CN108862189B - Photocatalytic hydrogen production device - Google Patents

Photocatalytic hydrogen production device Download PDF

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CN108862189B
CN108862189B CN201810753779.2A CN201810753779A CN108862189B CN 108862189 B CN108862189 B CN 108862189B CN 201810753779 A CN201810753779 A CN 201810753779A CN 108862189 B CN108862189 B CN 108862189B
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graphene
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layer
hydrogen production
silicon
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CN108862189A (en
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高超
彭蠡
沈颖
俞丹萍
卡西克燕.戈坡塞米
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a photocatalytic hydrogen production device which has a two-layer structure, wherein one layer is a silicon layer, the other layer is a graphene layer, and the graphene layer is attached to the silicon layer; graphene layer thickness is not more than 20nm, and the cross-linking degree is within 1-5%, and film thickness is within 20nm, has certain luminousness, can absorb for silicon to graphite alkene/silicon interface layer exists, and light refracts at the interface layer repeatedly, has increased photoabsorption and conversion, provides the condition for the hydrogen production of photocatalysis.

Description

Photocatalytic hydrogen production device
Technical Field
The invention relates to a high-performance nano material device, in particular to a photocatalytic hydrogen production device.
Background
In 2010, Andre GeiM and Konstantin Novoselov, two professors of Manchester university in England, raised the worldwide hot trend of graphene research because of the first successful separation of stable graphene to obtain the Nobel prize of physics. The graphene has excellent electrical properties (the electron mobility can reach 2 multiplied by 105cM2/Vs at room temperature), outstanding heat conduction properties (5000W/(MK)), extraordinary specific surface area (2630M2/g), Young modulus (1100GPa) and breaking strength (125GPa), excellent electric conduction and heat conduction properties of the graphene completely exceed those of metal, meanwhile, the graphene has the advantages of high temperature resistance and corrosion resistance, and the good mechanical properties and the low density of the graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials.
The graphene film of macroscopically assembled graphene oxide or graphene nanosheets is the main application form of nanoscale graphene, and common preparation methods are a suction filtration method, a scraping method, a spin-coating method, a spraying method, a dip-coating method and the like. Through further high-temperature treatment, the defects of graphene can be repaired, the conductivity and the thermal conductivity of the graphene film can be effectively improved, and the graphene film can be widely applied to the fields of battery materials, heat conduction materials, conductive materials and the like.
At present, hydrogen prepared by photocatalytic water is mainly a compound with a d0 electronic structure such as titanium dioxide, a p-region metal compound with a d10 configuration such as In3+, a graphene/silicon composite material and the like. The metal oxide has low solar energy absorptivity and low light quantum yield; the band gap is high, and only ultraviolet light can be absorbed, so that the light utilization efficiency is extremely low. Graphene/silicon solar cells are gradually familiar to researchers at present, but they have not been applied to photocatalytic reactions. The main reasons are as follows:
firstly, the graphene has high light transmittance, high silicon interface reflectivity and low light conversion efficiency;
secondly, large-area graphene/silicon materials cannot be prepared in a large area;
and thirdly, the graphene is of a zero band gap structure, and the coupling effect of only one layer of electronic holes is large, so that sunlight cannot be effectively utilized.
Therefore, a high-strength independent self-supporting film is designed, the film has an interlayer cross-linking structure and a certain band gap, and the coupling time of electronic holes can be prolonged; the film has a certain thickness, so that the light absorption rate is greatly increased, and the electron hole pair is diffused from high concentration to low concentration and is separated by a space charge area; the film has an interlayer cross-linking structure and high strength; the film has a thickness of less than 20nm, has certain light transmittance and can be absorbed by silicon, and the graphene/silicon interface layer exists, so that light is repeatedly refracted at the interface layer, the light absorption and conversion are increased, and conditions are provided for photocatalytic hydrogen production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a photocatalytic hydrogen production device.
The purpose of the invention is realized by the following technical scheme: a photocatalytic hydrogen production device has a two-layer structure, wherein one layer is a silicon layer, the other layer is a graphene layer, and the graphene layer is attached to the silicon layer; the thickness of the graphene layer is not more than 20nm, the graphene layers are crosslinked, and the crosslinking degree is 1-5%. The preparation method comprises the following steps:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and filtering to form a film.
(2) And (3) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating at the high temperature of 80-100 ℃ from the bottom to the top for 0.1-1 h.
(3) And uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and cooling at room temperature until the film is separated from the substrate.
(4) Heating the reduced graphene oxide film treated in the step 3 to sublimate or volatilize the solid transfer agent;
(5) heating the reduced graphene oxide film at 1 ℃/min to 300 ℃ (slowly heating to increase the area of the graphene film in the unit space of the surface fold expansion of the graphene film); and then heating at the temperature of 10 ℃/min, placing at the temperature of 2000 ℃, and preserving heat for 6-12 hours to remove most of atomic defects in the graphene without recovering the stacking structure in the graphene.
(6) And (5) spraying a layer of metal nanoparticles on the surface of the graphene film treated in the step (5) in a magnetron sputtering mode. The metal nanoparticles are selected from titanium, tungsten, iron, magnesium and molybdenum. The molar amount of sputtered metal nanoparticles is no greater than 30% of the molar amount of carbon atoms in the graphene film. And then chlorinating the graphene film sputtered with the metal nanoparticles at 800-1200 ℃ so that the metal nanoparticles escape in the form of chlorides.
(7) And (3) processing the chlorinated graphene film at the high temperature of 2000 ℃ to obtain the interlayer crosslinked graphene film.
(8) Flatly laying the interlayer crosslinked graphene film on a silicon substrate to prepare 2 x 2cm2The device of (1).
Further, the solid transfer agent is selected from materials such as paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, rosin and other small molecule solid materials which can be sublimated or volatilized under certain conditions and are insoluble in water.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
Further, the chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
Further, in step 7, the 2000 ℃ high temperature process temperature rise process is as follows: below 1500 ℃, 5-20 ℃ per minute; above 1500 ℃ and 2-5 ℃ per minute.
Further, the silicon layer is P-type silicon.
Firstly, slowly heating (1 ℃/min) to increase the surface wrinkles of the graphene film and expand the area of the graphene film in unit space; and then heating at a speed of 10 ℃/min and placing at 2000 ℃ to remove most of atomic defects in the graphene, but not recovering the stacking structure in the graphene. Further sputtering metal particles on the surface of the ultrathin graphene film, and reacting the metal particles with the graphene at high temperature to form metal carbide; furthermore, the metal carbide forms metal chloride under the action of chlorine, and meanwhile, the carbon structure is converted into a diamond structure, so that the strength and the thermal stability of the film are greatly improved; the graphene film structure is recovered to a great extent by high-temperature treatment at 2000 ℃, but an interlayer cross-linking structure is not influenced, an AB accumulation structure is not formed, and a foundation is provided for high light absorption and high conductivity of graphene; the film has an interlayer cross-linking structure and a certain band gap, and can increase the coupling time of the electron holes; the film has a certain thickness, so that the light absorption rate is greatly increased, the electron hole pair is diffused from high concentration to low concentration and is separated by a space charge area, and the photoelectric conversion efficiency is improved; the thickness of the film is within 20nm, the film has certain light transmittance, and the transmitted light can be absorbed by silicon, so that a stable space charge region with high intensity is quickly established; the graphene/silicon interface layer exists, light is repeatedly refracted on the interface layer, and light absorption and conversion are increased. All of the above steps, the light utilization rate of the graphene/silicon solar cell is improved, and the purpose of high-efficiency hydrogen production is finally achieved.
Drawings
FIG. 1 is a schematic diagram of the principle of photocatalytic hydrogen production.
Detailed Description
Example 1:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 80 ℃ from the bottom to the top for 1 h.
(3) And uniformly coating the melted solid transfer agent paraffin on the surface of the reduced graphene oxide film, and cooling at room temperature until the film is separated from the AAO film substrate.
(4) Heating the reduced graphene oxide film treated in the step 3 at 200 ℃ to volatilize the solid transfer agent;
(5) heating the reduced graphene oxide film at 1 ℃/min to 300 ℃ (slowly heating to increase the area of the graphene film in the unit space of the surface fold expansion of the graphene film); and then heating at the temperature of 10 ℃/min, placing at the temperature of 2000 ℃, and preserving heat for 6 hours to remove most of atomic defects in the graphene without recovering the stacking structure in the graphene.
(6) And (3) spraying a layer of titanium nano particles on the surface of the graphene film treated in the step (5) in a magnetron sputtering mode, and controlling sputtering parameters to finally obtain the mol weight of the sputtered metal nano particles, which is 29.1% of the mol weight of carbon atoms in the graphene film. The graphene film sputtered with the metal nanoparticles is then chlorinated at 800 ℃ and the titanium nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 0.5% for heating treatment for 0.1 h.
(7) Placing the chlorinated graphene film in a high-temperature furnace, and heating to 1500 ℃ at 5 ℃ per minute; and raising the temperature to 2000 ℃ per minute at the temperature of 2 ℃ to obtain the interlayer crosslinked graphene film.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 1.4% as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The silicon nano particles are loaded on the surface of the graphene film to form a silicon nano film; the thickness of the graphene film is 11nm, and the defect density ID/IG is less than or equal to 0.01.
(8) Flatly laying the interlayer crosslinked graphene film on a silicon substrate to prepare 2 x 2cm2The device of (1).
Catalyzing the graphene/silicon composite film under the irradiation of visible light and infrared light to prepare hydrogen: the above device was placed in a reactor having a capacity of 30ml, and steam was introduced until the system pressure reached 70 kPa. Respectively taking ultraviolet light and infrared light as light sources to irradiate the graphene surface of the device; during the photocatalytic reaction, 0.5ml of each gas was injected into the reactor at intervals of 10 minutes to a gas chromatograph (Shimadzu GC-2014C) to measure the hydrogen production.
Under the ultraviolet irradiation reaction condition, the gas collected after 1 hour contained 54.3% of hydrogen. Under the infrared light reaction condition, the gas collected after 8 hours contained 49.6% of hydrogen.
Example 2
(1) Preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 0.1 h.
(3) And uniformly coating the melted solid transfer agent camphor on the surface of the reduced graphene oxide film, and cooling at room temperature until the film is separated from the AAO film substrate.
(4) Heating the reduced graphene oxide film treated in the step (3) at 80 ℃ to sublimate or volatilize the solid transfer agent;
(5) heating the reduced graphene oxide film at 1 ℃/min to 300 ℃ (slowly heating to increase the area of the graphene film in the unit space of the surface fold expansion of the graphene film); and then heating at the temperature of 10 ℃/min, placing at the temperature of 2000 ℃, and preserving heat for 8 hours to remove most of atomic defects in the graphene without recovering the stacking structure in the graphene.
(6) And (3) spraying a layer of iron nanoparticles on the surface of the graphene film treated in the step (5) in a magnetron sputtering mode, and controlling sputtering parameters to finally obtain the sputtered metal nanoparticles with the molar weight of 16.7% of the molar weight of carbon atoms in the graphene film. The graphene film sputtered with the metal nanoparticles is then chlorinated at 1200 c, and the iron nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 10% for heating treatment for 4 h.
(7) Placing the chlorinated graphene film in a high-temperature furnace, and heating to 1500 ℃ at 20 ℃ per minute; raising the temperature to 2000 ℃ per minute at 5 ℃, and preserving the heat for 1h to obtain the interlayer crosslinked graphene film.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 2.9%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The silicon nano particles are loaded on the surface of the graphene film to form a silicon nano film; the thickness of the graphene film is 18nm, and the defect density ID/IG is less than or equal to 0.01.
(8) Flatly laying the interlayer crosslinked graphene film on a silicon substrate to prepare 2 x 2cm2The device of (1).
Catalyzing the graphene/silicon composite film under the irradiation of visible light and infrared light to prepare hydrogen: the above device was placed in a reactor having a capacity of 30ml, and steam was introduced until the system pressure reached 70 kPa. Respectively taking ultraviolet light and infrared light as light sources to irradiate the graphene surface of the device; during the photocatalytic reaction, 0.5ml of each gas was injected into the reactor at intervals of 10 minutes to a gas chromatograph (Shimadzu GC-2014C) to measure the hydrogen production.
Under the ultraviolet irradiation reaction condition, the gas collected after 1 hour contained 57.5% of hydrogen. Under the infrared light reaction condition, the gas collected after 8 hours contains 50.3 percent of hydrogen.
Example 3
(1) Preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 5ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 1 h.
(3) And uniformly coating the melted solid transfer agent paraffin on the surface of the reduced graphene oxide film, and cooling at room temperature until the film is separated from the AAO film substrate.
(4) Heating the reduced graphene oxide film treated in the step 3 at 200 ℃ to volatilize the solid transfer agent;
(5) heating the reduced graphene oxide film at 1 ℃/min to 300 ℃ (slowly heating to increase the area of the graphene film in the unit space of the surface fold expansion of the graphene film); and then heating at the temperature of 10 ℃/min, placing at the temperature of 2000 ℃, and preserving heat for 12 hours to remove most of atomic defects in the graphene without recovering the stacking structure in the graphene.
(6) And (3) spraying a layer of molybdenum nanoparticles on the surface of the graphene film treated in the step (5) in a magnetron sputtering mode, and controlling sputtering parameters to finally obtain the molar weight of the sputtered metal nanoparticles which is 24.9% of the molar weight of carbon atoms in the graphene film. Then, carrying out chlorination treatment on the graphene film sputtered with the metal nanoparticles at 1000 ℃, wherein the molybdenum nanoparticles escape in the form of chloride; the method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 5% for heating treatment for 1 h.
(7) Placing the chlorinated graphene film in a high-temperature furnace, and heating to 1500 ℃ at 10 ℃ per minute; and raising the temperature to 2000 ℃ per minute at the temperature of 2 ℃ to obtain the interlayer crosslinked graphene film.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 4.8%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The silicon nano particles are loaded on the surface of the graphene film to form a silicon nano film; the thickness of the graphene film is 9nm, and the defect density ID/IG is less than or equal to 0.01.
(8) Flatly laying the interlayer crosslinked graphene film on a silicon substrate to prepare 2 x 2cm2The device of (1).
Catalyzing the graphene/silicon composite film under the irradiation of visible light and infrared light to prepare hydrogen: the above device was placed in a reactor having a capacity of 30ml, and steam was introduced until the system pressure reached 70 kPa. Respectively taking ultraviolet light and infrared light as light sources to irradiate the graphene surface of the device; during the photocatalytic reaction, 0.5ml of each gas was injected into the reactor at intervals of 10 minutes to a gas chromatograph (Shimadzu GC-2014C) to measure the hydrogen production.
Under the ultraviolet irradiation reaction condition, the gas collected after 1 hour contained 56.3% of hydrogen. Under the infrared light reaction condition, the gas collected after 8 hours contains 51.2 percent of hydrogen.

Claims (6)

1. A photocatalytic hydrogen production device is characterized by having a two-layer structure, wherein one layer is a silicon layer, the other layer is a graphene layer, and the graphene layer is attached to the silicon layer; the thickness of the graphene layers is not more than 20nm, the graphene layers are crosslinked, the degree of crosslinking is 1-5%, and the graphene is prepared by the following method:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating the graphene oxide film from the bottom to the top at the HI high temperature of 80-100 ℃ for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step (3) to sublimate or volatilize the solid transfer agent;
(5) heating the reduced graphene oxide film at 1 ℃/min to 300 ℃; then heating at the temperature of 10 ℃/min, placing at 2000 ℃, and preserving heat for 6-12 hours to remove most of atomic defects in the graphene without recovering the stacking structure in the graphene;
(6) spraying a layer of metal nanoparticles on the surface of the graphene film treated in the step (5) in a magnetron sputtering mode; the metal nanoparticles are selected from titanium, tungsten, iron, magnesium and molybdenum, the molar weight of the sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film, and then the graphene film sputtered with the metal nanoparticles is subjected to chlorination treatment at 800-1200 ℃ so that the metal nanoparticles escape in the form of chlorides;
(7) processing the chlorinated graphene film at a high temperature of 2000 ℃ to obtain an interlayer crosslinked graphene film;
(8) laying the interlayer cross-linked graphene film on a silicon substrate to obtain2×2cm2The device of (1).
2. The device for photocatalytic hydrogen production as in claim 1, wherein the solid transfer agent is selected from the group consisting of paraffin, camphor, and rosin.
3. The photocatalytic hydrogen production device as in claim 2, wherein the sublimation temperature of the solid transfer agent is controlled to be less than 320 ℃.
4. The photocatalytic hydrogen production device of claim 2, wherein the chlorination treatment is: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
5. The photocatalytic hydrogen production device according to claim 2, characterized in that in step (7), the 2000 ℃ high-temperature process temperature rise process is as follows: below 1500 deg.C, 5-20 deg.C per minute; above 1500 deg.C, 2-5 deg.C per minute.
6. The photocatalytic hydrogen production device according to claim 1, characterized in that the silicon layer is P-type silicon.
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