CN109675596A - Titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method and application - Google Patents
Titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method and application Download PDFInfo
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- CN109675596A CN109675596A CN201910069006.7A CN201910069006A CN109675596A CN 109675596 A CN109675596 A CN 109675596A CN 201910069006 A CN201910069006 A CN 201910069006A CN 109675596 A CN109675596 A CN 109675596A
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- titanium carbide
- titanium
- titanium dioxide
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- molybdenum
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 184
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 35
- 239000011733 molybdenum Substances 0.000 claims abstract description 35
- 238000004073 vulcanization Methods 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000013049 sediment Substances 0.000 claims description 25
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 241000446313 Lamella Species 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 73
- 229960005196 titanium dioxide Drugs 0.000 description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000002055 nanoplate Substances 0.000 description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006303 photolysis reaction Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- -1 titanium dioxide molybdenum sulfide Chemical compound 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- CNNJSHYPMMLNPU-UHFFFAOYSA-N [S].[Ti].[Mo] Chemical compound [S].[Ti].[Mo] CNNJSHYPMMLNPU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
-
- B01J35/23—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalyst technology field more particularly to titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method and applications.The composite material include the titanium carbide of sheet, the titanium dioxide of nano-sheet, nanometer plaque-like molybdenum sulfide, the molybdenum sulfide its by 1T and 2H mixing phase composition；Wherein, the titanium dioxide of the nano-sheet is interspersed is grown on the titanium carbide of sheet, the molybdenum sulfide of the nanometer plaque-like be distributed in the titanium carbide of sheet, nano-sheet titanium dioxide surface.Titanium carbide/titanium dioxide/vulcanization molybdenum composite material produced by the present invention is double co-catalysts of non precious metal, and the transmission of light induced electron and the separation of photo-generate electron-hole pairs are effectively facilitated, photocatalysis effect is significantly improved, is a kind of high efficiency photocatalyst haveing excellent performance.
Description
Technical field
The present invention relates to photocatalyst technology fields, specifically, being related to titanium carbide/titanium dioxide/vulcanization molybdenum composite material
And its preparation method and application.
Background technique
With the worsening of global fossil energy rapidly depleted with environment, environmental-friendly, low in cost, resource is developed
Renewable energy abundant has become the urgent problem to be solved of facing mankind.As a kind of environmentally friendly energy, hydrogen
Calorific value it is high, be readily transported, be renewable, thus convert solar energy into Hydrogen Energy be the optimal method to tap a new source of energy it
One.Photolysis water hydrogen can directly utilize decomposing water with solar energy hydrogen making, not consume other energy, and to environment without dirt
Dye, by the extensive concern of researcher, becomes optimal hydrogen manufacturing approach.TiO2Because have stable photoelectrochemical behaviour,
The excellent properties such as low in cost, corrosion-resistant, redox ability is strong, become one of most promising photochemical catalyst.
In photochemical catalyzing, co-catalyst is essential auxiliary substances in photocatalytic water, it can promote light
The transmission of raw electronics and the separation of electron hole pair, it is effective to improve photocatalytic water efficiency.But co-catalysis commonly used at present
Agent is noble metal platinum, gold etc., it is presently believed that due to factors, the new co-catalyst of development utilization such as it is expensive, yield is few
It is very necessary.Ideal photochemical catalyst can decompose water under the conditions of non precious metal co-catalyst, while generate hydrogen or oxygen,
And catalyst itself should be nontoxic, pollution-free, not to environmental concerns.
Summary of the invention
For some problem and shortage existing for above-mentioned, the present invention is intended to provide titanium carbide/titanium dioxide/molybdenum sulfide is multiple
Condensation material and its preparation method and application.Titanium carbide/titanium dioxide/vulcanization molybdenum composite material produced by the present invention is non precious metal
Double co-catalysts, and effectively facilitated the transmission of light induced electron and the separation of photo-generate electron-hole pairs, significantly improved light
Catalytic effect is a kind of high efficiency photocatalyst haveing excellent performance.
The first object of the present invention is to provide titanium carbide/titanium dioxide/vulcanization molybdenum composite material.
The second object of the present invention is to provide the preparation method of the titanium carbide/titanium dioxide/vulcanization molybdenum composite material.
The third object of the present invention is to provide the titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method
Application.
For achieving the above object, the invention discloses following technical proposals:
Firstly, the present invention discloses titanium carbide/titanium dioxide/vulcanization molybdenum composite material, the composite material includes sheet
Titanium carbide, the titanium dioxide of nano-sheet, nanometer plaque-like molybdenum sulfide, the molybdenum sulfide its by 1T and 2H mixing phase composition；
Wherein, the titanium dioxide of the nano-sheet is interspersed is grown on the titanium carbide of sheet, the molybdenum sulfide point of the nanometer plaque-like
Cloth is on the surface of the titanium carbide of sheet, the titanium dioxide of nano-sheet.
This composite material of the invention is since titanium dioxide nanoplate is plugged in titanium carbide lamella, 1T and 2H mixed phase
Molybdenum sulfide nanometer spot is distributed in titanium carbide lamella and titanium dioxide nanoplate surface, to constitute 3-D heterojunction structure, is carbonized
Titanium sheet layer and 1T phase molybdenum sulfide have superior electrical conductivity, are conducive to the transmission of electronics, the 2H phase of molybdenum sulfide can also be with titanium dioxide
Titanium constructs the molecule that heterojunction structure promotes photo-generate electron-hole, to enhance the photocatalysis effect of titanium dioxide nanoplate.
Further, the ratio of the titanium carbide, titanium dioxide, molybdenum sulfide are as follows: 6:4:1.5.
The nanometer spot molybdenum sulfide refers to: nanometer spot (nanopatches) refers to the molybdenum sulfide that image patch point is equally distributed, this
The molybdenum sulfide of kind shape has more inactive edge positions.
Titanium carbide is a kind of two-dimentional transition metal carbide, it is due to hydrophilic surface, good electron conduction
And possess the unique lamellar structure of large specific surface area, just because of the good electric conductivity of titanium carbide, and possess big ratio
The unique lamellar structure of surface area, therefore it has the potentiality as good co-catalyst.Again due to the 1T gold in molybdenum sulfide
Symbolic animal of the birth year has good electric conductivity, and 2H phase is that semiconductor Xiang Keyu titanium dioxide forms heterojunction structure.This bimetallic, which helps, urges
The presence of agent, so that titanium carbide lamella/titanium dioxide nanoplate/1T and 2H mixed phase molybdenum sulfide nanometer spot composite material has
Excellent photocatalytic water hydrogen-producing speed.Therefore, the present invention carries out 1T and 2H mixed phase molybdenum sulfide with titanium dioxide, titanium carbide organic
In conjunction with the unique effect and mutual effect of these components being made full use of, to obtain with efficient photocatalytic water effect
Ideal photochemical catalyst, to realize application of the composite material prepared by the present invention in terms of photolysis water hydrogen.
The layer structure of molybdenum sulfide shows its huge specific surface area, and more active site makes it have good
Absorption property also provides possibility for the fast transferring of electronics, and there are mainly three types of crystal form forms for molybdenum sulfide: semiconductor 2H phase and gold
Belong to 1T phase.Furthermore molybdenum sulfide pattern also will affect the performance of photocatalytic water.
Secondly, the preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material of the present invention, includes the following steps:
(1) by with MXene material structure titanium carbide, containing the hydrochloric acid solution of sodium fluoborate, deionization is added jointly
It is stirred in water, prepares the first mixed liquor；
(2) by the first mixed liquor of step (1) into 5~20h of hydro-thermal reaction at 100~200 DEG C, preparation second is mixed
Liquid；
(3) the second mixed liquor of filtration step (2) obtains titanium carbide/composite titania material, by titanium carbide/titanium dioxide
Titanium composite material and molybdenum trioxide solution containing potassium rhodanide, common be added in deionized water are stirred, and third mixed liquor is prepared；
(4) by the third mixed liquor of step (3) at 150~250 DEG C 10~30h of hydro-thermal reaction, prepare the 4th mixed liquor；
(5) the 4th mixed liquor of filtration step (4) obtains sediment one, obtained sediment one is washed with water, then
Sediment one after washing is dried under vacuum conditions, can be prepared by titanium carbide/titanium dioxide/vulcanization molybdenum composite material.
The titanium carbide with MXene material structure refers to what utilization was prepared by corroding the material with MAX phase
MXene material titanium carbide, for example, corroding Ti in room temperature in HF aqueous solution3AlC2, Al atom is removed to the property of can choose, thus
The titanium carbide for having laminar structured is obtained, the titanium carbide of this structure possesses the unique lamellar structure of bigger serface, can
Express passway is provided with the transfer for electronics in catalytic process, to significantly promote catalytic capability and catalytic efficiency.
In step (1), the adding proportion of the titanium carbide, hydrochloric acid solution containing sodium fluoborate are as follows: titanium carbide: fluoboric acid
Sodium: hydrochloric acid=50-150mg:5-15mg:5-15mmol.
In step (1), in the hydrochloric acid solution containing sodium fluoborate, the concentration of hydrochloric acid is 1mol/L.
In step (1), the stirring includes magnetic agitation, mixing time 10-30min.
Further, in step (2), 160 DEG C of the temperature of the hydro-thermal reaction, time 129h.
In step (2), in the molybdenum trioxide solution containing potassium rhodanide, molybdenum element and titanium carbide/titanium dioxide are multiple
The mass ratio of condensation material is (0.1~0.3): 1；Preferably 0.15:1.
In step (3), the stirring includes magnetic agitation, mixing time 10-60min.
Further, in step (4), 200 DEG C of the temperature of the hydro-thermal reaction, time 18h.
In step (5), the condition of the drying is to keep the temperature 10-14h at 60-80 DEG C.
Finally, the present invention discloses the titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method in photocatalysis
Application in field, the application especially in photochemical catalyzing；Because the composite catalyzing object proposed by the present invention is tool
There are the double co-catalysts of non precious metal, has efficient photodissociation outlet capacity.
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) it for preparation process, is received firstly, the present invention obtains titanium carbide/titanium dioxide by first time hydro-thermal reaction
Rice piece composite material, wherein titanium dioxide nanoplate is interspersed to be grown in lamellar titanium carbide structure, and then, the present invention passes through
Hydro-thermal reaction obtains the molybdenum sulfide of titanium carbide lamella and the attachment 1T and 2H mixing phase composition of titanium dioxide nanoplate surface again
The composite material of nanometer spot, since 1T phase is that metal phase has preferable electric conductivity, 2H phase is semiconductor Xiang Keyu titanium dioxide
Heterojunction structure is formed, when the composite material of this bimetallic mixed phase is as co-catalyst, imparts excellent photodissociation aquatic products
Hydrogen rate.
(2) it for aspect of performance, is tested by the specific embodiment of the invention, titanium carbide/dioxy prepared by the present invention
Change titanium/vulcanization molybdenum composite material relative to simple titanium dioxide and titanium carbide/composite titania material, either in photodissociation
In terms of aquatic products hydrogen amount, or in terms of photocatalytic water hydrogen-producing speed, have greatly improved, it was demonstrated that titanium carbide of the invention/
Significant advantage of the titanium dioxide/vulcanization molybdenum composite material in the application of photocatalytic water.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the scanning electron microscope (SEM) photograph of titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in the embodiment of the present invention 2.
Fig. 2 transmits electricity for the low power of titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in the embodiment of the present invention 2
Mirror figure.
Fig. 3 transmits electricity for the high power of titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in the embodiment of the present invention 2
Mirror figure.
Fig. 4 is titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in 1-4 of the embodiment of the present invention, be carbonized titanium sheet
Layer/titanium dioxide nanoplate composite material and titanium dioxide nanoplate the photocatalytic water hydrogen output figure under simulated solar irradiation irradiation.
Fig. 5 is titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in 1-4 of the embodiment of the present invention, be carbonized titanium sheet
Layer/titanium dioxide nanoplate composite material and titanium dioxide nanoplate the photocatalytic water hydrogen-producing speed under simulated solar irradiation irradiation
Figure.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As described in background, due to factors, the new co-catalyst of development utilization such as it is expensive, yield is few
It is very necessary.Ideal photochemical catalyst can decompose water under the conditions of non precious metal co-catalyst, while generate hydrogen or oxygen,
And catalyst itself should be nontoxic, pollution-free, not to environmental concerns.Therefore, the invention proposes titanium carbide/titanium dioxides
Titanium/molybdenum sulfide composite material and preparation method and application, now in conjunction with the drawings and specific embodiments to the present invention further into
Row explanation.
In the following example, test titanium dioxide used in photocatalytic water hydrogen output and hydrogen-producing speed under simulated solar irradiation irradiation
Titanium nanometer sheet be it is commercially available, be purchased from Chinese medicines group.
In following embodiments, the raw material of use include: hydrofluoric acid solution, titanium aluminium carbon dust, hydrochloric acid solution, sodium fluoborate,
Molybdenum trioxide, potassium rhodanide and deionized water.
Used equipment include: for mixed beaker, magnetic stirring apparatus, hydrothermal reaction kettle, scanning electron microscope,
Transmission electron microscope and gas-chromatography photocatalytic activity evaluation system.
As a kind of exemplary embodiments of the invention, it includes as follows for preparing titanium carbide/titanium dioxide/vulcanization molybdenum composite material
Step:
(1) hydrofluoric acid solution and titanium aluminium carbon dust are mixed with the first mixed liquor；Then the first mixed liquor is filtered to incite somebody to action
To sediment one；
It should be noted that this step is prepared in such a way that hydrofluoric acid is by etching with MXene material structure
The process of titanium carbide, the present invention are only to provide a kind of specific illustrative methods, in order to which technical staff understands the present invention, show
So, it realizes the method that the purpose of this step is not limited to the offer of this step, such as can also adopt and prepare this with other methods
Kind titanium carbide, or use the commercially available carbonization titanium products for meeting above-mentioned requirements.
(2) starch one and hydrochloric acid solution containing sodium fluoborate are added in deionized water and prepare the second mixed liquor；
(3) the second mixed liquor is placed in hydro-thermal reaction in hydrothermal reaction kettle and prepares third mixed liquor；
(4) filtering third mixed liquor will obtain sediment two, and sediment two and molybdenum trioxide containing potassium rhodanide is molten
Liquid is added to deionized water and prepares the 4th mixed liquor；
(5) the 4th mixed liquor is placed in hydro-thermal reaction in hydrothermal reaction kettle and prepares the 5th mixed liquor；
(6) the 5th mixed liquor of filtering will obtain sediment three, dried after washing precipitate three to get.
(7) step (6) is finally obtained by scanning electron microscope, transmission electron microscope and gas-chromatography photocatalytic activity evaluation system
Product carry out observation analysis and performance test.
Embodiment 1
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, includes the following steps:
(1) hydrofluoric acid solution that 100 milliliters of mass fractions are 40% is measured, 1 gram of titanium aluminium carbon dust is weighed, by hydrofluoric acid
Solution and titanium aluminium carbon dust, which are sufficiently mixed, is stirred at room temperature 72 hours the first mixed liquors of preparation；Then the first mixed liquor is filtered,
Obtained sediment is the titanium carbide with MXene material structure, and the titanium carbide is multi-layer sheet structure, and granularity about exists
200 mesh；
(2) titanium carbide of 100 milligrams of steps (1) and 10 milligrams of sodium fluoborates are added to 10 milliliters of concentration is 1mol/L's
In hydrochloric acid solution, magnetic agitation 30 minutes the second mixed liquors of preparation；
(3) the second mixed liquor of step (2) is placed in hydrothermal reaction kettle, hydro-thermal reaction 12 hours at 160 DEG C, is prepared
Third mixed liquor；Then filtering third mixed liquor will obtain sediment, as titanium carbide/titanium dioxide nanoplate composite material；
(4) sediment for taking 60 milligrams of steps (3), by itself and 5.4 milligrams of molybdenum trioxide solution and 15.4 milligrams of thiocyanic acids
Potassium is added in deionized water, magnetic agitation 60 minutes, prepares the 4th mixed liquor；
(5) the 4th mixed liquor of step (4) is placed in hydrothermal reaction kettle, hydro-thermal reaction 18 hours at 200 DEG C, is prepared
5th mixed liquor；
(6) the 5th mixed liquor of filtration step (5) will obtain sediment and be washed with deionized, then in 60 DEG C of vacuum
Dry 12 hours to get.
Embodiment 2
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, with embodiment 1, difference is: step
(4) in, the sediment of 60 milligrams of steps (3) is taken, it is added with 8.1 milligrams of molybdenum trioxide solution and 23.15 milligrams of potassium rhodanides
It is added in deionized water, magnetic agitation 60 minutes, prepares the 4th mixed liquor.
Embodiment 3
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, with embodiment 1, difference is: step
(4) in, the sediment of 60 milligrams of steps (3) is taken, it is added with 13.5 milligrams of molybdenum trioxide solution and 38.6 milligrams of potassium rhodanides
It is added in deionized water, magnetic agitation 60 minutes, prepares the 4th mixed liquor.
Embodiment 4
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, with embodiment 1, difference is: step
(4) in, the sediment of 60 milligrams of steps (3) is taken, it is added with 16.2 milligrams of molybdenum trioxide solution and 46.3 milligrams of potassium rhodanides
It is added in deionized water, magnetic agitation 60 minutes, prepares the 4th mixed liquor.
Embodiment 5
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, includes the following steps:
(1) hydrofluoric acid solution that 100 milliliters of mass fractions are 50% is measured, 5 grams of titanium aluminium carbon dust is weighed, by hydrofluoric acid
Solution and titanium aluminium carbon dust, which are sufficiently mixed, is stirred at room temperature 72 hours the first mixed liquors of preparation；Then the first mixed liquor is filtered,
Obtained sediment is the titanium carbide with MXene material structure, and the titanium carbide is multi-layer sheet structure；
(2) titanium carbide of 150 milligrams of steps (1) and 5 milligrams of sodium fluoborates are added to 15 milliliters of concentration is 1mol/L's
In hydrochloric acid solution, magnetic agitation 10 minutes the second mixed liquors of preparation；
(3) the second mixed liquor of step (2) is placed in hydrothermal reaction kettle, hydro-thermal reaction 5 hours at 200 DEG C, is prepared
Third mixed liquor；Then filtering third mixed liquor will obtain sediment, as titanium carbide/titanium dioxide nanoplate composite material；
(4) sediment for taking 60 milligrams of steps (3), by itself and 5.4 milligrams of molybdenum trioxide solution and 15.4 milligrams of thiocyanic acids
Potassium is added in deionized water, magnetic agitation 60 minutes, prepares the 4th mixed liquor；
(5) the 4th mixed liquor of step (4) is placed in hydrothermal reaction kettle, hydro-thermal reaction 30 hours at 150 DEG C, is prepared
5th mixed liquor；
(6) the 5th mixed liquor of filtration step (5) will obtain sediment and be washed with deionized, then in 80 DEG C of vacuum
Dry 10 hours to get.
Embodiment 6
A kind of preparation method of titanium carbide/titanium dioxide/vulcanization molybdenum composite material, includes the following steps:
(1) hydrofluoric acid solution that 100 milliliters of mass fractions are 40% is measured, 3 grams of titanium aluminium carbon dust is weighed, by hydrofluoric acid
Solution and titanium aluminium carbon dust, which are sufficiently mixed, is stirred at room temperature 72 hours the first mixed liquors of preparation；Then the first mixed liquor is filtered,
Obtained sediment is the titanium carbide with MXene material structure, and the titanium carbide is multi-layer sheet structure；
(2) titanium carbide of 50 milligrams of steps (1) and 15 milligrams of sodium fluoborates are added to the salt that 5 milliliters of concentration are 1mol/L
In acid solution, magnetic agitation 10 minutes the second mixed liquors of preparation；
(3) the second mixed liquor of step (2) is placed in hydrothermal reaction kettle, hydro-thermal reaction 20 hours at 100 DEG C, is prepared
Third mixed liquor；Then filtering third mixed liquor will obtain sediment, as titanium carbide/titanium dioxide nanoplate composite material；
(4) sediment for taking 60 milligrams of steps (3), by itself and 5.4 milligrams of molybdenum trioxide solution and 15.4 milligrams of thiocyanic acids
Potassium is added in deionized water, magnetic agitation 10 minutes, prepares the 4th mixed liquor；
(5) the 4th mixed liquor of step (4) is placed in hydrothermal reaction kettle, hydro-thermal reaction 10 hours at 250 DEG C, is prepared
5th mixed liquor；
(6) the 5th mixed liquor of filtration step (5) will obtain sediment and be washed with deionized, then in 70 DEG C of vacuum
Dry 14 hours to get.
Performance test
(1) titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in embodiment 2 is observed under scanning electron microscope, is tied
Fruit is as shown in Figure 1, as can be seen from the figure: titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained includes the carbon of sheet
Change titanium, nano-sheet titanium dioxide and load on titanium dioxide molybdenum sulfide composition.
(2) titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained in embodiment 2 is carried out under transmission electron microscope picture
Low power and high power observation, as a result respectively as shown in Figure 2,3, it can be seen that titanium carbide/titanium dioxide/sulphur obtained from Fig. 2,3
Change molybdenum composite material include the titanium carbide of sheet, the titanium dioxide of nano-sheet, nanometer plaque-like molybdenum sulfide, the molybdenum sulfide
It is by 1T and 2H mixing phase composition；Wherein, the titanium dioxide nanoplate with a thickness of 75~100nm, width is 300~
500nm, the molybdenum sulfide diameter of nanometer plaque-like are 5-15nm；Moreover, the titanium dioxide of the nano-sheet is interspersed to be grown in lamella
On the titanium carbide of shape, the molybdenum sulfide of the nanometer plaque-like be distributed in the titanium carbide of sheet, nano-sheet titanium dioxide table
Face；This is because: (1) the present embodiment passes through first time hydro-thermal reaction first, titanium dioxide nanoplate is interted and grows into synusia
In shape titanium carbide structure, then by hydro-thermal reaction again, 1T and 2H mixed phase molybdenum sulfide nanometer spot lamella has been prepared into
The surface of the titanium carbide of shape, the titanium dioxide of nano-sheet；Titanium carbide good conductivity, and molybdenum sulfide 1T phase be metal phase have compared with
Good electric conductivity, molybdenum sulfide 2H phase is that semiconductor Xiang Keyu molybdenum sulfide 1T phase forms heterojunction structure, just because of this bimetallic
The presence of property co-catalyst, has effectively facilitated the transmission of light induced electron and the separation of photo-generate electron-hole pairs, has significantly improved light
Catalytic effect；In addition, imparting the carbonization of preparation due to the synergistic effect of three kinds of ingredient titanium carbides, titanium dioxide and molybdenum sulfide
Titanium/titanium dioxide/vulcanization molybdenum composite material can play excellent catalytic performance in photocatalytic water.
(3) titanium carbide/titanium dioxide/vulcanization molybdenum composite material obtained, embodiment 2 in the step of Example 1-4 (6)
Titanium carbide lamella/titanium dioxide nanoplate composite material made from step (3), titanium dioxide nanoplate, in simulated solar illumination
Lower photocatalytic water hydrogen output and hydrogen-producing speed test are penetrated, as a result respectively as shown in Figure 4,5, as can be seen from Figure 4: relative to carbonization
Titanium sheet layer/titanium dioxide nanoplate composite material and titanium dioxide nanoplate, the composite material of embodiment 1-4 preparation is in photocatalytic water
Excellent performance is shown in terms of hydrogen output and hydrogen-producing speed, wherein in the test of photocatalytic water hydrogen output, with the time
Extend, the hydrogen output of the composite material of embodiment 1-4 preparation increases continuously and healthily, and titanium dioxide does not show catalytic
Can, titanium carbide lamella/titanium dioxide nanoplate composite material catalytic capability maintains very faint level always；In photodissociation
In the test of water hydrogen-producing speed, the hydrogen-producing speed of the composite material of embodiment 1-4 preparation is titanium carbide lamella/nano titania
6.31-10.84 times of piece composite material is 77.06-132.49 times of titanium dioxide nanoplate.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. titanium carbide/titanium dioxide/vulcanization molybdenum composite material, which is characterized in that the composite material includes the carbonization of sheet
Titanium, the titanium dioxide of nano-sheet, nanometer plaque-like molybdenum sulfide, the molybdenum sulfide its by 1T and 2H mixing phase composition；Wherein, institute
The titanium dioxide for stating nano-sheet, which interts, to be grown on the titanium carbide of sheet, and the molybdenum sulfide of the nanometer plaque-like is distributed in lamella
The surface of the titanium carbide of shape, the titanium dioxide of nano-sheet.
2. titanium carbide/titanium dioxide/vulcanization molybdenum composite material as described in claim 1, which is characterized in that the titanium carbide,
The ratio of titanium dioxide, molybdenum sulfide are as follows: 6:4:1.5.
3. titanium carbide/titanium dioxide/vulcanization molybdenum composite material preparation method, which comprises the steps of:
(1) by with MXene material structure titanium carbide, containing the hydrochloric acid solution of sodium fluoborate, it is common to be added in deionized water
Stirring prepares the first mixed liquor；
(2) the first mixed liquor of step (1) is prepared into the second mixed liquor into 5~20h of hydro-thermal reaction at 100~200 DEG C；
(3) the second mixed liquor of filtration step (2) obtains titanium carbide/composite titania material, and titanium carbide/titanium dioxide is multiple
Condensation material and molybdenum trioxide solution containing potassium rhodanide, common be added in deionized water are stirred, and third mixed liquor is prepared；
(4) by the third mixed liquor of step (3) at 150~250 DEG C 10~30h of hydro-thermal reaction, prepare the 4th mixed liquor；
(5) the 4th mixed liquor of filtration step (4) obtains sediment one, and obtained sediment one is washed with water, then will be washed
Sediment one after washing is dried under vacuum conditions, can be prepared by titanium carbide/titanium dioxide/vulcanization molybdenum composite material.
4. preparation method as claimed in claim 3, which is characterized in that in step (1), the titanium carbide contains sodium fluoborate
Hydrochloric acid solution adding proportion are as follows: titanium carbide: sodium fluoborate: hydrochloric acid=50-150mg:5-15mg:5-15mmol.
5. preparation method as claimed in claim 3, which is characterized in that in step (1), the hydrochloric acid containing sodium fluoborate is molten
In liquid, the concentration of hydrochloric acid is 1mol/L；
Alternatively, the stirring includes magnetic agitation, mixing time 10-30min in step (1).
6. preparation method as claimed in claim 3, which is characterized in that in step (2), 160 DEG C of the temperature of the hydro-thermal reaction,
Time is 12h.
7. preparation method as claimed in claim 3, which is characterized in that in step (2), three oxidations containing potassium rhodanide
In molybdenum solution, molybdenum element and titanium carbide/composite titania material mass ratio are 0.1~0.3:1；Preferably 0.15:1；
Alternatively, the stirring includes magnetic agitation, mixing time 10-60min in step (3).
8. preparation method as claimed in claim 3, which is characterized in that in step (4), 200 DEG C of the temperature of the hydro-thermal reaction,
Time is 18h.
9. preparation method as claimed in claim 3, which is characterized in that in step (5), the condition of the drying is in 60-80
10-14h is kept the temperature at DEG C.
10. titanium carbide/titanium dioxide/vulcanization molybdenum composite material as claimed in claim 1 or 2 and/or such as claim 3-9 institute
Titanium carbide/titanium dioxide/application of the vulcanization molybdenum composite material in photocatalysis field for the method preparation stated, is especially urged in light
Change the application decomposed in water.
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| CN110433847A (en) * | 2019-08-22 | 2019-11-12 | 华南理工大学 | A kind of two dimension composite photo-catalyst h-BN/Ti3C2/TiO2And the preparation method and application thereof |
| CN110544767A (en) * | 2019-09-25 | 2019-12-06 | 西南大学 | Carbon-coated sodium trititanate composite material and preparation method and application thereof |
| CN111849145A (en) * | 2020-07-15 | 2020-10-30 | 福州大学 | Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof |
| CN111905768A (en) * | 2020-01-14 | 2020-11-10 | 华南理工大学 | MoS2/MoO3/TiO2Composite photocatalytic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110433847A (en) * | 2019-08-22 | 2019-11-12 | 华南理工大学 | A kind of two dimension composite photo-catalyst h-BN/Ti3C2/TiO2And the preparation method and application thereof |
| CN110544767A (en) * | 2019-09-25 | 2019-12-06 | 西南大学 | Carbon-coated sodium trititanate composite material and preparation method and application thereof |
| CN111905768A (en) * | 2020-01-14 | 2020-11-10 | 华南理工大学 | MoS2/MoO3/TiO2Composite photocatalytic material and preparation method and application thereof |
| CN111849145A (en) * | 2020-07-15 | 2020-10-30 | 福州大学 | Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof |
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