CN103601178A - Method for synthesizing graphene from solid organic acid - Google Patents
Method for synthesizing graphene from solid organic acid Download PDFInfo
- Publication number
- CN103601178A CN103601178A CN201310577471.4A CN201310577471A CN103601178A CN 103601178 A CN103601178 A CN 103601178A CN 201310577471 A CN201310577471 A CN 201310577471A CN 103601178 A CN103601178 A CN 103601178A
- Authority
- CN
- China
- Prior art keywords
- organic acid
- solid organic
- acid
- solid
- graphite alkene
- 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
Images
Abstract
The invention relates to a method for synthesizing graphene from solid organic acid, which comprises the following steps: mixing solid organic acid and a catalyst, putting the mixture in a reactor in an inert or protective atmosphere, reacting, and cooling to room temperature in the same protective atmosphere to obtain a solid product; and washing the solid product, filtering, and drying to obtain the graphene product. The method has the advantages of no pollution, low cost and simple technique, and can implement large-scale preparation.
Description
Technical field
The invention belongs to a kind of method of synthesizing graphite alkene, be specifically related to a kind of method of solid organic acid synthesizing graphite alkene.
Background technology
Graphene be success first in 2004 obtain by individual layer sp
2the two-dimentional carbonaceous crystal that hydridization carbon forms, has the specific surface area of excellent electroconductibility, mechanical property, superelevation and to good the passing through and transporting etc. of guest molecule/ion, at numerous areas, all has potential using value.Along with going deep into of research, the demand that magnanimity obtains Graphene is day by day strong.Therefore, how to realize mass-producing preparation and become one of problem demanding prompt solution that restriction Graphene further studied and apply.
Early stage preparation method uses adhesive tape or micromechanics method to peel off graphite to obtain Graphene.This process cost is high, and efficiency is low, is difficult to obtain a large amount of Graphenes, only limits to laboratory scale research and application.The surface that monocrystalline silicon carbide (0001) wafer is analysed in pyrolysis also can obtain Graphene, and adopts lithography process can be directly applied to electron device.But in this process, need high temperature, energy consumption is high; In order to control the bed thickness of Graphene, need the strict temperature of reaction of controlling; The area of gained Graphene is limited to used wafer size simultaneously, be difficult to realize macroscopic preparation of graphene [Graphene and the application aspect fuel cell catalytic material thereof: summary, < < Asia-Pacific chemical engineering > >, 2013, the 8th volume, the 218th page of (Graphene and its application in fuel cell catalysis:a review, Asia-Pac. J. Chem. Eng., 2013, Vol. 8,218)].
Graphite oxide stripping method is considered to the current effective ways that can obtain in a large number Graphene, uses strong oxidizer by graphite oxidation and further ultrasonicly peels off acquisition graphene oxide, and then being reduced into Graphene with reductive agent.The use havoc of strong oxidizer the conjugated structure of Graphene, produce defect, cause the property loss of energies such as its intrinsic electricity, need to carry out follow-up reduction and process to repair its electric property [multi-functional ultralight azepine Graphene network structure, < < Germany applied chemistry > >, 2012, the 51st volume, the 11371st page of (A Versatile, Ultralight, Nitrogen-Doped Graphene Framework, Angew. Chem. Int. Ed., 2012, Vol. 51, 11371)], and preparation process is loaded down with trivial details, consume a large amount of energy, a large amount of use meetings of strong oxidizer and reductive agent simultaneously cause very large harm to environment.
It is substrate that chemical Vapor deposition process (CVD) be take monocrystalline or polycrystalline transition metal, to and deposit to containing carbon matrix precursor pyrolytic decomposition and in metal base, obtain Graphene [multi-functional big area Graphene that can be curling or folding, < < nature material > >, 2013, the 12nd volume, the 321st page of (Multifunctionality and Control of the Crumpling and Unfolding of Large-Area Graphene, Nat. Mater., 2013, Vol. 12, 321)], in process carbon under the guide effect of metal base along two-dimensional directional oriented growth, can form even single-layer graphene of high-quality minority layer, but experiment condition is harsh, the accumulation causing for fear of π-π effect, must strictly control reactant concn and depositing time, could obtain high-quality Graphene.In addition, in subsequent applications, need Graphene to shift from substrate, or use the removal templates such as strong acid, be difficult to realize preparation in macroscopic quantity.
Summary of the invention
The object of this invention is to provide that a kind of pollution-free, low-cost, technique is simple, the method for the synthesizing graphite alkene that can prepare on a large scale.
It is raw material that present method be take solid organic acid and sodium carbonate, without raw material is carried out to pre-treatment, and one-step synthesis Graphene.Gained Graphene is three-dimensional net structure, when effectively suppressing Graphene reunion, has kept its excellent performance.Simultaneously in mass-producing, there is clear superiority aspect preparing.
Preparation method of the present invention is as follows:
(1) by solid organic acid and catalyst mix;
(2) mixture is positioned in the reactor with the protection of inertia or reducing gas and reacts, after reaction under identical atmosphere protection cool to room temperature, obtain solid product;
(3) by above-mentioned solid product washing, filtration, the dry Graphene product that obtains.
Described solid organic acid comprises propanedioic acid, succinic acid, methylene-succinic acid, hexanodioic acid, butene dioic acid, gluconic acid, tartrate, phenylformic acid, citric acid, lauric acid, styracin or stearic acid etc.
Described catalyzer is sodium carbonate.
Described inert atmosphere is argon gas or nitrogen; Reducing atmosphere is hydrogen etc.
The mol ratio of described solid organic acid and catalyzer carbonic acid sodium is 1:0.1-24.
Described mixing comprises that mechanical mill mixes, pickling process is mixed (by a kind of solid impregnating wherein in the solution of another kind of solid, then remove solvent and obtain solid mixture), solution mixes modes such as (solid organic acid and sodium carbonate are made respectively after solution mixing, removed solvent and obtain solid mixture).
Described temperature of reaction is 700-1500 ℃.
The described reaction times is 0.1-120min.
Tool of the present invention has the following advantages:
(1) raw material such as solid organic acid used and sodium carbonate is cheap and easy to get, without pre-treatment, is conducive to reduce costs.
(2) synthesis technique flow process is simple, easy and simple to handle, and influence factor is few, is convenient to control, reproducible.
(3) synthetic Graphene can keep its pattern and not reunite.
(4) the recyclable rear recycle of sodium carbonate.
(5) be convenient to a large amount of synthesizing graphite alkenes of mass-producing.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the embodiment of the present invention 1 Graphene.
Fig. 2 is scanning electron microscope (SEM) photo of the embodiment of the present invention 6 Graphenes.
Fig. 3 is scanning electron microscope (SEM) photo of the embodiment of the present invention 12 Graphenes.
Embodiment
Embodiment 1
Adopt mechanical mill mode by succinic acid and sodium carbonate in molar ratio 1:4 mix, get 1.5g and be positioned in the reactor that argon atmospher protects.At 1000 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.0%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～4.5 nm.
Embodiment 2
Adopting solution hybrid mode, is 1:1 by succinic acid and sodium carbonate mol ratio, and after succinic acid and sodium carbonate are made respectively to solution and mixed, removal solvent obtains solid mixture, gets in the reactor that 2g is positioned over nitrogen atmosphere protection.At 700 ℃ of reaction 120min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～4nm
Embodiment 3
Adopt mechanical mill mode by propanedioic acid and sodium carbonate in molar ratio 1:0.1 mix, get in the reactor that 1.5g is positioned over nitrogen atmosphere protection.At 1300 ℃ of reaction 0.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～2.2nm.
Embodiment 4
Adopt mechanical mill mode by succinic acid and sodium carbonate in molar ratio 1:24 mix, get 1.5g and be positioned in nitrogen atmosphere protection reactor.At 750 ℃ of reaction 30min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～5nm.
Embodiment 5
Adopt mechanical mill mode by methylene-succinic acid and sodium carbonate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 ℃ of reaction 100min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 9.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～3.5nm.
Embodiment 6
Adopting pickling process, is 1:12 by hexanodioic acid and sodium carbonate mol ratio, and hexanodioic acid is mixed with sodium carbonate solution, then removes solvent and obtains solid mixture.Get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 1000 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 6.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～4.0 nm.
Embodiment 7
Adopt mechanical mill mode by tartrate and sodium carbonate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 ℃ of reaction 50min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～3.5 nm.
Embodiment 8
Adopt mechanical mill mode by gluconic acid and sodium carbonate mixing of 1:16 in molar ratio, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 900 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.8%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～5.5 nm.
Embodiment 9
Adopt mechanical mill mode by butene dioic acid and sodium carbonate in molar ratio 1:0.5 mix, get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 1050 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～5.5 nm.
Embodiment 10
Adopt mechanical mill mode by citric acid and sodium carbonate in molar ratio 1:2 mix, get 2g and be positioned in the reactor that argon atmospher protects.At 1200 ℃ of reaction 1.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 6.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～3.0 nm.
Embodiment 11
Adopt mechanical mill mode by phenylformic acid and sodium carbonate in molar ratio 1:0.5 mix, get 2g and be positioned in the reactor that argon atmospher protects.At 1100 ℃ of reaction 2.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～2.8nm.
Embodiment 12
Adopting impregnation method, is 1:2 by stearic acid and sodium carbonate mol ratio, and sodium carbonate be impregnated in stearic solution, then removes solvent and obtains solid mixture.Get in the reactor that 2g is positioned over argon atmospher protection.At 1500 ℃ of reaction 0.1min.After product is cooling, product is taken out, with deionized water wash, filter, 60 ℃ of vacuum-drying 24h, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～3.5nm.
Embodiment 13
Adopt mechanical mill mode by styracin and sodium carbonate in molar ratio 1:4 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 ℃ of reaction 120min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～4nm.
Embodiment 14
Adopting pickling process, is 1:1 by lauric acid and sodium carbonate mol ratio, and lauric acid solid impregnating, in the solution of sodium carbonate, is then removed to solvent and obtained solid mixture.Get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 1300 ℃ of reaction 0.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～2.2nm.
Claims (10)
1. a method for solid organic acid synthesizing graphite alkene, is characterized in that comprising the steps:
By solid organic acid and catalyst mix;
Mixture is positioned in the reactor with the protection of inertia or reducing gas and is reacted, after reaction under identical atmosphere protection cool to room temperature, obtain solid product;
By above-mentioned solid product washing, filtration, the dry Graphene product that obtains.
2. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described solid organic acid comprises propanedioic acid, succinic acid, methylene-succinic acid, hexanodioic acid, butene dioic acid, gluconic acid, tartrate, phenylformic acid, citric acid, lauric acid, styracin or stearic acid.
3. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described catalyzer is sodium carbonate.
4. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described solid organic acid and the mol ratio of catalyzer carbonic acid sodium are 1:0.1-24.
5. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described inert atmosphere is argon gas or nitrogen, and reducing atmosphere is hydrogen.
6. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described mixing comprises that mechanical mill mixes, and pickling process is mixed or solution mixes.
7. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 6, is characterized in that it is that a kind of solid impregnating wherein, in the solution of another kind of solid, is then removed to solvent and obtained solid mixture that described pickling process is mixed.
8. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 6, is characterized in that it is that solid organic acid and sodium carbonate are made respectively after solution mixing that described solution mixes, and removes solvent and obtains solid mixture.
9. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described temperature of reaction is 700-1500 ℃.
10. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that the described reaction times is 0.1-120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310577471.4A CN103601178B (en) | 2013-11-19 | 2013-11-19 | Method for synthesizing graphene from solid organic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310577471.4A CN103601178B (en) | 2013-11-19 | 2013-11-19 | Method for synthesizing graphene from solid organic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103601178A true CN103601178A (en) | 2014-02-26 |
| CN103601178B CN103601178B (en) | 2015-06-17 |
Family
ID=50119468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310577471.4A Active CN103601178B (en) | 2013-11-19 | 2013-11-19 | Method for synthesizing graphene from solid organic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103601178B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
| CN104925795A (en) * | 2015-06-16 | 2015-09-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aza-graphene through solid nitrogenous organic acid |
| CN110422840A (en) * | 2019-09-04 | 2019-11-08 | 河北医科大学 | A kind of method of solid organic acid synthesis azepine graphene |
| CN110577214A (en) * | 2018-06-08 | 2019-12-17 | 中国科学院宁波材料技术与工程研究所 | liquid-phase automatic dispersion graphene solid, and preparation method and application thereof |
| CN112194119A (en) * | 2020-10-13 | 2021-01-08 | 河北医科大学 | Method for synthesizing three-dimensional graphene from solid sugar |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090308520A1 (en) * | 2008-06-12 | 2009-12-17 | Samsung Electronics Co., Ltd. | Method for exfoliating carbonization catalyst from graphene sheet, method for transferring graphene sheet from which carbonization catalyst is exfoliated to device, graphene sheet and device using the graphene sheet |
| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| US20130157034A1 (en) * | 2009-01-15 | 2013-06-20 | Samsung Electronics Co., Ltd. | Method for chemical modification of a graphene edge, graphene with a chemically modified edge and devices including the graphene |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
-
2013
- 2013-11-19 CN CN201310577471.4A patent/CN103601178B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| US20090308520A1 (en) * | 2008-06-12 | 2009-12-17 | Samsung Electronics Co., Ltd. | Method for exfoliating carbonization catalyst from graphene sheet, method for transferring graphene sheet from which carbonization catalyst is exfoliated to device, graphene sheet and device using the graphene sheet |
| US20130157034A1 (en) * | 2009-01-15 | 2013-06-20 | Samsung Electronics Co., Ltd. | Method for chemical modification of a graphene edge, graphene with a chemically modified edge and devices including the graphene |
| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
| CN104925795A (en) * | 2015-06-16 | 2015-09-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aza-graphene through solid nitrogenous organic acid |
| CN110577214A (en) * | 2018-06-08 | 2019-12-17 | 中国科学院宁波材料技术与工程研究所 | liquid-phase automatic dispersion graphene solid, and preparation method and application thereof |
| CN110577214B (en) * | 2018-06-08 | 2022-08-02 | 中国科学院宁波材料技术与工程研究所 | Liquid-phase automatic dispersion graphene solid, and preparation method and application thereof |
| CN110422840A (en) * | 2019-09-04 | 2019-11-08 | 河北医科大学 | A kind of method of solid organic acid synthesis azepine graphene |
| CN112194119A (en) * | 2020-10-13 | 2021-01-08 | 河北医科大学 | Method for synthesizing three-dimensional graphene from solid sugar |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
| CN115321525B (en) * | 2022-08-19 | 2024-02-27 | 河南师范大学 | Preparation method of graphene nano-network with macroporous structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103601178B (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103601178B (en) | Method for synthesizing graphene from solid organic acid | |
| CN103601177A (en) | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst | |
| Khan et al. | Well-designed 2D/2D Ti3C2TA/R MXene coupled g-C3N4 heterojunction with in-situ growth of anatase/rutile TiO2 nucleates to boost photocatalytic dry-reforming of methane (DRM) for syngas production under visible light | |
| Yuan et al. | Highly selective electroreduction of N 2 and CO 2 to urea over artificial frustrated Lewis pairs | |
| Ma et al. | Ultrahigh surface density of Co-N2C single-atom-sites for boosting photocatalytic CO2 reduction to methanol | |
| Zhang et al. | Defect-engineering of mesoporous TiO2 microspheres with phase junctions for efficient visible-light driven fuel production | |
| Luo et al. | Preparation of 3D reticulated ZnO/CNF/NiO heteroarchitecture for high-performance photocatalysis | |
| Liu et al. | Pivotal roles of artificial oxygen vacancies in enhancing photocatalytic activity and selectivity on Bi2O2CO3 nanosheets | |
| Li et al. | Highly efficient and stable photocatalytic reduction of CO 2 to CH 4 over Ru loaded NaTaO 3 | |
| Muroyama et al. | Ammonia decomposition over Ni/La2O3 catalyst for on-site generation of hydrogen | |
| CN101774570B (en) | Method for preparing graphite alkyne film and application | |
| Wu et al. | Ni–Co–B catalyst-promoted hydrogen generation by hydrolyzing NaBH4 solution for in situ hydrogen supply of portable fuel cells | |
| Zhang et al. | Enhanced H 2 evolution from photocatalytic cellulose conversion based on graphitic carbon layers on TiO 2/NiO x | |
| CN104876217B (en) | A kind of preparation method of graphene | |
| CN109678146A (en) | A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application | |
| Li et al. | Monolithically integrated NiCoP nanosheet array on Ti mesh: An efficient and reusable catalyst in NaBH4 alkaline media toward on-demand hydrogen generation | |
| Wang et al. | Ultrathin 2D/2D Ti 3 C 2 T x/semiconductor dual-functional photocatalysts for simultaneous imine production and H 2 evolution | |
| CN106179446B (en) | The method of cobalt/nitrating porous carbon composite and its preparation method and catalysis silane oxidation | |
| Chai et al. | High sintering-/coke-resistance Ni@ SiO 2/Al 2 O 3/FeCrAl-fiber catalyst for dry reforming of methane: one-step, macro-to-nano organization via cross-linking molecules | |
| CN104341006A (en) | Three-dimensional MoS2@MWNTs nanostructure and preparation method thereof | |
| Sun et al. | Photocatalytic H2 evolution of porous silicon derived from magnesiothermic reduction of mesoporous SiO2 | |
| CN102814198A (en) | Metal/graphene nanometer catalyst, and preparation method and application thereof | |
| CN103570004A (en) | Simple large-scale preparation and functionalization method of graphene | |
| CN106207197A (en) | A kind of method using hair to prepare bifunctional electrocatalyst | |
| Barreca et al. | CVD Co3O4 nanopyramids: a nano-platform for photo-assisted H2 production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |