CN114471612A - Amorphous iron oxide nanosheet composite material, and preparation method and application thereof - Google Patents
Amorphous iron oxide nanosheet composite material, and preparation method and application thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002135 nanosheet Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical group [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical group [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002055 nanoplate Substances 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract description 71
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 238000001228 spectrum Methods 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- 229910002552 Fe K Inorganic materials 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 2
- 229910000069 nitrogen hydride 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
- 230000004044 response Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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Abstract
The invention provides an amorphous iron oxide nanosheet composite material, which consists of amorphous iron oxide nanosheets and ruthenium monoatomic atoms compounded on the surfaces of the amorphous iron oxide nanosheets, wherein the ruthenium monoatomic atoms and the amorphous iron oxide nanosheets form Ru-O and Ru-Fe bonding, and a high-efficiency electron transfer channel from an iron oxide carrier to Ru monoatomic catalytic sites is constructed. The application also provides a preparation method and application of the amorphous iron oxide nanosheet composite material. The ruthenium-loaded amorphous iron oxide nanosheet composite material is obtained by adopting a solid-phase synthesis method, and has excellent catalytic performance in a photocatalytic nitrogen fixation reaction; in addition, the composite material of the invention can be recycled as a catalyst. Therefore, the composite material prepared by the preparation method is used for improving the photocatalytic nitrogen fixation reaction performance, and has good economic and environmental benefits.
Description
Technical Field
The invention relates to the technical field of nanosheet materials and catalysis, in particular to an amorphous iron oxide nanosheet composite material, a preparation method and application thereof.
Background
The synthesis of ammonia is an important inorganic chemical process in which nitrogen and hydrogen are directly combined to generate ammonia under the action of a catalyst. In the modern chemical industry, ammonia is the main raw material for the fertilizer industry and for basic organic chemicals. The current industrial ammonia synthesis technology is mainly based on the Haeberg method using an iron-based catalyst, the reaction is usually carried out under the conditions of 250 atmospheric pressure and 400 ℃, and the consumed energy accounts for more than 1 percent of the total global energy consumption. Therefore, the research on green, clean and sustainable strategies to realize the high-efficiency nitrogen fixation catalysis under mild conditions has very important scientific significance and industrial value. Under the condition of illumination, nitrogen and water are respectively used as a nitrogen source and a proton source to synthesize ammonia, the reaction condition is mild, and the method is environment-friendly and sustainable, and is a research hotspot in the energy field at present.
The monatomic photocatalyst has high atom utilization rate, unsaturated coordination and an adjustable electronic structure, and has great advantages in the aspects of improving the activity and selectivity of surface catalytic reaction. For example, atom dispersed Ru can promote N2Adsorption and activation. Notably, monatomic photocatalysts consist of light absorbing units and supported active sites, and the overall performance depends to a large extent on the efficiency of transfer of the photo-generated electrons from the support to the monatomic catalytic sites. Therefore, how to reasonably construct the catalyst and design a high-efficiency monatomic photocatalyst capable of realizing the enrichment of photo-generated electrons in monatomic active sites and increasing the capability of reducing nitrogen is still a great challenge.
Aiming at the series of challenges, the Sunzhou-Gangyu team of Beijing university of chemical industry dopes Ru atoms in TiO2The oxygen vacancy site of the catalyst promotes the adsorption and activation of nitrogen molecules in the photocatalytic system. However, in the research, the synthesis process of the catalyst is complicated, and the photocatalytic nitrogen fixation performance is still low.
Disclosure of Invention
The invention aims to provide an amorphous iron oxide nanosheet composite material which has good catalytic performance when used as a catalyst for photocatalytic nitrogen fixation.
In view of the above, the present application provides an amorphous iron oxide nanosheet composite material, which is composed of amorphous iron oxide nanosheets and ruthenium monoatomic atoms compounded on the surfaces of the amorphous iron oxide nanosheets, wherein the ruthenium monoatomic atoms and the amorphous iron oxide nanosheets form Ru-O and Ru-Fe bonding.
Preferably, the loading amount of the ruthenium in the amorphous iron oxide nanosheet composite material is 0.3-3.0%.
The application also provides a preparation method of the amorphous iron oxide nanosheet composite material, which comprises the following steps:
mixing a ruthenium source, ferric acetylacetonate and a salt template in a solvent, and drying to obtain mixed powder;
calcining the mixed powder and then cooling to obtain an amorphous iron oxide nanosheet composite material;
the temperature of the calcination is below the melting temperature of the salt template.
Preferably, the salt template is selected from potassium bromide, sodium chloride or sodium nitrate.
Preferably, the ruthenium source is selected from ruthenium acetylacetonate, the salt template is selected from potassium bromide, and the mass ratio of the ruthenium acetylacetonate to the iron acetylacetonate to the potassium bromide is 300 μ g: 5 mg: 24 mg.
Preferably, the calcining temperature is 280-320 ℃, and the calcining time is 2-3 h.
Preferably, the solvent is prepared from (8-10) by mass: 1 ethanol and water.
Preferably, the cooling further comprises:
and washing the cooled powder with ethanol and deionized water for more than 5 times, and drying.
Preferably, the drying is vacuum drying, and the volume ratio of the ethanol to the deionized water is 1: 1.
The application also provides the application of the amorphous iron oxide nanosheet composite material or the amorphous iron oxide nanosheet composite material prepared by the preparation method in photocatalysis nitrogen fixation.
The application provides an amorphous iron oxide nanosheet composite material, which consists of amorphous iron oxide nanosheets and ruthenium monoatomic atoms compounded on the surfaces of the amorphous iron oxide nanosheets. The amorphous iron oxide nanosheet composite material is an amorphous iron oxide nanosheet modified by a ruthenium monoatomic atom, and shows excellent nitrogen fixation catalytic activity in a photocatalytic curing reaction.
Drawings
FIG. 1 is a TEM image of catalysts of comparative examples 1 to 3 and examples 1 to 3 of the present invention;
FIG. 2 is a HADDF-STEM of the catalyst of example 1 of the present invention and its corresponding EDS-mapping image;
FIG. 3 is an Abstract-Corrected HAADF-STEM image of the catalyst of example 1 of the present invention;
FIG. 4 is an XRD pattern of catalysts of comparative examples 1 to 3 and examples 1 to 3 of the present invention;
FIG. 5 is a graph showing the photocatalytic nitrogen fixation performance of the catalysts of comparative examples 1 to 3 and examples 1 to 3 of the present invention;
FIG. 6 is a photo-catalytic nitrogen fixation cycle test chart of the catalyst of example 1 of the present invention;
FIG. 7 is a Ru-K edge XANES (A) and EXAFS (B) spectra of the catalyst of example 1 of the present invention;
FIG. 8 is a Fe-K edge XANES (A) and EXAFS (B) spectra of the catalyst of example 1 of the present invention;
FIG. 9 is a UV-vis spectrum of catalysts of comparative examples 1 to 3 and example 1 of the present invention;
FIG. 10 is a secondary electron cut-off spectrum of the catalysts of comparative examples 1 to 3 and example 1 of the present invention;
FIG. 11 is a valence band diagram of catalysts of comparative examples 1 to 3 and example 1 of the present invention;
FIG. 12 shows band gap structure spectra of catalysts of comparative examples 1 to 3 and example 1 of the present invention;
FIG. 13 is a graph of photocurrent responses of catalysts of comparative example 1 and example 1 of the present invention under different atmospheric conditions;
FIG. 14 is a graph showing femtosecond transient absorption spectra of catalysts of comparative example 1 and example 1 of the present invention;
FIG. 15 shows the change spectra before and after light irradiation of Fe L-edge of the catalysts of comparative example 1 and comparative example 3 of the present invention (A), the change spectra before and after light irradiation of Fe L-edge of the catalysts of comparative example 2 and example 1 of the present invention (B), and the change spectra before and after light irradiation of Ru M-edge of the catalysts of comparative example 2 and example 1 of the present invention (C).
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses an amorphous iron oxide nanosheet composite material, which consists of amorphous iron oxide nanosheets and ruthenium monoatomic atoms compounded on the surfaces of the amorphous iron oxide nanosheets, wherein the ruthenium monoatomic atoms and the amorphous iron oxide nanosheets form Ru-O and Ru-Fe bonding.
In the amorphous iron oxide nanosheet composite material provided by the application, ruthenium is dispersed on the amorphous iron oxide nanosheets in a monoatomic form, and forms Ru-O bonds and Ru-Fe bonds with the amorphous iron oxide nanosheets, but no bonds are formed between ruthenium atoms, so that a high-efficiency photo-generated electron transfer channel from an iron oxide carrier to Ru monoatomic atoms is constructed.
More specifically, in the amorphous iron oxide nanosheet composite material, the loading amount of the ruthenium monoatomic atom is 0.3-3.0%, and in specific embodiments, the loading amount of the ruthenium monoatomic atom is 0.3%, 1.0%, or 3.0%.
The application also provides a preparation method of the amorphous iron oxide nanosheet composite material, which comprises the following steps:
mixing a ruthenium source, ferric acetylacetonate and a salt template in a solvent, and drying to obtain mixed powder;
calcining the mixed powder and then cooling to obtain an amorphous iron oxide nanosheet composite material;
the temperature of the heating is lower than the melting temperature of the salt template.
In the preparation process, firstly, a ruthenium source, ferric acetylacetonate and a salt template are mixed in a solvent and dried to obtain mixed powder; the process enables the iron source and the ruthenium source to be uniformly mixed, so that the uniform growth of the iron oxide substrate on the salt template and the uniform dispersion of Ru atoms are facilitated. The ruthenium source is one or two of ruthenium acetylacetonate and ruthenium trichloride; the salt template enables the amorphous iron oxide to grow into two-dimensional nanosheets, is mainly used for controlling the morphology, and can be removed through a water washing operation after calcination. The salt template can be selected from potassium bromide, sodium chloride or sodium nitrate; in the present application, the salt template is selected from potassium bromide. In the present application, the ruthenium source is selected from ruthenium acetylacetonate, the salt template is selected from potassium bromide, and the mass ratio of the ruthenium acetylacetonate, the iron acetylacetonate and the potassium bromide is 300 μ g: 5 mg: 24 mg. The solvent is selected from the following components in a mass ratio of (8-10): 1 ethanol and water.
The application then calcines the mixed powder and then cools the calcined mixed powder to obtain the amorphous iron oxide nanosheet composite material; the above calcination is carried out to form iron oxide amorphous nanoplatelets in which ruthenium is dispersed in a monoatomic form. The calcining temperature is 280-320 ℃, and the calcining time is 2-3 h.
According to the invention, the cooled powder is washed more than 5 times by ethanol and deionized water and dried.
In the process, the volume ratio of the ethanol to the deionized water is 1:1, and the drying is vacuum drying. The washing removes the salt template, but the ions in the salt template are not incorporated into the iron oxide during the calcination.
The ruthenium-loaded amorphous iron oxide nanosheet composite material is obtained by adopting a solid-phase synthesis method, and the ruthenium-loaded amorphous iron oxide nanosheet composite material has excellent catalytic performance in a photocatalytic nitrogen fixation reaction. In addition, the ruthenium-supported amorphous iron oxide nanosheet composite material can be recycled as a catalyst. Therefore, the catalyst obtained by the preparation method is used for improving the photocatalytic nitrogen fixation reaction performance, and has good economic and environmental benefits.
The ruthenium-loaded amorphous iron oxide nanosheet composite material provided by the invention can show excellent catalytic performance in a photocatalytic nitrogen fixation reaction, namely NH3The yield is high, so the application also provides the ruthenium-loaded amorphous iron oxide nanosheet composite material as a photocatalytic nitrogen fixed catalystThe use of (1).
Specifically, the invention mixes the catalyst and water, and the obtained mixed solution adopts N2Bubbling, and carrying out photocatalytic nitrogen fixation reaction on the bubbled suspension under the irradiation of a xenon lamp to obtain NH3. The catalyst is the ruthenium-supported amorphous iron oxide nanosheet composite described above.
In certain embodiments of the present invention, the water is deionized water.
In certain embodiments of the invention, the catalyst to water is present in a ratio of 10 mg: 20 mL.
In certain embodiments of the present invention, N is employed2N for carrying out bubbling2The flow rate was 30 mL/min-1By using N2The bubbling time was 30 min.
In certain embodiments of the invention, the photocatalytic nitrogen fixation reaction is performed at room temperature and atmospheric pressure.
In certain embodiments of the invention, the photocatalytic nitrogen fixation reaction is performed for 0.5 h.
In certain embodiments of the invention, the photocatalytic nitrogen fixation reaction is performed under agitation. The method of stirring is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be employed.
In certain embodiments of the invention, the photocatalytic nitrogen fixation reaction is performed in a vacuum thick-walled pressure-resistant reaction vessel.
In the photocatalytic nitrogen fixation reaction, N is used2And deionized water as reactants, without adding any sacrificial agent and organic solvent, and producing NH at room temperature3The speed can reach 213 mu mol gcat. –1·h–1。
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further understand the present invention, the following detailed description is made on the amorphous iron oxide nanosheet composite material, the preparation method thereof and the application thereof, which are provided by the present invention, with reference to the following examples, and the scope of the present invention is not limited by the following examples.
The starting materials used in the following examples are all generally commercially available.
Comparative example 1
(1) Mixing iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) to a homogeneous solution;
(2) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
(3) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
(4) and washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain the amorphous iron oxide nanosheet photocatalyst (2 DAF).
Comparative example 2
(1) Ruthenium acetylacetonate powder (300ug), iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) were mixed into a homogeneous solution;
(2) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
(3) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
(4) washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain powder;
(5) calcining the powder in a tubular furnace to 450 ℃ in the air atmosphere, keeping the temperature for 100 minutes and increasing the temperature at 8 ℃/min.
(6) Washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain ruthenium-loaded crystalline iron oxide nanosheet photocatalyst (Ru)1/2DCF)。
Comparative example 3
(1) Mixing iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) to a homogeneous solution;
(2) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
(3) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
(4) washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain powder;
(5) calcining the powder in a tubular furnace to 450 ℃ in the air atmosphere, keeping the temperature for 100 minutes, and raising the temperature at 8 ℃/min;
(6) and washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain the crystalline iron oxide nanosheet photocatalyst (2 DCF).
Example 1
A) Ruthenium acetylacetonate powder (300ug), iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) were mixed into a homogeneous solution;
B) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
C) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
D) washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain ruthenium monoatomic modified amorphous iron oxide nanosheet photocatalyst (Ru)12DAF), the Ru loading was 1%.
Example 2
A) Ruthenium acetylacetonate powder (90ug), iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) were mixed into a homogeneous solution;
B) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
C) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
D) washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain ruthenium monoatomic modified amorphous iron oxide nanosheet photocatalyst (Ru)0.32DAF), the Ru loading was 0.3%.
Example 3
A) Ruthenium acetylacetonate powder (900ug), iron acetylacetonate powder (5mg) and potassium bromide powder (24mg) were mixed into a homogeneous solution;
B) drying the obtained mixed solution to obtain dry powder and uniformly grinding the dry powder;
C) heating the ground powder to 300 ℃ in a tube furnace in the air atmosphere, maintaining the temperature for 120 minutes, and naturally cooling;
D) washing the cooled powder with ethanol and deionized water for more than 5 times, and drying to obtain ruthenium monoatomic modified amorphous iron oxide nanosheet photocatalyst (Ru)3/2DAF), Ru loading was 3%.
The TEM spectra of the catalysts obtained in comparative examples 1-3 and examples 1-3 were analyzed, and the results are shown in FIG. 1, FIG. 1 is the TEM spectra of the catalysts of comparative examples 1-3 and examples 1-3, and it can be seen from FIG. 1 that several samples have a nano-sheet structure.
The invention also carries out EDX spectrogram analysis on the catalyst obtained in the example 1, the result is shown in figure 2, figure 2 is the EDX spectrogram of the catalyst in the example 1, and the figure 2 shows that the Ru, Fe and O elements in the sample are uniformly distributed.
The catalyst obtained in example 1 is further analyzed by a spherical aberration electron microscope test, and it can be seen from fig. 3 that Ru is uniformly distributed on the amorphous iron oxide substrate.
The XRD of the catalysts obtained in comparative examples 1-3 and examples 1-3 was obtained by analyzing the catalysts obtained in comparative examples 1-3 and examples 1-3 with an X-ray diffractometer, and the results are shown in FIG. 4, wherein FIG. 4 is the XRD spectrum of the catalysts of comparative examples 1-3 and examples 1-3 of the present invention; as can be seen from FIG. 4, comparative examples 2 and 3 are crystalline Fe having better crystallinity2O3In the embodiment 1 and the comparative examples 1 to 3, the particles were amorphous and no characteristic peak of Ru particles appeared.
The invention respectively carries out photocatalytic nitrogen fixation reaction on the catalysts obtained in comparative examples 1-3 and examples 1-3, and the specific steps are as follows: 10mg catalyst and 20mL deionized water were added to a 100mL vacuum thick-walled pressure-resistant reaction vessel, N2At a rate of 30 mL/min-1Bubbling for 30min at the flow rate, and then stirring the obtained suspension for reaction for 0.5h under the irradiation of a xenon lamp; after the reaction, NH detected by ion chromatography and colorimetry3Yield of (1) to (3) and example 1 to (3) to obtain photocatalytic nitrogen of the catalystFIG. 5 shows a graph of gas fixing performance, and FIG. 5 shows graphs of photocatalytic nitrogen gas fixing performance of comparative examples 1 to 3 and examples 1 to 3. As can be seen from FIG. 5, the photocatalytic nitrogen fixation using the 2DCF catalyst resulted in an ammonia production rate of 28.4. mu. mol. gcat. –1·h–1(ii) a Using Ru1The catalyst/2 DCF was used for photocatalytic nitrogen fixation with an ammonia production rate of 47.7. mu. mol gcat. –1·h–1(ii) a 2DAF catalyst is adopted for carrying out photocatalytic nitrogen fixation, and the ammonia production rate is 101.8 mu mol gcat. –1·h–1(ii) a Using Ru0.3The catalyst/2 DAF is used for carrying out photocatalytic nitrogen fixation, and the ammonia production rate is 140.1 mu mol gcat. –1·h–1(ii) a Using Ru3The catalyst/2 DAF is used for carrying out photocatalytic nitrogen fixation, and the ammonia production rate is 178.2 mu mol gcat. –1·h–1(ii) a By using Ru1The catalyst/2 DAF was used for photocatalytic nitrogen fixation with an ammonia production rate of 213. mu. mol. gcat. –1·h–1；Ru1The photocatalytic nitrogen fixation performance of the/2 DAF catalyst is optimal.
The invention also analyzes the photocatalytic nitrogen fixed cycle performance of the catalyst obtained in example 1, the result is shown in fig. 6, fig. 6 is a graph of the photocatalytic nitrogen fixed cycle performance of the catalyst of example 1, and fig. 6 shows that Ru is contained in fig. 61The ammonia production rate of the catalyst used for the first time is 213 mu mol g for the first time of the 2DAF catalystcat. –1·h–1The ammonia production rate after five times of circulation is 212 mu mol gcat. –1·h–1. Obviously, the catalyst has better stability, and the performance is not obviously reduced after six times of circulation.
The catalyst obtained in example 1 was subjected to the XANES spectrum analysis with Ru-K edges, and the result is shown in FIG. 7; FIG. 7 is a graph of the spectrum of Ru-K edge XANES of example 1 of the present invention; as can be seen from fig. 7A, Ru exhibits an oxidation state. As can be seen from FIG. 7B, the monoatomic atom of Ru mainly exists in the Ru-O coordination structure, and secondly, the Ru-Fe coordination structure also exists.
The catalyst obtained in example 1 was further subjected to Fe-K edge XANES spectral decompositionThe results are shown in FIG. 8; FIG. 8 is a graph showing a Fe-K edge XANES spectrum of comparative example 2 of the present invention; as can be seen from fig. 8A and 8B, the short-range structure of Fe in example 1 is very close to Fe2O3Whereas the long-range structure is a disordered state.
The catalysts obtained in comparative examples 1-3 and example 1 were subjected to UV-vis spectrum analysis, and the results are shown in FIG. 9; FIG. 9 is a UV-vis spectrum of catalysts of comparative examples 1 to 3 and example 1 of the present invention; as can be seen from FIG. 9, the amorphous structure is such that Fe2O3The band gap of the silicon nitride is slightly shortened, and the position of a conduction band is moved upwards, so that the reduction reaction is more favorably carried out.
UPS tests were also conducted on the catalysts obtained in comparative examples 1 to 3 and example 1, and the results are shown in FIGS. 10 and 11; FIG. 10 is a secondary electron cut-off spectrum of the catalysts of comparative examples 1 to 3 and example 1 of the present invention; FIG. 11 is a valence band diagram of catalysts of comparative examples 1 to 3 and example 1 of the present invention; with reference to fig. 10 and 11, band gap structure spectra of the catalysts of comparative examples 1 to 3 and example 1 of the present invention can be obtained, and the results are shown in fig. 12; as can be seen from FIG. 12, Ru1The reduction capability of the/2 DAF catalyst is strongest, namely the introduction of Ru monoatomic group and the amorphous structure are favorable to N thermodynamically2And (4) reducing the molecules.
The present invention also performed photocurrent tests on the catalysts obtained in comparative example 1 and example 1, and the results are shown in fig. 13. FIG. 13 is a transient response spectrum of the catalysts of comparative example 1 and example 1 of the present invention, and it can be seen from FIG. 13 that Ru is contained in Ar atmosphere1The/2 DAF catalyst has longer carrier life, and is beneficial to the utilization of photon-generated carriers in catalytic reaction. N is a radical of2After saturation of adsorption, Ru1The drop of the photo-generated carriers of the/2 DAF catalyst is more, which shows that the introduction of Ru monoatomic atoms is more favorable for electrons to be adsorbed to N2Transfer of molecules to activate N2。
The invention also compares the comparative example 1 and example 1 catalyst obtained femtosecond transient absorption spectrum test, the results are shown in figure 14; fig. 14 is a femtosecond transient absorption spectrum test spectrum of the catalysts of comparative example 1 and example 1 of the present invention, and it can be seen from fig. 14 that the enrichment of photo-generated electrons from the amorphous carrier to Ru single atoms illustrates the generation of photo-generated electron channels from the amorphous carrier to the Ru catalytic sites.
The catalysts obtained in comparative examples 1-3 and example 1 were subjected to the test of L-edge of Fe before and after polishing, and the catalysts obtained in comparative example 2 and example 1 were subjected to the test of M-edge of Ru before and after polishing, and the results are shown in FIG. 15; FIG. 15(A) is a graph showing an L-edge spectrum of Fe before and after polishing for catalysts of comparative example 1 and comparative example 3 of the present invention, FIG. 15(B) is a graph showing an M-edge spectrum of Ru before and after polishing for catalysts of comparative example 2 and example 1 of the present invention, and FIG. 15(C) is a graph showing an M-edge spectrum of Ru before and after polishing for catalysts of comparative example 2 and example 1 of the present invention; as can be seen from the comprehensive analysis of FIG. 15, the amorphous structure is more favorable for the transition of the photo-generated electrons to the 4d orbit of the catalytic site Ru, and the photo-generated electrons enriched in the Ru site further promote N2The reduction of molecules realizes better photocatalytic nitrogen fixation catalytic performance.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The amorphous iron oxide nanosheet composite material consists of amorphous iron oxide nanosheets and ruthenium monoatomic atoms compounded on the surfaces of the amorphous iron oxide nanosheets, wherein the ruthenium monoatomic atoms and the amorphous iron oxide nanosheets form Ru-O and Ru-Fe bonding.
2. The amorphous iron oxide nanoplate composite of claim 1, wherein the loading of ruthenium in the amorphous iron oxide nanoplate composite is 0.3-3.0%.
3. A method of preparing an amorphous iron oxide nanoplate composite as claimed in claim 1, comprising the steps of:
mixing a ruthenium source, ferric acetylacetonate and a salt template in a solvent, and drying to obtain mixed powder;
calcining the mixed powder and then cooling to obtain an amorphous iron oxide nanosheet composite material;
the temperature of the calcination is below the melting temperature of the salt template.
4. The method of claim 3, wherein the salt template is selected from potassium bromide, sodium chloride, or sodium nitrate.
5. The preparation method according to claim 3, wherein the ruthenium source is selected from ruthenium acetylacetonate, the salt template is selected from potassium bromide, and the mass ratio of the ruthenium acetylacetonate, the iron acetylacetonate, and the potassium bromide is 300 μ g: 5 mg: 24 mg.
6. The preparation method according to claim 3, wherein the calcination temperature is 280-320 ℃, and the calcination time is 2-3 h.
7. The preparation method according to claim 3, wherein the solvent is prepared from (8-10) by mass: 1 ethanol and water.
8. The method of claim 3, further comprising, after the cooling:
and washing the cooled powder with ethanol and deionized water for more than 5 times, and drying.
9. The preparation method according to claim 8, wherein the drying is vacuum drying, and the volume ratio of the ethanol to the deionized water is 1: 1.
10. The amorphous iron oxide nanosheet composite material of any one of claims 1 to 2 or the amorphous iron oxide nanosheet composite material prepared by the preparation method of any one of claims 3 to 9, for use in photocatalytic nitrogen fixation.
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