CN108862189A - A kind of photocatalysis hydrogen production device - Google Patents
A kind of photocatalysis hydrogen production device Download PDFInfo
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- CN108862189A CN108862189A CN201810753779.2A CN201810753779A CN108862189A CN 108862189 A CN108862189 A CN 108862189A CN 201810753779 A CN201810753779 A CN 201810753779A CN 108862189 A CN108862189 A CN 108862189A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
The invention discloses a kind of photocatalysis hydrogen production devices, have double-layer structure, wherein one layer is silicon layer, another layer is graphene layer, and graphene layer is bonded with silicon layer；Graphene layer thickness is not more than 20nm, it is crosslinked between graphene layer, the degree of cross linking is in 1-5%, within film thickness 20nm, there is certain light transmittance, can be absorbed by silicon, and graphene/silicon boundary layer exists, light reflects repeatedly in boundary layer, increases light absorption and conversion, provides condition for Photocatalyzed Hydrogen Production.
Description
Technical field
The present invention relates to high-performance nano material devices more particularly to a kind of photocatalysis hydrogen production devices.
Background technique
2010, two professor Andre GeiM and Konstantin Novoselov of Univ Manchester UK because
It is successfully separated out stable graphene for the first time and obtains Nobel Prize in physics, has started the upsurge that graphene is studied in the whole world.
Graphene has excellent electric property (electron mobility is up to 2 × 105cM2/Vs at room temperature), heating conduction outstanding
(5000W/ (MK), extraordinary specific surface area (2630M2/g), Young's modulus (1100GPa) and breaking strength (125GPa).Stone
The excellent electrical and thermal conductivity performance of black alkene is well beyond metal, while graphene has the advantages that corrosion-and high-temp-resistant, and it is good
Mechanical performance and lower density more allow it to have the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of nanoscale graphite alkene
Form, common preparation method are suction methods, scrape embrane method, spin-coating method, spray coating method and dip coating etc..At further high temperature
Reason, can repair the defect of graphene, can effectively improve the electric conductivity and thermal conductance of graphene film, can be widely applied to
The fields such as battery material, Heat Conduction Material, conductive material.
Currently, it is mainly that titanium dioxide etc. has compound and In3+ of d0 electronic structure etc. that photocatalysis water, which prepares hydrogen,
With the composite materials such as the area the p metallic compound of d10 configuration and graphene/silicon.Wherein, metal oxide solar absorptance
Low, quantum yield is low；Band gap is high, can only absorb ultraviolet light, thus light utilization ratio is extremely low.Graphene/silicon solar energy at present
Battery is gradually familiar with by researcher, but it also fails to be applied to light-catalyzed reaction.Main cause has some：
First, graphene light transmittance is high, silicon interface reflectivity is high, and phototransformation efficiency is low；
Second, large-area graphene/silicon materials are unable to large area preparation；
Third, graphene is zero bandgap structure, and the number of plies only has one layer of electronics hole coupling larger, cannot be effectively sharp
Use sunlight.
For this purpose, we devise the film of high-intensitive independent self-supporting, this film has interlayer cross-linked structure, there is certain band
Gap can increase electronics hole coupling time；Film has certain thickness, substantially increases absorptivity, electronics hole to by
High concentration is spread to low concentration, is separated by space-charge region；Film has interlayer cross-linked structure, and intensity is very high；Film thickness 20nm
Within, there is certain light transmittance, can be absorbed by silicon, and graphene/silicon boundary layer exists, light is rolled over repeatedly in boundary layer
It penetrates, increases light absorption and conversion, provide condition for Photocatalyzed Hydrogen Production.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of photocatalysis hydrogen production device.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of photocatalysis hydrogen production device has double-layer structure,
Wherein one layer is silicon layer, and another layer is graphene layer, and graphene layer is bonded with silicon layer；Graphene layer thickness is not more than 20nm, stone
Black alkene interlayer crosslinking, the degree of cross linking is in 1-5%.It is prepared by the following method to obtain：
(1) graphene oxide is configured to concentration is 0.5-10ug/mL graphene oxide water solution, filters film forming.
(2) graphene oxide membrane filtered in substrate will be attached to be placed in closed container, 80-100 degree HI high temperature is the bottom of from
Up fumigate 0.1-1h in portion.
(3) the solid transfer agent even application of thawing is cooled down in redox graphene film surface, and at room temperature, directly
It is separated to film and substrate.
(4) to step 3, treated that redox graphene film heats so that the distillation of solid transfer agent or
Volatilization；
(5) redox graphene film is heated up 300 DEG C with 1 DEG C/min and (is slowly heated, increases graphene membrane surface folds
Extend the area of graphene film in unit space)；Then 10 DEG C/min heating is placed in 2000 DEG C, keeps the temperature 6-12 hours, with removal
Most atom defects inside graphene, but do not restore stacked structure inside graphene.
(6) one layer of metal nanoparticle is sprayed in step 5 treated graphene membrane surface by the way of magnetron sputtering.
The metal nanoparticle is selected from titanium, tungsten, iron, magnesium, molybdenum.The mole of the metal nanoparticle of sputtering is no more than in graphene film
The 30% of carbon atom mole.Then the graphene film of metal nanoparticle carries out at chlorination sputtering at 800-1200 DEG C
Reason, so that metal nanoparticle loss in a chloride-form.
(7) graphene film after chlorination is obtained into the graphene film of interlayer crosslinking in 2000 DEG C of high-temperature process.
(8) graphene film that interlayer is crosslinked is laid in silicon base, 2 × 2cm is made2Device.
Further, the solid transfer agent, be selected from following substance, such as paraffin, naphthalene, arsenic trioxide, camphor,
The small molecule solid matter not soluble in water that sulphur, norbornene, rosin etc. can distil or volatilize under certain conditions.
Further, the sublimation temperature of the solid transfer agent will be controlled at 320 degree or less.
Further, the chlorination processing refers to：There is the graphene film of metal nanoparticle to be placed in chlorine content sputtering
To be heated in the environment of 0.5-10%, time 0.1-4h.
Further, in step 7,2000 degree of pyroprocess temperature-rise periods are as follows：1500 degrees Celsius hereinafter, 5-20 degrees Celsius
Per minute；1500 degrees Celsius or more, 2-5 centigrade per minute.
Further, silicon layer is P-type silicon.
The present invention passes through (1 DEG C/min) processing that slowly heats up first, increases graphene membrane surface fold, extends unit space
The area of interior graphene film；Then 2000 DEG C are set with 10 DEG C/min heating, to remove most atom defects inside graphene,
But stacked structure inside graphene is not restored.Further by under ultra-thin graphene membrane surface splash-proofing sputtering metal particle, high temperature, gold
Belong to particle and graphite alkene reaction, forms metal carbides；Further, metal carbides form metal under the action of chlorine
Chloride, meanwhile, carbon structure changes to diamond lattic structure, greatly improves film strength and thermal stability；At 2000 degree of high temperature
Reason, so that graphene film structure obtains the recovery of high degree, but will not influence interlayer cross-linked structure and not will form AB
Packed structures provide the foundation for the high light absorption of graphene is highly conductive；This film has interlayer cross-linked structure, there is certain band
Gap can increase electronics hole coupling time；Film has certain thickness, substantially increases absorptivity, electronics hole to by
High concentration is spread to low concentration, is separated by space-charge region, and incident photon-to-electron conversion efficiency is promoted；Within film thickness 20nm, have certain
Light transmittance, the light of transmission can absorb by silicon, quickly establish and stablize high-intensitive space-charge region；Graphene/silicon
Boundary layer exists, and light reflects repeatedly in boundary layer, increases light absorption and conversion.It is all these, improve the graphene/silicon sun
The light utilization efficiency of energy battery is finally reached the purpose that high efficiency produces hydrogen.
Detailed description of the invention
Fig. 1 is photocatalysis hydrogen production schematic illustration.
Specific embodiment
Embodiment 1：
(1) graphene oxide is configured to concentration is 0.5ug/mL graphene oxide water solution, is filtered by substrate of AAO film
Film forming.
(2) graphene oxide membrane for being attached at AAO film is placed in closed container, 80 degree of HI high temperature are up fumigated from bottom
1h。
(3) the solid transfer agent paraffin even application of thawing is cold in redox graphene film surface, and at room temperature
But, until film and AAO film substrate separate.
(4) to step 3, treated that redox graphene film heats at 200 DEG C, so that solid transfer agent is waved
Hair；
(5) redox graphene film is heated up 300 DEG C with 1 DEG C/min and (is slowly heated, increases graphene membrane surface folds
Extend the area of graphene film in unit space)；Then 10 DEG C/min heating is placed in 2000 DEG C, 6 hours is kept the temperature, to remove graphite
Most atom defects inside alkene, but do not restore stacked structure inside graphene.
(6) one layer of titanium nanoparticle is sprayed in step 5 treated graphene membrane surface by the way of magnetron sputtering, led to
Control sputtering parameter is crossed, the mole of the metal nanoparticle finally sputtered is carbon atom mole in graphene film
29.1%.Then the graphene film of metal nanoparticle carries out chlorination processing sputtering at 800 DEG C, titanium nanoparticle is with chlorine
Compound form loss.Specially：The graphene film that sputtering has metal nanoparticle is placed in the environment that chlorine content is 0.5%
Heated, time 0.1h.
(7) graphene film after chlorination is placed in high temperature furnace, 5 centigrade per minutes are warming up to 1500 degrees Celsius；2 is Celsius
Degree is warming up to 2000 degrees Celsius per minute, obtains the graphene film of interlayer crosslinking.
It is tested through Raman, which has the graphene film of numerous cross-linked structures to have stronger sp3The bonded peak of carbon
(1360cm-1), it is measured by ID/IG area ratio, the degree of cross linking (content-mass percent that the degree of cross linking is sp3 carbon) is
1.4%；The graphene film electronic diffraction striped interlamellar spacing of crosslinking structure is smaller than normal graphene film electronic diffraction interlamellar spacing.
Nano silicon particles are supported on graphene membrane surface, form silicon nanometer film；The graphene film with a thickness of 11nm, defect concentration
ID/IG≤0.01。
(8) graphene film that interlayer is crosslinked is laid in silicon base, 2 × 2cm is made2Device.
By above-mentioned graphene/silicon composite membrane under visible light and Infrared irradiation catalyzing manufacturing of hydrogen：Above-mentioned device is placed in one
Capacity is to be passed through vapor until system pressure reaches 70kPa in the reactor of 30ml.Respectively using ultraviolet light, infrared light as
Light source is irradiated the graphene face of device；During light-catalyzed reaction, the gas of 0.5ml was respectively taken from reactor every 10 minutes
Body injects the output of gas chromatograph (Shimadzu GC-2014C) detection hydrogen.
Under ultraviolet lighting reaction condition, in the gas that acquires after 1 hour, contain 54.3% hydrogen.It is shone in infrared light
Under reaction condition, in the gas that acquires after 8 hours, contain 49.6% hydrogen.
Embodiment 2
(1) graphene oxide is configured to concentration is 10ug/mL graphene oxide water solution, is filtered by substrate of AAO film
Film forming.
(2) graphene oxide membrane for being attached at AAO film is placed in closed container, 100 degree of HI high temperature are up smoked from bottom
Steam 0.1h.
(3) the solid transfer agent camphor even application of thawing is cold in redox graphene film surface, and at room temperature
But, until film and AAO film substrate separate.
(4) to step 3, treated that redox graphene film heats at 80 degrees celsius, so that solid turns
Move agent distillation or volatilization；
(5) redox graphene film is heated up 300 DEG C with 1 DEG C/min and (is slowly heated, increases graphene membrane surface folds
Extend the area of graphene film in unit space)；Then 10 DEG C/min heating is placed in 2000 DEG C, 8 hours is kept the temperature, to remove graphite
Most atom defects inside alkene, but do not restore stacked structure inside graphene.
(6) one layer of Fe nanometer particles are sprayed in step 5 treated graphene membrane surface by the way of magnetron sputtering, led to
Control sputtering parameter is crossed, the mole of the metal nanoparticle finally sputtered is carbon atom mole in graphene film
16.7%.Then at 1200 DEG C will sputtering have metal nanoparticle graphene film carry out chlorination processing, Fe nanometer particles with
Chloride form loss.Specially：The graphene film that sputtering has metal nanoparticle is placed in the environment that chlorine content is 10%
In heated, time 4h.
(7) graphene film after chlorination is placed in high temperature furnace, 20 centigrade per minutes are warming up to 1500 degrees Celsius；5 take the photograph
Family name's degree is warming up to 2000 degrees Celsius per minute, keeps the temperature 1h, obtains the graphene film of interlayer crosslinking.
It is tested through Raman, which has the graphene film of numerous cross-linked structures to have stronger sp3The bonded peak of carbon
(1360cm-1), it is measured by ID/IG area ratio, the degree of cross linking (content-mass percent that the degree of cross linking is sp3 carbon) is
2.9%；The graphene film electronic diffraction striped interlamellar spacing of crosslinking structure is smaller than normal graphene film electronic diffraction interlamellar spacing.
Nano silicon particles are supported on graphene membrane surface, form silicon nanometer film；The graphene film with a thickness of 18nm, defect concentration
ID/IG≤0.01。
(8) graphene film that interlayer is crosslinked is laid in silicon base, 2 × 2cm is made2Device.
By above-mentioned graphene/silicon composite membrane under visible light and Infrared irradiation catalyzing manufacturing of hydrogen：Above-mentioned device is placed in one
Capacity is to be passed through vapor until system pressure reaches 70kPa in the reactor of 30ml.Respectively using ultraviolet light, infrared light as
Light source is irradiated the graphene face of device；During light-catalyzed reaction, the gas of 0.5ml was respectively taken from reactor every 10 minutes
Body injects the output of gas chromatograph (Shimadzu GC-2014C) detection hydrogen.
Under ultraviolet lighting reaction condition, in the gas that acquires after 1 hour, contain 57.5% hydrogen.It is shone in infrared light
Under reaction condition, in the gas that acquires after 8 hours, contain 50.3% hydrogen.
Embodiment 3
(1) by graphene oxide be configured to concentration be 5ug/mL graphene oxide water solution, using AAO film be substrate suction filtration at
Film.
(2) graphene oxide membrane for being attached at AAO film is placed in closed container, 100 degree of HI high temperature are up smoked from bottom
Steam 1h.
(3) the solid transfer agent paraffin even application of thawing is cold in redox graphene film surface, and at room temperature
But, until film and AAO film substrate separate.
(4) to step 3, treated that redox graphene film heats at 200 DEG C, so that solid transfer agent is waved
Hair；
(5) redox graphene film is heated up 300 DEG C with 1 DEG C/min and (is slowly heated, increases graphene membrane surface folds
Extend the area of graphene film in unit space)；Then 10 DEG C/min heating is placed in 2000 DEG C, 12 hours is kept the temperature, to remove stone
Most atom defects inside black alkene, but do not restore stacked structure inside graphene.
(6) one layer of molybdenum nanoparticle is sprayed in step 5 treated graphene membrane surface by the way of magnetron sputtering, led to
Control sputtering parameter is crossed, the mole of the metal nanoparticle finally sputtered is carbon atom mole in graphene film
24.9%.Then at 1000 DEG C will sputtering have metal nanoparticle graphene film carry out chlorination processing, molybdenum nanoparticle with
Chloride form loss；Specially：The graphene film that sputtering has metal nanoparticle is placed in the environment that chlorine content is 5%
Heated, time 1h.
(7) graphene film after chlorination is placed in high temperature furnace, 10 centigrade per minutes are warming up to 1500 degrees Celsius；2 take the photograph
Family name's degree is warming up to 2000 degrees Celsius per minute, obtains the graphene film of interlayer crosslinking.
It is tested through Raman, which has the graphene film of numerous cross-linked structures to have stronger sp3The bonded peak of carbon
(1360cm-1), it is measured by ID/IG area ratio, the degree of cross linking (content-mass percent that the degree of cross linking is sp3 carbon) is
4.8%；The graphene film electronic diffraction striped interlamellar spacing of crosslinking structure is smaller than normal graphene film electronic diffraction interlamellar spacing.
Nano silicon particles are supported on graphene membrane surface, form silicon nanometer film；The graphene film with a thickness of 9nm, defect concentration ID/
IG≤0.01。
(8) graphene film that interlayer is crosslinked is laid in silicon base, 2 × 2cm is made2Device.
By above-mentioned graphene/silicon composite membrane under visible light and Infrared irradiation catalyzing manufacturing of hydrogen：Above-mentioned device is placed in one
Capacity is to be passed through vapor until system pressure reaches 70kPa in the reactor of 30ml.Respectively using ultraviolet light, infrared light as
Light source is irradiated the graphene face of device；During light-catalyzed reaction, the gas of 0.5ml was respectively taken from reactor every 10 minutes
Body injects the output of gas chromatograph (Shimadzu GC-2014C) detection hydrogen.
Under ultraviolet lighting reaction condition, in the gas that acquires after 1 hour, contain 56.3% hydrogen.It is shone in infrared light
Under reaction condition, in the gas that acquires after 8 hours, contain 51.2% hydrogen.
Claims (6)
1. a kind of photocatalysis hydrogen production device, which is characterized in that there is double-layer structure, wherein one layer is silicon layer, another layer is graphite
Alkene layer, graphene layer are bonded with silicon layer；Graphene layer thickness is not more than 20nm, is crosslinked between graphene layer, the degree of cross linking in 1-5%,
It is prepared by the following method to obtain：
(1) graphene oxide is configured to concentration is 0.5-10ug/mL graphene oxide water solution, filters film forming；
(2) graphene oxide membrane that will be attached in suction filtration substrate is placed in closed container, and 80-100 degree HI high temperature is past from bottom
Upper stifling 0.1-1h；
(3) the solid transfer agent even application of thawing is cooled down in redox graphene film surface, and at room temperature, until thin
Film and substrate separation；
(4) to step 3, treated that redox graphene film heats, so that the distillation of solid transfer agent or waving
Hair；
(5) redox graphene film is heated up 300 DEG C with 1 DEG C/min and (is slowly heated, increases the extension of graphene membrane surface fold
The area of graphene film in unit space)；Then 10 DEG C/min heating is placed in 2000 DEG C, 6-12 hours is kept the temperature, to remove graphite
Most atom defects inside alkene, but do not restore stacked structure inside graphene；
(6) one layer of metal nanoparticle is sprayed in step 5 treated graphene membrane surface by the way of magnetron sputtering；It is described
Metal nanoparticle is selected from titanium, tungsten, iron, magnesium, molybdenum, and the mole of the metal nanoparticle of sputtering is former no more than carbon in graphene film
Then sputtering is had the graphene film of metal nanoparticle to carry out chlorination processing by the 30% of sub- mole at 800-1200 DEG C,
So that metal nanoparticle loss in a chloride-form,
(7) graphene film after chlorination is obtained into the graphene film of interlayer crosslinking in 2000 DEG C of high-temperature process；
(8) graphene film that interlayer is crosslinked is laid in silicon base, 2 × 2cm is made2Device.
2. photocatalysis hydrogen production device as claimed in claim 2, which is characterized in that the solid transfer agent is selected from following object
What matter, such as paraffin, naphthalene, arsenic trioxide, camphor, sulphur, norbornene, rosin etc. can distil or volatilize under certain conditions
Small molecule solid matter not soluble in water.
3. photocatalysis hydrogen production device as claimed in claim 2, which is characterized in that the sublimation temperature of the solid transfer agent is wanted
Control is at 320 degree or less.
4. photocatalysis hydrogen production device as claimed in claim 2, which is characterized in that the chlorination processing refers to：Sputtering there is into gold
The graphene film for belonging to nanoparticle, which is placed in the environment that chlorine content is 0.5-10%, to be heated, time 0.1-4h.
5. photocatalysis hydrogen production device as claimed in claim 2, which is characterized in that in step 7,2000 degree of pyroprocesses heated up
Journey is as follows：1500 degrees Celsius hereinafter, 5-20 centigrade per minute；1500 degrees Celsius or more, 2-5 centigrade per minute.
6. photocatalysis hydrogen production device according to claim 1, which is characterized in that the silicon layer is P-type silicon.
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| WO2013012393A1 (en) * | 2011-07-15 | 2013-01-24 | National University Of Singapore | A photocatalyst for water splitting |
| CN104477889A (en) * | 2014-12-03 | 2015-04-01 | 连丽君 | Method for directly growing graphene membrane on silicon substrate |
| CN104495829A (en) * | 2014-12-30 | 2015-04-08 | 南京航空航天大学 | Method for preparing graphene film on low-temperature substrate |
| CN105233842A (en) * | 2015-10-14 | 2016-01-13 | 上海理工大学 | Preparation method of multi-metal sulfide/graphene composite visible-light-driven photocatalyst |
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