CN108201893B - FeSxThin film, hydrazinophenylene compound, and deposition method and preparation method thereof - Google Patents
FeSxThin film, hydrazinophenylene compound, and deposition method and preparation method thereof Download PDFInfo
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- CN108201893B CN108201893B CN201611183072.XA CN201611183072A CN108201893B CN 108201893 B CN108201893 B CN 108201893B CN 201611183072 A CN201611183072 A CN 201611183072A CN 108201893 B CN108201893 B CN 108201893B
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- 238000000151 deposition Methods 0.000 title claims abstract description 63
- -1 hydrazinophenylene compound Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 47
- 229910005432 FeSx Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000012692 Fe precursor Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002829 reductive effect Effects 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000231 atomic layer deposition Methods 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- CRUHJZMRDPMANI-UHFFFAOYSA-N C(N)(=N)[Fe] Chemical class C(N)(=N)[Fe] CRUHJZMRDPMANI-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 45
- 239000003054 catalyst Substances 0.000 abstract description 26
- 239000010409 thin film Substances 0.000 abstract description 22
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000427 thin-film deposition Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
Abstract
The invention discloses a FeSxA thin film, a hydrazinophenylcompound, a deposition method and a preparation method, wherein the deposition method comprises the following steps: feeding an iron precursor and a sulfur precursor into a deposition chamber with a substrate, setting the temperature of the deposition chamber to be 20-400 ℃, and performing FeSxDepositing a film; after the deposition is finished, cooling treatment is carried out, and after the temperature is reduced to room temperature, the coating is coated with FeSxAnd taking out the substrate of the film. The invention prepares the nano-scale FeS on the substrate by using the ALD processxThin film (catalyst) and use of the prepared FeSxThe catalyst catalyzes the selective reduction of aryl azo compounds to hydrazinophenyl compounds. FeS prepared using ALDxThe catalyst can be selectively reduced for various aryl azo compounds, and can realize high activity and selective catalytic reaction under mild reaction conditions, so the FeS prepared by the ALD processxHas wide application prospect in the aspect of organic synthesis.
Description
Technical Field
The invention relates to the field of material synthesis and organic catalysis, in particular to FeSxThin films, hydrazinophenyls compounds, and methods of deposition and preparation.
Background
Iron sulfide (FeS)x) Is an important and abundant material, and is applied to solar cells, lithium ion batteries and lithium ion batteries in recent yearsHydrogen catalysis, oxygen reduction catalysis, CO2Research in the application fields of reduction catalysis, organic synthesis catalysis and the like has attracted great attention of researchers. Some of these applications use nanostructured FeSxAs an active material, this is because nanostructured materials typically contain a relatively high surface area, exposing a large number of active sites, and thus can significantly improve the performance of the active material. To make nanostructured FeSxMany synthetic methods have been attempted in the past, including solution-based methods, mechanical ball milling, vapor phase sulfiding, and chemical vapor deposition, among others.
However, FeS prepared in the prior artxThe activity and catalytic performance of the catalyst are still to be improved.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide FeSxA film, a hydrazinophenylcompound, a deposition method and a preparation method, aiming at solving the problem of FeS prepared by the prior artxBoth the activity and the catalytic performance have yet to be improved.
The technical scheme of the invention is as follows:
FeS deposition method adopting atomic layer depositionxA method of thin film, comprising the steps of:
feeding an iron precursor and a sulfur precursor into a deposition chamber with a substrate, setting the temperature of the deposition chamber to be 20-400 ℃, and performing FeSxDepositing a film;
after the deposition is finished, cooling treatment is carried out, and after the temperature is reduced to room temperature, the coating is coated with FeSxAnd taking out the substrate of the film.
The method for depositing FeS by adopting atomic layer depositionxA method of thin film, wherein the iron precursor is an N, N' -alkyl substituted amidino iron compound.
The method for depositing FeS by adopting atomic layer depositionxA method of thin film, wherein the sulfur precursor is H2S。
The method adopting atomic layer depositionMethod for deposition of FeSxMethod of thin film, wherein the substrate is single crystal silicon, silicon dioxide or porous gamma-Al2O3And the substrate is powder or porous medium.
FeSxA film, wherein the film is deposited by a method as described in any of the above.
A method for preparing a hydrazinophenyl compound, comprising the steps of:
will be coated with FeSxMixing a substrate of the film, azobenzene or derivatives thereof and a solvent, reacting in an inert atmosphere, adding a hydrogen source in the reaction process, and obtaining a reaction product, namely a hydrazinophenyl compound after the reaction is finished.
The preparation method of the hydrazinophenylene compound comprises the step of carrying out reaction under the atmosphere of argon or nitrogen.
The preparation method of the hydrazinophenyl compound comprises the following steps of preparing hydrogen, sodium hydride, lithium aluminum hydride, ammonia borane and NaBH4。
The preparation method of the hydrazinophenylcompound is characterized in that the solvent is an organic solvent.
A hydrazinophenylcompound wherein the preparation process is as described in any one of the above.
Has the advantages that: the invention prepares the nano-scale FeS on the substrate by using the ALD processxThin film (catalyst) and use of the prepared FeSxThe catalyst catalyzes the selective reduction (hydrogenation) of aryl azo compounds to hydrazinoaryl compounds. FeS prepared using ALDxThe catalyst, the selective reduction of various aryl azo compounds, can realize the high activity and selective catalytic reaction of the hydrazino-group compound under the mild reaction condition, so the FeS prepared by the ALD processxHas wide application prospect in the aspect of organic synthesis.
Drawings
FIG. 1 is an atomic layer deposition FeSxThe growth behavior of the film is as a result.
FIG. 2 shows FeS at different deposition temperaturesxTEM image of thin film and corresponding electron derivativesAnd emits an image.
FIG. 3 is a graph of deposited FeSxThe tendency of the iron/sulphur atomic percentage in the film to vary with temperature.
FIG. 4 shows deposition of 25 nm FeS at 160 deg.CxXPS characterization results of the films.
FIG. 5 shows FeS with a thickness of 20 nm obtained at different deposition temperaturesxAFM and SEM images of the films.
FIG. 6 shows FeS deposition in a trench with an aspect ratio of 10:1xCross-sectional SEM images of the thin film.
FIG. 7 shows porous gamma-Al2O3Preparation of nano-scale FeSxSEM and EDS characterization of the films.
Detailed Description
The invention provides FeSxThe thin film, the hydrazinophenylcompound, the deposition method and the preparation method are further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for depositing FeS by adopting atomic layer depositionxA method of making a film comprising the steps of:
feeding an iron precursor and a sulfur precursor into a deposition chamber with a substrate, setting the temperature of the deposition chamber to be 20-400 ℃, and performing FeSxDepositing a film;
after the deposition is finished, cooling treatment is carried out, and after the temperature is reduced to room temperature, the coating is coated with FeSxAnd taking out the substrate of the film.
The invention is FeS by adopting an Atomic Layer Deposition (ALD) method (namely ALD process)xAnd (3) preparing a film. ALD employs the growth principle of surface saturation self-limiting chemical reactions, allowing designed materials to grow layer by layer at atomic level thickness, theoretically any complex 3D structure can be conformally and uniformly coated by ALD, while the process has excellent repeatability, and can control the composition and thickness of the prepared thin film with atomic level precision. In the preparation of the catalyst material (FeS) of the inventionx) Process for producing a metal oxideIn the method, the size, the composition and the active sites of the catalyst can be precisely controlled by ALD atomic level, so that the catalyst material is well controlled and uniformly distributed, the activity, the selectivity and the stability of the catalyst can be improved, and the reaction mechanism and the structure-performance relationship of the catalyst can be promoted to be clarified.
The invention enables to follow the ideal ALD self-limiting growth behavior over a rather wide temperature range, with detailed analysis of the variation of the film growth rate and properties (such as crystal structure, chemical composition and surface morphology) with temperature, which results show that the ALD method deposits FeSxThe film has high purity, smooth surface and good crystallinity. In addition, the ALD method deposits FeSxThe thin film can achieve trenches with aspect ratios as high as 10:1, indicating that the ALD process is well suited for the preparation of conformal and uniform FeS on complex 3D composites or porous nanostructuresxThe film can be widely applied to the nanometer science and the nanometer engineering.
The iron precursor in the present invention is an N, N '-alkyl-substituted amidino iron compound, for example, bis (N, N' -di-t-butylacetamidino) iron [ Fe (amd)2]. In addition, the iron precursor Fe (amd)2The tert-butyl group in (A) may be replaced by an alkyl group such as an ethyl group, an isopropyl group, a sec-butyl group, a tert-pentyl group or a sec-pentyl group, and the acetamidinyl group in (B) may be replaced by a formamidino group, an isopropylamidino group or a n-butyl group.
Preferably, the sulfur precursor is H2And S. In the preparation process, the H2The S precursor is diluted in N2Medium volume content of 1% H2And S mixed gas.
In an atomic layer deposition process, FeSxIn the process conditions of the film, the deposition temperature of the deposition chamber is 80-300 ℃, and the deposition pressure of the deposition chamber is 0.3-20 Torr.
Further, the substrate is monocrystalline silicon, silicon dioxide or porous gamma-Al2O3The substrate is a powder or porous media, and the substrate of the present invention may be any substrate commonly used in the art. The monocrystalline silicon and silica substrates may be pretreated first, for example in succession in acetone, isopropanol, wineRespectively performing ultrasonic treatment on the refined deionized water and the deionized water for 10 min, then purging the refined deionized water with high-purity nitrogen, and then treating the refined deionized water with UV/ozone for 5 min. Porous gamma-Al2O3(powder state) was activated by heating at 900 ℃ for 24 hours.
Placing the treated substrate on a substrate table in a deposition chamber, heating the iron precursor, the deposition chamber and the substrate, raising the temperature to a specified temperature, setting the pulse frequency and the nitrogen purging time of the iron precursor, and setting H2Pulse frequency of S and nitrogen purging time, setting period number, and performing atomic layer deposition (FeS)xA film. Wherein the heating temperature of the iron precursor is 75 ℃.
One preferred example is as follows: putting the cleaned substrate on a substrate table in a deposition chamber, heating the iron precursor, the deposition chamber and the substrate after the air pressure in the deposition chamber is pumped to the background, introducing nitrogen with the pressure of 0.3 Torr into the deposition chamber, and preheating the deposition chamber for 0.5 h after the temperature is raised to a specified temperature (namely the set temperature of the deposition chamber); the pulse times and nitrogen purging time of the iron precursor were set to 4 times and 30s, respectively, H2The pulse frequency and the nitrogen purging time of the S precursor are respectively 4 times and 30S, the period number is set, and the atomic layer deposition FeS is carried outxA film.
The temperature of the deposition chamber is set to 20-400 ℃, i.e. from room temperature to 400 ℃, preferably, the temperature of the deposition chamber is set to 120-180 ℃, for example, 160 ℃, under the condition, FeS can be well maintainedxFilm properties.
The invention also provides FeSxA thin film deposited using the method described above.
Will deposit on porous gamma-Al2O3FeS of (2)xFilm dissolved in HCl HNO3Determining the concentration of iron in the mixed solution with the mass ratio of 3:1 by using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine FeSxAmount of film.
To further demonstrate the utility of this process in organic synthesis catalysts. The invention uses the prepared FeSxCatalyst (i.e., FeS as described above)xFilm) catalytic arylazo compounds (A), (B), (C), (I.e., azobenzene or its derivatives) to the hydrazinoarylene compound. Since hydrazine is generally susceptible to reductive cleavage of the NH-NH bond to form an amine, selective reduction of the azo compound to a hydrazino compound is an important reaction process. FeS prepared using ALDxCatalysts, various types of aryl azo compounds (including both types of electron donors and different substituents) can be selectively reduced (hydrogenated) and highly active and selective catalytic reactions can be achieved under mild reaction conditions, thus indicating that FeS prepared by ALD processxHas application prospect in organic synthesis.
The present invention also provides a method for preparing a hydrazinophenyl compound, which comprises the steps of:
will be coated with FeSxMixing a substrate of the film, azobenzene or derivatives thereof and a solvent, reacting in an inert atmosphere, adding a hydrogen source in the reaction process, and obtaining a reaction product, namely a hydrazinophenyl compound after the reaction is finished. In the above process, the aryl azo compound is selectively reduced to the hydrazinoaryl compound, and can be carried out in a low temperature state such as room temperature.
The inert atmosphere is preferably an argon or nitrogen atmosphere, and the hydrogen source is preferably hydrogen, sodium hydride, lithium aluminum hydride, ammonia borane, NaBH4. The solvent is preferably an organic solvent, such as methanol, although other organic solvents are possible. Monitoring of the progress of the catalytic reaction can be achieved by changing the color of the solution or by observing thin layer chromatography on silica gel GF254 plates.
One preferred example is as follows: the catalyst thus prepared (i.e., FeS)xThin film), 0.2 mmol of azobenzene or its derivative and 5 mL of methanol are placed in a 25 mL Schlenk tube under the protection of argon atmosphere, reaction is carried out, the reaction mixture is stirred vigorously, and 2 mmol of NaBH is added step by step4。
After the catalytic reaction, filtering and removing methanol under reduced pressure to obtain a crude product, dissolving the crude product in 20 mL ethyl acetate, washing with water and saturated brine, extracting an organic layer, removing water with magnesium sulfate, and removing ethyl acetate under reduced pressure to obtain a solid reaction product, namely the hydrazinoarylene compoundA compound (I) is provided. By using1H NMR determines the conversion of product to quantitative reactant.1H NMR in CDCl3Is measured, CH2Br2As an internal standard.
The invention also provides a hydrazinophenylcompound which is prepared by the preparation method.
A complete example is as follows:
the synthesized Fe (amd)2The precursor was ground to a powder in a glove box under Ar atmosphere and charged into a clean source bottle. The source bottle is designed in a carrier gas mode, and the pulse nitrogen carrier gas carries Fe (amd)2The precursor enters a deposition chamber. Charging Fe (amd)2The source bottle of the precursor is arranged in a heating oven, heated to 75 ℃, preheated for 1 h to enable the source bottle to be aligned with Fe (amd)2The precursor is activated and the vapor pressure of the precursor is stabilized. Carrying out FeSxIn the thin film deposition experiment, Fe (amd) was set2The exposure of the precursor was 0.025 Torr s.
Using 1% H in nitrogen2The S mixed gas is used as a sulfur source, and about 5 mL of mixed gas enters the deposition chamber in each pulse. Carrying out FeSxIn the thin film deposition experiment, H is set2The exposure of the S precursor was 0.062 Torr S.
The nitrogen passed through a gas purifier as Fe (amd)2Precursor carrier gas and purge gas were set to a pressure of 0.3 Torr in the chamber during purging.
Porous gamma-Al2O3The powder was placed in the deposition chamber after 24 hours of activation at 900 ℃. The temperature of the deposition chamber is set to be 160 ℃, and after the temperature is stable, LabView software is set to perform FeS for 1500 periodsxAnd (5) depositing a thin film.
After the deposition is finished, the temperature is reduced in the nitrogen atmosphere of 0.3 Torr, and FeS is deposited after the temperature is reduced to the room temperaturexPorous gamma-Al of thin film2O3And (5) taking out the powder.
The prepared catalyst, 0.2 mmol of azobenzene and 5 mL of methanol were placed in a 25 mL Schlenk tube under an argon atmosphere. The reaction mixture was stirred vigorously and 2 mmol of NaBH added stepwise4As a source of hydrogen.
After the completion of the catalytic reaction, the crude product was obtained by filtration and methanol was removed under reduced pressure, and the crude product was dissolved in 20 mL of ethyl acetate, washed with water and saturated brine, and after extraction of the organic layer, water was removed with magnesium sulfate, and ethyl acetate was removed under reduced pressure to obtain a solid reaction product.
Use of1H NMR determined the product to be hydrazinobenzene and the conversion of the reactant was 97% within 20 min.1H NMR in CDCl3Is measured, CH2Br2As an internal standard.
FIG. 1 is an atomic layer deposition FeSxThe growth behavior of the film is as a result. Wherein (a) is the thickness of the film following Fe (amd)2Tendency toward increased input, where H2The input amount of S is fixed at 0.062 Torr S; (b) the thickness of the film is dependent on H2S tendency of increasing amount of S, wherein Fe (amd)2The amount of the catalyst (2) was fixed at 0.025 Torr s; (c) FeS for atomic layer depositionxThe variation trend of the film thickness along with the deposition period number; (d) FeS for atomic layer depositionxFilm growth rate (in thickness/per cycle) was temperature dependent and film thickness was measured by XRR and XRF. From the data in the figure, the atomic layer deposition FeS of the invention can be obtainedxThe thin film technology conforms to the ALD saturation self-limiting growth mode, and the saturation growth rate at 120 ℃ is 0.025 nm/cycle.
FIG. 2 is a TEM image and corresponding electron diffraction image at different deposition temperatures, respectively (a) 80 ℃, (b)120 ℃, (c) 160 ℃, (d) 200 ℃, (e)250 ℃; (f) is an electron diffraction image. It is apparent from the figure that FeS at different temperatures is observedxThe film has high crystallinity, and FeS of tetragonal pyrite phase is obtained at low temperaturexFilm, FeS of pyrrhotite phase with better thermal stability at high temperaturexA film.
FIG. 3 is a graph of deposited FeSxThe tendency of the iron/sulphur atomic percentage in the film to vary with temperature. XRF and RBS characterization results show that FeS is obtained at different temperaturesxIn the film, the iron/sulfur atomic percentage is close to 1.
FIG. 4 shows the dip at 160 ℃Product of 25 nm FeSxThe XPS characterization result of the film, in FIG. 4, a represents XPS full spectrum element scanning spectrum, b represents XPS iron element high resolution spectrum, c represents XPS sulfur element high resolution spectrum, d represents XPS carbon element high resolution spectrum, e represents XPS nitrogen element high resolution spectrum, and from the graph, the FeS obtained by deposition can be seenxThe film has a higher purity.
FIG. 5 shows FeS with a thickness of 20 nm obtained at different deposition temperaturesxThe thin film AFM and SEM images are shown in the figures, wherein a, c, e, g and i represent AFM images, b, d, f, h and j represent SEM images, and the last table represents a relationship graph of surface roughness and deposition temperature. It can be seen from the figure that the film crystal grains become larger with the increase of the temperature, and the roughness also increases with the increase of the temperature.
FIG. 6 shows FeS deposition in a trench with an aspect ratio of 10:1xCross-sectional SEM images of thin films indicate that the ALD process employed in the present invention has the conformal deposition characteristics of atomic layer deposition.
FIG. 7 shows porous gamma-Al2O3Preparation of nanoscale FeS on powdersxThe thin film is characterized by SEM and EDS, wherein a in FIG. 7 is SEM picture, b-e are respectively oxygen, aluminum, sulfur and iron element surface distribution diagram, and f is EDS energy spectrum. It can be seen from the figure that porous gamma-Al2O3FeS deposition on powderxThe film has a high uniform distribution characteristic.
Table 1 is porous gamma-Al2O3FeS deposition on powderxComparison of the results of the selective hydrogenation catalytic reaction of the diazobenzene with the other catalysts, it can be seen from the results in Table 1 that the ALD deposited FeSx/γ-Al2O3The catalytic performance is much higher than other catalysts. Wherein, the entry is a label, the Catalyst is Catalyst, the conversion is conversion rate, and the selectivity is selectivity.
The reaction principle is as follows:
table 1
TABLE 2 porous gamma-Al2O3FeS deposition on powderxAnd comparing the results of the film on the azobenzene selective hydrogenation catalytic reaction of different substituents. The catalyst has higher catalytic conversion efficiency on azobenzene with different substituents (including electron-donating substituents and electron-withdrawing substituents). Wherein time is catalytic reaction time, and product is a product.
The reaction principle is as follows:
table 2
In summary, the present invention prepares nano-sized FeS on a substrate using ALD processxThin film (catalyst) and use of the prepared FeSxThe catalyst catalyzes the selective reduction (hydrogenation) of aryl azo compounds to hydrazinoaryl compounds. FeS prepared using ALDxThe catalyst, the selective reduction of various aryl azo compounds, can realize the high activity and selective catalytic reaction of the hydrazino-group compound under the mild reaction condition, so the FeS prepared by the ALD processxHas wide application prospect in the aspect of organic synthesis.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A process for preparing a hydrazinophenyl compound comprising the steps of:
will be coated with FeSxMixing the substrate of the film, azobenzene or its derivative and solvent, and reacting under inert atmosphere inAdding a hydrogen source in the reaction process, and obtaining a reaction product, namely a hydrazinophenylcompound after the reaction is finished;
the FeSxThe film is prepared by adopting an atomic layer deposition method, and the FeSxThe preparation method of the film comprises the following steps:
feeding an iron precursor and a sulfur precursor into a deposition chamber with a substrate, setting the temperature of the deposition chamber to be 20-400 ℃, and performing FeSxDepositing a film;
after the deposition is finished, cooling treatment is carried out, and after the temperature is reduced to room temperature, the coating is coated with FeSxAnd taking out the substrate of the film.
2. The method for producing a hydrazinophenylcompound according to claim 1, wherein the iron precursor is an N, N' -alkyl-substituted amidino iron compound.
3. The method for producing a hydrazinophenyl compound according to claim 1, wherein the sulfur precursor is H2S。
4. The method of preparing a hydrazinophenyl compound according to claim 1, wherein the substrate is single crystal silicon, silicon dioxide or porous γ -Al2O3And the substrate is powder or porous medium.
5. The process for producing a hydrazinophenyl compound according to claim 1, wherein the reaction is carried out under an argon or nitrogen atmosphere.
6. The method for producing a hydrazinophenyl compound according to claim 1, wherein the hydrogen source is hydrogen gas, sodium hydride, lithium aluminum hydride, ammonia borane, NaBH4。
7. The process for preparing a hydrazinophenyl compound according to claim 1, wherein the solvent is an organic solvent.
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| JPS61192792A (en) * | 1985-02-22 | 1986-08-27 | Agency Of Ind Science & Technol | Liquefaction of coal by hydrogenation using supported iron sulfide colloid catalyst |
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN104480453A (en) * | 2014-11-28 | 2015-04-01 | 电子科技大学 | Method for preparing porous composite nano thin film |
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| JPS61192792A (en) * | 1985-02-22 | 1986-08-27 | Agency Of Ind Science & Technol | Liquefaction of coal by hydrogenation using supported iron sulfide colloid catalyst |
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN104480453A (en) * | 2014-11-28 | 2015-04-01 | 电子科技大学 | Method for preparing porous composite nano thin film |
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