CN110124721A - A kind of nitrogen-doped porous carbon material and its preparation method and application of load C oB nanoparticle - Google Patents
A kind of nitrogen-doped porous carbon material and its preparation method and application of load C oB nanoparticle Download PDFInfo
- Publication number
- CN110124721A CN110124721A CN201910438482.1A CN201910438482A CN110124721A CN 110124721 A CN110124721 A CN 110124721A CN 201910438482 A CN201910438482 A CN 201910438482A CN 110124721 A CN110124721 A CN 110124721A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- load
- nanoparticle
- nitrogen
- carbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 116
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- 230000001788 irregular Effects 0.000 claims abstract description 6
- 238000003795 desorption Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract 2
- 230000000802 nitrating effect Effects 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 230000004087 circulation Effects 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003349 semicarbazides Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000011056 performance test Methods 0.000 description 14
- 238000011068 loading method Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 235000011201 Ginkgo Nutrition 0.000 description 4
- 241000218628 Ginkgo Species 0.000 description 4
- 235000008100 Ginkgo biloba Nutrition 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 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
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C01B3/065—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 from a hydride
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of nitrogen-doped porous carbon materials of load C oB nanoparticle, nitrogenous compound is added in porous carbon materials, pass through hydro-thermal method, activation method and high-temperature heat treatment method, obtain irregular spherical nitrogen-doped porous carbon material, then the method Jing Guo in-situ reducing loads to CoB on nitrogen-doped porous carbon material, obtain the nitrogen-doped porous carbon material of load C oB nanoparticle, uniform load CoB nanoparticle in irregular spherical nitrogen-doped porous carbon material surface and duct, final spherical in rule, specific surface area is 1359-2524 m2g‑1, pore-size distribution is 1.60-2.40 nm.Preparation method includes the following steps: 1) preparation of nitrogen-doped porous carbon material；2) load of CoB nanoparticle.Hydrogen release catalyst is hydrolyzed as sodium borohydride, hydrogen discharging rate reaches 1200-2500 ml/min/g, and cycle performance is good, and hydrogen desorption capacity is maintained at 50-60%.Therefore, present invention preparation is simple and has more excellent catalytic performance, has broad application prospects in the fields such as the application of Hydrogen Energy and fuel cell.
Description
Technical field
The present invention relates to technical field of catalytic chemistry, and in particular to a kind of N doping porous carbon of load C oB nanoparticle
Material and its preparation method and application.
Background technique
The energy is most important substance for the survival of mankind, is most important resource in human development.The modern industry flies
Speed development, increasing to the consumption of the energy, bring problem of environmental pollution and lack of energy problem be also more and more at the same time
Seriously.Secondary energy sources of the Hydrogen Energy as high effect cleaning, get more and more people's extensive concerning in recent years.As a kind of hydrogen storage material
NaBH4There is very high hydrogen-storage density (10.6 wt.%), moreover, in NaBH4In the reaction for hydrolyzing hydrogen release, the hydrogen released has one
Partly come from water, that is to say, that whenever there is 1 g NaBH4When hydrolysis, maximum can release the hydrogen of 0.212 g.NaBH4Water
The hydrogen purity for solving hydrogen manufacturing output is high, is free of CO, CO2Etc. foreign gases, can satisfy requirement of the fuel cell to purity, in addition
It also has many advantages, such as that reaction is easy to control, highly-safe, nontoxic and pollution-free.
Boron hydride can discharge hydrogen by being pyrolyzed and hydrolyzing two ways, but pyrolysis needs hot environment, therefore
Limit its practical application.Borohydride hydrolytic process is easy to operate, convenient and easy, is added after suitable catalyst at room temperature
Hydrogen can quickly be discharged.In addition, the hydrogen in reaction product has half to be derived from water, its energy for producing hydrogen is more improved
Power.But simple borohydride hydrolytic rate is especially slow, therefore, the catalyst for finding high efficiency low cost is borohydride hydrolytic
The committed step of hydrogen release application.
There is noble metal catalyst very high catalytic efficiency noble metal can be made equal by porous carbon as carrier
It is even to disperse and do not reunite, catalytic effect can be improved；And by carrying out the wetting that N doping improves catalyst to porous carbon
Property, while more active sites are provided for nanoparticle.Chinese patent CN109046419A in the prior art discloses one kind
Using ginkgo leaf as the method for carrier to load metal ruthenium, using ginkgo leaf as carbon source, after low-temperature carbonization, nitrogenous compound is added
And alkali inorganic substance, ginkgo leaf base porous carbon materials are obtained after calcining and activating, are then born metal Ru by local reduction way
It is downloaded on porous carbon materials, obtains a kind of ginkgo leaf base porous carbon materials for loading ruthenium.As ammonia borane hydrolysis hydrogen manufacturing catalyst,
Hydrogen discharging rate reaches 3718 ml s-1 g-1.Although the prior art hydrogen-producing speed of noble metal catalyst class is relatively high,
The technical issues of it is expensive that there are the precious metal raw materials such as ruthenium cost prices, is unable to satisfy large-scale production.
Solve the problems, such as noble metal, common method is to substitute using base metals such as Co, Ni to noble metal.To adopt
For base metal cobalt element, a kind of N doping CoB alloy of Chinese patent CN107170972A disclosure of the invention, by hydroboration
Sodium solution restored under conditions of ultrasound cobalt chloride, nitrogen-containing basic compound mixed solution after, then it is washed, vacuum drying system
, on the secondary battery with good chemical property.As cell negative electrode material in application, electrochemistry capacitance exists
Under the discharge current density of 100 mA/g, first discharge specific capacity value reaches 500-1000mAh/g, is 300- after 100 circulations
500mAh/g, capacity retention ratio 30-50%, Limited diffusion current density are 1000 ~ 6000mA/g.
Chinese patent CN107159214A discloses a kind of porous active carbon material load cobalt nanometer particle material, by grape
Sugar and nitrogenous compound, are prepared into porous structure carbon material by hydro-thermal method and subsequent processing, then pass through dipping electronation
It is obtained on method load cobalt particle to carbon material, as catalysis ammonia borane hydrolysis hydrogen release catalyst in application, 10 min completion is put
Hydrogen, hydrogen discharging rate reach 865.2 mL min-1 g-1。
The prior art replaces ruthenium element using cobalt element, significantly reduces cost of material, but catalytic effect also occurs greatly
The decline of width, is unable to satisfy application demand.
Summary of the invention
The invention aims to provide a kind of nitrogen-doped porous carbon material of load C oB nanoparticle.Pass through cobalt element
Guarantee good catalytic performance while realizing reduction cost of material instead of ruthenium element.
Concrete principle are as follows: and local reduction way is used, make cobalt element steady load on the carbon material；With the replacement of ammonia borine
The prior art often uses reducing agent sodium borohydride, to realize introducing boron element, and avoids introduce sodium element in reduction process simultaneously
Residual；Finally be embodied as hydrogen-producing speed have compared with the prior art be substantially improved and the technology of catalyst agglomeration, poor circulation effect
Fruit.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A certain amount of nitrogenous compound is added in porous carbon materials by a kind of nitrogen-doped porous carbon material of load C oB nanoparticle,
By hydro-thermal method, activation method and high-temperature heat treatment method, irregular spherical nitrogen-doped porous carbon material is obtained, then by situ
The method of reduction loads to CoB on nitrogen-doped porous carbon material, obtains the nitrogen-doped porous carbon of load C oB nanoparticle
Material, the nitrogen-doped porous carbon material of the load C oB nanoparticle be on irregular spherical nitrogen-doped porous carbon material surface and
Uniform load CoB nanoparticle in duct, final spherical in rule, specific surface area is 1359-2524 m2g-1, pore-size distribution
For 1.60-2.40 nm.
The preparation method of the nitrogen-doped porous carbon material of load C oB nanoparticle the following steps are included:
Porous carbon materials and nitrogenous compound and alkali inorganic substance are pressed certain mass ratio by the pretreatment of step 1) porous carbon materials
Mixing is impregnated in deionized water, is dried after 2h is stirred at room temperature；Then it under the conditions of protecting gas, is calcined with certain condition
Activation；It is most impregnated afterwards through dilute hydrochloric acid solution, by washing, filtering, drying, grinding, obtains nitrating porous carbon materials；
The nitrogenous compound of the step 1 is semicarbazides, urea or guanidine carbonate；The alkali inorganic substance of the step 1 is hydroxide
Potassium, sodium hydroxide or potassium carbonate；The porous carbon materials of the step 1 and the mass ratio of nitrogenous compound, alkali inorganic substance are
1.0:3.0:(1.5-6.0)；
The condition of the calcining and activating of the step 1, calcination temperature are 600-800 DEG C, and activation time is 1-6 h；
Step 1 gained nitrating porous carbon materials are added with certain load capacity for the load of step 2 CoB nanoparticle
CoCl2.6H2Mixed solution is obtained after O aqueous solution ultrasonic treatment 1h, ethyl alcohol again is dissolved using a certain amount of ammonia borine as reducing agent
Aqueous solution in, be added dropwise in aforementioned mixed solution, obtain the suspension of black, be filtered, washed, dried to get to negative
Carry the nitrogen-doped porous carbon material of CoB nanoparticle；
The CoCl of the step 22.6H2The load capacity of O is 1wt%-50wt%, reducing agent ammonia borine and CoCl2.6H2The substance of O
The ratio between amount is 12:(17-20), ammonia Borane solution is added dropwise to CoCl2.6H2In O solution, until bubble-free generates.
Application of the nitrogen-doped porous carbon material of load C oB nanoparticle as sodium borohydride hydrolyst, hydrogen release speed
Rate reaches 1200-2500 ml/min/g, and by five circulations, hydrogen desorption capacity remains at the 50-60% of hydrogen release for the first time.
The nitrating porous carbon materials load front and back of load C oB nanoparticle of the present invention is scanned Electronic Speculum detection: load C oB
Scanning electron microscope testing result before the nitrating porous carbon materials load of nanoparticle shows that carbon material shows porous structure.
As the result is shown, porous carbon surface is negative for scanning electron microscope after the nitrating porous carbon materials load of load C oB nanoparticle
Many particles are carried, these are evengranular to be dispersed in around hole, and pattern is good, and homogeneity is good, and it is more to be supported on nitrating
There is no reuniting for CoB nanoparticle on the carbon of hole.
EDS figure after the nitrating porous carbon materials load of load C oB nanoparticle, it can clearly be seen that cobalt boron element is deposited
Nitrogen is also doped with into well.
The nitrating porous carbon materials of load C oB nanoparticle carry out the performance test of low temperature nitrogen isothermal adsorption, test condition
To deaerate 10 hours under the conditions of 180 DEG C, isothermal nitrogen adsorption is then carried out under the conditions of 77 K.Test result shows preparation
Nitrating porous carbon materials its specific surface areas with higher, up to 2524m2 g-1, a large amount of micropore and suitable mesoporous, put down
Equal aperture is 1.92 nm, Kong Rongwei 1.25cm3g-1。
The nitrating porous carbon materials of load C oB nanoparticle carry out catalysis sodium borohydride hydrogen discharging performance test, weigh catalysis
Agent is distributed in the NaOH solution of sodium borohydride, and sealing is controlled the temperature of solution by water bath with thermostatic control, the hydrogen of generation is passed through
Drainage is collected, and the volume of the hydrogen generated in record unit time obtains hydrogen discharging performance.Test result shows that load C oB receives
The nitrating porous carbon materials of rice corpuscles, hydrogen discharging rate are 1200-2500 mLmin-1g-1。
The cycle performance of the nitrating porous carbon materials of load C oB nanoparticle is tested, and the catalysis of hydrogen release test will have been carried out
Agent by magnetite carry out adsorption recovery, it is dry after, carry out hydrogen release test again, then repeatedly above step, obtain hydrogen discharging rate.
Test result shows that the hydrogen-producing speed after circulation can still keep the 50-60% of original hydrogen-producing speed.
The present invention compared with the existing technology, has the advantage that
1. the present invention is using the nitrating porous carbon materials of local reduction way preparation load C oB nanoparticle, wherein in porous carbon
Nitrogen atom doping is introduced on material can modify its outer electronic structure, to influence its physical and chemical performance, change urging for material
Change performance.
2. the specific surface area of the nitrating porous structure carbon material of this method preparation is 1359-2524m2 g-1, average pore size
For 1.60-2.40 nm, pore-size distribution is uniform.
3. nitrating porous carbon materials of load C oB nanoparticle of the present invention and preparation method thereof are in borohydride hydrolytic system
Application in hydrogen, allows to realize catalyzing hydrolysis at normal temperatures and pressures, hydrogen desorption capacity 100%, and the rate for hydrolyzing hydrogen release is reachable
2446.23 mL min-1g-1, can achieve 80% or so of precious metal catalyst effect；
4. the present invention replaces noble metal with base metal, cost has greatly been saved, has been suitble to produce in enormous quantities, and the present invention
The catalyst of production has magnetism, is conducive to recycling, and the rate of recovery is up to 100%；
Therefore, the present invention has more excellent catalytic performance compared with prior art, improves catalytic rate, in boron hydride water
Application field in solution hydrogen manufacturing has broad application prospects.
Detailed description of the invention:
Fig. 1 is the scanning electron microscope (SEM) photograph before the nitrating porous carbon materials load of load C oB nanoparticle in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph after the nitrating porous carbon materials load of load C oB nanoparticle in embodiment 1；
Fig. 3 is the nitrating porous carbon materials EDS image of load C oB nanoparticle in embodiment 1；
Fig. 4 is the nitrating porous carbon materials low temperature nitrogen adsorption isothermal curve of load C oB nanoparticle in embodiment 1；
Fig. 5 is the pore size distribution curve of the nitrating porous carbon materials of load C oB nanoparticle in embodiment 1；
Fig. 6 is that the nitrating porous carbon materials of load C oB nanoparticle in embodiment 1 hydrolyze hydrogen release figure；
Fig. 7 is the nitrating porous carbon materials cycle performance test chart of load C oB nanoparticle in embodiment 1；
Fig. 8 is the nitrating porous carbon materials scanning electron microscope (SEM) photograph of loading NiB nanoparticle in comparative example.
Specific embodiment
The following examples are a further detailed description of the invention, but are not limitations of the present invention.
Embodiment 1
The preparation method of the nitrating porous carbon materials of load C oB nanoparticle, specific steps are as follows:
The preparation of step 1) nitrogen-doped porous carbon material mixes carbon matrix precursor and KOH and urea in mass ratio for 1.0:3.0:1.0
It closes, is immersed in 30ml ionized water, magnetic agitation 2 hours, puts into tube furnace after drying and be calcined under nitrogen protection, be calcined
Activation temperature is 700 DEG C, and calcination activation time is 2 h, obtains the porous active Carbon Materials of N doping；By above-mentioned product 1M
HCl solution impregnates, and is washed with deionized, filters to neutrality, grinds after drying, obtains nitrogen-doped porous carbon material；
The load of step 2 CoB nanoparticle, weighing load capacity is 40wt% CoCl2.6H2O is put into 10ml deionized water,
The nitrating porous carbon of certain mass is weighed, 1h is ultrasonically treated, weighs reducing agent ammonia borine 11mg (reducing agent NH3BH3With
CoCl2.6H2The molar ratio of O is 12:17), it is dissolved in the aqueous solution of ethyl alcohol (1:1), is added dropwise in above-mentioned solution, is obtained
To the solution of black, it is filtered, washed, the nitrating porous carbon materials of drying to obtain load C oB nanoparticle.
The nitrating porous carbon materials load front and back of load C oB nanoparticle in embodiment 1 is scanned to the test of Electronic Speculum:
Load C oB nanoparticle nitrating porous carbon materials load before scanning electron microscope testing result such as Fig. 1 show, carbon material
Show porous structure.
Load C oB nanoparticle nitrating porous carbon materials load after scanning electron microscope result such as Fig. 2 show, porous carbon table
Face has loaded many particles, these are evengranular to be dispersed in around hole, and pattern is good, and homogeneity is good, and is supported on and mixes
There is no reuniting for CoB nanoparticle on nitrogen porous carbon.
EDS figure after the nitrating porous carbon materials of the load C oB nanoparticle prepared in embodiment 1 are loaded, as Fig. 3 is aobvious
Show, it can clearly be seen that the presence of cobalt boron element, nitrogen are also doped with into well.
The nitrating porous carbon materials of the load C oB nanoparticle prepared in embodiment 1 are subjected to low temperature nitrogen isothermal adsorption
Performance test, test condition are to deaerate 10 hours under the conditions of 180 DEG C, and isothermal nitrogen adsorption is then carried out under the conditions of 77 K.
Test results are shown in figure 4, and the nitrating porous carbon specific surface area of load C oB nanoparticle is 2524 m2 g-1。
The nitrating porous carbon materials of the load C oB nanoparticle prepared in embodiment 1 are subjected to low temperature nitrogen isothermal adsorption
Performance test, test condition are to deaerate 10 hours under the conditions of 180 DEG C, and isothermal nitrogen adsorption is then carried out under the conditions of 77 K.
Test results are shown in figure 5, and the nitrating porous carbon materials pore-size distribution of load C oB nanoparticle is in 2nm or so.
The nitrating porous carbon materials of room temperature load C oB nanoparticles different in embodiment 1 are carried out catalysis sodium borohydride to put
Hydrogen performance test, the specific steps are as follows: the nitrating porous carbon materials for weighing load C oB nanoparticle prepared by 0.1g are distributed to
0.1 M NaBH41wt% NaOH solution in, sealing, by water bath with thermostatic control control solution temperature, the hydrogen of generation is passed through
Drainage is collected, and the volume of the hydrogen generated in record unit time obtains hydrogen discharging performance, test result shows hydrogen discharging rate
As shown in fig. 6, hydrogen discharging rate can be up to 2446.23 mL min at 25 DEG C-1g-1。
The nitrating porous carbon materials cycle performance test of load C oB nanoparticle is prepared in embodiment 1, specific steps are such as
Under: the nitrating porous carbon materials for weighing load C oB nanoparticle prepared by 0.1g are distributed to 0.1 M NaBH41wt%
In NaOH solution, sealing controls the temperature of solution by water bath with thermostatic control, the hydrogen of generation is collected by drainage, record
The volume of the hydrogen generated in the time of position, obtains the rate of hydrogen release.Catalyst collection is put after repeating above step 5 times
Hydrogen rate.Test results are shown in figure 7, and the hydrogen-producing speed after circulation 5 times can still keep the 55% of original hydrogen-producing speed.
The nitrating porous carbon materials of load C oB nanoparticle are hydrolyzed in order to show the different loads amount of CoB nanoparticle
The influence of performance, present invention offer following example 2,3 and 4 are described in detail.
Embodiment 2
The preparation method of the nitrating porous carbon materials of load C oB nanoparticle, not specified concrete operation step with it is above-mentioned
Embodiment 1 is identical, the difference is that: the step 3) CoCl2.6H2O load capacity is 20wt%.
Characterization test method is identical as above-described embodiment 1.
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 2 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials specific surface area of load C oB nanoparticle are 2524 m2 g-1。
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 2 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials pore-size distribution of load C oB nanoparticle is in 2nm or so.
The nitrating porous carbon materials of room temperature load C oB nanoparticles different in embodiment 2 are carried out catalysis sodium borohydride to put
Hydrogen performance test, hydrogen discharging rate can be up to 1234.78 mL min at 25 DEG C-1g-1。
The nitrating porous carbon materials cycle performance test that load C oB nanoparticle is prepared in embodiment 2, after recycling 5 times
Hydrogen-producing speed can still keep the 52% of original hydrogen-producing speed.
Embodiment 3
The preparation method of the nitrating porous carbon materials of load C oB nanoparticle, not specified concrete operation step with it is above-mentioned
Embodiment 1 is identical, the difference is that: the step 3) CoCl2.6H2O load capacity is 30wt%.
Characterization test method is identical as above-described embodiment 1.
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 3 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials specific surface area of load C oB nanoparticle are 2524 m2 g-1。
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 3 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials pore-size distribution of load C oB nanoparticle is in 2nm or so.
The nitrating porous carbon materials of room temperature load C oB nanoparticles different in embodiment 3 are carried out catalysis sodium borohydride to put
Hydrogen performance test, hydrogen discharging rate can be up to 1487.68 mL min at 25 DEG C-1g-1。
The nitrating porous carbon materials cycle performance test that load C oB nanoparticle is prepared in embodiment 3, after recycling 5 times
Hydrogen-producing speed can still keep the 54% of original hydrogen-producing speed.
Embodiment 4
The preparation method of the nitrating porous carbon materials of load C oB nanoparticle, not specified concrete operation step with it is above-mentioned
Embodiment 1 is identical, the difference is that: the step 3) CoCl2.6H2O load capacity is 50wt%.
Characterization test method is identical as above-described embodiment 1.
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 4 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials specific surface area of load C oB nanoparticle are 2524 m2 g-1。
The nitrating porous carbon materials of load C oB nanoparticle in embodiment 4 are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials pore-size distribution of load C oB nanoparticle is in 2nm or so.
The nitrating porous carbon materials of room temperature load C oB nanoparticles different in embodiment 4 are carried out catalysis sodium borohydride to put
Hydrogen performance test, hydrogen discharging rate can reach 1329.69mL min at 25 DEG C-1g-1。
The nitrating porous carbon materials cycle performance test that load C oB nanoparticle is prepared in embodiment 4, after recycling 5 times
Hydrogen-producing speed can still keep the 53% of original hydrogen-producing speed.
In order to show the metal types of load to the shadow of the nitrating porous carbon materials hydrolysis property of load C oB nanoparticle
It rings, the present invention provides following comparative example and is described in detail.
Comparative example
The preparation method of the nitrating porous carbon materials of load C oB nanoparticle, not specified concrete operation step with it is above-mentioned
Embodiment 1 is identical, the difference is that: the step 1) is by CoCl2.6H2O is changed to NiCl2.6H2O。
Characterization test method is identical as above-described embodiment 1.
With the porous nitrating porous carbon by loading NiB nanoparticle in comparative example of nitrating of room temperature loading NiB nanoparticle
Material is scanned the test of Electronic Speculum load front and back, the scanning electricity before the nitrating porous carbon materials load of loading NiB nanoparticle
Microscopy is surveyed, and carbon material shows porous structure.
Scanning electron microscope such as Fig. 8 after the nitrating porous carbon materials load of loading NiB nanoparticle shows that porous carbon surface is negative
There is part reunion in load after metal.
The nitrating porous carbon materials of loading NiB nanoparticle in comparative example are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials specific surface area of loading NiB nanoparticle are 2524 m2 g-1。
The nitrating porous carbon materials of loading NiB nanoparticle in comparative example are carried out low temperature nitrogen isothermal adsorption performance to survey
Examination, the nitrating porous carbon materials pore-size distribution of loading NiB nanoparticle is in 2nm or so.
By carbon material does not carry out catalysis sodium borohydride hydrogen discharging performance test in comparative example, hydrogen discharging rate can reach at 25 DEG C
465.32mL min-1g-1。
Conclusion: load C oB nanoparticle is changed to loading NiB nanoparticle, hydrogen-producing speed reduces more than twice, much
The effect of CoB nano particle catalysis is not achieved, mainly Ni Base Metal cannot act synergistically well with this carbon material.
Claims (6)
1. a kind of nitrogen-doped porous carbon material of load C oB nanoparticle, it is characterised in that: porous carbon materials are added certain
The nitrogenous compound of amount obtains irregular spherical nitrogen-doped porous carbon by hydro-thermal method, activation method and high-temperature heat treatment method
Material, then the method Jing Guo in-situ reducing loads to CoB on nitrogen-doped porous carbon material, obtains load C oB nanoparticle
Nitrogen-doped porous carbon material, the nitrogen-doped porous carbon material of the load C oB nanoparticle are more in irregular spherical N doping
Uniform load CoB nanoparticle in hole carbon material surface and duct is finally in spherical, the specific surface area 1359-2524 of rule
m2g-1, pore-size distribution is 1.60-2.40 nm.
2. the preparation method of the nitrogen-doped porous carbon material of load C oB nanoparticle according to claim 1, it is characterised in that
The following steps are included:
Porous carbon materials and nitrogenous compound and alkali inorganic substance are pressed certain mass ratio by the pretreatment of step 1) porous carbon materials
Mixing is impregnated in deionized water, is dried after 2h is stirred at room temperature；Then it under the conditions of protecting gas, is calcined with certain condition
Activation；It is most impregnated afterwards through dilute hydrochloric acid solution, by washing, filtering, drying, grinding, obtains nitrating porous carbon materials；
Step 1 gained nitrating porous carbon materials are added with certain load capacity for the load of step 2 CoB nanoparticle
CoCl2.6H2Mixed solution is obtained after O aqueous solution ultrasonic treatment 1h, ethyl alcohol again is dissolved using a certain amount of ammonia borine as reducing agent
Aqueous solution in, be added dropwise in aforementioned mixed solution, obtain the suspension of black, be filtered, washed, dried to get to negative
Carry the nitrogen-doped porous carbon material of CoB nanoparticle.
3. preparation method according to claim 2, it is characterised in that: the nitrogenous compound of the step 1 is semicarbazides, urine
Element or guanidine carbonate；The alkali inorganic substance of the step 1 is potassium hydroxide, sodium hydroxide or potassium carbonate；The step 1 it is porous
The mass ratio of carbon material and nitrogenous compound, alkali inorganic substance is 1.0:3.0:(1.5-6.0).
4. preparation method according to claim 2, it is characterised in that: the condition of the calcining and activating of the step 1, calcining temperature
Degree is 600-800 DEG C, and activation time is 1-6 h.
5. preparation method according to claim 2, it is characterised in that: the CoCl of the step 22.6H2The load capacity of O is
1wt%-50wt%, reducing agent ammonia borine and CoCl2.6H2The ratio between amount of substance of O is 12:(17-20), dropwise by ammonia Borane solution
It is added to CoCl2.6H2In O solution, until bubble-free generates.
6. the nitrogen-doped porous carbon material of load C oB nanoparticle according to claim 1 is urged as sodium borohydride hydrolysis
The application of agent, it is characterised in that: hydrogen discharging rate reaches 1200-2500 ml/min/g, and by five circulations, hydrogen desorption capacity is still
It is maintained at the 50-60% of hydrogen release for the first time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910438482.1A CN110124721B (en) | 2019-05-24 | 2019-05-24 | CoB nanoparticle-loaded nitrogen-doped porous carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910438482.1A CN110124721B (en) | 2019-05-24 | 2019-05-24 | CoB nanoparticle-loaded nitrogen-doped porous carbon material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110124721A true CN110124721A (en) | 2019-08-16 |
| CN110124721B CN110124721B (en) | 2022-10-04 |
Family
ID=67573154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910438482.1A Active CN110124721B (en) | 2019-05-24 | 2019-05-24 | CoB nanoparticle-loaded nitrogen-doped porous carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110124721B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479351A (en) * | 2019-09-16 | 2019-11-22 | 桂林电子科技大学 | A kind of load C oNiB phenolic resin base nitrating carbon aerogels material and its preparation method and application |
| CN110993975A (en) * | 2019-10-12 | 2020-04-10 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN111569933A (en) * | 2020-06-22 | 2020-08-25 | 中认英泰检测技术有限公司 | Porous carbon-based metal catalyst, preparation method and application thereof |
| CN112892610A (en) * | 2021-01-21 | 2021-06-04 | 四川大学 | Non-noble metal doped ZIF-67@ Co catalytic ammonia borane hydrolysis material and preparation and application thereof |
| CN113976120A (en) * | 2021-11-30 | 2022-01-28 | 西安工业大学 | Preparation method of high-activity CoB catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107311172A (en) * | 2017-07-18 | 2017-11-03 | 桂林电子科技大学 | A kind of passion fruit shell base porous carbon materials 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 |
| 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 |
-
2019
- 2019-05-24 CN CN201910438482.1A patent/CN110124721B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107311172A (en) * | 2017-07-18 | 2017-11-03 | 桂林电子科技大学 | A kind of passion fruit shell base porous carbon materials 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 |
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479351A (en) * | 2019-09-16 | 2019-11-22 | 桂林电子科技大学 | A kind of load C oNiB phenolic resin base nitrating carbon aerogels material and its preparation method and application |
| CN110993975A (en) * | 2019-10-12 | 2020-04-10 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN110993975B (en) * | 2019-10-12 | 2021-06-01 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN111569933A (en) * | 2020-06-22 | 2020-08-25 | 中认英泰检测技术有限公司 | Porous carbon-based metal catalyst, preparation method and application thereof |
| CN111569933B (en) * | 2020-06-22 | 2021-08-03 | 中认英泰检测技术有限公司 | Porous carbon-based metal catalyst, preparation method and application thereof |
| WO2021258425A1 (en) * | 2020-06-22 | 2021-12-30 | 中认英泰检测技术有限公司 | Porous carbon-based metal catalyst and preparation method therefor and application thereof |
| CN112892610A (en) * | 2021-01-21 | 2021-06-04 | 四川大学 | Non-noble metal doped ZIF-67@ Co catalytic ammonia borane hydrolysis material and preparation and application thereof |
| CN113976120A (en) * | 2021-11-30 | 2022-01-28 | 西安工业大学 | Preparation method of high-activity CoB catalyst |
| CN113976120B (en) * | 2021-11-30 | 2023-12-01 | 西安工业大学 | Preparation method of high-activity CoB catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110124721B (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110124721A (en) | A kind of nitrogen-doped porous carbon material and its preparation method and application of load C oB nanoparticle | |
| CN108963276A (en) | Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction | |
| CN108486605A (en) | A kind of carbon coating selenizing nickel cobalt nano material and preparation method thereof with excellent electrolysis water performance | |
| CN109499576A (en) | A kind of Co-B/NGO composite nano materials and its preparation method and application | |
| CN109594101B (en) | Preparation method of porous carbon supported ruthenium catalyst | |
| Dou et al. | Shaggy-like Ru-clusters decorated core-shell metal-organic framework-derived CoOx@ NPC as high-efficiency catalyst for NaBH4 hydrolysis | |
| CN105271217A (en) | Method for preparing nitrogen-doped three-dimensional graphene | |
| CN108103517B (en) | A kind of metal nanoparticle of self-supporting/porous nitrogen carbon dope film and its preparation method and application | |
| CN110745784B (en) | Metal oxide nano-particles and preparation method and application thereof | |
| CN103318978A (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN109092296A (en) | A kind of carbon load palladium oxide nanocluster catalyst and the preparation method and application thereof | |
| CN109012704A (en) | A kind of two cobaltous selenide of nanometer load carbon nano-fiber composite material and its preparation method and application | |
| CN110813335A (en) | Preparation method of nickel phosphide cocatalyst by performing photo-deposition on cadmium sulfide | |
| CN111841598B (en) | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof | |
| CN113881965A (en) | Metal nanoparticle-loaded catalyst taking biomass carbon source as template and preparation method and application thereof | |
| CN112663076A (en) | Iron-doped molybdenum diselenide nano material with hollow structure, preparation method thereof and application of iron-doped molybdenum diselenide nano material in electrocatalytic nitrogen reduction | |
| CN113699549B (en) | Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof | |
| Ma et al. | Lignin-derived hierarchical porous flower-like carbon nanosheets decorated with biomass carbon quantum dots for efficient oxygen reduction | |
| CN109112563A (en) | A kind of phosphatization ruthenium/carbon nano tube compound material and its preparation method and application | |
| Chi et al. | Enhanced electrocatalytic performance of 2D Ni-MOF for ethanol oxidation reaction by loading carbon dots | |
| Liu et al. | Electrospun Fe2C-loaded carbon nanofibers as efficient electrocatalysts for oxygen reduction reaction | |
| Xing et al. | Synergistical enhancement of the electrocatalysis of N-doped porous carbon for fuel cell application | |
| CN105148918B (en) | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst | |
| CN101138721A (en) | Process for preparation of catalysts for catalytic decomposition of hydrogen iodide | |
| He et al. | Black phosphorous dots phosphatized bio-based carbon nanofibers/bimetallic organic framework as catalysts for oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |