CN110354879B - Composite material and preparation method thereof - Google Patents
Composite material and preparation method thereof Download PDFInfo
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- CN110354879B CN110354879B CN201810314658.8A CN201810314658A CN110354879B CN 110354879 B CN110354879 B CN 110354879B CN 201810314658 A CN201810314658 A CN 201810314658A CN 110354879 B CN110354879 B CN 110354879B
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 117
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 46
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 sulfur ion Chemical class 0.000 claims description 7
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract description 4
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- 239000001301 oxygen Substances 0.000 abstract description 4
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- 239000010703 silicon Substances 0.000 description 24
- 229910052710 silicon Inorganic materials 0.000 description 24
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- 238000001291 vacuum drying Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
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- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XJLXINKUBYWONI-NNYOXOHSSA-O NADP(+) Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](OP(O)(O)=O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 XJLXINKUBYWONI-NNYOXOHSSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- 238000010672 photosynthesis Methods 0.000 description 1
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- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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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 composite material and a preparation method thereof, wherein the composite material comprises silicon carbide particles; reduced graphene oxide bonded to the surface of the silicon carbide particles; and inorganic semiconductor nanoparticles combined on the surface of the reduced graphene oxide, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, and the valence band is greater than 1.60 ev. Under the condition of light excitation, electrons on a conduction band of the semiconductor nano-particles can be transferred to a valence band of silicon carbide through graphene and then are compounded with holes of the silicon carbide to form a Z-type reaction, degradation or oxygen generation reaction occurs on the valence band of the semiconductor nano-particles, hydrogen generation reaction occurs on the conduction band of the silicon carbide, and the photocatalysis performance is improved.
Description
Technical Field
The invention relates to the field of photocatalysts, in particular to a composite material and a preparation method thereof.
Background
Titanium dioxide (TiO)2) The discovery of hydrogen production and degradation capability opens a new era for photocatalysts. In the research hereafter, bismuth vanadate, carbon nitride, cadmium sulfide, silicon carbide and other materials are also found to have the capability of producing hydrogen or degrading, and such materials capable of producing hydrogen or degrading organic pollutants are called semiconductor photocatalysts. They provide a two-in-one idea for solving the problems of energy crisis and environmental pollution, because the photocatalyst can not only directly convert sunlight into hydrogen energy to solve the problem of energy crisis, but also degrade organic pollutants through sunlight irradiationSolves the problem of environmental pollution. However, achieving both reactions simultaneously must rely on the use of photocatalysts with a broad absorption range, long-term stability, high carrier separation efficiency, and strong redox capabilities. A photocatalytic system having only one single component (a photocatalyst) cannot simultaneously satisfy all of the above requirements.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a composite material and a preparation method thereof, which aims to solve the problems of narrow photoresponse range and poor redox ability of the existing composite material.
The technical scheme of the invention is as follows:
a composite material, wherein,
silicon carbide particles;
reduced graphene oxide bonded to the surface of the silicon carbide particles;
and inorganic semiconductor nanoparticles combined on the surface of the reduced graphene oxide, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, and the valence band is greater than 1.60 ev.
A method of making a composite material, comprising the steps of:
mixing silicon carbide particles and graphene to enable the graphene to be bonded to the surfaces of the silicon carbide particles to obtain the silicon carbide particles with the graphene bonded to the surfaces;
and combining inorganic semiconductor nanoparticles on the surface of the graphene to obtain the composite material, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, and the valence band is more than 1.60 ev.
Has the advantages that: the composite material provided by the invention comprises silicon carbide particles, reduced graphene oxide combined on the surfaces of the silicon carbide particles and cadmium sulfide particles combined on the surfaces of the reduced graphene oxide. Under the condition of light excitation, electrons on a conduction band of the semiconductor nano-particles can be transferred to a valence band of silicon carbide through graphene and then are compounded with holes of the silicon carbide to form a Z-type reaction, degradation or oxygen generation reaction occurs on the valence band of the semiconductor nano-particles, hydrogen generation reaction occurs on the conduction band of the silicon carbide, and the photocatalysis performance is improved; meanwhile, because the semiconductor nano particles are a visible light response catalyst and the silicon carbide is an ultraviolet light response catalyst, the composite material can cover most of the sunlight, and the utilization rate of the sunlight is improved.
Drawings
FIG. 1 is a cross-sectional view of a preferred embodiment of the composite material of the present invention.
FIG. 2 is a mechanism diagram of the hydrogen production and degradation reaction of the composite material of the present invention.
Detailed Description
The present invention provides a composite material and a preparation method thereof, and the present invention is further described in detail below in order to make the purpose, technical scheme and effect of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a cross-sectional view of a preferred embodiment of a composite material according to the present invention, wherein the composite material includes silicon carbide particles; reduced graphene oxide bonded to the surface of the silicon carbide particles; and inorganic semiconductor nanoparticles combined on the surface of the reduced graphene oxide, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, and the valence band is greater than 1.60 ev.
Specifically, the photocatalytic reaction should be performed in accordance with thermodynamic and kinetic requirements, and the photocatalyst should have both a narrow energy gap for absorbing more light energy to generate photo-generated electrons and holes and a suitably large energy gap for having a suitable redox potential to perform the catalytic reaction. Intensive research on plant photosynthesis finds that it mainly consists of two light systems and one photosynthetic chain. After light is absorbed by light system ii (ps ii), an oxidation reaction of water occurs, and electrons generated by the oxidation reaction are transmitted to light system i (ps i) through a "photosynthetic chain" of a transmission channel. PS I absorbs light energy to generate electrons to form coenzyme II (NADP) with strong reduction state for reducing CO2Production of saccharidesThe substance, itself, is reduced by electrons transferred from PS II. The electron transport chain is "Z" shaped and is therefore called a Z-type reaction, the quantum efficiency of which is close to 100%. The artificial Z-type photocatalytic system consists of an oxidation reaction catalyst, a reduction reaction catalyst and an electron mediator. Under the irradiation of light, both catalysts of the Z-type photocatalytic system generate photo-generated charges, photo-generated electrons of the oxidation reaction catalyst are transferred to an electron mediator and then are compounded with photo-generated holes of the reduction reaction catalyst, the photo-generated electrons in the reduction reaction catalyst undergo a reduction reaction, and the photo-generated holes in the oxidation reaction catalyst undergo an oxidation reaction. As shown in fig. 2, the silicon carbide (SiC) particles have a band gap energy of 2.4 to 3.4 eV, a relatively negative conduction band position and a relatively positive valence band position, and when excited by light, the silicon carbide generates a photogenerated electron having a relatively strong reducibility, and a photogenerated hole having a relatively less prominent oxidizing property. Therefore, the invention selects inorganic semiconductor nano particles with conduction bands of-1 ev to 0ev and valence bands of more than 1.60 ev. However, the valence band position of silicon carbide is too far away from the conduction band position of inorganic semiconductor nanoparticles, a bridge is required to be added to enable electrons and holes to be easily compounded, reduced graphene oxide (rGO) is selected as the bridge (electron mediator) of silicon carbide and inorganic semiconductor nanoparticles, the Fermi level of the reduced graphene oxide (rGO) is 0eV and is located between the valence band of silicon carbide and the conduction band of the inorganic semiconductor nanoparticles, the energy level difference can be effectively reduced, the reaction is easy to occur, and graphene is used as sp2The planar structure of the substance hybridized with the two-dimensional planar structure is beneficial to the construction of a composite material, and the carrier separation efficiency can be effectively improved through good interface contact and high electron transmission rate.
In one embodiment, as shown in fig. 1, the composite material comprises silicon carbide particles, reduced graphene oxide and cadmium sulfide particles, and the cadmium sulfide (CdS) semiconductor nanoparticles are visible light-responsive composite materials with a band gap energy of 2.4 eV, and have a wide response range to light, the valence band position of the composite materials is positive to silicon carbide, and the conduction band of the composite materials is negative to silicon carbide, so that the composite materials meet the Z-type reaction condition. Meanwhile, the cadmium sulfide semiconductor nano particles are used as visible light response catalysts, and the silicon carbide is used as an ultraviolet light response catalyst, so that the composite material can cover most regions of sunlight, and the utilization rate of the sunlight is improved.
In one embodiment, the silicon carbide is preferably beta-SiC having a diamond structure and better photocatalytic performance, as shown in fig. 2, the band gap energy of the beta-SiC is about 3.0eV, the particles thereof are spheroidal and chemically stable, and therefore, the beta-SiC powder is easily combined with graphene and is not easily chemically reacted to generate excessive impurities during the mixing process with the graphene.
In one embodiment, after the silicon carbide particles and the graphene are dispersed in the solvent, the graphene may be fully coated or partially coated on the surfaces of the silicon carbide particles.
In one embodiment, the silicon carbide particles have a particle size of 0.5 to 5 microns.
In one embodiment, the size of the reduced graphene is 100-1000nm, and under the size condition, the inorganic nanoparticles can uniformly grow on the surface of the graphene without agglomeration.
In one embodiment, the cadmium sulfide particles have a particle size of 10 to 20 nm.
Based on the composite material, the invention also provides a preparation method of the composite material, wherein the preparation method comprises the following steps:
mixing silicon carbide particles and graphene to enable the graphene to be bonded to the surfaces of the silicon carbide particles to obtain the silicon carbide particles with the graphene bonded to the surfaces;
and combining inorganic semiconductor nanoparticles on the surface of the graphene to obtain the composite material, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, and the valence band is more than 1.60 ev.
In some embodiments, the inorganic semiconductor is directly added to the silicon carbide particles with graphene bonded on the surface, and the mixture is stirred or calcined at normal temperature to bond inorganic semiconductor nanoparticles on the surface of the graphene.
In a preferred embodiment, the silicon carbide particles with graphene bonded on the surface are mixed with a cadmium ion precursor and a sulfur ion precursor, and cadmium sulfide particles grow on the surface of the graphene under hydrothermal conditions to obtain the composite material.
In one embodiment, the graphene is prepared by a Hummers method, graphite powder is added into a mixed solvent of phosphoric acid and sulfuric acid, and potassium permanganate is slowly added after stirring in an ice-water bath and is continuously stirred; and continuously dropwise adding hydrogen peroxide with the mass fraction of 30% into the mixed solvent until the mixture turns golden yellow, centrifuging the product, washing off redundant metal ions by hydrochloric acid, and repeatedly centrifuging until the pH value is 7 to obtain the graphene.
In one embodiment, the silicon carbide particles are pre-treated before use at 600-oAnd C, calcining the silicon carbide particles to remove residual organic matters on the silicon carbide particles, and soaking the silicon carbide particles without the organic matters in hydrofluoric acid to prepare the silicon carbide particles with less surface oxidation content, wherein the less the oxide, the better the conductivity. Preferably, the silicon carbide particles are placed in a muffle furnace 600-800oCalcining for 3h to remove organic residue, soaking in 40% hydrofluoric acid for 24h to remove surface oxide, washing with deionized water, and drying in a drying oven for 60 hoAnd C, drying for 12h to obtain pretreated silicon carbide particles.
Mixing the pretreated silicon carbide particles and the graphene according to the weight ratio of 1:0.025-0.125 to obtain the silicon carbide particles with the graphene bonded on the surfaces. The graphene is few, the specific surface area is small, the electron transmission rate is reduced, and the photocatalytic performance is reduced; the graphene is abundant, electrons are easy to disperse, the electrons are not easy to be transferred to a silicon carbide valence band, the electron transfer efficiency of a Z-shaped structure is reduced, and the photocatalytic performance is reduced.
In a specific embodiment, the pretreated silicon carbide particles are dispersed in a solvent and added with graphene for mixing, then the mixed solution is transferred to a high-pressure reaction kettle, the silicon carbide particles with the graphene bonded on the surfaces are obtained by heating at 120-180 ℃ for 6-24h, the product is respectively cleaned by deionized water and absolute ethyl alcohol, and the product is ground into powder in an agate mortar after being dried, so that silicon carbide powder with the graphene bonded on the surfaces is obtained for later use.
Preferably, the solvent is selected from one or more of deionized water, ethanol, ethylene glycol and glycerol, but is not limited thereto.
In one embodiment, the cadmium ion precursor solution and the sulfur ion precursor solution are added into a silicon carbide suspension with graphene bonded on the surface according to the molar ratio of 1:1-1:2, and mixed, and cadmium sulfide particles grow on the surface of the graphene under a hydrothermal condition to obtain the composite material. Fig. 1 is a cross-sectional view of a composite material prepared according to the present invention, wherein the reduced graphene oxide is bonded to the surface of silicon carbide particles, and the cadmium sulfide semiconductor nanoparticles formed from a cadmium ion precursor and a sulfur ion precursor are bonded to the surface of the reduced graphene oxide.
In a preferred embodiment, the silicon carbide powder with graphene bonded on the surface is dispersed in deionized water, a silicon carbide suspension with graphene bonded on the surface is obtained after ultrasonic treatment, a cadmium ion precursor solution and a sulfur ion precursor solution are added into the suspension and stirred, then the suspension is transferred to a reaction kettle for hydrothermal treatment, and cadmium sulfide particles grow on the surface of graphene to obtain the composite material. Through hydrothermal treatment, the graphene can be reduced into reduced graphene oxide under the condition of not increasing any impurities, the composite material is prepared, the preparation process is simple, the conditions are controllable, and reduction of the graphene, synthesis of cadmium sulfide and in-situ growth of the cadmium sulfide on the graphene can be realized simultaneously.
Preferably, the temperature of the hydrothermal treatment is 160-200 ℃,
preferably, the time of the hydrothermal treatment is 12-24 h.
Preferably, the cadmium ion precursor solution is selected from one or more of cadmium nitrate, cadmium chloride and cadmium acetate solutions, but is not limited thereto.
Preferably, the sulfide ion precursor solution is selected from one or more of sodium sulfide, thiourea, L-cysteine, thioacetamide and thiazole solutions, but is not limited thereto.
Under the condition of light excitation, electrons on the cadmium sulfide conduction band can be transferred to the valence band of silicon carbide through graphene and then are compounded with holes of the silicon carbide to form a Z-type reaction, degradation or oxygen generation reaction occurs in the valence band of cadmium sulfide, hydrogen generation reaction occurs in the conduction band of silicon carbide, and the photocatalysis performance is improved; meanwhile, cadmium sulfide is a visible light response catalyst, and silicon carbide is an ultraviolet light response catalyst, so that the composite material can cover most of sunlight areas, and the utilization rate of the sunlight is improved.
Further, the composite material prepared by the invention can be used for degrading methylene blue solution, and the specific implementation method comprises the following steps:
1) respectively dispersing 0.2g of the composite material and the silicon carbide particles with the graphene bonded on the surfaces into 500 mL of methylene blue solution with the concentration of 10 mg/L, introducing air, adsorbing and balancing for 30 min under a dark condition, electrifying, lighting a 125W high-pressure mercury lamp, taking 10 mL of solution every 30 min, and turning off the lamp after 2 h.
2) And placing the obtained solution sample into a centrifuge to centrifuge for 10 min at 3000 rpm, testing absorbance, and calculating the degradation rate. The following are all the test results obtained from the optimal concentration of the type of sample:
the silicon carbide particles with the surfaces combined with the graphene have a degradation rate of 42% after 2h of an experiment, while the silicon carbide-graphene-cadmium sulfide (composite material) has a degradation rate of 71% after 2h of an experiment. The degradation rate of the ternary composite material silicon carbide-graphene-cadmium sulfide is greatly improved compared with that of silicon carbide particles combined with graphene on the surface of the binary composite material, and the silicon carbide, graphene and cadmium sulfide Z-shaped structures play a role, so that the separation efficiency of electrons and holes is improved.
Furthermore, the composite material can also carry out hydrogen production reaction, and the specific implementation method comprises the following steps:
respectively dispersing 50 mg of the composite material and the silicon carbide particles with the graphene combined on the surfaces into 200 mL of distilled water, adding 1mL of chloroplatinic acid or chloroauric acid with the concentration of 1 mmol/L, vacuumizing, starting a xenon lamp to irradiate a sample, taking the sample every 1 h, injecting the sample into a gas chromatograph, measuring the peak area, turning off the lamp after 4h, and calculating the hydrogen yield. The following are all the test results obtained from the optimal concentration of the type of sample:
the silicon carbide particle with the graphene bonded on the surface generates 205.6 mu mol ∙ g of hydrogen after 4h of experiment-1∙h-1The hydrogen yield of the silicon carbide-graphene-cadmium sulfide (composite material) after 4 hours of experiment is 1057.1 mu mol ∙ g-1∙h-1. The hydrogen yield of the ternary composite material silicon carbide-graphene-cadmium sulfide is greatly improved compared with that of silicon carbide particles combined with graphene on the surface of the binary composite material, and the silicon carbide, graphene and cadmium sulfide Z-shaped structures play a role, so that the separation efficiency of electrons and holes is improved.
The following examples illustrate the preparation of the composite material in detail.
Example 1: the following description will be made in detail by taking an example of preparing a composite material by using graphene, silicon carbide particles, cadmium nitrate and sodium sulfide.
(1) Pretreatment of silicon carbide particles: commercial silicon carbide particles are placed in a muffle 600oCalcining for 3h to remove organic residue, soaking in 40% hydrofluoric acid for 24h to remove surface oxide, cleaning with deionized water, and vacuum drying in oven 60 hoC, drying for 12 hours to obtain pretreated silicon carbide particles;
(2) preparation of silicon carbide particles with graphene bonded on the surface: ultrasonically dispersing 200 mg of pretreated silicon carbide powder in 35 mL of deionized water, adding 1mL of graphene solution with the concentration of 5 mg/mL prepared by a traditional Hummers method, ultrasonically treating for 30 min, transferring the graphene solution into a 50 mL high-pressure reaction kettle, and carrying out ultrasonic treatment on the graphene solution for 180 minoReacting for 24 hours under C, washing 3 times respectively by deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven 80oDrying for 12h, and grinding the mixture in an agate mortar to obtain powder, namely silicon carbide particles with graphene combined on the surfaces;
(3) preparing a silicon carbide-graphene-cadmium sulfide composite material: uniformly dispersing the silicon carbide particles with the graphene bonded on the surfaces in 35 mL of deionized waterPerforming ultrasonic treatment for 30 min to obtain silicon carbide-graphene turbid liquid with different graphene oxide doping amounts, adding 5mL of 1 mol/L cadmium nitrate solution, dropwise adding 5mL of 1 mol/L sodium sulfide solution (the molar ratio of a cadmium source to a sulfur source is 1: 1), stirring for 2h, transferring to a reaction kettle, and transferring to 180 DEG CoC, reacting for 12 h. Washing with deionized water and anhydrous ethanol for 3 times, respectively, and vacuum drying in oven 80oAnd C, drying for 12h, and grinding the mixture in an agate mortar to obtain powder, thus obtaining the silicon carbide-graphene-cadmium sulfide composite material.
Carrying out a methylene blue solution degradation test on the silicon carbide-graphene-cadmium sulfide sample obtained in example 1, and measuring that the methylene blue degradation rate is 71% after 2 hours; the silicon carbide-graphene-cadmium sulfide sample obtained in example 1 was subjected to a hydrogen production test, and the hydrogen production amount after 4 hours was 302.6. mu. mol ∙ g-1∙h-1。
Example 2: the following description will be made in detail by taking an example of preparing a composite material by using graphene, silicon carbide particles, cadmium acetate and thioacetamide.
(1) Pretreatment of silicon carbide particles: placing commercial silicon carbide particles in a muffle furnace 800oCalcining for 3h to remove organic residue, soaking in 40% hydrofluoric acid for 24h to remove surface oxide, cleaning with deionized water, and vacuum drying in oven 60 hoC, drying for 12 hours to obtain pretreated silicon carbide particles;
(2) preparation of silicon carbide particles with graphene bonded on the surface: ultrasonically dispersing 200 mg of pretreated silicon carbide particles into a mixed solvent of 10 mL of ethylene glycol and 25 mL of deionized water, adding 5mL of graphene oxide solution with the concentration of 5 mg/mL prepared by a traditional Hummers method, ultrasonically treating for 30 min, transferring the graphene oxide solution into a 50 mL high-pressure reaction kettle, and treating the mixture in a 150 mL high-pressure reaction kettleoC, reacting for 12 hours, washing 3 times respectively by deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven 80oDrying for 12h, and grinding the mixture in an agate mortar to obtain powder, namely silicon carbide particles with graphene combined on the surfaces;
(3) preparing a silicon carbide-graphene-cadmium sulfide composite material: uniformly dispersing the silicon carbide particles with the graphene bonded on the surfaces in 35 mL for separationUltrasonically treating the mixture in water for 30 min to obtain silicon carbide-graphene turbid liquids with different graphene doping amounts, adding 5mL of 0.2 mol/L cadmium acetate solution into the turbid liquids, dropwise adding 5mL of 0.2 mol/L thioacetamide solution (the molar ratio of the cadmium source to the sulfur source is 1: 1), stirring the mixture for 2h, transferring the mixture into a reaction kettle, and transferring the reaction kettle to the reaction kettle for 180 hoC, reacting for 24 hours. Washing with deionized water and anhydrous ethanol for 3 times, respectively, and vacuum drying in oven 80oAnd C, drying for 12h, and grinding the mixture in an agate mortar to obtain powder, thus obtaining the silicon carbide-graphene-cadmium sulfide composite material.
Carrying out a methylene blue solution degradation test on the silicon carbide-graphene-cadmium sulfide sample obtained in the example 2, and measuring that the methylene blue degradation rate is 52% after 2 hours; the silicon carbide-graphene-cadmium sulfide sample obtained in example 2 is subjected to hydrogen production test, and the hydrogen production amount after 4 hours is determined to be 571.4 mu mol ∙ g-1∙h-1。
Example 3: the following description will be made in detail by taking an example of preparing a composite material by using graphene, silicon carbide particles, cadmium chloride and thiourea.
(1) Pretreatment of silicon carbide particles: placing commercial silicon carbide particles in a muffle furnace 800oCalcining for 3h to remove organic residue, soaking in 40% hydrofluoric acid for 24h to remove surface oxide, cleaning with deionized water, and vacuum drying in oven 60 hoC, drying for 12 hours to obtain pretreated silicon carbide particles;
(2) preparation of silicon carbide particles with graphene bonded on the surface: ultrasonically dispersing 200 mg of pretreated silicon carbide particles in a mixed solvent of 5mL of ethylene glycol, 5mL of glycerol and 25 mL of deionized water, adding 2 mL of graphene solution with the concentration of 5 mg/mL prepared by a traditional Hummers method, ultrasonically treating for 30 min, transferring the graphene solution into a 50 mL high-pressure reaction kettle, and carrying out a reaction for 120 minoC, reacting for 12 hours, washing 3 times respectively by deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven 80oDrying for 12h, and grinding the mixture in an agate mortar to obtain powder, namely silicon carbide particles with graphene combined on the surfaces;
(3) preparing a silicon carbide-graphene-cadmium sulfide composite material: uniformly dispersing the silicon carbide particles with the graphene bonded on the surfaces in 35Carrying out ultrasonic treatment for 30 min in mL of deionized water to obtain silicon carbide-graphene turbid liquid with different graphene doping amounts, adding 5mL of 0.01 mol/L cadmium chloride solution, dropwise adding 5mL of 0.01 mol/L thiourea solution (the molar ratio of the cadmium source to the sulfur source is 1: 1), stirring for 2h, transferring to a reaction kettle, and carrying out 180-degree stirringoC, reacting for 18 h. Washing with deionized water and anhydrous ethanol for 3 times, respectively, and vacuum drying in oven 80oAnd C, drying for 12h, and grinding the mixture in an agate mortar to obtain powder, thus obtaining the silicon carbide-graphene-cadmium sulfide composite material.
Carrying out a methylene blue solution degradation test on the silicon carbide-graphene-cadmium sulfide sample obtained in the example 3, and measuring that the methylene blue degradation rate is 61.9% after 2 hours; the silicon carbide-graphene-cadmium sulfide sample obtained in example 3 is subjected to a hydrogen production test, and the hydrogen production amount after 4 hours is 816.2 mu mol ∙ g-1∙h-1。
Example 4: the following description will be made in detail by taking an example of preparing a composite material by using graphene, silicon carbide particles, cadmium chloride and thiourea.
(1) Pretreatment of silicon carbide particles: placing commercial silicon carbide particles in a muffle furnace 800oCalcining for 3h to remove organic residue, soaking in 40% hydrofluoric acid for 24h to remove surface oxide, cleaning with deionized water, and vacuum drying in oven 60 hoC, drying for 12 hours to obtain pretreated silicon carbide particles;
(2) preparation of silicon carbide particles with graphene bonded on the surface: ultrasonically dispersing 200 mg of pretreated silicon carbide particles into a mixed solvent of 5mL of ethylene glycol, 5mL of glycerol and 25 mL of deionized water, adding 2.5 mL of graphene solution with the concentration of 5 mg/mL prepared by a traditional Hummers method, ultrasonically treating for 30 min, transferring the graphene solution into a 50 mL high-pressure reaction kettle, and carrying out a reaction for 120 minoC, reacting for 6 hours, washing 3 times respectively by deionized water and absolute ethyl alcohol, and 80 times in a vacuum drying ovenoDrying for 12h, and grinding the mixture in an agate mortar to obtain powder, namely silicon carbide particles with graphene combined on the surfaces;
(3) preparing a silicon carbide-graphene-cadmium sulfide composite material: uniformly dispersing the silicon carbide particles with the graphene bonded on the surfaces inPerforming ultrasonic treatment for 30 min in 35 mL of deionized water to obtain silicon carbide-graphene turbid liquid with different graphene oxide doping amounts, adding 5mL of 0.5mol/L cadmium chloride solution, dropwise adding 5mL of 0.5mol/L thiourea solution (the molar ratio of the cadmium source to the sulfur source is 1: 1), stirring for 2h, transferring to a reaction kettle, and transferring to 180 DEGoC, reacting for 18 h. Washing with deionized water and anhydrous ethanol for 3 times, respectively, and vacuum drying in oven 80oAnd C, drying for 12h, and grinding the mixture in an agate mortar to obtain powder, thus obtaining the silicon carbide-graphene-cadmium sulfide composite material.
Carrying out a methylene blue solution degradation test on the silicon carbide-graphene-cadmium sulfide sample obtained in the example 4, and measuring that the methylene blue degradation rate is 48.6% after 2 hours; the silicon carbide-graphene-cadmium sulfide sample obtained in example 4 is subjected to a hydrogen production test, and the hydrogen production amount after 4 hours is 1057.1 mu mol ∙ g-1∙h-1。
In summary, the composite material provided by the invention comprises graphene coated on the surface of silicon carbide and cadmium sulfide growing on the surface of the graphene, under the condition of light excitation, electrons on a conduction band of the cadmium sulfide can be transferred to a valence band of the silicon carbide through the graphene and then are compounded with a cavity of the silicon carbide to form a Z-type reaction, the degradation or oxygen generation reaction is carried out on the valence band of the cadmium sulfide, and a hydrogen production reaction is carried out on the conduction band of the silicon carbide, so that the photocatalysis performance is improved; meanwhile, cadmium sulfide is a visible light response catalyst, and silicon carbide is an ultraviolet light response catalyst, so that the composite material can cover most of sunlight areas, and the utilization rate of the sunlight is improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (6)
1. The application of the composite material in the photocatalytic hydrogen production reaction is characterized in that the composite material comprises:
silicon carbide particles;
reduced graphene oxide bonded to the surface of the silicon carbide particles;
and inorganic semiconductor nanoparticles bonded to the surface of the reduced graphene oxide, wherein the conduction band of the inorganic semiconductor nanoparticles is-1 ev to 0ev, the valence band is greater than 1.60ev, the silicon carbide particles are beta-SiC having a diamond structure, the inorganic semiconductor nanoparticles are cadmium sulfide particles, the weight ratio of the silicon carbide particles to the graphene is 16-20:1, and the ratio of the mass of the silicon carbide particles to the molar amount of the cadmium sulfide is 100(g):0.025(mol) or 100(g):1.25 (mol).
2. The application of the composite material in the photocatalytic hydrogen production reaction according to claim 1, wherein the particle size of the silicon carbide particles is 0.5-5 microns.
3. The application of the composite material in the photocatalytic hydrogen production reaction according to claim 1, wherein the size of the graphene is 100-1000 nm.
4. The application of the composite material in the photocatalytic hydrogen production reaction according to claim 1, wherein the preparation method of the composite material comprises the following steps:
mixing silicon carbide particles and graphene according to the weight ratio of 16-20:1 of the silicon carbide particles to the graphene, and enabling the temperature for bonding the graphene to the surfaces of the silicon carbide particles to be 120-180 ℃ to obtain the silicon carbide particles with the graphene bonded to the surfaces;
and combining inorganic semiconductor nanoparticles on the surface of the graphene, wherein the inorganic semiconductor nanoparticles are cadmium sulfide particles to obtain the composite material, the conduction band of the inorganic semiconductor nanoparticles is-1 ev-0 ev, the valence band is more than 1.60ev, and the silicon carbide particles are beta-SiC with a diamond structure.
5. The application of the composite material in photocatalytic hydrogen production reaction according to claim 4, wherein the composite material is obtained by mixing the silicon carbide particles with the graphene bonded on the surface with a cadmium ion precursor and a sulfur ion precursor, and growing cadmium sulfide particles on the surface of the graphene under a hydrothermal condition to bond inorganic semiconductor nanoparticles on the surface of the graphene.
6. The application of the composite material in photocatalytic hydrogen production reaction, according to claim 4, is characterized in that in the step of mixing the silicon carbide particles with the surfaces combined with graphene, the cadmium ion precursor and the sulfur ion precursor are mixed, and the molar ratio of the cadmium ion precursor to the sulfur ion precursor is 1:1-1: 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886270A (en) * | 2011-07-19 | 2013-01-23 | 中国科学院物理研究所 | SiC nanocrystalline/graphene heterojunction and its preparation method and use |
| WO2014120722A1 (en) * | 2013-01-31 | 2014-08-07 | Sunpower Technologies Llc | Photocatalyst for the reduction of carbon dioxide |
| WO2014169258A1 (en) * | 2013-04-11 | 2014-10-16 | Pacific Integrated Energy, Inc. | Photocatalytic metamaterial based on plasmonic near perfect optical absorbers |
| CN106345533A (en) * | 2016-08-25 | 2017-01-25 | 常州大学 | Preparation method of titanium dioxide/polyaniline/carbon nitride Z-form heterojunction photocatalytic material |
| CN107185574A (en) * | 2017-05-19 | 2017-09-22 | 南京师范大学 | A kind of compound nanometer photocatalyst without metallic element and its preparation method and application |
-
2018
- 2018-04-10 CN CN201810314658.8A patent/CN110354879B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886270A (en) * | 2011-07-19 | 2013-01-23 | 中国科学院物理研究所 | SiC nanocrystalline/graphene heterojunction and its preparation method and use |
| WO2014120722A1 (en) * | 2013-01-31 | 2014-08-07 | Sunpower Technologies Llc | Photocatalyst for the reduction of carbon dioxide |
| WO2014169258A1 (en) * | 2013-04-11 | 2014-10-16 | Pacific Integrated Energy, Inc. | Photocatalytic metamaterial based on plasmonic near perfect optical absorbers |
| CN106345533A (en) * | 2016-08-25 | 2017-01-25 | 常州大学 | Preparation method of titanium dioxide/polyaniline/carbon nitride Z-form heterojunction photocatalytic material |
| CN107185574A (en) * | 2017-05-19 | 2017-09-22 | 南京师范大学 | A kind of compound nanometer photocatalyst without metallic element and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| Hierarchically CdS Decorated 1D ZnO Nanorods-2D Graphene Hybrids: Low Temperature Synthesis and Enhanced Photocatalytic Performance;Chuang Han et al;《Materials Views》;20141013;第25卷;第226页图5 * |
| Improved H2 evolution under visible light in heterostructured SiC/CdS photocatalyst: Effect of lattice match;Yuan Peng et al;《International Journal of Hydrogen Energy》;20170511;第42卷;第14410页实验部分第2段和第5段，第14416页结论部分 * |
| Self-Powered Photoelectrochemical Biosensor Based on CdS/RGO/ZnO Nanowire Array Heterostructure;Kun Zhao et al;《Materials Views》;20151130;第12卷;第245页摘要，第245页摘要和第250页4合成RGO/ZnO部分 * |
| 二维Z型光催化材料及其在环境净化和太阳能转化中的应用;张圆正等;《化学进展》;20161030;第28卷(第10期);全文 * |
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