CN109954508A - A kind of composite photocatalyst material and its preparation method and application - Google Patents
A kind of composite photocatalyst material and its preparation method and application Download PDFInfo
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- CN109954508A CN109954508A CN201910306955.2A CN201910306955A CN109954508A CN 109954508 A CN109954508 A CN 109954508A CN 201910306955 A CN201910306955 A CN 201910306955A CN 109954508 A CN109954508 A CN 109954508A
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019441 ethanol Nutrition 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 23
- 238000005530 etching Methods 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000007540 photo-reduction reaction Methods 0.000 claims description 11
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 12
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 229960002050 hydrofluoric acid Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052946 acanthite Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalysis technology field more particularly to a kind of composite photocatalyst material and its preparation method and application, composite photocatalyst material provided by the invention, the composite photo-catalyst is ternary heterojunction structure, including stratiform Ti3C2TxBe dispersed in the Ti3C2TxAg and Ag in layer structure2S;Layered Ti3C2TxIn TxFor Ti3C2The terminal functional group on surface.Record according to the embodiment, for composite photo-catalyst of the present invention for being catalyzed carbon dioxide, the yield for generating methanol is 68.73~107.39 μm of ol/gcat, the yield for generating ethyl alcohol is 17.84~28.19 μm of ol/gcat。
Description
Technical field
The present invention relates to photocatalysis technology field more particularly to a kind of composite photocatalyst material and preparation method thereof and answer
With.
Background technique
Currently, global warming caused by room temperature effect is on the rise, wherein carbon dioxide is imitated as main greenhouse
Gas is answered, reducing the amount of carbon dioxide in air is the key that administer greenhouse effects.Therefore more and more people focus on now
By carbon dioxide conversion be organic-fuel by solar energy and photochemical catalyst, this method can not only reduce the content of carbon dioxide but also
Useful fuel source can be generated for human use, solve the status of present fossil fuel shortages.
Ti3C2TxIt is a kind of stratified material, conducts electricity very well, chemical stability is good and surface area is high.Ti3C2TxSpecial
Layer structure can quickly transmit photo-generated carrier, and its special layer structure is that the active site that photocatalysis provides is more.But it is single
Pure Ti3C2TXPhoto-generate electron-hole on material causes it to be mainly used in battery fuel, light degradation under study for action to easily compound
Organic pollutant and water hydrogen manufacturing etc..Therefore, it is expanded in CO2Reduction prepare in terms of organic-fuel using necessary.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of composite photocatalyst material and preparation method thereof and answer
With the composite photocatalyst material catalytic activity with higher provided by the invention.
In order to achieve the above-mentioned object of the invention, the present invention provides technical solution in detail below:
The present invention provides a kind of composite photocatalyst material, the composite photo-catalyst is ternary heterojunction structure, including
Stratiform Ti3C2TxAnd it is dispersed in the Ti3C2TxAg and Ag in layer structure2S;
Layered Ti3C2TxIn TxFor Ti3C2The terminal functional group on surface.
Preferably, the Ag and Ag2The partial size of S independently is 10~40nm;
The Ag and Ag2The gross mass of S and layered Ti3C2TxMass ratio be (0.05~0.08): 1;
The quality of the Ag is with Ag2The quality meter of S.
The present invention also provides the preparation methods of the composite photo-catalyst described in above-mentioned technical proposal, comprising the following steps:
By Ti3AlC2It mixes, performs etching with hydrofluoric acid, obtain stratiform Ti3C2Tx;
By Ti3C2TxDispersion liquid, AgNO3Solution and Na2The mixing of S solution, carries out photo-reduction, obtains composite photo-catalyst.
Preferably, the mass concentration of the hydrofluoric acid is 35%~45%;
The Ti3AlC2Amount ratio with the hydrofluoric acid is (0.8~1.2) g:(8~12) mL.
Preferably, the temperature of the etching is 20~30 DEG C, and the time of the etching is 30~40h.
Preferably, the Ti3C2TxThe concentration of dispersion liquid is 2.0~3.0mg/mL;
The AgNO3The concentration of solution is 0.08~0.12mol/L;
The Na2The concentration of S solution is 0.04~0.06mol/L.
Preferably, the photo-reduction carries out under xenon lamp irradiation;
The time of the photo-reduction is 25~35min.
It preferably, further include post-processing the product after etching after the etching;It is described post-processing include successively into
Capable washing, centrifugation and drying.
Preferably, the speed of the centrifuge separation is 7000~9000rpm, and the time of the centrifuge separation is 4~6min.
The present invention also provides the composite photocatalyst material described in above-mentioned technical proposal or as described in above-mentioned technical proposal
The composite photocatalyst material that preparation method is prepared generates the application of methanol and ethyl alcohol in photocatalytic reduction of carbon oxide.
The present invention provides a kind of composite photocatalyst material, the composite photo-catalyst is ternary heterojunction structure, including
Stratiform Ti3C2TxAnd it is dispersed in the Ti3C2TxAg and Ag in layer structure2S;Layered Ti3C2TxIn TxFor Ti3C2
The terminal functional group on surface.Ag of the present invention2Material can be improved to the utilization rate of visible light in S, improves the utilization of solar energy
Rate;Ag has lower fermi level, can be used as the electron acceptor in catalytic process and reactivity site.It is irradiated in light
Under, the Ag in composite photo-catalyst of the present invention2S and Ti3C2TXPhoto-generated carrier is generated, wherein light induced electron has stronger
Reducing property can restore CO2Generate organic-fuel.The hetero-junctions can allow the more negative Ag of conduction band2Light on S semiconductor material
The Ti that raw electronics transfer is corrected to conduction band3C2TXOn semiconductor, the compound of photo-generated carrier is hindered.The composite photocatalyst material
The low metal Ag of middle fermi level is as electron acceptor and reactivity site, Ag2S and Ti3C2TXIt is excited by light the photoproduction of generation
Electronics is transferred to the CO on metal Ag to absorption on the surface of the material by hetero-junctions2It is restored.Record according to the embodiment, this
For the invention composite photo-catalyst for being catalyzed carbon dioxide, the yield for generating methanol is 68.73~107.39 μm of ol/gcat,
The yield for generating ethyl alcohol is 17.84~28.19 μm of ol/gcat。
Detailed description of the invention
Fig. 1 is the Ti that comparative example 1 is prepared3C2TXSEM figure;
Fig. 2 is the SEM figure for the composite photo-catalyst that embodiment 1 is prepared;
Fig. 3 is Ag2S, the Ti that comparative example 1 is prepared3C2TXThe composite photo-catalyst being prepared with Examples 1 to 5
XRD diagram.
Specific embodiment
The present invention provides a kind of composite photocatalyst material, the composite photo-catalyst is ternary heterojunction structure, including
Stratiform Ti3C2TxAnd it is dispersed in the Ti3C2TxAg and Ag in layer structure2S;
Layered Ti3C2TxIn TxFor Ti3C2The terminal functional group on surface.
In the present invention, layered Ti3C2TxThickness be preferably 50~100nm, more preferably 60~80nm;It is described
Ag and Ag2The partial size of S is independently preferably 10~40nm, more preferably 15~35nm, most preferably 20~30nm.
In the present invention, the Ag and Ag2S nanoparticle is dispersed on the lamella of stratified material, can prevent nanometer
The reunion of particle, while also helping the separation of light induced electron, significantly enhances photocatalysis efficiency, can effective activation it is stable two
Carbon molecules are aoxidized, it is made to be converted into methanol and ethyl alcohol in aqueous solution.
In the present invention, the Ag and Ag2The gross mass of S and layered Ti3C2TxMass ratio be preferably (0.05~
0.08): 1, more preferably (0.06~0.08): 1, most preferably 0.07:1;In the present invention, the Ag and Ag2The mass ratio of S
Preferably 1:(1.2~2), more preferably 1:(1.4~1.6).In the present invention, the quality of the Ag is with Ag2The quality meter of S.
In the present invention, the terminal functional group be-F, it is-OH, several in-O.The present invention is to above-mentioned terminal functional group
Match no any special restriction.
The present invention also provides the preparation methods of the composite photo-catalyst described in above-mentioned technical proposal, comprising the following steps:
By Ti3AlC2It mixes, performs etching with hydrofluoric acid, obtain stratiform Ti3C2Tx;
By Ti3C2TxDispersion liquid, AgNO3Solution and Na2The mixing of S solution, carries out photo-reduction, obtains composite photo-catalyst.
In the present invention, if without any special explanation, all raw material components are city well known to those skilled in the art
Sell product.
The present invention is by Ti3AlC2It mixes, performs etching with hydrofluoric acid, obtain stratiform Ti3C2Tx;In the present invention, the hydrogen
The mass concentration of fluoric acid is preferably 35%~45%, and more preferably 38%~42%, most preferably 40%.
In the present invention, the Ti3AlC2With the dosage of the hydrofluoric acid preferably than for (0.8~1.2) g:(8~12) mL,
More preferably (0.9~1.1) g:(9~11) mL, most preferably 1.0g:10mL.
In the present invention, the temperature of the etching is preferably 20~30 DEG C, and more preferably 22~28 DEG C, most preferably 24~
26℃;The time of the etching is preferably 30~40h, more preferably 32~38h, most preferably 34~36h.
After the completion of etching, the present invention preferably post-processes the product after etching;The post-processing preferably includes successively
Washing, centrifugation and the vacuum drying of progress.In the present invention, the washing is preferably washed with deionized water repeatedly, until pH
Reach in the range of 6~7.In the present invention, the speed of the centrifugation is preferably 7000~9000rpm, more preferably 7500~
8500rpm, most preferably 8000rpm;The time of the centrifugation is preferably 4~6min, more preferably 5min.
In the present invention, the vacuum drying temperature is preferably 70~100 DEG C, and more preferably 80~90 DEG C, most preferably
It is 80 DEG C;The vacuum drying time is preferably 10~15h, more preferably 12h.
Obtain stratiform Ti3C2TxAfterwards, the present invention is by Ti3C2TxDispersion liquid, AgNO3Solution and Na2The mixing of S solution, carries out light also
Original obtains composite photo-catalyst.
In the present invention, the Ti3C2TxThe dispersing agent of dispersion liquid is preferably deionized water, the Ti3C2TxDispersion liquid
Concentration is preferably 2.0~3.0mg/mL, more preferably 2.2~2.8mg/mL, most preferably 2.4~2.6mg/mL.
In the present invention, the Ti3C2TxDispersion liquid is preferably by by Ti3C2TxIt is mixed with deionized water, and stirs 30min
After obtain;The present invention to the no any special restriction of the stirring, using whipping process well known to those skilled in the art into
Row.
In the present invention, the AgNO3The concentration of solution is preferably 0.08~0.12mol/L, more preferably 0.09~
0.11mol/L, most preferably 0.10mol/L;The Na2The concentration of S solution is preferably 0.04~0.06mol/L, more preferably
0.05mol/L;The Na2The solute of S solution is preferably Na2S·9H2O。
In the present invention, the Ti3C2TxDispersion liquid, AgNO3Solution and Na2The mode of S solution mixing is preferred are as follows:
Ti3C2TxAgNO is added in dispersion liquid3After solution stirs 1h and ultrasound 15min, Na is added2S solution & stir 2h.
In the present invention, silver ion first can be adsorbed onto Ti by above-mentioned order by merging3C2TxMaterial surface reacts again generates Ag2S
And Ag, it is effectively prevented Ag2The reunion of S and Ag particle.
In the present invention, the photo-reduction preferably carries out under the xenon lamp irradiation of 300W;The time of the photo-reduction is preferred
For 25~35min, more preferably 28~32min, most preferably 30min.
After completing the photo-reduction, the present invention preferably filters obtained product system, collect sediment, spend from
Sub- water washing precipitate and drying;The drying is preferably dried in vacuo;The vacuum drying temperature is preferably 80 DEG C, the time
Preferably 12h.
The present invention also provides the composite photocatalyst material described in above-mentioned technical proposal or as described in above-mentioned technical proposal
The composite photocatalyst material that preparation method is prepared generates the application of methanol and ethyl alcohol in photocatalytic reduction of carbon oxide.
Composite photocatalyst material provided by the invention and its preparation method and application is carried out below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
By 1gTi3AlC2It is mixed with the hydrofluoric acid of 10mL40%, performs etching 36h at 25 DEG C, washed with deionized water
It washs, be centrifugated (8000rpm, 5min, pH 6), be dried in vacuo 12 hours at 80 DEG C, obtain Ti3C2Tx;
By 0.1g Ti3C2TxIt is mixed and stirred for 30min with 40mL deionized water, adds the AgNO of 0.1mol/L3Solution
(according to Ag2S and Ti3C2TXTheoretical Mass ratio is 6% addition) 1h and ultrasound 15min are stirred, add the Na of 0.05mol/L2S·
9H2After O solution (being 2:1 addition according to the molar ratio of Ag and S) stirring 2h, under xenon lamp irradiation, the photo-reduction (xenon of 300W is carried out
Lamp, 30min), sediment and vacuum drying (80 DEG C, 12h) is washed with deionized in collected by suction sediment, obtains complex light
Catalyst.
Embodiment 2~5
The difference of embodiment 2~5 and embodiment 1 is only that AgNO3The additional amount of solution and corresponding Na2S·9H2O
The additional amount of solution;
AgNO in embodiment 2~53The additional amount of solution is respectively as follows: according to Ag2S and Ti3C2TXTheoretical Mass ratio is respectively
6.5%, it 7%, 7.5% and 8% is added.
Comparative example 1
By 1gTi3AlC2It is mixed with the hydrofluoric acid of 10mL40%, performs etching 36h at 25 DEG C, washed with deionized water
It washs, be centrifugated (8000rpm, 5min, pH 6), be dried in vacuo 12 hours at 80 DEG C, obtain Ti3C2Tx。
Embodiment 3
The Ti that comparative example 1 is prepared3C2TXSEM test is carried out with the composite photo-catalyst that embodiment 1 is prepared,
Test result is as depicted in figs. 1 and 2, wherein Fig. 1 is the Ti that comparative example 1 is prepared3C2TXSEM figure;Fig. 2 is embodiment 1
The SEM for the composite photo-catalyst being prepared schemes;By Fig. 1 and Fig. 2 it is found that the Ti of composite photo-catalyst of the present invention3C2TX
The nano particle that loading in smooth lamellar structure has nano particle, and load on lamella does not generate reunion.
By pure Ag2S, the Ti that comparative example 1 is prepared3C2TXIt is carried out with the composite photo-catalyst that embodiment 1 is prepared
XRD test, test results are shown in figure 3, from the figure 3, it may be seen that including Ag in the composite photo-catalyst2S、Ti3C2TXAnd Ag, it
Better crystallinity degree and crystal structure all there is no variation.
The Ti that composite photo-catalyst described in Examples 1 to 5, comparative example 1 are prepared3C2TXWith pure Ag2S carries out light
Catalysis reduction carbon dioxide prepares the reaction of methanol and ethyl alcohol;The reaction carries out in closed quartz reactor, temperature control
At 4 DEG C, it is added 30mL ultrapure water and 30mg sample to be tested in the reactor, under the conditions of magnetic agitation, vacuumizes and remove in water
After gas, it is continuously passed through high-purity CO2Gas (flow 50mL/min).It is connected to air when vacuum degree is 0, and continues logical CO2Gas
Body, after dark reaction half an hour under wavelength >=420nm 300W Xenon light shining carry out light reaction 4h after, measure product in methanol and
The content of ethyl alcohol, the methanol of different catalysts and the yield of ethyl alcohol are as shown in table 1:
The Ti that composite photo-catalyst described in 1 Examples 1 to 5 of table, comparative example 1 are prepared3C2TXWith
Pure Ag2The methanol of S and the yield of ethyl alcohol
As seen from the above embodiment, composite photo-catalyst catalytic activity with higher provided by the invention, is used for
It is catalyzed carbon dioxide, the yield for generating methanol is 68.73~107.39 μm of ol/gcat, the yield of ethyl alcohol is 17.84~28.19 μ
mol/gcat, catalytic efficiency with higher.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of composite photocatalyst material, the composite photo-catalyst is ternary heterojunction structure, including stratiform Ti3C2TxWith point
It is dispersed in the Ti3C2TxAg and Ag in layer structure2S;
Layered Ti3C2TxIn TxFor Ti3C2The terminal functional group on surface.
2. composite photocatalyst material as described in claim 1, which is characterized in that the Ag and Ag2The partial size of S independently is 10
~40nm;
The Ag and Ag2The gross mass of S and layered Ti3C2TxMass ratio be (0.05~0.08): 1;
The quality of the Ag is with Ag2The quality meter of S.
3. the preparation method of composite photo-catalyst of any of claims 1 or 2, comprising the following steps:
By Ti3AlC2It mixes, performs etching with hydrofluoric acid, obtain stratiform Ti3C2Tx;
By Ti3C2TxDispersion liquid, AgNO3Solution and Na2The mixing of S solution, carries out photo-reduction, obtains composite photo-catalyst.
4. preparation method as claimed in claim 3, which is characterized in that the mass concentration of the hydrofluoric acid is 35%~45%;
The Ti3AlC2Amount ratio with the hydrofluoric acid is (0.8~1.2) g:(8~12) mL.
5. preparation method as claimed in claim 3, which is characterized in that the temperature of the etching is 20~30 DEG C, the etching
Time be 30~40h.
6. preparation method as claimed in claim 3, which is characterized in that the Ti3C2TxThe mass concentration of dispersion liquid be 2.0~
3.0mg/mL;
The AgNO3The concentration of solution is 0.08~0.12mol/L;
The Na2The concentration of S solution is 0.04~0.06mol/L.
7. preparation method as claimed in claim 3, which is characterized in that the photo-reduction carries out under xenon lamp irradiation;
The time of the photo-reduction is 25~35min.
8. preparation method as claimed in claim 3, which is characterized in that after the etching, further include product after etching into
Row post-processing;The post-processing includes washing, centrifugation and the drying successively carried out.
9. preparation method as claimed in claim 8, which is characterized in that the speed of the centrifugation is 7000~9000rpm, described
The time of centrifugation is 4~6min.
10. composite photocatalyst material of any of claims 1 or 2 or by the described in any item preparation method systems of claim 3~9
Standby obtained composite photocatalyst material generates the application of methanol and ethyl alcohol in photocatalytic reduction of carbon oxide.
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