CN105498823A - Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst - Google Patents
Preparation method and application of nitrogen-doped porous carbon-loaded cobalt catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 34
- 239000010941 cobalt Substances 0.000 title claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 9
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 8
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- HTYQIJOJHXNLIU-UHFFFAOYSA-L dichlorocobalt;ethane-1,2-diamine Chemical compound Cl[Co]Cl.NCCN HTYQIJOJHXNLIU-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002114 nanocomposite Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 229910000085 borane Inorganic materials 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- MREPUZZHXBXWLW-UHFFFAOYSA-N cobalt(2+);ethane-1,2-diamine Chemical compound [Co+2].NCCN MREPUZZHXBXWLW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010189 synthetic method 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
-
- B01J35/60—
-
- 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
Abstract
The invention discloses a preparation method of a nitrogen-doped porous carbon-loaded cobalt catalyst. The preparation method includes: adding N, N-bis(salicylidene) ethylene dimino cobalt (II) or bi(3-methoxysalicylaldehyde) ethylenediamine cobalt chloride into a crucible, placing into a tubular furnace, and heating to 400-900 DEG C for calcining for 1-10 h in a hydrogen-argon mixed atmosphere; cooling to room temperature to obtain the nitrogen-doped porous carbon-loaded cobalt catalyst which is used for hydrolytic dehydrogenation of ammonia borane. The preparation method has the advantages that the catalyst is prepared by adopting a one-step pyrolysis synthesis method, the preparation method is simple, cobalt loading quantity is greatly increased, and industrial production is facilitated; the catalyst is used for catalyzing hydrolytic dehydrogenation of ammonia borane, maximum dehydrogenation rate reaches 1383 mL H2min-1gCo-1, and activation energy is 31.0kJ/mol; especially, after cobalt nanoparticles are embedded in nitrogen-doped porous carbon, circulating stability is improved greatly.
Description
Technical field
The present invention relates to hydrogen storage material field, particularly a kind of preparation method and application of N doping porous carbon load cobalt catalyst.
Background technology
The aggravation of and environmental pollution increasingly exhausted along with fossil energy, the clean energy resource finding a kind of alternative fossil energy has become the necessity of social sustainable development.Hydrogen Energy has the advantages such as rich reserves, renewable, combustion heat value is large, is considered to a kind of and compares the green energy resource having application prospect.Hydrogen storage technology and material are the key factors of restriction hydrogen economic development safely and efficiently.In numerous hydrogen storage technology and material, ammonia borine storage hydrogen, can stable existence under room temperature because of capacity high (19.6wt%), becomes one of very potential hydrogen storage material of one.
Ammonia borine dehydrogenation mode has three kinds: hydrolysis, pyrolysis and alcoholysis.Hydrolysis/dehydrogenation is simple to operate, and room temperature just can be carried out and cleanliness without any pollution, is conducive to practical application.In the catalyst promoting ammonia borane hydrolysis, although noble metal catalyst Pt, Ru, Rh etc. show good catalytic activity, its expensive, resource scarcity, be unfavorable for large-scale application.Compared with noble metal catalyst, base metal cobalt resource enriches, with low cost, and shows superior catalytic activity, has very large application prospect.Cobalt is easily reunited in preparation process, and usually adopt Graphene, silicon, silica etc. to be used to dispersed metal cobalt nano-particle, catalytic activity obviously strengthens, but after a few circle of circulation, cobalt nano-particle still can be reunited, and catalytic activity reduces greatly.Meanwhile, the load capacity of metal nanoparticle is lower, is unfavorable for large-scale application.
In order to improve cyclical stability and the load capacity of Co catalysts, double salicylaldehyde contracting ethylenediamine cobalt (II) [Co (salen)] and analog thereof are calcined by the present invention in argon atmosphere, obtain that decentralization is high, particle size is little and uniform N doping porous carbon Supported Co nano particle, and called after CoN-C.By this kind of method, cobalt loading improves greatly, and what is more important shows and superior recycles performance in catalyze ammonia borane hydrolysis.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, provide a kind of preparation method and application of N doping porous carbon load cobalt catalyst, this year Co catalysts stability is high and can promote ammonia borine fast hydrolyzing; The present invention, calcines in argon gas or hydrogen-argon-mixed atmosphere for presoma with Co (salen) and analog thereof, obtained high degree of dispersion and undersized N doping porous carbon Supported Co nano particle; The preparation method of this catalyst is simple, cobalt loading large, good dispersion, not only increases catalytic activity, also enhances the cyclical stability of catalyst.
Technical scheme of the present invention:
A preparation method for N doping porous carbon load cobalt catalyst, step is as follows:
By N, N-double salicylaldehyde triethylenediamine cobalt (II) or two (3-methoxysalicyl aldehyde) contracting ethylenediamine cobalt chloride add in crucible, then tube furnace is put into, under the hydrogen-argon-mixed atmosphere that the volume ratio of argon gas and hydrogen is 95:5, be heated to 400-900 DEG C of calcining, heating rate is 1-10 °/min, and calcination time is 1-10h; After question response terminates, be cooled to room temperature, obtained N doping porous carbon load cobalt catalyst, called after CoN-C nano-composite catalyst.
An application for prepared N doping porous carbon load cobalt catalyst, be dispersed in by CoN-C nano-composite catalyst in the ammonia borine aqueous solution, for the dehydrogenation of ammonia borane hydrolysis, method is as follows:
1) the CoN-C nano-composite catalyst of above-mentioned preparation is dispersed in water ultrasonic vibration 5-60min, the amount ratio of CoN-C nano-composite catalyst and water is 10-40mg:4-15mL, then the container filling solution is placed in the water-bath of 25-55 DEG C, stir 2-15min, container is connected with water-filled gauge line;
2) in above-mentioned solution, adding the ammonia borine of 10-100mg, timing from first bubble, remembering that single step of releasing hydrogen volume is for calculating hydrogen discharging rate every 30s-2min.
Advantage of the present invention: N doping porous carbon load cobalt catalyst adopts a step pyrolysis synthetic method, method is simple, and cobalt loading improves greatly, is conducive to realizing industrialization large-scale production; This catalyst is used for catalyze ammonia borane hydrolysis and puts hydrogen, and maximum hydrogen discharging rate reaches 1383mLH
2min
-1g
co -1, activation energy is 31.0kJ/mol; Especially after cobalt nano-particle embeds N doping porous carbon, cyclical stability strengthens greatly, and after circulation 10 circle, catalytic activity still can keep 97.2% of original catalytic activity.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the CoN-C nano-complex prepared under different temperatures.
Fig. 2 is the TEM figure of CoN-C-600 nano-complex
Fig. 3 is the TEM figure of CoN-C-700 nano-complex
Fig. 4 is the TEM figure of CoN-C-800 nano-complex
Fig. 5 is the CoN-C complex catalysts ammonia borane hydrolysis performance that different temperatures obtains.
Fig. 6 is Hydrogen desorption isotherms and activation energy under CoN-C-700 nano-complex catalyze ammonia borine different temperatures
Fig. 7 is the cyclic curve of CoN-C-700 catalyze ammonia borine
Detailed description of the invention
Embodiment:
A preparation method for N doping porous carbon load cobalt catalyst, step is as follows:
By three parts of 100mgN, N-double salicylaldehyde triethylenediamine cobalt (II) adds in respective crucible respectively, then tube furnace is put into, under the hydrogen-argon-mixed atmosphere that the volume ratio of argon gas and hydrogen is 95:5, heat temperature raising respectively to 600 DEG C, 700 DEG C, 800 DEG C calcinings, heating rate is 5 °/min, and calcination time is 1h; After question response terminates, be cooled to room temperature, obtained N doping porous carbon load cobalt catalyst, respectively called after CoN-C-600, CoN-C-700 and CoN-C-800 nano-composite catalyst.
As shown in Figure 1, wherein 2 θ equal the diffraction maximum that 26 ° is carbon to the XRD of CoN-C-600, CoN-C-700 and CoN-C-800 nano-composite catalyst prepared by this embodiment, and its excess-three peak is the diffraction maximum of simple substance cobalt.Along with the rising of temperature, the diffraction maximum of simple substance cobalt is stronger.
The TEM of CoN-C-600, CoN-C-700 and CoN-C-800 prepared by this embodiment respectively as shown in Figure 2,3, 4.The product of 600 and 700 DEG C of calcining preparations, cobalt nano-particle is evenly dispersed in the porous carbon of N doping, the about 8nm of size of particle.Temperature is increased to 800 DEG C, and cobalt nano-particle there occurs reunion, illustrates that higher temperature is unfavorable for the dispersion of cobalt nano-particle.
The load capacity of CoN-C-600, CoN-C-700 and CoN-C-800 nano-composite catalyst cobalt prepared by this embodiment is respectively 16.5,19.7 and 25.3wt%, and along with the rising of temperature, the load capacity of cobalt also increases.The product of 600 and 700 DEG C of calcining preparations, cobalt nano-particle is not only uniformly dispersed, and load capacity also increases, and this large-scale production being conducive to catalyst utilizes.
The application of the N doping porous carbon load cobalt catalyst prepared by this embodiment, be dispersed in by CoN-C nano-composite catalyst in the ammonia borine aqueous solution, for the dehydrogenation of ammonia borane hydrolysis, method is as follows:
1) the CoN-C nano-composite catalyst of above-mentioned for 20mg preparation is dispersed in ultrasonic vibration 5min in 8mL water, is then placed in by the container filling solution in the water-bath of 25 DEG C, stir 5min, container is connected with water-filled gauge line;
2) in above-mentioned solution, adding the ammonia borine of 40mg, timing from first bubble, remembering that single step of releasing hydrogen volume is for calculating hydrogen discharging rate every 1min.
Test the catalytic activity of CoN-C-600, CoN-C-700 and CoN-C-800 nano-composite catalyst respectively, as shown in Figure 5: CoN-C-700 catalytic activity is the highest, maximum hydrogen discharging rate is 1383mLH
2min
-1g
co -1.
The test of the activation energy of CoN-C-700 nano-composite catalyst is carried out respectively in the water-bath of 25,35,45 and 55 DEG C.Fig. 6 is the Hydrogen desorption isotherms figure under different temperatures, and along with the rising of temperature, hydrogen discharging rate increases.By the hydrogen discharging rate under different temperatures, recording activation energy is 31.0kJ/mol, and activation energy is lower, is conducive to carrying out fast of catalytic reaction.
CoN-C-700 nano-composite catalyst stable circulation linearity curve prepared by embodiment as shown in Figure 7.After circulation 10 circle, catalytic activity is almost undamped, still keeps 97.2% of original catalytic activity, shows superior to recycle performance, and this is conducive to the use cost and the practical application that reduce catalyst.
Claims (2)
1. a preparation method for N doping porous carbon load cobalt catalyst, is characterized in that step is as follows:
By N, N-double salicylaldehyde triethylenediamine cobalt (II) or two (3-methoxysalicyl aldehyde) contracting ethylenediamine cobalt chloride add in crucible, then tube furnace is put into, under the hydrogen-argon-mixed atmosphere that the volume ratio of argon gas and hydrogen is 95:5, be heated to 400-900 DEG C of calcining, heating rate is 1-10 °/min, and calcination time is 1-10h; After question response terminates, be cooled to room temperature, obtained N doping porous carbon load cobalt catalyst, called after CoN-C nano-composite catalyst.
2. an application for the N doping porous carbon load cobalt catalyst prepared by claim 1, it is characterized in that being dispersed in by CoN-C nano-composite catalyst in the ammonia borine aqueous solution, for the dehydrogenation of ammonia borane hydrolysis, method is as follows:
1) the CoN-C nano-composite catalyst of above-mentioned preparation is dispersed in water ultrasonic vibration 5-60min, the amount ratio of CoN-C nano-composite catalyst and water is 10-40mg:4-15mL, then the container filling solution is placed in the water-bath of 25-55 DEG C, stir 2-15min, container is connected with water-filled gauge line;
2) in above-mentioned solution, adding the ammonia borine of 10-100mg, timing from first bubble, remembering that single step of releasing hydrogen volume is for calculating hydrogen discharging rate every 30s-2min.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106215968A (en) * | 2016-07-26 | 2016-12-14 | 宁波大学 | A kind of carbon cladding CuO composite of the nitrogen that adulterates and preparation method thereof |
| CN107051571A (en) * | 2017-06-13 | 2017-08-18 | 兰州理工大学 | A kind of preparation method of Heteroatom doping carbon load cobalt catalyst |
| 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 |
| CN108067278A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the porous nitrogen-doped carbon elctro-catalyst of base metal |
| CN108570691A (en) * | 2018-03-28 | 2018-09-25 | 中国科学院合肥物质科学研究院 | A kind of oxide composite nano materials and the preparation method and application thereof of carbon coating cobalt and cobalt |
| CN108704654A (en) * | 2018-05-24 | 2018-10-26 | 山西大学 | A kind of nitrating carbon inlays non-precious metal catalyst and its preparation method and application |
| CN109046419A (en) * | 2018-07-03 | 2018-12-21 | 桂林电子科技大学 | A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium |
| CN110233270A (en) * | 2019-04-23 | 2019-09-13 | 武汉理工大学 | Load the nitrogen-doped carbon microballoon and its preparation method and application of cobalt nano-particle |
| CN110479340A (en) * | 2018-05-14 | 2019-11-22 | 南京理工大学 | A kind of nanometer cobalt/nitrogen-doped graphene composite material and preparation method |
| 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 |
| CN111883783A (en) * | 2020-06-19 | 2020-11-03 | 上海交通大学 | Preparation method and application of hollow non-noble metal oxygen reduction catalyst |
| CN112023945A (en) * | 2020-09-01 | 2020-12-04 | 广州大学 | Preparation method of mesoporous carbon-based electrocatalyst |
| CN113546660A (en) * | 2021-07-05 | 2021-10-26 | 南京理工大学 | Alloy catalyst and application thereof in efficient hydrogen production of borane derivative |
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Cited By (21)
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| CN106215968B (en) * | 2016-07-26 | 2018-07-13 | 宁波大学 | A kind of carbon coating CuO composite material and preparation methods of doping nitrogen |
| CN106215968A (en) * | 2016-07-26 | 2016-12-14 | 宁波大学 | A kind of carbon cladding CuO composite of the nitrogen that adulterates and preparation method thereof |
| CN108067278A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the porous nitrogen-doped carbon elctro-catalyst of base metal |
| CN107051571A (en) * | 2017-06-13 | 2017-08-18 | 兰州理工大学 | A kind of preparation method of Heteroatom doping carbon load cobalt catalyst |
| 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 |
| CN108570691A (en) * | 2018-03-28 | 2018-09-25 | 中国科学院合肥物质科学研究院 | A kind of oxide composite nano materials and the preparation method and application thereof of carbon coating cobalt and cobalt |
| CN110479340A (en) * | 2018-05-14 | 2019-11-22 | 南京理工大学 | A kind of nanometer cobalt/nitrogen-doped graphene composite material and preparation method |
| CN110479340B (en) * | 2018-05-14 | 2022-05-27 | 南京理工大学 | Nano cobalt/nitrogen doped graphene composite material and preparation method thereof |
| CN108704654B (en) * | 2018-05-24 | 2020-08-04 | 山西大学 | Nitrogen-doped carbon-inlaid non-noble metal catalyst and preparation method and application thereof |
| CN108704654A (en) * | 2018-05-24 | 2018-10-26 | 山西大学 | A kind of nitrating carbon inlays non-precious metal catalyst and its preparation method and application |
| CN109046419A (en) * | 2018-07-03 | 2018-12-21 | 桂林电子科技大学 | A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium |
| CN110233270A (en) * | 2019-04-23 | 2019-09-13 | 武汉理工大学 | Load the nitrogen-doped carbon microballoon and its preparation method and application of cobalt nano-particle |
| CN110233270B (en) * | 2019-04-23 | 2022-03-01 | 武汉理工大学 | Nitrogen-doped carbon microsphere loaded with cobalt nanoparticles as well as preparation method and application of nitrogen-doped carbon microsphere |
| CN111883783A (en) * | 2020-06-19 | 2020-11-03 | 上海交通大学 | Preparation method and application of hollow non-noble metal oxygen reduction catalyst |
| 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 |
| US11370659B2 (en) * | 2020-06-22 | 2022-06-28 | Cqc Intime Testing Technology Co., Ltd. | Porous carbon-based metal catalyst as well as preparation method and application thereof |
| CN112023945A (en) * | 2020-09-01 | 2020-12-04 | 广州大学 | Preparation method of mesoporous carbon-based electrocatalyst |
| CN113546660A (en) * | 2021-07-05 | 2021-10-26 | 南京理工大学 | Alloy catalyst and application thereof in efficient hydrogen production of borane derivative |
| CN113546660B (en) * | 2021-07-05 | 2023-10-13 | 南京理工大学 | Alloy catalyst and application thereof in efficient hydrogen production of borane derivatives |
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