CN109806897A - A kind of graphene-based composite material and preparation method and application - Google Patents
A kind of graphene-based composite material and preparation method and application Download PDFInfo
- Publication number
- CN109806897A CN109806897A CN201711159257.1A CN201711159257A CN109806897A CN 109806897 A CN109806897 A CN 109806897A CN 201711159257 A CN201711159257 A CN 201711159257A CN 109806897 A CN109806897 A CN 109806897A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- single layer
- hydrogen
- water
- 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
Classifications
-
- 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
- Y02E60/32—Hydrogen storage
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention belongs to catalysis material and hydrogen storage material field more particularly to a kind of graphene-based composite material and preparation method and applications.Graphene-based composite material provided by the invention includes single layer carbon-nitrogen material；With the graphene for being integrated to single layer carbon-nitrogen material two sides by Van der Waals force.Composite material provided by the invention has good light absorpting ability in the ultraviolet and visible-range of solar energy, can efficiently collect solar energy, therefore the composite material is suitable for photocatalysis field.On the other hand, using the selective permeability of graphene high-efficiency, composite material provided by the invention allows proton to penetrate graphene participation reaction, and newly generated hydrogen cannot then escape, while obstruct OH and O2Deng entering system, it is suppressed that back reaction occurs, it can be achieved that the effective of hydrogen purifies and secure storage, therefore the composite material is also applied for hydrogen storage field.
Description
Technical field
The invention belongs to catalysis material and hydrogen storage material field more particularly to a kind of graphene-based composite material and its systems
Preparation Method and application.
Background technique
Fossil energy shortage and environmental pollution are the two big main problems that mankind nowadays development faces, and photocatalytic cleavage water
Reaction can pass through solar energy activated water molecule H2O promotes reaction, reduces potential barrier, generates this clean energy resource carrier of hydrogen.Due to
The burning of hydrogen is clean water using generation, and photocatalytic water technology is in terms of new energy and environmental improvement, with low cost, environment
The significant advantages such as friendly and sustainable development illustrate huge potentiality.
TiO is utilized from Tokyo Univ Japan Fujishima2After monocrystalline progress light-catalyzed reaction makes water resolve into hydrogen and oxygen,
A large amount of theoretical and experiment is dedicated in catalysis material development and application research.In recent years, the photochemical catalyst emerged in large numbers has gold
Belong to oxide or sulfide, pure metal and the semiconductor material without metal etc..Meanwhile class grapheme two-dimension material is with higher
Chemical stability, semiconductive and excellent optical property also show superior photocatalysis performance.Recent University Of Suzhou Kang Zhen
Brightness professor has synthesized a kind of novel carbon nano dot-carbonitride (C3N4) nano-complex photochemical catalyst, height is able to achieve using the sun
The complete decomposition water of effect, the energy conversion efficiency of solar energy to hydrogen can reach 2%.
However, Hydrogen collection and the technical bottleneck of storage inhibit the widespread adoption of photolysis water hydrogen.The generation of hydrogen
Dependent on the separation of photo-generate electron-hole, in order to enable electron hole high efficiency drive to react, photochemical catalyst reduction and oxidation activity
Site pitch-limited is in charge maximum migration circle.In addition, being precipitated in the proton transfer generated in oxidation site to reduction site
Hydrogen also requires distance between reduction and oxidation site should not be too large.Shorter active site spacing increases back reaction
Probability, while also for except deoxygenating and then collect and store pure H2Bring difficulty.
Therefore, efficient hydrogen manufacturing, purification H are being designed and developed out2Before the method for safe hydrogen storage, photocatalytic cleavage aquatic products hydrogen
It will be unable to be able to really a wide range of implement.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of graphene-based composite material and preparation method and application,
Graphene-based composite material provided by the invention can be in catalytic pyrolysis water hydrogen manufacturing under illumination condition, while can have to hydrogen obtained
Effect purification and safe storage.
The present invention provides a kind of graphene-based composite materials, comprising:
Single layer carbon-nitrogen material；
With the graphene for being integrated to single layer carbon-nitrogen material two sides by Van der Waals force.
Preferably, the single layer carbon-nitrogen material includes single layer C3N4。
Preferably, the graphene includes the graphene of unmodified graphene and/or modified with functional group；The functional group repairs
The graphene of decorations includes graphene oxide, metal-doped graphene, nonmetal doping graphene, metal and nonmetallic common insertion
One of graphene and defect graphene are a variety of.
Preferably, the graphene oxide includes hydroxylating graphene oxide and/or epoxy graphene oxide；
The doping metals of the metal-doped graphene include one of Zn, Cu, Fe, Co and Ni or a variety of；
The nonmetallic doping of the nonmetal doping graphene includes Si and/or N；
The insert material of the metal and nonmetallic common insertion graphene includes TiN4。
The present invention provides the preparation methods of graphene-based composite material described in above-mentioned technical proposal, comprising the following steps:
A1), it is atomized after mixing single layer carbon-nitrogen material with water, obtains fog；
A2), the fog is contacted with single layer graphene film, is covered later in the fog contact side of the single layer graphene film
Another single layer graphene film is covered, it is dry, obtain graphene-based composite material.
Preferably, step a2) in, before covering another single layer graphene film, second first is added to fog contact side
Alcohol.
The present invention provides a kind of preparation methods of graphene-based composite material described in above-mentioned technical proposal, including following step
It is rapid:
B1), single layer carbon-nitrogen material, graphene, ammonia and hydrazine hybrid reaction in water, obtains reaction solution；
B2), the reaction solution filtering coating, it is dry, obtain graphene-based composite material.
Preferably, step b1) in, the temperature of the reaction is 90~99 DEG C；The time of the reaction is 4~8h.
Preferably, step b1) it specifically includes:
Single layer carbon-nitrogen material, graphene, ammonia are mixed in water, obtain mixed liquor；The mixed liquor is mixed with hydrazine later
Reaction is closed, reaction solution is obtained.
The present invention provides a kind of methods of hydrogen manufacturing and hydrogen storage, comprising the following steps:
Under illumination condition, water composite material described in above-mentioned technical proposal or above-mentioned technical proposal the method preparation
It is cracked in the presence of composite material, obtains hydrogen；The hydrogen storage is in the composite material.
Compared with prior art, the present invention provides a kind of graphene-based composite material and preparation method and applications.This
The graphene-based composite material that invention provides includes single layer carbon-nitrogen material；The monolayer carbon nitrogen material is integrated to by Van der Waals force
Expect the graphene of two sides.In the present invention, the mode of action of the graphene in the composite material and carbon-nitrogen material is intermolecular
Van der Waals force, carbon-nitrogen material are among two layers graphene, and in conjunction with can be relatively strong, composite construction can be stabilized；And it is compound
Material has good light absorpting ability in the ultraviolet and visible-range of solar energy, can efficiently collect solar energy, because
This composite material is suitable for photocatalysis field.In the present invention, the process of the composite material catalytic pyrolysis water is as follows: described
There are the differences of work function between graphene and carbon-nitrogen material in composite material, after carbon-nitrogen material absorbs photon energy, generate electricity
Lotus polarization, photo-generate electron-hole separate in the composite, and in hole transport to outer layer graphene, and electrons stay is being wrapped up
In the carbon-nitrogen material of internal layer；The graphene in composite material can efficient catalytic pyrolysis with the help of photohole later
Water generates proton；Then, the proton that photohole driving generates in composite material can by the effect of carbon-nitrogen material electrostatic attraction
It to penetrate graphene, moves on carbon-nitrogen material, reduction reaction occurs with the light induced electron on carbon-nitrogen material, generates hydrogen.?
In the present invention, due to the H generated in the composite material2Graphene cannot be penetrated, the internal layer knot of composite material will be stored in
In structure, and OH and O2Deng being also isolated on the outside of graphene, therefore the composite material can effectively mention hydrogen made from splitting water
Pure and mild safe storage.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is GR/GO-C provided in an embodiment of the present inventionxNyThe UV-vis absorption spectrum figure of-GR/GO；
Fig. 2 is g-C provided in an embodiment of the present inventionxNyWith GR/GO-CxNyThe band structure figure of-GR/GO；
Fig. 3 is GR, GO and C provided in an embodiment of the present inventionxNyWork function figure；
Fig. 4 is the differential charge distribution map of GR/GO-CN-GR/GO provided in an embodiment of the present invention；
Fig. 5 is GR/GO-C provided in an embodiment of the present invention2The differential charge distribution map of N-GR/GO；
Fig. 6 is GR/GO-C provided in an embodiment of the present invention3N4The differential charge distribution map of-GR/GO；
Fig. 7 is the hole evolution distribution map of GR-CN provided in an embodiment of the present invention；
Fig. 8 is catalytic pyrolysis water adsorptive behavior and the photohole distribution of grapheme material provided in an embodiment of the present invention
Figure；
Fig. 9 is that the proton that present invention implementation provides penetrates GR-C3N4Procedure chart；
Figure 10 is the GR-C that present invention implementation provides3N4- GR adsorbs the most steady of one hydrogen molecule of a H atom and storage
Determine configuration picture；
Figure 11 is the GR-C that present invention implementation provides3N4- GR stores the preferred configuration figure of the hydrogen of different number；
Figure 12 is the GR-C that present invention implementation provides3N4Graphene deformation can be schemed when-GR difference hydrogen storage rate；
Figure 13 be the present invention implementation provideApply the variation diagram of external pressure under interlamellar spacing when different hydrogen storage rates.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of graphene-based composite materials, comprising:
Single layer carbon-nitrogen material；
With the graphene for being integrated to single layer carbon-nitrogen material two sides by Van der Waals force.
Graphene-based composite material provided by the invention includes single layer carbon-nitrogen material and is integrated to the single layer carbon-nitrogen material
The graphene of two sides forms " sandwich " structure.Wherein, the single layer carbon-nitrogen material is preferably class graphite-phase carbonization nitrogen material,
Including but not limited to single layer CN, single layer C2N or single layer C3N4.The present invention does not limit the source of the single layer carbon-nitrogen material especially
It is fixed, it can be commercially available, can also be prepared according to method well known to those skilled in the art, with single layer C3N4For, it can be according to
Following methods are prepared:
I), melamine is carbonized, obtains body phase C3N4；
II), by the body phase C3N4It is heated after pulverizing, obtains C3N4Nanometer sheet；
III), by the C3N4Nanometer sheet is based on carrying out ultrasonic centrifugation in liquid phase, obtains single layer C3N4。
In above-mentioned preparation method provided by the invention, step I) described in the temperature of carbonization be preferably 500~600 DEG C,
More preferably 550~560 DEG C；Step I) described in time of carbonization be preferably 2~6h, more preferably 3~4h.Step II) in
The temperature of the heating is preferably 480~580 DEG C, and more preferably 530~540 DEG C；Step II) described in heating time it is preferred
For 100~200min, more preferably 150~160min.Step III) described in liquid phase be preferably isopropanol water solution；Step
III the time of the centrifugation of ultrasound described in) is preferably 2~6h.More preferably 3~4h.
In the present invention, the graphene is integrated to single layer carbon-nitrogen material two sides by Van der Waals force.Wherein, described
Graphene including unmodified graphene (abbreviation GR) and/or modified with functional group.In the present invention, the stone of the modified with functional group
Black alkene includes but is not limited to graphene oxide, metal-doped graphene, nonmetal doping graphene, metal and nonmetallic common embedding
Enter one of graphene and defect graphene or a variety of.In the present invention, the graphene oxide includes but is not limited to hydroxyl
Change graphene oxide (abbreviation GOOH) and/or epoxy graphene oxide (abbreviation GOo)；The metal-doped graphene is mixed
Miscellaneous metal includes but is not limited to one of Zn, Cu, Fe, Co and Ni or a variety of；The doping of the nonmetal doping graphene is non-
Metal includes but is not limited to Si and/or N；The insert material of the metal and nonmetallic common insertion graphene includes but is not limited to
TiN4.The source of the graphene is not particularly limited in the present invention, can be commercially available, can also be according to those skilled in the art
The preparation of method known to member, by taking unmodified graphene as an example, can be prepared in accordance with the following methods:
I), in deposition on substrate nickel, nickel layer is formed；
Ii), graphene is deposited on the nickel layer, forms graphene layer；
Iii), the graphene layer is transferred in transfer substrate.
In above-mentioned preparation method provided by the invention, SiO is may be selected in substrate described in step i)2/ Si piece；In step i)
The mode of the deposition is preferably electron beam evaporation deposition.Step ii) described in deposition mode preferably be vapor-deposited, it is described
The process of vapor deposition preferably includes first to be filled with Ar and H in the reactor for being placed with nickel layer2, then it is re-filled with CH4And H2Occur
Vapor deposition reaction；Wherein, it is filled with the Ar and H2Temperature be preferably 900~1000 DEG C, the time is preferably 20~30min；
It is filled with the CH4And H2Temperature be preferably 1000~1100 DEG C, the time is preferably 5~10min.Step iii) described in shift
Substrate is preferably polyethylene terephthalate (abbreviation PET) film.
By taking graphene oxide as an example, it can be prepared in accordance with the following methods:
S1), graphite and the concentrated sulfuric acid are mixed, KMnO is added in mixed system later4, obtain mixed liquor；
S2), the mixed liquor heating is reacted, and obtains the first reaction solution；
S3), first reaction solution and water and hydrogen peroxide hybrid reaction, obtain the second reaction solution；
S4), second reaction solution is successively stood, is separated by solid-liquid separation, obtains solid；
S5), after the solid is washed and dried, graphene oxide is obtained.
In above-mentioned preparation method provided by the invention, step s1) described in the amount ratio of graphite and the concentrated sulfuric acid be preferably
(1~5) g:(20~100) mL, more preferably (2~3) g:(50~60) mL；Step s1) described in graphite and KMnO4Quality
Than being preferably 1:(0.5~2), more preferably 1:1.Step s2) described in the temperature of reaction be preferably 25~50 DEG C, more preferably
35~40 DEG C；Step s2) described in time of reaction be preferably 10~60min, more preferably 30~40min.Step s3) in institute
State water and step s1) in graphite amount ratio be preferably (400~600) mL:(1~5) g, more preferably (450~500) mL:(2
~3) g；Step s3) described in hydrogen peroxide and step s1) in the amount ratio of graphite be preferably (10~30) mL:(1~5) g, more
Preferably (15~20) mL:(2~3) g；Step s3) described in the temperature of reaction be preferably 25~50 DEG C, more preferably 35~40
℃；Step s3) in the time of the reaction is not particularly limited, preferably stop when reaction solution color becomes golden yellow anti-
It answers；Step s3) in preferably first first reaction solution is mixed with part water, later again by the water of hydrogen peroxide and surplus and its
Mixing, wherein the amount ratio of the part water and graphite in step s1) is preferably (80~150) mL:(1~5) g, more preferably
(100~120) mL:(2~3) g, the time that first reaction solution is mixed with part water is preferably 15~20min.Step s4)
Described in time of standing be preferably 8~20h, more preferably 12~15h.Step s5) described in the mode of washing preferably include
Pickling and washing is successively carried out, wherein the pickling solution of the pickling is preferably 5wt% aqueous hydrochloric acid solution.
The present invention also provides a kind of method for preparing graphene-based composite material described in above-mentioned technical proposal, including it is following
Step:
A1), it is atomized after mixing single layer carbon-nitrogen material with water, obtains fog；
A2), the fog is contacted with single layer graphene film, is covered later in the fog contact side of the single layer graphene film
Another single layer graphene film is covered, it is dry, obtain graphene-based composite material.
In above-mentioned composite material and preparation method thereof provided by the invention, carried out after first mixing single layer carbon-nitrogen material with water
Atomization.Wherein, the device for carrying out the atomization is preferably humidifier.The fog of the carbon-nitrogen material containing single layer is obtained after atomization.
After obtaining fog, the fog is contacted with single layer graphene film, makes connecing for the single layer graphene film and fog
Touching side can adhere to single layer carbon-nitrogen material.In the present invention, fog is preferably first passed through in container by the mode of the contact,
Single layer graphene film is covered on fog again.Another single layer stone is covered in the fog contact side of the single layer graphene film later
Black alkene film.In the present invention, in order to reduce surface tension, enable single layer graphene film it is smooth be layered on single layer carbon-nitrogen material table
Ethyl alcohol first is added to fog contact side preferably before covering another single layer graphene film in face.Cover another mono-layer graphite
After alkene film, it is dried.Wherein, the temperature of the drying is preferably 50~60 DEG C；The time of the drying is preferably 0.5~
1h.After drying, graphene-based composite material is obtained.
The present invention also provides the methods of graphene-based composite material described in another preparation above-mentioned technical proposal, including with
Lower step:
B1), single layer carbon-nitrogen material, graphene, ammonia and hydrazine hybrid reaction in water, obtains reaction solution；
B2), the reaction solution filtering coating, it is dry, obtain graphene-based composite material.
In above-mentioned composite material and preparation method thereof provided by the invention, first by single layer carbon-nitrogen material, graphene, ammonia and hydrazine
Hybrid reaction in water, the process specifically include:
First single layer carbon-nitrogen material, graphene and part water are mixed, obtain mixing suspension；It is described suspension mixed dense
Degree is preferably 0.05~5mg/mL, more preferably 0.1~0.2mg/mL.Then the mixing suspension is mixed with ammonia, wherein
The ammonia is preferably ammonium hydroxide, and the concentration of the ammonium hydroxide is preferably 25~26wt%, the ammonium hydroxide and the suspension mixed body
Product is than being preferably (0.5~2): (100~500), more preferably (0.7~1): (200~300)；The mixing is preferably in ultrasound
Under the conditions of carry out, the mixed time is preferably 1~2h.Mixing suspension is mixed with the mixture that ammonia forms with hydrazine later
Reaction, wherein the hydrazine is preferably (0.05~0.2): (100~500) with the suspension mixed volume ratio, more preferably
(0.08~0.1): (200~300)；The temperature of the reaction is preferably 90~95 DEG C, and the time of the reaction is preferably 4~
8h, more preferably 5~6h.After reaction, reaction solution is obtained.
After obtaining the reaction solution, the reaction solution filtering coating.Wherein, the device of the filtering is preferably composite fibre
Cellulose ester film filter；The mode of the filtering is preferably vacuum filter.Film is removed from filter device after film forming, is done
It is dry, obtain graphene-based composite material.Wherein, the mode of the drying is preferably lyophilized.
The mode of action of graphene and carbon-nitrogen material in composite material provided by the invention is intermolecular Van der Waals force,
Carbon-nitrogen material is among two layers graphene, and in conjunction with can be relatively strong, composite construction can be stabilized；And composite material is in the sun
There is good light absorpting ability in the ultraviolet and visible-range of energy, can efficiently collect solar energy, therefore the composite wood
Material is suitable for photocatalysis field.On the other hand, using the selective permeability of graphene high-efficiency, composite material of the present invention is permitted
Perhaps proton penetrates graphene and participates in reaction, and newly generated hydrogen cannot then escape, while obstruct OH and O2Deng enter system,
Back reaction is inhibited, realizes the effective purification and secure storage of hydrogen, therefore the composite material is also applied for hydrogen storage field.
The working mechanism of composite material catalytic pyrolysis water provided by the invention are as follows: (1) composite material is by absorbing visible light
And ultraviolet light, light-generated excitons are generated, light-generated excitons are rapidly separated as high energy holes and electronics, and move to the graphite of outer layer respectively
On olefinic base material (oxidation site) and the carbon-nitrogen material of internal layer (reduction site)；(2) photoproduction on graphene-based material is moved to
Void coalescence attacks the hydrone of adsorption near active site, and driving water occurs cracking and generates proton；(3) by interior
The driving of electrostatic attraction, newly generated proton will penetrate the graphene-based material of outer layer, move to carbon nitrogen on layer carbon-nitrogen material
On material；(4) proton on carbon-nitrogen material is moved to converge at around the N atom of enrichment light induced electron, by photoproduction electric drive,
It reacts, generates hydrogen；(5) since hydrogen cannot penetrate graphene-based material, it will be retained in outer layer two sides graphene
It is interior, and O simultaneously2, OH etc. also cannot be introduced into composite material, it is suppressed that the generation of back reaction realizes the hydrogen under high hydrogen storage rate
It is effective purification and secure storage.
Graphene-based composite material provided by the invention mainly has the advantage that
1) the efficient selective permeability of graphite alkenes material, is cleverly utilized, i.e., only allows proton to penetrate participation reaction,
And the hydrogen generated cannot escape, while obstruct OH and O2Deng enter composite material, it is suppressed that back reaction occur, realize hydrogen
It is effective purification and secure storage.
2), with the lower cost materials seldom containing metal, clean solar energy is converted to Hydrogen Energy, integrated photocatalysis splitting water system
Hydrogen and safety are hydrogen-storing integrated, effectively reduce hydrogen-preparing hydrogen-storing cost, are advantageously implemented the large-scale application of Hydrogen Energy.
3) Hydrogen Separation and secure storage most difficult in hydrogen utilization, are solved simultaneously and transports two bottleneck problems, is
Realize that solar energy splitting water is converted to the theory design of Hydrogen Energy and practical application opens new road.
The present invention also provides a kind of methods of hydrogen manufacturing and hydrogen storage, comprising the following steps:
Under illumination condition, the composite wood of composite material or above-mentioned preparation method preparation of the water described in above-mentioned technical proposal
It is cracked in the presence of material, obtains hydrogen；The hydrogen storage is in the composite material.
In hydrogen manufacturing provided by the invention and hydrogen storage method, using the composite material as the catalysis material of water-splitting,
It not only can be in catalytic pyrolysis water hydrogen manufacturing under illumination condition, while can effectively purify to hydrogen obtained and safe storage.This
The method provided is provided and solves Hydrogen Separation and secure storage two bottleneck problems of transport most difficult in hydrogen utilization simultaneously,
To realize that solar energy splitting water is converted to the theory design of Hydrogen Energy and practical application opens new road.
The present invention also provides composite material described in a kind of above-mentioned technical proposal or above-mentioned preparation method prepare it is compound
Application of the material in photolysis water hydrogen.
In application provided by the invention, the composite material can be used as catalysis material use, not only can be in light
The catalytic pyrolysis water hydrogen manufacturing according under the conditions of, while hydrogen obtained can effectively be purified and safe storage.Application provided by the invention
It solves Hydrogen Separation and secure storage most difficult in hydrogen utilization simultaneously and transports two bottleneck problems, to realize that solar energy is split
Xie Shui is converted to the theory design of Hydrogen Energy and practical application opens new road.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
Prepare single layer C3N4:
(1) it using melamine as presoma, is put into crucible, places it in Muffle furnace and be warming up to after closeing the lid
It 550 DEG C, is carbonized 4 hours, then stands cooling, the C of body phase can be obtained3N4；
(2) C that previous step is prepared3N4Grind into powder is put into crucible, places it in pipe after closeing the lid
150min is heated in formula furnace under the conditions of 530 DEG C, cooling is stood, obtains C3N4Nanometer sheet；
(3) by C3N4Nanometer sheet is put into aqueous isopropanol, and ultrasound centrifugation 4h, vacuum drying obtains single layer C3N4。
Embodiment 2
Prepare graphene (GR):
In SiO2/ Si on piece deposited by electron beam evaporation deposits one layer of nickel, is then filled with Ar and H at about 900~1000 DEG C2About
Then 20min is filled with the CH of 5~10min at 1000 DEG C4And H2, CVD reaction can occur, graphene is deposited in nickel sheet.
It is transferred to the graphene of generation is wet on pet vector, obtains graphene/PET film.
Embodiment 3
Prepare graphene oxide (GO):
It takes 2g graphite to be added in the 50mL concentrated sulfuric acid, is stirred well to dispersion.Then it is slowly added to while stirring under ice bath
2g KMnO4.Then mixed liquor is reacted into 30min in 35~40 DEG C of water-bath, after addition 100mL water is stirred to react 15min,
Continuously add the water of 350mL and the H of 15mL2O2, it is vigorously stirred, when solution becomes golden yellow, stands 12h, remove supernatant.It is remaining
Bottom solid rinsed with the hydrochloric acid of 5wt% after, then repeatedly rinsed with high purity water, be then centrifuged for washing, be dried in vacuo, obtain oxygen
Graphite alkene.
Embodiment 4
Prepare graphene-based composite material (GR-C3N4- GR):
By single layer C made from embodiment 13N4It is atomized after being dissolved in water with business humidifier.Then by the C of atomization3N4It is passed through burning
In cup, is covered with graphene film prepared by embodiment 2, obtain GR-C3N4Film.
Then in obtained GR-C3N4The C of film3N4Upper instillation ethyl alcohol covers rapidly the graphite of another layer of embodiment 2 preparation
Alkene film finally the dry half an hour at 60 DEG C, obtains graphene-based composite material.
Referring to method provided in this embodiment, graphene/PET film is replaced with to graphene/PET film of modified with functional group,
By single layer C3N4Other single layer carbon-nitrogen materials are replaced with, other graphene-based composite materials can be prepared.
Embodiment 5
Prepare graphene-based composite material (GR-C3N4- GR):
Single layer C prepared by embodiment 13N4The graphene oxide prepared with embodiment 3 mixes in water, is made into 0.1mg/
The mixing suspension 200mL of mL, ammonia 700 the μ L, ultrasonic 1h that 25wt% is then added are uniformly mixed, are subsequently added into 80 μ L hydrazines,
It after reacting 6h at 95 DEG C, is filtered with mixed cellulose ester membrane Filter Vacuum, product is removed from filter membrane, be lyophilized, obtain
Graphene-based composite material.
Referring to method provided in this embodiment, graphene oxide is replaced with into the graphene of other modified with functional group or is not changed
Property graphene, by single layer C3N4Other single layer carbon-nitrogen materials are replaced with, other graphene-based composite materials can be prepared.
Embodiment 6
Initial configuration is constructed by Material Studio, structure optimization is carried out using VASP software package, verifies composite wood
Material can be stabilized；Based on structural stability, optical property, distribution of charges, hole evolutionary process of material etc. are calculated, confirmation is multiple
The efficient absorbing properties of condensation material and separation of charge ability；Then the grapheme material photohole for calculating modified with functional group drives
The adsorption energy of dynamic splitting water, activation energy, Gibbs can be waited, the photocatalytic water reactivity worth of COMPOSITE MATERIALS；Then simulation proton by
Electrostatic attraction penetrates grapheme material and enters internal layer carbon-nitrogen material process, and verifying proton can penetrate grapheme material, and examine
It examines and moves to the generation hydrogen (H under electronics help of the proton on carbon-nitrogen material2) performance；Finally to composite material hydrogen storage rate into
Row research, the hydrogen storage property of analog composite material.It has specifically included:
1, electron hole separates
(a) composite material stability
According to known CxNy(single layer carbon-nitrogen material) and GRF(grapheme material) configuration, builds GRF–CxNy–GRFIt is compound
Material model is optimized in the case where considering Van der Waals correction conditions.With CxNyWith GR (unmodified graphene)/GO (graphite oxide
Alkene) for, we have chosen more stable class graphite-phase carbon-nitrogen material (g-CN, g-C2N,g-C3N4), composite material after optimization
Interlamellar spacing and combine can as shown in table 1:
GR/GO-C in 1 present invention implementation of tablexNyThe combination energy and interlamellar spacing of-GR/GO
As shown in Table 1, C in embodimentxNyIt is respectively with GR/GO interlamellar spacing and in conjunction with energy rangeWith
1.02~3.73eV shows that composite material can be stabilized.
(b) absorbing properties
Based on structural stability, the absorbing properties and energy information of composite material are calculated, with CxNy, GR, GR/GO-CxNy–
For GR/GO, absorption spectrum and band structure are shown in that Fig. 1 and Fig. 2, Fig. 1 are GR/GO-C provided in an embodiment of the present inventionxNy–GR/GO
UV-vis absorption spectrum figure, Fig. 2 is g-C provided in an embodiment of the present inventionxNy(class graphite-phase carbon-nitrogen material) and GR/GO-
CxNyThe band structure figure of-GR/GO.
It can be seen that pure CxNyIt is main to absorb ultraviolet light.After it is compound with GR/GO, coupling between the two is made
With so that its band gap narrows, reflection is then equal in the visible light of solar energy and ultraviolet light range for composite material on light absorption
There is good absorbability, can effectively capture solar energy, generates light-generated excitons.
(c) electron hole separates
The light-generated excitons of generation need to occur to separate and move to oxidation and reduction activation site respectively, and driving force is stone
Work function difference between black alkene material and carbon-nitrogen material.With CxNy, for GR/GO, as a result as shown in figure 3, Fig. 3 is of the invention real
GR, GO and C of example offer are providedxNyWork function figure.
As can be known from Fig. 3, CxNyBigger than GR/GO work function, difference range is 1.7~2.91eV.It is driven by work function difference
It is dynamic, after two kinds of Material claddings, charge polarization occurs, photoinduced electron and hole generate different flow directions, realize separation.
The Bader charge and differential charge result of composite construction also demonstrate this conclusion.With GR/GO-CxNy- GR/GO is
Example, charge analysis result is as shown in table 2 and Fig. 4~6, and wherein Fig. 4 is GR/GO-CN-GR/GO's provided in an embodiment of the present invention
Differential charge distribution map, Fig. 5 are GR/GO-C provided in an embodiment of the present invention2The differential charge distribution map of N-GR/GO, Fig. 6 are these
GR/GO-the C that inventive embodiments provide3N4The differential charge distribution map of-GR/GO.In Fig. 4~6, neutrality refers to that system is in ground state,
Add 1e- to refer to that system adds a light induced electron, adds 1h+Finger system adds a photohole, and blue region indicates hole, yellow area
Indicate electronics；Fig. 4~6 are divided into 9 small figures by two horizontal two vertical dotted lines respectively, and each small figure is made of upper and lower two images again,
By taking the small figure of upper left in Fig. 4 as an example, the image of top similar " diamond shape " is the top view of GR-CN-GR composite material in figure, in figure
The image of similar " sandwich " structure in lower section is the side view of GR-CN-GR composite material.
2 GR/GO-C of tablexNyThe Bader charge analysis table of-GR/GO
By table 2 and Fig. 4~6 it is found that internal layer displaced 0.34~0.72 respectively in composite material before light excitation
(compound with CN), 0.18~0.20 are (with C2N is compound) and 0.16~0.25 (with C3N4It is compound) positive charge (hole) of unit is to outer
On the GR/GO material of layer, the good electron hole separating capacity of composite construction is demonstrated.
Further hole Evolution Simulation then more supports this ability of composite material.By taking GR-CN as an example, as a result such as
Shown in Fig. 7, Fig. 7 is the hole evolution distribution map of GR-CN provided in an embodiment of the present invention, and Fig. 7 a and 7b are respectively low energy and high energy
The evolutionary process in hole.As can be known from Fig. 7, about 14% low energy hole will transports in 3ps from CN material in composite material
It moves on GR layer；And hole energy it is higher when, 80% or more hole can be quickly transferred to GR layers in several ps.It is this ultrafast
Electric charge transfer is enough mutually to compete with electron-hole recombinations, realizes efficiently separating for electron hole.
By table 2 and Fig. 4~7 it is found that generating charge polarization, it will lure after internal layer carbon-nitrogen material absorbs photon energy
Photo-generate electron-hole in composite material is led to separate.With GR/GO-CxNyFor-GR/GO, after a photohole is added, meeting
There are 1.17~1.59 (compound with CN), 1.01~1.10 (with C2N is compound) and 1.01~1.23 (with C3N4It is compound) sky of a unit
Cave moves on the GR/GO material of outer layer；And correspondingly, will have 0.68~0.87,0.33 after a light induced electron is added~
The electronics of 0.45 and 0.32~0.33 unit is gathered in the CN of internal layer, C respectively2N and C3N4On material.
It is found that by work function variance drive, effective electronics can occur for composite material of the invention for complex chart 3-7 and table 2
Hole separation, electrons stay is in the carbon-nitrogen material for being wrapped in internal layer, and hole is then transferred on the graphene-based material of outer layer.
2, photohole drives splitting water
(a) surface water adsorbs
Water-splitting reaction originates in the graphene surface adsorbed water molecule of modified with functional group in composite material.With GRZn(Zn mixes
Miscellaneous graphene), GRCu(Cu doped graphene), GRFe(Fe doped graphene), GRCo(Co doped graphene), GRNi(Ni adulterates stone
Black alkene), GRSi(Si doped graphene), GRN(N doped graphene), GRTiN4(TiN4Doped graphene), GRCv(defect graphite
Alkene), GOOH、GOOFor, the absorption energy range of hydrone is 0.07~1.05eV, shows that hydrone can be stablized and is adsorbed on function
On the graphene of group's modification, reaction is participated in.
(b) photohole is distributed
On the other hand, the photohole being transferred on outer layer grapheme material can be gathered near active site, provide water
Energy needed for cracking.With GRCo/GO–CN–GRCoFor/GO, grapheme material adsorbs structural stability and a plus photoproduction sky after water
Distribution of charges behind cave as shown in figure 8, Fig. 8 be grapheme material provided in an embodiment of the present invention catalytic pyrolysis water adsorptive behavior and
Photohole distribution map, wherein upper figure is structural stability after grapheme material absorption water, the following figure is that grapheme material adds a light
Charge pattern behind raw hole.It can be seen that photohole local drives water that oxidation occurs anti-in reactivity site region
It answers.
(c) water-splitting energy barrier
In addition, the presence of functional group can effectively reduce the energy barrier of water-splitting.With GRZn, GRCu, GRFe, GRCo, GRNi,
GRSi, GRN, GRTiN4, GRCv, GOOH, GOOFor, splitting water energy barrier is as shown in table 3:
Adsorption energy (E of 3 grapheme material of table to hydroneads) and splitting water energy barrier (Eb)
It is found that water-splitting energy barrier (Eb) 3.64eV that graphene is dropped to from the 5.13eV of pure water, it is finally down to again relatively low
About 0.5eV.In the reaction of actual photocatalytic water, the photohole being gathered on graphene-based material can overcome these energy
It builds, driving water cracks.
(d) water-splitting Gibbs free energy
The addition in hole, which is also beneficial to water-splitting reaction Gibbs free energy, to be reduced.By taking GO as an example, the results are shown in Table 4:
4 GO splitting water Gibbs free energy of table
| It is neutral | GOOH | GOO |
| ΔG(eV) | 1.55 | 2.34 |
| Add 1h+ | GOOH | GOO |
| ΔG(eV) | 1.08 | 1.67 |
It can be seen that the Gibbs of water-splitting can be from the GO under neutrallty condition before behind injection holeOHAnd GOO1.55eV and
2.34eV is reduced to 1.08eV and 1.67eV, shows that hole can also help hydrolysis from thermodynamics.
It is comprehensive it is found that driving is adsorbed at grapheme material active site by photohole in composite material of the invention
Hydrone cracks, and generates proton.
3, proton penetrates graphene-based material
The proton that photohole driving generates is acted on, it will penetrate outer layer by the electrostatic attraction of the carbon-nitrogen material of internal layer
Graphene-based material moves on internal layer carbon-nitrogen material.With GR/GO-CxNyFor-GR/GO, balance under spacing, proton and internal layer
The Coulomb interactions energy range of GR/GO is as shown in table 5:
5 GR/GO-C of tablexNyC among-GR/GOxNyTo the coulomb electrostatic interaction energy of proton
By table 5 it is found that under balance spacing, the Coulomb interactions energy range of proton and internal layer GR/GO is 1.48~
4.04eV.This interaction can be enough that proton is overcome to penetrate graphene-based energy barrier (about 1.23eV), so that proton penetrates process
Smoothly realize.
With GR-C3N4For, further Molecular Dynamics Calculation, which simulates proton and penetrates graphene, enters carbon-nitrogen material
Motion process, as a result as shown in figure 9, Fig. 9 is that the proton that present invention implementation provides penetrates GR-C3N4Procedure chart, wherein left figure is
Proton does not penetrate graphene, and middle figure is that proton just penetrates graphene, and right figure is on proton movement to carbon-nitrogen material.Pass through Fig. 9
It knows that proton can penetrate grapheme material, realizes separation and transmission.
It is comprehensive it is found that proton can penetrate the graphene-based material of outer layer in composite material of the invention, move to internal layer carbon
On nitrogen material.
4, electric drive evolving hydrogen reaction
The proton on internal layer carbon-nitrogen material is moved to, with the help of light induced electron, is reacted, hydrogen is generated.With GR-
C3N4For-GR, the results are shown in Figure 10, and Figure 10 is GR-C provided by the invention3N4- GR adsorb a H atom (Figure 10 a) and
Store most structural stability (Figure 10 b) figure of a hydrogen molecule.As can be seen from Figure 10, after proton penetrates graphene, structural stability is
With C3N4Upper N atom combination bonding.At this point, electronics will Assembled distribution around N atom, these enrichment electronics pass through electrostatic
Effect attracts other protons, by photoproduction electric drive, hydrogen is generated in conjunction with the proton adsorbed before.Since hydrogen cannot be worn
Saturating graphene-based material, and OH and O2Deng being also isolated in graphene-based outside, it is suppressed that the generation of back reaction realizes hydrogen
Effective purification & isolation.
It is comprehensive it is found that the proton being transferred on internal layer carbon-nitrogen material in composite material of the invention will be by the drive of light induced electron
It is dynamic, hydrogen is precipitated, and be retained in composite material.
5, the safe hydrogen storage of composite material
After internal layer carbon-nitrogen material absorbs sunlight, it is possible to provide enough photoholes and electronics respectively drive outer layer water crack
Solution reaction and internal layer evolving hydrogen reaction, generate more hydrogen.Due to the high efficiency selected penetrability of graphene-based material, cannot escape
The new generation hydrogen gone out will being stored in composite material by safety.With GR-C3N4For-GR, pass through quantum chemical method, mould
The hydrogen storage property for having intended composite material, as a result as shown in Figure 11~12, Figure 11 is GR-C provided by the invention3N4- GR storage is different
The preferred configuration figure of the hydrogen of quantity, Figure 12 are GR-C provided by the invention3N4Graphene deformation can be schemed when-GR difference hydrogen storage rate.It is logical
Figure 11~12 are crossed it is found that decontroling completely in composite construction, for hydrogen storage rate from 0 to 5.2wt% when (mass percent), interlamellar spacing is maximum
It increases toThe deformation of outer layer graphene at this time can be only 0.001~0.012eV, illustrate under such condition, storage
Hydrogen hardly leads to the deformation of outer layer graphene.
In addition, outer layer graphene is taken in after applying pressure, interlamellar spacing can be maintained under conditions of storing different number hydrogen
Range.With GR-C3N4- GR composite material, interlamellar spacingFor, as a result as shown in figure 13, Figure 13 is provided by the invention
?Apply the variation diagram of external pressure under interlamellar spacing when different hydrogen storage rates.As shown in Figure 13, when the external pressurized for applying about 56bar
After power is on outer layer graphene, Ke YiThe hydrogen storage rate of 5.2wt%, this pressure value and document report are realized under interlamellar spacing
The external pressurized force value of the other materials in road is still comparable.Importantly, hydrogen storage rate is already close to american energy office at this time
Business hydrogen storage standard (6.5wt%).
For synthesis it is found that the high efficiency selected penetrability of graphene is utilized in composite material of the invention, permission proton penetrates ginseng
With react, prevent newly generated H2Escape and outer layer OH, O2Deng entrance, realize hydrogen it is effective purification and secure storage.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of graphene-based composite material, comprising:
Single layer carbon-nitrogen material；
With the graphene for being integrated to single layer carbon-nitrogen material two sides by Van der Waals force.
2. composite material according to claim 1, which is characterized in that the single layer carbon-nitrogen material includes single layer C3N4。
3. composite material according to claim 1, which is characterized in that the graphene include unmodified graphene and/or
The graphene of modified with functional group；The graphene of the modified with functional group includes graphene oxide, metal-doped graphene, nonmetallic
Doped graphene, metal and one of nonmetallic common insertion graphene and defect graphene or a variety of.
4. composite material according to claim 3, which is characterized in that the graphene oxide includes hydroxylating graphite oxide
Alkene and/or epoxy graphene oxide；
The doping metals of the metal-doped graphene include one of Zn, Cu, Fe, Co and Ni or a variety of；
The nonmetallic doping of the nonmetal doping graphene includes Si and/or N；
The insert material of the metal and nonmetallic common insertion graphene includes TiN4。
5. the preparation method of graphene-based composite material described in a kind of claim 1, comprising the following steps:
A1), it is atomized after mixing single layer carbon-nitrogen material with water, obtains fog；
A2), the fog is contacted with single layer graphene film, it is another in the fog contact side covering of the single layer graphene film later
One single layer graphene film, it is dry, obtain graphene-based composite material.
6. preparation method according to claim 5, which is characterized in that step a2) in, covering another single layer graphene film
Before, ethyl alcohol first is added to fog contact side.
7. the preparation method of graphene-based composite material described in a kind of claim 1, comprising the following steps:
B1), single layer carbon-nitrogen material, graphene, ammonia and hydrazine hybrid reaction in water, obtains reaction solution；
B2), the reaction solution filtering coating, it is dry, obtain graphene-based composite material.
8. preparation method according to claim 7, which is characterized in that step b1) in, the temperature of the reaction is 90~99
℃；The time of the reaction is 4~8h.
9. preparation method according to claim 7, which is characterized in that step b1) it specifically includes:
Single layer carbon-nitrogen material, graphene, ammonia are mixed in water, obtain mixed liquor；The mixed liquor is mixed instead with hydrazine later
It answers, obtains reaction solution.
10. a kind of method of hydrogen manufacturing and hydrogen storage, comprising the following steps:
Under illumination condition, water is in any one of any one of Claims 1 to 4 composite material or claim 5~9 side
It is cracked in the presence of the composite material of method preparation, obtains hydrogen；The hydrogen storage is in the composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711159257.1A CN109806897B (en) | 2017-11-20 | 2017-11-20 | Graphene-based composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711159257.1A CN109806897B (en) | 2017-11-20 | 2017-11-20 | Graphene-based composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109806897A true CN109806897A (en) | 2019-05-28 |
| CN109806897B CN109806897B (en) | 2020-08-28 |
Family
ID=66598692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711159257.1A Active CN109806897B (en) | 2017-11-20 | 2017-11-20 | Graphene-based composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109806897B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114408913A (en) * | 2022-02-08 | 2022-04-29 | 咸阳师范学院 | Graphene oxide/carbon nitride three-dimensional composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056985A (en) * | 2015-09-29 | 2015-11-18 | 李若然 | g-C3N4/graphene oxide/nano-iron visible-light response catalytic membrane |
-
2017
- 2017-11-20 CN CN201711159257.1A patent/CN109806897B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056985A (en) * | 2015-09-29 | 2015-11-18 | 李若然 | g-C3N4/graphene oxide/nano-iron visible-light response catalytic membrane |
Non-Patent Citations (2)
| Title |
|---|
| FEI ZHAO ET AL.: "Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing", 《SCIENTIFIC REPORTS》 * |
| LI YANG ET AL.: "Combining photocatalytic hydrogen generation and capsule storage in graphene based sandwich structures", 《NATURE COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114408913A (en) * | 2022-02-08 | 2022-04-29 | 咸阳师范学院 | Graphene oxide/carbon nitride three-dimensional composite material and preparation method and application thereof |
| CN114408913B (en) * | 2022-02-08 | 2023-10-20 | 咸阳师范学院 | Graphene oxide/carbon nitride three-dimensional composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109806897B (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Malik et al. | State-of-the-art review of morphological advancements in graphitic carbon nitride (g-CN) for sustainable hydrogen production | |
| Liu et al. | Facile synthesis of C-doped hollow spherical g-C3N4 from supramolecular self-assembly for enhanced photoredox water splitting | |
| Liu et al. | A sandwich-like heterostructure of TiO2 nanosheets with MIL-100 (Fe): a platform for efficient visible-light-driven photocatalysis | |
| Han et al. | Atomically thin mesoporous nanomesh of graphitic C3N4 for high-efficiency photocatalytic hydrogen evolution | |
| Zhu et al. | Efficient hydrogen production by photocatalytic water-splitting using Pt-doped TiO2 hollow spheres under visible light | |
| Zhang et al. | Hydrogen generation, storage and utilization | |
| Wang et al. | Recent advances on porous materials for synergetic adsorption and photocatalysis | |
| CN109554176B (en) | g-C embedded with carbon quantum dots3N composite material and preparation method and application thereof | |
| CN104525168B (en) | Method for synthesizing anatase/brookite nano composite material for photocatalytic decomposition of water into hydrogen through one-step hydrothermal method | |
| He et al. | Significantly influenced photocatalytic performance for H2O2 generation over ultrathin g-C3N4 through regulating the migration orientation of photogenerated charge carriers | |
| CN109550516B (en) | Carbon/carbon nitrogen (C)xNy) Composite nanotube composite material and preparation method and application thereof | |
| Lu et al. | Nanomaterials for adsorption and conversion of CO2 under gentle conditions | |
| CN112191259A (en) | MXene/Au photocatalytic nitrogen fixation material, and preparation method and application thereof | |
| Prasad et al. | Recent progress on the development of g-C3N4 based composite material and their photocatalytic application of CO2 reductions | |
| Yan et al. | Photocatalytic H2O2 Generation Reaction with a Benchmark Rate at Air‐Liquid‐Solid Joint Interfaces | |
| Ma et al. | Significantly enhanced photocatalytic hydrogen generation over a 2D/2D Z-scheme La2NiO4/g-C3N4 hybrid free of noble metal cocatalyst | |
| Jin et al. | Graphdiyne (C n H2n− 2) based S-scheme heterojunction to promote carrier transfer for efficiently photocatalytic hydrogen evolution | |
| CN112717974B (en) | Phosphorus-doped ultrathin hollow carbon nitride nanosphere catalyst for efficient photocatalytic water splitting hydrogen production | |
| CN103691420A (en) | Mesoporous niobium pentoxide/graphene compound photocatalyst prepared by one-step self-assembly method | |
| CN109806897A (en) | A kind of graphene-based composite material and preparation method and application | |
| Comanescu | Graphene Supports for Metal Hydride and Energy Storage Applications | |
| CN105312090B (en) | One kind (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst | |
| CN110038641B (en) | Bismuth vanadate/chromium porphyrin/graphene quantum dot two-dimensional composite Z-type photocatalytic material, preparation method and application | |
| Zhao et al. | Recent advances in design and engineering of MXene-based heterostructures for sustainable energy conversion | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221021 Address after: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee after: Jiang Jun Patentee after: Luo Yi Address before: 230026 Jinzhai Road, Baohe District, Hefei, Anhui Province, No. 96 Patentee before: University of Science and Technology of China Effective date of registration: 20221021 Address after: Room 1102-a009, 11 / F, Zhongxin Wangan building, northeast corner, intersection of Chuangxin Avenue and Wangjiang West Road, high tech Zone, Hefei City, Anhui Province 230000 Patentee after: Hefei Jiqian Quantum Technology Co.,Ltd. Address before: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee before: Jiang Jun Patentee before: Luo Yi |
|
| TR01 | Transfer of patent right |