CN109967113A - A kind of preparation method of the monatomic catalyst of metal - Google Patents
A kind of preparation method of the monatomic catalyst of metal Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 239000002184 metal Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 22
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000012805 post-processing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000013384 organic framework Substances 0.000 claims description 12
- 239000010953 base metal Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000004075 alteration Effects 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 5
- 230000005469 synchrotron radiation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- -1 that is Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003738 black carbon Substances 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical class N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 229910003298 Ni-Ni Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019253 formic acid 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- B01J35/33—Electric or magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of the monatomic catalyst of metal.This method selection has the metal-organic framework material of bipyridyl group, and metal salt presoma is coordinated on bipyridyl group, then carrying out carbonization under an inert atmosphere and acid etch obtains the monatomic catalyst of metal by post-processing method of modifying.This method is simple and easy, has universality, can be to avoid generation miscellaneous phase, and can have a good application prospect to avoid the aggregation of metallic atom.
Description
Technical field
The invention belongs to chemical catalysis technical fields, and in particular to a kind of preparation method of the monatomic catalyst of metal.
Background technique
The monatomic catalyst of metal shows extremely excellent catalysis because of its metal active centres with atom level dispersion
Active and maximum atom service efficiency.Metal is proposed from Dalian Inst of Chemicophysics, Chinese Academy of Sciences great waves academician in 2011
Since the concept of monatomic catalysis, by the development of a few years, the monatomic catalyst of metal has rapidly become catalysis neck
The study frontier and hot spot in domain.The strategy for preparing the monatomic catalyst of metal at present mainly has liquid impregnation, atomic layer deposition, gold
Belong to hydroxide/polymer core-shell structure strategy and optical electro-chemistry strategy.However these methods are only applicable to certain metal list original
The preparation of son, is not extended to the method for universality.So far the preparation of the monatomic catalyst of metal is still a major challenge, this master
If because monoatomic high surface energy causes it to be easy to be gathered into nano particle.In order to further promote the monatomic catalysis of metal
The extensive use of agent needs to develop advanced technology of preparing, especially with the technology of preparing of universality.
Metal-organic framework materials (Metal-Organic Frameworks, abbreviation MOFs) are that by metal ion and have
A kind of hybrid inorganic-organic porous material with net-like frame structure that machine ligand is formed by coordination, it is main special
Point is high-ratio surface, Kong Rong and adjustable aperture.The Nomenclature Composition and Structure of Complexes characteristic based on MOFs material, researcher propose with
MOFs material is that template prepares metal carbides and metal nitride.Recently, researchers report from MOFs material system
Standby the monatomic catalyst of metal (Angew.Chem.Int.Ed.2017,56,6937-6941), main method is in MOFs material
The metal salt presoma of the monatomic catalyst of metal is prepared needed for being added in preparation stoste.It is well known, however, that MOFs crystal
Growth course is extremely complex, is difficult artificially to be controlled.Therefore, the main of the preparation method of the monatomic catalyst of this metal lacks
Point is that the metal salt presoma being added is possible to react the unknown miscellaneous phase of generation with the organic ligand in MOFs preparation stoste.
Summary of the invention
Status in view of the above technology, the present invention provide a kind of preparation method of monatomic catalyst of metal, technology path
Simply, there is universality, and the elctro-catalysts such as redox reactions can be can be used as to avoid miscellaneous phase is generated.
Technical solution provided by the present invention are as follows: a kind of preparation method of the monatomic catalyst of metal, selection have connection pyrrole
Metal salt presoma is coordinated by post-processing method of modifying and arrives bipyridyl group by the metal-organic framework material of piperidinyl group
On, carbonization and acid etch are then carried out under an inert atmosphere, obtain the monatomic catalyst of metal.
The metal-organic framework material with bipyridyl group is unlimited, it is however preferred to have the Zr base of bipyridyl group
Metal-organic framework material.The preparation method of the Zr Base Metal organic framework materials with bipyridyl group is unlimited, makees
For a kind of implementation, by zirconium chloride and 2,2 '-bipyridyl -5,5 '-dicarboxylic acids react in N, N '-solvent dimethylformamide
It is made, reaction temperature is preferably at 90~150 DEG C.
The metal salt presoma is unlimited, including metal chloride and its hydrate, nitrate and its hydrate, sulfuric acid
Salt and its hydrate.
The post-processing method of modifying is by metal salt presoma, with the metal organic frame material of bipyridyl group
Material and solvent mixing, are centrifuged after being stirred to react, clean, is dry.Preferably, the mole of the metal salt presoma
With the ratio between the mole of bipyridyl in metal-organic framework material between 0~1.Preferably, the post-processing modification side
The solvent used in method is one of tetrahydrofuran, acetonitrile or two kind.
Preferably, the particle size of the monatomic catalyst of prepared metal is between 20nm-200nm.
Preferably, temperature is 600 DEG C -1000 DEG C, further preferably 700 DEG C during carbonization；
Preferably, carbonization time is 1 hour~5 hours, further preferably 3 hours.
Preferably, heating rate is 1~10 DEG C/min, preferably 2 DEG C/min during carbonization.
Preferably, the inert atmosphere is one of argon gas, nitrogen or two kinds.
Preferably, the acid etch is that the acid that uses includes hydrofluoric acid, hydrochloric acid, in sulfuric acid in hydroflouric acid etching
It is one or several kinds of.
It is experimentally confirmed that the preparation method of the monatomic catalyst of metal provided by the invention have the advantages that following features and:
(1) the porous metals organic framework materials loading metal-salt presoma containing bipyridyl group is used.Porous metals
Organic framework materials have the characteristics such as high-ratio surface and high porosity, are conducive to the uniform diffusion of metal salt presoma；
(2) with it has been reported that in the preparation stoste of metal-organic framework material be added metal salt presoma method phase
Than the present invention uses the metal-organic framework material containing bipyridyl group, is matched metal salt presoma by post-processing modification
Position is acted on by the unoccupied orbital of the lone pair electrons of N atom in bipyridyl and metal ion by metal salt into bipyridyl group
Presoma is anchored on the organic ligand of metal-organic framework material.The coordination is extremely important for preparing monatomic catalyst,
Locality specific of the one side metal salt presoma in metal-organic framework material, i.e., the bipyridyl group on organic ligand
On, so as to avoid the generation of miscellaneous phase, on the other hand due to metallic atom during high temperature cabonization because violent warm-up movement is held
It is mutually easily gathered into nano particle, so that the monatomic catalyst of metal cannot be formed, and metal ion and bipyridyl in the present invention
The strong coordination of group prevents the aggregation of high temperature cabonization process metallic atom.
(3) at present it has been reported that the preparation method of the monatomic catalyst of metal to be often only applicable to a certain metal list former
The preparation of muonic catalysis agent, preparation method provided by the invention have universality, can prepare the monatomic catalyst of any metal, example
The monatomic catalyst of such as Fe, the monatomic catalyst of Co, the monatomic catalyst of Ni and the monatomic catalyst of Cu.
(4) on the monatomic C-material for being dispersed in N doping of the metal prepared using method of the invention, metal list is former
Son forms chemical bond/coordinate bond with N, can be applied in electro-catalysis redox reactions, shows excellent catalytic activity and most
Big atom service efficiency.
Detailed description of the invention
System in Zr Base Metal organic framework materials obtained and step (2) in the step of Fig. 1 is the embodiment of the present invention 1 (1)
The comparison of the PXRD of the PXRD and fitting of the Zr Base Metal organic framework materials of the load iron chloride obtained.
Fig. 2 is the spherical aberration electron microscopic picture of the monatomic catalyst of Fe made from the embodiment of the present invention 1.
Fig. 3 is the synchrotron radiation EXAFS of the monatomic catalyst of Fe made from the embodiment of the present invention 1, wherein Fe foil and FeOOH
As referring to comparison.
Fig. 4 is the electrochemical oxygen reducing property of the monatomic catalyst of Fe obtained in the embodiment of the present invention 1.
Fig. 5 is the spherical aberration electron microscopic picture of the monatomic catalyst of Co obtained in the embodiment of the present invention 2.
Fig. 6 is the spherical aberration electron microscopic picture of the monatomic catalyst of Ni obtained in the embodiment of the present invention 2.
Fig. 7 is the spherical aberration electron microscopic picture of the monatomic catalyst of Cu obtained in the embodiment of the present invention 2.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail with attached drawing, it should be pointed out that reality as described below
It applies example to be intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
The monatomic catalyst of Fe the preparation method is as follows:
(1) the Zr Base Metal organic framework materials containing bipyridyl group are prepared
By 0.246g ZrCl4, 2,2 '-bipyridyl -5 0.260g, 5 '-dicarboxylic acids and 7mL formic acid is added to 100mL N,
In N '-solvent dimethylformamide, it is transferred in the stainless steel cauldron containing polytetrafluoroethylliner liner after completely dissolution,
120 DEG C of reactions are for 24 hours.By the product after reaction by being centrifuged and with, in 80 DEG C of drying 2h, and then being transferred to after acetone washing 2-3 time
160 DEG C of vacuum drying 12h, obtained white product are Zr Base Metal organic framework materials in vacuum oven, and structure is
Metal-organic framework material with UiO type, as shown in Figure 1, its PXRD is consistent with the PXRD of fitting.
(2) preparation load iron chloride Zr Base Metal organic framework materials
By 0.02g Iron(III) chloride hexahydrate, Zr Base Metal organic framework materials made from 0.2g step (1) are added to 40mL
It in tetrahydrofuran, is centrifuged, and is dried after washing 2 times with tetrahydrofuran at 80 DEG C, obtained Huang after reaction 12h is stirred at room temperature
Color powder is the Zr Base Metal organic framework materials for loading ferric trichloride.As shown in Figure 1, there is Zr Base Metal after load iron chloride
There is no variations for the crystal structure of machine frame frame material.
(3) the monatomic catalyst of Fe is prepared
The Zr Base Metal organic framework materials 0.1g for weighing step (1) load iron chloride obtained is placed into tube furnace,
700 DEG C of progress high temperature cabonization 3h are warming up in argon atmosphere, heating rate is 5 DEG C/min.Then it is naturally cooling to room temperature, is taken
Black carbon compound is obtained out.
Black carbon compound is added in the hydrofluoric acid of 15mL 2.5mol/L and is stirred etching 3h to remove ZrO2?
Grain, place the product in vacuum oven after being then centrifuged for and being washed with water 2 times, the monatomic catalysis of Fe is dried to obtain at 100 DEG C
Agent.
The spherical aberration electron microscopic picture of the monatomic catalyst of Fe obtained above is as shown in Figure 2, it can be seen that Fe is monatomic uniformly
It is scattered in C substrate.The synchrotron radiation EXAFS of the monatomic catalyst of Fe obtained above is as shown in figure 3, wherein Fe foil and hydrogen-oxygen
Change iron to be used as referring to comparison, it can be seen that there is no Fe-Fe key in the monatomic catalyst of the Fe, that is, Fe nano particle is not present.
The electrochemical oxygen reducing property test of the monatomic catalyst of Fe obtained above is as follows:
The monatomic catalyst ink of Fe is prepared first, preparation method is specifically: the monatomic catalyst of the Fe of 4mg is added to
1mL contains the water and alcohol mixed solution (volume ratio 3:1) of 30 μ L naphthols, and ultrasound obtains uniform black catalysis after 30 minutes
Agent ink.It is 0.197625cm that the ink for drawing 15 μ L, which drips to surface area,2Rotating ring disk electrode (r.r.d.e) on, be dried at room temperature for shape
At one layer of working electrode film.It is tested using three-electrode battery, glass-carbon electrode is working electrode, is platinum filament, reference electricity to electrode
Extremely Ag/AgCl electrode, electrolyte are 0.1M KOH, and test voltage range is 0-1.1Vvs.RHE.
In order to compare, the electrochemical oxygen reducing property of business Pt/C is tested under the same test conditions.
Test results are shown in figure 4, and the half way up the mountain current potential of business Pt/C is 0.84V, the half way up the mountain current potential of the monatomic catalyst of Fe
For 0.89V.
Embodiment 2:
In the present embodiment, the preparation method of the monatomic catalyst of Co is essentially identical with the preparation method in embodiment 1 as follows,
Except that: with the ferric chloride hexahydrate in cobalt chloride hexahydrate alternative steps (2).
The spherical aberration electron microscopic picture of the monatomic catalyst of Co obtained above is as shown in Figure 5, it can be seen that Co is monatomic uniformly
It is scattered in C substrate.
The synchrotron radiation EXAFS result of the monatomic catalyst of Co obtained above is similar to Example 1, shows that the Co is mono- former
There is no Co-Co key in muonic catalysis agent, that is, Co nano particle is not present.
Embodiment 3:
In the present embodiment, the preparation method of the monatomic catalyst of Ni is essentially identical with the preparation method in embodiment 1 as follows,
Except that: with the ferric chloride hexahydrate in Nickel dichloride hexahydrate alternative steps (2), solvent is changed to acetonitrile.
The spherical aberration electron microscopic picture of the monatomic catalyst of Ni obtained above is as shown in Figure 6, it can be seen that Ni is monatomic uniformly
It is scattered in C substrate.
The synchrotron radiation EXAFS result of the monatomic catalyst of Ni obtained above is similar to Example 1, shows that the Co is mono- former
There is no Ni-Ni key in muonic catalysis agent, that is, Ni nano particle is not present.
Embodiment 4:
In the present embodiment, the preparation method of the monatomic catalyst of Cu is essentially identical with the preparation method in embodiment 1 as follows,
Except that: with the ferric chloride hexahydrate in Copper dichloride dihydrate alternative steps (2).
The spherical aberration electron microscopic picture of the monatomic catalyst of Ni obtained above is as shown in Figure 7, it can be seen that Ni is monatomic uniformly
It is scattered in C substrate.
The synchrotron radiation EXAFS result of the monatomic catalyst of Ni obtained above is similar to Example 1, shows that the Co is mono- former
There is no Cu-Cu key in muonic catalysis agent, that is, Cu nano particle is not present.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the monatomic catalyst of metal, it is characterized in that: there is the metal of bipyridyl group to have machine frame for selection
Metal salt presoma is coordinated on bipyridyl group, then under an inert atmosphere by frame material by post-processing method of modifying
Carbonization and acid etch are carried out, the monatomic catalyst of metal is obtained.
2. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: described has bipyridyl
The metal-organic framework material of group includes Zr Base Metal organic framework materials.
3. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: the metal salt presoma
Including metal chloride and its hydrate, nitrate and its hydrate, sulfate and its hydrate.
4. the preparation method of the monatomic catalyst of metal as described in claim 1, is urged it is characterized in that: the metal is monatomic
Agent includes the monatomic catalyst of Fe, the monatomic catalyst of Co, the monatomic catalyst of Ni and the monatomic catalyst of Cu.
5. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: the post-processing modification side
Method be by metal salt presoma, the metal-organic framework material with bipyridyl group and solvent mix, after being stirred to react from
The heart, cleaning, drying.
6. the preparation method of the monatomic catalyst of metal as described in claim 5, it is characterized in that: the metal salt presoma
The ratio between mole of bipyridyl is between 0~1 in mole and metal-organic framework material；
Preferably, the solvent is one of tetrahydrofuran, acetonitrile or two kinds.
7. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: carbonisation are as follows: in inertia
It is carbonized under atmosphere at 600 DEG C~1000 DEG C；
Preferably, being carbonized at 700 DEG C；
Preferably, carbonization time is 1 hour~5 hours, further preferably 3 hours.
8. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: in carbonisation, heating speed
Rate is 1~10 DEG C/min, preferably 2 DEG C/min；
Preferably, locating inert atmosphere includes nitrogen and/or argon gas.
9. the preparation method of the monatomic catalyst of metal as described in claim 1, it is characterized in that: being used in the acid etch
Acid include one of hydrofluoric acid, hydrochloric acid, sulfuric acid or several.
10. the preparation method of the monatomic catalyst of metal as described in any claim in claim 1 to 9, it is characterized in that:
The monatomic catalyst of the metal can be applied to electro-catalysis redox reactions.
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