CN112264049A - Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Process for preparing catalyst - Google Patents
Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Process for preparing catalyst Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 226
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 113
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 65
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 35
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 97
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 48
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007605 air drying Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004201 L-cysteine Substances 0.000 claims abstract description 22
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 19
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical group Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910015221 MoCl5 Inorganic materials 0.000 claims description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011941 photocatalyst Substances 0.000 description 30
- 238000004435 EPR spectroscopy Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910015667 MoO4 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- -1 Fe (III) modified carbon nitride Chemical class 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical compound [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation1‑xIn2S4A method for preparing the catalyst. The method comprises the following steps: dissolving zinc nitrate hexahydrate, indium nitrate and L-cysteine into deionized water under the condition of magnetic stirring, adding inorganic salt containing molybdenum or iron, transferring the mixed solution into a hydrothermal reaction kettle after magnetic stirring, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, cooling to room temperature after carrying out hydrothermal reaction for 15-24 hours to obtain yellow-green precipitates, washing the yellow-green precipitates by using the deionized water and ethanol in sequence, repeatedly carrying out centrifugal washing for 3-5 times, and drying at 60-100 ℃ in the forced air drying oven overnight to obtain Mo or Fe doped Zn1‑xIn2S4A photocatalytic nitrogen fixation catalyst. The Mo or Fe of the invention is doped with Zn1‑xIn2S4The photocatalytic nitrogen fixation catalyst has high nitrogen fixation efficiency, simple preparation method and good application prospect.
Description
Technical Field
The invention relates to the field of photocatalysts, in particular to Mo or Fe doped Zn for synthesizing ammonia by photocatalytic nitrogen fixation1-xIn2S4A method for preparing the catalyst.
Background
Ammonia is not only a widely used chemical raw material, but also an important energy carrier. The haber method for synthesizing ammonia is considered as one of the most great inventions in the 20 th century, and makes a great contribution to the development of the human society. At the same time, the ammonia synthesis process is required to consume 1% -2% of the world's total energy annually. Therefore, the development of green and clean ammonia synthesis processes has been a focus of attention in industry and academia worldwide. With the vigorous development of the research of artificial photosynthesis of solar fuel, the realization of ammonia synthesis under mild conditions by means of solar photocatalysis attracts more and more researchers, because it is a most ideal energy utilization approach, i.e. the direct utilization of solar energy to convert nitrogen and water into ammonia (catalytic science, 2018, (39): 1180 and 1188).
Currently, the research finds that the catalysts with the performance of photocatalytic nitrogen fixation for ammonia synthesis mainly belong to the following types: (1) bi-based photocatalytic nitrogen-fixing material. The invention patent with the application number of CN201811388166.X discloses preparation of a nano carbon fiber supported bismuth oxyhalide (BiOI/BiOBr/CNFs) photocatalyst and application of the photocatalyst in solar nitrogen fixation. The invention patent with the application number of CN201810784797.7 discloses a preparation method and application of a BiS/BiOBr composite photocatalytic material. Invention with application number CN201711218003.2The patent discloses a synthetic ammonia catalyst (Bi)xTM1yTM2zOCl) and a preparation method and application thereof. Application number CN201911359180.1 discloses a nitrogen-doped attapulgite/carbon/bismuth oxybromide (BiOBr) composite nitrogen fixation photocatalyst and a preparation method and application thereof. The invention patent with the application number of CN201610015669.7 discloses a Bi2O3-x/nBiaMObSolar nitrogen fixation photocatalytic material. (2) The carbon nitride is a photocatalytic nitrogen fixation material. The invention patent with the application number of CN109317180A discloses a preparation method of a photocatalytic nitrogen fixation g-CN/oxide composite material. The invention patent with the application number of CN201811101338.0 discloses an Fe (III) modified carbon nitride nanosheet and application thereof in photocatalysis nitrogen fixation. The invention patent with the application number of CN202010138708.9 discloses a carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and a preparation method thereof. (3) Other photocatalytic nitrogen fixation catalysts. The invention patent with the application number of CN201811514532.1 discloses lithium niobate (LiNbO)3) The oxide/attapulgite nonlinear optical composite photocatalytic material can adsorb partial nitrogen in the photocatalytic nitrogen fixation process and improve the photocatalytic nitrogen fixation efficiency as well as the preparation method and the application thereof. Chinese patent No. CN10953491A discloses a Lanthanum Titanate (LTO) nanosheet photocatalyst containing oxygen vacancies, and its application in photocatalytic nitrogen fixation; the oxygen vacancy-containing LTO nanosheet has obviously improved photocatalytic nitrogen fixation performance. Chinese patent with application number CN109225194A discloses a preparation method and application of a Zn-doped indium oxide photocatalytic nitrogen fixation material, wherein the photocatalyst material is a ferromanganese ore type metal oxide and shows excellent chemical stability in application of photocatalytic nitrogen fixation and ammonia synthesis. The invention patent with the application number of CN201910864772.2 discloses a preparation method and application of a black phosphorus nanosheet/cadmium sulfide photocatalytic nitrogen fixation catalyst. Chinese patent application No. CN201910893860.5 discloses the application of titanium-based metal organic framework material in photocatalytic nitrogen fixation.
However, in summary, the prior art has the following problems:
(1) the main problem of the Bi-based photocatalytic nitrogen fixation catalyst is thatThe oxidation capability and the reduction capability of the composite material are stronger due to the fact that the valence band potential is more positive, and the reaction formula of the composite material due to photocatalysis nitrogen fixation is as follows: n is a radical of2 + 6H+ + 6e− → 2NH3，-0.09 V vs.NHE. It can be seen that this is a reduction reaction in which photo-generated electrons participate, and therefore, it is a better choice to select a photocatalyst having a more negative conduction band potential (i.e., a stronger reducing power).
(2) The main problem of the carbon nitride-based photocatalytic nitrogen fixation catalyst is that nitrogen in the carbon nitride catalyst is generally separated out in the photocatalytic nitrogen fixation reaction process, which greatly interferes with the accuracy of the yield detection of ammonia synthesized by photocatalytic nitrogen fixation.
(3) The currently developed photocatalyst for nitrogen fixation and ammonia synthesis has low ammonia synthesis efficiency, which is generally dozens of mu mol g-1·h-1The method is far from the target of actual industrial production, so that a new photocatalytic nitrogen fixation catalyst system needs to be developed to improve the efficiency of synthesizing ammonia by photocatalytic nitrogen fixation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Preparation method of catalyst, the preparation method is simpler, and the synthesized Mo or Fe doped Zn1-xIn2S4The photocatalysis nitrogen fixation catalyst is nontoxic and harmless and has good application prospect.
Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4The preparation method of the catalyst comprises the following specific steps: under the condition of magnetic stirring, zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), indium nitrate (In (NO)3)3) Dissolving L-cysteine into deionized water, adding inorganic salt containing molybdenum (Mo) or iron (Fe), magnetically stirring for 10-30 min, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 15-24 h, and cooling the reaction system to room temperature to obtain yellow greenColor precipitation, washing the yellow-green precipitate with deionized water and ethanol sequentially, centrifuging and washing for 3-5 times, and drying at 60-100 deg.C in a forced air drying oven overnight to obtain Mo or Fe doped Zn1- xIn2S4A photocatalytic nitrogen fixation catalyst.
Preferably, the zinc nitrate hexahydrate Zn (NO)3)2·6H2O and indium nitrate In (NO)3)3The molar ratio of (A) to (B) is 1: 2-3.
Preferably, the zinc nitrate hexahydrate Zn (NO)3)2·6H2The molar ratio of O to L-cysteine is 1: 8-12.
Preferably, the inorganic salt containing molybdenum Mo element is molybdenum pentachloride MoCl5Or sodium molybdate Na2MoO4Wherein the inorganic salt containing Fe is Fe nitrate Nonahydrate (NO)3)3·9H2O。
Preferably, the doped Mo or Fe is In (NO) relative to indium nitrate3)3The mole percentage of (A) is 1-5%.
Preferably, the hydrothermal reaction temperature is 180-.
The invention benefits from the nitrogen fixation mechanism and the inspiration of biological nitrogen fixation enzyme (such as Mo-based nitrogen fixation enzyme) in agricultural production, and finds that the structure design of the photocatalyst is utilized to construct a catalytic center on the surface of a semiconductor to simulate ferromolybdenum (Mo-Fe) cofactor on adsorbed N2The activation of the molecule is an important way for realizing the photocatalysis nitrogen fixation.
The invention selects ZnIn with a layered structure2S4As the photocatalytic nitrogen fixation catalyst, the following three reasons are based: (1) ZnIn2S4Has a conduction band potential of-0.88Vvs.NHE, ratio N2Potential for reduction reaction with 6 electrons and 6 protons (-0.09V)vs.NHE) more negative, indicating ZnIn2S4Has stronger photocatalytic reduction capability, namely ZnIn2S4Is a more suitable photocatalysis nitrogen fixation catalyst; (2) doping Zn containing Zn vacancies by Mo or Fe1-xIn2S4Make it form unsaturated site and promote N2Activation of molecules on the catalyst surface; (3) ZnIn2S4The forbidden band width of the photocatalyst is about 2.3 eV, most of visible light can be absorbed, the absorption utilization rate of the photocatalyst to sunlight is enhanced, and the photocatalytic nitrogen fixation efficiency is improved.
Has the advantages that:
compared with the prior art, the Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4The preparation method of the catalyst has the following advantages:
(1) by utilizing the method provided by the invention, Zn vacancy is introduced and Fe is doped3+、Mo5+、Mo6+Can improve the efficiency of synthesizing ammonia by photocatalytic nitrogen fixation, in particular 4 percent of Mo6+Doped Zn1-xIn2S4The photocatalytic nitrogen fixation catalyst has the best performance, and the efficiency of synthesizing ammonia by photocatalytic nitrogen fixation reaches 358.98 mu mol g-1·h-1Is pure ZnIn2S4The ammonia yield of the photocatalysis nitrogen fixation catalyst is 61 times, which shows that the efficiency of synthesizing ammonia by photocatalysis nitrogen fixation can be greatly improved by the technology provided by the invention.
(2) Photocurrent response test shows Mo6+Doped Zn1-xIn2S4The photo-catalytic nitrogen fixation catalyst has the maximum photo-current density, which shows that Mo6+Doped Zn1-xIn2S4The photocatalytic nitrogen fixation catalyst has higher separation and migration rate of photon-generated carriers.
(3) Mo or Fe doped Zn synthesized by the invention1-xIn2S4The photocatalysis nitrogen fixation catalyst is nontoxic and harmless, and the preparation method and the process flow are simpler, so that the photocatalysis nitrogen fixation catalyst has better application prospect.
Drawings
FIG. 1 is an XRD spectrum of different prepared nitrogen-fixing photocatalysts, wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, and (e) is example 5;
FIG. 2 shows Electron Paramagnetic Resonance (EPR) spectra of different prepared nitrogen-fixing photocatalysts, wherein (a) is example 1 and (b) is example 2;
FIG. 3 is a TEM image of a nitrogen-fixing photocatalyst prepared by example 5, wherein (a) is 20nm and (b) is 5 nm;
FIG. 4(A) is a graph showing the change in ammonia production concentration with time of irradiation of visible light for different nitrogen-fixing photocatalysts prepared according to examples 1 to 5, wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, and (e) is example 5;
FIG. 4(B) is a graph showing the comparison of the effect of the photocatalysts for fixing nitrogen and synthesizing ammonia after 120 min of visible light irradiation for different nitrogen-fixing photocatalysts prepared in examples 1-5, wherein (a) is example 1, (B) is example 2, (c) is example 3, (d) is example 4, and (e) is example 5;
FIG. 5 shows different Mo's prepared in examples 5 to 96+The yield effect of the nitrogen fixation and ammonia synthesis by photocatalysis after 120 min visible light irradiation of the nitrogen fixation photocatalyst with doping amount is shown schematically, wherein (a) is example 5, (b) is example 6, (c) is example 7, (d) is example 8, and (e) is example 9;
FIG. 6 is a graph showing the comparison of the effect of the photocatalysts for fixing nitrogen and synthesizing ammonia after 120 min of visible light irradiation on different nitrogen-fixing photocatalysts prepared in examples 10-14, wherein (a) is example 10, (b) is example 11, (c) is example 12, (d) is example 13, and (e) is example 14;
fig. 7 is a graph showing photocurrent responses of different prepared nitrogen-fixing photocatalysts, wherein (a) is example 1, (b) is example 2, (c) is example 4, and (d) is example 5.
Detailed Description
The invention will be described below with reference to the accompanying drawings and specific embodiments.
Example 1 pure ZnIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0744g (i.e. 0.25 mmol) of zinc nitrate hexahydrate (Zn (NO) was added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol)Indium nitrate (In (NO)3)3) 0.2420g (namely 2 mmol) of L-cysteine is dissolved in 30mL of deionized water, the mixture is magnetically stirred for 10 minutes, then the mixed solution is transferred to a hydrothermal reaction kettle, the hydrothermal reaction kettle and the hydrothermal reaction kettle are put into a forced air drying oven for hydrothermal reaction at 180 ℃ for 18 hours, a yellow-green precipitate is obtained after the mixture is cooled to room temperature, the yellow-green precipitate is centrifugally washed by deionized water and ethanol in sequence, the washing is repeated for 3 times, and the mixture is dried in the forced air drying oven at 60 ℃ overnight to obtain pure ZnIn2S4A photocatalytic nitrogen fixation catalyst.
EXAMPLE 2 Zn with Zn vacancies1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (namely 2 mmol) of L-cysteine is dissolved in 30mL of deionized water, the mixture is magnetically stirred for 10 minutes, then the mixed solution is transferred to a hydrothermal reaction kettle, the hydrothermal reaction kettle and the hydrothermal reaction kettle are put into a forced air drying oven, the hydrothermal reaction is carried out for 18 hours at 200 ℃, yellow-green precipitates are obtained after the mixture is cooled to room temperature, the yellow-green precipitates are centrifugally washed by deionized water and ethanol in sequence, the washing is repeated for 3 times, and the mixture is dried in the forced air drying oven at 60 ℃ overnight to obtain Zn containing Zn vacancy1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 31% Fe3+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (i.e., 2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0021g (i.e., 0.005 mmol) of iron nitrate nonahydrate (Fe (NO)3)3·9H2O), magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, and putting the hydrothermal reaction kettle and the hydrothermal reaction kettle into a drum for air dryingCarrying out hydrothermal reaction for 18 hours at 200 ℃ in a drying box, cooling to room temperature to obtain yellow-green precipitates, carrying out centrifugal washing on the yellow-green precipitates by using deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying in a forced air drying box at 60 ℃ overnight to obtain 1% Fe3+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 41% Mo5+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0013g (0.005 mmol) of molybdenum pentachloride (MoCl) was added5) Magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 18 hours at 200 ℃, cooling to room temperature to obtain a yellow-green precipitate, carrying out centrifugal washing on the yellow-green precipitate by using deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying in the forced air drying oven at 60 ℃ overnight to obtain 1% Mo5+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 51% Mo6+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (i.e., 2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0012g (i.e., 0.005 mmol) of sodium molybdate (Na)2MoO4) Magnetically stirring for 10 min, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction at 200 ℃ for 18 h, cooling to room temperature to obtain yellow-green precipitate, and sequentially centrifuging by using deionized water and ethanolWashing the yellow-green precipitate, repeating the washing for 3 times, and drying in a forced air drying oven at 60 deg.C overnight to obtain 1% Mo6+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 62% Mo6+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0024g (0.01 mmol) of sodium molybdate (Na) was added2MoO4) Magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 18 hours at 200 ℃, cooling to room temperature to obtain a yellow-green precipitate, carrying out centrifugal washing on the yellow-green precipitate by using deionized water and ethanol in sequence, washing for 3 times repeatedly, and drying at 60 ℃ in the forced air drying oven overnight to obtain 2% Mo6+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 73% Mo6+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0036g (0.015 mmol) of sodium molybdate (Na) was added2MoO4) Magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 18 hours at 200 ℃, cooling to room temperature to obtain a yellow-green precipitate, carrying out centrifugal washing on the yellow-green precipitate by using deionized water and ethanol in sequence, washing for 3 times repeatedly, and drying at 60 ℃ in the forced air drying oven overnight to obtain 3% Mo6+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 84% Mo6+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (i.e., 2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0048g (i.e., 0.02 mmol) of sodium molybdate (Na) was added2MoO4) Magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 18 hours at 200 ℃, cooling to room temperature to obtain a yellow-green precipitate, sequentially carrying out centrifugal washing with deionized water and ethanol, repeatedly washing for 3 times, and drying at 60 ℃ in the forced air drying oven overnight to obtain 4% Mo6+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 95% Mo6+Doped with Zn1-xIn2S4Preparation of photocatalysis nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) were added under magnetic stirring3)2·6H2O), 0.1504g (i.e. 0.5 mmol) of indium nitrate (In (NO)3)3) 0.2420g (2 mmol) of L-cysteine was dissolved in 30mL of deionized water, and 0.0060g (0.025 mmol) of sodium molybdate (Na) was added2MoO4) Magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a forced air drying oven, carrying out hydrothermal reaction for 18 hours at 200 ℃, cooling to room temperature to obtain a yellow-green precipitate, sequentially washing the yellow-green precipitate with deionized water and ethanol, repeatedly washing for 3 times, and drying at 60 ℃ in the forced air drying oven overnight to obtain 5% Mo6+Doped with Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
Example 10
Similar to example 8, except that Zn (NO)3)2·6H2O and In (NO)3)3In a molar ratio of 1:3, i.e. 0.0595g (i.e. 0.2 mmol), zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 0.1805g (i.e. 0.6 mmol) of indium nitrate (In (NO)3)3）。
Example 11
Similar to example 8, except that Zn (NO)3)2·6H2A molar ratio of O to L-cysteine of 1:8, i.e., 0.0595g (i.e., 0.2 mmol), of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 0.1936g (i.e. 1.6 mmol) of L-cysteine.
Example 12
Similar to example 8, except that Zn (NO)3)2·6H2A molar ratio of O to L-cysteine of 1:12, i.e., 0.0595g (i.e., 0.2 mmol), of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 0.2904g (i.e. 2.4 mmol) of L-cysteine.
Example 13
Similar to example 8, except that the hydrothermal reaction temperature was 180 ℃.
Example 14
Similar to example 8, except that the hydrothermal reaction temperature was 230 ℃.
Characterization of materials
1. XRD analysis
FIGS. 1 (a) -1 (e) are XRD patterns of different nitrogen-fixing photocatalysts prepared in examples 1-5, and it can be seen that XRD diffraction peaks of all samples are similar to those of hexagonal ZnIn2S4The diffraction peaks of the crystalline phases coincide (PDF Standard card No. 72-0773), with no other impurity peaks, indicating that the formation of Zn vacancies, Mo or Fe doping, did not alter ZnIn2S4The crystalline phase of (1).
2. EPR analysis
Fig. 2 (a) is an EPR profile of a nitrogen-fixing photocatalyst prepared by example 1 with almost no EPR signal (g = 2.003); fig. 2 (b) is an EPR profile of the nitrogen-fixing photocatalyst prepared by example 2, and a strong EPR signal (g = 2.003) can be clearly seen. The EPR signal (g = 2.003) should be due to Zn vacancies, as they can trap electrons, resulting in an EPR signal (adv. mater. 2016, 28, 3928).
The nitrogen-fixing photocatalyst prepared in example 2 exhibited an EPR signal attributed to Zn vacancies, which should be due to the absence of stoichiometric additions of starting materials during the preparation: zn in the added raw materials2+And In3+In a molar ratio of 1:2.5, to ZnIn2S4Middle Zn2+And In3+Is clearly Zn compared with the stoichiometric ratio (1: 2)2+Is not sufficient, thereby causing the occurrence of Zn vacancy. The nitrogen-fixing photocatalyst prepared in example 1 did not exhibit an EPR signal attributed to Zn vacancy due to Zn during the preparation process2+And In3+The raw materials of (a) are weighed strictly in a stoichiometric ratio (1: 2), so that no Zn vacancies are produced in the catalyst prepared. This indicates that Zn can be added to the raw material by changing the amount of Zn added2+And In3+Thereby obtaining a molar ratio of ZnIn2S4In the process, Zn vacancy is generated to form Zn1-xIn2S4。
3. TEM analysis
FIG. 3 is 1% Mo prepared by example 56+Doped with Zn1-xIn2S4The TEM image of the photocatalytic nitrogen fixation catalyst shows that the catalyst is in an extremely thin sheet shape; in addition, the sheet is composed of 3-5 layers of ZnIn as seen from the edge of the sheet2S4The layers are composed.
Second, performance test
1. The method for testing the performance of the photocatalytic nitrogen fixation synthetic ammonia comprises the following steps:
a150 mL double-layer jacket beaker is used as a reactor for testing the performance of the photocatalytic nitrogen fixation and ammonia synthesis, wherein circulating cooling water is introduced into a jacket of the double-layer jacket beaker to eliminate heat generated by a light source in the process of photocatalytic reaction, so that the photocatalytic nitrogen fixation and ammonia synthesis test is carried out at normal temperature and normal pressure. The inner wall of the reactor is washed three times by deionized water to ensure that the reactor is not usedAfter cleaning of any impurities, 100 mL of deionized water was added into the reactor, 50 mg of the photocatalytic nitrogen fixation catalyst prepared in the examples was weighed with an electronic balance, added into the reactor, the gas needle was inserted into the reactor, the magnetic stirrer was placed, the magnetic stirrer was opened, the appropriate rotation speed was adjusted, and the quartz glass plate was covered on the upper part of the reactor. Then, the gas valve of the nitrogen cylinder is opened, the pressure reducing valve is adjusted, and the flow rate of nitrogen on the gas flowmeter is controlled to be 40 min.L-1(ii) a Introducing nitrogen under dark conditions and stirring for 30 min to discharge oxygen, carbon dioxide and other gases dissolved in the solution; then, a 300W xenon lamp light source is turned on, a 420 nm filter is inserted into the lower part of the light source, and the current of the light source is set to be 20A; and introducing circulating cooling water, sucking 3mL of the upper-layer solution by using a disposable plastic suction pipe every 30 min after turning on the lamp for illumination, transferring the upper-layer solution into a centrifuge tube, and sucking the upper-layer solution for 5 times in total after illuminating for 120 min. Subsequently, the centrifuge tube is placed into a centrifuge for centrifugal separation, and the parameters of the centrifuge are set as follows: the rotating speed is set to 7000 r min-1The centrifugation time was set to 10 min. After the centrifugation is finished, 2 mL of supernatant is sucked by a disposable pipette and transferred to corresponding new test tubes according to time sequence, and the ammonia nitrogen concentration is measured by using a Nashin reagent spectrophotometry (national environmental protection Standard of the people's republic of China (HJ 535-2009)): adding 0.2 mL of Narse reagent and 0.2 mL of potassium sodium tartrate into a new test tube, fully shaking, finally adding deionized water to dilute to 10 mL, standing for 10 min, carrying out ultraviolet-visible absorption spectrum (UV-2450) test on the diluted solution, taking the absorbance at 420 nm in the measured absorption spectrum as the characteristic absorption intensity, and determining the ammonia concentration (unit: mu mol. L) by using a standard curve of a Narse reagent spectrophotometry method-1) Finally, the obtained ammonia concentration (unit: mu mol. L-1) The data were divided by the mass of the added photocatalytic nitrogen fixation catalyst and the light irradiation time and the average was calculated to obtain the ammonia yield per unit time, per unit mass of the catalyst (unit: mu mol g-1·h-1）。
FIG. 4(A) shows that ammonia production concentration (unit: mu mol. L) of different photocatalytic nitrogen fixation catalysts is increased along with illumination time-1) Of (2) aIt can be seen that the ammonia concentration gradually increases with the increase of the illumination time, and basically conforms to the linear change rule. On the basis of the data of FIG. 4(A), the ammonia yield (unit: μmol. g) per unit time and unit mass of the catalyst was obtained by dividing the mass of the catalyst added and the light irradiation time and calculating the average value-1·h-1) As shown in fig. 4 (B). It can be seen that the pure ZnIn prepared by example 12S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is only 5.84 mu mol g-1·h-1Zn containing Zn vacancies prepared by example 21-xIn2S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is 11.00 mu mol g-1·h-1The increase is about 1 time, and the introduction of Zn vacancy defect can improve the efficiency of synthesizing ammonia by photocatalysis nitrogen fixation. 1% Fe prepared by example 33+Doped with Zn1-xIn2S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is 11.38 [ mu ] mol/g-1·h-11% Mo prepared by example 45+Doped with Zn1-xIn2S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is 19.89 mu mol g-1·h-11% Mo prepared by example 56+Doped with Zn1-xIn2S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is 37.50 [ mu ] mol/g-1·h-1It can be seen that Fe3+、Mo5+、Mo6+Of the three doped classes of catalysts, Mo6+Doped with Zn1-xIn2S4The ammonia yield of the photocatalytic nitrogen fixation catalyst is highest.
FIG. 5 shows different Mo's prepared in examples 5 to 96+The yield effect of the nitrogen fixation synthetic ammonia through photocatalysis after the nitrogen fixation photocatalyst with doping amount is irradiated by 120 min visible light is shown in a comparison chart, and it can be seen that along with Mo6+The doping amount is increased, the ammonia yield is gradually increased, when Mo is6+When the doping amount reaches 4%, the ammonia yield reaches the maximum value of 358.98 [ mu ] mol & g-1·h-1(ii) a Continue to increase Mo6+When the doping amount reached 5%, the ammonia yield began to decrease. This shows that 4% Mo was prepared by example 86+Doped with Zn1-xIn2S4Photocatalytic nitrogen fixation synthesisWith highest ammonia yield, i.e. Mo6+The optimum doping amount is 4%.
FIG. 6 is a graph showing the comparison of the effect of the photocatalysts for fixing nitrogen and synthesizing ammonia after 120 min of visible light irradiation on different nitrogen-fixing photocatalysts prepared in examples 10-14, wherein (a) is example 10, (b) is example 11, (c) is example 12, (d) is example 13, and (e) is example 14. And the maximum value of the ammonia yield (358.98 mu mol g)-1·h-1) Example 8 (Zn to In molar ratio 1: 2.5) compared to Zn (NO) In example 103)2·6H2O and In (NO)3)3At a molar ratio of 1:3, the ammonia yield drops to 237.49 [ mu ] mol g-1·h-1This indicates that when the molar ratio of Zn to In is too large, the ammonia yield begins to decrease. And the maximum value of the ammonia yield (358.98 mu mol g)-1·h-1) Example 8 (Zn (NO)3)2·6H2Molar ratio of O to L-cysteine 1: 10), Zn (NO) in example 113)2·6H2The molar ratio of O to L-cysteine was 1:8, at which time the ammonia yield dropped to 188.24 μmol g-1·h-1Zn (NO) in example 123)2·6H2The molar ratio of O to L-cysteine was 1:12, at which time the ammonia yield dropped to 129.53 μmol g-1·h-1This indicates that Zn (NO)3)2·6H2The optimal molar ratio of O to L-cysteine is 1: 10. And the maximum value of the ammonia yield (358.98 mu mol g)-1·h-1) Example 8 (hydrothermal reaction temperature of 200 ℃ C.) in example 13, the hydrothermal reaction temperature was 180 ℃ C. and the ammonia yield was reduced to 158.57 μmol g-1·h-1In example 14, the hydrothermal reaction temperature was 230 ℃ at which the ammonia yield was reduced to 330.45 [ mu ] mol g-1·h-1This indicates that the optimum hydrothermal reaction temperature is 200 ℃.
2. Photocurrent response test
The photocurrent response was tested using the electrochemical workstation of shanghai chen CHI 660E. First, a working electrode was prepared: 1 Mg of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) andadding 5 mg of photocatalytic nitrogen fixation catalyst into a 20 mL quartz bottle, then adding 10 mL of isopropanol, stirring for 5 minutes by using a magnetic stirrer to enable sample particles to be suspended in the solution, and performing ultrasonic treatment for 10 min to enable the sample particles to be uniformly dispersed; secondly, taking a piece of ITO conductive glass, testing the conductive surface of the ITO conductive glass by using a universal meter, clamping the ITO conductive glass piece by using an electrode as a negative electrode, inserting a platinum wire as a positive electrode, oppositely placing the platinum wire and the conductive surface of the ITO conductive glass piece, enabling the bottom end of the ITO conductive glass piece and the bottom end of the platinum wire to be in the same horizontal line, and enabling the distance between the ITO conductive glass piece and the platinum wire to be 1 cm; thirdly, using a direct current voltage and current stabilization power supply to carry out electrophoretic deposition to prepare a working electrode: connecting the positive electrode with a platinum wire, connecting the negative electrode with an ITO conductive glass sheet, performing electrophoresis coating for 30 min under the voltage condition of 30V, uniformly coating a catalyst on the conductive surface of the ITO conductive glass sheet, taking off the ITO conductive glass sheet, and naturally drying the coated surface upwards to obtain the working electrode. Secondly, testing the photocurrent response by using a three-electrode system of an electrochemical workstation: 200 mL of 0.5 mol. L was added-1Na of (2)2SO4The solution is used as electrolyte, a film prepared by electrophoretic deposition is used as a working electrode, a saturated Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and a focused xenon lamp is used for irradiating the working electrode, so that a photocurrent signal is generated; the light-on and light-off operations are carried out at intervals of 10 seconds to obtain photocurrent intensity values, and the photocurrent intensity values are divided by the area of the working electrode to obtain photocurrent density (unit: muA-cm)-2）。
FIG. 7 reflects the photocurrent responses of different photocatalytic nitrogen fixation catalysts, and it can be seen that pure ZnIn was prepared by example 12S4The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.17 muA-cm-2Zn containing Zn vacancies prepared by example 21-xIn2S4The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.52 muA-cm-21% Mo prepared by example 45+Doped with Zn1-xIn2S4The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.57 muA-cm-21% Mo prepared by example 56+Doped with Zn1-xIn2S4The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.82 muA-cm-2It is clear that by Mo6+Doped with Zn1-xIn2S4The photo-catalytic nitrogen fixation catalyst has the maximum photo-current density, which shows that Mo6+Doped with Zn1-xIn2S4The photocatalytic nitrogen fixation catalyst has higher separation and migration rate of photon-generated carriers.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (6)
1. Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4The preparation method of the catalyst is characterized by comprising the following specific steps: under the condition of magnetic stirring, zinc nitrate hexahydrate Zn (NO) is added3)2·6H2O, indium nitrate In (NO)3)3Dissolving L-cysteine into deionized water, adding inorganic salt containing Mo or Fe, magnetically stirring for 10-30 min, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the hydrothermal reaction kettle into a forced air drying oven, carrying out hydrothermal reaction for 15-24 h, cooling the reaction system to room temperature to obtain yellow-green precipitate, sequentially washing the yellow-green precipitate with deionized water and ethanol, repeatedly centrifuging and washing for 3-5 times, and drying at 60-100 ℃ in the forced air drying oven overnight to obtain Mo or Fe doped Zn1-xIn2S4A photocatalytic nitrogen fixation catalyst.
2. The Mo or Fe doped Zn for photocatalytic nitrogen fixation ammonia synthesis according to claim 11-xIn2S4Process for the preparation of a catalyst, characterized in that the zinc nitrate hexahydrate Zn (NO)3)2·6H2O and indium nitrate In (NO)3)3The molar ratio of (A) to (B) is 1: 2-3.
3. The Mo or Fe doped Zn for photocatalytic nitrogen fixation ammonia synthesis according to claim 11-xIn2S4Process for the preparation of a catalyst, characterized in that the zinc nitrate hexahydrate Zn (NO)3)2·6H2The molar ratio of O to L-cysteine is 1: 8-12.
4. The Mo or Fe doped Zn for photocatalytic nitrogen fixation ammonia synthesis according to claim 11-xIn2S4The preparation method of the catalyst is characterized in that the inorganic salt containing molybdenum Mo element is molybdenum pentachloride MoCl5Or sodium molybdate Na2MoO4Wherein the inorganic salt containing Fe is Fe nitrate Nonahydrate (NO)3)3·9H2O。
5. The Mo or Fe doped Zn for photocatalytic nitrogen fixation ammonia synthesis according to claim 11-xIn2S4A method for producing a catalyst, characterized In that doped Mo or Fe is added to indium nitrate In (NO)3)3The mole percentage of (A) is 1-5%.
6. The Mo or Fe doped Zn for photocatalytic nitrogen fixation ammonia synthesis according to claim 11-xIn2S4The preparation method of the catalyst is characterized in that the hydrothermal reaction temperature is 180-230 ℃.
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| CN114130408A (en) * | 2021-12-17 | 2022-03-04 | 永高股份有限公司 | Z-type alpha-Fe2O3/ZnIn2S4Preparation method and application of composite photocatalyst |
| CN115155564A (en) * | 2022-07-11 | 2022-10-11 | 重庆邮电大学 | Preparation method of Mo-doped tungsten oxide compound nanowire, product and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114130408A (en) * | 2021-12-17 | 2022-03-04 | 永高股份有限公司 | Z-type alpha-Fe2O3/ZnIn2S4Preparation method and application of composite photocatalyst |
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| CN115155564A (en) * | 2022-07-11 | 2022-10-11 | 重庆邮电大学 | Preparation method of Mo-doped tungsten oxide compound nanowire, product and application thereof |
| CN115155619A (en) * | 2022-08-25 | 2022-10-11 | 淮北师范大学 | Preparation method of S-doped defect state solid solution and application of S-doped defect state solid solution in photocatalysis nitrogen fixation reaction |
| CN115155619B (en) * | 2022-08-25 | 2023-08-22 | 淮北师范大学 | Preparation method of S-doped defect solid solution and application of S-doped defect solid solution in photocatalytic nitrogen fixation reaction |
| CN115709079A (en) * | 2022-09-28 | 2023-02-24 | 南昌航空大学 | Mo-modified sulfur-indium-zinc photocatalyst, and synthesis method and application thereof |
| CN115805095A (en) * | 2022-12-12 | 2023-03-17 | 东南大学 | High-specific-surface-area porous composite photocatalyst, preparation method, integrated treatment system and treatment method |
| CN115805095B (en) * | 2022-12-12 | 2024-02-06 | 东南大学 | High specific surface area porous composite photocatalyst, preparation method, integrated treatment system and treatment method |
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