CN109046419A - A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium - Google Patents
A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium Download PDFInfo
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- CN109046419A CN109046419A CN201810713714.5A CN201810713714A CN109046419A CN 109046419 A CN109046419 A CN 109046419A CN 201810713714 A CN201810713714 A CN 201810713714A CN 109046419 A CN109046419 A CN 109046419A
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- ginkgo leaf
- ruthenium
- porous carbon
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- hydrogen
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 103
- 241000218628 Ginkgo Species 0.000 title claims abstract description 95
- 235000011201 Ginkgo Nutrition 0.000 title claims abstract description 95
- 235000008100 Ginkgo biloba Nutrition 0.000 title claims abstract description 95
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000011068 loading method Methods 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- 239000002585 base Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000007062 hydrolysis Effects 0.000 claims abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007599 discharging Methods 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000004087 circulation Effects 0.000 claims abstract description 7
- 238000003795 desorption Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- -1 nitrogenous compound Chemical class 0.000 claims abstract 4
- 230000003213 activating effect Effects 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 241000921313 Phyllopodium Species 0.000 claims description 20
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 229910000085 borane Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QTTMOCOWZLSYSV-QWAPEVOJSA-M equilin sodium sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4C3=CCC2=C1 QTTMOCOWZLSYSV-QWAPEVOJSA-M 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- ZENDWEPAVHORFD-UHFFFAOYSA-N pyrimidine;urea Chemical compound NC(N)=O.C1=CN=CN=C1 ZENDWEPAVHORFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 14
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical compound B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000006229 carbon black Substances 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
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of ginkgo leaf base porous carbon materials for loading ruthenium, ginkgo leaf is as carbon source, after low-temperature carbonization, nitrogenous compound and alkali inorganic substance is added, ginkgo leaf base porous carbon materials are obtained after calcining and activating, then metal Ru is loaded on porous carbon materials by local reduction way, obtains a kind of ginkgo leaf base porous carbon materials for loading ruthenium.Preparation method includes the following steps: 1) low-temperature carbonization of ginkgo leaf；2) activation and post-processing of ginkgo leaf base porous carbon materials；3) load of metal Ru.As ammonia borane hydrolysis hydrogen manufacturing catalyst, 40 s complete hydrogen release at room temperature, and hydrogen desorption capacity is the 92% of theoretical value, and hydrogen discharging rate reaches 3718 ml s‑1 g‑1.It can be recycled, after five circulations, 60 s complete hydrogen release, and hydrogen discharging rate is 2158 ml s‑1 g‑1, keep the 58% of first hydrogen discharging rate.By being catalyzed the test of ammonia borane hydrolysis under different temperatures, lower activation energy is shownE a=23.86 kJ mol‑1.It has broad application prospects in fields such as hydrogen manufacturing material, fuel cells.
Description
Technical field
The present invention relates to porous carbon materials and the technical fields of catalysis ammonia borane hydrolysis hydrogen manufacturing, and in particular to a kind of load ruthenium
Ginkgo leaf base porous carbon materials preparation method and application.
Background technique
With the continuous growth of economic rapid development and population, demand of the people to the energy is more nervous.Although fossil
Fuel still occupies the substantially ratio of energy resource structure, but fossil fuel is non-renewable resources, and certain pollution is brought to environment,
Resulting problem of energy crisis more highlights.The key technology for solving problems is the novel renewable low-carbon green of exploitation
The energy and its high-efficiency cleaning store transformation technology.Hydrogen Energy is as a kind of rich reserves, energy density is high, it is easy to use, using wide
General secondary energy sources receive the extensive concern of domestic and international researcher.Ammonia borine (NH3BH3, AB) with 19.6 wt%
Hydrogen content and be widely concerned by researchers at home and abroad.Ammonia borine has nontoxicity at room temperature, stability and environmental-friendly
The advantages that property, by as a kind of potential hydrogen manufacturing material.The dehydrogenation mode of ammonia borine has 3 kinds, respectively alcoholysis, thermal decomposition
And hydrolysis.Biomass carbon material is widely used in the fields such as battery, capacitor, hydrogen storage with its high-specific surface area, with people
Yearning to good life, biomass carbon material receive researcher with the features such as its abundance, pattern uniqueness, unique structure
Extensive concern.
Discarded biomass is to prepare one of ideal material of porous carbon materials, can be with using discarded biomass as raw material
Pollution is reduced, house refuse is effectively reduced, while obtaining porous carbon materials, turns waste into wealth, be a kind of very promising preparation
Method.
With supported metal ruthenium the characteristics of porous carbon big specific surface area and surface holes, ruthenium nano particle can be allowed evenly dispersed
And do not reunite, ruthenium nano particle is steadily supported on the surface of porous carbon, to efficiently be catalyzed ammonia borane hydrolysis system
Hydrogen, and the catalyst prepared can be reused by the method for filtering, be had a extensive future, it is practical.
Liang et al. is reverted to metal Ru on carbon black by local reduction way, but carbon black specific surface is little, carbon materials
Expect that surface holes are also few, prepared catalyst effect is general.Therefore, seek that a kind of preparation method is simple, large specific surface area, hole
Structure-rich, practical carbon material become the hot spot of current research.
Summary of the invention
The object of the present invention is to provide a kind of ginkgo leaf base porous carbon materials and preparation method thereof for loading ruthenium, and as ammonia
The application of borane hydrolysis catalyst for preparing hydrogen obtains big specific surface area material and pore-size distribution, allows by preparing porous carbon materials
Metal Ru particle, which can be uniformly dispersed on porous carbon materials, does not reunite, thus realize efficient catalytic ammonia borane hydrolysis hydrogen manufacturing,
And there is good cycle performance, while it is unstable to solve low current ammonia borane hydrolysis hydrogen discharging rate, catalyst agglomeration, catalyst
The problems such as.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is carbon source, hydrochloric acid using ginkgo leaf biomass
Semicarbazides or urea pyrimidine are nitrogen source, use alkali inorganic substance KOH etc. for activator, and semicarbazide hydrochloride or urea pyrimidine are as high nitrogenous
Nitrogen not only can successfully be entrained in carbon material, be also used as pore creating material by the nitrogen source of amount, in carbonisation and
Pyrolytic reaction occurs for carbon matrix precursor, to increase the specific surface area of material as far as possible, and then loads a large amount of metal Ru particle, high
Effect catalysis ammonia borane hydrolysis hydrogen manufacturing.
Realizing the specific technical solution of the object of the invention is:
It is a kind of load ruthenium ginkgo leaf base porous carbon materials, by ginkgo leaf by low-temperature carbonization processing, then with nitrogen
Object and alkali inorganic substance mixing are closed, porous carbon materials are obtained after calcining and processing, then passes through local reduction way for metal Ru
It loads on porous carbon materials, the ginkgo leaf base porous carbon materials of ruthenium must be loaded.
Load ruthenium ginkgo leaf porous carbon materials preparation method the following steps are included:
The low-temperature carbonization of step 1) ginkgo leaf by ginkgo leaf wash clean, is cut into piece, drying.Then, it is put into cryogenic carbon in Muffle furnace
Change, temperature is 300 ~ 450 DEG C, and be carbonized 1 ~ 3 h.Later, carbonized product is filtered, washed, dried, ground, obtain ginkgo phyllopodium
Carbon material.
The activation of step 2 ginkgo phyllopodium carbon material, the ginkgo phyllopodium carbon material that step 1) is obtained and nitrogenous precursor and
Alkali inorganic substance is 1.0:(0.5 ~ 6 in mass ratio): (1.5 ~ 8.0) mixing is impregnated, after drying, and the tubular type full of nitrogen is put into
It is 600 ~ 900 DEG C in furnace with activation temperature to calcine, activation time is 1 ~ 6 h, obtains nitrogen-doped modified ginkgo phyllopodium carbon materials
Material.The middle nitrogenous precursor is one or two kinds of mixing of semicarbazide hydrochloride and urea pyrimidine, alkali inorganic substance be inorganic base or
Alkaline, inorganic salts, potassium hydroxide, sodium hydroxide, potassium carbonate etc..Product is impregnated with hydrochloric acid solution, is washed out, filters, dries
Dry, grinding obtains nitrogen-doped modified ginkgo phyllopodium carbon material.
The load of step 3) metal Ru, meeting mass ratio by ruthenium element and carbon is 1:(5 ~ 20), take ruthenium trichloride water
Close object and above-mentioned steps 2) made from nitrogen-doped modified ginkgo phyllopodium carbon material add water wiring solution-forming, solution passes through ultrasonic agitation
After processing, using ammonia borine as reducing agent, the concentration of ammonia Borane solution is 0.1 ~ 1.0 mol L-1, the object of ruthenic chloride and ammonia borine
The ratio between amount of matter range is 1:(50 ~ 100), under the conditions of 25 DEG C of temperature constant magnetic stirrings, ammonia Borane solution is added rapidly to chlorine
Change in ruthenium solution, guarantee that solution reaction is abundant, after bubble-free generation, is washed repeatedly with water and ethyl alcohol, decompression filters, 70-
5 ~ 10 h are dried in vacuo under the conditions of 100 DEG C.Obtain the ginkgo leaf base porous carbon materials of load ruthenium.
The ginkgo leaf base porous carbon materials of load ruthenium are efficiently catalyzed ammonia borane hydrolysis hydrogen manufacturing at room temperature, and first catalysis is put
Hydrogen is completed in 30 ~ 100 s, and hydrogen desorption capacity is the 90 ~ 100% of theoretical value, and hydrogen discharging rate reaches 3718 ml s-1 g-1.It can pass through
The method be filtered, washed, dried is recycled, and after undergoing five circulations, properties are completed in 50 ~ 100 s, and hydrogen discharging rate is protected
It holds in 2158 ml s-1 g-1, hydrogen discharging rate remains the 58% of first hydrogen discharging rate.Load the ginkgo leaf base porous carbon materials of ruthenium
Catalysis ammonia borane hydrolysis hydrogen manufacturing at different temperatures, temperature is respectively 20,25,40,50 DEG C, by Arrhenius equation
It is fitted to obtain activation energyE a = 23.86 kJ mol-1。
Electronic Speculum detection is scanned to the porous carbon materials load front and back of the load ruthenium nano particle of above-mentioned preparation:
The carbon material supported preceding scanning electron microscope testing result in ginkgo leaf Quito hole for loading ruthenium shows that porous carbon blanking aperture disperses
More uniform, there are a large amount of microcellular structures on porous carbon materials surface.
Load ruthenium ginkgo leaf Quito hole it is carbon material supported after scanning electron microscope the results show that porous supported on carbon surface is permitted
More particles, these are evengranular to be dispersed in around hole, and pattern is preferable, and homogeneity is good, and is supported on the gold on porous carbon
Belonging to ruthenium particle, there is no reuniting.
XRD detection is carried out to the ginkgo leaf base porous carbon materials of the load ruthenium of above-mentioned preparation, loads the silver of ruthenium as the result is shown
Apricot phyllopodium porous carbon materials are 29.8 ° and 42.1 ° in 2 θ and two apparent Bao Feng nearby occur, can be attributed to the peak of carbon, bear
The wide and weak peak that the ginkgo leaf base porous carbon materials of ruthenium occur in 2 θ=42.8 ° is carried, Ru (002) diffraction maximum can be attributed to.
The ginkgo leaf base porous carbon materials of the load ruthenium of above-mentioned preparation are for being catalyzed ammonia borane hydrolysis hydrogen manufacturing, by filtration drying
The ginkgo leaf base porous carbon materials of load ruthenium afterwards are put into container, and magnetic stirrer is added, container is then placed in 25 DEG C
In water-bath, container is connected with water-filled gauge line；Hydrogen is surveyed by draining weight method, the water of discharge is surveyed with precision balance
Amount first detects the air-tightness of pipeline three times.It then is 0.1 ~ 1.0 mol L by 4 ml concentration-1Ammonia Borane solution stirred in constant temperature
It under the conditions of mixing, is added rapidly in container, then magnetic stirrer is allowed to stir always, it is seen that balance number is not increasing, and terminates
Reaction.
Test result shows that the ginkgo leaf base porous carbon materials for loading ruthenium are efficiently catalyzed ammonia borane hydrolysis system at room temperature
Hydrogen, first properties are completed in 30 ~ 100 s, and hydrogen desorption capacity is the 90 ~ 100% of theoretical value, and hydrogen discharging rate reaches 3718 ml s-1
g-1。
The ginkgo leaf base porous carbon materials of the load ruthenium of above-mentioned preparation carry out catalysis ammonia borane hydrolysis hydrogen manufacturing circularity test:
The ginkgo leaf base porous carbon materials of load ruthenium after having reacted are washed by deionized water, filtering, are dried, and are by 4 ml concentration
0.5 mol L-1Ammonia Borane solution under 25 DEG C of constant temperature stirring conditions, be added rapidly to drying load ruthenium ginkgo phyllopodium
On porous carbon materials, carry out reperformance test five times.Test result shows after undergoing five circulations that properties are 50 ~ 100
S is completed, and hydrogen discharging rate is maintained at 2158 ml s-1 g-1, hydrogen discharging rate remains the 58% of first hydrogen discharging rate.
The ginkgo leaf base porous carbon materials of load ruthenium carry out catalysis ammonia borane hydrolysis hydrogen manufacturing at different temperatures, and 4 ml are dense
Degree is 0.5 mol L-1Ammonia Borane solution in the case where temperature is respectively 20,25,40,50 DEG C of constant temperature stirring conditions, be added rapidly to
On the ginkgo leaf base porous carbon materials of the load ruthenium of preparation, activation energy is fitted to obtain by Arrhenius equationE a = 23.86
kJ mol-1。
Therefore, the porous carbon materials that the present invention loads ruthenium nano particle have the advantage that the prior art
One, the raw materials used in the present invention is commercially available, low in cost, is advantageously implemented large-scale standardized production；
Two, it selects discarded ginkgo leaf as carbon source in the present invention, turns waste into wealth, improve the utilization rate of ginkgo leaf, obtain high price
The product of value, meets sustainable development.
Three, it is decomposed, is advantageously formed more micro- in the condition of high temperature for nitrogen source using semicarbazide hydrochloride in the present invention
In addition hole can mix different types of nitrogen-atoms on carbon wall, to form a large amount of micropore on the surface of carbon and obtain big
Specific surface area.
Four, by simple local reduction way one-step synthesis catalyst, ammonia borine is as reducing agent.The load of this method preparation
The ginkgo leaf base porous carbon materials catalyst of ruthenium, metal Ru particle can be uniformly dispersed in carbon surrounding, and metal Ru particle, which can be stablized, to be deposited
Do not reunite on porous carbon materials, reuse is recycled by simple filtration, dry realize, cycle performance is good.
Five, the application as properties material, the ginkgo leaf base porous carbon materials for loading ruthenium are efficiently urged at room temperature
Change ammonia borane hydrolysis hydrogen manufacturing, 30 ~ 100 s are completed, and hydrogen desorption capacity is the 90 ~ 100% of theoretical value, and hydrogen discharging rate reaches 3718 ml s-1
g-1.After undergoing five circulations, properties are completed in 50 ~ 100 s, and hydrogen discharging rate is maintained at 2158 ml s-1 g-1, hydrogen release speed
Rate remains the 58% of first hydrogen discharging rate.
Six, as the application as properties material, the ginkgo leaf base porous carbon materials of ruthenium are loaded at different temperatures
It is catalyzed ammonia borane hydrolysis hydrogen manufacturing, it is 23.86 kJ mol that activation energy, which is calculated,-1。
Therefore, the present invention has broad application prospects in fields such as hydrogen manufacturing material, fuel cells.
Detailed description of the invention:
Fig. 1 is the carbon material supported preceding scanning electron microscope (SEM) photograph in ginkgo leaf Quito hole that ruthenium is loaded in embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph after ginkgo leaf Quito hole of load ruthenium in embodiment is carbon material supported；
Fig. 3 is the XRD analysis figure that the ginkgo leaf base porous carbon materials of ruthenium are loaded in embodiment；
Fig. 4 is the ginkgo leaf base porous carbon materials hydrolysis hydrogen release figure that ruthenium is loaded in embodiment；
Fig. 5 is the ginkgo leaf base porous carbon materials cycle performance test chart that ruthenium is loaded in embodiment；
Fig. 6 be embodiment in load ruthenium ginkgo leaf base porous carbon materials different temperatures under be catalyzed ammonia borane hydrolysis hydrogen release figure and
Activation energy figure.
Specific embodiment
The present invention is described in further detail the content of present invention in conjunction with Figure of description, but be not pair by embodiment
Limitation of the invention.
Embodiment
A kind of preparation method for the ginkgo leaf base porous carbon materials loading ruthenium, the specific steps are as follows:
The low-temperature carbonization of step 1) ginkgo leaf by ginkgo leaf wash clean, is cut into 1 cm*1 cm piece, drying.Then, it is put into Muffle
Low-temperature carbonization in furnace, temperature are 300 DEG C, and be carbonized 2 h.Later, carbonized product is filtered, washed, dried, ground, obtain ginkgo
Phyllopodium carbon material.
The activation of step 2 ginkgo phyllopodium carbon material, the ginkgo phyllopodium carbon material that step 1) is obtained and semicarbazide hydrochloride and
Potassium hydroxide is 1.0:0.5:3 mixing in mass ratio, and 50 ml deionized waters are added, and impregnates, after drying, is put into full of nitrogen
It is 800 DEG C in tube furnace with activation temperature to calcine, activation time is 2 h, obtains nitrogen-doped modified ginkgo phyllopodium carbon material.
The product hydrochloric acid solution of 1 M is impregnated, is washed out, filters, drying, grinding and obtain nitrogen-doped modified ginkgo phyllopodium carbon materials
Material.
The load of step 3) metal Ru, meeting mass ratio by ruthenium element and carbon is 1:10, takes ruthenium trichloride hydrate
With above-mentioned steps 2) made from nitrogen-doped modified ginkgo phyllopodium carbon material, 20 ml deionized water wiring solution-formings are added, solution is logical
After spending after 10 min of ultrasound stir process a whole night, using ammonia borine as reducing agent, the concentration of ammonia Borane solution is 0.5 mol
L-1, the ratio between ruthenic chloride and the amount of substance of ammonia borine are 1:100, under the conditions of 25 DEG C of temperature constant magnetic stirrings, by ammonia Borane solution
It is added rapidly in chlorination ruthenium solution, guarantees that solution reaction is abundant, after bubble-free generation, washed repeatedly with water and ethyl alcohol,
Decompression filters, and is dried in vacuo 10 h under the conditions of 80 DEG C.Obtain the ginkgo leaf base porous carbon materials of load ruthenium.
Electronic Speculum detection is scanned to the carbon material supported front and back in ginkgo leaf Quito hole of load ruthenium prepared in the above embodiments:
The carbon material supported preceding scanning electron microscope testing result in ginkgo leaf Quito hole of ruthenium is loaded as shown in Figure 1, scanning electron microscope result is aobvious
Show, there are a large amount of micropores, aperture dispersion is more uniform on porous carbon material surface；
Load ruthenium ginkgo leaf Quito hole it is carbon material supported after scanning electron microscope result as shown in Fig. 2, scanning electron microscope the results show that
The many particles of porous supported on carbon surface, these particles are more uniform to be dispersed in around hole, and pattern is good, homogeneity is good, and
And be supported on the metal Ru particle on porous carbon there is no reunite.
XRD detection is carried out to the ginkgo leaf base porous carbon materials of load ruthenium prepared in the above embodiments, as a result such as Fig. 3 institute
Show, the ginkgo leaf base porous carbon materials for loading ruthenium as the result is shown are 29.8 ° and 42.1 ° in 2 θ and two apparent packets nearby occur
Peak can be attributed to the peak of carbon, and loading wide and weak peak that the ginkgo leaf base porous carbon materials of ruthenium occur in 2 θ=42.8 ° can be with
It is attributed to Ru (002) diffraction maximum.
The ginkgo leaf base porous carbon materials of load ruthenium prepared in the above embodiments carry out catalysis ammonia borane hydrolysis hydrogen manufacturing test,
The porous carbon materials of the load ruthenium nano particle made are put into wide-mouth bottle, magnetic stirrer is added, is then placed in container
In 25 DEG C of thermostat water bath, container is connected with water-filled gauge line；Hydrogen, the water of discharge are detected by draining weight method
It is measured with precision balance, first examines the air-tightness of pipeline three times.Take the 0.5 mol L of 4 ml-1Ammonia borine, be then quickly added into
In container, then magnetic stirrer is allowed to stir always, it is seen that balance number is not increasing, and reaction was completed.
Test result, as shown in figure 4, the ginkgo leaf base porous carbon materials of load ruthenium are efficiently catalyzed ammonia borine at room temperature
Hydrolytic hydrogen production, about 40 s are completed, and hydrogen desorption capacity is the 92% of theoretical value, and hydrogen discharging rate reaches 3718 ml s-1 g-1.And same quality
Metal Ru particle-catalytic ammonia borane hydrolysis hydrogen manufacturing about completes hydrogen release in 200 s, and catalyst is efficiently catalyzed ammonia borane hydrolysis hydrogen manufacturing.
The ginkgo leaf base porous carbon materials of load ruthenium prepared in the above embodiments carry out catalysis ammonia borane hydrolysis hydrogen manufacturing circulation
Performance test: the ginkgo leaf base porous carbon materials of the load ruthenium after having reacted after distillation water washing, filtering, drying by repeating
It uses, takes the 0.5 mol L of 4 ml-1Ammonia borine, be added rapidly to drying load ruthenium ginkgo leaf base porous carbon materials in,
Then it carries out reperformance test five times.Test result is illustrated in figure 5 the ginkgo leaf base porous carbon materials cycle performance of load ruthenium
Test chart, after five circulations, properties are completed in 60 s, and hydrogen discharging rate is maintained at 2158 ml s-1 g-1, hydrogen discharging rate
The 58% of first hydrogen discharging rate is remained, cycle performance is good.
The ginkgo leaf base porous carbon materials of load ruthenium prepared in the above embodiments carry out catalysis ammonia borine at different temperatures
Hydrogen manufacturing test, the porous carbon materials of the load ruthenium nano particle made are put into wide-mouth bottle, and magnetic stirrer is added, and then will
It is respectively in 20,25,40,50 DEG C of thermostat water bath that container, which is placed in temperature, and container is connected with water-filled gauge line；Pass through
It drains weight method and detects hydrogen, the water of discharge is measured with precision balance, first examines the air-tightness of pipeline three times.Take the 0.5 of 4 ml
mol L-1Ammonia borine, be then quickly added into container, then magnetic stirrer allowed to stir always, it is seen that balance number does not exist
Increase, reaction was completed.
Test result, as shown in fig. 6, the ginkgo leaf base porous carbon materials of load ruthenium can be efficiently catalyzed at different temperatures
Ammonia borane hydrolysis hydrogen manufacturing, set temperature are respectively 20,25,40,50 DEG C, are fitted to obtain activation energy by Arrhenius equationE a
= 23.86 kJ mol-1。
Claims (9)
1. a kind of ginkgo leaf base porous carbon materials for loading ruthenium, it is characterised in that: by ginkgo leaf as carbon source, by low-temperature carbonization
Afterwards, a certain amount of nitrogenous compound is added, then uses alkali inorganic substance, ginkgo leaf base porous carbon is obtained after calcining and activating
Material, is then loaded to metal Ru on porous carbon materials by local reduction way, obtains a kind of ginkgo leaf Quito hole for loading ruthenium
Carbon material.
2. the ginkgo leaf base porous carbon materials of load ruthenium according to claim 1, it is characterised in that: carbon material surface is deposited
In a large amount of micropore, the dispersion of this some holes is more uniform, as catalysis ammonia borane hydrolysis hydrogen manufacturing catalyst, at room temperature, maximum hydrogen release speed
Rate is up to 3718 ml s-1 g-1。
3. according to claim 1 load ruthenium ginkgo leaf base porous carbon materials preparation method, it is characterised in that including with
Lower step:
The low-temperature carbonization of step 1) ginkgo leaf: by ginkgo leaf wash clean, being cut into piece, drying,
Then, it is put into Muffle furnace low-temperature carbonization under certain condition, later, carbonized product is filtered, washed, dry, is ground, is obtained
To ginkgo phyllopodium carbon material；
The activation of step 2 ginkgo phyllopodium carbon material: the ginkgo phyllopodium carbon material and nitrogenous precursor and alkalinity that step 1) is obtained
Inorganic matter, than mixing, impregnating, after drying, is put into the tube furnace full of nitrogen to calcine and live under certain condition by certain mass
Change, product hydrochloric acid solution is impregnated, washing, filtering, is dried, grinding obtains nitrogen-doped modified ginkgo phyllopodium carbon material；
The load of step 3) metal Ru: being met certain mass ratio by ruthenium element and carbon, takes ruthenium trichloride hydrate and upper
It states ginkgo phyllopodium carbon material nitrogen-doped modified made from step 2 and adds water wiring solution-forming, solution passes through ultrasound and stir process
Afterwards, using ammonia borine as reducing agent, wherein ruthenic chloride and ammonia borine meet the ratio between the amount of certain substance, under certain condition, will
Ammonia Borane solution and the mixing of chlorination ruthenium solution, obtain the ginkgo leaf base porous carbon materials of load ruthenium after washing, filtering, drying.
4. preparation method according to claim 3, it is characterised in that: the ginkgo leaf low-temperature carbonization condition of the step 1)
For, it is put into Muffle furnace, is 300 ~ 450 DEG C in temperature, 1 ~ 3 h of low-temperature carbonization.
5. preparation method according to claim 3, it is characterised in that: the nitrogenous compound of the step 2 is hydrochloric acid ammonia
Base urea and the one or two kinds of of urea pyrimidine mix, and the alkali inorganic substance in the step 2 is inorganic base or alkaline, inorganic salts, hydrogen
Potassium oxide, sodium hydroxide, potassium carbonate etc., the ginkgo phyllopodium carbon material of the step 2 and nitrogenous precursor and alkali inorganic substance
Mass ratio is 1.0:(0.5 ~ 6): (1.5 ~ 8.0), the calcination temperature of the step 2 are 600 ~ 900 DEG C, and calcination time is 1 ~ 6
h。
6. preparation method according to claim 3, it is characterised in that: the ruthenium element of the step 3) and the matter of carbon
Amount is than being 1:(5 ~ 20), ammonia borine is 0.1 ~ 1.0 mol L as reducing agent, the concentration of ammonia Borane solution-1, ruthenic chloride and ammonia boron
The ratio between amount of substance of alkane range is 1:(50 ~ 100), the ammonia Borane solution and chlorination ruthenium solution mixing condition are at 25 DEG C
Under the conditions of temperature constant magnetic stirring, ammonia Borane solution is added rapidly in chlorination ruthenium solution, guarantees that solution reaction is abundant, Zhi Daowu
It after bubble generates, is washed repeatedly with water and ethyl alcohol, decompression filters, and 5 ~ 10 h are dried in vacuo under the conditions of 70-100 DEG C.
7. loading the ginkgo leaf base porous carbon materials of ruthenium according to claim 1 as ammonia borane hydrolysis hydrogen manufacturing catalyst
Using, it is characterised in that: the ginkgo leaf base porous carbon materials for loading ruthenium are efficiently catalyzed ammonia borane hydrolysis hydrogen manufacturing at room temperature, just
Secondary properties are completed in 30 ~ 100 s, and hydrogen desorption capacity is the 90 ~ 100% of theoretical value, and hydrogen discharging rate reaches 3718 ml s-1 g-1。
8. the ginkgo leaf base porous carbon materials of load ruthenium according to claim 1 are as ammonia borane hydrolysis hydrogen manufacturing catalyst
Application, it is characterised in that: the ginkgo leaf base porous carbon materials for loading ruthenium can be recycled by the method that is filtered, washed, dries
It uses, after undergoing five circulations, properties are completed in 50 ~ 100 s, and hydrogen discharging rate is maintained at 2158 ml s-1 g-1, hydrogen release
Rate remains the 58% of first hydrogen discharging rate.
9. the ginkgo leaf base porous carbon materials of load ruthenium according to claim 1 are as ammonia borane hydrolysis hydrogen manufacturing catalyst
Application, it is characterised in that: load the catalysis ammonia borane hydrolysis hydrogen manufacturing of the ginkgo leaf base porous carbon materials of ruthenium at different temperatures,
Temperature is respectively 20,25,40,50 DEG C, is fitted to obtain activation energy by Arrhenius equationE a = 23.86 kJ mol-1。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499576A (en) * | 2018-12-29 | 2019-03-22 | 桂林电子科技大学 | A kind of Co-B/NGO composite nano materials and its preparation method and application |
| CN111732102A (en) * | 2019-12-04 | 2020-10-02 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
| CN112941552A (en) * | 2021-01-27 | 2021-06-11 | 云南电网有限责任公司电力科学研究院 | Porous carbon-supported ruthenium catalyst and preparation method thereof |
| CN114836787A (en) * | 2022-04-27 | 2022-08-02 | 东南大学 | Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498823A (en) * | 2016-02-26 | 2016-04-20 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst |
| CN106099096A (en) * | 2016-07-07 | 2016-11-09 | 上海交通大学 | Trimanganese tetroxide nano particulate composite that porous carbon supports and preparation method thereof |
| CN106971866A (en) * | 2017-05-14 | 2017-07-21 | 徐俊鸽 | A kind of preparation method of activated carbon/cobalt hydroxide combination electrode material |
| CN107055504A (en) * | 2017-03-13 | 2017-08-18 | 符策煌 | Porous carbon sill of sheet from blade and preparation method thereof |
| CN107159214A (en) * | 2017-06-22 | 2017-09-15 | 桂林电子科技大学 | A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application |
| CN108160073A (en) * | 2017-12-29 | 2018-06-15 | 桂林电子科技大学 | A kind of porous carbon materials for loading ruthenium nano particle and its preparation method and application |
-
2018
- 2018-07-03 CN CN201810713714.5A patent/CN109046419A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498823A (en) * | 2016-02-26 | 2016-04-20 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst |
| CN106099096A (en) * | 2016-07-07 | 2016-11-09 | 上海交通大学 | Trimanganese tetroxide nano particulate composite that porous carbon supports and preparation method thereof |
| CN107055504A (en) * | 2017-03-13 | 2017-08-18 | 符策煌 | Porous carbon sill of sheet from blade and preparation method thereof |
| CN106971866A (en) * | 2017-05-14 | 2017-07-21 | 徐俊鸽 | A kind of preparation method of activated carbon/cobalt hydroxide combination electrode material |
| CN107159214A (en) * | 2017-06-22 | 2017-09-15 | 桂林电子科技大学 | A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application |
| CN108160073A (en) * | 2017-12-29 | 2018-06-15 | 桂林电子科技大学 | A kind of porous carbon materials for loading ruthenium nano particle and its preparation method and application |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499576A (en) * | 2018-12-29 | 2019-03-22 | 桂林电子科技大学 | A kind of Co-B/NGO composite nano materials and its preparation method and application |
| CN111732102A (en) * | 2019-12-04 | 2020-10-02 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
| CN111732102B (en) * | 2019-12-04 | 2021-06-15 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
| CN112941552A (en) * | 2021-01-27 | 2021-06-11 | 云南电网有限责任公司电力科学研究院 | Porous carbon-supported ruthenium catalyst and preparation method thereof |
| CN112941552B (en) * | 2021-01-27 | 2024-04-09 | 云南电网有限责任公司电力科学研究院 | Porous carbon supported ruthenium catalyst and preparation method thereof |
| CN114836787A (en) * | 2022-04-27 | 2022-08-02 | 东南大学 | Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst |
| CN114836787B (en) * | 2022-04-27 | 2023-12-08 | 东南大学 | Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst |
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