CN108212173A - A kind of colloid production hydrogen catalyst and preparation method thereof - Google Patents
A kind of colloid production hydrogen catalyst and preparation method thereof Download PDFInfo
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- CN108212173A CN108212173A CN201810051689.9A CN201810051689A CN108212173A CN 108212173 A CN108212173 A CN 108212173A CN 201810051689 A CN201810051689 A CN 201810051689A CN 108212173 A CN108212173 A CN 108212173A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000084 colloidal system Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000003223 protective agent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 229920003081 Povidone K 30 Polymers 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003797 solvolysis reaction Methods 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B01J35/23—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of colloid production hydrogen catalysts and preparation method thereof, and this method is protected using Organic structure directing agent PVP K30, and under nitrogen atmosphere and cryogenic conditions, Ru@Co/rGO nanocrystalline colloid materials are made by sodium borohydride reduction.Preparation method economy provided by the invention, safety, environmental protection are of low cost and easy to operate.Ru@Co/rGO nanocrystalline colloids material prepared by the present invention has smaller nanocrystalline size, good dispersibility and stability, hydrogen colloidal materials are produced as catalysis, by the way that electric charge transfer occurs between Ru atoms and Co atoms hydrogen is produced so as to accelerate the hydrolysis of sodium borohydride, if it is well dispersed on two-dimensional material reduced graphene simultaneously, effectively prevent it is nanocrystalline between reunion, it is protected by the structure directing of PVP colloids, metallic nano crystal and weak reduced graphene is made to be well dispersed into colloidal solution, again reduce the reunion of catalyst, so as to improve the H2-producing capacity of material and good stability.
Description
Technical field
The invention belongs to produce hydrogen energy source technical field, and in particular to a kind of colloid production hydrogen catalyst and preparation method thereof.
Background technology
Hydrogen Energy is greatly promoted the development of field of renewable energy as a kind of clean energy resource, its use.However,
In the application of Hydrogen Energy, most production hydrogen technique is confined to the factors such as the controlled release poor performance of hydrogen, practice have shown that most effective
It is that production hydrogen is catalyzed by catalyst with safest method, solid hydride can generally pass through thermal decomposition and solvolysis etc.
Method, but the longer induction time (about 3h) of needs and higher temperature are thermally decomposed, therefore limit its application, solvolysis
Rule can realize the efficient release of hydrogen under arbitrary temperature condition by suitable catalyst.Catalytic chemistry hydrogenation produce hydrogen
There are many catalyst type, general mainly to include three classes：Single-metal reforming catalyst, bimetallic catalyst and loaded catalyst etc..
Single-metal reforming catalyst research is most widely Pt metal and the catalyst of Ru, and relatively low activation energy and higher specific surface area determine
The shortcomings of its high catalytic activity, but because its cost is higher, the reunion that ingredient is single to be easy to cause, limits the extensive of its
Using.Therefore, it under the premise of the catalytic activity of catalyst is not influenced, solves to be met by developing bimetal supported catalyst
The shortcomings that.Ru noble metal nanocrystallines have higher specific surface energy, can greatly reduce the activation energy of hydride hydrolysis production hydrogen, but
It is confined to that Ru is nanocrystalline easily to reunite, has severely impacted the service life cycle of noble metal catalyst, can only often reach
To the high catalysis production hydrogen activity of 1 to 2 times.
Invention content
It is an object of the invention in view of the above problems, provide a kind of Ru@Co/rGO nanocrystalline colloid materials,
With relatively low activation energy (53.2 kJ mol-1) and higher specific surface area, be conducive to improve the dispersion degree of active component,
Realize that catalyst up to repeatedly utilizes, while its cost is low, cost-effective, safety and environmental protection.
The technical solution that the present invention realizes is as follows:A kind of preparation method of colloid production hydrogen catalyst, by nitrogen atmosphere
Under cryogenic conditions, according to a certain ratio with order by cobaltous dichloride solution, solution of ruthenium trichloride, graphene solution and PVP glue
Liquid solution mixes, then restores above-mentioned mixed solution with certain density sodium borohydride solution and Ru@Co/rGO nanocrystalline colloids are made
Material.
The above method specifically includes following steps：
Step（1）：Using natural flake graphite powder as raw material, graphite oxide solution, Ran Houzai are prepared using improved Hummer methods
It is removed with ultrasound and graphene oxide solution is made.
Step（2）：By cobaltous dichloride solution and solution of ruthenium trichloride using molar ratio as 1:1 ratio is sufficiently mixed.
Step（3）：Take the graphene oxide of a concentration of 0.7 mg/mL of 1 mL（GO）Solution is instilled in 23 mL deionized waters,
And with step 2 obtained by 0.5-1 h of solution mixing ultrasonic disperse.
Step（4）：7 g protective agents polyvinylpyrrolidones (PVP) is taken to be dissolved in 20 mL deionized waters, and with step 3
The mixed solution mixing of gained.
Step（5）：Step（4）Gained mixed solution is placed under nitrogen atmosphere and cryogenic conditions, then into mixed solution
Add in 10 mL, the NaBH of a concentration of 16.5 mM4Solution.
Step（6）：Step（5）Gained mixed solution reacts 12 h under the conditions of being placed in 0 DEG C, obtain Ru@Co/rGO and receive
The brilliant colloidal materials of rice.
Colloid made from above-mentioned preparation method produces hydrogen catalyst.
Compared with prior art, it is an advantage of the invention that：
1st, since Organic structure directing agent PVP-K30 is protected, the synergistic effect of noble metal Ru and cheap metal Co, base material
Peptizaiton improves catalysis production hydrogen activity (the 511.36 mol H of catalyst2.min-1.mol.M-1), it is protected compared to non-colloid
Same type solid catalyst (the 344mol H of shield2.min-1.mol.M-1), catalyst agglomeration is further reduced, is reached 5 times
Height catalysis production hydrogen cycle.
2nd, due to by cobaltous dichloride solution and solution of ruthenium trichloride using molar ratio as 1:1 ratio is sufficiently mixed to make
Catalyst reduces the half additive amount of noble metal, so greatly reducing cost.
Description of the drawings
Fig. 1 is the Ru prepared by embodiment 1X@Co1-XThe catalysis production hydrogen figure of/rGO nanocrystalline colloid materials；
Fig. 2 is the Ru prepared by embodiment 20.5@Co0.5The catalysis production hydrogen cycle life figure of/rGO nanocrystalline colloid materials.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
We make it disperse to be supported on satisfactory electrical conductivity well by cheap metal and precious metal alloys
The two-dimentional supporting substrate material of energy.Cheap metal Co, because its cheap cost and preferable catalytic activity, while make its crystallization
Noble metal nanocrystalline Ru is wrapped to prevent the reunion of noble metal.This new material of graphene has unique plane development knot
Structure, theoretical specific surface area (2630 m of bigger2∙g-1), higher electron mobility (2 × 105 cm2∙V-1∙s-1) and conductance
Rate (106 S m-1) and good mechanicalness and thermal stability.Big specific surface area is conducive to improve the dispersion of active component
Degree, excellent characteristic electron can be greatly promoted the transmission of electronics in oxidation-reduction process, so as to accelerate that catalysis reacts into
Row.
The present invention makes it be well dispersed into two-dimentional base material graphite by cheap metal Co coating noble metal Ru
On alkene, catalysis hydrogen-producing speed (TOF) value has reached 511.36 mol H2.min-1.mol.M-1, significantly larger than same type
Solid catalyst (344mol H2.min-1.mol.M-1) hydrogen-producing speed.Hydrogen colloidal materials are produced as catalysis, pass through Ru atoms
Electric charge transfer occurs between Co atoms so as to accelerate the hydrolysis of sodium borohydride production hydrogen.Meanwhile it is well dispersed into two-dimentional material
If material reduced graphene on, effectively prevent it is nanocrystalline between reunion, so as to improve the H2-producing capacity of material.
Embodiment：
The present embodiment prepares Ru@Co/rGO nanocrystalline colloid materials, specifically includes following steps：
Step（1）：Using natural flake graphite powder as raw material, graphite oxide solution, Ran Houzai are prepared using improved Hummer methods
Graphene oxide is removed with ultrasound, graphene (GO) solution that mass concentration is 0.7 mg/mL is made.
Step（2）：It is 1 by molar ratio:1 cobaltous dichloride solution and solution of ruthenium trichloride is sufficiently mixed.
Step（3）：Take a concentration of 0.7 mg/mL of 1 mL GO solution instill 23 mL deionized waters in, and with step 2 institute
1 h of solution mixing ultrasonic disperse obtained.
Step（4）：7 g protective agents polyvinylpyrrolidones (PVP) is taken to be dissolved in 20 mL deionized waters, and with step 3
The mixed solution mixing of gained.
Step（5）：Step（4）Gained mixed solution is placed under nitrogen atmosphere and cryogenic conditions, then into mixed solution
Add in 10 mL, the NaBH of a concentration of 16.5 mM4Solution.
Step（6）：Step（5）Gained mixed solution reacts 12 h under the conditions of being placed in 0 DEG C, obtain Ru@Co/rGO and receive
The brilliant colloidal materials of rice.
Step（1）The graphene oxide is prepared using improved Hummer methods.
The concrete technology flow process of graphene oxide is prepared using improved Hummer methods：Weigh 5 g natural flake graphite powder
It is added in the 130 mL concentrated sulfuric acids with 2.5 g sodium nitrate, 2 h is stirred under condition of ice bath.It is slowly added to 15 g after completion of the reaction
Potassium permanganate, and the reaction was continued 2 h under ice bath.Ice bath is removed, above-mentioned reactant is transferred in 35 DEG C of water-baths, reaction 1
H is slowly added to 230 mL deionized waters into above-mentioned reaction system, then raises temperature to 98 DEG C of 30 min of reaction, adds in 400 mL
Deionized water and 10 mL hydrogen peroxide, and 1 h is stirred, cooled and filtered is washed till no sulfuric acid with the HCl solution that mass fraction is 3 %
Root, then it is 7 to be washed with deionized water to PH, obtains graphite oxide solution, ultrasonic disperse is until be uniformly mixed, obtained graphene oxide
Aqueous solution.
The contrast experiment of the colloid catalyst of different metal ions proportioning：
The colloid catalyst of different metal ions proportioning is prepared first
Step（1）：Configuration concentration be 0.66 mM cobaltous dichloride solution and solution of ruthenium trichloride, by take x mL (20,18,
14,10,6,2,0) cobaltous dichloride solution and y mL (0,2,6,10,14,18,20) solution of ruthenium trichloride be successively
Uniform mixed preparing molar ratio is Cox@RuyThe colloid catalyst of/rGO.
Step（2）：Take a concentration of 0.7 mg/mL of 1mL GO solution instill 23 mL deionized waters in, and with step 2 obtained by
1 h of solution mixing ultrasonic disperse.
Step（3）：7 g protective agents polyvinylpyrrolidones (PVP) is taken to be dissolved in 20 mL deionized waters, and with step 3
The mixed solution mixing of gained.
Step（4）：Step（3）Gained mixed solution is placed under nitrogen atmosphere and cryogenic conditions, then into mixed solution
Add in 10 mL, the NaBH of a concentration of 16.5 mM4Solution.
Step (5)：Step（4）Gained mixed solution reacts 12 h under the conditions of being placed in 0 DEG C, obtain Cox@Ruy/ rGO receives
The brilliant colloid catalyst of rice.
Secondly it is tested using following step：
Ru@Co/rGO nanocrystalline colloids material is catalyzed sodium borohydride highly effective hydrogen yield.
Measure alkalinity NaBH4Solution (pH=12) generates H under the effect of the catalyst2Volume and rate, it is basic herein
The upper hydrogen desorption capacity calculated in the catalyst unit interval, and carry out with this catalytic activity of comparative catalyst.The test of catalytic performance
Journey is as follows：Prepared 40 mL of bimetallic Ru@Co/rGO nanocrystalline colloids solution is added in into three-necked flask, adjusts reaction temperature
It is 30 DEG C to spend, and adds in 10 mL, the alkaline NaBH of 30 mM into three-necked flask by separatory funnel4Solution treats that catalysis reaction is opened
After beginning, H under different time is measured by drainage2Yield.
Conclusion explanation：
With reference to figure 1, prepared Ru can be significantly found0.5@Co0.5The catalytic activity highest of/rGO nanocrystalline colloid materials,
The sodium borohydride of its every 0.3 mmol can generate the hydrogen of 2.52 mmol.
With reference to figure 2, it can be seen that prepared Ru0.5@Co0.5/ rGO nanocrystalline colloids material has the good service life,
The catalysis hydrogen output that cycle is 5 times is all relatively good.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, it is that claim of the invention is covered.
Claims (3)
1. the preparation method of a kind of colloid production hydrogen catalyst, which is characterized in that by under nitrogen atmosphere and cryogenic conditions, by one
Fixed proportioning and order are by cobaltous dichloride solution, solution of ruthenium trichloride, graphene solution and the mixing of PVP colloidal solution, then with one
Ru@Co/rGO nanocrystalline colloid materials are made in the above-mentioned mixed solution of sodium borohydride solution reduction for determining concentration.
2. according to claim 1 colloid production hydrogen catalyst preparation method, which is characterized in that the above method specifically include with
Lower step：
Step（1）：Using natural flake graphite powder as raw material, graphite oxide solution, Ran Houzai are prepared using improved Hummer methods
It is removed with ultrasound and graphene oxide solution is made；
Step（2）：By cobaltous dichloride solution and solution of ruthenium trichloride using molar ratio as 1:1 ratio is sufficiently mixed；
Step（3）：Take the graphene oxide of a concentration of 0.7 mg/mL of 1 mL（GO）Solution is instilled in 23 mL deionized waters, and with
0.5-1 h of solution mixing ultrasonic disperse obtained by step 2；
Step（4）：7 g protective agents polyvinylpyrrolidones (PVP) is taken to be dissolved in 20 mL deionized waters, and with step 3 obtained by
Mixed solution mixing；
Step（5）：Step（4）Gained mixed solution is placed under nitrogen atmosphere and cryogenic conditions, then is added in into mixed solution
10 mL, the NaBH of a concentration of 16.5 mM4Solution；
Step（6）：Step（5）Gained mixed solution reacts 12 h under the conditions of being placed in 0 DEG C, it is nanocrystalline to obtain Ru@Co/rGO
Colloidal materials.
3. colloid made from preparation method produces hydrogen catalyst according to one claim of any of the above.
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| CN114210343A (en) * | 2022-01-24 | 2022-03-22 | 桂林电子科技大学 | Reduced graphene oxide loaded Ru-Ni bimetallic nanocluster catalytic material |
| CN114870874A (en) * | 2022-05-10 | 2022-08-09 | 桂林电子科技大学 | Nitrogen-doped porous carbon-coated ruthenium-embedded cobalt phosphide composite material based on graphene oxide |
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| CN114870874A (en) * | 2022-05-10 | 2022-08-09 | 桂林电子科技大学 | Nitrogen-doped porous carbon-coated ruthenium-embedded cobalt phosphide composite material based on graphene oxide |
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