CN102963876A - Preparation method of microporous carbon material - Google Patents
Preparation method of microporous carbon material Download PDFInfo
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- CN102963876A CN102963876A CN2012104293017A CN201210429301A CN102963876A CN 102963876 A CN102963876 A CN 102963876A CN 2012104293017 A CN2012104293017 A CN 2012104293017A CN 201210429301 A CN201210429301 A CN 201210429301A CN 102963876 A CN102963876 A CN 102963876A
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Abstract
The invention relates to a preparation method of a microporous carbon material. The method comprises the steps of; weighing a phenolic compound,a formaldehyde solution, water and sodium carbonate in a weight ratio of 1:4-7.5:60-90:0.01-0.015, mixing, reacting at 85 DEG C for 45-120 min, and then cooling to room temperature to obtain a phenolic prepolymer solution; then weighing polyhydroxy acid, zinc chloride, hydrochloric acid and water in a weight ratio of 1:0.4-3:5-7.5:15-25, and mixing to obtain a mixed solution; weighing the mixed solution and the phenolic prepolymer solution in a weight ratio of 1:2-6, adding the mixed solution into the phenolic prepolymer solution, mixing evenly, conducting a polymerization reaction at 85 DEG C for 2-4 days, cooling to room temperature after the reaction, washing the products with a solvent with low surface tension for 2-5 times, and then drying at 40-100 DEG C for 2-24 h to obtain solid blocks; heating the solid blocks to 900-1000 DEG C for carbonization, with heating rate of 0.5-10 DEG C / min in a tube furnace under protection of inert gas; and finally naturally cooling to a room temperature to obtain the microporous carbon material. According to tests, the obtained microporous carbon material has regular microporous structure and specific surface area higher than 1000m<2> / g.
Description
Technical field
The present invention relates to a kind of preparation method of micro-pore carbon material.Specifically refer to utilize the metal-complexing effect between polyhydroxy-acid and the zine ion, and the hydroxyl in the phenolic compound and the interaction of hydrogen bond between the hydroxyl in the polyhydroxy-acid, polyhydroxy-acid zinc is incorporated in the novolac polymer skeleton structure uniformly, and the method for preparing micro-pore carbon material is processed in last charing.
Background technology
Micro-pore carbon material is owing to have higher specific surface area and chemical stability preferably, adsorb with separate, there is very wide and very important application prospect in the fields such as support of the catalyst, electrode materials." preparation method of high absorption property gac " (Chinese invention patent for example, 02157271.2), " method for preparing alcohol at the charcoal supported catalysts of rhenium-containing " (Chinese invention patent the patent No.:, 01808523.7), " a kind of preparation method of super capacitance cell negative electrode material " (Chinese invention patent the patent No.:, 200710035056.0) and " preparation method of biomass high specific surface micro-pore carbon material " (Chinese invention patent, patent No.: 200710055490.5) patent No.:.But, common micro-pore carbon material comprises and has the irregular micropore of a large amount of islands in the gac, it is very limited in actual applications, for example, when these micro-pore carbon materials are applied to electrode material for super capacitor, electrolyte solution is not easy to enter into the irregular micropore of electrode, causes the electrode surface effective rate of utilization low.
Template can by selecting the template of different structure, be prepared the micro-pore carbon material with regular pore structure that ordinary method can't obtain.For example " have the porous charcoal of regular texture and high-specific surface area with template charring preparation " (Chinese invention patent, the patent No.: 200510046708.1) reported that by zeolite be the micro-pore carbon material that the template preparation has regular texture.But the deficiency of template is at first will prepare first zeolite etc. as template, then needs again remove template with HF or NaOH, and this can increase preparation time and the cost of micro-pore carbon material undoubtedly.In addition, bibliographical information having been arranged utilizes the metal-organic framework materials preparation to have the method for the micro-pore carbon material of regular pore structure.For example, (Porous carbons prepared by using metal-organic framework as the precursor for supercapacitors, Carbon, 48 (2010) 3599-3606.).Yet these methods generally need to be passed through the hydrothermal treatment consists process, but hydrothermal method exists that equipment requirements is high, technical difficulty large and the shortcoming such as poor safety performance.
Summary of the invention
The object of the invention is to disclose a kind of technique simple, easy to operate, have a preparation method of the micro-pore carbon material of comparison rule microvoid structure.
In order to achieve the above object, it is carbon source that the present invention selects phenolic compound and formaldehyde, utilize the metal-complexing effect between polyhydroxy-acid and the zine ion, and the hydroxyl on the phenolic compound and the interaction of hydrogen bond between the hydroxyl on the polyhydroxy-acid, polyhydroxy-acid zinc is incorporated in the novolac polymer skeleton structure uniformly, last charing is processed, and obtains micro-pore carbon material.Contain zine coordination compound and be decomposed in carbonization process and gasify, simultaneously zinc fume evaporation can be played again the chemical activation effect of similar water steam, so that the duct of micro-pore carbon material is very abundant.
Concrete technique is undertaken by following several steps:
By phenolic compound: formaldehyde solution: water: yellow soda ash=1:4 ~ 7.5:60 ~ 90:0.01 ~ 0.015 mass ratio is measured, and mixes, and in 85 ℃ of reaction 45 ~ 120min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by polyhydroxy-acid: zinc chloride: hydrochloric acid: water=1:0.4 ~ 3:5 ~ 7.5:15 ~ 25 mass ratioes are measured, and mix and obtain mixing solutions.Measure mixing solutions: the mass ratio=1:2 of phenolic aldehyde prepolymer solution ~ 6, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of polyreactions 2 ~ 4 days, reaction is cooled to room temperature after finishing, then the solvent wash of product usefulness low surface tension 2 ~ 5 times in 40 ~ 100 ℃ of lower dry 2 ~ 24h, obtains blocks of solid.In tube furnace, protection of inert gas is heated to 900 ~ 1000 ℃ of charings by the temperature rise rate of 0.5 ~ 10 ℃/min with blocks of solid, naturally is cooled to room temperature at last and namely gets micro-pore carbon material.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Above-mentioned phenolic compound is selected a kind of in phenol, Resorcinol, the Phloroglucinol.
Above-mentioned polyhydroxy-acid is selected tartrate, 2, a kind of in 5-dihydroxyl hexanodioic acid, the citric acid.
The solvent of above-mentioned low surface tension is selected a kind of in methyl alcohol, ethanol, the acetone.
Above-mentioned rare gas element is selected a kind of in nitrogen, helium, the argon gas.
Above raw material is commercially available technical grade product.
The present invention has following advantage:
1. the present invention does not need template in preparation process, does not need the water-heat process of condition harshness yet, has simple, the easy to operate advantage of condition.
2. the present invention utilizes the metal-complexing effect between polyhydroxy-acid and the zine ion, and the hydroxyl on the phenolic compound and the interaction of hydrogen bond between the hydroxyl on the polyhydroxy-acid, polyhydroxy-acid zinc can be incorporated in the novolac polymer skeleton structure uniformly, therefore, the micro-pore carbon material of preparation has the microvoid structure of comparison rule.
3. contain zine coordination compound and be decomposed in carbonization process and gasify, simultaneously zinc fume evaporation can be played again the chemical activation effect of similar water steam, so that the duct of micro-pore carbon material is very abundant, the micro-pore carbon material of preparation has the 1000m of being higher than
2The specific surface area of/g.
Embodiment
Embodiment 1:
By phenol: formaldehyde solution: water: yellow soda ash=1:4:60:0.01 mass ratio is measured, and mixes, and in 85 ℃ of reaction 45min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by tartrate: zinc chloride: hydrochloric acid: water=1:0.4:5:25 mass ratio is measured, and mixes and obtains mixing solutions.Measure mixing solutions: the mass ratio=1:2 of phenolic aldehyde prepolymer solution, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of polyreactions 2 days, reaction was cooled to room temperature after finishing, and product is with methanol wash 2 times, then in 40 ℃ of lower dry 24h, obtain blocks of solid.In tube furnace, nitrogen protection is heated to 900 ℃ of charings by the temperature rise rate of 0.5 ℃/min with blocks of solid, naturally is cooled to room temperature at last and namely gets micro-pore carbon material.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Above raw material is commercial reagent level product.
Embodiment 2:
By Resorcinol: formaldehyde solution: water: yellow soda ash=1:7.5:90:0.015 mass ratio is measured, and mixes, and in 85 ℃ of reaction 120min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by citric acid: zinc chloride: hydrochloric acid: water=1:3:7.5:15 mass ratio is measured, and mixes and obtains mixing solutions.Measure mixing solutions: the mass ratio=1:6 of phenolic aldehyde prepolymer solution, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of reactive polymerics 4 days, reaction was cooled to room temperature after finishing, and product is with washing with alcohol 5 times, then in 100 ℃ of lower dry 2h, obtain blocks of solid.In tube furnace, argon shield is heated to 1000 ℃ of charings by the temperature rise rate of 10 ℃/min with blocks of solid, naturally is cooled to room temperature at last and namely gets micro-pore carbon material.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Embodiment 3:
By Phloroglucinol: formaldehyde solution: water: yellow soda ash=1:5:75:0.012 mass ratio is measured, and mixes, and in 85 ℃ of reaction 60min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by tartrate: zinc chloride: hydrochloric acid: water=1:1.5:6:20 mass ratio is measured, and mixes and obtains mixing solutions.Measure mixing solutions: the mass ratio=1:3 of phenolic aldehyde prepolymer solution, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of polyreactions 3 days, reaction was cooled to room temperature after finishing, and product is with washing with acetone 3 times, then in 80 ℃ of lower dry 12h, obtain blocks of solid.In tube furnace, helium protection is heated to 950 ℃ of charings by the temperature rise rate of 5 ℃/min with blocks of solid, naturally is cooled to room temperature and namely gets micro-pore carbon material at last.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Embodiment 4:
By phenol: formaldehyde solution: water: yellow soda ash=1:4.5:80:0.013 mass ratio is measured, and mixes, and in 85 ℃ of reaction 90min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by 2,5-dihydroxyl hexanodioic acid: zinc chloride: hydrochloric acid: water=1:2:7:20 mass ratio is measured, and mixes and obtains mixing solutions.Measure mixing solutions: the mass ratio=1:4 of phenolic aldehyde prepolymer solution, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of polyreactions 3 days, reaction was cooled to room temperature after finishing, and product is with methanol wash 4 times, then in 60 ℃ of lower dry 18h, obtain blocks of solid.In tube furnace, nitrogen protection is heated to 950 ℃ of charings by the temperature rise rate of 3 ℃/min with blocks of solid, naturally is cooled to room temperature at last and namely gets micro-pore carbon material.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Embodiment 5:
By Resorcinol: formaldehyde solution: water: yellow soda ash=1:6:75:0.011 mass ratio is measured, and mixes, and in 85 ℃ of reaction 90min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution.Then by 2,5-dihydroxyl hexanodioic acid: zinc chloride: hydrochloric acid: water=1:0.8:5:15 mass ratio is measured, and mixes and obtains mixing solutions.Measure mixing solutions: the mass ratio=1:5 of phenolic aldehyde prepolymer solution, this mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of reactive polymerics 3 days, reaction was cooled to room temperature after finishing, and product is with washing with acetone 5 times, then in 75 ℃ of lower dry 16h, obtain blocks of solid.In tube furnace, argon shield is heated to 950 ℃ of charings by the temperature rise rate of 5 ℃/min with blocks of solid, naturally is cooled to room temperature at last and namely gets micro-pore carbon material.After measured, the gained micro-pore carbon material has the microvoid structure of comparison rule, specific surface area 1000m
2More than/the g.
Claims (1)
1. the preparation method of a micro-pore carbon material is characterized in that:
First by phenolic compound: formaldehyde solution: water: yellow soda ash=1:4 ~ 7.5:60 ~ 90:0.01 ~ 0.015 mass ratio is measured, and mixes, and in 85 ℃ of reaction 45 ~ 120min, then is cooled to room temperature and obtains the phenolic aldehyde prepolymer solution; Then by polyhydroxy-acid: zinc chloride: hydrochloric acid: water=1:0.4 ~ 3:5 ~ 7.5:15 ~ 25 mass ratioes are measured, and mix and obtain mixing solutions.Measure mixing solutions: the mass ratio=1:2 of phenolic aldehyde prepolymer solution ~ 6, mixing solutions is added in the phenolic aldehyde prepolymer solution, mix, in 85 ℃ of polyreactions 2 ~ 4 days, reaction is cooled to room temperature after finishing, then the solvent wash of product usefulness low surface tension 2 ~ 5 times in 40 ~ 100 ℃ of lower dry 2 ~ 24h, obtains blocks of solid; In tube furnace, protection of inert gas is heated to 900 ~ 1000 ℃ of charings by the temperature rise rate of 0.5 ~ 10 ℃/min with blocks of solid; at last naturally be cooled to room temperature and namely get micro-pore carbon material; after measured, the well-regulated microvoid structure of gained micro-pore carbon material, specific surface area 1000m
2More than/the g;
Above-mentioned phenolic compound is selected a kind of in phenol, Resorcinol, the Phloroglucinol;
Above-mentioned polyhydroxy-acid is selected tartrate, 2, a kind of in 5-dihydroxyl hexanodioic acid, the citric acid;
The solvent of above-mentioned low surface tension is selected a kind of in methyl alcohol, ethanol, the acetone;
Above-mentioned rare gas element is selected a kind of in nitrogen, helium, the argon gas;
Above raw material is commercially available technical grade product.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553018A (en) * | 2013-08-16 | 2014-02-05 | 同济大学 | Regular microporous carbon preparation method |
| CN103723702A (en) * | 2013-12-31 | 2014-04-16 | 太原理工大学 | Preparation method of porous composite material and carbon material |
| CN103880005A (en) * | 2014-03-13 | 2014-06-25 | 常州中科海纳碳素科技有限公司 | Preparation method for activated carbon rich in mesopores |
| CN105016326A (en) * | 2015-07-15 | 2015-11-04 | 大连理工大学 | Method for preparation of high-strength and easy-forming porous carbon material |
| CN105013439A (en) * | 2015-06-26 | 2015-11-04 | 同济大学 | Preparation method of nitrogen and sulfur functionalized carbon foam magnetic microspheres |
| CN105731455A (en) * | 2016-05-07 | 2016-07-06 | 浙江农林大学 | Method for preparing active carbon from wastes of traditional Chinese medicines |
| CN106311142A (en) * | 2016-09-09 | 2017-01-11 | 上海电力学院 | Preparation method of carbon aerogel desulfurizer for high-temperature desulfuration |
| CN108383118A (en) * | 2018-05-25 | 2018-08-10 | 常州大学 | A kind of physically activated preparation method of the microporous carbon of superhigh specific surface area |
| CN109663569A (en) * | 2019-02-14 | 2019-04-23 | 齐鲁工业大学 | A kind of micro-pore carbon material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872674A (en) * | 2006-06-09 | 2006-12-06 | 江西财经大学 | Method for preparing active mesopore carbon with high specific surface area in use for electrochemical capacitor |
| CN1891622A (en) * | 2005-07-06 | 2007-01-10 | 同济大学 | Method for preparing high specific area carbon aerogel |
| CN101234759A (en) * | 2007-01-29 | 2008-08-06 | 北京航空航天大学 | Method of preparing micropore carbon |
| CN101314468A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for preparing nano-zinc oxide doped high-specific surface area block body stephanoporate carbon |
-
2012
- 2012-10-31 CN CN2012104293017A patent/CN102963876A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891622A (en) * | 2005-07-06 | 2007-01-10 | 同济大学 | Method for preparing high specific area carbon aerogel |
| CN1872674A (en) * | 2006-06-09 | 2006-12-06 | 江西财经大学 | Method for preparing active mesopore carbon with high specific surface area in use for electrochemical capacitor |
| CN101234759A (en) * | 2007-01-29 | 2008-08-06 | 北京航空航天大学 | Method of preparing micropore carbon |
| CN101314468A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for preparing nano-zinc oxide doped high-specific surface area block body stephanoporate carbon |
Non-Patent Citations (2)
| Title |
|---|
| HAI-LONG JIANG ET AL.: "From Metal-Organic Framework to Nanoporous Carbon:Toward a Very High Surface Area and Hydrogen Uptake", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 133, 13 July 2011 (2011-07-13) * |
| LOGUDURAI RADHAKRISHNAN ET AL.: "Preparation of Microporous Carbon Fibers through Carbonization of Al-Based Porous Coordination Polymer (Al-PCP) with Furfuryl Alcohol", 《CHEMISTRY OF MATERIALS》, vol. 23, 27 January 2011 (2011-01-27) * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553018A (en) * | 2013-08-16 | 2014-02-05 | 同济大学 | Regular microporous carbon preparation method |
| CN103723702B (en) * | 2013-12-31 | 2015-06-17 | 太原理工大学 | Preparation method of porous composite material and carbon material |
| CN103723702A (en) * | 2013-12-31 | 2014-04-16 | 太原理工大学 | Preparation method of porous composite material and carbon material |
| CN103880005B (en) * | 2014-03-13 | 2015-12-02 | 常州中科海纳碳素科技有限公司 | A kind of preparation method being rich in mesopore activated carbon |
| CN103880005A (en) * | 2014-03-13 | 2014-06-25 | 常州中科海纳碳素科技有限公司 | Preparation method for activated carbon rich in mesopores |
| CN105013439A (en) * | 2015-06-26 | 2015-11-04 | 同济大学 | Preparation method of nitrogen and sulfur functionalized carbon foam magnetic microspheres |
| CN105016326A (en) * | 2015-07-15 | 2015-11-04 | 大连理工大学 | Method for preparation of high-strength and easy-forming porous carbon material |
| CN105016326B (en) * | 2015-07-15 | 2017-04-12 | 大连理工大学 | Method for preparation of high-strength and easy-forming porous carbon material |
| CN105731455A (en) * | 2016-05-07 | 2016-07-06 | 浙江农林大学 | Method for preparing active carbon from wastes of traditional Chinese medicines |
| CN105731455B (en) * | 2016-05-07 | 2018-02-16 | 浙江农林大学 | A kind of method that activated carbon is prepared in the residue from Chinese medicine |
| CN106311142A (en) * | 2016-09-09 | 2017-01-11 | 上海电力学院 | Preparation method of carbon aerogel desulfurizer for high-temperature desulfuration |
| CN108383118A (en) * | 2018-05-25 | 2018-08-10 | 常州大学 | A kind of physically activated preparation method of the microporous carbon of superhigh specific surface area |
| CN109663569A (en) * | 2019-02-14 | 2019-04-23 | 齐鲁工业大学 | A kind of micro-pore carbon material and preparation method thereof |
| CN109663569B (en) * | 2019-02-14 | 2021-03-02 | 齐鲁工业大学 | Microporous carbon material and preparation method thereof |
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Application publication date: 20130313 |