CN102515095B - Metal manganese oxide-loaded ammonia borane hydrogen storage material, and preparation method thereof - Google Patents
Metal manganese oxide-loaded ammonia borane hydrogen storage material, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal manganese oxide-loaded ammonia borane hydrogen storage material, wherein the metal manganese oxide-loaded ammonia borane hydrogen storage material is prepared by loading ammonia borane through a metal manganese oxide, and the metal manganese oxide is manganese dioxide hollow cubes, manganese dioxide hollow spheres or manganese dioxide porous nanoparticles. The preparation steps comprise: 1) dispersing the metal manganese oxide in a tetrahydrofuran solvent through an ultrasonic treatment; 2) dissolving the ammonia borane in a tetrahydrofuran solvent; 3) mixing the two solutions, and uniformly stirring; 4) carrying out vacuum drying on the uniformly-mixed solution to remove the solvent to prepare the target product. The metal manganese oxide-loaded ammonia borane hydrogen storage material and the preparation method have the following advantages that: the ammonia borane and the metal manganese oxide are adopted as the raw materials, and the metal manganese oxide-loaded ammonia borane hydrogen storage material is prepared at the low temperature, such that the pyrolysis hydrogen desorption temperature of the ammonia borane can be effectively reduced, and the generations of borazole, diborane, ammonia and other harmful substances can be effectively inhibited; the heat release is small during the hydrogen desorption process, such that the regeneration of the reaction product is easily achieved through the solid-gas reaction or the chemical engineering process under the relatively mild conditions.
Description
Technical field
The hydrogen storage material and the technology that the present invention relates to new forms of energy Hydrogen Energy, be specially a kind of metal manganese oxide-loaded ammonia borane hydrogen storage material and preparation method thereof.
Background technology
Because the whole world rapidly increases the demand of the energy, limited fossil energy can not meet the demand of rapid economic development, and people strive to find the substitute energy of fossil energy, comprising renewable energy source and other new forms of energy.Develop a kind of renewable, tool high combustion value, be easy to utilize again New-type fuel free from environmental pollution to become people's common aspiration.Hydrogen is the efficient energy carrier of a kind of cleaning, is the secondary energy that a kind of people expect, is considered the surrogate of fossil energy.In following energy system, Hydrogen Energy can become lays equal stress on electric energy and complementary terminal energy sources, permeates and serves all respects of social and economic activities, thereby make significant contribution for national energy security and environment protection.In recent years, the fast development of hydrogen fuel cell and association area thereof has effectively promoted the progress of Hydrogen Technology, yet storing hydrogen technology has become the bottleneck of restriction Hydrogen Energy development.Therefore, the hydrogen storaging and transport technology of development high-energy-density, high-level efficiency and safety is the key technical problem that must solve.Solid-state storage hydrogen, due to advantages such as mass density are high, safety performance is good, is considered to a kind of hydrogen storage mode most with prospects.Traditional metal hydrogen storage material, as AB, AB
2and AB
5type alloy, though have high volume hydrogen-storage density, the virtual mass hydrogen storage capability under mild conditions is many lower than 3%, lower than International Energy Agency (IEA), proposes the target that quality hydrogen-storage density is greater than 5%.By the elementary composition hydroborate of lightweight, as lithium borohydride (LiBH
4), sodium borohydride (NaBH
4), ammonia borine (NH
3bH
3) scheduling theory quality hydrogen storage capability is all far away higher than 5%, become the hydrogen storage material very with application prospect.
Ammonia borine (NH
3bH
3, AB) there is higher quality hydrogen storage capability (19.6wt%) and volume hydrogen storage capability (145kgH
2/ m
3), the target proposing far above International Energy Agency, these character make AB and its associated materials become the important materials of on-the-spot hydrogen manufacturing application.AB can emit by the mode of pyrolysis and hydrolysis the hydrogen of 3 equivalents.The controlled hydrogen of putting that the hydrolytic process of ammonia borine conventionally need to improve the hydrogen discharging speed of AB and realize the ammonia borine aqueous solution by metal-based catalyst.Catalyst activity and metal species, particle size, pattern, catalyst precursor and solid support material have close relationship (Chandra, M.; Xu, Q.J.Power Sources2006,156,190.; Kalidindi, S.B.; Indirani, M.; Jagirdar, B.R.Inorg.Chem.2008,47,7424.).But ammonia borane hydrolysis also exists the problem that volume hydrogen-storage density is lower, be difficult to meet practical application request.The pyrolysis of ammonia borine can realize the hydrogen of emitting at a lower temperature 2 equivalents, has been subject in recent years paying close attention to widely.By research, find, the pyrolysis of ammonia borine also exists some problem, first its preliminary hydrogen discharging temperature is higher than the working temperature (114 ℃ of >) of Proton Exchange Membrane Fuel Cells, and hydrogen desorption kinetics under lesser temps is slow, make under low temperature in molecule the utilization ratio of hydrogen not high.In addition, the release of the obnoxious flavour impurity such as borazole (borazine), diborane (diborane), ammonia (ammonia) is often followed and is put in hydrogen process in the pyrolysis of ammonia borine, these obnoxious flavoures can make metal catalyst poisoning and deactivation in fuel cell, thereby have limited the practical application of ammonia borine.In order to address these problems, main technological method has at present: utilize nanometer confinement effect, AB is loaded in the nano pore of mesoporous material or metal organic frame, reduced activation energy (Gutowska, A. that hydrogen is put in pyrolysis hydrogen discharging temperature and pyrolysis; Li, L.; Shin, Y., et al.Angew.Chem.Int.Ed.2005,44,3578.; Li, Z.Y.; Zhu, G.S.; Lu, G.Q., et al.J.Am.Chem.Soc.2010,132,1490.); By noble metal catalyst, improve pyrolysis hydrogen discharging performance (Denney, the M.C. that ammonia borine is done; Pons, V.; Hebden, T.J., et al.J.Am.Chem.Soc.2006,128,12048.); With alkaline earth metal hydride, react with ammonia borine and generate novel metal-ammonia borane compound, improve its pyrolysis hydrogen discharging rate and reduce hydrogen discharging temperature (Diyabalanage, H.V. K.; Shrestha, R.P.; Semelsberger, T.A., et al.Angew.Chem.Int.Ed.2007,46,8995.).Recently, our seminar has researched and developed a kind of novel hollow silica ball load ammonia borine hydrogen storage material, and this material has obviously reduced the hydrogen discharging temperature of ammonia borine, and has suppressed obnoxious flavour impurity, the generation of borazole, diborane and ammonia (Zhang, T. for example; Yang, X.; Yang, S., et al.Phys.Chem.Chem.Phys.2011,13,18592.).
Although the research of hydrogen is put in the pyrolysis of ammonia borine, obtain certain progress, still lacked at present the ripe system that meets practical demand.Therefore the exploitation of metal manganese oxide-loaded ammonia borane hydrogen storage material system that, there is good hydrogen discharging performance for the actual application value that improves ammonia borine by significant.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of metal manganese oxide-loaded ammonia borane hydrogen storage material and preparation method thereof is provided, easy, efficient blend-desiccating method that the present invention adopts is prepared the compound ammonia borine of organism hydrogen storage material, this hydrogen storage material has to be put fast hydrogen and can effectively suppress the remarkable advantage that obnoxious flavour impurity produces under lesser temps, energy density is high and safe and efficient, aspect vehicle-mounted Chu Qing, has application prospect.
Technical scheme of the present invention:
A kind of metal manganese oxide-loaded ammonia borane hydrogen storage material, by the oxide carried ammonia borine of manganese metal (AB), made, described manganese metal oxide compound is hollow manganese dioxide cubes (MHC), manganese dioxide hollow sphere (MHS) or Manganse Dioxide porous nano particle (MNP).
A preparation method for described metal manganese oxide-loaded ammonia borane hydrogen storage material, comprises the following steps:
1) by the ultrasonic tetrahydrofuran solvent being scattered in after purifying of manganese metal oxide compound, make manganese metal oxide compound tetrahydrofuran solution;
2) ammonia borine is dissolved in the tetrahydrofuran solvent after purifying, makes ammonia borine tetrahydrofuran solution;
3) above-mentioned two kinds of solution are mixed, mixed solution is slowly stirred to even mixed solution;
4) above-mentioned even mixed solution is carried out to vacuum-drying except after desolventizing, can make this metal manganese oxide-loaded ammonia borane hydrogen storage material.
The amount ratio of described manganese metal oxide compound and tetrahydrofuran solvent is 40-60mg/mL.
The amount ratio of described ammonia borine and tetrahydrofuran solvent is 12-20mg/mL.
In described two kinds of solution mixed solutions, the mass ratio of manganese metal oxide compound and ammonia borine is 3: 1.
The whipping temp of described mixed solution and vacuum-drying temperature are 20 ℃, and the vacuum drying time is 12-24 hour.
The vacuum drying vacuum tightness of described even mixed solution is 0.05-0.1MPa.
Advantage of the present invention and beneficial effect are: it is raw material that ammonia borine and manganese metal oxide compound are take in the present invention, at lower temperature, prepare metal manganese oxide-loaded ammonia borane hydrogen storage material, can effectively reduce the pyrolysis hydrogen discharging temperature of ammonia borine, effectively suppress the generation of the obnoxious flavour impurity such as borazole, diborane, ammonia, there is hydrogen desorption kinetics faster; In putting hydrogen process, release of heat is little in addition, and the enthalpy change of decomposition reaction, close to hankering property, is conducive under relative mild conditions by the regeneration of solid-solid/liquid/gas reactions or chemical process realization response product.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of pure AB and 3MHC/AB sample.
Fig. 2 is that MHC sample (a) is schemed with the scanning electron microscope (SEM) of MHC/AB sample (b).
Fig. 3 is temperature programmed control desorption-mass spectrum (TPD-MS) curve of pure AB and 3MHC/AB sample.
Fig. 4 is thermogravimetric (TG) curve of pure AB and 3MHC/AB sample.
Fig. 5 is means of differential scanning calorimetry (DSC) curve of pure AB and 3MHC/AB sample.
Fig. 6 is thermogravimetric (TG) and means of differential scanning calorimetry (DSC) curve of 3MHS/AB sample.
Fig. 7 is thermogravimetric (TG) and means of differential scanning calorimetry (DSC) curve of 3MNP/AB sample.
Embodiment
Below by embodiment, further illustrate the present invention.
Embodiment 1:
A preparation method for described metal manganese oxide-loaded ammonia borane hydrogen storage material, comprises the following steps:
1) by the ultrasonic tetrahydrofuran solvent being scattered in after 1.5mL purifying of 60mg hollow manganese dioxide cubes (MHC), make manganese metal oxide compound tetrahydrofuran solution;
2) 20mg ammonia borine is dissolved in the 1mL tetrahydrofuran solvent after purifying, makes ammonia borine tetrahydrofuran solution;
3) above-mentioned two kinds of solution are mixed, in mixed solution, the mass ratio of manganese metal oxide compound and ammonia borine is 3: 1, in temperature, is, under 20 ℃ of conditions, mixed solution is slowly stirred to even mixed solution;
4) by above-mentioned even mixed solution, in vacuum tightness, be that 0.05MPa, temperature are under 20 ℃ of conditions, to carry out vacuum-drying except after desolventizing, can make this metal manganese oxide-loaded ammonia borane hydrogen storage material, identified as samples is designated as 3MHC/AB.
According to the XRD spectra of the prepared 3MHC/AB of aforesaid method as shown in Figure 1, and compare with pure AB.From spectrogram, can find out: pure AB has obvious crystalline diffraction peak, the characteristic peak that 3MHC/AB sample still has AB exists, and shows that 3MHC/AB is that AB and MHC are physical load effect.
Fig. 2 is the stereoscan photograph (SEM) of MHC sample (a) and MHC/AB sample (b), from Fig. 2 (a), can find out, and the open hollow structure of the monodispersed size uniform of hollow manganese dioxide cubes, the cubes length of side is approximately 400nm.As shown in Fig. 2 (b), after MHC load AB, still kept the pattern of monodispersion cubic, the result shows, application aforesaid method, AB loads in the surfaces externally and internally and hole of MHC uniformly.
Fig. 3 is temperature programmed control desorption-mass spectrum (TPD-MS) curve of pure AB and 3MHC/AB sample.Result shows: the initial hydrogen discharging temperature of pure AB is 100 ℃, and hydrogen discharge reaction carries out in two steps, and peak temperature is respectively 118 ℃ and 160 ℃.Yet 3MHC/AB sample has 60 ℃ of lower initial hydrogen discharging temperatures, hydrogen discharge reaction only carries out with a step, and its peak temperature is 97 ℃, than pure AB, has reduced by 21 ℃.And without any obnoxious flavour impurity, produce in putting hydrogen process whole.Visible, the hydrogen discharging performance of hollow manganese dioxide cubes load ammonia borine hydrogen storage material 3MHC/AB sample is obviously better than pure AB.
Fig. 4 is thermogravimetric (TG) curve of pure AB and 3MHC/AB sample.As can be seen from Fig., pure AB is that two steps are weightless, corresponding to the two step certain embodiments of TPD-MS.And 3MHC/AB sample starts weightlessness in the time of about 60 ℃, a whole weightless step occurs, and weight loss is far smaller than pure AB, illustrate that 3MHC/AB sample can put the generation of hydrogen and inhibition by product at a lower temperature.
Fig. 5 is means of differential scanning calorimetry (DSC) curve of pure AB and 3MHC/AB sample.Before can finding out pure AB dehydrogenation exothermic peak, at 110 ℃, locate to exist one to melt endotherm(ic)peak, this has also explained why pure AB hydrogen desorption kinetics is poor, yet 3MHC/AB sample only has the exothermic peak of a certain embodiments.The reaction enthalpy that calculates pure AB and 3MHC/AB sample by the exothermic peak area to curve is respectively Δ H=-22kJ/mol and Δ H=-6.0kJ/mol.As can be seen here, 3MHC/AB sample has obviously improved the thermomechanical property of pure AB.
Embodiment 2:
A preparation method for described metal manganese oxide-loaded ammonia borane hydrogen storage material, comprises the following steps:
1) by the ultrasonic tetrahydrofuran solvent being scattered in after 1.5mL purifying of 60mg manganese dioxide hollow sphere (MHS), make manganese metal oxide compound tetrahydrofuran solution;
2) 20mg ammonia borine is dissolved in the tetrahydrofuran solvent after 1mL purifying, makes ammonia borine tetrahydrofuran solution;
3) above-mentioned two kinds of solution are mixed, in mixed solution, the mass ratio of manganese metal oxide compound and ammonia borine is 3: 1, in temperature, is, under 20 ℃ of conditions, mixed solution is slowly stirred to even mixed solution;
4) by above-mentioned even mixed solution, in vacuum tightness, be that 0.07MPa, temperature are under 20 ℃ of conditions, to carry out vacuum-drying except after desolventizing, can make this metal manganese oxide-loaded ammonia borane hydrogen storage material, identified as samples is designated as 3MHS/AB.
Thermogravimetric (TG) and means of differential scanning calorimetry (DSC) curve that Fig. 6 is the novel metal oxide load ammonia borine hydrogen storage material 3MHS/AB sample prepared according to aforesaid method.TG result shows: 3MHS/AB sample starts weightless at 60 ℃, and a whole weightless step generation, and weight loss is far smaller than pure AB.By DSC curve, can find out that 3MHS/AB sample only has the exothermic peak of a certain embodiments.The reaction enthalpy that calculates 3MHS/AB sample by the exothermic peak area to curve is Δ H=-7.8kJ/mol, lower than the reaction enthalpy (Δ H=-22kJ/mol) of pure AB.The above results shows that 3MHS/AB sample has obviously improved the pyrolysis hydrogen discharging performance of pure AB.
Embodiment 3:
A preparation method for described metal manganese oxide-loaded ammonia borane hydrogen storage material, comprises the following steps:
1) by the ultrasonic tetrahydrofuran solvent being scattered in after 1.5mL purifying of 60mg manganese dioxide nano particle (MNP), make manganese metal oxide compound tetrahydrofuran solution;
2) 20mg ammonia borine is dissolved in the tetrahydrofuran solvent after 1mL purifying, makes ammonia borine tetrahydrofuran solution;
3) above-mentioned two kinds of solution are mixed, in mixed solution, the mass ratio of manganese metal oxide compound and ammonia borine is 3: 1, in temperature, is, under 20 ℃ of conditions, mixed solution is slowly stirred to even mixed solution;
4) by above-mentioned even mixed solution, in vacuum tightness, be that 0.1MPa, temperature are under 20 ℃ of conditions, to carry out vacuum-drying except after desolventizing, can make this metal manganese oxide-loaded ammonia borane hydrogen storage material, identified as samples is designated as 3MNP/AB.
Thermogravimetric (TG) and means of differential scanning calorimetry (DSC) curve that Fig. 7 is the novel metal Mn oxide load ammonia borine hydrogen storage material 3MNP/AB sample prepared according to aforesaid method.By TG curve, can find out that 3MNP/AB sample starts at 60 ℃ weightless, and a whole weightless step generation, weight loss is far smaller than pure AB.DSC curve shows that 3MNP/AB sample only has the exothermic peak of a certain embodiments.The reaction enthalpy that calculates 3MNP/AB sample by the exothermic peak area to curve is Δ H=-9.2kJ/mol, lower than the reaction enthalpy (Δ H=-22kJ/mol) of pure AB.As can be seen here, 3MNP/AB sample has obviously improved the pyrolysis hydrogen discharging performance of pure AB.
Detected result shows: metal manganese oxide-loaded ammonia borane hydrogen storage material provided by the invention and preparation method thereof, easy, efficient, easy handling.The compound ammonia borine of novel organism provided by the invention hydrogen storage material, can reduce ammonia borine pyrolysis hydrogen discharging temperature, accelerates hydrogen desorption kinetics, and has effectively suppressed borazole (borazine), diborane (diborane), ammonia (NH
3) etc. the release of detrimental impurity gas, aspect vehicle-mounted mobile Chu Qing, having a good application prospect.
Claims (1)
1. the preparation method of a metal manganese oxide-loaded ammonia borane hydrogen storage material, the oxide carried ammonia borine storage of described manganese metal hydrogen material is made by the oxide carried ammonia borine of manganese metal, wherein manganese metal oxide compound is hollow manganese dioxide cubes, manganese dioxide hollow sphere or Manganse Dioxide porous nano particle, it is characterized in that comprising the following steps:
1) by the ultrasonic tetrahydrofuran solvent being scattered in after purifying of manganese metal oxide compound, make manganese metal oxide compound tetrahydrofuran solution;
2) ammonia borine is dissolved in the tetrahydrofuran solvent after purifying, makes ammonia borine tetrahydrofuran solution;
3) above-mentioned two kinds of solution are mixed, mixed solution is slowly stirred to even mixed solution;
4) above-mentioned even mixed solution is carried out to vacuum-drying except after desolventizing, can make this metal manganese oxide-loaded ammonia borane hydrogen storage material;
The amount ratio of described manganese metal oxide compound and tetrahydrofuran solvent is 40-60mg/mL, and the amount ratio of ammonia borine and tetrahydrofuran solvent is 12-20mg/mL, and in two kinds of solution mixed solutions, the mass ratio of manganese metal oxide compound and ammonia borine is 3:1;
The whipping temp of described mixed solution and vacuum-drying temperature are 20 ℃, and the vacuum drying time is 12-24 hour, and vacuum drying vacuum tightness is 0.05-0.1MPa.
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