social development.Along with the excessive development and utilization of this type of fossil fuel, the mankind are faced with the Double jeopardy of severe lack of energy and environment deterioration.Therefore exploitation source more extensively, clean, green novel energy source is significant efficiently.Wherein, Hydrogen Energy, as a kind of secondary energy sources of Novel clean, enjoy people to pay close attention to, and the development of Hydrogen Technology also will bring the great change of energy resource structure because of its many advantages in physical and chemical performance.Produce concrete application from hydrogen, the storage of hydrogen and transport are absolutely necessary a ring, therefore develop suitable hydrogen storage material or storage hydrogen technique for vehicle-mounted hydrogen-storing device be must faced by problem.Store up hydrogen and liquified hydrogen with high-pressure bottle to store and compare, the solid state hydrogen based on hydrogen storage material stores has the good and outstanding advantages such as weight, volume hydrogen-storage density height of security, is generally considered storing hydrogen mode most with prospects.But the hydrogen storage capability of traditional clearance-type metal hydride is on the low side (<3wt%), is difficult to the hydrogen-storage density requirement meeting practical hydrogen storage system.Therefore, the research and development of novel high-capacity hydrogen storage material promote the practical key of Hydrogen Energy.At present, the research emphasis of hydrogen storage material mainly concentrates on metal coordinate hydride hydrogen-storing material.Wherein with NaAlH
4for the metallic aluminium hydrogen compound based hydrogen storage material of representative is with its higher quality hydrogen storage capability and moderate thermodynamic property, be considered to closest to one of practical class hydrogen storage material.But, pure NaAlH
4the suction hydrogen desorption kinetics poor-performing of hydrogen storage material and reversible capacity low be most urgent problem in practical process always.At present, for improving NaAlH
4the research of hydrogen storage property aspect, mainly concentrates on NaAlH
4nanometer and exploitation effective catalyst two aspects.
As everyone knows, reduce the particle size of material, excellent physical and chemical performance can be obtained.Therefore, nanoscale NaAIH
4preparation and hydrogen storage property research receive much concern always.The most effective NaAlH at present
4the method of nanometer is the nanometer confinement method based on micropore/mesoporous template.But say from practical standpoint, the introducing of permeability medium can cause the obvious reduction of effective weight hydrogen-storage density.At present, the capacity brought for nanometer confinement reduces problem, and scientific research personnel both domestic and external mainly tends to development of new lightweight permeability medium, nonetheless also cannot tackle the problem at its root
Compare nanometer confinement, add catalyst and can improve NaAlH equally
4hydrogen storage property, and be more conducive to the maintenance of capacity.1996,
naAlH is reported Deng people
4doping obviously can improve hydrogen discharging rate containing Ti catalyst, and can realize Reversible Cycle, after this NaAlH
4receive much concern in hydrogen storage material research.Except containing Ti catalyst, people find that Zr-, Ce-, Nb-, V-and carbon class catalyst are to NaAlH successively
4de-/hydrogenation dynamic performance also has some improvement, but existing NaAlH
4the performance of hydrogen storage system still can not meet practical needs.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of porous carbon loaded with nano metal oxide the hydrogen initial temperature of putting of hydrogen storage material can be made obviously to reduce by adding this catalyst, hydrogen discharging rate is accelerated, and improves suction and puts reversible hydrogen.
For achieving the above object, the preparation method of the catalyst of a kind of porous carbon loaded with nano of the present invention metal oxide, comprising:
(1) metal organic frame (MOFs) is immersed in the mixed liquor of furfuryl alcohol and ethanol obtain mixed system, this mixed system is stirred 12 ~ 60 hours under air-proof condition.
As preferably, described furfuryl alcohol and ethanol are respectively anhydrous furfuryl alcohol and absolute ethyl alcohol, and the volume ratio of anhydrous furfuryl alcohol and absolute ethyl alcohol is 1:(1 ~ 2).
As preferably, when preparing mixed liquor, the mixed process of anhydrous furfuryl alcohol and absolute ethyl alcohol needs to carry out under the condition of lucifuge, and after mixing, the magnetic agitation time is 10 ~ 30min.
As preferably, described metal organic frame (MOFs) is the metal organic frame centered by transition metal or centered by lanthanide series metal, as preferred again, described metal organic frame (MOFs) is: Ti base MOF, Zr base MOF, Co base MOF, Ni base MOF, Ce base MOF, Sc base MOF or Nd base MOF.
As preferably, the mass fraction of described metal organic frame (MOFs) in mixed system is 0.1 ~ 1wt%.
As preferably, described metal organic frame (MOFs) heat-activated in advance, to improve activity.
As preferably, described mixed system stirs 24h under air-proof condition.
(2) the product filtration of step (1) is obtained pressed powder, under inert atmosphere protection, carry out first time is warming up to 70 ~ 90 DEG C of insulation 18 ~ 30h, then carries out second time and be warming up to 140 ~ 165 DEG C, insulation 4 ~ 8h under vacuum.
As preferably, be warming up to 80 ~ 85 DEG C for the first time, insulation 18 ~ 24h, this process can impel the intermolecular generation dehydrating condensation of furfuryl alcohol.
As preferably, when first time heats up, heating rate is 5-10 DEG C/min, is rapidly heated and furfuryl alcohol molecule can be avoided to volatilize, be conducive to furfuryl alcohol intermolecular polymerization.
As preferably, be warming up to 150 ~ 160 DEG C for the second time, under vacuum, be incubated 5 ~ 6h.When being incubated under vacuum, adopting the dynamic vacuum mode vacuumized continuously, make vacuum be not less than 1 × 10
-3torr.
As preferably, when second time heats up, heating rate is 1-5 DEG C/min.According to carbon content demand, second time can be heated up, be incubated the process that afterproduct repeats step (1) ~ (2), carbon content is made to reach final index, after generally carrying out step (1) ~ (2) for the first time, product carbon content can reach about 20-25wt%, second time cyclic carbon content can be increased to about 25-30wt%, third time, cyclic carbon content can be increased to 30-40wt%, and after this continuation increases cycle-index carbon content and substantially no longer changes.
(3) product (pressed powder after heating) of step (2) is warming up to 700 ~ 1000 DEG C under inert gas protection, insulation 3 ~ 5h, obtains the catalyst of described porous carbon loaded with nano metal oxide after cooling.
The intensification of step (3) namely completes carbonisation, and as preferably, heating rate is 1 ~ 5 DEG C/min.
As preferably, during inert gas protection, gas flow is 80 ~ 120ml/min.Air-flow is unsuitable too small, otherwise does not have protected effect, the easy oxygen reaction with infiltrating of the carbon in product; Air-flow is also unsuitable excessive, otherwise powder is easily blown and flies.
Step (2), when heating up, the existing equipments such as quartz tube furnace can be adopted (3) each time.
Generally can be cooled to room temperature during cooling, be transferred in inert-atmosphere glove box rapidly by product afterwards and preserve, transfer process should reduce product as far as possible and cruelly leak the aerial time, avoids high specific surface carbon in atmosphere spontaneous combustion to occur.
The present invention also provides a kind of catalyst of porous carbon loaded with nano metal oxide, is obtained by preparation method of the present invention.
The present invention also provides a kind of hydrogen storage material, is composited by described porous carbon loaded with nano metal oxide catalyst and metal hydride.
Described metal hydride is NaAlH
4or MgH
2.
The method of described compound comprises:
By NaAlH
4or MgH
2obtain mixture with described porous carbon loaded with nano metal oxide catalyst Homogeneous phase mixing, by mixture as in ball grinder, under inert gas shielding atmosphere, carry out ball milling.The ratio of grinding media to material of mechanical milling process is: (60 ~ 120): 1, and mechanical milling process rotating speed is: 300 ~ 500rpm, and Ball-milling Time is 5 ~ 36h.
Alternatively, the method for described compound comprises:
Mg or (mixture of NaH and Al) are obtained mixture with described porous carbon loaded with nano metal oxide catalyst Homogeneous phase mixing, by mixture as in ball grinder, under 30 ~ 50bar hydrogen pressure atmosphere, carries out ball milling.The ratio of grinding media to material of mechanical milling process is: (60 ~ 120): 1, and mechanical milling process rotating speed is: 300 ~ 500rpm, and Ball-milling Time is 20 ~ 60h.
In the method for each compound, the mass fraction of described porous carbon loaded with nano metal oxide catalyst in hydrogen storage material (said mixture) is 1 ~ 10wt%.
The present invention is using metal organic frame (MOFs) material as hard template, and furfuryl alcohol molecule, as soft template and carbon source, infiltrates in the duct of metal organic frame (MOFs) by the mode stirring dipping by furfuryl alcohol; Can promote that the condensation of furfuryl alcohol molecular dehydration forms poly furfuryl alcohol by heating, mixture carbonization at different temperatures (700 ~ 1000 DEG C) can be obtained porous carbon loaded with nano metal oxide catalyst.By the porous carbon loaded with nano metal oxide catalyst of acquisition and NaAlH
4, MgH
2under an argon atmosphere ball-milling or with (mixture of NaH and Al), Mg ball-milling under 30 ~ 50bar hydrogen pressure, the NaAlH of the porous carbon loaded with nano metal oxide catalyst that finally obtains adulterating
4or MgH
2hydrogen storage material.
The present invention is owing to have employed above technical scheme, and beneficial effect is as follows:
(1) the present invention using metal organic frame (MOFs) material as hard template, furfuryl alcohol is as soft template and carbon source, through stirring dipping, furfuryl alcohol is imported in the duct of metal organic frame (MOFs), the amount of the furfuryl alcohol molecule infiltrated in duct can be regulated by changing dipping and the number of times of heat polymerization process, achieve the controlled modulation to metal oxide in product and porous carbon relative amount, the product with different carbon content can be prepared, to meet the needs under different situations.
(2) for some special metal organic frame (as Ti base MOFs), the present invention can regulate TiO in product by changing carburizing temperature
2phase composition, prepare the catalyst with different Rutile Type and Anatase content, and preparation method is simple, mild condition.As preferably, when carburizing temperature is 900 DEG C, TiO
2in catalyst, Rutile Type and Anatase content are close to 1:1, and catalytic effect is better.
(3) compared with existing metal oxide or chloride catalyst, use catalyst prepared by the inventive method, owing to being the nano-metal-oxide porous carbon compound that fabricated in situ goes out, therefore the distribution of metal oxide particle on porous carbon matrix is more even, particle size maintains about 10nm, there is very high activity, significantly can improve NaAlH
4, MgH
2the suction hydrogen desorption kinetics performance of hydrogen storage material.Wherein add the NaAlH of Ti or Ce base porous carbon loaded with nano metal oxide catalyst
4system put hydrogen initial temperature lower than 100 DEG C.
(4) catalyst using the inventive method to prepare, due to containing porous carbon, therefore, it is possible to suppress to inhale the reunion of putting catalyst in hydrogen cyclic process, make this catalyst still can keep higher catalytic activity after hydrogen circulation is put in the multiple suction of experience, and then improve NaAlH
4, MgH
2the stability of hydrogen storage material in cyclic process, wherein adds the NaAlH of Ti base porous carbon loaded with nano metal oxide catalyst
4system experiences 5 circulations, puts hydrogen capacity and remains on more than 98%.
Accompanying drawing explanation
Fig. 1 is with MIL-125 (Ti) for template, the nano-TiO that 900 DEG C of carbonizations obtain
2porous carbon catalyst (TiO
2c-900) XRD collection of illustrative plates.
Fig. 2 is with MIL-125 (Ti) for template, the nano-TiO that 900 DEG C of carbonizations obtain
2(a) SEM picture of porous carbon catalyst, (b) TEM picture.
Fig. 3 is NaAlH
4+ 9wt%TiO
2c-900 sample and pure NaAlH
4hydrogen desorption kinetics curve comparison diagram after sample ball milling.
Fig. 4 is MgH
2+ 10wt%TiO
2c-900 sample and pure MgH
2hydrogen desorption kinetics curve comparison diagram after sample ball milling.
Fig. 5 is with Ce base MOF for template, the nano Ce O that 700 DEG C of carbonizations obtain
2porous carbon catalyst (CeO
2c-700) XRD collection of illustrative plates.
Fig. 6 is with Ce base MOF for template, the nano Ce O that 700 DEG C of carbonizations obtain
2(a) SEM picture of porous carbon catalyst, (b) TEM picture.
Fig. 7 is NaH+Al+9wt%CeO
2c-700 sample and pure NaAlH
4hydrogen desorption kinetics curve comparison diagram after sample ball milling.
Detailed description of the invention:
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Nano-TiO
2the preparation of porous carbon composite catalyst:
(1) by absolute ethyl alcohol (60ml) and anhydrous furfuryl alcohol (30ml) lucifuge magnetic agitation 20min in flask, taking MIL-125 (Ti) (0.5g) that heat-activated crosses pours in flask, lucifuge magnetic agitation 24h after sealing.
(2) filtration obtains pressed powder, loads in silica crucible and be warming up to 80 DEG C of insulation 24h with the heating rate of 10 DEG C/min under inert atmosphere protection, impel the intermolecular generation dehydrating condensation of furfuryl alcohol; 150 DEG C are warming up to subsequently, the dynamic vacuum (1 × 10 vacuumized continuously with the heating rate of 5 DEG C/min
-3torr) under under condition, insulation 6h.
(3) pressed powder after step (2) heating that obtains is taken out, repeat step (1) ~ (2) process once, again product is loaded in quartz tube furnace under Ar air-flow protection (100ml/min), be warming up to 900 DEG C of insulation 3h with the heating rate of 5 DEG C/min; When product is cooled to room temperature, product is transferred in inert-atmosphere glove box rapidly and preserves.
The sample prepared in said process is: nano-TiO
2porous carbon composite catalyst (TiO
2c-900), Figure 1 shows that the XRD collection of illustrative plates of product, as can be seen from the figure, Anatase TiO in the sample that at 900 DEG C, carbonization obtains
2with Rutile Type TiO
2content suitable; Fig. 2 a is depicted as product S EM pattern, and as can be seen from the figure the catalyst particle size of preparation is 1-2 μm at 900 DEG C, and particle mostly is irregularly shaped, and Fig. 2 b is depicted as the TEM picture of product, as can be seen from the figure, and TiO
2nano particle is evenly distributed on carbon base body, and particle size maintains about 10nm substantially.
Embodiment 2
Nano-TiO
2c-900 catalyzing N aAlH
4the preparation of hydrogen storage material: with the nano-TiO of embodiment 1
2c-900 is catalyst, NaAlH
4for matrix material mixes according to certain proportioning in argon gas atmosphere glove box, wherein TiO
2the shared in the mixture mass fraction of C-900 is respectively: 3wt%, 5wt%, 7wt%, 9wt%, 10wt%.Be placed in respectively in stainless steel jar mill by each mixture, high energy ball mill carries out ball milling, milling atmosphere is argon gas atmosphere, and rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h, and correspondence obtains five parts of hydrogen storage materials, is numbered respectively:
NaAlH
4+3wt％TiO
2C-900，
NaAlH
4+5wt％TiO
2C-900，
NaAlH
4+7wt％TiO
2C-900，
NaAlH
4+9wt％TiO
2C-900，
NaAlH
4+10wt％TiO
2C-900。
Adopt volumetric method to test the hydrogen desorption kinetics performance of five parts of hydrogen storage materials, (initial depression is 1 × 10 to prepared material under vacuum
-3torr), 250 DEG C are heated to the heating rate of 2 DEG C/min.The results are shown in Table 1.
Table 1NaAlH
4+ xwt%TiO
2the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-900 sample
Table 1 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.Known from the data table: the NaAlH that with the addition of catalyst
4its hydrogen desorption capacity of hydrogen storage material all at more than 4wt%, the equal <100 DEG C of initial hydrogen discharging temperature, and reducing gradually along with the increase of addition.
Comparative example 1
In the glove box being full of argon gas, by a certain amount of pure NaAlH
4load in ball grinder and carry out ball milling on high energy ball mill, milling atmosphere is argon gas atmosphere, and rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h, and (initial depression is 1 × 10 to the sample after ball milling under vacuum
-3torr), be heated to 250 DEG C with the heating rate of 2 DEG C/min, carry out hydrogen discharge reaction test.Figure 3 shows that the NaAlH of embodiment 2
4+ 9wt%TiO
2c-900 sample and the pure NaAlH of this comparative example
4hydrogen desorption kinetics curve comparison diagram after sample ball milling.As can be seen from the figure, NaAlH after interpolation catalyst
4hydrogen operating temperature of putting reduce 80 DEG C, hydrogen desorption kinetics performance be improved significantly.
Embodiment 3
Nano-TiO
2the preparation process of porous carbon composite catalyst is identical with embodiment 1.
Nano-TiO
2c-900 catalyzing N aAlH
4the preparation of hydrogen storage material: with the nano-TiO of embodiment 1
2c-900 is catalyst, NaAlH
4for matrix material mixes according to certain proportioning in argon gas atmosphere glove box, wherein TiO
2the shared in the mixture mass fraction of C-900 is: 9wt%.Be placed in by mixture in stainless steel jar mill, high energy ball mill carries out ball milling, milling atmosphere is argon gas atmosphere, and rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h, corresponding hydrogen storage material called after: NaAlH
4+ 9wt%TiO
2c-900.
Hydrogen cycle performance is put in the suction adopting volumetric method to test above-mentioned hydrogen storage material.Putting hydrogen process is: under vacuum condition, (initial depression is 1 × 10
-3torr), be heated to 140 DEG C of insulation 1h with the heating rate of 10 DEG C/min, carry out isothermal dehydrogenation reaction test.Inhaling hydrogen process is: under the hydrogen pressure of 100bar, is heated to 120 DEG C of insulation 1h, carries out the test of isothermal hydrogen abstraction reaction with the heating rate of 10 DEG C/min.5 suctions put the hydrogen desorption capacity of hydrogen circulation in table 2.
Comparative example 2
In the glove box being full of argon gas, by a certain amount of pure NaAlH
4load in ball grinder and carry out ball milling on high energy ball mill, milling atmosphere is argon gas atmosphere, and rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h.
Volumetric method is adopted to test the cycle performance of above-mentioned hydrogen storage material.Putting hydrogen process is: under vacuum condition, (initial depression is 1 × 10
-3torr), be heated to 240 DEG C of insulation 12h with the heating rate of 10 DEG C/min, carry out isothermal dehydrogenation reaction test.Inhaling hydrogen process is: under the hydrogen pressure of 100bar, is heated to 220 DEG C of insulation 12h, carries out the test of isothermal hydrogen abstraction reaction with the heating rate of 10 DEG C/min.5 suctions put the hydrogen desorption capacity of hydrogen circulation and capability retention in table 2
Table 2NaAlH
4+ 9wt%TiO
2c-900 sample and pure NaAlH
4the circulation hydrogen desorption capacity of sample and 5 circulation after capability retention
List in table 2 and add 9wt%NaAlH
4+ 9wt%TiO
2c-900 sample and pure NaAlH
4the hydrogen desorption capacity of 5, sample circulation, can draw capability retention by hydrogen desorption capacity, the data as can be seen from table 2, and the hydrogen storage material added after catalyst experiences 5 circulations, puts hydrogen capacity and remains on more than 98%, pure NaAlH
4put hydrogen capacity after experiencing 5 circulations and only remain 31.3%.Add this catalyst and obviously can improve NaAlH
4cyclical stability.
Embodiment 4
Nano-TiO
2the preparation process of porous carbon composite catalyst is identical with embodiment 1.
Nano-TiO
2c-900 catalysis MgH
2the preparation of hydrogen storage material: with nano-TiO
2c-900 is catalyst, MgH
2for matrix material mixes according to certain proportioning in argon gas atmosphere glove box, wherein TiO
2the shared in the mixture mass fraction of C-900 is: 3wt%, 5wt%, 7wt%, 10wt%.Mixture is placed in stainless steel jar mill respectively, after being vacuumized by ball grinder, is filled with 50bar hydrogen, high energy ball mill carries out ball milling.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h.Correspondence obtains four parts of hydrogen storage materials, is numbered respectively:
MgH
2+3wt％TiO
2C-900，
MgH
2+5wt％TiO
2C-900，
MgH
2+7wt％TiO
2C-900，
MgH
2+10wt％TiO
2C-900。
(initial depression is 1 × 10 to sample after ball milling under vacuum
-3torr), be heated to 400 DEG C with the heating rate of 2 DEG C/min, carry out hydrogen discharge reaction test, the results are shown in Table 3.
Table 3MgH
2+ xwt%TiO
2the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-900 sample
Table 3 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.As can be known from the table data, above-mentioned sample put hydrogen initial temperature all within 200 DEG C, the equal >6.5wt% of hydrogen desorption capacity.
Comparative example 3
In the glove box being full of argon gas, by a certain amount of pure MgH
2load ball grinder.Be filled with 50bar hydrogen pressure after being evacuated by ball grinder and be arranged on ball milling on high energy ball mill.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h.Sample after ball milling carries out hydrogen discharge reaction test.Figure 4 shows that the MgH of enforcement 3
2+ 10wt%TiO
2c-900 sample and pure MgH
2hydrogen desorption kinetics curve comparison diagram after sample ball milling.As can be seen from the figure, MgH after interpolation catalyst
2initial hydrogen discharging temperature reduce 90 DEG C; Put hydrogen operating temperature and reduce 70 DEG C, hydrogen desorption kinetics performance be improved significantly.
Embodiment 5
Nano Ce O
2the preparation of porous carbon composite catalyst: preparation method is identical with embodiment 1, difference is with Ce-MOF to be hard template, temperature is controlled at 700 DEG C during carbonization, insulation 3h.
The sample prepared in said process is: CeO
2c-700, Figure 5 shows that the XRD collection of illustrative plates of product, and result display only has CeO
2diffraction maximum, in Fig. 6, (a) is depicted as product S EM pattern, and as can be seen from the figure prepared catalyst mostly is club shaped structure, and in Fig. 6, (b) is depicted as the TEM pattern of product, as can be seen from the figure, CeO
2nano particle is evenly distributed on carbon base body, and particle size maintains about 5nm.
Embodiment 6
Nano Ce O
2c-700 catalyzing N aAlH
4the preparation of hydrogen storage material: the nano Ce O of embodiment 5
2c-700 is catalyst, and NaH and Al is matrix material according to the mixture of mol ratio 1:1, mixes in argon gas atmosphere glove box according to certain proportioning, and is placed in respectively in stainless steel jar mill by mixture, wherein CeO
2the shared in the mixture mass fraction of C-700 is: 3wt%, 5wt%, 7wt%, 9wt%, 10wt%.Ball grinder is vacuumized and is filled with the hydrogen pressure of 50bar, high energy ball mill carries out ball milling.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 60h.Correspondence obtains five parts of hydrogen storage materials, is numbered respectively:
NaAlH
4+3wt％CeO
2C-900，
NaAlH
4+5wt％CeO
2C-900，
NaAlH
4+7wt％CeO
2C-900，
NaAlH
4+9wt％CeO
2C-900，
NaAlH
4+10wt％CeO
2C-900。Adopt the hydrogen desorption kinetics performance of volumetric method test material, (initial depression is 1 × 10 to prepared material under vacuum
-3torr), be heated to 250 DEG C with the heating rate of 2 DEG C/min, test result is in table 4.
Table 4NaAlH
4+ xwt%CeO
2the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-700 sample
Table 4 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.Known from the data table: the NaAlH that with the addition of catalyst
4its hydrogen desorption capacity of hydrogen storage material, all at more than 4wt%, is put the equal <100 of hydrogen initial temperature DEG C and reduces gradually along with the increase of addition.
Comparative example 4
In the glove box being full of argon gas, by a certain amount of pure NaAlH
4load ball grinder.Be filled with 50bar hydrogen pressure after being evacuated by ball grinder and be arranged on ball milling on high energy ball mill.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 60h.Sample after ball milling carries out hydrogen discharge reaction test.Figure 7 shows that the NaAlH of embodiment 5
4+ 5wt%CeO
2c-700 sample and pure NaAlH
4hydrogen desorption kinetics curve comparison diagram after sample ball milling.As can be seen from the figure, the NaAlH that after adding catalyst prepared by ball milling
4initial hydrogen discharging temperature reduces 80 DEG C; Put hydrogen operating temperature and reduce 81 DEG C, hydrogen desorption kinetics performance be improved significantly.
Embodiment 7
Nano Ce O
2the preparation process of porous carbon composite catalyst is identical with embodiment 5.
Nano Ce O
2c-700 catalysis MgH
2the preparation of hydrogen storage material: with above-mentioned nano Ce O
2c-700 is catalyst, MgH
2for matrix material mixes according to certain proportioning in argon gas atmosphere glove box, wherein CeO
2the shared in the mixture mass fraction of C-700 is: 3wt%, 5wt%, 7wt%, 10wt%.Mixture is placed in stainless steel jar mill respectively, after being vacuumized by ball grinder, is filled with 50bar hydrogen, high energy ball mill carries out ball milling.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h.Correspondence obtains four parts of hydrogen storage materials, is numbered respectively:
MgH
2+3wt％CeO
2C-900，
MgH
2+5wt％CeO
2C-900，
MgH
2+7wt％CeO
2C-900，
MgH
2+10wt％CeO
2C-900。
(initial depression is 1 × 10 to sample after ball milling under vacuum
-3torr), be heated to 400 DEG C with the heating rate of 2 DEG C/min, carry out hydrogen discharge reaction test, test result is in table 5.
Table 5MgH
2+ xwt%CeO
2the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-700 sample
Table 5 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.As can be known from the table data, above-mentioned sample put hydrogen initial temperature all within 200 DEG C, the equal >6.5wt%. of hydrogen desorption capacity
Embodiment 8
Nanometer ZrO
2the preparation of porous carbon composite catalyst: preparation method is identical with embodiment 1, difference is with Zr-MOF (Uio-66) as hard template.The sample prepared in said process is: ZrO2C-900.
Nanometer ZrO
2c-900 catalyzing N aAlH
4the preparation of hydrogen storage material: identical with embodiment 2 method.Different sample tests is in table 6.
Table 6NaAlH
4+ xwt%ZrO
2the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-900 sample
Table 6 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.Known from the data table: the NaAlH that with the addition of catalyst
4its hydrogen desorption capacity of hydrogen storage material all at more than 4wt%, the equal <100 of initial hydrogen discharging temperature DEG C and reduce gradually along with the increase of addition.
Embodiment 9
Nano Co
2o
3the preparation of porous carbon composite catalyst: preparation method is identical with embodiment 1, difference is with MOF-74 (Co) as hard template.The sample prepared in said process is: Co
2o
3c-900.
Nano Co
2o
3c-900 DEG C of catalysis MgH
2the preparation of hydrogen storage material: with above-mentioned nano Co
2o
3c-900 is catalyst, and Mg is that matrix material mixes according to certain proportioning in argon gas atmosphere glove box, wherein Co
2o
3the shared in the mixture mass fraction of C-900 is: 3wt%, 5wt%, 7wt%, 10wt%.Mixture is placed in stainless steel jar mill respectively, after being vacuumized by ball grinder, is filled with 50bar hydrogen pressure, high energy ball mill carries out ball milling.Rotating speed is: 500rpm, and ratio of grinding media to material is: 120:1, and Ball-milling Time is 24h.Correspondence obtains four parts of hydrogen storage materials, is numbered respectively:
MgH
2+3wt％Co
2O
3C-900，
MgH
2+5wt％Co
2O
3C-900，
MgH
2+7wt％Co
2O
3C-900，
MgH
2+10wt％Co
2O
3C-900。
(initial depression is 1 × 10 to sample after ball milling under vacuum
-3torr), be heated to 400 DEG C with the heating rate of 2 DEG C/min, carry out hydrogen discharge reaction test, the results are shown in Table 7.
Table 7MgH
2+ xwt%Co
2o
3the putting hydrogen initial temperature, put hydrogen termination temperature and hydrogen desorption capacity of C-900 sample
Table 7 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.As can be known from the table data, above-mentioned sample put hydrogen initial temperature all within 200 DEG C, the equal >6.5wt% of hydrogen desorption capacity.
Embodiment 10
Nano NiO porous carbon composite catalyst, nanometer Sc
2o
3porous carbon composite catalyst, nanometer Nd
2o
5the preparation of porous carbon composite catalyst: preparation method is identical with embodiment 1, difference be respectively with Ni base MOF, Sc base MOF, Nd base MOF for hard template.The sample prepared in said process is respectively as NiOC-750, Sc
2o
3-850, Nd
2o
5c-800.
Nano NiO C-750, Sc
2o
3-850, Nd
2o
5c-800 catalyzing N aAlH
4the preparation of hydrogen storage material: identical with embodiment 2 method.Different sample tests is in table 6.
Table 8NaAlH
4, MgH
2add putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of different catalysts sample
Table 8 lists putting hydrogen initial temperature, putting hydrogen termination temperature and hydrogen desorption capacity of above-mentioned biased sample.Known from the data table: the NaAlH that with the addition of catalyst
4its hydrogen desorption capacity of hydrogen storage material all at more than 4.7wt%, the equal <100 DEG C of initial hydrogen discharging temperature.With the addition of the MgH of catalyst
2its hydrogen desorption capacity of hydrogen storage material all at more than 7.2wt%, the equal <200 DEG C of initial hydrogen discharging temperature.
Claims (8)
1. a hydrogen storage material, is characterized in that, be composited by the catalyst of porous carbon loaded with nano metal oxide and metal hydride, the preparation method of the catalyst of described porous carbon loaded with nano metal oxide comprises the following steps:
(1) metal organic frame is immersed in the mixed liquor of furfuryl alcohol and ethanol and obtain mixed system, this mixed system is stirred 12 ~ 60 hours under air-proof condition;
(2) the product filtration of step (1) is obtained pressed powder, under inert atmosphere protection, carry out first time is warming up to 70 ~ 90 DEG C, insulation 18 ~ 30h, then carries out second time and be warming up to 140 ~ 165 DEG C, insulation 4 ~ 8h under vacuum;
(3) product of step (2) is warming up to 700 ~ 1000 DEG C under inert gas protection, insulation 3 ~ 5h, obtains the catalyst of described porous carbon loaded with nano metal oxide after cooling.
2. hydrogen storage material as claimed in claim 1, it is characterized in that, described metal hydride is NaAlH
4or MgH
2.
3. hydrogen storage material as claimed in claim 1, it is characterized in that, the mass fraction of catalyst in hydrogen storage material of described porous carbon loaded with nano metal oxide is 1 ~ 10wt%.
4. hydrogen storage material as claimed in claim 1, it is characterized in that, described in step (1), furfuryl alcohol and ethanol are respectively anhydrous furfuryl alcohol and absolute ethyl alcohol, and the volume ratio of anhydrous furfuryl alcohol and absolute ethyl alcohol is 1:1 ~ 2.
5. hydrogen storage material as claimed in claim 1, it is characterized in that, described in step (1), metal organic frame is: Ti base MOF, Zr base MOF, Co base MOF, Ni base MOF, Ce base MOF, Sc base MOF or Nd base MOF.
6. hydrogen storage material as claimed in claim 1, it is characterized in that, described in step (1), the mass fraction of metal organic frame in mixed system is 0.1 ~ 1wt%.
7. hydrogen storage material as claimed in claim 1, is characterized in that, in step (2), when first time heats up, heating rate is 5-10 DEG C/min; When second time heats up, heating rate is 1-5 DEG C/min.
8. hydrogen storage material as claimed in claim 1, is characterized in that, in step (3), heating rate is 1 ~ 5 DEG C/min.
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