CN110038605A - AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The methods for making and using same of nanocatalyst - Google Patents
AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The methods for making and using same of nanocatalyst Download PDFInfo
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- CN110038605A CN110038605A CN201910415328.2A CN201910415328A CN110038605A CN 110038605 A CN110038605 A CN 110038605A CN 201910415328 A CN201910415328 A CN 201910415328A CN 110038605 A CN110038605 A CN 110038605A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 62
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 56
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 41
- 230000009467 reduction Effects 0.000 title claims abstract description 41
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 51
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 98
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 60
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 47
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910003373 AgInS2 Inorganic materials 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 23
- 239000004201 L-cysteine Substances 0.000 claims abstract description 21
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 12
- 239000010935 stainless steel Substances 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 239000000047 product Substances 0.000 claims description 66
- 229910001868 water Inorganic materials 0.000 claims description 44
- 229910052738 indium Inorganic materials 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 101710134784 Agnoprotein Proteins 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 2
- 229910009818 Ti3AlC2 Inorganic materials 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 3
- 238000000926 separation method Methods 0.000 description 28
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 18
- 235000018417 cysteine Nutrition 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- -1 Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide] Chemical compound 0.000 description 9
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- 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
Abstract
The invention discloses a kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, takes Ti3AlC2It is put into hydrogen fluoride solution, mixed liquor is put and is stirred at room temperature, later clean mixed liquor with deionized water, dry to obtain a product under vacuum conditions；It takes a product to be put into deionized water to stir evenly, sequentially adds AgNO3、In(OAC)3·6H2O, L-cysteine and Thioacetamide stirring, obtain mixing salt solution b product, b product are put in stainless steel autoclave and heat to obtain c product；The progress deionized water cleaning of obtained c product or alcohol are washed, are dried in vacuo to get required to AgInS2/Ti3C2Nanocatalyst.The layer structure of the catalyst increases its surface area, adsorbs and activates N2Ability enhancing, is conducive to N2Reduction synthesis ammonia.
Description
Technical field
The present invention relates to a kind of AgInS2/Ti3C2The preparation of nanocatalyst and its application method, especially a kind of application
In the AgInS of photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation of nanocatalyst and its application method.
Background technique
Nitrogen (N) is the basis of all life and many industrial process, before 20th century, the form of nitrogen reduction, especially
It is that reduction forms ammonia (NH3), microorganism both largely is to N in atmosphere2Fixation, until German chemist Fritz breathe out
Uncle has invented by converting ammonia (N with hydrogen for the nitrogen in air2 + 3H2 ⇄ 2NH3), this method in 1913 for the first time
Ammonia is produced at industrial scale.This has the reaction process of one-hundred-year history, is so far still the main method of industry synthetic ammonia.Cause
This, Haber-Bosch process is referred to as one of 20th century most influential invention, but needs to consume about 1 % of the world every year
The energy to 2 % exports, and main energy demand comes from high reaction temperature (~ 700 K) and pressure (~ 100 atm) among these.Again
Person will maintain such reaction condition to need to consume a large amount of energy, and brings many ecological problems (such as fossil energy disappears
Consumption, atmosphere pollution and water pollution etc.).According to " Paris weather agreement " and " global climate agreement " defined, chemical industry is just
Related greenhouse gas emission is produced with ammonia in the method for finding innovation to reduce.In order to solve this demand, modern nitrogen chemical
One common-denominator target of area research is by developing more effectively homogeneous or heterogeneous photo-electrocatalytic technology or by adjusting certainly
Enzymatic process under right nitrogen cycle reduces the use of fossil fuel.
Currently, Novel low-consumption green syt ammonia process mainly includes electrocatalytic method, and biological catalysis, thermocatalytic method, etc.
Gas ions catalysis method, photocatalytic method etc..Electro-catalysis mainly passes through external power supply, and adjustment applied voltage realizes N2Reduction synthesis
Ammonia.Its disadvantage is exactly: need to be precisely controlled applied voltage, meanwhile, it will appear liberation of hydrogen process in reaction process, evolving hydrogen reaction can be robbed
Take the yield that electronics is significantly reduced synthesis ammonia by force.Biological catalysis: mainly by simulation biological nitrogen fixation process, biological enzyme is utilized
N is realized in effect2Reduction synthesis ammonia.Its disadvantage is exactly: bioprocesses are slow, and needing to control reaction condition prevents the mistake of enzyme
It is living.And plasma-catalytic method: it is mainly electrified by carrying out material, form gaseous state charged particle, confession with higher
Electronic capability.Its disadvantage is exactly: thermodynamics is uneven, unstable, needs to apply high voltage and certain electric voltage frequency, reaction master
Body is N2And H2.Since 1977, Schrauzer et al. (G.N. Schrauzer, T.D. Guth, J. Am. Chem.
Soc. 99 (1977) 7189-7193.) first passage TiO2N is realized under ultraviolet light2The reaction of reduction synthesis ammonia, is opened
The gate of new era green syt ammonia is opened.Photocatalytic method is since its efficiency is higher, and cleaning causes global concern.
But in photocatalytic method implementation process, need using catalysis material is arrived, such as Xiong et al. (Refining
Defect States in W18O49 by Mo Doping: A Strategy for Tuning N2 Activation
Towards Solar-Driven Nitrogen Fixation) prepare the W that Mo is adulterated18O49Nano wire, in all band condition
Under, photocatalytic synthesis ammonification may be implemented, but ultraviolet light is needed, it is lower to the utilization rate of sunlight.Meanwhile there are also researchs to pass through
Utilize AuRu Nanoalloy particle (Surface Plasmon Enabling Nitrogen Fixation in Pure Water
Through a Dissociative Mechanism under Mild Conditions), realize the light under visible light conditions
Ammonia is catalyzed and synthesized, still, the gold in the experiment is precious metal, is unfavorable for practical application.
Summary of the invention
The object of the present invention is to provide a kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanometer
The preparation of catalyst and its application method.The layer structure of the catalyst increases its surface area, adsorbs and activates N2Ability increases
By force, be conducive to N2Reduction synthesis ammonia.
A kind of technical solution of the present invention: AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nano-catalytic
The preparation method of agent, the AgInS2/Ti3C2Nanocatalyst is by AgInS2And Ti3C2It is compound to obtain, preparation method include just like
Lower step:
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is taken3AlC2It is put into 20 mL hydrogen fluoride solutions, mixed liquor is placed on
45~52 h are stirred at room temperature, later clean mixed liquor up to pH >=6, in 55~65 DEG C of vacuum conditions with deionized water
18~30h of lower drying obtains a product；
B, it the preparation of mixing salt solution: takes a product of 30~270 mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 17~34mg3, a certain amount of In (OAC)3·6H2O, the L-cysteine and 30~60mg of 100~200mg
Thioacetamide, stirring, obtains mixing salt solution b product, and wherein the molar ratio of Ag and In is 1:1；
C, crystallization: being put in stainless steel autoclave for b product, and heats 3~7 h at 130~180 DEG C and obtain c product；
D, it washs: obtained c product being subjected to deionized water cleaning or alcohol is washed 4~5 times, are dried in vacuo under conditions of 45~75 DEG C
8~16h arrives AgInS to get required2/ Ti3C2Nanocatalyst.
AgInS above-mentioned applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2In the preparation method of nanocatalyst,
The volume ratio of water and hydrogen fluoride is 2:3 in hydrogen fluoride solution in step A.
AgInS above-mentioned applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2In the preparation method of nanocatalyst,
It is that deionized water or ethyl alcohol are added in the solution that step A and the cleaning of step D deionized water or alcohol, which wash concrete operation method,
It is then placed in centrifuge and is centrifugated, get rid of supernatant.
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
15~25mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and exposed
Then gas is stirred container, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis
Ammonia.
AgInS above-mentioned applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2In the application method of nanocatalyst,
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3~5.
AgInS above-mentioned applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2In the application method of nanocatalyst,
Nitrogen intake is 15~25ml/min, and nitrogen gas purity is 90% or more.
AgInS above-mentioned applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2In the application method of nanocatalyst,
The intensity of illumination of light source is 8000~10000lux.
Beneficial effects of the present invention: compared with prior art, AgInS of the invention2/Ti3C2Nanocatalyst is due to the material
The layer structure of material increases its surface area, adsorbs and activates N2Ability enhancing, is conducive to N2Reduction synthesis ammonia.And this method is also
During original synthesis ammonia, it is only necessary at normal temperatures and pressures, can be by water and N using visible light and catalyst2Synthesize NH3, greatly
Reduce energy consumption and cost, while the reaction is by H2Use H2O replaces, and provides greatly for the transport and preservation of raw material
It is convenient.
During using nanocatalyst reduction synthesis ammonia of the invention, sampled every a hour, and use indigo
Phenol indigo plant spectrophotometry synthesizes the concentration of ammonia, and the first hour yield of composite nano materials adulterated using 30% is the largest of about
38 μm of ol/g, the gross production rate of 5 hours is up to 90 μm of ol/g.
Detailed description of the invention
Attached drawing 1 is prepared AgInS2/ Ti3C2The x-ray diffraction pattern (XRD) of nanocatalyst, abscissa is two
The angle of diffraction (degree) again, ordinate is the intensity (a.u.) of diffraction maximum；
Attached drawing 2 is the AgInS prepared2/ Ti3C2The scanning electron microscope (SEM) photograph (SEM) of nanocatalyst, transmission electron microscope (TEM) and power spectrum
It analyzes (EDS).
Attached drawing 3 is the AgInS prepared2/ Ti3C2The uv-visible absorption spectroscopy (DRS) of nanocatalyst；
Attached drawing 4 is the AgInS prepared2/ Ti3C2The x-ray photoelectron spectroscopy figure (XPS) of nanocatalyst, abscissa are knots
Energy (eV) is closed, ordinate is signal strength (a.u.)；
Attached drawing 5 is the AgInS prepared2/ Ti3C2The production ammonia efficiency of nanocatalyst；
Attached drawing 6 is the AgInS prepared2/ Ti3C2The fluorescence spectra (PL) of nanocatalyst.
By being can be seen that in Fig. 1 in 2 θ=24.9 °, 26.6 °, 28.3 ° and 44.5 °, Spinel is corresponded to
AgInS2(120), (002), (121), (320) four crystal faces, this is complete with standard card (JCPDS:25-1328)
Meet, in addition, 2 θ=8.5 °, 35.9 °, 41.7 °, 60.4 ° respectively correspond Ti3C2(002), (008), (0010) and (110)
Four crystal faces, this and pure Ti3C2XRD diagram it is consistent, with Ti3C2The reduction of amount, AgInS2The increase of content, be located at 2 θ=
35.9 ° and 41.7 ° of characteristic peaks are also gradually reduced, and are located at AgInS22 θ=24.9 ° of characteristic peak, 26.6 °, 28.3 °
Dramatically increase.XRD is the result shows that be successfully prepared AgInS2/ Ti3C2Composite nano materials.
In Fig. 2,2a and 2b are scanning electron microscope (SEM) photograph (SEM), and 2c transmission electron microscope (TEM) figure, 2d is energy spectrum analysis (EDS) figure.
The AgInS it can be seen from Fig. 2 c2/ Ti3C2Composite nano materials show layer structure, can increase the specific surface area of material,
Promote N2The absorption of molecule on the surface of the material, while little particle above is AgInS2Nano particle illustrates that two kinds of materials can be very
Good is combined together, and forms hetero-junctions, and the EDS figure of Fig. 2 d can be seen that the component of the material, and wherein F element is to corrode
It introduces in the process, but its content is too low negligible.
The UV-vis DRS figure of different doping ratio materials is shown in Fig. 3, it can be seen from the figure that absorbing boundary is close
800 nm illustrate that the composite material shows stronger absorption characteristic to visible light, furthermore adulterate ratio and are classified as 30%AgInS2/
Ti3C2The peak of composite nano materials is most wide, illustrates that the absorption to light is maximum, adulterates Ti3C2The utilization rate of light is improved, is had most
Big photoresponse effect.
Fig. 4 is by XPS come the surface composition and chemical form of COMPOSITE MATERIALS, and full spectrum spectrogram is as the result is shown
AgInS2/ Ti3C2Material is mainly by Ag, In, S, and the elements such as Ti, C composition, the presence of F element may be because molten in hydrogen fluoride
Remaining F stays in material surface in liquid erosion process.
Fig. 5 shows the AgInS of different doping contents2/ Ti3C2Under composite nano materials illumination condition synthesize ammonia yield with
The variation of time, it can be seen from the figure that first hour yield of composite nano materials the largest of about 38 μm of ol/g of 30% doping,
The gross production rate of 5 hours is up to 90 μm of ol/g
Fig. 6 shows the AgInS of different doping contents2/ Ti3C2Composite nano materials fluorescence spectra, for studying light induced electron
With separation, transfer and the combining case of hole on the surface of the material, the power at fluorescence spectral characteristic peak characterizes material surface photoproduction
The separative efficiency of electrons and holes, fluorescence intensity is smaller, illustrates e-And h+Recombination rate it is lower.30% doping in the composite
Composite nano materials characteristic peak it is most weak, the e on surface-And h+Separative efficiency highest, have higher photocatalysis performance.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples, but be not intended as to the present invention limit according to
According to.
The embodiment of the present invention 1:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 48h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then it is dried under 60 DEG C of vacuum conditions and obtains a product, i.e. Ti for 24 hours3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 270mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 17mg3, 30mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 100mg) and
30mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 5 h at 150 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 12h to arrive to get required under conditions of 60 DEG C
AgInS2/ Ti3C2Nanocatalyst.
10wt % AgInS can be obtained in the embodiment2/ Ti3C2。
The embodiment of the present invention 2:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 48h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then it is dried under 60 DEG C of vacuum conditions and obtains a product, i.e. Ti for 24 hours3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 120mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 17mg3, 30mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 100mg) and
30mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 5 h at 150 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 12h to arrive to get required under conditions of 60 DEG C
AgInS2/ Ti3C2Nanocatalyst.
20wt % AgInS can be obtained in the embodiment2/ Ti3C2。
The embodiment of the present invention 3:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 48h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then it is dried under 60 DEG C of vacuum conditions and obtains a product, i.e. Ti for 24 hours3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 70mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 34mg3, 60mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 200mg) and
60mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 5 h at 150 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 12h to arrive to get required under conditions of 60 DEG C
AgInS2/ Ti3C2Nanocatalyst.
30wt % AgInS can be made in the embodiment2/ Ti3C2。
The embodiment of the present invention 4:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 48h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then it is dried under 60 DEG C of vacuum conditions and obtains a product, i.e. Ti for 24 hours3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 45mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 34mg3, 60mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 200mg) and
60mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 5 h at 150 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 12h to arrive to get required under conditions of 60 DEG C
AgInS2/ Ti3C2Nanocatalyst.
40wt % AgInS can be made in the embodiment2/ Ti3C2。
The embodiment of the present invention 5:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 48h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then it is dried under 60 DEG C of vacuum conditions and obtains a product, i.e. Ti for 24 hours3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 30mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 34mg3, 60mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 200mg) and
60mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 5 h at 150 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 12h to arrive to get required under conditions of 60 DEG C
AgInS2/ Ti3C2Nanocatalyst.
50wt % AgInS can be made in the embodiment2/ Ti3C2。
The embodiment of the present invention 6:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 45h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then 30h is dried under 55 DEG C of vacuum conditions obtain a product, i.e. Ti3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 150mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 25mg3, 44mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 150mg) and
45mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 7 h at 130 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 16h to arrive to get required under conditions of 45 DEG C
AgInS2/ Ti3C2Nanocatalyst.
The embodiment of the present invention 7:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 52h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then 18h is dried under 65 DEG C of vacuum conditions obtain a product, i.e. Ti3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 150mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 25mg3, 44mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 150mg) and
45mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: being put in stainless steel autoclave for b product, and heats 3h at 180 DEG C and obtain c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 8h to arrive to get required under conditions of 75 DEG C
AgInS2/ Ti3C2Nanocatalyst.
The embodiment of the present invention 8:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 45h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then 30h is dried under 55 DEG C of vacuum conditions obtain a product, i.e. Ti3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 100mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 30mg3, 53mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 165mg) and
50mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 7 h at 130 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 16h to arrive to get required under conditions of 45 DEG C
AgInS2/ Ti3C2Nanocatalyst.
The embodiment of the present invention 9:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, preparation method
It comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is weighed3AlC2It is put into 20 mL hydrogen fluoride solutions and mixes, pass through fluorine
Change hydrogen attack Ti3AlC2 In Al, wherein in hydrogen fluoride solution the volume ratio of water and hydrogen fluoride be 2:3, mixed liquor is placed on room
Temperature is lower to stir 52h, later cleans mixed liquor with deionized water until pH >=6, deionized water cleaning process are in mixed liquor
Middle addition deionized water, is then placed in centrifuge and is centrifuged, supernatant is removed after separation.Repeatedly, until it is molten
Until pH >=6 of liquid.Then 18h is dried under 65 DEG C of vacuum conditions obtain a product, i.e. Ti3C2The presoma of nanometer sheet.
B, it the preparation of mixing salt solution: takes a product of 100mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 30mg3, 53mg In (OAC)3·6H2Six water acetic acid indium of O(), the L-cysteine(cysteine of 165mg) and
50mg Thioacetamide [2- (2,4- dichlorophenoxy) thioacetamide], stirring, obtains mixing salt solution b product.Wherein
The molar ratio of Ag and In is 1:1.L-cysteine(cysteine) main function be binder, for adsorbing Ag ion, and
Thioacetamide is mainly used for providing element sulphur.
C, crystallization: b product are put in stainless steel autoclave, and heats 3 h at 180 DEG C and obtains c product；
D, it washs: after deionized water or ethyl alcohol is added in obtained c product, putting into a centrifuge centrifuge separation, got rid of after separation
Supernatant, 4~5 times repeatedly.Isolated substance is dried in vacuo to 8h to arrive to get required under conditions of 75 DEG C
AgInS2/ Ti3C2Nanocatalyst.
The embodiment of the present invention 10:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
15mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 15ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 8000lux.
The embodiment of the present invention 11:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
25mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:5, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 25ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 10000lux.
The embodiment of the present invention 12:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
20mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:4, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 20ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 8880lux.
The embodiment of the present invention 13:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
18mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:4, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 18ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 8500lux.
The embodiment of the present invention 14:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
22mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
Also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3.5, be added methanol be mainly used for away it is molten
Hole in liquid.
Nitrogen intake is 22ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 9500lux.
The embodiment of the present invention 15:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
15mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 15ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 10000lux.
The embodiment of the present invention 16:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
15mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:5, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 15ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 10000lux.
The embodiment of the present invention 17:
A kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The application method of nanocatalyst, weighs
25mgAgInS2/Ti3C2Nanocatalyst is put into container, is added in 100 mL water, and be passed through nitrogen thereto and be aerated, so
Container is stirred afterwards, the mixed liquor is placed under light source irradiates later, collects the gas of generation up to required synthesis ammonia.
It also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3, and methanol is added and is mainly used for away solution
In hole.
Nitrogen intake is 25ml/min, and nitrogen gas purity is 90% or more.
The intensity of illumination of light source is 8000lux.
Claims (7)
1. a kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2The preparation method of nanocatalyst, feature
It is: the AgInS2/Ti3C2Nanocatalyst is by AgInS2And Ti3C2Compound to obtain, preparation method comprises the following steps that
A、Ti3C2The preparation of ultrathin nanometer piece: the Ti of 1g is taken3AlC2It is put into 20 mL hydrogen fluoride solutions, mixed liquor is placed on room
Temperature is lower to stir 45~52 h, later cleans mixed liquor up to pH >=6, under 55~65 DEG C of vacuum conditions with deionized water
18~30h of drying obtains a product；
B, it the preparation of mixing salt solution: takes a product of 30~270 mg to be put into 40 mL deionized waters and stirs evenly, sequentially add
The AgNO of 17~34mg3, a certain amount of In (OAC)3·6H2O, the L-cysteine and 30~60mg of 100~200mg
Thioacetamide, stirring, obtains mixing salt solution b product, and wherein the molar ratio of Ag and In is 1:1；
C, crystallization: being put in stainless steel autoclave for b product, and heats 3~7 h at 130~180 DEG C and obtain c product；
D, it washs: obtained c product being subjected to deionized water cleaning or alcohol is washed 4~5 times, are dried in vacuo under conditions of 45~75 DEG C
8~16h arrives AgInS to get required2/ Ti3C2Nanocatalyst.
2. the AgInS according to claim 1 applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanocatalyst,
Be characterized in that: the volume ratio of water and hydrogen fluoride is 2:3 in hydrogen fluoride solution in step A.
3. the AgInS according to claim 1 applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanocatalyst,
Be characterized in that: to wash concrete operation method be that deionized water is added in the solution for step A and the cleaning of step D deionized water or alcohol
Or ethyl alcohol, it is then placed in centrifuge and is centrifugated, get rid of supernatant.
4. a kind of AgInS applied to photocatalysis nitrogen reduction synthesis ammonia as described in any one of claim 1-32/
Ti3C2The application method of nanocatalyst, it is characterised in that: weigh 15~25mgAgInS2/Ti3C2Nanocatalyst is put into appearance
Device is added in 100 mL water, and is passed through nitrogen thereto and is aerated, and is then stirred to container, later by the mixed liquor
It is placed under light source and irradiates, collect the gas of generation up to required synthesis ammonia.
5. the AgInS according to claim 4 applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanocatalyst
Application method, it is characterised in that: also include methanol in 100 mL water, the volume ratio of methanol and water is 1:3~5.
6. the AgInS according to claim 4 applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanocatalyst
Application method, it is characterised in that: nitrogen intake is 15~25ml/min, and nitrogen gas purity is 90% or more.
7. the AgInS according to claim 4 applied to photocatalysis nitrogen reduction synthesis ammonia2/Ti3C2Nanocatalyst
Application method, it is characterised in that: the intensity of illumination of light source is 8000~10000lux.
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| CN110711598B (en) * | 2019-10-25 | 2023-02-03 | 齐鲁工业大学 | Silver/silver phosphate/titanium carbide ternary composite material and preparation method and application thereof |
| CN110743575A (en) * | 2019-11-21 | 2020-02-04 | 南昌航空大学 | AgIn with adsorption-photocatalysis synergistic effect5S8/SnS2Method for preparing solid solution catalyst |
| CN110743575B (en) * | 2019-11-21 | 2021-10-26 | 南昌航空大学 | AgIn with adsorption-photocatalysis synergistic effect5S8/SnS2Method for preparing solid solution catalyst |
| CN115605291A (en) * | 2020-05-15 | 2023-01-13 | 北京光合启源科技有限公司（Cn） | Method for producing urea by means of energy radiation |
| CN112058280A (en) * | 2020-09-17 | 2020-12-11 | 南昌航空大学 | Preparation method and application of indium silver sulfide |
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