CN113457653A - Photocatalytic composite material, preparation method and application thereof - Google Patents
Photocatalytic composite material, preparation method and application thereof Download PDFInfo
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- CN113457653A CN113457653A CN202110533315.2A CN202110533315A CN113457653A CN 113457653 A CN113457653 A CN 113457653A CN 202110533315 A CN202110533315 A CN 202110533315A CN 113457653 A CN113457653 A CN 113457653A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical group N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 20
- 239000002912 waste gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006249 magnetic particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910009112 xH2O Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- B01J35/39—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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 provides an S, N-doped amorphous carbon/bimetal sulfide photocatalytic composite material, and a preparation method of the photocatalytic composite material comprises the following steps: mixing and grinding two different metal salts and melamine or urea uniformly to obtain a mixed material; placing the mixed material in a reaction furnace in H2S and N2The mixed gas is roasted at constant temperature and then cooled to room temperature, and the photocatalytic composite material is prepared. The photocatalytic composite material has high-efficiency photoelectron capturing capability and rapid separation capability of photon-generated carriers, and is high-efficiency catalyticGreen novel catalyst with effect. The photocatalytic composite material is applied to photocatalytic decomposition of aquatic hydrogen, and is beneficial to improvement of photocatalytic hydrogen production efficiency. In addition, the preparation method of the photocatalytic composite material is simple and convenient.
Description
Technical Field
The invention belongs to the technical field of environmental materials, and particularly relates to a photocatalytic composite material as well as a preparation method and application thereof.
Background
At present, the problems of environmental pollution, energy shortage and the like present a trend of limiting the rapid development of society, protecting and improving the ecological environment, realizing the continuous development of human society, and are urgent and difficult tasks of all human beings. Solar energy is one of clean energy existing in nature, can promote water to be decomposed to generate hydrogen, and hydrogen is clean energy with the advantages of high energy density, environmental protection, renewability and the like and is considered to be one of the most potential clean energy for coping with environmental problems and energy crisis. The photocatalytic hydrogen production technology promotes water to be decomposed to generate hydrogen by utilizing clean energy, namely solar energy, existing in nature, is favored by global researchers due to the advantages of low cost, simple operation method, no need of specific equipment, strong practicability and the like, but has key technical problems in the aspects of low efficiency and the like, so that the research of seeking a novel green catalyst with high-efficiency catalytic effect and simple and convenient preparation method to improve the efficiency of photocatalytic hydrogen production becomes a research hotspot of the scientific community.
The metal sulfide is widely applied to the fields of hydrogen production by photolysis of water, pollutant degradation, photochemical synthesis and the like due to the narrow forbidden band width and good photoelectric property of the metal sulfide. Compared with other metal sulfides, the structure of the bimetallic sulfide has the advantages of higher controllability and more stable property. Recently, bimetallic sulfides AB represented by II-III-VI type2S4The (a ═ Zn, Cu, Cd, Mn, Ni, etc., and B ═ Cr, In, Ga, Fe, Bi, etc.) attracts great attention, and photocatalytic reaction performance can be enhanced by a method of changing the composition thereof.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a photocatalytic composite material and a preparation method and application thereof.
In order to achieve the above object, in one aspect, the present invention provides a photocatalytic composite material, wherein the photocatalytic composite material is an S, N-doped amorphous carbon/bimetallic sulfide photocatalytic composite material.
Another aspect of the present invention provides a method for preparing the photocatalytic composite material as described above, comprising:
step S10, mixing and grinding metal salt and melamine or urea uniformly to obtain a mixed material;
step S20, placing the mixed material in a reaction furnace, and reacting in a reaction furnace at H2S and N2The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the photocatalytic composite material.
Preferably, in step S10, the metal salt includes a first metal salt and a second metal salt, wherein the first metal salt is zinc nitrate, cadmium nitrate, copper nitrate, nickel nitrate, manganese chloride or copper chloride, and the second metal salt is indium nitrate, gallium nitrate, ferric nitrate, chromium nitrate or ferric chloride.
Further preferably, the molar ratio of the first metal salt to the second metal salt is 1: 2.
More preferably, in the step S10, the metal salt is 30 to 100 parts by mass, and the melamine or urea is 50 to 150 parts by mass.
Preferably, the step S20 specifically includes:
placing the mixed material in a high-temperature converter, and introducing H into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and roasting the mixture at a constant temperature to obtain a roasted productAnd (4) burning the product.
Further preferably, the temperature rise speed of the high-temperature converter is 5-20 ℃/min, the roasting temperature is 400-600 ℃, and the constant-temperature roasting time is 2-6 h.
Preferably, in the step S30, the temperature reduction rate of the roasted product is 5 ℃/min to 20 ℃/min, and the roasted product is reduced to room temperature.
Further preferably, said H2S and N2In the mixed gas of (2), H2The volume percentage of S is 10-100%; in the step S20, the H2S and N2The flow rate of the mixed gas is 20mL/min to 100 mL/min; in the step S30, the H2S and N2The flow rate of the mixed gas is 30mL/min to 60 mL/min.
The invention also provides application of the photocatalytic composite material in photocatalytic decomposition of hydrogen produced by water.
The S, N-doped amorphous carbon/bimetallic sulfide photocatalytic composite material provided by the embodiment of the invention has high-efficiency photoelectron capture capability and rapid separation capability of photon-generated carriers, and can enhance the photocatalytic reaction performance. Therefore, the composite material can improve the efficiency of photocatalytic hydrogen production, and is a novel green catalyst with high-efficiency catalytic effect. In addition, the preparation method of the photocatalytic composite material is simple and convenient.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a photocatalytic composite material in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a photocatalytic composite material, wherein the photocatalytic composite material is an S, N-doped amorphous carbon/bimetallic sulfide photocatalytic composite material.
In the process of generating hydrogen by decomposing water by photocatalysis, a photocatalyst dispersed in water is excited by illumination, electrons on a valence electron band jump to a conductive band to generate high-activity electron holes and valence electrons on the valence electron band respectively, and H in water is generated when the water contacts the photocatalyst+Reduced by high energy valence electrons to produce hydrogen.
The bimetal sulfide can effectively adjust the energy band structure by changing the composition of the bimetal sulfide, and the absorption range of light is widened. The amorphous carbon doped with S and N or the bimetallic sulfide photocatalytic composite material prepared by the invention has a good band gap structure by modifying the bimetallic sulfide through the amorphous carbon doped with the non-metal elements S and N, can widen the absorption range of the material to light and enhance the photocatalytic reaction performance of the material, and can effectively promote the rapid separation of electrons and holes of the catalyst material in the photocatalytic process by doping the non-metal elements such as boron, nitrogen, carbon, sulfur and the like, thereby further enhancing the photocatalytic performance of the composite material. Therefore, the photocatalytic composite material can be helpful to promoting water decomposition to generate hydrogen by utilizing light energy, improves the photocatalytic hydrogen production efficiency, and is a green novel catalyst with high-efficiency catalytic effect.
The embodiment of the present invention also provides a preparation method of the photocatalytic composite material, referring to fig. 1, the preparation method includes:
and step S10, mixing and grinding the metal salt and melamine or urea uniformly to obtain the mixed material.
Specifically, metal salt, melamine or urea are placed into a mortar according to a predetermined mass part ratio and are uniformly mixed and ground to obtain the mixed material. Wherein the grinding time is 10 min-30 min.
Preferably, the metal salt includes a first metal salt and a second metal salt, wherein the first metal salt is zinc nitrate, cadmium nitrate, copper nitrate, nickel nitrate, manganese chloride or copper chloride, and the second metal salt is indium nitrate, gallium nitrate, ferric nitrate, chromium nitrate or ferric chloride.
Further preferably, the molar ratio of the first metal salt to the second metal salt is 1: 2.
More preferably, in the step S10, the metal salt is 30 to 100 parts by mass, and the melamine or urea is 50 to 150 parts by mass.
The invention prepares the bimetallic sulfide by two different metal salts, and the expression general formula of the bimetallic sulfide is AB2S4Wherein, the metal element A is the metal element in the first metal salt, and the metal element B is the metal element in the second metal salt.
Step S20, placing the mixed material in a reaction furnace, and reacting in a reaction furnace at H2S and N2The mixed gas atmosphere of (2) is roasted to obtain a roasted product.
Specifically, the mixed material is placed in a high-temperature converter, and H is introduced into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
Preferably, the rotating speed of the high-temperature converter is 5 r/min-30 r/min, the heating speed of the high-temperature converter is 5 ℃/min-20 ℃/min, the roasting temperature is 400-600 ℃, and the constant-temperature roasting time is 2-6 h.
Further preferably, said H2S and N2In the mixed gas of (2), H2The volume percentage of S is 10-100%; said H2S and N2The flow rate of the mixed gas is 20mL/min to 100 mL/min.
Preferably, the waste gas generated in the reaction process of step S20 is countercurrent absorbed by lime water, the absorbed waste gas is evacuated after reaching the standard by detection, and the solid waste obtained by evaporating the waste liquid is sent to a third-party company for treatment.
Further preferably, the concentration of the lime water is 0.3-3.0 g/L, the flow rate of the lime water is 5-10L/min, and the flow rate of the waste gas absorbed by the lime water is 130-150 mL/min.
Step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the photocatalytic composite material.
Preferably, the cooling rate of the roasted product is 5-20 ℃/min, and the roasted product is cooled to room temperature.
Further preferably, said H2S and N2In the mixed gas of (2), H2The volume percentage of S is 10-100%; said H2S and N2The flow rate of the mixed gas is 30mL/min to 60 mL/min.
The preparation method of the S, N-doped amorphous carbon/bimetallic sulfide photocatalytic composite material provided by the invention is simple and convenient, the preparation cost is low, and the practicability is strong. And moreover, the waste gas generated in the reaction process is absorbed by lime water in a countercurrent way, and the absorbed waste gas is discharged after reaching the standard through detection, so that the damage of three-waste discharge to the ecological environment is reduced.
The embodiment of the invention also provides application of the photocatalytic composite material. The photocatalytic composite material can promote the photocatalytic decomposition of water to produce hydrogen, so that the photocatalytic hydrogen production efficiency is improved.
The above-mentioned photocatalytic composite material, its preparation method and application will be described with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above-mentioned photocatalytic composite material of the present invention, its preparation method and application, and are not intended to limit the entirety thereof.
Example 1
Step one, weighing 2mmol of zinc nitrate (Zn (NO)3)2·6H2O), 4mmol gallium nitrate (Ga (NO)3)3·xH2O) and 1.8g of melamine are placed in a mortar, the mixture is ground for about 10 minutes, and the mixed material is obtained after the mixture is uniformly mixed into a mud shape.
Step two, moving the mixed material into a combustion boat, conveying the mixed material into a high-temperature converter with the rotating speed of 10r/min, and introducing H2H with S volume fraction of 20% and flow rate of 15mL/min2S/N2And (3) removing air in the furnace from the mixed gas, heating to 550 ℃ at the speed of 10 ℃/min in the atmosphere, and roasting for 3 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using lime water of 5L/min, the absorbed waste gas is discharged after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, putting the roasted product in H2H with S volume fraction of 10% and flow rate of 30mL/min2S/N2Cooling to room temperature at a rate of 5 ℃/min in the mixed atmosphere, slightly grinding to powder after cooling to obtain S, N doped ZnGa2S4Composite materials, i.e. S, N doped amorphous carbon/ZnGa2S4A composite material.
The photocatalytic hydrogen production performance of the composite material is tested at 15 ℃: weighing 20mg of prepared photocatalytic composite material, placing the photocatalytic composite material in a three-mouth glass bottle with the capacity of 150mL containing magnetic particles, then placing 100mL of triethanolamine mixed aqueous solution sacrificial agent with the prepared volume fraction of 10% in the bottle upside down, and then adding 1% of Pt as a cocatalyst (Pt refers to a platinum simple substance and a noble metal, and the effect of the Pt in the generation of hydrogen gas through photocatalytic decomposition of water is mainly to transfer electrons and promote the separation of electron-hole, so the reaction rate of photocatalysis can be improved by adding Pt as the cocatalyst. Then nitrogen gas is introduced for 25min to ensure that residual gas in the glass bottle is discharged to prevent the experimental result from being influenced, and finally the three-mouth glass bottle is sealed. A xenon lamp provided with an optical filter capable of filtering lambda <420nm is used as a light source, three glass bottles are placed at a certain distance (the reaction center of the glass bottle is 10cm away from the light source) from the light source of the xenon lamp for illumination, the illumination time is 1 hour, a gas chromatograph is used for analyzing the concentration of the product hydrogen immediately after the reaction is finished, and the yield of the hydrogen is 1160 mu mol/(h.g).
Example 2:
step one, weighing 7.0mmol indium nitrate (In (NO)3)3·xH2O), 3.5mmol of cadmium nitrate (Cd (NO)3)2·4H2O) and 2g of urea are placed in a mortar, the mixture is ground for about 10 minutes, and the mixed material is obtained after the mixture is uniformly mixed into a mud shape.
Step two, moving the mixed material into a combustion boat, conveying the mixed material into a high-temperature converter with the rotating speed of 10r/min, and introducing H2H with S volume fraction of 25% and flow rate of 20mL/min2S/N2And (3) removing air in the furnace from the mixed gas, heating to 580 ℃ at the speed of 15 ℃/min in the atmosphere, and roasting for 3 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using lime water of 4L/min, the absorbed waste gas is discharged after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, putting the roasted product in H2H with S volume fraction of 25% and flow rate of 20mL/min2S/N2Cooling to room temperature at a rate of 5 ℃/min in the mixed atmosphere, slightly grinding to powder after cooling to obtain the S, N doped CdIn2S4Composite materials, i.e. S, N doped amorphous carbon/CdIn2S4A composite material.
And (3) carrying out photocatalytic hydrogen production performance test on the composite material at room temperature: weighing 50mg of the prepared photocatalytic composite material, placing the photocatalytic composite material into a three-opening glass bottle with the capacity of 100mL and containing magnetic particles, and then pouring 80mL of the prepared 0.35mol/LNa into the bottle2S and 0.25mol/L Na2SO3The sacrificial agent was mixed with nitrogen for 15min to ensure that the residual gas in the glass bottle was vented to prevent outgassingThe experimental result causes influence, and finally the three-mouth glass bottle is sealed. By means of arrangements capable of filtering λ<A xenon lamp with a 420nm optical filter is used as a light source, a three-mouth glass bottle is placed at a certain distance (the reaction center of the glass bottle is 15cm away from the light source) from the xenon lamp light source for illumination, the illumination time is 1 hour, a gas chromatograph is used for analyzing the concentration of the product hydrogen immediately after the reaction is finished, and the yield of the hydrogen is 1732 mu mol/(h.g).
Example 3:
step one, weighing 2.07mmol of zinc nitrate (Zn (NO)3)2·6H2O), 5.14mmol of indium nitrate (In (NO)3)3·xH2O) and 1.2g of melamine in a mortar, the mixture was ground for about 10 minutes, and a mixed material was obtained after the mixture was uniformly mixed in a slurry state.
Step two, moving the mixed material into a combustion boat, conveying the mixed material into a high-temperature converter at the rotating speed of 10r/min, and introducing H2H with S volume fraction of 10% and flow rate of 50mL/min2S/N2And (3) removing air in the furnace from the mixed gas, heating to 550 ℃ at the speed of 5 ℃/min in the atmosphere, and roasting for 3 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using 10L/min lime water, the absorbed waste gas is discharged after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, putting the roasted product in H2H with S volume fraction of 10% and flow rate of 30mL/min2S/N2Cooling to room temperature at a speed of 5 ℃/min in the mixed atmosphere, slightly grinding to powder after cooling to obtain the S, N doped amorphous carbon modified ZnIn2S4Composite materials, i.e. S, N doped amorphous carbon/ZnIn2S4A composite material.
And (3) carrying out photocatalytic hydrogen production performance test on the composite material at room temperature: weighing 25mg of the prepared photocatalytic composite material, placing the photocatalytic composite material into a three-opening glass bottle with the capacity of 100mL and containing magnetic particles, pouring 80mL of the prepared triethanolamine mixed aqueous solution sacrificial agent with the volume fraction of 10% into the bottle, introducing nitrogen for 25min to ensure that residual gas in the glass bottle is discharged to prevent the residual gas from influencing experimental results, and finally sealing the three-opening glass bottle. Xenon lamps equipped with filters capable of filtering λ <420nm were used as light sources. Placing the three-mouth glass bottle at a certain distance (the reaction center of the glass bottle is 10cm away from the light source) from the xenon lamp light source for illumination, wherein the illumination time is 1 hour, immediately analyzing the concentration of the product hydrogen by using a gas chromatograph after the reaction is finished, and measuring the hydrogen yield to be 2960 mu mol/(h.g).
Example 4:
step one, weighing 1.2mmol of manganese chloride (MnCl)2·4H2O), 2.4mmol of indium nitrate (In (NO)3)3·xH2O) and 1.5g of melamine in a mortar, and after grinding the mixture for about 10 minutes, obtaining a mixed material after the mixture is uniformly mixed into a slurry.
Step two, moving the mixed material into a combustion boat, conveying the mixed material into a high-temperature converter at the rotating speed of 10r/min, and introducing H2H with S volume fraction of 25% and flow rate of 20mL/min2S/N2And (3) removing air in the furnace from the mixed gas, heating to 550 ℃ at the speed of 10 ℃/min in the atmosphere, and roasting for 3 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using 8L/min lime water, the absorbed waste gas is discharged after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, putting the roasted product in H2H with S volume fraction of 10% and flow rate of 30mL/min2S/N2Cooling to room temperature at 10 deg.C/min in mixed atmosphere. Slightly grinding the mixture into powder after the temperature is reduced to obtain the S, N doped amorphous carbon modified MnIn2S4Composite materials, i.e. S, N doped amorphous carbon/MnIn2S4A composite material.
And (3) carrying out a photocatalytic hydrogen production performance test on the composite material at room temperature: weighing 10mg of the prepared photocatalyst, placing the photocatalyst into a three-opening glass bottle with the capacity of 200mL and containing magnetic particles, pouring 100mL of the prepared triethanolamine mixed aqueous solution sacrificial agent with the volume fraction of 10% into the bottle, introducing nitrogen for 25min to ensure that residual gas in the glass bottle is discharged to prevent the residual gas from influencing experimental results, and finally sealing the three-opening glass bottle. A xenon lamp provided with an optical filter capable of filtering lambda <420nm is used as a light source, a three-mouth glass bottle is placed at a certain distance (the reaction center of the glass bottle is 15cm away from the light source) from the light source of the xenon lamp for illumination, the illumination time is 1 hour, a gas chromatograph is used for analyzing the concentration of the product hydrogen immediately after the reaction is finished, and the hydrogen yield is 940 mu mol/(h.g).
The amorphous carbon modified bimetallic sulfide prepared by the invention has a good band gap structure by taking the carbon element in melamine or urea as a carbon source, can widen the absorption range of light, and is beneficial to promoting water decomposition to generate hydrogen by utilizing light energy. Therefore, the photocatalytic composite material can improve the efficiency of photocatalytic hydrogen production, and is a novel green catalyst with high-efficiency catalytic effect. The photocatalyst is applied to photocatalytic decomposition of hydrogen in aquatic products, and can promote photocatalytic decomposition of water to produce hydrogen, so that the photocatalytic hydrogen production efficiency is improved. In addition, the preparation method of the photocatalytic composite material is simple and convenient, the preparation cost is low, and the practicability is high.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. The photocatalytic composite material is characterized in that the photocatalytic composite material is an S, N doped amorphous carbon/bimetal sulfide photocatalytic composite material.
2. The method of preparing a photocatalytic composite material as set forth in claim 1, comprising:
step S10, mixing and grinding metal salt and melamine or urea uniformly to obtain a mixed material;
step S20, placing the mixed material in a reaction furnace, and reacting in a reaction furnace at H2S and N2The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the photocatalytic composite material.
3. The method of claim 2, wherein in the step S10, the metal salt includes a first metal salt and a second metal salt, wherein the first metal salt is zinc nitrate, cadmium nitrate, copper nitrate, nickel nitrate, manganese chloride or copper chloride, and the second metal salt is indium nitrate, gallium nitrate, ferric nitrate, chromium nitrate or ferric chloride.
4. The method of claim 3, wherein the molar ratio of the first metal salt to the second metal salt is 1: 2.
5. The method for preparing a photocatalytic composite material as set forth in any one of claims 2 to 4, wherein in step S10, the metal salt is 30 to 100 parts by mass, and the melamine or urea is 50 to 150 parts by mass.
6. The method for preparing a photocatalytic composite material as set forth in claim 2, wherein the step S20 specifically includes: placing the mixed material in a high-temperature converter, and introducing H into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
7. The method for preparing the photocatalytic composite material as set forth in claim 6, wherein the temperature rise speed of the high-temperature converter is 5 ℃/min to 20 ℃/min, and the baking temperature is 400 ℃ to 600 ℃.
8. The method for preparing a photocatalytic composite material as set forth in claim 2, wherein in step S30, the temperature of the baked product is lowered to room temperature at a rate of 5 ℃/min to 20 ℃/min.
9. The method for preparing a photocatalytic composite material according to any one of claims 6 to 8, wherein the H is2S and N2In the mixed gas of (2), H2The volume percentage of S is 10-100%; in the step S20, the H2S and N2The flow rate of the mixed gas is 20mL/min to 100 mL/min; in the step S30, the H2S and N2The flow rate of the mixed gas is 30mL/min to 60 mL/min.
10. Use of a photocatalytic composite material as set forth in claim 1 for photocatalytic decomposition of hydrogen produced from water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115532284A (en) * | 2022-10-14 | 2022-12-30 | 东莞理工学院 | Multi-element sulfide heterojunction microsphere, preparation method and application thereof, and photocatalytic hydrogen production method |
| CN115608388A (en) * | 2022-11-07 | 2023-01-17 | 吉林化工学院 | Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation method and application thereof |
| CN115739125A (en) * | 2022-11-28 | 2023-03-07 | 湖南工商大学 | Cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst and preparation method and application thereof |
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2021
- 2021-05-17 CN CN202110533315.2A patent/CN113457653A/en active Pending
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| XIAOJIN FU ET AL.: ""One-pot sulfurized synthesis of ZnIn2S4/S，N-codoped carbon composites for solar light driven water splitting"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 李建成 主编: "《基础应用化学》", 30 April 2000, 机械工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532284A (en) * | 2022-10-14 | 2022-12-30 | 东莞理工学院 | Multi-element sulfide heterojunction microsphere, preparation method and application thereof, and photocatalytic hydrogen production method |
| CN115608388A (en) * | 2022-11-07 | 2023-01-17 | 吉林化工学院 | Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation method and application thereof |
| CN115608388B (en) * | 2022-11-07 | 2023-11-24 | 吉林化工学院 | Shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, preparation method and application thereof |
| CN115739125A (en) * | 2022-11-28 | 2023-03-07 | 湖南工商大学 | Cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst and preparation method and application thereof |
| CN115739125B (en) * | 2022-11-28 | 2024-02-20 | 湖南工商大学 | Cobalt boride supported sulfur defect indium zinc sulfide photocatalyst and preparation method and application thereof |
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