CN103785360A - Supported oxidized graphene/metal organic framework composite material and preparation method thereof - Google Patents
Supported oxidized graphene/metal organic framework composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a supported oxidized graphene/metal organic framework composite material and a preparation method thereof. The composite material comprises Pt-supported oxidized graphene and a copper-based metal organic framework, wherein the copper-based metal organic framework consists of copper ions and a bidentate ligand under a coordination bonding effect; the bidentate ligand is trimesic acid. The preparation method comprises the following steps: dissolving soluble copper salt and the trimesic acid in N,N'-dimethyl formamide, and adding ethanol and deionized water with stirring to obtain a mixed solution; adding the Pt-supported oxidized graphene into the formed mixed solution, uniformly stirring, and performing ultrasonic dispersion, so as to obtain a reaction solution; performing solvothermal reaction on the reaction solution under programmed temperature control, soaking, centrifuging and drying a product obtained from suction filtration, so as to obtain the supported oxidized graphene/metal organic framework composite material. The supported oxidized graphene/metal organic framework composite material has the high room temperature hydrogen storage capacity and the high experimental controllability and is simple in process and low in cost.
Description
Technical field
The invention belongs to the synthesis technical field of hydrogen storage material, particularly a kind of synthetic and application of support type graphene oxide/metallic organic framework composite.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks; be called for short MOFs) advantage such as density is little, heat endurance is high, specific area is large owing to having, duct can regulate and control and reversible suction/hydrogen desorption kinetics is fast; be considered to have very much at present the novel hydrogen storage material of research and development prospect; as Furukawa, H.; Cordova, K.E.; O ' Keeffe, M.; Yaghi, O.M.Science, studies in 2013,341,1230444..People are by designing or select the assembling of polycarboxylic acid or nitrogen-containing hetero lopps part and metal ion to obtain the porous MOFs of a large amount of novel structures in recent years, as Sculley, and J.; Yuan, D.Q.; Zhou, H.C.Energy Environ.Sci., studies in 2011,4,2721..But, the adhesion take physical absorption between machine-processed MOFs and hydrogen a little less than, only can under low temperature (as 77K), show good hydrogen storage property, and room temperature hydrogen storage content is generally less than 1.0wt%.Therefore, how improving MOFs hydrogen storage property is at ambient temperature current people key scientific problems urgently to be resolved hurrily.
Hydrogen overflow technology becomes the study hotspot in current Chu Qing field owing to can significantly improving the room temperature hydrogen storage content of MOFs, as Wang, and L.F.; Yang, R.T.Energy Environ.Sci., studies in 2008,1,268..It is active carbon that the people such as U.S. Yang mix Pt/AC(AC by polishing to machinery in MOFs), and between Pt/AC and MOF, construct carbon bridge, significantly promote the reversible suction of room temperature of MOFs/put hydrogen level, hydrogen storage content when 298K is up to 4.0wt%, as Li, Y.W.; Yang.R.T.J.Am.Chem.Soc., 2006,128,726; Li, Y.W.; Yang, R.T.J.Am.Chem.Soc., studies in 2006,128,8136..Subsequently, the people such as U.S. Ganz, Taiwan Tsao and Korea S Park have also carried out related work in MOFs hydrogen overflow field, as Suri, and M.; Dornfeld, M.; Ganz, E.J.Chem.Phys., 2009,131,174703; Tsao, C.S.; Yu, M.S.; Wang, C.Y.; Liao, P.Y.; Chen, H.L.; Jeng, U.S.; Tzeng, Y.R.; Chung, T.Y.; Wu, H.C.J.Am.Chem.Soc., 2009,131,1404; Lee, S.Y.; Park, S.J.Int.J.Hydrogen Energy, studies in 2011,36,8381..But also there are problems in field in current MOFs hydrogen overflow, for example, utilize hydrogen overflow to carry out the room temperature hydrogen storage content of MOFs of Chu Qing current only up to 4.7wt%, the commercialization index of hydrogen storage material being formulated with USDOE also has larger gap; Existing several pieces of documents be all adopt polishing by MOF and Pt/AC mechanical mixture, test controllability undesirable, the nuance in sample making course all can cause hydrogen overflow effect reduce even disappear, as Luzan, S.M.; Talyzin, A.V.Micropor.Mesopor.Mat., 2010,135,201; Campesi, R.; Cuevas, F.; Latroche, M.; Hirscher.M.Phys.Chem.Chem.Phys., 2010,12,10457; Stucket, N.R.; Wang, L.F.; Yang, R.T.Langmuir, studies in 2010,26,11963..
Summary of the invention
The object of the invention is to overcome the deficiency of hydrogen overflow technology in existing MOFs field, a kind of support type graphene oxide/metallic organic framework composite and preparation method thereof is provided.The means such as introducing, the catalysis by nanostructured modifies, heterogeneous compound and original position is synthetic, realize the controlled preparation of the novel hydrogen storage material of high room temperature hydrogen storage capability.
For achieving the above object, the technical scheme that the present invention takes is:
Support type graphene oxide/metallic organic framework composite, comprises graphene oxide and the copper base metal organic backbone of supporting Pt.Described copper base metal organic backbone consists of cooperate and bond function copper ion and bidentate ligand, and described bidentate ligand is trimesic acid.
The present invention also provides a kind of preparation method of support type graphene oxide/metallic organic framework composite, comprises the steps:
(1) soluble copper salt and trimesic acid are dissolved in to N, in N '-dimethyl formamide, under stirring, add ethanol and deionized water, obtain mixed liquor for subsequent use;
Soluble copper salt is copper nitrate or copper sulphate;
The mass ratio of soluble copper salt and trimesic acid is 1～2:1;
Mantoquita is at N, and the concentration in N '-dimethyl formamide is 0.059～0.118g/mL;
N, the volume ratio of N '-dimethyl formamide, ethanol and deionized water is 1:0.5～1:0.5～1;
(2) to the graphene oxide that adds supporting Pt in above-mentioned mixed liquor, stir, ultrasonic dispersion;
The ultrasonic time is 15～30min.
The quality of the graphene oxide of supporting Pt is 5～10% of mantoquita and trimesic acid quality sum, and the mass fraction of Pt is 20%; The particle diameter of Pt particle is 3～4nm; According to document Xu, C.; Wang, X.; Zhu, J.W.J.Phys.Chem., 2008, C112, the method providing in 19841. prepares, and concrete method for making is: get in the ultrasonic 50mL of the being scattered in deionized water of 50mg graphite oxide, ultrasonic 30min, forms stable dispersions.Under stirring action, by the H of the ethylene glycol of 100mL and 2.5mL
2ptCl
6(0.01M) aqueous solution joins in above-mentioned dispersion liquid, and at 100 ℃ of constant temperature 6h.Product through suction filtration, washing and centrifugal after, be placed in 60 ℃ of dry 12h of baking oven.
(3) reactant liquor carries out solvent thermal reaction under temperature programmed control, the product after suction filtration through soaking, centrifugal, dry after, obtain support type graphene oxide/metallic organic framework composite.
The process of temperature programmed control is: the speed with 5～10 ℃/h rises to 95～100 ℃ by reacting liquid temperature from room temperature, after constant temperature 4～6h, naturally cools to room temperature.
Soaking the solvent adopting is carrene, and soaking number of times is 2～3 times/3 days.
Centrifugal rotating speed is 3000～5000r/min, and the time is 10～15min.
Dry temperature is 160～180 ℃, and the time is 24～36h.
The present invention compared with prior art, has following beneficial effect:
(1) support type graphene oxide/metallic organic framework composite that prepared by the present invention, in room temperature storage hydrogen process, first hydrogen molecule is dissociated into hydrogen atom on active metal Pt, the hydrogen diffusion of atomic state, move on graphene oxide sheet, in metallic organic framework surface and hole time, also can arrive in the new hole at graphene oxide and metallic organic framework two-phase interface place, thereby improve suction at ambient temperature of material/put hydrogen level.The room temperature hydrogen storage content of composite is better than traditional HKUST-1 material.
(2) situ solvent process for thermosynthesizing of the present invention not only makes Pt nano particle dispersed in graphene oxide/metallic organic framework composite, and compared with traditional mechanical mixing method for making sample, has effectively improved the controllability of experiment.
(3) preparation technology of the present invention is simple, and cost is low, is easy to realize industrialization.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 and n) the powder x-ray diffraction spectrogram of material of traditional HKUST-1((Cu3 (BTC) 2 (H20) 3);
Fig. 2 is the embodiment of the present invention 1 and the nitrogen adsorption isotherm of traditional HKUST-1 material in the time of 77K;
Fig. 3 is the embodiment of the present invention 1 and the hydrogen adsorption thermoisopleth of traditional HKUST-1 material in the time of 298K.
The specific embodiment
The present invention is illustrated by the following examples, but the present invention is not limited to following embodiment, and before and after not departing from, in the scope of described aim, change is included in technical scope of the present invention.
The N that 2g copper nitrate and 1g trimesic acid is dissolved in to 17mL, in N '-dimethyl formamide, adds 17mL ethanol and 17mL deionized water, then adds 0.15 under stirring
xthe graphene oxide (mass fraction of Pt is that the particle diameter of 20%, Pt particle is 3～4nm) of supporting Pt, stirs and carries out ultrasonic dispersion 15min, and the reactant liquor obtaining rises to 100 ℃ with the speed of 10 ℃/h from room temperature, after constant temperature 4h, naturally cools to room temperature.Product after suction filtration is immersed in carrene, and soaking number of times is 2 times/3 days, the centrifugal 15min of 3000r/h, and 170 ℃ of dry 36h, obtain support type graphene oxide/metallic organic framework composite.
Embodiment 2
By 1
gcopper sulphate and 1
gtrimesic acid is dissolved in the N of 17mL, in N '-dimethyl formamide, adds 8.5mL ethanol and 8.5mL deionized water, then add 0.20 under stirring
gthe graphene oxide (mass fraction of Pt is that the particle diameter of 20%, Pt particle is 3～4nm) of supporting Pt, stirs and carries out ultrasonic dispersion 30min, and the reactant liquor obtaining rises to 95 ℃ with the speed of 5 ℃/h from room temperature, after constant temperature 6h, naturally cools to room temperature.Product after suction filtration is immersed in carrene, and soaking number of times is 3 times/3 days, the centrifugal 10min of 5000r/h, and 180 ℃ of dry 24h, obtain support type graphene oxide/metallic organic framework composite.
Embodiment 3
1.5g copper nitrate and 1g trimesic acid are dissolved in to the N of 17mL, in N '-dimethyl formamide, under stirring, add 13mL ethanol and 13mL deionized water, (mass fraction of Pt is 20% to add the graphene oxide of 0.2g supporting Pt again, the particle diameter of Pt particle is 3～4nm), stir and carry out ultrasonic dispersion 15min, the reactant liquor obtaining rises to 100 ℃ with the speed of 8 ℃/h from room temperature, after constant temperature 5h, naturally cool to room temperature.Product after suction filtration is immersed in carrene, and soaking number of times is 2 times/3 days, the centrifugal 12min of 4000r/h, and 160 ℃ of dry 30h, obtain support type graphene oxide/metallic organic framework composite.
To the sign of embodiment 1
(1) powder x-ray diffraction of embodiment 1 is characterized
The powder x-ray diffraction Data Collection of the embodiment of the present invention 1 completes on the XRD-6000 of Shimadzu company type X-ray diffractometer.Test condition is: tube voltage 40kV, tube current 30mA, the CuK of use graphite monochromatization
αray.Data Collection adopts θ/2 θ scan patterns, completes to continuous sweep within the scope of 50o at 5o, and sweep speed is 4o/min.Powder x-ray diffraction spectrogram is shown in Fig. 1: the powder x-ray diffraction spectrogram of the embodiment of the present invention 1 and traditional HKUST-1 material.As shown in Figure 1, support type graphene oxide/metallic organic framework composite prepared by embodiment 1 has the diffraction pattern identical with traditional HKUST-1 material, this show supporting Pt graphene oxide add the formation that does not affect HKUST-1 elementary cell.
(2) porous of embodiment 1 is characterized
The BET specific area test of composite prepared by embodiment 1 completes on the ASAP-2020 of Merck & Co., Inc type specific area pore-size distribution instrument, and probe temperature is 77K.Test is front by sample vacuum activating 24h at 180 ℃.Nitrogen adsorption isotherm is shown in Fig. 2, and as seen from the figure, the nitrogen adsorption isotherm of support type graphene oxide/metallic organic framework composite prepared by embodiment 1 is the first kind, and its BET specific area is 848cm
2/ g, lower than the 937cm of traditional HKUST-1 material
2/ g, have certain influence to the specific area of composite this adding of graphene oxide that shows supporting Pt.
(3) the hydrogen storage property test to embodiment 1
The high-pressure hydrogen storing property detection of composite prepared by embodiment 1 completes on the ISOSORP-HyGra+V of Rubotherm company type magnetic suspension adsorbent equipment, and probe temperature is 298K.Test is front by sample vacuum activating 24h at 180 ℃.Hydrogen adsorption thermoisopleth is shown in Fig. 3, as seen from the figure, the hydrogen adsorption thermoisopleth of support type graphene oxide/metallic organic framework composite prepared by embodiment 1 is the first kind, composite prepared by the embodiment 1 quality hydrogen storage capability in the time of 298K and 80bar reaches 0.77%, far above traditional HKUST-1 material under same test condition 0.41%.This shows, supporting Pt graphene oxide add the obvious room temperature hydrogen storage content that has promoted material, this is attributable to due to the existence of hydrogen overflow effect.When normal temperature, first hydrogen molecule is dissociated into hydrogen atom on active metal Pt, the hydrogen migration of atomic state, be diffused into graphene oxide surface, overflow to again in HKUST-1 surface and hole, in the new hole of graphene oxide and metallic organic framework two interfaces, hydrogen level is put in the suction that has therefore greatly promoted material.
Table 1 is the room temperature hydrogen storage property comparative result of the current material of support type graphene oxide/metallic organic framework composite of the present invention and bibliographical information.
The adsorbance data comparison of table 1 hydrogen on different adsorbents
Claims (9)
1. support type graphene oxide/metallic organic framework composite, is characterized in that, comprises graphene oxide and the copper base metal organic backbone of supporting Pt; Described copper base metal organic backbone consists of cooperate and bond function copper ion and bidentate ligand; Described bidentate ligand is trimesic acid.
2. the preparation method of support type graphene oxide/metallic organic framework composite claimed in claim 1, is characterized in that, comprises the steps:
(1) soluble copper salt and trimesic acid are dissolved in to N, in N '-dimethyl formamide, under stirring, add ethanol and deionized water;
(2) graphene oxide of supporting Pt is joined in the mixed solution of step (1) formation, stir, and carry out ultrasonic dispersion, obtain reactant liquor;
(3) reactant liquor of step (2) is carried out to solvent thermal reaction under temperature programmed control, the product after suction filtration through soaking, centrifugal, dry after, obtain support type graphene oxide/metallic organic framework composite.
3. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, is characterized in that, described in step (1), soluble copper salt is nitrate or sulfate.
4. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, it is characterized in that, described in step (1), the mass ratio of soluble copper salt and trimesic acid is 1～2:1, soluble copper salt is at N, concentration in N '-dimethyl formamide is 0.059～0.118g/mL, N, the volume ratio of N '-dimethyl formamide, ethanol and deionized water is 1:0.5～1:0.5～1.
5. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, it is characterized in that, the quality of the graphene oxide of supporting Pt described in step (2) is 5～10% of mantoquita and trimesic acid quality sum, the mass fraction of Pt is that the particle diameter of 20%, Pt particle is 3～4nm.
6. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, is characterized in that, the ultrasonic time described in step (2) is 15～30min.
7. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, it is characterized in that, described in step (3), temperature programmed control process is: the speed with 5～10 ℃/h rises to 95～100 ℃ by the temperature of reactant liquor from room temperature, after constant temperature 4～6h, naturally cool to room temperature.
8. the preparation method of support type graphene oxide/metallic organic framework composite according to claim 2, is characterized in that, in step (3), soaking the solvent adopting is carrene, and soaking number of times is 2～3 times/3 days; Centrifugal rotating speed is 3000～5000r/min, and the time is 10～15min; Dry temperature is 160～180 ℃, and the time is 24～36h.
9. support type graphene oxide/metallic organic framework composite that claim 1 obtains is as the application of hydrogen storage material.
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| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
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| CN107029673A (en) * | 2017-06-06 | 2017-08-11 | 广州星帮尼环保科技有限公司 | A kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application |
| CN107158964A (en) * | 2017-07-04 | 2017-09-15 | 中国石油大学(华东) | A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation |
| CN107158964B (en) * | 2017-07-04 | 2020-03-03 | 中国石油大学(华东) | Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation |
| CN108598431A (en) * | 2018-04-28 | 2018-09-28 | 江苏科技大学 | Grapheme foam-nickel oxide combination electrode material and preparation method thereof |
| CN111420640A (en) * | 2020-04-14 | 2020-07-17 | 佛山科学技术学院 | HKUST-1 composite material and preparation method thereof |
| CN111420640B (en) * | 2020-04-14 | 2022-12-23 | 佛山科学技术学院 | HKUST-1 composite material and preparation method thereof |
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