CN112264049B - Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 Process for preparing catalyst - Google Patents
Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 Process 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 232
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 116
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 63
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000011701 zinc Substances 0.000 claims abstract description 92
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 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 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 22
- 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
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical group Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- 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 abstract description 12
- 238000003760 magnetic stirring Methods 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004435 EPR spectroscopy Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000005286 illumination Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 2
- 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-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
- 230000004913 activation Effects 0.000 description 2
- 238000007605 air drying 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
- 230000008901 benefit Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 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
- 230000003287 optical 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
- 239000002994 raw material 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
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-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
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 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
- 238000012271 agricultural production Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000006555 catalytic reaction Methods 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 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
- 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
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002073 nanorod Substances 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
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
-
- 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 Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1‑x In 2 S 4 A method for preparing the catalyst. The method comprises the following steps: under the condition of magnetic stirring, dissolving zinc nitrate hexahydrate, indium nitrate and L-cysteine into deionized water, adding inorganic salt containing molybdenum or iron element, magnetically stirring, transferring the mixed solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a blast drying box together with the hydrothermal reaction kettle, performing hydrothermal reaction for 15-24 hours, cooling to room temperature to obtain a yellowish green precipitate, washing the yellowish green precipitate with deionized water and ethanol in sequence, repeatedly centrifuging and washing for 3-5 times, and drying at 60-100 ℃ in the blast drying box for overnight to obtain Mo or Fe doped Zn 1‑x In 2 S 4 A photocatalytic nitrogen fixation catalyst. Mo or Fe doped Zn of the invention 1‑x In 2 S 4 The photocatalysis 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 a Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 A method for preparing the catalyst.
Background
Ammonia is not only a widely used chemical raw material, but also can be used as an important energy carrier. The Haber method for synthesizing ammonia is considered to be one of the most significant inventions in the 20 th century, and makes great contribution to the development of human society. At the same time, the ammonia synthesis process consumes 1% -2% of the total energy of the world each year. Therefore, development of a green clean ammonia synthesis process has been a hotspot of interest in industry and academia worldwide. With the vigorous development of artificial light synthesis solar fuel research, the realization of ammonia synthesis under mild conditions by means of solar photocatalysis has attracted more and more researchers' interest, because it is the most ideal energy utilization way, namely, directly utilizing solar energy to convert nitrogen and water into ammonia (catalysis report, 2018, (39): 1180-1188).
Currently, the research finds that the following catalysts with photocatalytic nitrogen fixation ammonia synthesis performance mainly exist: (1) Bi-based photocatalytic nitrogen fixation material. The invention patent with the application number of CN201811388166.X discloses preparation and solar nitrogen fixation application of a nano carbon fiber supported bismuth oxyhalide (BiOI/BiOBr/CNFs) photocatalyst. The invention patent with the application number of CN201810784797.7 discloses a preparation method and application of a BiS/BiOBr composite photocatalytic material. The invention patent with the application number of CN201711218003.2 discloses a synthetic ammonia catalyst (Bi x TM1 y TM2 z OCl) 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 Bi 2 O 3-x /nBi a MO b Solar nitrogen fixation photocatalytic material. (2) carbon nitride-based photocatalytic nitrogen fixation material. The invention patent with the application number of CN109317180A discloses a preparation method of a photocatalysis nitrogen fixation g-CN/oxide composite material. The invention patent with the application number of CN201811101338.0 discloses a Fe (III) -modified carbon nitride nano-sheet 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 a lithium niobate（LiNbO 3 ) The oxide/attapulgite nonlinear optical composite photocatalytic material and the preparation method and application thereof adsorb part of nitrogen in the photocatalytic nitrogen fixation process, thereby improving the photocatalytic nitrogen fixation efficiency. Chinese patent No. CN10953491a discloses a Lanthanum Titanate (LTO) nanosheet photocatalyst containing oxygen vacancies and its application in photocatalytic nitrogen fixation; the LTO nanosheets containing oxygen vacancies have obviously improved photocatalytic nitrogen fixation performance. The Chinese patent with the application number of CN109225194A discloses a preparation method and application of a Zn-doped indium oxide photocatalytic nitrogen fixation material, wherein the photocatalytic material is a manganese iron ore type metal oxide and has excellent chemical stability in the application of photocatalytic nitrogen fixation synthesis of ammonia. The invention patent with the application number of CN201910864772.2 discloses a preparation method and application of a black phosphorus nano-sheet/cadmium sulfide photocatalysis nitrogen fixation catalyst. Chinese patent application number CN201910893860.5 discloses the use of titanium-based metal organic framework materials in photocatalytic nitrogen fixation.
However, in summary, the prior art has the following problems:
(1) The Bi-based photocatalytic nitrogen fixation catalyst has the main problems that the oxidation capacity is strong and the reduction capacity is weak due to the positive valence band potential, and the reaction formula generated by photocatalytic nitrogen fixation is as follows: n (N) 2 + 6H + + 6e − → 2NH 3 ，-0.09 V vs.NHE. It can be seen that this is a reduction reaction in which the photo-generated electrons participate, and therefore, it is a better choice to select a photocatalyst with 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 the photocatalytic nitrogen fixation synthetic ammonia.
(3) The efficiency of nitrogen fixation and ammonia synthesis of the currently developed photocatalyst is still low, and is generally tens of mu mol & g -1 ·h -1 Further away from the aim of practical industrial production, therefore, 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 a Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 The preparation method of the catalyst is simpler, and the synthesized Mo or Fe doped Zn 1-x In 2 S 4 The photocatalysis nitrogen fixation catalyst is nontoxic and harmless and has good application prospect.
Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 The preparation method of the catalyst comprises the following specific steps: zinc nitrate hexahydrate (Zn (NO 3 ) 2 ·6H 2 O), indium nitrate (In (NO) 3 ) 3 ) Dissolving L-cysteine into deionized water, adding inorganic salt containing molybdenum (Mo) or iron (Fe) element, magnetically stirring for 10-30 min, transferring the mixed solution into a hydrothermal reaction kettle, placing the mixed solution into a blast drying box together with the hydrothermal reaction kettle, performing hydrothermal reaction for 15-24 h, cooling the reaction system to room temperature to obtain yellowish green precipitate, washing the yellowish green precipitate with deionized water and ethanol sequentially, repeatedly centrifuging and washing for 3-5 times, and drying at 60-100deg.C in the blast drying box for overnight to obtain Mo or Fe doped Zn 1- x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Preferably, the zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 O and indium In Nitrate (NO) 3 ) 3 The molar ratio of (2) is 1:2-3.
Preferably, the zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to L-cysteine is 1:8-12.
Preferably, the inorganic salt containing molybdenum Mo element is molybdenum pentachloride MoCl 5 Or sodium molybdate Na 2 MoO 4 The inorganic salt of Fe element containing iron is ferric nitrate nonahydrate Fe (NO) 3 ) 3 ·9H 2 O。
Preferably, the doped Mo or Fe is relative to indium In nitrate (NO 3 ) 3 The mole percentage of (2) is 1-5%.
Preferably, the hydrothermal reaction temperature is 180-230 ℃.
The invention benefits from the nitrogen fixation mechanism and the demonstration of biological nitrogen fixation enzyme (such as Mo-based nitrogen fixation enzyme) in agricultural production, and discovers that the structural design of a photocatalyst utilizes a semiconductor surface structure to catalyze the center to simulate the adsorption of ferromolybdenum (Mo-Fe) cofactor to N 2 Activation of molecules is an important way to achieve photocatalytic nitrogen fixation.
The invention selects ZnIn with layered structure 2 S 4 As a photocatalytic nitrogen fixation catalyst, the following three reasons are based: (1) ZnIn 2 S 4 Has a conduction band potential of-0.88Vvs.NHE, ratio N 2 Potential for reduction reaction with 6 electrons and 6 protons (-0.09V)vs.NHE) is more negative, indicating ZnIn 2 S 4 Has stronger photocatalytic reduction capability, namely ZnIn 2 S 4 Is a more suitable photocatalysis nitrogen fixation catalyst; (2) Doping Zn containing Zn vacancies with Mo or Fe 1-x In 2 S 4 To form unsaturated sites and promote N 2 Activation of molecules on the catalyst surface; (3) ZnIn 2 S 4 The forbidden bandwidth of (2) is about 2.3 eV, and most of visible light can be absorbed, so that the absorption and utilization rate of sunlight is enhanced, and the photocatalysis nitrogen fixation efficiency is improved.
The beneficial effects are that:
compared with the prior art, the Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 The preparation method of the catalyst has the following advantages:
(1) By using the method provided by the invention, zn vacancy is introduced and Fe is doped 3+ 、Mo 5+ 、Mo 6+ Can improve the efficiency of synthesizing ammonia by photocatalysis and nitrogen fixation, in particular to 4 percent Mo 6+ Doped Zn 1-x In 2 S 4 The photocatalysis nitrogen fixation catalyst has best performance, and the efficiency of the photocatalysis nitrogen fixation synthesis ammonia reaches 358.98 mu mol.g -1 ·h -1 Is pure ZnIn 2 S 4 61 times of the ammonia production rate of the photocatalytic nitrogen fixation catalyst, which shows that the invention providesThe technology of the (2) can greatly improve the efficiency of synthesizing ammonia by photocatalysis nitrogen fixation.
(2) Photocurrent response test showed Mo 6+ Doped Zn 1-x In 2 S 4 The photo-catalytic nitrogen fixation catalyst has the greatest photo-current density, which indicates Mo 6+ Doped Zn 1-x In 2 S 4 The photocatalytic nitrogen fixation catalyst has higher photogenerated carrier separation and migration rate.
(3) Mo or Fe doped Zn synthesized by the invention 1-x In 2 S 4 The photocatalysis nitrogen fixation catalyst is nontoxic and harmless, and the preparation method and the process flow are simpler, thereby having better application prospect.
Drawings
FIG. 1 is an XRD spectrum of various nitrogen-fixing photocatalysts prepared, wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, and (e) is example 5;
FIG. 2 is an Electron Paramagnetic Resonance (EPR) spectrum of different nitrogen-fixing photocatalysts prepared, wherein (a) is example 1 and (b) is example 2;
FIG. 3 is a TEM image of the nitrogen-fixing photocatalyst prepared by example 5, where (a) is 20nm on a scale and (b) is 5nm on a scale;
FIG. 4 (A) is a graph showing the change in ammonia production concentration with time under irradiation of visible light for different nitrogen fixation photocatalysts prepared according to 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. 4 (B) is a comparative schematic diagram showing the effect of the different nitrogen-fixing photocatalysts prepared in examples 1-5 on the yield of the photocatalytic nitrogen-fixing synthetic ammonia after 120 min of visible light irradiation, 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 the different Mo's prepared in examples 5-9 6+ The effect of the doped nitrogen fixation photocatalyst on the yield of the photocatalytic nitrogen fixation synthetic ammonia after 120 min visible light irradiation is comparatively schematic, 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 comparative schematic diagram showing the effect of the photocatalytic nitrogen-fixing ammonia synthesis after 120 min of visible light irradiation on the 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 of photocurrent response of various 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 following describes the invention with reference to the drawings and specific examples.
EXAMPLE 1 pure ZnIn 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
Under magnetic stirring, 0.0744g (i.e. 0.25 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.1504g (i.e., 0.5 mmol) of indium nitrate (In (NO) 3 ) 3 ) Dissolving 0.2420g (2 mmol) of L-cysteine into 30mL of deionized water, magnetically stirring for 10 min, transferring the mixed solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle together with the mixed solution into a blast drying box, performing hydrothermal reaction at 180 ℃ for 18 h, cooling to room temperature to obtain a yellow-green precipitate, centrifugally washing the yellow-green precipitate with deionized water and ethanol sequentially, repeatedly washing for 3 times, and drying at 60 ℃ in the blast drying box for overnight to obtain pure ZnIn 2 S 4 A photocatalytic nitrogen fixation catalyst.
EXAMPLE 2 Zn containing Zn vacancies 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.1504g (i.e., 0.5 mmol) of indium nitrate (In (NO) 3 ) 3 ) 0.2420g (2 mmol) of L-cysteine are dissolved in 30mL of deionized water, and after magnetic stirring for 10 minutes, the mixed solution is transferred into a hydrothermal reaction kettle, and is put into a blast drying box together with the hydrothermal reaction kettle to be subjected to hydrothermal reaction at 200 ℃ for 18 hours, and the mixture is cooledCooling to room temperature to obtain yellow-green precipitate, centrifuging with deionized water and ethanol, washing for 3 times, and drying at 60deg.C in a forced air drying oven for whole night to obtain Zn containing Zn vacancy 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
EXAMPLE 3 1% Fe 3+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O), after 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 blast drying box together, carrying out hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain yellow-green precipitate, centrifugally washing the yellow-green precipitate with deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying at 60 ℃ in the blast drying box for whole night to obtain 1% Fe 3+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 4 1% Mo 5+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 0.0013g (i.e., 0.005 mmol) of molybdenum pentachloride (MoCl) was added 5 ) After magnetically stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the hydrothermal reaction kettle into a blast drying box, performing hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain a yellowish green precipitate, centrifugally washing the yellowish green precipitate with deionized water and ethanol sequentially, and repeating the stepsWashing for 3 times, and drying at 60deg.C in a forced air drying oven for whole night to obtain 1% Mo 5+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 5 1% Mo 6+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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) 2 MoO 4 ) After magnetic stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the mixed solution into a blast drying box together, carrying out hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain yellow-green precipitate, centrifugally washing the yellow-green precipitate with deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying in the blast drying box at 60 ℃ for whole night to obtain 1% Mo 6+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 6 2% Mo 6+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 0.0024g (i.e., 0.01 mmol) of sodium molybdate (Na 2 MoO 4 ) After magnetic stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the mixed solution into a blast drying box together with the hydrothermal reaction kettle, performing hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain a yellow-green precipitate, centrifugally washing the yellow-green precipitate with deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying at 60 ℃ in the blast drying box for whole night to obtain 2% Mo 6+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 7 3% Mo 6+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 0.0036g (i.e., 0.015 mmol) of sodium molybdate (Na 2 MoO 4 ) After magnetic stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the mixed solution into a blast drying box together with the hydrothermal reaction kettle, performing hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain a yellow-green precipitate, centrifugally washing the yellow-green precipitate with deionized water and ethanol in sequence, repeatedly washing for 3 times, and drying at 60 ℃ in the blast drying box for whole night to obtain 3% Mo 6+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 8 4% Mo 6+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 2 MoO 4 ) After magnetic stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the hydrothermal reaction kettle into a blast drying box, performing hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain yellow-green precipitate, sequentially centrifugally washing with deionized water and ethanol, repeating washing for 3 times, and drying at 60 ℃ in the blast drying box for whole night to obtain 4% Mo 6+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 9 5% Mo 6+ Zn doped 1-x In 2 S 4 Preparation of photocatalytic nitrogen fixation catalyst
0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 0.0060g (i.e., 0.025 mmol) of sodium molybdate (Na 2 MoO 4 ) After magnetic stirring for 10 minutes, transferring the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle and the hydrothermal reaction kettle into a blast drying box, carrying out hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature to obtain a yellowish green precipitate, washing the yellowish green precipitate with deionized water and ethanol in sequence, repeating washing for 3 times, and drying at 60 ℃ in the blast drying box for whole night to obtain 5% Mo 6+ Zn doped 1-x In 2 S 4 A photocatalytic nitrogen fixation catalyst.
Example 10
Similar to example 8, except that Zn (NO 3 ) 2 ·6H 2 O and In (NO) 3 ) 3 Is 1:3, i.e. 0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 ·6H 2 The molar ratio of O to L-cysteine was 1:8, i.e. 0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.1936g (i.e., 1.6 mmol) of L-cysteine.
Example 12
Similar to example 8, except that Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to L-cysteine was 1:12, i.e. 0.0595g (i.e. 0.2 mmol) of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), 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 ℃.
1. 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 identical to those of hexagonal ZnIn 2 S 4 Diffraction peaks of the crystalline phases were matched (PDF Standard card No. 72-0773) and no other impurity peaks, indicating that Zn vacancies, mo or Fe doping were formed without changing ZnIn 2 S 4 Is a crystalline phase of (a).
2. EPR analysis
Fig. 2 (a) is an EPR spectrum of the nitrogen fixation photocatalyst prepared by example 1, with almost no EPR signal (g=2.003); fig. 2 (b) is an EPR spectrum 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, since Zn vacancies can trap electrons, thereby generating an EPR signal (adv. Mate. 2016, 28, 3928).
The nitrogen fixation photocatalyst prepared in example 2 exhibited EPR signals attributed to Zn vacancies due to the fact that the starting materials were not added in stoichiometric proportions during the preparation: zn in the added raw material 2+ With In 3+ Is 1:2.5, this is compared with ZnIn 2 S 4 Medium Zn 2+ With In 3+ Compared to the stoichiometric ratio (1:2), zn is evident 2+ Insufficient addition amount, thereby causing Zn vacancy to occur. The nitrogen fixation photocatalyst prepared in example 1 did not exhibit EPR signals attributed to Zn vacancies due to Zn during the preparation process 2+ With In 3+ Is strictly stoichiometric (1:2) and thus no Zn vacancies are produced in the catalyst prepared. This suggests that Zn added to the raw material can be changed 2+ With In 3+ Molar ratio of (c) to ZnIn 2 S 4 In the production of Zn voidBit, form Zn 1-x In 2 S 4 。
3. TEM analysis
FIG. 3 is 1% Mo prepared by example 5 6+ Zn doped 1-x In 2 S 4 TEM image of the photocatalytic nitrogen fixation catalyst, it can be seen that the catalyst is in an extremely thin sheet form; in addition, it can be seen from the edges of the sheet that the sheet is composed of 3-5 layers of ZnIn 2 S 4 Layer composition.
2. Performance testing
1. The performance test method of the photocatalytic nitrogen fixation synthetic ammonia comprises the following steps:
the double-layer jacket beaker of 150 mL is used as a reactor for testing the performance of the photocatalytic nitrogen fixation synthetic ammonia, wherein circulating cooling water is introduced into the jacket of the double-layer jacket beaker to eliminate heat generated by a light source in the photocatalytic reaction process, so that the photocatalytic nitrogen fixation synthetic ammonia test is performed at normal temperature and normal pressure. The inner wall of the reactor was washed three times with deionized water to ensure no impurity, 100 mL deionized water was added into the reactor after the completion of the cleaning, 50 mg photocatalytic nitrogen fixation catalyst prepared by the example was weighed by an electronic balance, added into the reactor, an air needle was inserted into the reactor, a magnetic stirrer was placed, the magnetic stirrer was turned on, the proper rotation speed was adjusted, and a quartz glass plate was covered on the upper portion of the reactor. Then, the nitrogen cylinder gas valve is opened, the pressure reducing valve is regulated, and the flow rate of nitrogen on the gas flowmeter is controlled to be 40 min L -1 The method comprises the steps of carrying out a first treatment on the surface of the Firstly, introducing nitrogen under the dark condition and stirring for 30 min to discharge other gases such as oxygen, carbon dioxide and the like dissolved in the solution; turning on the xenon lamp light source of 300W, inserting a 420 nm optical filter at the lower part of the light source, and setting the current of the light source to be 20A; and then circulating cooling water is introduced, after the lamp is turned on and illumination is performed, 3mL of upper layer solution is sucked by a disposable plastic suction pipe every 30 min and transferred into a centrifuge tube, total illumination is performed for 120 min, and total suction of the upper layer solution is performed for 5 times. Then, the centrifuge tube is put into a centrifuge for centrifugal separation, and the parameters of the centrifuge are set: the rotation speed is set to r min -1 The centrifugation time was set to 10 min. After centrifugation, the supernatant of 2 mL is sucked by a disposable suction tube and transferred to a corresponding new one in time sequenceIn a test tube, the concentration of ammonia nitrogen was measured using a Nahner reagent spectrophotometry (environmental protection Standard of the people's republic of China (HJ 535-2009)): adding 0.2 mL NaL reagent and 0.2 mL potassium sodium tartrate into a new test tube, shaking thoroughly, adding deionized water to dilute to 10 mL, standing for 10 min, performing ultraviolet-visible absorption spectrum (UV-2450) test on the diluted solution, taking the absorbance at 420 nm in the measured absorption spectrum as characteristic absorption intensity, and determining ammonia concentration (unit: [ mu ] mol.L by using NaL reagent spectrophotometry standard curve -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 time and the average calculated to give the ammonia yield per unit time, per unit mass of catalyst (unit: mu mol g -1 ·h -1 ）。
FIG. 4 (A) is a graph showing the ammonia production concentration (in [ mu ] mol.L) of different photocatalytic nitrogen fixation catalysts over time -1 ) It can be seen that as the illumination time is prolonged, the ammonia concentration is gradually increased, which basically accords with the linear change rule. Based on the data of FIG. 4 (A), the mass of catalyst added and the illumination time were divided and the average was calculated to give the ammonia yield per unit time, per unit mass of catalyst (unit: [ mu ] mol. G -1 ·h -1 ) As shown in fig. 4 (B). It can be seen that pure ZnIn prepared by example 1 2 S 4 The ammonia yield of the photocatalysis nitrogen fixation catalyst is only 5.84 mu mol g -1 ·h -1 Zn containing Zn vacancies prepared by example 2 1-x In 2 S 4 The ammonia yield of the photocatalytic nitrogen fixation catalyst is 11.00 mu mol g -1 ·h -1 The method increases about 1 time, and can improve the efficiency of synthesizing ammonia by photocatalytic nitrogen fixation by introducing Zn vacancy defects. 1% Fe prepared by example 3 3+ Zn doped 1-x In 2 S 4 The ammonia yield of the photocatalytic nitrogen fixation catalyst is 11.38 mu mol.g -1 ·h -1 1% Mo prepared by example 4 5+ Zn doped 1-x In 2 S 4 The ammonia yield of the photocatalytic nitrogen fixation catalyst is 19.89 mu mol.g -1 ·h -1 1 prepared by example 5% Mo 6+ Zn doped 1-x In 2 S 4 The ammonia yield of the photocatalytic nitrogen fixation catalyst is 37.50 mu mol.g -1 ·h -1 It can be seen that Fe 3+ 、Mo 5+ 、Mo 6+ Of the three types of doped catalysts, mo 6+ Zn doped 1-x In 2 S 4 The ammonia yield of the photocatalytic nitrogen fixation catalyst is highest.
FIG. 5 shows the different Mo's prepared in examples 5-9 6+ Compared with the effect of the doping amount of the nitrogen fixation photocatalyst on the photocatalytic nitrogen fixation synthesis ammonia yield after 120 min of visible light irradiation, the comparison of the effect of the doping amount of the nitrogen fixation photocatalyst on the photocatalytic nitrogen fixation synthesis ammonia yield can be seen that along with Mo 6+ The ammonia yield gradually increases as Mo increases due to the increase of the doping amount 6+ When the doping amount reaches 4%, the ammonia yield reaches the maximum value 358.98 mu mol.g -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the Continue to increase Mo 6+ When the doping amount reaches 5%, the ammonia yield starts to decrease. This shows that 4% Mo prepared by example 8 6+ Zn doped 1-x In 2 S 4 The highest yield of the photocatalytic nitrogen fixation synthetic ammonia, namely Mo 6+ The optimum value of the doping amount was 4%.
FIG. 6 is a comparative schematic diagram of the effect of the different nitrogen fixation photocatalysts prepared in examples 10-14 on the yield of the photocatalytic nitrogen fixation ammonia synthesis after 120 min of visible light irradiation, wherein (a) is example 10, (b) is example 11, (c) is example 12, (d) is example 13, and (e) is example 14. With the maximum value of ammonia yield (358.98 [ mu ] mol.g -1 ·h -1 ) In example 10, zn (NO) was contained In the composition of example 8 (molar ratio of Zn to In: 1:2.5) 3 ) 2 ·6H 2 O and In (NO) 3 ) 3 The molar ratio of (2) was 1:3, at which time the ammonia yield was reduced to 237.49. Mu. Mol.g -1 ·h -1 This indicates that when the Zn to In molar ratio is too large, the ammonia yield starts to decrease. With the maximum value of ammonia yield (358.98 [ mu ] mol.g -1 ·h -1 ) Example 8 (Zn (NO) 3 ) 2 ·6H 2 O to L-cysteine molar ratio of 1:10), zn (NO 3 ) 2 ·6H 2 The molar ratio of O to L-cysteine is 1:8, and the ammonia yield is reduced to 188.24 mu mol g -1 ·h -1 Zn (NO) in example 12 3 ) 2 ·6H 2 The molar ratio of O to L-cysteine is 1:12, and the ammonia yield is reduced to 129.53 mu mol g -1 ·h -1 This indicates that Zn (NO 3 ) 2 ·6H 2 The optimal molar ratio of O to L-cysteine is 1:10. With the maximum value of ammonia yield (358.98 [ mu ] mol.g -1 ·h -1 ) In comparison with example 8 (hydrothermal reaction temperature 200 ℃ C.) of example 13, the hydrothermal reaction temperature was 180 ℃ C., at which the ammonia yield was reduced to 158.57. Mu. Mol. G -1 ·h -1 The hydrothermal reaction temperature in example 14 was 230℃and the ammonia yield was reduced to 330.45. Mu. Mol. G -1 ·h -1 This indicates that the optimal hydrothermal reaction temperature is 200 ℃.
2. Photocurrent response test
Photocurrent response was tested using the Shanghai Chenhua CHI 660E electrochemical workstation. First, a working electrode is prepared: (1) magnesium nitrate hexahydrate of 1 Mg (Mg (NO 3 ) 2 ·6H 2 Adding O) and 5 mg photocatalysis nitrogen fixation catalyst into a 20 mL quartz bottle, then adding 10 mL isopropanol, stirring for 5 minutes by a magnetic stirrer to suspend sample particles in the solution, and then carrying out ultrasonic treatment for 10 minutes to uniformly disperse the sample particles; (2) 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 by using an electrode to serve as a negative electrode, and inserting a platinum wire to serve as a positive electrode, so that the conductive surfaces of the platinum wire and the ITO conductive glass are oppositely placed, the bottom end of the ITO conductive glass and the bottom end of the platinum wire are positioned on the same horizontal line, and the distance between the ITO conductive glass and the platinum wire is 1 cm; (3) electrophoretic deposition is carried out by using a direct current voltage-stabilizing and current-stabilizing power supply to prepare a working electrode: and connecting the positive electrode with a platinum wire, connecting the negative electrode with an ITO conductive glass sheet, and carrying out electrophoresis coating for 30 min under the voltage condition of 30V, so that the catalyst is uniformly coated on the conductive surface of the ITO conductive glass sheet, and taking down the ITO conductive glass sheet to naturally dry the coated surface upwards, thereby obtaining the working electrode. Secondly, a three-electrode system of an electrochemical workstation is adopted to test photocurrent response: 0.5 mol.L of 200 mL is added -1 Na of (2) 2 SO 4 The 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, and platinum is used as a reference electrodeThe sheet is used as a counter electrode, and a working electrode is irradiated by utilizing a focused xenon lamp, so that a photocurrent signal is generated; the light-turning-on and light-off operations are carried out every 10 seconds to obtain a light current intensity value, and the obtained light current intensity value is divided by the area of the working electrode to obtain the light current density (unit: mu A cm) -2 ）。
FIG. 7 reflects the photocurrent response of different photocatalytic nitrogen fixation catalysts, it can be seen that pure ZnIn prepared by example 1 2 S 4 The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.17 mu A cm -2 Zn containing Zn vacancies prepared by example 2 1-x In 2 S 4 The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.52 mu A cm -2 1% Mo prepared by example 4 5+ Zn doped 1-x In 2 S 4 The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.57 mu A cm -2 1% Mo prepared by example 5 6+ Zn doped 1-x In 2 S 4 The photocurrent density of the photocatalytic nitrogen fixation catalyst is about 0.82 mu A cm -2 It is apparent that by Mo 6+ Zn doped 1-x In 2 S 4 The photo-catalytic nitrogen fixation catalyst has the greatest photo-current density, which indicates Mo 6+ Zn doped 1-x In 2 S 4 The photocatalytic nitrogen fixation catalyst has higher photogenerated carrier separation and migration rate.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes 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 disclosed in the present invention fall within the protection scope of the present invention.
Claims (3)
1. Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 The preparation method of the catalyst is characterized by comprising the following specific steps: zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 O, indium In Nitrate (NO) 3 ) 3 Dissolving L-cysteine to removeAdding inorganic salt containing Mo or Fe element into the sub-water, magnetically stirring for 10-30 min, transferring the mixed solution into a hydrothermal reaction kettle, placing the mixed solution into a blast drying box together with the hydrothermal reaction kettle, carrying out hydrothermal reaction for 15-24 h at 200-230 ℃, cooling the reaction system to room temperature to obtain yellow-green precipitate, washing the yellow-green precipitate with deionized water and ethanol in sequence, repeatedly centrifuging and washing for 3-5 times, and drying at 60-100 ℃ in the blast drying box for overnight to obtain Mo or Fe doped Zn 1-x In 2 S 4 Photocatalytic nitrogen fixation catalyst, and Mo or Fe doped with Zn 1-x In 2 S 4 The catalyst is used for synthesizing ammonia by photocatalytic nitrogen fixation, wherein the zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 O and indium In Nitrate (NO) 3 ) 3 The mol ratio of the zinc nitrate hexahydrate Zn (NO) is 1:2.5-3 3 ) 2 ·6H 2 The mol ratio of O to L-cysteine is 1:8-12; doped Mo or Fe relative to indium In nitrate (NO 3 ) 3 The mole percentage of (2) is 1-5%.
2. Mo or Fe doped Zn for photocatalytic nitrogen fixation synthesis of ammonia according to claim 1 1-x In 2 S 4 The preparation method of the catalyst is characterized in that the inorganic salt of molybdenum Mo element is molybdenum pentachloride MoCl 5 Or sodium molybdate Na 2 MoO 4 The inorganic salt of Fe element containing iron is ferric nitrate nonahydrate Fe (NO) 3 ) 3 ·9H 2 O。
3. Mo or Fe doped Zn for photocatalytic nitrogen fixation synthesis of ammonia according to claim 1 1-x In 2 S 4 The preparation method of the catalyst is characterized in that the hydrothermal reaction temperature is 200 ℃.
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