CN104525125A - Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof - Google Patents
Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof Download PDFInfo
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- CN104525125A CN104525125A CN201410785160.1A CN201410785160A CN104525125A CN 104525125 A CN104525125 A CN 104525125A CN 201410785160 A CN201410785160 A CN 201410785160A CN 104525125 A CN104525125 A CN 104525125A
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Abstract
The invention discloses a supported metal organic skeleton/graphene oxide hydrogen storage material and a preparation method thereof. The hydrogen storage material is formed by steeping palladium metal in a metal organic skeleton/graphene oxide carrier, wherein the loading capacity of the palladium metal is 1.0-5.0% of the mass of the carrier; and the metal organic skeleton is ZIF-8. The preparation method comprises the following steps: firstly heating reactants of dissolvable zinc salt, 2-methylimidazole and graphene oxide to prepare a metal organic skeleton/graphene oxide carrier material, and then loading dissolvable palladium salt in the metal organic skeleton/graphene oxide carrier to obtain the supported metal organic skeleton/graphene oxide hydrogen storage material under the condition of existence of a reductant and a dispersant by adopting an excessive steeping method. The supported metal organic skeleton/graphene oxide hydrogen storage material has good hydrogen storage performance at room temperature, and the process is simple.
Description
Technical field
The invention belongs to the synthesis technical field of hydrogen storage material, be specifically related to a kind of load type metal organic backbone/graphene oxide hydrogen storage material and preparation method thereof.
Background technology
Hydrogen enjoys people to pay close attention to as a kind of green regenerative energy sources, and the features such as specific area is high because having for metal-organic framework materials (MOFs), porosity large, structure controllable are considered to have the hydrogen storage material of development prospect, as Suh, and M.P.; Park, H.J.; Prasad, T.K.; Lim, D.W.Chem.Rev., 2008,112, study in 782..Regrettably, only can could store a large amount of hydrogen under extremely low temperature based on the MOFs of physical absorption mechanism, and its room temperature hydrogen storage content is extremely low.Hydrogen spillover technology is owing to significantly can promote the room temperature hydrogen-sucking amount of MOFs and the study hotspot become in current Chu Qing field.Recently, the composite that Pt/ activated-carbon catalyst and MOFs mechanical mixture obtain at room temperature is shown good hydrogen storage property, as Wang, L.F. by people; Yang, R.T.Energy Environ.Sci., 2008,1, study in 268..Although people have achieved certain progress in this field, but still there are the problems such as room temperature hydrogen storage content is not high enough, experiment controllability is poor.In addition, the particle size of active component and decentralization, the character of carrier and all can have an impact to Hydrogen spillover effect in conjunction with situation etc. between active component and carrier, as Wang, L.F.; Lachawiec Jr, A.J.; Yang, R.T.RSC Adv., 2013,3, study in 23935., therefore the Hydrogen spillover mechanism of MOFs still needs further investigation.
Summary of the invention
The object of the present invention is to provide a kind of load type metal organic backbone/graphene oxide storage hydrogen material, have good hydrogen sucking function in a mild condition, active component palladium particle diameter is little, decentralization is high.
The preparation method of load type metal organic backbone/graphene oxide storage hydrogen material, with metallic organic framework/graphene oxide for carrier material, be active component with precious metal palladium, adopt excessive infusion process to prepare novel hydrogen storage material, overcome Problems existing in current MOFs Hydrogen spillover field.
Object of the present invention is achieved through the following technical solutions:
Load type metal organic backbone/graphene oxide hydrogen storage material, is formed by metallic organic framework/graphene oxide carrier impregnated activated components be soluble palladium salt.Metallic organic framework is ZIF-8, is be reactant by soluble zinc salt and glyoxal ethyline, obtains after heating; Metallic organic framework/graphene oxide carrier is reactant by soluble zinc salt, glyoxal ethyline and graphene oxide, obtains after heating.
The preparation method of load type metal organic backbone/graphene oxide hydrogen storage material, step is as follows:
(1) with soluble zinc salt, glyoxal ethyline and graphene oxide for reactant, be dissolved in solvent methanol, under stirring condition, add thermal response and prepare metallic organic framework/graphene oxide carrier material; Metallic organic framework is ZIF-8, is by soluble zinc salt and glyoxal ethyline, add thermal response obtain;
In step (1), soluble zinc salt is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride; Concentration in methyl alcohol is 8.9 ~ 12.8g/L; The mass ratio of soluble zinc salt and glyoxal ethyline is 1:1.7 ~ 2.8; The addition of graphene oxide is 5% of soluble zinc salt and glyoxal ethyline gross mass;
In step (1), heating-up temperature is 10 ~ 50 DEG C, and the reaction time is 2 ~ 6 hours;
(2) adopt excessive infusion process, under reducing agent and dispersant existence condition, by the load of soluble palladium salt in metallic organic framework/graphene oxide carrier, prepare load type metal organic backbone/graphene oxide hydrogen storage material; Wherein the load capacity of palladium metal is 1.0 ~ 5.0% of carrier quality.
In step (2), the mass ratio of palladium salt and metallic organic framework/graphene oxide carrier is 1:4.8 ~ 23.9; Soluble palladium salt is palladium bichloride, palladium nitrate, tetrachloro close palladium acid, tetrachloro closes palladium acid potassium or palladium acetylacetonate;
In step (2), reducing agent is sodium borohydride, potassium borohydride or hydrazine hydrate, and the mass ratio of reducing agent and metallic organic framework/graphene oxide carrier is 1:2.7 ~ 13.3;
In step (2), dispersant is polyvinyl alcohol, and the mass ratio of dispersant and metallic organic framework/graphene oxide carrier is 1:1.9 ~ 9.7.
The present invention compared with prior art, has following beneficial effect:
(1) by traditional metal-organic framework materials (ZIF-8) after overdoping and chemical modification, due to the existence of active metal palladium particle, make hydrogen molecule on palladium atom, be dissociated into the hydrogen of atomic state, and realizing hydrogen atom to the diffusion in ZIF-8/ graphene oxide carrier and migration, the room temperature effectively improving material inhales hydrogen level.
(2) adopt excessive infusion process can make palladium particle high degree of dispersion and be anchored in metallic organic framework/graphene oxide carrier.Compared with traditional mechanical mixture sample preparation method, greatly improve the controllability of experimentation.
(3) mature preparation process of the present invention, process is simple, and cost is low, is easy to realize industrialization.
Accompanying drawing explanation
Fig. 1 is the powder x-ray diffraction spectrogram of embodiment of the present invention 1-3 gained hydrogen storage material and conventional metals organic framework material (ZIF-8).Visible embodiment 1-3 gained hydrogen storage material maintains the main body framework of ZIF-8, and the diffraction maximum of 40 degree and about 46 degree is the characteristic peak of zeroth order Pd, shows the successful load of Pd nano particle.
Fig. 2 is embodiment of the present invention 1-3 gained hydrogen storage material and the hydrogen adsorption thermoisopleth of conventional metals organic framework material (ZIF-8) when 298K.Visible embodiment 1,2 and 3 gained hydrogen storage material reaches 0.31,0.45 and 0.45mmol/g, far above conventional metals organic framework material (ZIF-8) 0.04mmol/g under same test condition respectively with the hydrogen-sucking amount when 298K and 860mmHg.
Detailed description of the invention
The present invention is illustrated by the following examples, but the present invention is not limited to following embodiment, and in the scope not departing from the described aim in front and back, change is included in technical scope of the present invention.
Embodiment 1
(1) zinc nitrate of 2.933g, the glyoxal ethyline of 4.867g are dissolved in 230mL methyl alcohol, add the graphene oxide of 0.390g subsequently, stir 6 hours under 10 DEG C of conditions.Product with methylalcohol after centrifugal washs three times (each 10mL), obtained ZIF-8/ graphene oxide carrier material.
(2) polyvinyl alcohol of the palladium bichloride and 20.6mg of getting 8.38mg is dissolved in 42mL deionized water, stirs 1 hour.Add the ZIF-8/ graphene oxide of 200mg again, stir 2 hours, slowly add the sodium borohydride of 15mg subsequently, stir 5 hours.Product washing twice (each 10mL) after centrifugal, 60 DEG C of dryings 24 hours, obtain load type metal organic backbone/graphene oxide hydrogen storage material.
Embodiment 2
(1) zinc sulfate of 2.933g, the glyoxal ethyline of 6.489g are dissolved in 280mL methyl alcohol, add the graphene oxide of 0.471g subsequently, stir 4 hours under 30 DEG C of conditions.Product with methylalcohol after centrifugal washs three times (each 10mL), obtained ZIF-8/ graphene oxide carrier material.
(2) tetrachloro getting 25.14mg closes palladium polyvinyl alcohol that is sour and 61.80mg and is dissolved in 126mL deionized water, stirs 1 hour.Add the ZIF-8/ graphene oxide of 200mg again, stir 2 hours, slowly add the potassium borohydride of 45mg subsequently, stir 5 hours.Product washing twice (each 10mL) after centrifugal, 60 DEG C of dryings 24 hours, obtain load type metal organic backbone/graphene oxide hydrogen storage material.
Embodiment 3
(1) zinc chloride of 2.933g, the glyoxal ethyline of 8.111g are dissolved in 330mL methyl alcohol, add the graphene oxide of 0.552g subsequently, stir 2 hours under 50 DEG C of conditions.Product with methylalcohol after centrifugal washs three times (each 10mL), obtained ZIF-8/ graphene oxide carrier material.
(2) polyvinyl alcohol of the palladium acetylacetonate and 103.00mg of getting 41.90mg is dissolved in 210mL deionized water, stirs 1 hour.Add the ZIF-8/ graphene oxide of 200mg again, stir 2 hours, slowly add the hydrazine hydrate of 75mg subsequently, stir 5 hours.Product washing twice (each 10mL) after centrifugal, 60 DEG C of dryings 24 hours, obtain load type metal organic backbone/graphene oxide hydrogen storage material.
The room temperature storage hydrogen test of hydrogen storage material prepared by embodiment 1-3 completes, by sample vacuum outgas 24 hours at 160 DEG C before test on ASAP 2020 device of Merck & Co., Inc of the U.S..Embodiment 1-3 and the hydrogen adsorption thermoisopleth of conventional metals organic framework material (ZIF-8) when 298K are shown in Fig. 2.
Claims (7)
1. load type metal organic backbone/graphene oxide hydrogen storage material, it is characterized in that being formed by metallic organic framework/graphene oxide carrier palladium-impregnated metal; The load capacity of palladium metal is 1.0 ~ 5.0% of carrier quality; Metallic organic framework is ZIF-8.
2. load type metal organic backbone/graphene oxide hydrogen storage material according to claim 1, is characterized in that the precursor of palladium metal is soluble palladium salt.
3. the preparation method of load type metal organic backbone/graphene oxide hydrogen storage material, is characterized in that step is as follows:
Step (1), with soluble zinc salt, glyoxal ethyline and graphene oxide for reactant, be dissolved in solvent methanol, under stirring condition, add thermal response and prepare metallic organic framework/graphene oxide carrier material; Metallic organic framework is ZIF-8, is by soluble zinc salt and glyoxal ethyline, add thermal response obtain;
(2) adopt excessive infusion process, under reducing agent and dispersant existence condition, by the load of soluble palladium salt in metallic organic framework/graphene oxide carrier, prepare load type metal organic backbone/graphene oxide hydrogen storage material; Wherein the load capacity of palladium metal is 1.0 ~ 5.0% of carrier quality.
4. the preparation method of load type metal organic backbone/graphene oxide hydrogen storage material according to claim 3, is characterized in that in step (1), soluble zinc salt is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride; Concentration in methyl alcohol is 8.9 ~ 12.8g/L; The mass ratio of soluble zinc salt and glyoxal ethyline is 1:1.7 ~ 2.8; The addition of graphene oxide is 5% of soluble zinc salt and glyoxal ethyline gross mass.
5. the preparation method of load type metal organic backbone/graphene oxide hydrogen storage material according to claim 3, it is characterized in that in step (1), heating-up temperature is 10 ~ 50 DEG C, the reaction time is 2 ~ 6 hours.
6. the preparation method of load type metal organic backbone/graphene oxide hydrogen storage material according to claim 3, is characterized in that in step (2), soluble palladium salt is palladium bichloride, palladium nitrate, tetrachloro close palladium acid, tetrachloro closes palladium acid potassium or palladium acetylacetonate; The mass ratio of soluble palladium salt and metallic organic framework/graphene oxide carrier is 1:4.8 ~ 23.9.
7. the preparation method of load type metal organic backbone/graphene oxide hydrogen storage material according to claim 3, it is characterized in that in step (2), reducing agent is sodium borohydride, potassium borohydride or hydrazine hydrate, the mass ratio of reducing agent and metallic organic framework/graphene oxide carrier is 1:2.7 ~ 13.3; Dispersant is polyvinyl alcohol, and the mass ratio of dispersant and metallic organic framework/graphene oxide carrier is 1:1.9 ~ 9.7.
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| CN105344380A (en) * | 2015-12-08 | 2016-02-24 | 镇江市高等专科学校 | Metal organic frame/graphene carried palladium nano-composite catalyst and preparing method and application thereof |
| CN105951304A (en) * | 2016-06-24 | 2016-09-21 | 华南理工大学 | ZIF-8/poly(vinyl alcohol) (PVA) composite nanofiber membrane as well as preparation method and application thereof |
| CN106064806A (en) * | 2016-05-27 | 2016-11-02 | 中国工程物理研究院材料研究所 | Modified IRMOF 1 material and preparation method thereof |
| CN106140094A (en) * | 2016-07-04 | 2016-11-23 | 复旦大学 | The synthetic method of the magnetic graphene composite that metallic organic framework is modified and application |
| CN106435766A (en) * | 2016-11-14 | 2017-02-22 | 安徽名杰净化科技有限公司 | Reinforced heat-resistant electrostatic-spinning/electret composite fiber membrane filtering material and preparing method thereof |
| CN106916110A (en) * | 2017-03-10 | 2017-07-04 | 国家纳米科学中心 | A kind of carried noble metal nano composition and preparation method thereof |
| CN106927458A (en) * | 2017-02-21 | 2017-07-07 | 青岛科技大学 | A kind of Graphene and the composite aerogels of ZIF 8 and preparation method thereof |
| CN108079954A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of functional graphene oxide composite nano materials and preparation and application |
| CN108421532A (en) * | 2018-03-16 | 2018-08-21 | 江苏科技大学 | It is a kind of using metal-organic framework materials as absorbent for carbon monooxide of carrier and its preparation method and application |
| CN109248674A (en) * | 2018-11-23 | 2019-01-22 | 知合环境（北京）有限责任公司 | A kind of graphene-supported nano zero-valence zinc composite material and preparation method and application |
| CN109734740A (en) * | 2019-03-04 | 2019-05-10 | 中国石油大学(华东) | A kind of borate family metal organic framework compound and preparation method thereof |
| CN110237816A (en) * | 2019-06-13 | 2019-09-17 | 江苏科技大学 | A kind of preparation method and applications of the metal organic framework adsorbent material of nitric acid modified by silver |
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| CN110632146A (en) * | 2019-09-24 | 2019-12-31 | 东南大学 | Enzyme-free glucose electrochemical sensor and detection method thereof |
| CN112675913A (en) * | 2019-10-18 | 2021-04-20 | 南京理工大学 | Palladium-loaded titanium-based metal organic framework catalyst, preparation method and application |
| CN113716521A (en) * | 2021-09-06 | 2021-11-30 | 深圳华中科技大学研究院 | Composite hydrogen storage material and preparation method thereof |
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