CN109499602A - A kind of synthetic method of systematization regulation loading type iron elementide atom number - Google Patents
A kind of synthetic method of systematization regulation loading type iron elementide atom number Download PDFInfo
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- CN109499602A CN109499602A CN201910031428.5A CN201910031428A CN109499602A CN 109499602 A CN109499602 A CN 109499602A CN 201910031428 A CN201910031428 A CN 201910031428A CN 109499602 A CN109499602 A CN 109499602A
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- Prior art keywords
- iron
- nitrogen
- source compound
- nano material
- elementide
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 89
- 238000011068 loading method Methods 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 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
- 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 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000005253 cladding Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- -1 nitrogen dimethyl methyl Amide Chemical compound 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 32
- 125000004429 atom Chemical group 0.000 description 26
- 229910002549 Fe–Cu Inorganic materials 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000004075 alteration Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012937 correction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000002604 ultrasonography Methods 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 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
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 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
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
- B01J27/24—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
This application discloses a kind of synthetic methods of systematization regulation loading type iron elementide atom number, it include: to obtain in default reaction temperature and under the default reaction time metal organic frame cladding iron presoma nano material after mixing Fe source compound, zinc source compound and small organic molecule bridging agent in a solvent；Nano material is calcined to obtain the loading type iron elementide catalyst containing specific iron atom number in inert gas high temperature.Energy systematization of the present invention prepares single iron atom, two iron and three-iron metallic atom cluster, and method and process is simple, and reaction condition is mild, and yield is high, and purity is high is suitable for being mass produced.
Description
Technical field
This application involves technical field of function materials more particularly to a kind of systematization to regulate and control loading type iron elementide atom
The synthetic method of number.
Background technique
In common chemical reaction, in order to significantly improve the rate of chemical reaction usually require that catalyst, catalysis is added
The effect of agent can be usually summarized as follows: one, change the dynamics of chemical reaction, improves reaction rate；Two, change the road of reaction
Diameter improves the selectivity of specific product；Three, the energy barrier of reaction is reduced, reaction temperature is reduced.In general, in catalysis reaction,
Significant change does not occur for the structure and quality of catalyst itself.Modern chemical industry industry largely uses catalyst, and as fuel electricity
Pond, vehicle maintenance service etc. also largely rely on the catalyst of high-activity high-selectivity.Therefore, catalyst is to push modernization industrial and commercial bank
The auxiliary agent of industry, the research of catalyst are extremely important for modern chemical industry industry.
Relative to the noble metal catalyst of traditional high activity, transition-metal catalyst due to the rich reserves in the earth's crust,
Price is relatively cheap, and catalytic activity is moderate widely to be paid close attention to.In order to sufficiently improve the catalytic activity of transition-metal catalyst,
The strategy generallyd use is the active site of more exposing metal atom.Wherein, by the size reduction of transition metal to atom
Rank is able to achieve maximization exposure catalytic site.However, the catalytic activity of transition-metal catalyst is not for loaded catalyst
It is only related with the number of metallic atom active site, also with matching around the valence state and metallic atom of catalytic center metallic atom
Position environment has very big association.The electron density of central metal atom valence state and metallic atom d track has a close association, and d rail
Hydridization between electronics on road and catalysis substrate molecule significantly affects absorption and desorption of the substrate molecule in catalyst surface
Ability, thus significantly affect the catalytic activity of catalyst.Equally, the coordination atom around metallic atom also changed dramatically gold
Valence state and the substrate molecule absorption for belonging to atom, activate thermodynamics.
It is a kind of very important catalyst, knot that the transition metal atoms of atom level dispersion, which are anchored on nitrogen-doped carbon surface,
Structure feature highly significant: it firstly, the transition metal atoms of atom level dispersion can maximize exposed active site, significantly improves
Catalytic activity；Furthermore metallic atom is coordinated by forming metal-nitrogen, is very stably anchored on substrate surface, and the kind of nitrogen
The electronic structure of the adjustable transition metal atoms of the difference of class and content；Finally, the carbon substrate of nitrogen atom doping has very
Good conductive capability.These excellent design features react this kind of catalyst in fuel battery negative pole, the cracking reaction of water,
Organic molecule oxidation reaction, chemical nitrogen fixation reaction etc. show excellent performance.Wherein, nitrogen-doped carbon load iron is monatomic
Catalyst shows optimal performance in alkaline fuel cell cathode oxygen reduction reaction.Stage now, energy crisis and environment
Pollution is so that clean energy resource gets more and more people's extensive concerning, and fuel cell technology is considered as the representative of next-generation new energy,
Currently, existing company's design and volume production a new generation hydrogen fuel cell.The key of fuel cell be Cathodic oxygen reduction height according to
Rely precious metals platinum catalyst, therefore develop high activity, high stability non-platinum catalyst is used for fuel battery negative pole oxygen reduction reaction
It is the key that the bottleneck that breakthrough.
Therefore, the oxygen reduction activity and stability of atom level dispersion iron atom catalyst how be can be further improved, entirely
Face substitutes application of the platinum based catalyst in fuel cell car, it has also become forward position scholar urgent problem to be solved in the industry.Currently
Result of study show that loading type iron elementide catalyst is able to achieve the adsorptive behavior of oxygen molecule and was adsorbed by super oxygen state
The transformation of oxygen state adsorptive behavior is adsorbed, the better activating oxygen molecule of peroxide state adsorption energy of oxygen relative to super oxygen state, is improved
The activity of catalytic oxygen reduction.However, how to realize that the loading type iron cluster catalyst with specific iron atom number is a public affairs
The problem recognized.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing easy systematization regulates and controls loading type iron atomic group
The loading type iron elementide of the synthetic method of cluster atom number, synthetic method preparation provided by the invention is anchored on nitrogen-doped carbon
Surface realizes iron atom cluster from single iron atom, prepared by the systematization to two iron and three-iron elementide.Particularly
It is, it is prepared by the present invention that there is very big specific surface area containing two iron atom cluster catalyst, it is anti-in electro-catalysis acidity hydrogen reduction
Very high activity and stability are shown in answering, activity has approached business platinum/C catalyst.In addition, provided by the invention
Synthetic method has the characteristics that reaction condition is mild, yield is high and purity is good, is suitable for the large-scale production of catalyst.
The present invention provides a kind of synthetic methods of systematization regulation loading type iron elementide atom number, comprising:
After Fe source compound, zinc source compound and small organic molecule bridging agent are mixed in a solvent, in default reaction temperature
Metal organic frame cladding iron presoma nano material is obtained under degree and default reaction time；
The nano material is calcined to obtain the original of the loading type iron containing specific iron atom number in inert gas high temperature
Sub- cluster catalyst.
Preferably, the Fe source compound is ferric trichloride, ferric acetyl acetonade, carbonyl iron, nine carbonyls conjunction two iron, 12 carbonyls
Base closes one of three-iron；
The zinc source compound is the compound containing divalent zinc.
Preferably, the solvent includes: that tetrahydrofuran, nitrogen, nitrogen dimethylformamide, methanol are one such or several.
Preferably, the default reaction temperature are as follows: 10~120 degrees Celsius；The default reaction time are as follows: 10~120 points
Clock.
Preferably, the temperature of high-temperature calcination is 500~1000 degrees Celsius, and the time of high-temperature calcination is 60~240 minutes.
Preferably, the molar ratio of the Fe source compound and zinc source compound are as follows: 1:50~150.
Preferably, the mass ratio of the zinc source compound and the solvent are as follows: 1:20~60.
Preferably, when including methanol in the solvent, nitrogen, when nitrogen dimethylformamide or tetrahydrofuran, methanol, nitrogen, nitrogen
The volume ratio of dimethylformamide or tetrahydrofuran is 1:(0.3~0.9): (0.4~0.8).
Preferably, the nano material has adjustable iron atom number and very high specific surface area.
Preferably, the size of the nano particle of the nano material is 150~300nm.
In conclusion the present invention provides a kind of synthesis sides of systematization regulation loading type iron elementide atom number
Method, comprising: after mixing Fe source compound, zinc source compound and small organic molecule bridging agent in a solvent, in default reaction temperature
Metal organic frame cladding iron presoma nano material is obtained under degree and default reaction time；By nano material in inert gas
High-temperature calcination obtains the loading type iron elementide catalyst containing specific iron atom number.Compared with prior art, of the invention
The synthetic method of offer be able to achieve systematization regulation iron atom cluster atom number, realize iron atom cluster from single iron atom to
Two iron and Effective Regulation to three Fe-Cu deposits.Synthetic method provided by the invention can be realized a variety of loading type iron elementides
Synthesis, have the characteristics that simple process, mild condition, yield are high and purity is good, be suitable for being mass produced.
The nitrogen-doped carbon load Fe-Cu deposits catalyst that the present invention obtains has very high specific surface area, high specific surface area energy
Maximize the active site of exposure transition metal atoms.The requirement of catalysis aspect, such as electro-catalysis oxygen reduction can be met extensively
Reaction, organic molecule oxidation reaction, electro-catalysis water-splitting reaction etc. are suitable for further applying in research and industrial production；Together
When, there is different number of iron atom can significantly change substrate molecule in the adsorptive behavior of catalytic center.For example, oxygen molecule
It is to be adsorbed by super oxygen state in Single Iron atomic surface, and in two Fe-Cu deposits surface oxygen molecules is adsorbed by peroxide state.Its
In, peroxide state is adsorbed due to oxygen molecule and two iron atom bondings, so that the activation degree of oxygen molecule is higher, thus very
Suitable for catalytic oxygen molecule reduction reaction.The experimental results showed that two Fe-Cu deposits nanocatalyst of support type prepared by the present invention,
Free from admixture with high purity, partial size are about 150~300nm, have very excellent electro-catalysis oxygen reduction activities and stability.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of application for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the stream for the synthetic method that a kind of systematization disclosed by the invention regulates and controls loading type iron elementide atom number
Cheng Tu；
Fig. 2 is the nano material containing Single Iron elementide of nitrogen-doped carbon load prepared by the embodiment of the present invention 1
Transmission electron microscope photo, scale 200nm；
Fig. 3 is that nitrogen-doped carbon prepared by the embodiment of the present invention 1 loads the spherical aberration correction scanning containing Single Iron elementide
Transmission electron microscope photo, scale 2nm；
Fig. 4 is that nitrogen-doped carbon prepared by the embodiment of the present invention 1 loads the nitrogen adsorption desorption containing Single Iron elementide
Curve；
Fig. 5 is the transmission electron microscope photo that nitrogen-doped carbon prepared by the embodiment of the present invention 2 loads two iron atom clusters, and scale is
200nm；
Fig. 6 is the spherical aberration correction scanning transmission electricity that nitrogen-doped carbon prepared by the embodiment of the present invention 2 loads two iron atom clusters
Mirror photo, scale 2nm；
Fig. 7 is that the nitrogen adsorption of nitrogen-doped carbon two iron atom cluster nano materials of load prepared by the embodiment of the present invention 2 is de-
Attached curve；
Fig. 8 is the transmission electron microscope photograph that nitrogen-doped carbon prepared by the embodiment of the present invention 3 loads three-iron elementide nano material
Piece, scale 200nm；
Fig. 9 is that the spherical aberration correction of nitrogen-doped carbon load three-iron elementide nano material prepared by the embodiment of the present invention 3 is swept
Retouch transmission electron microscope photo, scale 2nm；
Figure 10 is the nitrogen adsorption desorption that nitrogen-doped carbon prepared by the embodiment of the present invention 3 loads three-iron elementide nano material
Curve；
Figure 11 is the oxygen reduction curve graph that nano material prepared by the embodiment of the present invention 2 is catalyzed under acid condition；
Figure 12 is the oxygen reduction stability curve that nano material prepared by the embodiment of the present invention 2 is catalyzed under acid condition
Figure.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present application, technical solutions in the embodiments of the present application carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of embodiments of the present application, instead of all the embodiments.It is based on
Embodiment in the application, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall in the protection scope of this application.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, pure present invention preferably employs analyzing.
Device therefor of the present invention, is not particularly limited, and can be flask commonly used in the art, beaker or reaction kettle etc.,
And other can satisfy the device of technical solution of the present invention.
As shown in Figure 1, for a kind of synthesis of systematization regulation loading type iron elementide atom number disclosed by the invention
Method, comprising the following steps:
S101, it after mixing Fe source compound, zinc source compound and small organic molecule bridging agent in a solvent, is presetting instead
It answers temperature and obtains metal organic frame cladding iron presoma nano material under the default reaction time；
S102, nano material is calcined to obtain the original of the loading type iron containing specific iron atom number in inert gas high temperature
Sub- cluster catalyst.
Fe source compound of the present invention is preferably ferric trichloride, ferric acetyl acetonade, carbonyl iron, nine carbonyls conjunction two iron and ten
Dicarbapentaborane closes one of three-iron.The zinc source compound is preferably the compound containing divalent zinc.The present invention contains to described
The compound of divalent zinc is not particularly limited, with the compound well known to those skilled in the art containing divalent zinc, this hair
It is bright to preferably include the one or more of zinc nitrate, zinc sulfate, zinc chloride, zinc bromide and zinc acetate, most preferably zinc nitrate.
The molar ratio of Fe source compound and zinc source compound of the present invention is preferably 1:(50~150), more preferably 1:
(100~140), more preferably 1:(120~140), most preferably 1:140；The zinc source compound and small organic molecule connection
The molar ratio of agent is preferably 1:(2~12), more preferably 1:(2~8), more preferably 1:(2~4) and, most preferably 1:4；It is described
The mass ratio of zinc source and solvent is preferably 1:(20~60), more preferably 1:(20~50), more preferably 1:(20~40) and, optimal
It is selected as 1:30；Solvent used in the present invention be methanol, nitrogen, one of nitrogen dimethylformamide, tetrahydrofuran or a variety of,
In, when including methanol in the solvent, nitrogen, when nitrogen dimethylformamide or tetrahydrofuran, methanol, nitrogen, nitrogen dimethylformamide
Or tetrahydrofuran volume ratio is preferably 1:(0.3~0.9): (0.4~0.8), more preferably 1:(0.4~0.8): (0.4~
0.7), more preferably 1:(0.6~0.8): (0.4~0.6), most preferably 1:0.75:0.5.The present invention is to the source of iron chemical combination
The ratio of object and zinc source compound is not particularly limited, those skilled in the art can according to the actual situation, product requirement and
Particular use is voluntarily adjusted, and the present invention preferentially selects different source of iron presomas to be coated in the duct of metal organic frame
The Effective Regulation of iron atom cluster atom number may be implemented by high-temperature calcination for face.Iron accounts in finally formed nano material
Total mass fraction is preferably 1 ‰~8%, and the iron content of higher quality score can make the iron atom clusters to be formed formation receive
Scale particles.
Default reaction temperature of the present invention is preferably 10~120 degrees Celsius, more preferably 20~100 degrees Celsius, more excellent
It is selected as 30~60 degrees Celsius, most preferably 30~50 degrees Celsius.The default reaction time of the present invention is preferably 10~120 points
Clock, more preferably 10~100 minutes, more preferably 50~70 minutes.The temperature of high-temperature calcination of the present invention is preferably 500~
1000 degrees Celsius, more preferably 700~900 degrees Celsius, more preferably 800~900 degrees Celsius.Calcination time of the present invention
Preferably 60~240 minutes, more preferably 120~180 minutes.The inert gas of calcining of the present invention is preferably high-purity
Argon gas or high pure nitrogen.
Above-mentioned preparation method provided by the invention, the method for increasing temperature calcining using low-temperature atmosphere-pressure liquid phase synthesis are industry
On be widely used the universal method for preparing catalyst, scale volume production can be realized simply by amplification feed ratio.The work
Process has the advantages that simple process, yield are high and are easy to amplify batch production.
It is provided by the invention that there is microcellular structure abundant by loading type iron elementide obtained by the above method, it is very high
Specific surface area, can maximumlly expose catalytic site, be conducive to substrate molecule adsorption/desorption and quick mass transport process.Gold
Belong to iron as activated centre, nitrogen-doped carbon surface, and iron atom number in iron atom cluster are distributed to atom level cluster state
Accuracy controlling may be implemented, from single iron atom to the transformation of two iron and three-iron, this lives for research iron atom number and catalysis
Structure-activity relationship between property provides good model.The loading type iron elementide catalyst that the present invention obtains is due to rich
Rich microcellular structure, the iron atom number of very high specific surface area and accuracy controlling can meet the requirement of catalysis aspect extensively,
Catalytic activity with higher, such as the electrochemical reducting reaction of oxygen molecule, the oxidation reaction of small organic molecule, electro-chemical water
Cracking reaction etc. is suitable for further applying in research and industrial production, is especially used for fuel battery cathod catalyst.Experiment
The result shows that the support type that the present invention is prepared contains two iron atom cluster catalyst, the purity is high of Fe-Cu deposits, in acid electricity
Higher activity and stability are shown in chemical oxygen reduction reaction.
In order to further illustrate the present invention, below with reference to embodiment to loading type iron elementide nanometer provided by the invention
Material and its synthetic method are described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Nitrogen-doped carbon loads Single Iron catalyst atom
By 16 milligrams of ferric acetyl acetonades, 1190 milligrams of zinc nitrate hexahydrate ultrasonic dissolutions to 10 milliliters of tetrahydrofurans and 20 millis
It rises in methanol mixed solution.1314 milligrams of methylimidazole is dissolved in another mixed solution simultaneously, which includes 6
Milliliter nitrogen, nitrogen dimethylformamide and 4 ml methanols, ultrasound obtains white in 10 minutes after two mixed solutions are mixed at room temperature
Precipitating, drying.White precipitate to be calcined 3 hours in high temperature process furnances, 5 degree of heating rate are per minute, and 800 degree of calcination temperature,
High-purity argon gas does carrier gas and obtains final product.
The sample for loading single iron atom to the nitrogen-doped carbon of above method preparation detects, and testing result shows ginseng
See that Fig. 2, Fig. 2 are the transmission electron microscope photo that nitrogen-doped carbon prepared by the embodiment of the present invention 1 loads single iron atom nano material, mark
Ruler is 200nm.Referring to Fig. 3, Fig. 3 is the ball that nitrogen-doped carbon prepared by the embodiment of the present invention 1 loads single iron atom nano material
Difference correction annular dark field scanning transmission electron microscope photo, scale 2nm.It can be seen that from spherical aberration electromicroscopic photograph with black dotted lines circle
The single iron atom marked.Referring to fig. 4, Fig. 4 is that nitrogen-doped carbon prepared by the embodiment of the present invention 1 loads single iron atom nanometer material
The nitrogen adsorption desorption curve of material, from adsorption/desorption curve it is found that the specific surface area of obtained nano material is 1028 square metres
Every gram.So big specific surface area illustrates that the material of preparation can more expose the active site of iron atom.
Embodiment 2
Nitrogen-doped carbon loads two Fe-Cu deposits
11 milligram of nine carbonyl is closed into two iron, 1190 milligrams of zinc nitrate hexahydrate ultrasonic dissolutions to 10 milliliters of tetrahydrofurans and 20
In ml methanol mixed solution, while 1314 milligrams of methylimidazole being dissolved in another mixed solution, the mixed solution packet
6 milliliters of nitrogen, nitrogen dimethylformamide and 4 ml methanols are included, ultrasound obtains for 10 minutes after two mixed solutions are mixed at room temperature
White precipitate, drying.White precipitate is calcined 3 hours in high temperature process furnances, 5 degree of heating rate per minute, calcination temperatures 800
Degree, high-purity argon do carrier gas and obtain final product.
To the above method preparation nitrogen-doped carbon load two Fe-Cu deposits sample detect, testing result show referring to
Fig. 5, Fig. 5 are the transmission electron microscope photo that nitrogen-doped carbon prepared by the embodiment of the present invention 2 loads two Fe-Cu deposits nano materials, and scale is
200nm.It is that nitrogen-doped carbon prepared by the embodiment of the present invention 2 loads the spherical aberration correction of two Fe-Cu deposits nano materials referring to Fig. 6, Fig. 6
Annular dark field scanning transmission electron microscope photo, scale 2nm.It can be seen that from spherical aberration electromicroscopic photograph and to be marked with black dotted lines circle
Two Fe-Cu deposits.It is that nitrogen-doped carbon prepared by the embodiment of the present invention 2 loads the nitrogen suction of two Fe-Cu deposits nano materials referring to Fig. 7, Fig. 7
Attached desorption curve, from adsorption/desorption curve it is found that the specific surface area of obtained nano material is 1080 square metres every gram.Equally,
So big specific surface area illustrates that the material of preparation can more expose the active site of two Fe-Cu deposits.
Embodiment 3
Nitrogen-doped carbon loads three Fe-Cu deposits
By 8 milligram of ten dicarbapentaborane close three-iron, 1190 milligrams of zinc nitrate hexahydrate ultrasonic dissolutions to 10 milliliters of tetrahydrofurans and
In 20 ml methanol mixed solutions, while 1314 milligrams of methylimidazole being dissolved in another mixed solution, the mixed solution
Including 6 milliliters of nitrogen, nitrogen dimethylformamide and 4 ml methanols obtain for ultrasound 10 minutes after mixing two mixed solutions at room temperature
To white precipitate, drying.White precipitate is calcined 3 hours in high temperature process furnances, 5 degree of heating rate per minute, calcination temperatures
800 degree, high-purity argon does carrier gas and obtains final product.
To the above method preparation nitrogen-doped carbon load three Fe-Cu deposits sample detect, testing result show referring to
Fig. 8, Fig. 8 are the transmission electron microscope photo that nitrogen-doped carbon prepared by the embodiment of the present invention 3 loads three Fe-Cu deposits nano materials, and scale is
200nm.It is that nitrogen-doped carbon prepared by the embodiment of the present invention 3 loads the spherical aberration correction of three Fe-Cu deposits nano materials referring to Fig. 9, Fig. 9
Annular dark field scanning transmission electron microscope photo, scale 2nm.It can be seen that from spherical aberration electromicroscopic photograph and to be marked with black dotted lines circle
Three Fe-Cu deposits.It is that nitrogen-doped carbon prepared by the embodiment of the present invention 3 loads the nitrogen of three Fe-Cu deposits nano materials referring to Fig. 9, Figure 10
Adsorption/desorption curve, from adsorption/desorption curve it is found that the specific surface of obtained nano material is 1024 square metres every gram.Equally,
So big specific surface area illustrates that the material of preparation can more expose the active site of three Fe-Cu deposits.
Embodiment 4
Electro-catalysis Cathodic oxygen reduction under acid condition
Nano material prepared by 2 milligrams of embodiments 2 is dispersed in 0.7 milliliter of distilled water, 0.25 milliliter of isopropanol and 0.05
Ultrasound obtains catalyst pulp in 30 minutes in milliliter naphthols mixed solution.40 microlitres of slurries are taken uniformly to drip to the electrode table polished
Face, the area of electrode are 0.19625 square centimeter.Electrochemical workstation used is occasion China electrochemical workstation, rotating circular disk
The equipment that test macro is produced using Pine company, the U.S..0.5 mole every liter of aqueous sulfuric acid is taken to be continually fed into nitrogen,
Cyclic voltammetry curve is done under conditions of nitrogen saturation until two adjacent curve co-insides, then changes to the 0.5 of oxygen saturation
Mole every liter of aqueous sulfuric acid tests its oxygen reduction performance, and 1600 rpms of electrode rotary speed, 10 milli of scanning speed
It lies prostrate per second.Figure 11 is the hydrogen reduction curve of catalyst in acid condition prepared by embodiment 2.As shown in Figure 11, of the invention
Two Fe-Cu deposits of nitrogen-doped carbon load prepared by embodiment 2 have excellent electrocatalytic oxidation reduction activation, and half wave potential exists
0.78 volt, take-off potential is at 0.95 volt.As shown in Figure 12, two Fe-Cu deposits of the nitrogen-doped carbon load that prepared by the embodiment of the present invention 2
Also there is excellent hydrogen reduction stability, half wave potential is reduced only by 20 millivolts after 20000 circle circulations.
The synthetic method of systematization provided by the present invention regulation loading type iron elementide atom number is carried out above
It is discussed in detail.Used herein specifically principle and implementation of the present invention are described for a example, the above implementation
The explanation of example is merely used to help understand method and its core concept of the invention.It should be pointed out that for the general of the art
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for logical technical staff, this
A little improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. a kind of synthetic method of systematization regulation loading type iron elementide atom number characterized by comprising
After Fe source compound, zinc source compound and small organic molecule bridging agent are mixed in a solvent, in default reaction temperature and
Metal organic frame cladding iron presoma nano material is obtained under the default reaction time；
The nano material is calcined to obtain the loading type iron atomic group containing specific iron atom number in inert gas high temperature
Cluster catalyst.
2. according to the method described in claim 1, wherein, the Fe source compound is ferric trichloride, ferric acetyl acetonade, carbonyl
Iron, nine carbonyls close two iron, ten dicarbapentaborane close one of three-iron；
The zinc source compound is the compound containing divalent zinc.
3. the method according to claim 1, wherein the solvent includes: tetrahydrofuran, nitrogen, nitrogen dimethyl methyl
Amide, methanol are one such or several.
4. the method according to claim 1, wherein the default reaction temperature are as follows: 10~120 degrees Celsius；Institute
State the default reaction time are as follows: 10~120 minutes.
5. the method according to claim 1, wherein the temperature of high-temperature calcination be 500~1000 degrees Celsius, high temperature
The time of calcining is 60~240 minutes.
6. the method according to claim 1, wherein the molar ratio of the Fe source compound and zinc source compound
Are as follows: 1:50~150.
7. the method according to claim 1, wherein the mass ratio of the zinc source compound and the solvent are as follows:
1:20~60.
8. according to the method described in claim 3, it is characterized in that, when including methanol, nitrogen, nitrogen dimethyl formyl in the solvent
When amine or tetrahydrofuran, methanol, nitrogen, the volume ratio of nitrogen dimethylformamide or tetrahydrofuran is 1:(0.3~0.9): (0.4~
0.8)。
9. the method according to claim 1, wherein the nano material have adjustable iron atom number and
Very high specific surface area.
10. according to the method described in claim 9, it is characterized in that, the size of the nano particle of the nano material be 150~
300nm。
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