CN109954509B - Preparation method and application of silicon carbide-based photocatalyst - Google Patents
Preparation method and application of silicon carbide-based photocatalyst Download PDFInfo
- Publication number
- CN109954509B CN109954509B CN201910377368.2A CN201910377368A CN109954509B CN 109954509 B CN109954509 B CN 109954509B CN 201910377368 A CN201910377368 A CN 201910377368A CN 109954509 B CN109954509 B CN 109954509B
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- mos
- sic
- suspension
- hydrogen production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 84
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000001291 vacuum drying Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910052961 molybdenite Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 4
- 239000002131 composite material Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 41
- 239000001257 hydrogen Substances 0.000 abstract description 41
- 238000004519 manufacturing process Methods 0.000 abstract description 36
- 239000003054 catalyst Substances 0.000 abstract description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 101001106045 Homo sapiens Regulator of nonsense transcripts 2 Proteins 0.000 description 2
- 102100021087 Regulator of nonsense transcripts 2 Human genes 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- NOIWSPXMNWKZPJ-UHFFFAOYSA-N 2-bromo-1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Br NOIWSPXMNWKZPJ-UHFFFAOYSA-N 0.000 description 1
- 101000579423 Homo sapiens Regulator of nonsense transcripts 1 Proteins 0.000 description 1
- 102100028287 Regulator of nonsense transcripts 1 Human genes 0.000 description 1
- 102100029938 Serine/threonine-protein kinase SMG1 Human genes 0.000 description 1
- 101710085356 Serine/threonine-protein kinase SMG1 Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a silicon carbide-based double-assistant hydrogen production photocatalyst, which comprises the following steps: a, pretreating silicon carbide; b, preparing a molybdenum disulfide suspension with the weight percent of 8 in the whole hydrothermal reaction system by taking molybdenum disulfide as a raw material; and c, putting 100mL of 8wt% molybdenum disulfide suspension into a beaker, sequentially adding silicon carbide (SiC), Graphene Oxide (GO) and 2 drops of 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, ultrasonically stirring to uniformly mix the materials, transferring the materials into a high-temperature reaction kettle, reacting for 20 hours at 200 ℃, then centrifugally washing until the pH value is =7, putting the materials into a vacuum drying oven, and drying in vacuum for later use. And carrying out hydro-thermal synthesis to obtain the silicon carbide-based double-assisted hydrogen production photocatalyst. The present invention utilizes GO and molybdenum disulfide (MoS)2) The silicon carbide-based double-assistant hydrogen production photocatalyst prepared by the synergistic effect of the double-assistant catalysts improves the performance of hydrogen production by photocatalytic decomposition of water by visible light, and can lay a certain foundation for the subsequent high-efficiency application of the visible light catalyst.
Description
Technical Field
The invention relates to a preparation method of a visible light photocatalyst, and particularly relates to a silicon carbide-based double-assisted hydrogen production photocatalyst and a preparation method thereof.
Background
At present, most of the known hydrogen-producing photocatalysts are TiO2The modified hydrogen-producing catalyst is modified on the basis, so that the modified hydrogen-producing catalyst meets the requirements of visible light photocatalysis hydrogen production and promotes the hydrogen production efficiency. The catalyst has a certain catalytic action, but the semiconductor material with narrow forbidden band width more meets the requirement of ultraviolet light photocatalysis hydrogen production. The SiC is used for preparing hydrogen by photocatalytic water splitting in view of good response of the SiC to visible light and the positions of a conduction band and a valence band of the SiC, which completely meet the requirement of water splitting by photolysis. But the defects of the method cause the method to have certain difficulty in photolyzing water, which is mainly shown in the following aspects: firstly, SiC has certain hydrophobicity, so that the SiC is difficult to contact with water molecules; and secondly, the electron holes are easy to recombine, so that the hydrogen production efficiency is low. Based on the defects, in order to improve the hydrogen production efficiency of SiC photocatalysis, the modification by using the cocatalyst is a common solution. The Yuanyxia topic group at present utilizes CdS and Pt to dope and modify SiC, and the hydrogen production rate is 259 mu mol.h-1g-1. However, Cd is a heavy metal and has a certain risk of secondary pollution, and Pt is a noble metal and has certain limitation on large-scale industrial application. Applicant utilizes MoS2Doping SiC by using coordination effect of Graphene Oxide (GO) double-promoter, and utilizing MoS2And the hydrogen production material of the SiC-based visible light catalyst is constructed by the advantages of GO so as to make up the defects of the SiC-based visible light catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon carbide-based double-assisted hydrogen production photocatalyst, wherein GO and MoS are introduced into the catalyst prepared by the method2As a double-promoter, SiC is modified by utilizing the synergistic effect of the double-promoter so as to improve the photocatalytic hydrogen production efficiency.
The technical solution adopted by the invention is as follows:
a preparation method of a silicon carbide-based photocatalyst specifically comprises the following steps:
(1) preparing pure SiC: roasting the SiC powder at high temperature, and naturally cooling to room temperature to remove impurity carbon; then the mass fraction isSoaking in 2% HF solution in sealed and light-proof condition to remove SiO2And other oxides; finally, repeatedly centrifuging and washing the SiC powder by using deionized water until the pH is =7, and placing the SiC powder in a vacuum drying oven to obtain pure SiC;
（2）MoS2suspension: mixing MoS2Placing in deionized water, and mixing uniformly to obtain MoS2A suspension;
(3) mixing: to MoS2Adding pure SiC, GO and ionic liquid into the suspension in sequence, and ultrasonically stirring to uniformly mix the pure SiC, the GO and the ionic liquid;
(4) preparing a silicon carbide-based double-promoter photocatalyst by a hydrothermal reaction: and (4) transferring the suspension obtained in the step (3) to a high-temperature reaction kettle, reacting at 200 ℃ for a period of time, then centrifugally washing until the pH is =7, and drying in vacuum to obtain the photocatalytic material.
Further, the roasting temperature in the step (1) is 600-800 ℃, preferably 700 ℃, the roasting time is 2-6h, preferably 5h, and the vacuum drying temperature is 60 ℃.
Further, in the hydrothermal system in the step (3), MoS is calculated by molybdenum element22-10% by weight, preferably 8%; the weight percentage of GO calculated by carbon element is 0.5-3%, preferably 2.5%.
Further, the ultrasonic stirring time in the step (3) is 10 hours, the hydrothermal reaction time in the step (4) is 20 hours, and the vacuum drying temperature is 60 ℃.
Further, the ionic liquid in step (3) includes, but is not limited to, one of 1-butyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole-tetrafluoroborate, bromo-1-butyl-3-methylimidazole and tetrafluoroborate-1-ethyl-3-methylimidazole.
The photocatalyst prepared by the method is applied to water photolysis, and the hydrogen production rate is 55 mu mol.h-1·g-1The above.
The beneficial technical effects of the invention are as follows:
MoS in the modification Process2As a layered transition metal sulfide, active S atoms of the layered transition metal sulfide are positioned at exposed edges, active sites for photocatalytic hydrogen production can be increased, and GO has a large surface areaAnd good electron transfer capacity, can improve the photocatalytic activity, and more importantly MoS2The catalyst and GO have a synergistic effect, so that the silicon carbide-based double-assisted hydrogen production photocatalyst has higher photocatalytic hydrogen production efficiency than silicon carbide and a silicon carbide-based single-assisted hydrogen production photocatalyst, and the synthesis method is simpler, is easy to operate and can be synthesized in one step.
Drawings
FIG. 1 shows MoS prepared according to the present invention2The XRD spectrogram of the silicon carbide-based double-assisted hydrogen production photocatalyst with variable load.
FIG. 2 is an XRD spectrogram of a GO-loading-variable silicon carbide-based double-assisted hydrogen production photocatalyst prepared by the method
FIG. 3 is a self-made photocatalytic reaction system.
FIG. 4 shows MoS prepared according to the present invention2And the silicon carbide-based double-assistant hydrogen production photocatalyst, pure silicon carbide and silicon carbide-based single-assistant hydrogen production photocatalyst with variable load capacity are shown in a 4-hour hydrogen production efficiency graph.
FIG. 5 is a 4h hydrogen production efficiency diagram of a silicon carbide-based double-assisted hydrogen production photocatalyst with variable GO loading prepared by the method.
FIG. 6 shows MoS prepared according to the present invention2The ultraviolet-visible diffuse reflection spectrogram of the silicon carbide-based double-assisted hydrogen production photocatalyst with variable load capacity and the pure silicon carbide.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
(1) Preparing pure SiC, namely placing SiC powder in a muffle furnace, roasting for 5 hours at 700 ℃, and naturally cooling to room temperature to remove impurity carbon; soaking in 2% HF solution in sealed dark condition for one night to remove SiO2And other oxides; repeatedly centrifuging and washing with deionized water for 11 times until pH =7, placing in a vacuum drying oven, and vacuum drying at 60 deg.C;
（2）MoS2suspension: 0.1741gMoS was added at room temperature2Placing the mixture in 100mL of deionized water, and uniformly mixing to obtain MoS2A suspension;
(3) mixing: to MoS at room temperature2In suspension in sequenceAdding 5.0g of pure SiC, 0.05gGO and 2 drops of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid, and stirring for 10 hours by ultrasonic waves to uniformly mix the materials;
(4) the silicon carbide-based double-assistant hydrogen production photocatalytic material is prepared by a hydrothermal synthesis method: and (3) placing the suspension subjected to ultrasonic treatment in a 300mL high-temperature reaction kettle, reacting at 200 ℃ for 20h, then centrifugally washing for 5 times until the pH =7, placing the suspension in a vacuum drying oven, and performing vacuum drying at 60 ℃ to obtain the SGM-2 photocatalytic material. MoS2The weight percentage of the catalyst in the hydrothermal reaction system is 2 percent (calculated by molybdenum element).
Example 2
This example removes MoS from step (2)2Is 0.4590gMoS2Otherwise, the same procedure as in example 1 was repeated to obtain an SGM-5 photocatalytic material; MoS2The weight percentage of the catalyst in the hydrothermal reaction system is 5 percent (calculated by molybdenum element).
Example 3
This example removes MoS from step (2)20.7769g MoS2Otherwise, the same procedure as in example 1 was repeated to obtain an SGM-8 photocatalytic material; MoS2The weight percentage of the catalyst in the hydrothermal reaction system is 8 percent (calculated by molybdenum element).
Example 4
This example removes MoS from step (2)2Is 1.01g MoS2Otherwise, the same procedure as in example 1 was repeated to obtain an SGM-10 photocatalytic material; MoS2The weight percentage of the catalyst in the hydrothermal reaction system is 10 percent (calculated by molybdenum element).
FIG. 1 is XRD spectra of pure SiC and silicon carbide-based double-assisted hydrogen-producing photocatalytic materials prepared in examples 1-4. As can be seen from fig. 1, the characteristic peaks of the other samples are shifted to the left compared to pure SiC, with SGM-8 being the most shifted and the intensity of the characteristic peak being the most enhanced. Thus, MoS2The change of the loading amount has the promotion effect on the growth of the SiC crystal form. The intensity of the characteristic peak of SGM-10 sample compared with SGM-8 sample is slightly weakened, indicating that MoS exists in the sample preparation process2The optimum load range. The sample SGM-8 has the best crystal form, and good crystallization can reduce the defects of semiconductor photocatalysis and is beneficial to the on-crystal generation of photon-generated carriersAnd the transfer between lattices can improve the photocatalytic activity.
Example 5
(1) Preparing pure SiC, namely placing SiC powder in a muffle furnace, roasting for 5 hours at 700 ℃, and naturally cooling to room temperature to remove impurity carbon; soaking in 2% HF solution in sealed dark condition for one night to remove SiO2 and other oxides; repeatedly centrifuging and washing with deionized water for 11 times until pH =7, placing in a vacuum drying oven, and vacuum drying at 60 deg.C;
（2）MoS2suspension: 0.7769g MoS was added at room temperature2Placing the mixture in 100mL of deionized water, and uniformly mixing to obtain MoS2A suspension;
(3) mixing: to MoS at room temperature2Adding 5.0g of pure SiC, 0.0583g of GO and 2 drops of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid into the suspension in sequence, and stirring for 10 hours by ultrasonic waves to uniformly mix the materials;
(4) the silicon carbide-based double-assistant hydrogen production photocatalytic material is prepared by a hydrothermal synthesis method: and (3) placing the suspension subjected to ultrasonic treatment in a 300mL high-temperature reaction kettle, reacting at 200 ℃ for 20h, then centrifugally washing for 5 times until the pH is =7, placing the suspension in a vacuum drying oven, and performing vacuum drying at 60 ℃ to obtain the SMG-1 photocatalytic material. The weight percentage of GO in the hydrothermal reaction system is 1% (calculated by carbon element).
Example 6
In this example, except that GO in step (3) is 0.0880gGO, the same procedure as in example 5 was repeated to obtain SMG-1.5 photocatalytic material; the mass percentage ratio of GO in the hydrothermal reaction system is 1.5% (calculated by carbon element).
Example 7
In the embodiment, except that GO in the step (3) is 0.1178gGO, the other steps are the same as those in the embodiment 5, so that the SMG-2 photocatalytic material is obtained; the weight percentage of GO in the hydrothermal reaction system is 2% (calculated by carbon element).
Example 8
In this example, except that GO in step (3) is 0.1481gGO, the same procedure as in example 5 was repeated to obtain SMG-2.5 photocatalytic material; the weight percentage of GO in the hydrothermal reaction system is 2.5% (calculated by carbon element).
Example 9
In this example, except that GO in step (3) is 0.1787gGO, the other steps are the same as those in example 5, and an SMG-3 photocatalytic material is obtained; the weight percentage of GO in the step (3) in the hydrothermal system is 3% (calculated by carbon element).
FIG. 2 is XRD spectra of pure SiC and the silicon carbide-based double-assisted hydrogen-producing photocatalytic materials prepared in examples 5-9. As can be seen from fig. 2, the characteristic peaks of the other samples are shifted to the right compared to pure SiC, with sample SMG-2.5 being shifted to the greatest extent and the characteristic peak intensity being enhanced to the greatest extent. Therefore, the change of GO loading has a promoting effect on the growth of SiC crystal forms. The intensity of the characteristic peak of sample SMG-3 compared to sample SMG-2.5 was slightly weaker and the degree of right shift decreased, indicating that there is a GO optimum loading range for the sample preparation process. The sample SMG-2.5 has the best crystal form, and good crystallization can reduce the defects of semiconductor photocatalysis and is beneficial to the transfer of photon-generated carriers in crystal lattices and among the crystal lattices, thereby improving the activity of photocatalysis.
Example 10
(1) Preparing pure SiC, namely placing SiC powder in a muffle furnace, roasting for 6 hours at the temperature of 600 ℃, and naturally cooling to room temperature to remove impurity carbon; soaking in 2% HF solution in sealed dark condition for one night to remove SiO2 and other oxides; repeatedly centrifuging and washing with deionized water for 11 times until pH =7, placing in a vacuum drying oven, and vacuum drying at 60 deg.C; (2) MoS2 suspension: 0.8g of MoS at room temperature2Placing the mixture in 100mL of deionized water, and uniformly mixing to obtain MoS2A suspension;
(3) mixing: at room temperature, sequentially adding 5.0g of pure SiC, 0.0583gGO and 2 drops of 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid into the MoS2 suspension, and ultrasonically stirring for 10 hours to uniformly mix the materials;
(4) the silicon carbide-based double-assistant hydrogen production photocatalytic material is prepared by a hydrothermal synthesis method: and (3) placing the suspension subjected to ultrasonic treatment in a 300mL high-temperature reaction kettle, reacting at 200 ℃ for 20h, then centrifugally washing for 5 times until the pH value is =7, placing the suspension in a vacuum drying oven, and performing vacuum drying at 60 ℃ to obtain the photocatalytic material.
Comparative example 1
Placing the SiC powder in a muffle furnace, roasting at 700 ℃ for 5h, naturally cooling to room temperature to remove impurity carbon, then sealing and soaking in 2% HF solution in dark place for one night to remove SiO2And other oxides; repeatedly centrifuging and washing with deionized water for 12 times until the pH is =7, placing in a vacuum drying oven, and vacuum drying at 60 ℃ to obtain pure SiC.
Comparative example 2
(1) Preparing pure SiC, namely placing SiC powder in a muffle furnace, roasting for 5 hours at 700 ℃, and naturally cooling to room temperature to remove impurity carbon; soaking in 2% HF solution in sealed dark condition for one night to remove SiO2And other oxides; repeatedly centrifuging and washing with deionized water for 11 times until pH =7, placing in a vacuum drying oven, and vacuum drying at 60 deg.C;
（2）MoS2suspension: 0.7769gMoS was added at room temperature2Placing the mixture in 100mL of deionized water, and uniformly mixing to obtain MoS2A suspension;
(3) mixing: at room temperature, 5.0g of pure SiC and 0.5898g of MoS are sequentially added into the molybdenum disulfide solution2(MoS calculated as molybdenum element)20.85 percent of hydrothermal system and 2 drops of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid are ultrasonically stirred for 10 hours to be uniformly mixed;
(4) preparing a SiC/M-8 hydrogen production photocatalytic material by a hydrothermal synthesis method: and (3) placing the suspension subjected to ultrasonic treatment in a 300mL high-temperature reaction kettle, reacting at 200 ℃ for 20h, then centrifugally washing for 5 times until the pH =7, placing the suspension in a vacuum drying oven, and performing vacuum drying at 60 ℃ to obtain the SiC/M-8 photocatalytic material.
Comparative example 3
(1) Preparing pure SiC, namely placing SiC powder in a muffle furnace, roasting for 3 hours at 700 ℃, and naturally cooling to room temperature to remove impurity carbon; soaking in 2% HF solution in sealed dark condition for one night to remove SiO2And other oxides; repeatedly centrifuging and washing with deionized water for 11 times until pH =7, placing in a vacuum drying oven, and vacuum drying at 60 deg.C;
(2) GO suspension: placing 0.4391gGO in 100mL of deionized water at room temperature, and uniformly mixing to obtain a GO suspension;
(3) at room temperature, sequentially adding 5.0g of pure SiC, 0.05gGO and 2 drops of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid into the GO suspension, and ultrasonically stirring for 10 hours to uniformly mix the materials;
(4) preparing a SiC/GO hydrogen production photocatalytic material by a hydrothermal synthesis method: and (3) placing the suspension subjected to ultrasonic treatment in a 300mL high-temperature reaction kettle, reacting for 20h at 200 ℃, then centrifuging and washing for 5 times until the pH value is =7, placing the suspension in a vacuum drying oven, and performing vacuum drying at 60 ℃ to obtain the SiC/GO photocatalytic material. The weight percentage of GO in the step (2) in the hydrothermal system is 8% (calculated by carbon element).
In a self-made photocatalytic reaction system (as shown in FIG. 3), 0.5g of the visible light photocatalyst prepared in examples 1-9 and comparative examples 2-3 was respectively weighed and dispersed in 100mL of a solution containing 0.1M Na2S·9H2O and 0.1M Na2SO3Is in aqueous solution of the sacrificial agent and the magnetic stirrer is turned on. Before light irradiation, N is introduced230min to ensure that the whole reaction system is in N2Under the protection of (3), after 4 hours, 1mL of gas was withdrawn with an airtight needle, and the amount of hydrogen produced was measured by gas chromatography. The hydrogen production efficiency after 4h is shown in fig. 4 and 5.
As can be seen from fig. 4 and 5, the hydrogen production efficiency of example 8 was the highest as compared with the hydrogen production efficiency of the other examples and comparative examples under the experimental conditions. By comparing the examples with comparative examples, it can be seen that GO and MoS2The double-promoter can improve the photocatalytic activity of SiC, thereby improving the hydrogen production efficiency.
The samples of examples 1-4 and comparative example 1 were characterized by uv-vis diffuse reflectance spectroscopy, respectively. The UV-visible diffuse reflectance spectrum is shown in FIG. 6.
As can be seen from fig. 6, in example, the absorption peak edge length was significantly red-shifted as compared with comparative example 1, and the red-shifts of example 3 and example 4 were close to each other.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes used in the present specification and applied to other related fields directly or indirectly are encompassed by the present invention.
Claims (5)
1. The preparation method of the silicon carbide-based photocatalyst is characterized by comprising the following steps:
(1) preparing pure SiC: roasting the SiC powder at high temperature, and naturally cooling to room temperature to remove impurity carbon; then soaking in HF solution with the mass fraction of 2% in a sealed and light-proof manner to remove SiO2And other oxides; finally, repeatedly centrifuging and washing the SiC powder by using deionized water until the pH is =7, and placing the SiC powder in a vacuum drying oven to obtain pure SiC;
（2）MoS2suspension: mixing MoS2Placing in deionized water, and mixing uniformly to obtain MoS2A suspension;
(3) mixing: to MoS2Adding pure SiC, GO and ionic liquid into the suspension in sequence, and ultrasonically stirring to uniformly mix the pure SiC, the GO and the ionic liquid;
(4) preparing a silicon carbide-based photocatalyst by a hydrothermal reaction: transferring the suspension obtained in the step (3) into a high-temperature reaction kettle, reacting for a period of time at 200 ℃, then centrifugally washing until the pH is =7, and drying in vacuum to obtain the photocatalytic material, wherein MoS is calculated by molybdenum in the hydrothermal reaction system22-10% of the total weight of the carbon-based composite material, wherein the weight percentage of GO is 0.5-3% calculated by carbon element;
the prepared photocatalyst is applied to the aspect of photolysis of water;
the ionic liquid in the step (3) is 1-butyl-3-methylimidazolium hexafluorophosphate.
2. The method as claimed in claim 1, wherein the calcination temperature in step (1) is 600-800 ℃, the calcination time is 2-6h, and the vacuum drying temperature is 60 ℃.
3. The method for preparing a silicon carbide-based photocatalyst according to claim 1, wherein the calcination temperature in the step (1) is 700 ℃ and the calcination time is 5 hours.
4. According to claim 1The preparation method of the silicon carbide-based photocatalyst is characterized in that MoS is calculated by molybdenum element in a hydrothermal reaction system2Is 8wt%, and the weight percentage of GO calculated by carbon element is 0.85 wt%.
5. The method for preparing the silicon carbide-based photocatalyst according to claim 1, wherein the ultrasonic stirring time in the step (3) is 10 hours, the hydrothermal reaction time in the step (4) is 20 hours, and the vacuum drying temperature is 60 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018114704465 | 2018-12-04 | ||
| CN201811470446.5A CN109453798A (en) | 2018-12-04 | 2018-12-04 | A kind of preparation method and application of silicon carbide-based photochemical catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109954509A CN109954509A (en) | 2019-07-02 |
| CN109954509B true CN109954509B (en) | 2021-11-02 |
Family
ID=65612347
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811470446.5A Pending CN109453798A (en) | 2018-12-04 | 2018-12-04 | A kind of preparation method and application of silicon carbide-based photochemical catalyst |
| CN201910377369.7A Active CN109926080B (en) | 2018-12-04 | 2019-05-04 | Visible light response hydrogen production photocatalyst GO/SiC/WO3Preparation method and application of |
| CN201910377368.2A Active CN109954509B (en) | 2018-12-04 | 2019-05-04 | Preparation method and application of silicon carbide-based photocatalyst |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811470446.5A Pending CN109453798A (en) | 2018-12-04 | 2018-12-04 | A kind of preparation method and application of silicon carbide-based photochemical catalyst |
| CN201910377369.7A Active CN109926080B (en) | 2018-12-04 | 2019-05-04 | Visible light response hydrogen production photocatalyst GO/SiC/WO3Preparation method and application of |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN109453798A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083339B (en) * | 2021-04-15 | 2022-11-08 | 万华化学(四川)有限公司 | Catalyst for preparing vitamin E and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110470A (en) * | 2004-10-14 | 2006-04-27 | Ueda Shikimono Kojo:Kk | Water cleaning agent |
| WO2008106300A2 (en) * | 2007-02-26 | 2008-09-04 | Envont Llc | Process for making photocatalytic materials |
| CN106587066A (en) * | 2016-11-23 | 2017-04-26 | 浙江大学 | Preparation method of ultrathin two-dimensional silicon carbide material |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101390619B1 (en) * | 2005-11-21 | 2014-04-30 | 나노시스, 인크. | Nanowire structures comprising carbon |
| DE102007028391A1 (en) * | 2007-06-15 | 2008-12-18 | Nano-X Gmbh | Particles or coating for splitting water |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102886270B (en) * | 2011-07-19 | 2016-01-13 | 中国科学院物理研究所 | SiC is nanocrystalline/Graphene hetero-junctions and preparation method and application |
| CN103011292A (en) * | 2012-12-04 | 2013-04-03 | 北京大学 | Nolybdenum disulfide nanometer particle, preparation method and application thereof |
| CN103111286B (en) * | 2013-01-22 | 2015-07-15 | 湖南元素密码石墨烯研究院（有限合伙） | Novel nano-composite visible light catalyst and preparation method thereof |
| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
| CN103280398B (en) * | 2013-05-30 | 2016-02-03 | 中国电子科技集团公司第十三研究所 | A kind of method preparing horizontal graphene PN junction |
| CN103638922B (en) * | 2013-12-13 | 2015-06-24 | 南通职业大学 | Preparation method of mesoporous tungsten trioxide/reduction-oxidation graphene composite photocatalyst |
| CN104291339B (en) * | 2014-09-29 | 2016-08-17 | 浙江大学 | A kind of preparation method of ultra-thin carbofrax material |
| CN104307536B (en) * | 2014-10-22 | 2016-12-07 | 上海大学 | Ternary Z-type visible ray photolytic hydrogen production catalyst and preparation method thereof |
| CN104495811B (en) * | 2014-12-12 | 2017-01-11 | 盐城市新能源化学储能与动力电源研究中心 | Graphene composite material and preparation method thereof |
| CN104785268A (en) * | 2015-01-30 | 2015-07-22 | 山东科技大学 | Magnetic Ce1-xSmxO2-delta/attapulgite nano composite preparation method |
| CN105013531A (en) * | 2015-07-02 | 2015-11-04 | 济南大学 | Preparation of silicon nitride-loaded ionic liquid-mounting nano palladium catalyst |
| CN105891298A (en) * | 2016-06-28 | 2016-08-24 | 集美大学 | Preparation method and application of repeatedly usable graphene ionic liquid electrode |
| CN106248747A (en) * | 2016-06-29 | 2016-12-21 | 燕园众欣纳米科技（北京）有限公司 | A kind of preparation method of Graphene mesoporous indium oxide nano composite material |
| CN106564887B (en) * | 2016-11-01 | 2018-12-28 | 日照鲁光电子科技有限公司 | A kind of graphene semiconductor composite material and preparation method |
| CN106654300B (en) * | 2016-12-19 | 2019-06-25 | 中国科学院山西煤炭化学研究所 | A kind of electrochemistry swelling graphite prepares single dispersion metal atom/graphene composite material method |
| CN107189493A (en) * | 2017-04-10 | 2017-09-22 | 桂林理工大学 | A kind of preparation method of ion liquid modified graphene |
| CN107913717B (en) * | 2017-11-27 | 2020-08-25 | 大连理工大学 | Preparation method and application of catalytic electrode for pollution control |
| CN108745412B (en) * | 2018-04-13 | 2021-02-23 | 青岛科技大学 | Ionic liquid functionalized graphene oxide and preparation method and application thereof |
| CN108615869B (en) * | 2018-05-18 | 2021-05-14 | 浙江美都海创锂电科技有限公司 | Preparation and application of oxide-coated nitrogenated graphene loaded nickel-cobalt-manganese positive electrode material |
| CN108845010A (en) * | 2018-06-25 | 2018-11-20 | 上海健康医学院 | Ionic liquid auxiliary synthesis of carbon/molybdenum disulfide and graphene oxide composite material are for detecting chloramphenicol |
-
2018
- 2018-12-04 CN CN201811470446.5A patent/CN109453798A/en active Pending
-
2019
- 2019-05-04 CN CN201910377369.7A patent/CN109926080B/en active Active
- 2019-05-04 CN CN201910377368.2A patent/CN109954509B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110470A (en) * | 2004-10-14 | 2006-04-27 | Ueda Shikimono Kojo:Kk | Water cleaning agent |
| WO2008106300A2 (en) * | 2007-02-26 | 2008-09-04 | Envont Llc | Process for making photocatalytic materials |
| CN106587066A (en) * | 2016-11-23 | 2017-04-26 | 浙江大学 | Preparation method of ultrathin two-dimensional silicon carbide material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109453798A (en) | 2019-03-12 |
| CN109954509A (en) | 2019-07-02 |
| CN109926080B (en) | 2021-08-27 |
| CN109926080A (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106914263B (en) | Preparation method of composite visible light catalyst | |
| CN112371105B (en) | Niobium pentoxide/titanium dioxide composite photocatalyst and preparation method and application thereof | |
| CN110586160A (en) | Preparation method of cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN112023938B (en) | Bimetallic ion doped nano composite photocatalyst and preparation method thereof | |
| CN111151275B (en) | MoS 2 /Mo 2 C Complex, MoS 2 /Mo 2 C/CdS composite material and preparation method and application thereof | |
| CN106076390A (en) | A kind of preparation method of titanium dioxide/graphite phase carbon nitride composite photo-catalyst | |
| CN114308079A (en) | Cadmium sulfide-double-cocatalyst composite photocatalytic material and preparation method and application thereof | |
| CN111672528A (en) | Modified carbon nitride photocatalyst and preparation method and application thereof | |
| CN114682241B (en) | Titanium dioxide-aluminum oxide composite desulfurization catalyst and preparation method and application thereof | |
| CN107175097B (en) | A kind of stannic disulfide package titanium dioxide composite photocatalyst and preparation method thereof | |
| CN115999614A (en) | Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst | |
| CN108479859A (en) | Composite photocatalyst material and the preparation method and application thereof is converted on praseodymium doped cerium fluoride/attapulgite | |
| CN109382088B (en) | SnO2/α～Bi2O3/β～Bi2O3Composite material and preparation method thereof | |
| CN109954509B (en) | Preparation method and application of silicon carbide-based photocatalyst | |
| CN109158117B (en) | Full-spectrum-response double-doped lanthanum fluoride/attapulgite up-conversion composite photocatalytic material and preparation method and application thereof | |
| CN107961785B (en) | Preparation method and application of high-activity bismuth chromate nano photocatalyst | |
| CN107970951B (en) | Preparation method of flower-like mesoporous structure CdS-ZnO composite material | |
| CN106732587B (en) | A kind of preparation method of the ZnO polycrystal nanobelt package assembly of high H2-producing capacity atomic state Ag modification | |
| CN111484074A (en) | Preparation method of photo-thermal enhanced photo-catalytic black titanium dioxide material | |
| CN115569658A (en) | CABB/UCNT heterojunction composite photocatalyst and preparation method and application thereof | |
| CN102179260B (en) | Multi-component doped photocatalytic material and preparation method thereof | |
| CN112619669B (en) | Nickel ion doped zinc oxide/cadmium sulfide high-performance water decomposition hydrogen production photocatalyst and preparation method thereof | |
| CN110116014A (en) | A kind of N-TiO with hollow structure2Photochemical catalyst preparation method | |
| CN112871165A (en) | Two-dimensional WO modified by noble metal loading3Preparation method of nanosheet photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |