CN115155619A - Preparation method of S-doped defect state solid solution and application of S-doped defect state solid solution in photocatalysis nitrogen fixation reaction - Google Patents
Preparation method of S-doped defect state solid solution and application of S-doped defect state solid solution in photocatalysis nitrogen fixation reaction Download PDFInfo
- Publication number
- CN115155619A CN115155619A CN202211025628.8A CN202211025628A CN115155619A CN 115155619 A CN115155619 A CN 115155619A CN 202211025628 A CN202211025628 A CN 202211025628A CN 115155619 A CN115155619 A CN 115155619A
- Authority
- CN
- China
- Prior art keywords
- solid solution
- reaction
- doped
- defect state
- state solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 55
- 239000006104 solid solution Substances 0.000 title claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- 230000007547 defect Effects 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 title abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- 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
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 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
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 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 16
- 238000000034 method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 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
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 44
- 229910021529 ammonia Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 13
- 241000282326 Felis catus Species 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 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
- 239000002904 solvent Substances 0.000 description 9
- 230000035484 reaction time Effects 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 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 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
- 238000012360 testing method Methods 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
- 238000002835 absorbance Methods 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 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
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000008569 process Effects 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
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 244000088401 Pyrus pyrifolia Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 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
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000003795 desorption Methods 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
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—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 state solid solution and application thereof in photocatalysis nitrogen fixation reaction, which is hydrated manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O or indium nitrate hydrate In (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 As raw materials, S-doped Mn is obtained through one-step hydrothermal reaction x Zn 1‑x S-defect solid solution or S-doped Mn x In 1‑x An S-defect solid solution. The S-doped defect state solid solution prepared by the invention is used as a photocatalyst and shows excellent photocatalytic synthetic ammonia activity in 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 fields of energy and photocatalysis.
Background
At present, the industry mainly utilizesThe heterogeneous composite catalyst is used for catalytically synthesizing ammonia under the conditions of high temperature and high pressure. This reaction is commercially expensive and produces large amounts of NO during the synthesis x And the method is not in accordance with the current green chemistry research concept. Solar-driven photocatalytic nitrogen fixation is a potential green new method that can be designed to simulate the ammonia production process. However, the activity efficiency of the photocatalyst reported at present is low, and the development of a suitable photocatalyst for the nitrogen fixation reaction is considered to be a technology with great research and application prospects.
Sulfides (e.g. CdS, znS and In) 2 S 3 Etc.) have received much attention because of their band gaps suitable for absorbing sunlight and appropriate band structures for nitrogen fixation. The composition and the preparation method are optimized, so that the photocatalytic performance can be further improved, such as doping elements, supporting promoters or forming solid solutions by combining with other sulfides. The multi-component sulfide solid solution has an adjustable energy band structure, so that the absorption of visible light of the catalyst can be enhanced. Meanwhile, due to the difference of ionic radius, some metal elements with small ionic radius are added to easily cause some surface vacancies. Such as Mn x Cd 1-x S is formed by compounding CdS and MnS, and has attracted much attention in recent years. Similarly, mnS can be doped into other metal sulfides such as ZnS and In by regulating the type of raw materials, the type of solvent and the reaction conditions 2 S 3 Formation of 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 problem of how to synthesize the S-MZS and S-MIS solid solutions and improve the photocatalytic nitrogen fixation activity of the S-MZS and S-MIS solid solutions. 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 technical scheme that:
the preparation method of the S-doped defect state solid solution is characterized by comprising the following steps: the S-doped defect state solid solution is S-doped Mn x Zn 1-x The S defect state solid solution is marked as S-MZS; or the S-doped defect state solid solution is S-doped Mn x In 1-x And the S defect state solid solution is marked as S-MIS. Wherein 0 < x < 1。
The S-MZS is hydrated manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O and thioacetamide CH 3 CSNH 2 The raw materials are obtained through one-step hydrothermal reaction, and the method comprises the following specific steps: mixing MnSO 4 ·H 2 O、Zn(NO 3 ) 2 ·6H 2 O, 10mmol of CH 3 CSNH 2 Adding the mixture into a 100mL polytetrafluoroethylene reaction kettle; then adding 60mL of deionized water into the reaction kettle, uniformly stirring, sealing the reaction kettle in a steel sleeve, and carrying out hydrothermal reaction at 180 ℃ for 24 hours; after the reaction is finished, cooling to room temperature, 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 In molar amount of MnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 O
3-4 times of the total molar weight.
The S-MIS is hydrated manganese sulfate MnSO 4 ·H 2 O, indium nitrate hydrate In (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 The raw materials are obtained through one-step hydrothermal reaction, and the method comprises the following specific steps: mixing MnSO 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 at 180 ℃ for 24 hours; after the reaction is finished, cooling to room temperature to obtainWashing 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 In molar amount of MnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 3 to 4 times of the total molar weight of O.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method has simple and convenient 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 The S nano material provides a simple and convenient reference new method for synthesizing other nano materials;
2. the invention optimizes the raw material type, solvent type and reaction conditions for preparing S-MZS and S-MIS defect state solid solutions, so that the S-MZS and S-MIS defect state solid solutions have optimal synthetic ammonia activity and catalytic stability.
3. Due to Mn 2+ Has a radius (67 pm) less than Zn 2+ (74 pm) and In 3+ (80 pm) radius, according to the preparation method of the present invention, easily causes defect sites of Mn in the process of forming a solid solution.
4. The S-doped defect state solid solution prepared by the invention is used as a photocatalyst and shows excellent photocatalytic synthetic ammonia activity in visible light photocatalytic nitrogen fixation reaction. When x =0.1, S-MZS and S-MIS show good nitrogen fixation activity under visible light irradiation (reaction time is 4 h), which is 295.11 mg.L -1 ·g cat -1 And 183.38 mg. L -1 ·g cat -1 Much larger 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.
FIGS. 3 (a) and 3 (b) are SEM images of S-MZS synthesized in example 1, and FIGS. 3 (c) and 3 (d) are SEM images of S-MIS synthesized in example 2.
FIGS. 4 (a) and 4 (b) are TEM and HR-TEM images of S-MZS synthesized in example 1, and FIGS. 4 (c) and 4 (d) are TEM and HR-TEM images of S-MIS synthesized in example 2.
FIG. 5 is an EPR chart 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 the amount of ammonia nitrogen of the S-MZS solid solution and the S-MIS solid solution in example 3;
FIG. 7 is a graph showing the visible-light photocatalytic synthesis ammonia activity of the S-MZS solid solution and the S-MIS solid solution in example 3;
fig. 8 is a screening experiment of the optimal synthesis conditions of the 0.1MZS photocatalyst, which sequentially comprises: different Zn sources (fig. 8 (a)), different Mn: zn ratio (fig. 8 (b)), different S source (fig. 8 (c)), different TAA amount (fig. 8 (d)), different reaction solvent (fig. 8 (e)), and different reaction temperature (fig. 8 (f)).
FIG. 9 shows a screening experiment of the optimal nitrogen fixation reaction conditions of the 0.1MZS photocatalyst, sequentially comprising different nitrogen fixation reaction solvents (FIG. 9 (a)) and different reactions N 2 Pressure (fig. 9 (b)), different reaction time (fig. 9 (c)), and different reaction times (fig. 9 (d)).
Fig. 10 shows screening experiments of 0.1MIS photocatalyst optimal synthesis conditions and optimal nitrogen fixation reaction conditions, in which different reaction temperatures (fig. 10 (a)), different In sources (fig. 10 (b)), different S sources (fig. 10 (c)), different reaction solvents (fig. 10 (d)), different Mn: in ratio (FIG. 10 (e)), different nitrogen-fixing reaction solvents (FIG. 10 (f)), and different reaction N 2 Pressure (fig. 10 (g)), different reaction time (fig. 10 (h)), and different reaction times (fig. 10 (i)).
Detailed Description
The present invention is further described with reference to the following specific embodiments, which are merely exemplary in nature, and the following embodiments are implemented based on the technical solutions of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
This example prepares S-doped Mn as follows x Zn 1-x S-defect solid solution (x =0.1 for example):
weighing 0.3mmol MnSO 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 at 180 ℃ for 24h; after the reaction is finished, cooling to room temperature, washing and drying the obtained product to obtain S doped Mn with x =0.1 x Zn 1-x S defect state solid solution, noted 0.1MZS.
Example 2
This example prepares S-doped Mn as follows x In 1-x S-defect solid solution (x =0.1 for example):
weighing 0.3mmol MnSO 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 at 180 ℃ for 24h; after the reaction is finished, cooling to room temperature, washing and drying the obtained product to obtain S doped Mn with x =0.1 x In 1-x Solid solution in S-defect state, noted 0.1MIS.
Example 3
This example tests the performance of 0.1MZS and 0.1MIS visible light photocatalytic nitrogen fixation as follows:
And 3, stirring for 30 minutes under the condition of no illumination to complete the dynamic balance of adsorption and 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 step 5, firstly centrifuging the solution after reaction, taking 5mL of centrifuged supernatant into a 50mL volumetric flask, adding deionized water to a constant volume until the volume reaches a marked line, shaking up, and standing. 1mL of potassium sodium tartrate solution and 1mL of Nashi reagent are respectively added into the solution and mixed evenly. Standing the solution for 10min, and detecting the absorbance at 420nm by using an ultraviolet visible diffuse reflection spectrometer.
Characterization of S-MZS and S-MIS solid solutions:
FIG. 1 is an XRD pattern of 0.1MZS, znS and MnS, from which it can be seen that 0.1MZS (JCPDSNo. 89-4957), znS (JCPDSNo. 77-2100) and MnS (JCPDSNo. 89-4952) all have corresponding Jade cards, and are in alignment. Wherein, impurity peaks appear in 0.1MZS and ZnS in XRD pattern, and the impurity peaks are found to be peaks of S8 simple substance by comparing with standard cards, and the corresponding card is (JCPDSNo. 89-2600). It has a distinct peak at 23.1 deg., corresponding to the (222) plane of S. From the XRD pattern of 0.1MZS, peaks at 28.4, 47.3, and 56.1 are clearly visible, which are assigned to the (111), (220), and (311) crystal planes of the cubic phase crystal MZS, respectively. The synthesized catalyst can thus be determined to be an S-doped MZS.
FIG. 2 shows 0.1MIS (JCPDSNo.85-1229) and In 2 S 3 (JCPDSNo. 84-1385) and MnS (JCPDSNo. 89-4952). For In 2 S 3 And the peaks of 0.1MIS, S (222) crystal face still exist, and the peaks of MIS at 27.5 degrees, 33.4 degrees, 43.8 degrees and 47.9 degrees are respectively attributed to the MIS (311), (400), (511) and (440) crystal faces of cubic phase crystal forms, which indicates 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 composed of nanoparticles. Fig. 3 (c) and 3 (d) are SEM images of 0.1MIS at different magnifications, and it can be seen that 0.1MIS is spherical composed of nanosheets. The TEM at 0.1MZS (fig. 4 a) further indicates that these spheres are composed of a close packing of many small particles, that in HR-TEM images lattice fringes with a lattice spacing of 0.31nm can be observed (fig. 4 b), and that the lattice spacing corresponds to the (111) lattice plane of the MZS. Fig. 4 (c) is a TEM image of 0.1MIS, which can be seen that MIS is a sphere composed of many nanosheets, and the existence of a plate shape can also be seen at the edge portion of the image. In the HR-TEM image of 0.1MIS (fig. 4 d), lattice fringes with a spacing of 0.62nm can be observed, and the lattice spacing corresponds to the (111) plane of the MIS.
Unpaired electrons in 0.1MZS and 0.1MIS nanomaterials were studied using an electron spin resonance spectrometer (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 photocatalysts all have vacancies, i.e., the surface has defect sites. These peak intensities are mainly attributed to Mn vacancies, whose intensities are as follows: 0.1MIS >. Since In has a larger ionic radius 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 UV absorption spectra of 0.1MZS, 0.1MIS, mnS and a blank sample after 4h irradiation with visible light, from which the absorbances of 0.1MZS, 0.1MIS and MnS at 420nm are 1.61, 1.05, 1.00 and 0.11, respectively, while the absorbance of the blank sample is 0.04. The ammonia amounts of 0.1MZS, 0.1MIS and MnS were calculated to be 295.11, 183.38, 19.52 and 2.40 mg. L -1 ·g cat -1 (FIG. 7). The amount of ammonia contained in the blank sample was negligible when nitrogen was fixed. 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 far higher than that of the monomer catalyst.
As shown in fig. 8, according to the method for testing nitrogen fixation performance of example 3, the present invention also conducted screening and searching 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 source (fig. 8 (c)), different TAA amount (fig. 8 (d)), different reaction solvent (fig. 8 (e)), and different reaction temperature (fig. 8 (f)), and optimal synthesis conditions were obtained. Zn (NO) 3 ) 2 ·6H 2 The ammonia amount produced by 0.1MZS synthesized by O as zinc source 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 with O as a zinc source was 18 times, and Zn (NO) was known 3 ) 2 ·6H 2 The 0.1MZS synthesized by taking O as a zinc source has higher nitrogen fixation activity. Meanwhile, mn: 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 charge) was found to show a tendency to increase and then decrease the amount of photocatalytically synthesized nitrogen, and the maximum amount of photocatalytically fixed nitrogen was found when the molar ratio of Mn to Zn was 0.1. Meanwhile, the S source was also examined (FIG. 8 (c)), and NH of the catalyst synthesized using L-cysteine (L-cys) and Thiourea (TA) as sulfur sources was found 4 + The concentration is respectively 10.26 mg.L -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 a sulfur source. Further, when the amount of TAA added was 10mmol, the nitrogen fixation amount reached the maximum value. The nitrogen fixation activity of 0.1MZS under the action of different reaction solvents (FIG. 8 (e)) is, in order, 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 (30mL each, 8.87mg. L -1 ·g cat -1 ). Different catalyst synthesis temperatures, N 2 The amount of conversion to nitrogen 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 a 0.1MZS photocatalyst synthesized at 200 ℃ is 96.71 mg.L -1 ·g cat -1 . NH when the temperature reached 180 ℃ compared to the samples prepared at 160 ℃ and 200 ℃ 4 + The concentration reaches the maximum value of 295.11 mg.L -1 ·g cat -1 . Thus, the optimal synthesis conditions are obtained: at 180 ℃ with Zn (NO) 3 ) 2 ·6H 2 The nitrogen fixing activity of the 0.1MZS photocatalyst synthesized by taking O as a zinc source, TAA as a sulfur source and deionized water as a solvent is best.
As shown in FIG. 9, after searching the synthesis conditions, the present inventors also searched the optimum conditions for the nitrogen fixation light reaction with 0.1MZS as the photocatalyst (the test was carried out by changing one of the conditions according to the method of example 3), such as the reaction solvent (FIG. 9 (a)), and the gas N 2 Pressure (fig. 9 (b)), reaction time (fig. 9 (c)), and number of reactions (fig. 9 (d)).
The invention uses H separately 2 O、CH 3 OH and CH 3 CH 2 OH as solvent for the 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 a solvent -1 ·g cat -1 Is greater than CH 3 CH 2 Ammonia production with OH as solvent (167.35 mg. L) -1 ·g cat -1 ) This is because of N 2 In CH 3 Greater solubility in OH, and CH 3 OH not only provides hydrogen protons, but also reacts 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 The nitrogen fixation amount at 0.3MPa 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 . The optimal reaction conditions are obtained, the light reaction is carried out by taking 0.3MPa nitrogen as reaction gas and methanol as reaction solvent, and the nitrogen fixation amount of 0.1MZS is the maximum.
In addition, the present invention utilizes the catalyst to perform light experiments and extend the light 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), the ammonia nitrogen amount fixed by the 0.1MZS photocatalyst increased and reached an equilibrium value of about 4 hours as the time the catalyst was illuminated with visible light increased. In the circulation experiment process, on the basis of ensuring that the reaction condition is not changed, 30mg of photocatalyst is weighed to carry out the illumination experiment, the catalyst is collected by centrifugation after 4 hours of illumination, and then the catalyst is dried for 10 hours in vacuum at 60 ℃ after being repeatedly cleaned by deionized water and ethanol. The resulting sample was ground for the next light experiment, resulting in fig. 9 (d) after 5 cycles. As can be seen from the figure, after the first cycle experiment, the ammonia yield is from 295.11 mg.L -1 ·g cat -1 Reduced to 235.71 mg.L -1 ·g cat -1 And relatively stable in the rest circulation experiments (after the S simple substance is consumed).Therefore, the existence of S simple substance plays an important role in the 0.1MZS ammonia synthesis reaction.
Finally, the present invention performed the same method for the synthesis conditions, nitrogen fixation reaction conditions and stability of 0.1MIS (FIG. 10), in (NO) at 180 ℃. (FIG. 10) 3 ) 2 ·6H 2 O is an indium source, TAA is a sulfur source, deionized water is a solvent, and the nitrogen fixing activity of the synthesized MIS photocatalyst is the best when the molar ratio of Mn to In is 0.1. Meanwhile, the optimal nitrogen fixation reaction condition is to take 0.3MPa nitrogen as reaction gas \ methanol as reaction solvent to carry out illumination reaction for 4 hours. In addition, as the number of reaction times increases, the activity of photocatalytic synthesis of ammonia gradually decreases, and stability needs to be improved.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
- 5363 a preparation method of 1.S doped defect state solid solution, which is characterized in that: the S-doped defect state solid solution is S-doped Mn x Zn 1-x The S defect state solid solution is marked as S-MZS; or the S-doped defect state solid solution is S-doped Mn x In 1-x The S defect state solid solution is marked as S-MIS;the S-MZS is hydrated manganese sulfate MnSO 4 ·H 2 O, zinc nitrate hydrate Zn (NO) 3 ) 2 ·6H 2 O and thioacetamide CH 3 CSNH 2 As raw materials, the catalyst is obtained by one-step hydrothermal reaction;the S-MIS is hydrated manganese sulfate MnSO 4 ·H 2 O, indium nitrate hydrate In (NO) 3 ) 3 ·yH 2 O and thioacetamide CH 3 CSNH 2 The raw material is obtained through one-step hydrothermal reaction.
- 2. The method of claim 1, wherein the step of preparing the S-MZS comprises:mixing MnSO 4 ·H 2 O、Zn(NO 3 ) 2 ·6H 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 at 180 ℃ for 24 hours; after the reaction is finished, cooling to room temperature, 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 In molar amount of MnSO 4 ·H 2 O and Zn (NO) 3 ) 2 ·6H 2 3 to 4 times of the total molar weight of O.
- 3. The method of manufacturing of claim 1, wherein the step of manufacturing S-MIS is:mixing MnSO 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 at 180 ℃ for 24 hours; after the reaction is finished, cooling to room temperature, 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 In a molar amount of MnSO 4 ·H 2 O and In (NO) 3 ) 3 ·yH 2 3 to 4 times of the total molar weight of O.
- 4. The production method according to claim 1, 2 or 3, characterized in that: 0-and x-are woven as a bundle of 1.
- 5. An S-doped defect state solid solution prepared by the preparation method of any one of claims 1 to 4.
- 6. Use of the S-doped defect state solid solution of claim 5 as a photocatalyst for photocatalytic nitrogen fixation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211025628.8A CN115155619B (en) | 2022-08-25 | 2022-08-25 | Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211025628.8A CN115155619B (en) | 2022-08-25 | 2022-08-25 | Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115155619A true CN115155619A (en) | 2022-10-11 |
| CN115155619B CN115155619B (en) | 2023-08-22 |
Family
ID=83481135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211025628.8A Active CN115155619B (en) | 2022-08-25 | 2022-08-25 | Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115155619B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050036938A1 (en) * | 2003-08-13 | 2005-02-17 | Taegwhan Hyeon | Method for synthesizing nanoparticles of metal sulfides |
| 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 |
-
2022
- 2022-08-25 CN CN202211025628.8A patent/CN115155619B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050036938A1 (en) * | 2003-08-13 | 2005-02-17 | Taegwhan Hyeon | Method for synthesizing nanoparticles of metal sulfides |
| 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 (2)
| Title |
|---|
| YIBIN SONG等: "Cu7S4/MnIn2S4 heterojunction for efficient photocatalytic hydrogen generation", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 884, pages 1 - 9 * |
| 王璐: "基于纳米硫化锌光催化材料的制备及性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 01, pages 43 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115155619B (en) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Hollow ZnCdS dodecahedral cages for highly efficient visible-light-driven hydrogen generation | |
| CN107115861B (en) | A kind of Au-TiO2-xCatalyst and its application | |
| CN108525677B (en) | Cerium dioxide/indium zinc sulfide nanosheet composite catalyst and application thereof in visible light catalysis of CO2Use in transformation | |
| CN107774294A (en) | A kind of novel photochemical catalyst K g C3N4And its prepare and apply | |
| CN110560105A (en) | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production | |
| CN109174145A (en) | A kind of dimolybdenum carbide/titanium dioxide composite photocatalyst and its preparation method and application | |
| CN110586166A (en) | Preparation of molybdenum oxide nanosheet and application of molybdenum oxide nanosheet in photocatalytic nitrogen fixation | |
| Wang et al. | WC and cobalt nanoparticles embedded in nitrogen-doped carbon 3D nanocage derived from H 3 PW 12 O 40@ ZIF-67 for photocatalytic nitrogen fixation | |
| Wang et al. | Rose spherical structure Ag2S/ZnIn2S4/ZnS composites with visible light response: enhanced photodegradation and hydrogen production performance | |
| CN105885847B (en) | A kind of cadmium sulfoselenide solid solution quantum dot and preparation method thereof and Photocatalyzed Hydrogen Production application | |
| Liu et al. | Enhancing photocatalytic nitrogen fixation performance of Co-doped bismuth molybdate through band engineering tuning | |
| Cui et al. | A novel cobalt-anchored covalent organic framework for photocatalytic conversion of CO 2 into widely adjustable syngas | |
| Li et al. | Synthesis of palladium-modified MnS photocatalysts with enhanced photocatalytic activity in the photoreduction of CO2 to CH4 | |
| Li et al. | Improved photocatalytic activity of ZnO via the modification of In2O3 and MoS2 surface species for the photoreduction of CO2 | |
| Perfecto-Irigaray et al. | Copper (II)-porphyrin functionalized titanium (IV) metal-organic aerogels for the visible-light driven conversion of CO2 to alcohols | |
| CN114534783A (en) | Method for preparing monatomic Pt-embedded covalent organic framework photocatalyst and application thereof | |
| CN114308079A (en) | Cadmium sulfide-double-cocatalyst composite photocatalytic material and preparation method and application thereof | |
| CN109876826B (en) | Preparation method of sulfur-rich vacancy photocatalyst | |
| CN115155619B (en) | Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction | |
| CN116726949A (en) | Cd (cadmium sulfide) 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis | |
| CN115025783B (en) | Synthetic method and application of multi-niobium oxygen cluster/ZIF-67 derivative composite material | |
| CN113856712B (en) | Preparation method of catalyst for photocatalytic decomposition of pure water | |
| CN113578311A (en) | WO with rich electrons on surface3Nanosheet and preparation method and application thereof | |
| CN110721716A (en) | Catalysis of CO2Selective hydrogenation to CH4And a process for preparing the same | |
| CN115893523A (en) | Preparation method and application of transition metal phosphide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |