CN115155619B - Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction - Google Patents
Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 55
- 239000006104 solid solution Substances 0.000 title claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 39
- 230000007547 defect Effects 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 5
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000000887 hydrating effect Effects 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 44
- 229910021529 ammonia Inorganic materials 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 241000282326 Felis catus Species 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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 preparation method of S-doped defect solid solution and application thereof in photocatalysis nitrogen fixation reaction, which is prepared by using hydrated manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O or hydrated indium In Nitrate (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 As raw material, S-doped Mn is obtained through one-step hydrothermal reaction x Zn 1‑x S-defect solid solutions or S-doped Mn x In 1‑x S-defect solid solution. The S-doped defect solid solution prepared by the invention is used as a photocatalyst to show excellent photocatalytic synthesis ammonia activity in a visible light photocatalytic nitrogen fixation reaction.
Description
Technical Field
The invention relates to the technical field of solid solution synthesis and photocatalysis, in particular to S-doped Mn x Zn 1-x S and Mn x In 1-x A preparation method of S defect state nano material and application thereof in the field of energy and photocatalysis.
Background
Currently, the industry mainly utilizes multiphase composite catalysts to catalyze and synthesize ammonia under the conditions of high temperature and high pressure. The industrial cost of this reaction is high and a large amount of NO is produced during the synthesis x Does not conform to the current green chemistry research concept. Solar-driven photocatalytic nitrogen fixation is a potential green new method, which can be designed to simulate the ammonia production process. However, the activity efficiency of the photocatalyst reported so far is low, and the development of a suitable photocatalyst for nitrogen fixation reaction is considered as a technology with great research and application prospects.
Sulfides (e.g., cdS, znS and In 2 S 3 Etc.), the band gap of which is suitable for absorbing sunlight and has a suitable energy band structure for nitrogen fixation, has been receiving attention. Optimizing the composition and preparation method thereof can further improve the photocatalytic performance, such as doping elements, supporting cocatalysts or mixing with themHe sulfides combine to form solid solutions. The multi-component sulfide solid solution can enhance the absorption of the visible light of the catalyst due to the adjustable energy band structure. Meanwhile, due to the difference of ionic radii, some surface vacancies are easily caused by adding some metal elements with small ionic radii. For example Mn x Cd 1-x S is formed by combining CdS and MnS, and has received great attention in recent years. Similarly, mnS can be doped into other metal sulfides such as ZnS and In by adjusting and controlling the type of raw materials, the type of solvent and the reaction conditions 2 S 3 Form Mn x Zn 1-x S and Mn x In 1-x S solid solution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a simple and convenient synthesis method of S-MZS and S-MIS solid solutions and application thereof in the fields of photocatalysis and energy, and aims to solve the problems of synthesizing the S-MZS and S-MIS solid solutions and improving the photocatalytic nitrogen fixation activity thereof. In order to obtain the optimal nitrogen fixation activity of the catalyst, the invention optimizes the synthesis conditions of the catalyst by adopting different Zn sources, in sources, S sources, solvents and temperatures, simultaneously explores the pressure, solution, time and times of the reaction of the synthetic ammonia, and systematically researches the influence of the synthesis conditions and the reaction conditions on the performance of the photocatalytic synthetic ammonia.
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
the preparation method of the S-doped defect solid solution is characterized by comprising the following steps: the S-doped defect state solid solution is S-doped Mn x Zn 1-x S defect solid solution is marked as S-MZS; alternatively, the S-doped defect state solid solution is S-doped Mn x In 1-x S defect solid solution is denoted as S-MIS. Wherein 0 is < x < 1。
The S-MZS is prepared by hydration of manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O and thioacetamide CH 3 CSNH 2 The material is obtained through one-step hydrothermal reaction, and comprises the following specific steps: mnSO is carried out 4 ·H 2 O、Zn(NO 3 ) 2 ·6H 2 O, 10mmol CH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL of deionized water into the reaction kettle, uniformly stirring, sealing the reaction kettle in a steel sleeve, and carrying out hydrothermal reaction for 24 hours at 180 ℃; after the reaction is finished, cooling to room temperature, and washing and drying the obtained product to obtain S-MZS; wherein: mnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O is x, 1-x, CH 3 CSNH 2 Molar mass of (2) to MnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 O
3 to 4 times of the total molar weight.
The S-MIS is prepared by hydrating manganese sulfate MnSO 4 ·H 2 O, hydrated indium In Nitrate (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 The material is obtained through one-step hydrothermal reaction, and comprises the following specific steps: mnSO is carried out 4 ·H 2 O、In(NO 3 ) 3 ·yH 2 O、
10mmol of CH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL of deionized water into the reaction kettle, uniformly stirring, sealing the reaction kettle in a steel sleeve, and carrying out hydrothermal reaction for 24 hours at 180 ℃; after the reaction is finished, cooling to room temperature, and washing and drying the obtained product to obtain S-MIS; wherein: mnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 The molar ratio of O is x, 1-x, CH 3 CSNH 2 Molar mass of (2) to MnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 3 to 4 times of the total mole amount of O.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method has simple steps, and Mn with S doping and defect sites can be obtained by one-step hydrothermal reaction x Zn 1-x S and Mn x In 1-x S nano material provides a simple and convenient new method for reference for synthesizing other nano materials;
2. the invention optimizes the raw material type, the solvent type and the reaction condition for preparing S-MZS and S-MIS defect solid solutions, so that the S-MZS and S-MIS defect solid solutions have optimal synthetic ammonia activity and catalytic stability.
3. Due to Mn 2+ Is smaller than Zn in radius (67 pm) 2+ (74 pm) and In 3+ (80 pm) radius, according to the production method of the present invention, easily caused defective sites of Mn during the formation of solid solutions.
4. The S-doped defect solid solution prepared by the invention is used as a photocatalyst to show excellent photocatalytic synthesis ammonia activity in a visible light photocatalytic nitrogen fixation reaction. When x=0.1, the S-MZS and S-MIS showed good nitrogen fixation activity (reaction time of 4 h) under irradiation of visible light, which was 295.11 mg.L, respectively -1 ·g cat -1 And 183.38 mg.L -1 ·g cat -1 Far greater than MnS monomer (19.52 mg.L) -1 ·g cat -1 )。
Drawings
FIG. 1 is an XRD pattern of the S-MZS solid solution synthesized in example 1.
FIG. 2 is an XRD pattern of the S-MIS solid solution synthesized in example 2.
Fig. 3 (a) and 3 (b) are SEM images of the S-MZS synthesized in example 1, and fig. 3 (c) and 3 (d) are SEM images of the S-MIS synthesized in example 2.
FIGS. 4 (a) and 4 (b) are a TEM image and an HR-TEM image of the S-MZS synthesized in example 1, and FIGS. 4 (c) and 4 (d) are a TEM image and an HR-TEM image of the S-MIS synthesized in example 2.
FIG. 5 is an EPR plot of the S-MZS solid solution synthesized in example 1 and the S-MIS solid solution synthesized in example 2;
FIG. 6 is an absorption spectrum of ammonia nitrogen amount of the S-MZS solid solution and the S-MIS solid solution in example 3;
FIG. 7 is a graph of the visible light photocatalytic ammonia synthesis activity of the S-MZS solid solution and the S-MIS solid solution of example 3;
FIG. 8 is a screening experiment of the optimal synthesis conditions for a 0.1MZS photocatalyst, in order: different Zn sources (fig. 8 (a)), different Mn: zn ratio (FIG. 8 (b)), different S sources (FIG. 8 (c)), different TAA amounts (FIG. 8 (d)), different reaction solvents (FIG. 8 (e)), and different reaction temperatures (FIG. 8 (f)).
FIG. 9 shows a screening experiment of the optimal nitrogen fixation reaction conditions of the 0.1MZS photocatalyst, which is sequentially different nitrogen fixation reaction solvents (FIG. 9 (a)), different reactions N 2 Pressure (fig. 9 (b)), different reaction times (fig. 9 (c)), and different reaction times (fig. 9 (d)).
Fig. 10 shows a screening experiment of the optimal synthesis condition and the optimal nitrogen fixation reaction condition of the 0.1MIS photocatalyst, which sequentially comprises different reaction temperatures (fig. 10 (a)), different In sources (fig. 10 (b)), different S sources (fig. 10 (c)), different reaction solvents (fig. 10 (d)), and different Mn: in ratio (FIG. 10 (e)), different nitrogen fixation reaction solvents (FIG. 10 (f)), different reactions N 2 Pressure (fig. 10 (g)), different reaction times (fig. 10 (h)), and different reaction times (fig. 10 (i)).
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are merely examples in nature, and on the basis of the technical solutions of the present invention, the following examples are given in detail, and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1
This example prepares S-doped Mn as follows x Zn 1-x S-defect solid solution (x=0.1 as an example):
weighing 0.3mmolMnSO 4 ·H 2 O、2.7mmolZn(NO 3 ) 2 ·6H 2 O、10mmolCH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL of deionized water into the reaction kettle, stirring for 30min, sealing the reaction kettle in a steel sleeve, and carrying out hydrothermal reaction for 24h at 180 ℃; after the reaction is finished, cooling to room temperature, washing and drying the obtained product to obtain the S-doped Mn with x=0.1 x Zn 1-x The S-defect solid solution was designated as 0.1MZS.
Example 2
This example prepares S-doped Mn as follows x In 1-x S-defect solid solution (x=0.1 as an example):
weighing 0.3mmolMnSO 4 ·H 2 O、2.7mmolIn(NO 3 ) 3 ·yH 2 O、10mmolCH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL of deionized water into the reaction kettle, stirring for 30min, sealing the reaction kettle in a steel sleeve, and carrying out hydrothermal reaction for 24h at 180 ℃; after the reaction is finished, cooling to room temperature, washing and drying the obtained product to obtain the S-doped Mn with x=0.1 x In 1-x S defect solid solution, designated 0.1MIS.
Example 3
This example tests the performance of 0.1MZS and 0.1MIS visible light photocatalytic nitrogen fixation as follows:
step 1, 0.03g of catalyst is weighed and added into 50mL of methanol solution, and the mixed solution is transferred into a lining of a 100mL high-pressure visible reactor.
Step 2, sealing the reaction system and introducing N 2 Placing into a reactor for 30min (at this time, keeping dark reaction condition), exhausting air in the reactor, closing the air outlet, completely opening the air inlet, and continuously charging N 2 The pressure was maintained at 0.3MPa.
And 3, stirring for 30 minutes under the condition of no illumination to finish dynamic balance of adsorption-desorption.
And 4, turning on a lamp, illuminating (the light is visible light with the wavelength of more than 420 nm), and taking the mixed solution after a given interval time.
And 5, centrifuging the reacted solution, taking 5mL of supernatant after centrifugation into a 50mL volumetric flask, adding deionized water to fix the volume to a marked line, shaking uniformly, and standing. 1mL of potassium sodium tartrate solution and 1mL of Nahner reagent are respectively added into the above solutions and uniformly mixed. After the above solution was allowed to stand for 10 minutes, the absorbance at 420nm was measured by an ultraviolet-visible diffuse reflectance spectrometer.
Characterization of S-MZS and S-MIS solid solutions:
FIG. 1 is an XRD pattern of 0.1MZS, znS and MnS, and it can be seen from the figure that 0.1MZS (JCCPDSNo. 89-4957), znS (JCCPDSNo. 77-2100) and MnS (JCCPDSNo. 89-4952) all have corresponding Jade cards and the correspondence is neat. Wherein, impurity peaks appear in 0.1MZS and ZnS in the XRD pattern, and the impurity peaks are found to be the peaks of S8 simple substance by comparing standard cards, and the corresponding cards are (JCPSDSNo. 89-2600). It has a distinct peak at 23.1 deg., corresponding to the (222) crystal plane of S. From the XRD pattern of the 0.1MZS, it is clear that the 28.4, 47.3 and 56.1 peaks are assigned to the (111), (220) and (311) planes of the cubic crystal form MZS, respectively. The catalyst synthesized can thus be determined to be an S-doped MZS.
FIG. 2 shows 0.1MIS (JCCPDSNo.85-1229), in 2 S 3 XRD patterns of (JCCPDSNo.84-1385) and MnS (JCCPDSNo.89-4952). For In 2 S 3 And 0.1MIS, the peaks of S (222) crystal planes remain, and the MIS peaks at 27.5 °, 33.4 °, 43.8 °, and 47.9 ° are assigned to MIS (311), (400), (511), and (440) crystal planes, respectively, of the cubic phase crystal form, indicating that the synthesized catalyst is S-doped MIS.
SEM and TEM can be used to better understand catalyst morphology, distribution and structure. Fig. 3 (a) and 3 (b) are SEM images of 0.1MZS at different magnifications, indicating that 0.1MZS is spherical consisting of nanoparticles. FIGS. 3 (c) and 3 (d) are SEM images of 0.1MIS at different magnifications, it being seen that 0.1MIS is spherical consisting of nanoplatelets. TEM of 0.1MZS (FIG. 4 a) further shows that these spheres consist of a number of small particles tightly packed, and that lattice fringes with a lattice spacing of 0.31nm (FIG. 4 b) can be observed in the HR-TEM image, and that the lattice spacing corresponds to the (111) crystal plane of the MZS. Fig. 4 (c) is a TEM image of 0.1MIS, and it can be seen that MIS is a sphere composed of many nano-platelets, and the presence of platelets can also be seen at the edge portion of the image. In the HR-TEM image of 0.1MIS (FIG. 4 d), lattice fringes at a spacing of 0.62nm were observed, and the lattice spacing corresponded to the (111) crystal planes of MIS.
Unpaired electrons in the 0.1MZS and 0.1MIS nanomaterials were studied using an electron spin resonance apparatus (EPR) and the results are shown in FIG. 5. It can be seen that MnS, 0.1MZS and 0.1MIS all have signal responses at g=2.003, indicating that the photocatalyst has vacancies, i.e. defect sites on the surface. These peak intensities are mainly due to Mn vacancies, the intensities of which are as follows: 0.1MIS >0.1MZS > MnS. Since In has an ionic radius greater than Zn,0.1MIS forms more Mn vacancies than 0.1MZS.
Catalytic Activity test of S-MZS and S-MIS solid solutions:
FIG. 6 is an ultraviolet absorption spectrum of 0.1MZS, 0.1MIS, mnS and blank samples after irradiation with visible light for 4 hours, as can be seen from the graph, the absorbance at 420nm of 0.1MZS, 0.1MIS and MnS is 1.61, 1.05, 1.00 and 0.11, respectively, while the absorbance of blank sample is 0.04. The calculated ammonia amounts of 0.1MZS, 0.1MIS and MnS were 295.11, 183.38, 19.52 and 2.40 mg.L, respectively -1 ·g cat -1 (FIG. 7). The blank sample contained a low ammonia content, which was negligible at the nitrogen fixation. The maximum nitrogen fixation amount of 0.1MZS photocatalysis is 295.11 mg.L -1 ·g cat -1 The ammonia synthesis amount of the solid solution is much higher than that of the monomer catalyst.
As shown in fig. 8, according to the nitrogen fixation performance test method of example 3, the present invention also performs screening search on the synthesis conditions of the 0.1MZS photocatalyst, such as different Zn sources (fig. 8 (a)), different Mn: zn ratio (FIG. 8 (b)), different S sources (FIG. 8 (c)), different TAA amounts (FIG. 8 (d)), different reaction solvents (FIG. 8 (e)), and different reaction temperatures (FIG. 8 (f)), and optimal synthesis conditions were obtained. Zn (NO) 3 ) 2 ·6H 2 O is synthesized by zinc source, and the ammonia produced by 0.1MZS is 295.11 mg.L -1 ·g cat -1 Is Zn (CH) 3 COO) 2 ·2H 2 The amount of ammonia produced by S-MZS synthesized from a zinc source was 18 times that produced by O, and it was found that Zn (NO 3 ) 2 ·6H 2 O is 0.1MZS synthesized by zinc source and has higher nitrogen fixation activity. Meanwhile, mn was examined: the optimum ratio of Zn (x=0, 0.05, 0.07, 0.1, 0.15, 1, where x represents the theoretical content based on Mn in the feed) found that the photocatalytic synthetic nitrogen amount showed a tendency to increase and decrease first, and the photocatalytic nitrogen fixation amount was the greatest when the molar ratio of Mn to Zn was 0.1. At the same time, S source was examined (FIG. 8 (c)), and NH was found as a catalyst for sulfur source synthesis using L-cysteine (L-cys) and Thiourea (TA) 4 + The concentration is 10.26 mg.L respectively -1 ·g cat -1 And 18.94 mg.L -1 ·g cat -1 Much lower than the amount of ammonia produced using Thioacetamide (TAA) as the sulfur source. Further, when the addition amount of TAA was 10mmol, the nitrogen fixation amount reached the highest value. Under the action of different reaction solvents (FIG. 8 (e)), the nitrogen fixation activity of 0.1MZS depends onThe second time is H 2 O(268.36mg·L -1 ·g cat -1 )>CH 3 OH(9.57mg·L -1 ·g cat -1 )>CH 3 OH+H 2 O (30 mL,8.87 mg.L respectively) -1 ·g cat -1 ). Catalyst synthesis temperature is different, N 2 The amount of nitrogen converted will also vary, as shown in FIG. 8 (f). The 0.1MZS photocatalyst synthesized at 160℃produced only 9.40 mg.L of ammonia -1 ·g cat -1 The ammonia produced by the 0.1MZS photocatalyst synthesized at 200 ℃ has 96.71 mg.L -1 ·g cat -1 . When the temperature reached 180℃compared with the samples prepared at 160℃and 200℃NH 4 + The concentration reaches the maximum value of 295.11 mg.L -1 ·g cat -1 . Thereby obtaining the optimal synthesis conditions: at 180℃with Zn (NO 3 ) 2 ·6H 2 O is a zinc source, TAA is a sulfur source, and deionized water is the best nitrogen fixation activity of the 0.1MZS photocatalyst synthesized by the solvent.
As shown in FIG. 9, after searching for the synthesis conditions, the present invention also explored the optimal conditions for the nitrogen fixation illumination reaction using 0.1MZS as the photocatalyst (according to the method of example 3, one of the conditions was modified for testing), such as the reaction solvent (FIG. 9 (a)), gas N 2 Pressure (fig. 9 (b)), reaction time (fig. 9 (c)), and number of reactions (fig. 9 (d)).
The invention uses H respectively 2 O、CH 3 OH and CH 3 CH 2 OH as solvent for photocatalytic reaction, H 2 O as a solvent does not produce ammonia. CH (CH) 3 The maximum ammonia yield can reach 295.11 mg.L when OH is used as solvent -1 ·g cat -1 Greater than CH 3 CH 2 Ammonia yield when OH was used as solvent (167.35 mg.L) -1 ·g cat -1 ) This is because of N 2 On CH 3 Solubility in OH is greater and CH 3 OH can not only provide hydrogen protons, but also react with holes generated by photoexcitation. Under different nitrogen pressures, the nitrogen fixation amount at 0.2Mpa is 154.88 mg.L -1 ·g cat -1 Nitrogen fixation at 0.3MpaThe amount is 295.11 mg.L -1 ·g cat -1 The nitrogen fixation amount at 0.4Mpa is 167.51 mg.L -1 ·g cat -1 . Thus, the optimal reaction conditions are obtained, 0.3MPa nitrogen is used as reaction gas, methanol is used as reaction solvent for carrying out illumination reaction, and the nitrogen fixation amount of 0.1MZS is maximum.
In addition, the invention uses the catalyst to carry out illumination experiments and prolong illumination time to evaluate the stability of the 0.1MZS photocatalyst. On the basis of ensuring that other experimental conditions are the same, the time of each illumination is prolonged. As shown in fig. 9 (c), as the time of irradiation of the catalyst with visible light increases, the amount of ammonia nitrogen immobilized by the 0.1MZS photocatalyst increases and reaches an equilibrium value of about 4 hours. In the cyclic experiment process, 30mg of photocatalyst is weighed for illumination experiment on the basis of ensuring the unchanged reaction condition, the catalyst is centrifugally collected after illumination for 4 hours, and then the catalyst is dried in vacuum at 60 ℃ for 10 hours after repeated cleaning by deionized water and ethanol. The obtained sample was ground, and the next light irradiation experiment was performed, and after 5 cycles, FIG. 9 (d) was obtained. As can be seen from the graph, after the first cycle experiment, the ammonia production amount was 295.11 mg.L -1 ·g cat -1 Reduced to 235.71 mg.L -1 ·g cat -1 Relatively stable in the rest of the cycling experiments (after the simple substance S is consumed). Thus, the presence of S element plays an important role in the 0.1MZS ammonia synthesis reaction.
Finally, the present invention tested synthesis conditions, nitrogen fixation reaction conditions and stability of 0.1MIS by the same method (FIG. 10), at 180℃in In (NO 3 ) 2 ·6H 2 The MIS photocatalyst synthesized by using O as an indium source, TAA as a sulfur source and deionized water as a solvent has the best nitrogen fixation activity when the molar ratio of Mn to In is 0.1. Meanwhile, the optimal nitrogen fixation reaction condition is that 0.3MPa nitrogen is used as reaction gas/methanol as reaction solvent to carry out illumination reaction for 4 hours. In addition, as the number of reactions increases, the activity of photocatalytic synthetic ammonia gradually decreases and stability is required to be improved.
The above description is illustrative of the invention and is not intended to be limiting, but is to be construed as being included within the spirit and scope of the invention.
Claims (3)
- The application of S-doped defect solid solution as a photocatalyst for photocatalytic nitrogen fixation reaction is characterized in that: the S-doped defect state solid solution is S-doped Mn x Zn 1-x S-defect solid solution, denoted S-MZS,0< x <1, a step of; alternatively, the S-doped defect state solid solution is S-doped Mn x In 1-x S-defect solid solution, designated S-MIS,0< x < 1；The S-MZS is prepared by hydration of manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O and thioacetamide CH 3 CSNH 2 As a raw material, the catalyst is obtained through one-step hydrothermal reaction;the S-MIS is prepared by hydrating manganese sulfate MnSO 4 ·H 2 O, hydrated indium In Nitrate (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 As a raw material, the catalyst is obtained through one-step hydrothermal reaction;the S-doped defect solid solution is used as a photocatalyst in the photocatalytic nitrogen fixation reaction, and CH is used as a catalyst 3 OH or CH 3 CH 2 OH as a solvent under visible light.
- 2. The use according to claim 1, wherein the S-MZS is prepared by the steps of:MnSO is carried out 4 ·H 2 O、Zn(NO 3 ) 2 ·6H 2 O, 10mmol CH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL deionized water into the reaction kettle, uniformly stirring, sealing the reaction kettle in a steel sleeve, and performing hydrothermal reaction at 180 ℃ for 24h; after the reaction is finished, cooling to room temperature, and washing and drying the obtained product to obtain S-MZS;wherein: mnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O is x, 1-x, CH 3 CSNH 2 Molar mass of (2) to MnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 3-4 times of the total molar quantity of O.
- 3. The use according to claim 1, wherein the S-MIS is prepared by the steps of:MnSO is carried out 4 ·H 2 O、In(NO 3 ) 3 ·yH 2 O, 10mmol CH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; adding 60mL deionized water into the reaction kettle, uniformly stirring, sealing the reaction kettle in a steel sleeve, and performing hydrothermal reaction at 180 ℃ for 24h; after the reaction is finished, cooling to room temperature, and washing and drying the obtained product to obtain S-MIS;wherein: mnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 The molar ratio of O is x, 1-x, CH 3 CSNH 2 Molar mass of (2) to MnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 3-4 times of the total molar quantity of O.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927173A (en) * | 2010-02-01 | 2010-12-29 | 黑龙江省科学院石油化学研究院 | Photocatalyst for preparing hydrogen and sulphur by decomposing hydrogen sulfide and preparation method thereof |
| CN103979598A (en) * | 2014-04-30 | 2014-08-13 | 南昌大学 | Method for preparing spinel-structure compound nanocrystal |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN109967092A (en) * | 2019-05-05 | 2019-07-05 | 中国科学技术大学 | A kind of metal-doped indium sulfide nanometer sheet, preparation method and application |
| CN112264049A (en) * | 2020-10-14 | 2021-01-26 | 盐城工学院 | Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Process for preparing catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927173A (en) * | 2010-02-01 | 2010-12-29 | 黑龙江省科学院石油化学研究院 | Photocatalyst for preparing hydrogen and sulphur by decomposing hydrogen sulfide and preparation method thereof |
| CN103979598A (en) * | 2014-04-30 | 2014-08-13 | 南昌大学 | Method for preparing spinel-structure compound nanocrystal |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN109967092A (en) * | 2019-05-05 | 2019-07-05 | 中国科学技术大学 | A kind of metal-doped indium sulfide nanometer sheet, preparation method and application |
| CN112264049A (en) * | 2020-10-14 | 2021-01-26 | 盐城工学院 | Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Process for preparing catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Cu7S4/MnIn2S4 heterojunction for efficient photocatalytic hydrogen generation;Yibin Song等;《Journal of Alloys and Compounds》;第884卷;1-9 * |
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