CN109499602B - Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster - Google Patents
Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster Download PDFInfo
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- CN109499602B CN109499602B CN201910031428.5A CN201910031428A CN109499602B CN 109499602 B CN109499602 B CN 109499602B CN 201910031428 A CN201910031428 A CN 201910031428A CN 109499602 B CN109499602 B CN 109499602B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 68
- 238000001308 synthesis method Methods 0.000 title abstract description 15
- 230000001105 regulatory effect Effects 0.000 title abstract description 12
- 230000001276 controlling effect Effects 0.000 title abstract description 8
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- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 150000003384 small molecules Chemical class 0.000 claims abstract description 6
- 239000012692 Fe precursor Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
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- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 3
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- 230000004075 alteration Effects 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
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- 239000000758 substrate Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
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- 229910052786 argon Inorganic materials 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
- 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 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 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 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000009149 molecular binding Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/618—
-
- 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
-
- 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
Abstract
The application discloses a synthesis method for systematically regulating and controlling the number of atoms of a load type iron atom cluster, which comprises the following steps: mixing an iron source compound, a zinc source compound and an organic small molecule connecting agent in a solvent, and obtaining a metal organic framework coated iron precursor nano material at a preset reaction temperature for a preset reaction time; and calcining the nano material in inert gas at high temperature to obtain the supported iron atom cluster catalyst containing the specific number of iron atoms. The method can systematically prepare the single iron atom, the di-iron and tri-iron metal atom clusters, has simple process, mild reaction conditions, high yield and high purity, and is suitable for large-scale production.
Description
Technical Field
The application relates to the technical field of functional materials, in particular to a synthesis method for systematically regulating and controlling the number of atoms of a load type iron atom cluster.
Background
In a typical chemical reaction, in order to significantly increase the rate of the chemical reaction, it is usually necessary to add a catalyst, the role of which can be generally summarized as follows: firstly, the kinetics of chemical reaction is changed, and the reaction rate is improved; secondly, the reaction path is changed, and the selectivity of a specific product is improved; and thirdly, the energy barrier of the reaction is reduced, and the reaction temperature is reduced. In general, in a catalytic reaction, the structure and quality of the catalyst itself does not change significantly. The modern chemical industry uses a large amount of catalysts, and the catalysts such as fuel cells, automobile exhaust treatment and the like also rely on high activity and high selectivity. Therefore, the catalyst is an auxiliary agent for promoting the modern chemical industry, and the research of the catalyst is extremely important for the modern chemical industry.
Compared with the traditional high-activity noble metal catalyst, the transition metal catalyst has abundant reserves in the earth crust, relatively low price and moderate catalytic activity, and is widely concerned. In order to sufficiently improve the catalytic activity of the transition metal catalyst, a strategy is generally adopted in which the active sites of the metal atoms are more exposed. Among other things, reducing the size of the transition metal to the atomic level can achieve maximum exposure of the catalytic sites. However, for the supported catalyst, the catalytic activity of the transition metal catalyst is not only related to the number of active sites of the metal atom, but also has a great correlation with the valence of the metal atom in the catalytic center and the coordination environment around the metal atom. The valence state of the central metal atom is closely related to the electron density of the d orbital of the metal atom, and the hybridization between the electrons on the d orbital and catalytic substrate molecules remarkably influences the adsorption and desorption capacity of the substrate molecules on the surface of the catalyst, so that the catalytic activity of the catalyst is remarkably influenced. Similarly, the coordinating atoms surrounding the metal atom also significantly change the valence state of the metal atom and the adsorption, activation thermodynamics of the substrate molecule.
The transition metal atoms dispersed at atomic level are anchored on the surface of nitrogen-doped carbon, and the catalyst is very important and has very remarkable structural characteristics: firstly, the transition metal atoms dispersed at the atomic level can maximally expose catalytic active sites, so that the catalytic activity is remarkably improved; moreover, the metal atoms are very stably anchored on the surface of the substrate by forming metal-nitrogen coordination, and the electronic structure of the transition metal atoms can be adjusted by the difference of the type and the content of nitrogen; finally, the nitrogen atom doped carbon substrate has good conductivity. The excellent structural characteristics enable the catalyst to show excellent performance in the aspects of fuel cell cathode reaction, water cracking reaction, organic molecule oxidation reaction, chemical nitrogen fixation reaction and the like. Among them, nitrogen-doped carbon-supported iron monatomic catalysts exhibit optimal performance in the alkaline fuel cell cathode oxygen reduction reaction. In the present stage, the energy crisis and environmental pollution cause the clean energy to be widely noticed by people, and the fuel cell technology is considered as a representative of the next generation of new energy, and at present, companies design and mass-produce a new generation of hydrogen fuel cells. The key of the fuel cell is that the cathode oxygen reduction reaction is highly dependent on the noble metal platinum catalyst, so the development of the non-platinum catalyst with high activity and high stability for the cathode oxygen reduction reaction of the fuel cell is the key for breaking through the bottleneck.
Therefore, how to further improve the oxygen reduction activity and stability of the atomic-level dispersed iron atomic catalyst and comprehensively replace the application of a platinum-based catalyst in fuel cell automobiles becomes a problem to be solved by leading-edge theories in the industry. The current research result shows that the supported iron atom cluster catalyst can realize the conversion of the adsorption configuration of oxygen molecules from a super-oxygen state adsorption configuration to a peroxide state adsorption configuration, and compared with the super-oxygen state adsorption, the peroxide state adsorption of oxygen can better activate the oxygen molecules and improve the activity of catalyzing oxygen reduction. However, how to achieve supported iron cluster catalysts with a specific number of iron atoms is a recognized challenge.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a simple synthesis method for systematically regulating and controlling the number of atoms of a supported iron atom cluster, where the supported iron atom cluster prepared by the synthesis method provided by the present invention is anchored on the surface of nitrogen-doped carbon, so as to realize the systematic preparation of the iron atom cluster from a single iron atom to di-iron and tri-iron atom clusters. In particular, the catalyst containing the cluster of the diiron atoms prepared by the invention has large specific surface area, and shows high activity and stability in the electrocatalytic acidic oxygen reduction reaction, and the activity of the catalyst is close to that of a commercial platinum/carbon catalyst. In addition, the synthesis method provided by the invention has the characteristics of mild reaction conditions, high yield, good purity and the like, and is suitable for large-scale production of the catalyst.
The invention provides a synthesis method for systematically regulating and controlling the number of atoms of a load type iron atom cluster, which comprises the following steps:
mixing an iron source compound, a zinc source compound and an organic small molecule connecting agent in a solvent, and obtaining a metal organic framework coated iron precursor nano material at a preset reaction temperature for a preset reaction time;
and calcining the nano material in inert gas at high temperature to obtain the supported iron atom cluster catalyst containing specific iron atom number.
Preferably, the iron source compound is one of ferric trichloride, ferric acetylacetonate, carbonyl iron, iron carbonyl nonacarbonyl and ferroferric oxide dodecacarbonyl;
the zinc source compound is a divalent zinc-containing compound.
Preferably, the solvent comprises: one or more of tetrahydrofuran, nitrogen dimethyl formamide and methanol.
Preferably, the preset reaction temperature is: 10-120 ℃; the preset reaction time is as follows: 10-120 minutes.
Preferably, the high-temperature calcination temperature is 500-1000 ℃, and the high-temperature calcination time is 60-240 minutes.
Preferably, the molar ratio of the iron source compound to the zinc source compound is: 1: 50 to 150.
Preferably, the mass ratio of the zinc source compound to the solvent is: 1: 20 to 60.
Preferably, when methanol, nitrogen dimethylformamide or tetrahydrofuran is included in the solvent, the volume ratio of methanol, nitrogen dimethylformamide or tetrahydrofuran is 1: (0.3-0.9): (0.4-0.8).
Preferably, the nanomaterial has an adjustable number of iron atoms and a high specific surface area.
Preferably, the size of the nano particles of the nano material is 150-300 nm.
In summary, the invention provides a synthesis method for systematically regulating and controlling the number of atoms of a load-type iron atom cluster, which comprises the following steps: mixing an iron source compound, a zinc source compound and an organic small molecule connecting agent in a solvent, and obtaining a metal organic framework coated iron precursor nano material at a preset reaction temperature for a preset reaction time; and calcining the nano material in inert gas at high temperature to obtain the supported iron atom cluster catalyst containing the specific number of iron atoms. Compared with the prior art, the synthesis method provided by the invention can realize systematic regulation of the number of iron atom cluster atoms and realize effective regulation of the iron atom cluster from a single iron atom to di-iron and to tri-iron clusters. The synthesis method provided by the invention can realize the synthesis of various supported iron atom clusters, has the characteristics of simple process, mild condition, high yield, good purity and the like, and is suitable for large-scale production.
The nitrogen-doped carbon-supported iron cluster catalyst obtained by the invention has very high specific surface area, and the high specific surface area can maximize the exposure of active sites of transition metal atoms. Can widely meet the requirements of catalysis, such as electrocatalytic oxygen reduction reaction, organic molecule oxidation reaction, electrocatalytic water cracking reaction and the like, and is suitable for further application in research and industrial production; meanwhile, the iron atoms with different numbers can obviously change the adsorption configuration of the substrate molecules at the catalytic center. For example, oxygen molecules are adsorbed by superoxide at the surface of a single iron atom, while oxygen molecules are adsorbed by peroxygen at the surface of a di-iron cluster. Wherein, the oxygen molecule is bonded with two iron atoms in the peroxide state adsorption, so that the activation degree of the oxygen molecule is higher, and the peroxide state adsorption is very suitable for catalyzing the reduction reaction of the oxygen molecule. Experimental results show that the supported type diiron cluster nano catalyst prepared by the invention is high in purity and free of impurities, has the particle size of about 150-300 nm, and has excellent electrocatalytic oxygen reduction activity and stability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a synthesis method for systematically regulating the number of atoms in a cluster of loaded iron atoms, which is disclosed by the invention;
fig. 2 is a transmission electron micrograph of the nitrogen-doped carbon-supported nanomaterial containing a single iron atom cluster prepared in example 1 of the present invention, with a scale of 200 nm;
FIG. 3 is a scanning transmission electron micrograph of N-doped carbon-supported single-iron-atom-cluster spherical aberration correction prepared in example 1 of the present invention, with a scale of 2 nm;
fig. 4 is a nitrogen adsorption and desorption curve of nitrogen-doped carbon supported cluster containing a single iron atom prepared in example 1 of the present invention;
fig. 5 is a transmission electron micrograph of the nitrogen-doped carbon-supported diiron atomic cluster prepared in example 2 of the present invention, with a scale of 200 nm;
fig. 6 is a scanning transmission electron micrograph of the nitrogen-doped carbon-supported di-iron cluster prepared in example 2 of the present invention showing 2nm on a scale;
fig. 7 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-supported diiron atom cluster nanomaterial prepared in example 2 of the present invention;
fig. 8 is a transmission electron microscope photograph of the nitrogen-doped carbon-supported ferroferric atom cluster nanomaterial prepared in example 3 of the present invention, with a ruler of 200 nm;
fig. 9 is a scanning electron microscope photograph of spherical aberration correction of the nitrogen-doped carbon-supported ferroferric atom cluster nanomaterial prepared in example 3 according to the present invention, with a 2nm ruler;
fig. 10 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-supported ferroferric atom cluster nanomaterial prepared in embodiment 3 of the present invention;
FIG. 11 is a graph of oxygen reduction under catalytic acidic conditions for nanomaterials prepared in example 2 of the present invention;
FIG. 12 is a graph of the oxygen reduction stability under the catalytic acidic condition of the nanomaterial prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and analytical purification is preferably employed in the present invention.
The apparatus used in the present invention is not particularly limited, and may be a flask, a beaker, a reaction kettle, etc. commonly used in the art, and other apparatuses capable of satisfying the technical scheme of the present invention.
As shown in fig. 1, the synthesis method for systematically regulating the number of atoms in a supported iron atom cluster disclosed by the invention comprises the following steps:
s101, mixing an iron source compound, a zinc source compound and an organic small molecule connecting agent in a solvent, and obtaining a metal organic framework coated iron precursor nano material at a preset reaction temperature for a preset reaction time;
s102, calcining the nano material in inert gas at high temperature to obtain the supported iron atom cluster catalyst containing the specific iron atom number.
The iron source compound is preferably one of ferric trichloride, ferric acetylacetonate, carbonyl iron, nine-carbonyl-ferric oxide and dodecacarbonyl-ferric oxide. The zinc source compound is preferably a divalent zinc-containing compound. The divalent zinc-containing compound is not particularly limited in the present invention, and may be any divalent zinc-containing compound known to those skilled in the art, and the present invention preferably includes one or more of zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, and zinc acetate, and most preferably zinc nitrate.
The molar ratio of the iron source compound to the zinc source compound in the present invention is preferably 1: (50 to 150), more preferably 1: (100 to 140), more preferably 1: (120-140), most preferably 1: 140 of a solvent; the mol ratio of the zinc source compound to the organic small molecule binding agent is preferably 1: (2-12), more preferably 1: (2-8), more preferably 1: (2-4), most preferably 1: 4; the mass ratio of the zinc source to the solvent is preferably 1: (20-60), more preferably 1: (20 to 50), more preferably 1: (20 to 40), most preferably 1: 30, of a nitrogen-containing gas; the solvent used in the invention is one or more of methanol, nitrogen dimethylformamide and tetrahydrofuran, wherein when the solvent comprises methanol, nitrogen dimethylformamide or tetrahydrofuran, the volume ratio of methanol, nitrogen dimethylformamide or tetrahydrofuran is preferably 1: (0.3-0.9): (0.4 to 0.8), more preferably 1: (0.4-0.8): (0.4 to 0.7), more preferably 1: (0.6-0.8): (0.4 to 0.6), most preferably 1: 0.75: 0.5. the proportion of the iron source compound and the zinc source compound is not particularly limited, and the technicians in the field can automatically adjust the proportion according to actual conditions, product requirements and specific purposes. The iron in the finally formed nano material accounts for 1 per thousand-8% of the total mass fraction, and the iron content with higher mass fraction can lead the formed iron atom clusters to aggregate to form nano particles.
The preset reaction temperature is preferably 10-120 ℃, more preferably 20-100 ℃, more preferably 30-60 ℃, and most preferably 30-50 ℃. The preset reaction time is preferably 10-120 minutes, more preferably 10-100 minutes, and more preferably 50-70 minutes. The high-temperature calcination temperature is preferably 500-1000 ℃, more preferably 700-900 ℃, and more preferably 800-900 ℃. The calcination time is preferably 60 to 240 minutes, and more preferably 120 to 180 minutes. The inert gas for calcination according to the present invention is preferably high-purity argon or high-purity nitrogen.
The preparation method provided by the invention adopts a method of low-temperature normal-pressure liquid phase synthesis and high-temperature calcination, is a universal method for preparing the catalyst which is widely adopted in industry, and can be simply realized by amplifying the feeding ratio in large-scale mass production. The process method has the advantages of simple process, high yield and easy amplification and batch production.
The supported iron atom cluster obtained by the method provided by the invention has a rich microporous structure and a high specific surface area, can maximally expose catalytic sites, and is beneficial to adsorption and desorption of substrate molecules and a rapid mass transfer process. The metallic iron is used as an active center and is dispersed to the surface of the nitrogen-doped carbon in an atomic cluster state, the number of iron atoms in the iron atom cluster can be accurately regulated and controlled, and the transition from a single iron atom to di-iron and tri-iron provides a good model for researching the structure-activity relationship between the number of iron atoms and the catalytic activity. The supported iron atom cluster catalyst obtained by the invention has rich microporous structure, very high specific surface area and accurately regulated and controlled iron atom number, can widely meet the requirements of catalysis, has higher catalytic activity, such as electrochemical reduction reaction of oxygen molecules, oxidation reaction of small organic molecules, electrochemical water cracking reaction and the like, is suitable for further application in research and industrial production, and is particularly used for fuel cell cathode catalysts. Experimental results show that the supported catalyst containing the iron-di-cluster-iron atoms prepared by the invention has high purity of the iron clusters, and shows higher activity and stability in the acidic electrochemical oxygen reduction reaction.
In order to further illustrate the present invention, the supported iron atom cluster nanomaterial and the synthesis method thereof provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Nitrogen-doped carbon-supported single iron atom catalyst
16 mg of iron acetylacetonate and 1190 mg of zinc nitrate hexahydrate were dissolved by sonication in a mixed solution of 10 ml of tetrahydrofuran and 20 ml of methanol. Meanwhile, 1314 mg of dimethyl imidazole is dissolved in another mixed solution which comprises 6 ml of nitrogen, nitrogen dimethyl formamide and 4 ml of methanol, and the two mixed solutions are mixed at room temperature and then are subjected to ultrasonic treatment for 10 minutes to obtain white precipitate which is dried. And calcining the white precipitate in a high-temperature tube furnace for 3 hours at the heating rate of 5 ℃ per minute and the calcining temperature of 800 ℃, and taking high-purity argon as a carrier gas to obtain a final product.
The detection result of the sample of the nitrogen-doped carbon-loaded single iron atom prepared by the method indicates that, referring to fig. 2, fig. 2 is a transmission electron microscope photograph of the nitrogen-doped carbon-loaded single iron atom nano material prepared in the embodiment 1 of the present invention, and the ruler is 200 nm. Referring to fig. 3, fig. 3 is a scanning transmission electron microscope photograph of spherical aberration corrected annular dark field of the nitrogen-doped carbon-loaded single iron atom nanomaterial prepared in example 1 of the present invention, with a 2nm ruler. The single iron atom marked by a black dashed circle can be seen from the spherical aberration electron micrograph. Referring to fig. 4, fig. 4 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-supported single iron atom nanomaterial prepared in example 1 of the present invention, and as can be seen from the adsorption and desorption curve, the specific surface area of the obtained nanomaterial is 1028 square meters per gram. Such a large specific surface area indicates that the prepared material can expose more active sites of iron atoms.
Example 2
Nitrogen-doped carbon-loaded diiron cluster
The method comprises the steps of dissolving 11 mg of nonacarbonyl diiron and 1190 mg of zinc nitrate hexahydrate in a mixed solution of 10 ml of tetrahydrofuran and 20 ml of methanol by ultrasonic waves, dissolving 1314 mg of dimethylimidazole in another mixed solution of 6 ml of nitrogen, nitrogen and dimethylformamide and 4 ml of methanol, mixing the two mixed solutions at room temperature, then performing ultrasonic waves for 10 minutes to obtain a white precipitate, and drying the white precipitate. And calcining the white precipitate in a high-temperature tube furnace for 3 hours at the heating rate of 5 ℃ per minute and the calcining temperature of 800 ℃, and taking high-purity argon as a carrier gas to obtain a final product.
The detection result of the sample of the nitrogen-doped carbon-loaded diiron cluster prepared by the method indicates that, referring to fig. 5, fig. 5 is a transmission electron microscope photograph of the nitrogen-doped carbon-loaded diiron cluster nanomaterial prepared in embodiment 2 of the present invention, and the ruler is 200 nm. Referring to fig. 6, fig. 6 is a transmission electron microscope photograph of spherical aberration corrected annular dark field scanning of the nitrogen-doped carbon-loaded di-iron cluster nanomaterial prepared in example 2 according to the present invention, with a 2nm ruler. The ferrous clusters marked by black dashed circles can be seen from the spherical aberration electron micrograph. Referring to fig. 7, fig. 7 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-supported diiron cluster nanomaterial prepared in example 2 of the present invention, and it can be known from the adsorption and desorption curve that the specific surface area of the obtained nanomaterial is 1080 square meters per gram. Again, such a large specific surface area indicates that the prepared material can more expose active sites of the diiron cluster.
Example 3
Nitrogen-doped carbon-supported ferroferric oxide cluster
Ultrasonic dissolving 8 mg of ferroferric dodecacarbonyl and 1190 mg of zinc nitrate hexahydrate in a mixed solution of 10 ml of tetrahydrofuran and 20 ml of methanol, simultaneously dissolving 1314 mg of dimethylimidazole in another mixed solution of 6 ml of nitrogen, nitrogen and dimethylformamide and 4 ml of methanol, mixing the two mixed solutions at room temperature, then performing ultrasonic treatment for 10 minutes to obtain a white precipitate, and drying. And calcining the white precipitate in a high-temperature tube furnace for 3 hours at the heating rate of 5 ℃ per minute and the calcining temperature of 800 ℃, and taking high-purity argon as a carrier gas to obtain a final product.
The nitrogen-doped carbon supported ferroferric oxide cluster sample prepared by the method is detected, and the detection result shows that the reference is made to fig. 8, fig. 8 is a transmission electron microscope photograph of the nitrogen-doped carbon supported ferroferric oxide cluster nano material prepared in embodiment 3 of the invention, and the ruler is 200 nm. Referring to fig. 9, fig. 9 is a transmission electron microscope photograph of spherical aberration correction annular dark field scanning of the nitrogen-doped carbon-supported ferroferric cluster nanomaterial prepared in example 3 of the present invention, with a 2nm ruler. From the spherical aberration electron micrograph, the ferroferric clusters marked by black dotted circles can be seen. Referring to fig. 9, fig. 10 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-supported ferroferric cluster nanomaterial prepared in example 3 of the present invention, and it can be seen from the adsorption and desorption curve that the specific surface area of the obtained nanomaterial is 1024 square meters per gram. Also, such a large specific surface area indicates that the prepared material can expose more active sites of the ferroferric clusters.
Example 4
Electrocatalytic cathodic oxygen reduction reaction under acidic condition
2 mg of the nanomaterial prepared in example 2 was dispersed in a mixed solution of 0.7 ml of distilled water, 0.25 ml of isopropyl alcohol and 0.05 ml of naphthol and sonicated for 30 minutes to obtain a catalyst slurry. 40 microliters of the slurry was uniformly dropped onto the surface of the polished electrode, the area of the electrode was 0.19625 square centimeters. The electrochemical workstation used was Chenghua electrochemical workstation, and the rotating disk test system used was the equipment produced by Pine corporation, USA. Continuously introducing nitrogen into 0.5 mol/L sulfuric acid aqueous solution, making cyclic voltammetry curves under the condition of nitrogen saturation until two adjacent curves are overlapped, and then switching to 0.5 mol/L sulfuric acid aqueous solution saturated by oxygen to test the oxygen reduction performance, wherein the electrode rotation speed is 1600 rpm, and the scanning speed is 10 millivolts/second. FIG. 11 is an oxygen reduction curve under acidic conditions for the catalyst prepared in example 2. As can be seen from fig. 11, the nitrogen-doped carbon-supported diiron cluster prepared in example 2 of the present invention has excellent electrocatalytic oxygen reduction activity, with a half-wave potential of 0.78 v and an initial potential of 0.95 v. As can be seen from fig. 12, the nitrogen-doped carbon-supported diiron cluster prepared in example 2 of the present invention also has excellent oxygen reduction stability, and the half-wave potential is reduced by only 20 mv after 20000 cycles.
The synthesis method for systematically regulating and controlling the number of atoms of the load type iron atom cluster provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. 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.
Claims (8)
1. A preparation method of a supported diiron atom cluster catalyst is characterized by comprising the following steps:
mixing an iron source compound, a zinc source compound and an organic small molecule connecting agent in a solvent, and obtaining a metal organic framework coated iron precursor nano material at a preset reaction temperature and a preset reaction time, wherein the preset reaction temperature is 10-120 ℃, and the preset reaction time is 10-120 minutes;
calcining the nano material in inert gas at high temperature to obtain a supported type di-iron atom cluster catalyst containing a specific iron atom number, wherein oxygen molecules on the surface of the di-iron atom cluster are adsorbed by a peroxy state;
wherein the iron source compound is nonacarbonyl diiron; the zinc source compound is a divalent zinc-containing compound.
2. The method of claim 1, wherein the solvent comprises: tetrahydrofuran, nitrogen, N-dimethylformamide and methanol.
3. The method according to claim 1, wherein the high-temperature calcination is performed at a temperature of 500 to 1000 ℃ for 60 to 240 minutes.
4. The method according to claim 1, wherein the molar ratio of the iron source compound to the zinc source compound is: 1: 50 to 150.
5. The production method according to claim 1, wherein the mass ratio of the zinc source compound to the solvent is: 1: 20 to 60.
6. The method according to claim 2, wherein when methanol, nitrogen dimethylformamide or tetrahydrofuran is included in the solvent, the volume ratio of methanol, nitrogen dimethylformamide or tetrahydrofuran is 1: (0.3-0.9): (0.4-0.8).
7. The method of claim 1, wherein the nanomaterial has a specific surface area of 1080 square meters per gram.
8. The method according to claim 7, wherein the nanoparticles of the nanomaterial have a size of 150 to 300 nm.
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