CN107252700A - A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method - Google Patents
A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method Download PDFInfo
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- CN107252700A CN107252700A CN201710495469.0A CN201710495469A CN107252700A CN 107252700 A CN107252700 A CN 107252700A CN 201710495469 A CN201710495469 A CN 201710495469A CN 107252700 A CN107252700 A CN 107252700A
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- metal phosphide
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 180
- 239000002184 metal Substances 0.000 title claims abstract description 176
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 239000002071 nanotube Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 65
- 239000013118 MOF-74-type framework Substances 0.000 claims description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052593 corundum Inorganic materials 0.000 claims description 35
- 239000010431 corundum Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 17
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 17
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 15
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 15
- 235000013495 cobalt Nutrition 0.000 claims description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 68
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000003643 water by type Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 150000002240 furans Chemical class 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000010926 purge Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 olefin hydrocarbon Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012224 working solution Substances 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
Abstract
The present invention relates to a kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method, many metal phosphide catalysts have hollow nanotube structure, are the equally distributed composite of catalytic center using carbon as support.This method obtains many metal phosphide catalysts with nano tube structure by the use of many metallized metal organic framework materials as template by simple low temperature phosphor reaction (200~350 DEG C).The many metal phosphide nano tube catalysts prepared maintain the pattern of presoma well, with larger specific surface area and pore volume, in multistage pore size distribution, and metal-doped ratio and thing phase with uniform, controllable, be conducive to the progress of electrochemical catalysis, hydrodesulfurization, selective hydrogenation and other hydrogenation reactions, have broad application prospects.
Description
Technical field
The present invention relates to a kind of equally distributed many metal phosphide nano tube catalysts of catalytic center and low temperature preparation side
Method, belongs to catalyst technical field.
Background technology
With the growth and expanding economy of population in the world, the energy has been considered as the most basic demand of human social development.
But the non-renewable resources such as oil, coal are increasingly exhausted, and a series of rings that fossil fuel is produced during exploitation
Border problem, seek a kind of green it is renewable, reduction energy use during pollutant emission clean energy resource it is imperative.
Hydrogen Energy, is generally acknowledged clean energy resource, is described as 21 century secondary energy sources most with prospects, and it helps to solve
Energy crisis, global warming and environmental pollution, its exploitation have obtained worldwide highest attention.Hydrogen Energy is hydrogen
The energy produced with oxygen reaction, as a kind of secondary energy sources, compares with the traditional energy such as oil, coal, wide with source
General, clean environment firendly, it is renewable the advantages of, therefore favored by people；In addition, hydrogen is also used as a variety of hydrofinishings
Raw material, is widely used in the fields such as petrochemical industry, for reduction fossil fuel use during sulphur, nitrogen compound discharge play
Vital effect.But, (such as hydrodesulfurization, hydrogenation are de- for common hydrogen manufacturing mode (such as water electrolysis hydrogen production) and hydrogenation mode
Nitrogen) etc. process be required for the participation of catalyst greatly, therefore, how to develop a kind of application easy to spread, cheap and easy to get, catalytic
The excellent catalyst of energy, is the key point for determining hydrogen utilization.
In recent years, transition metal phosphide is due to its abundant reserves, cheap price and can be with noble metal platinum, iridium phase
The catalytic activity matched in excellence or beauty, receives the extensive concern of scientists.Transition metal phosphide has with nitride, Carbide Phases seemingly
Physics and chemical property, there is metallicity and the compound of characteristic of semiconductor, with very high catalytic activity when being one similar
And stability.At present, transition metal phosphide catalyst is widely used in hydrogenation reaction, such as hydrodesulfurization (HDS), hydrodenitrogeneration
(HDN), hydrogenation deoxidation (HDO), hydrogenation-dechlorination, hydroisomerizing, the selective hydrogenation of alkene, aromatisation, catalysis pyrolysis, reformation system
Hydrogen etc. reacts.Therefore, transition metal phosphide with excellent hydrodesulfurization, hydrodenitrogeneration and stability due to turning into catalysis material
Expect the focus of area research.In addition, the scientific research of theoretical calculation and early stage is proved, multi-element metal doping can be significantly improved
The catalytic activity of catalyst, this mainly has benefited from the cooperative effect between activated centre.Such as doped chemical can be to catalyst
The electronic structure of body is optimized, the energy barrier of reduction catalyst matter lotus transfer, and then promotes the progress of catalytic reaction.But,
Because multi-element doping catalyst is limited to the valence state of element and the composition of thing phase during composite is formed, orientation is closed
It is very big into homogeneous compound phase difficulty.
The B of Chinese patent literature CN 101474568 disclose a kind of selective hydrogenation and olefin hydrocarbon removal double-metal phosphide catalysis
The preparation method of agent, this method comprises the following steps：(1) transition metal salt and diammonium hydrogen phosphate are prepared into presoma；(2) in hydrogen
300~500 DEG C are warming up in gas atmosphere with 1~10 DEG C/speed per minute to reduce 0~5 hour, afterwards with 1~10 DEG C/every point
The speed of clock is warming up to 500~800 DEG C, and reduces 1~5 hour at such a temperature.The invention is by metal oxide to Dan Jin
Catalyst made from belonging to the doping of phosphide has good catalytic activity.But, this method preparation process is complicated, and needs hydrogen
Gas is participated in and reacted at relatively high temperatures；In addition, bimetallic catalyst prepared by this method is monometallic phosphide and metal oxygen
The doping of compound co-catalyst, and heterogeneous many metal phosphide materials.
The B of Chinese patent literature CN 103157497 disclose a kind of double-metal phosphide hydrogenation refining catalyst WP-Ni2P
Preparation method, this method comprises the following steps：(1) weighed according to the stoichiometric relationship of the mol ratio 1.0~1.2 of phosphorus and tungsten
The two, is dissolved in deionized water by a certain amount of diammonium hydrogen phosphate and ammonium metatungstate under stirring at room temperature, 100 after stirring and dissolving~
130 DEG C of dryings 2~12 hours, are calcined 2~4 hours at 450~650 DEG C after drying, obtain presoma；(2) presoma is loaded
In fixed bed reactors, reacted 2~4 hours at 650~700 DEG C in hydrogen atmosphere, be down to after room temperature the passivation 1 in nitrogen small
When, obtain body phase phosphide catalyst.This method can synthesize a series of non-by the control of metal salt mol ratio in presoma
Support type and load type double-metal phosphide catalyst.But, this method preparation technology is complex, and needs higher temperature
Lower reaction；In addition, the metal in double-metal phosphide catalyst prepared by this method depends entirely on presoma in the solution
Mixing, does not ensure that homogeneity.
The A of Chinese patent literature CN 103464187 disclose a kind of based on metal oxide low temperature synthesis bimetallic phosphatization
The method of thing, this method is mixed a certain amount of dihydrogen phosphite salt and two kinds of metal oxides by certain mol proportion, and is ground
Uniformly, then mixture is contained in corundum porcelain boat, 300~500 DEG C of reactions 60~180 in the tube furnace for be passed through inert atmosphere
Minute can obtain unsupported catalyst.This method preparation technology is relatively simple, and reaction temperature is relatively low, can obtain a series of non-negative
Load type and load type double-metal phosphide catalyst.But the program still can not solve the equal of activated centre and catalyst thing phase
It is even scattered.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of equally distributed many metal phosphide nanotubes of catalytic center
Catalyst and low temperature preparation method.Many metal phosphide catalysts have hollow nanotube structure, are the catalysis using carbon as support
The equally distributed composite in center.
The preparation method of the present invention with low temperature, efficiently, low cost, be easy to industrialized method and prepare with three wieners
The mutually adjustable many metal phosphide catalysts of thing of nanotube structures.Preparation-obtained many metal phosphide nano tube catalyst tools
There are larger specific surface area and pore volume, in multistage pore size distribution, the metal-doped ratio and thing phase of uniform, controllable are conducive to electrification
Catalysis, hydrodesulfurization, selective hydrogenation and the progress of other hydrogenation reactions are learned, is had broad application prospects.
Technical scheme is as follows：
A kind of equally distributed many metal phosphide nano tube catalysts of catalytic center, many metal phosphide catalyst tools
There is hollow nanotube structure, be the equally distributed composite of catalytic center using carbon as support.
According to the present invention, a kind of preparation method of the equally distributed many metal phosphide nano tube catalysts of catalytic center,
It is as follows including step：
1) preparation of MOF-74 presomas：
Claim mixed metal salt to be dissolved in deionized water, obtain solution a；Weigh 2,5-Dihydroxyterephthalic acid and be dissolved in tetrahydrochysene
Furans obtains solution b；It is sufficiently stirred for being warming up to 105-120 DEG C after solution a is mixed with solution b to react 6-72 hours, by product
Cleaned after centrifugation, obtain many metal MOF-74 presomas；
2) many metal MOF-74 presomas are placed in corundum porcelain boat, be then placed in tube furnace, be warming up to 250-500 DEG C
Calcining 0.5-12 hours, obtains poly-metal deoxide intermediate；
3) poly-metal deoxide intermediate and hypophosphites are respectively placed in the two ends of corundum porcelain boat, are put into tube furnace,
250-400 DEG C is warming up in an inert atmosphere and is incubated 0.5-12 hours, obtains many metal phosphide nano tube catalysts.
, according to the invention it is preferred to, step 1) described in mixed metal salt be selected from the metal salt of cobalt, nickel, iron, zinc or manganese
In any two kinds or any two or more mixing.
, according to the invention it is preferred to, described cobalt, nickel, iron, the metal salt of zinc or manganese are cobalt, the nitre of nickel, iron, zinc or manganese
Hydrochlorate, acetate hydrate, sulfate or chloride.
It is further preferred that described mixed metal salt is cobalt, the acetate hydrate mixture of nickel, in mixture cobalt with
The mol ratio of nickel is 1:0.1~10.
Highly preferred, described mixed metal salt is the mixing of four acetate hydrate cobalts and nickel acetate tetrahydrate, cobalt and nickel
Mol ratio be 1:0.1~10.
According to currently preferred, step 1) in, the mass volume ratio of mixed metal salt and deionized water is：(0.1-
10)：(15-600), unit：G/mL, it is further preferred that mixed metal salt and the mass volume ratio of deionized water are：(0.1-
1)：(15-60), unit：G/mL, it is further preferred that mixed metal salt and the mass volume ratio of deionized water are：(0.4-
0.8)：(15-40), unit：g/mL.
According to currently preferred, step 1) in, the mass volume ratio of 2,5-Dihydroxyterephthalic acid and tetrahydrofuran
For：(0.297-11.89)：(15-600), unit：G/mL, it is further preferred that 2,5-Dihydroxyterephthalic acid and tetrahydrochysene furan
The mass volume ratio muttered is：(0.297-1.000)：(15-60), unit：G/mL, it is further preferred that 2,5- dihydroxy are to benzene
The mass volume ratio of dioctyl phthalate and tetrahydrofuran is：(0.297-0.600)：(15-40), unit：g/mL.
According to currently preferred, step 1) in, solution a is with the solution b volume ratios mixed：(1-2)：(1-2).
According to currently preferred, step 1) in, reaction temperature is：105-110 DEG C, the reaction time is 22-24h, centrifugation
Cleaned successively with deionized water, ethanol after separation, it is each to clean three times.
According to currently preferred, step 2) in, heating rate is 1~5 DEG C/min.
, according to the invention it is preferred to, step 2) calcining heat be 300~400 DEG C, calcining the reason time be 1~3 hour.
, according to the invention it is preferred to, step 3) hypophosphites be sodium hypophosphite or ammonium hypophosphite, poly-metal deoxide
The mass ratio of intermediate and hypophosphites is (0.01-30)：(0.05~900), it is preferred that poly-metal deoxide intermediate with time
Phosphatic mass ratio is (0.01-10)：(0.05~90), it is preferred that the matter of poly-metal deoxide intermediate and hypophosphites
Amount is than being (0.01-1)：(0.05~9), it is preferred that the mass ratio of poly-metal deoxide intermediate and hypophosphites is (0.01-
0.1)：(0.05~2).
, according to the invention it is preferred to, step 3) in inert atmosphere be argon gas, nitrogen or helium；
, according to the invention it is preferred to, step 3) in inert gas flow velocity be 1~500mL/min；It is further preferred that institute
Inert gas flow velocity is stated for 20~100mL/min；
, according to the invention it is preferred to, step 3) in, heating rate be 1~20 DEG C/min, it is preferred that heating rate be 5~
10℃/min。
, according to the invention it is preferred to, step 3) in, heat treatment temperature is 250~350 DEG C, and heat treatment time is 1~3 small
When.
Phosphate decomposes generation phosphine gas at a temperature of higher than 200 DEG C, passes through gas diffusion effect and oxide
React, step 3 of the present invention) poly-metal deoxide intermediate is separated with hypophosphites, on the one hand passes through gas phase reaction
It is more beneficial for protecting the peculiar pattern of presoma；Another aspect gas phase reaction directly phosphine gas and oxide occurs anti-
Should, phosphate will not be incorporated into catalyst system, be not required to carry out further washing purification, technique is simple.
The present invention by the use of the MOF-74 to form metal-organic framework material can be coordinated with various metals center as template,
Under the inert gas shieldings such as argon gas, nitrogen, single step reaction is carried out at a lower temperature with hypophosphites, three-dimensional manometer is prepared
Many metal phosphide catalysts of tubular construction.Prepared many metal phosphide catalysts inherit MOFs presomas well
Three-dimensional appearance simultaneously forms nano tubular structure in centre.
The present invention is dissolved in tetrahydrofuran solution using mixed salt solution and 2,5-Dihydroxyterephthalic acid and fully mixed
After conjunction, metal ion profile is uniform, is reacted at 105-120 DEG C, obtains many metal MOF-74 presomas, obtain metal ion equal
It is even to be distributed in many metal MOF-74 presomas, by further calcining, formed using carbon as support, be coordinated with various metals center
The distribution for forming metal center in metal organic frame, metal-organic framework materials is being uniformly distributed for molecular scale, relative to
Traditional supported catalysts, the phosphide catalyst distribution prepared using metal-organic framework materials as precursor is more equal
It is even, it is with the obvious advantage.
Beneficial effects of the present invention are as follows：
1. the present invention uses common metal-organic framework materials as presoma, metal-organic framework materials of the invention
The specific proportions of metal salt in presoma, can obtain the equally distributed many metal-organic framework materials of metal center, by letter
Single phosphating reaction obtains dispersed many metal phosphide catalysts with not jljl phase composition.Compared to conventional load
Type catalyst, the catalyst activity that the present invention is obtained is more uniformly spread, with the obvious advantage, and the process preparation condition is more
Gently, technique is simple, suitable for industrialized production.
2. many metal nano-tube catalyst of the present invention have special nano tube structure, larger specific surface area (55.6-
60m2/ g) and pore volume (0.22-0.35cm3/ g) and hierarchical porous structure, more active sites, and tool can be exposed
There is very high matter lotus transfer efficiency, improve catalytic efficiency, in addition, to material surface structure and electronics between metal in many metals
The influence of state and synergy further increase catalytic effect.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction pattern (PXRD) of many metal phosphide nano tube catalysts prepared by embodiment 1；
Fig. 2 is SEM (SEM) photo of many metal phosphide nano tube catalysts prepared by embodiment 1；
Fig. 3 is transmission electron microscope (TEM) photo of many metal phosphide nano tube catalysts prepared by embodiment 1；
Fig. 4 is the TEM corresponding element mapping distribution maps of many metal phosphide nano tube catalysts prepared by embodiment 1；
Fig. 5 is nitrogen physisorption curve and the aperture point of many metal phosphide nano tube catalysts prepared by embodiment 1
Butut；
Fig. 6 is the material catalytic electrochemical oxygen evolution reaction of many metal phosphide nano tube catalysts prepared by embodiment 1
(OER) linear sweep voltammetry curve map.
Fig. 7 is the material catalytic electrochemical evolving hydrogen reaction of many metal phosphide nano tube catalysts prepared by embodiment 1
(HER) linear sweep voltammetry curve map.
Embodiment
With reference to specific embodiment, the present invention is described further, but not limited to this.
Experimental method described in following embodiments, is conventional method unless otherwise specified simultaneously；The reagent and material
Material, unless otherwise specified, is commercially obtained.
The thing of many metal phosphide nano tube catalysts prepared by the present invention is determined by X-ray powder diffraction figure, is adopted
With the X'pert PRO powder diffractometers of Dutch PANalytical company.
The pattern of many metal phosphide nano tube catalysts prepared by the present invention passes through field emission scanning electron microscope
(SEM) photo is shown, using Japanese JSM-7500F field emission scanning electron microscopes.
The internal morphology and Elemental redistribution of many metal phosphide nano tube catalysts prepared by the present invention pass through transmitted electron
Microscope (TEM) photo and corresponding element mapping images are shown, using Japanese JEOL JEM2100F transmission electron microscopes.
The specific surface area of many metal phosphide nano tube catalysts prepared by the present invention is bent by low temperature nitrogen adsorption/desorption
Line is shown, using Kang Ta companies of U.S. Autosorb-iQ2Automatically than surface and pore-size distribution analyzer.
The electrocatalysis characteristic of many metal phosphide nano tube catalysts prepared by the present invention passes through Shanghai Chen Hua CHI760E electricity
Chem workstation is measured.
Embodiment 1
A kind of low temperature preparation method of the equally distributed many metal phosphide nano tube catalysts of catalytic center, step is such as
Under：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Obtain metal MOF-74 presomas.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in poly-metal deoxide intermediate and 1.0 grams of sodium hypophosphite be respectively placed in corundum
The two ends of porcelain boat, porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of argon gas emptying tube furnace；It is every with 5 DEG C
The heating rate of minute is heated to 300 DEG C, and insulation (persistently uses 100 milliliters every point in 2 hours at this temperature during being somebody's turn to do
Argon gas purging), you can much metal phosphide nano tube catalysts.
Obtained many metal phosphide nano tube catalyst X-ray powder diffraction figures are as shown in figure 1, as shown in Figure 1, the reality
It is NiCoP and Co to apply many metal phosphides that example prepares2P compound phase.SEM (SEM) and transmission electricity
Sub- microscope (TEM) as shown in Figure 2 and Figure 3, has hollow from Fig. 2, Fig. 3 many metal phosphide catalysts that can be seen that gained
Nano tube structure.Element arrangement in Fig. 4 also demonstrates the presence of the structure, in addition, being uniformly distributed by carbon
It can be seen that much metal phosphide nano tube catalyst is a class using carbon as support, the equally distributed composite wood of catalytic center for institute
Material.By Fig. 5 nitrogen physisorption curve and graph of pore diameter distribution, gained catalysis material has higher specific surface area
(55.6 square metres every gram), and with obvious hierarchical porous structure, each contribute to the performance of catalyst activity.For three-dimensional polyhedron
Structure, illustration demonstrates its porous.
Electrocatalysis characteristic is tested：
Many metal phosphide nano tube catalyst catalytic electrochemical evolving hydrogen reactions (HER) that the embodiment is prepared with
Oxygen evolution reaction (OER), concrete operations are as follows：5 milligrams of catalyst are weighed, 1 milliliter of (volume ratio, ethanol is distributed to：Water：nafion
=1:1:0.05) in solvent, ultrasound more than 30 minutes obtains uniform suspension, 5 microlitres of working solutions is added drop-wise into diameter 4
On the rotating disc electrode of millimeter (load capacity is 0.19 milligram every square centimeter), fully dry at room temperature, using the electricity of standard three
Electrode systems, are analyzed and evaluated by Shanghai Chen Hua CHI760E electrochemical workstations.Method of testing uses linear sweep voltammetry
Method, analysis is carried out in 1.0 moles every liter of potassium hydroxide solution, and test scope is 0.1 to minus 0.5 volt of (HER), 1.0 to 1.8
Lie prostrate (OER), above-mentioned electric window is the voltage relative to standard hydrogen electrode.Sweep speed is 5 millivolts per second.
Obtain linear sweep voltammetry curve map such as Fig. 6 and Fig. 7 institutes of catalytic electrochemical oxygen evolution reaction and evolving hydrogen reaction
Show.It can be seen that current density reaches 10mA cm during gained catalyst reacts at two-2Required overpotential point
Not Zhi You 245mV and 129mV, there is obvious gain effect compared to most of phosphide catalysis materials disclosed at present.
This be due to many metal phosphide nano tube catalysts of preparation have nano tube structure, larger specific surface area and many
Level pore structure, can expose more active sites, and with very high matter lotus transfer efficiency, it is anti-that this both contributes to catalysis
The progress answered, in addition, the influence and synergy in many metals between metal to material surface structure and electronic state are also favourable
In the progress of catalytic reaction.
Embodiment 2
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.6719 gram of four acetate hydrate cobalt and 0.0747 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) MOF-74 presomas and it is placed in corundum porcelain boat, porcelain boat is put into tube furnace, in air in weighing 0.5 gram 1)
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under atmosphere；
3) intermediate and 1.0 grams of sodium hypophosphite in weighing 0.05 gram 2) are respectively placed in the two ends of corundum porcelain boat, by porcelain
Boat is put into tube furnace, is passed through the air in 100 milliliters every point of argon gas emptying tube furnace；With 5 DEG C of heating rates per minute
300 DEG C are heated to, and is incubated 2 hours at this temperature (argon gas during this persistently using 100 milliliters every point is purged), i.e.,
Much metal phosphide nano tube catalysts.
Embodiment 3
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:2 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 48 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 30 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (argon gas during this persistently using 30 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 4
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:2 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) 1.0 grams of steps 1 are weighed) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 30 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (argon gas during this persistently using 30 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 5
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 2 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) 1.0 grams of steps 1 are weighed) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
400 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 30 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (argon gas during this persistently using 30 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 6
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 3 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 100 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heatings per minute
Speed is heated to 300 DEG C, and is incubated 2 hours at this temperature (inert gas purge is persistently used during being somebody's turn to do), you can
Many metal phosphide nano tube catalysts.
Embodiment 7
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.1 gram of step 2) in intermediate and 2.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat, will
Porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of nitrogen purge tube furnace；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (nitrogen during this persistently using 100 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 8
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate, 0.5 gram of sodium hypophosphite is respectively placed in the two ends of corundum porcelain boat, will
Porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of nitrogen purge tube furnace；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (argon gas for persistently rising every point using 100 nitrogen during this is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 9
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 100 milliliters every point of argon gas emptying tube furnace is passed through；With 2 DEG C of heatings per minute
Speed is heated to 300 DEG C, and insulation (is persistently blown for 2 hours during this using 100 milliliters every point of argon gas at this temperature
Sweep), you can much metal phosphide nano tube catalysts.
Embodiment 10
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:2 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.1 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat, will
Porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of nitrogen purge tube furnace；With 1 DEG C of heating speed per minute
Rate is heated to 325 DEG C, and is incubated 3 hours at this temperature (nitrogen during this persistently using 100 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 11
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.5972 gram of four acetate hydrate cobalt and 0.1495 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 24 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.2 gram of step 2) in intermediate and 2.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat, will
Porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of argon gas emptying tube furnace；With 2 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 3 hours at this temperature (argon gas during this persistently using 100 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 12
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.2488 gram of four acetate hydrate cobalt, 0.2491 gram of nickel acetate tetrahydrate and
0.1739 gram of ferrous acetate, which is dissolved in 30 ml deionized waters, obtains solution a；Weigh 0.5944 gram of 2,5- dihydroxy terephthaldehyde
Acid is dissolved in 30 milliliters of tetrahydrofurans and obtains solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is sufficiently stirred for
It is transferred to afterwards in the autoclave with polytetrafluoro liner, 110 DEG C are reacted 24 hours, product are centrifuged, and use deionization
Water is cleaned three times with ethanol, you can obtain many metal MOF-74 presomas of different metal ratio.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 100 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heatings per minute
Speed is heated to 300 DEG C, and insulation (is persistently blown for 2 hours during this using 100 milliliters every point of argon gas at this temperature
Sweep), you can much metal phosphide nano tube catalysts.
Embodiment 13
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.2488 gram of four acetate hydrate cobalt, 0.2491 gram of nickel acetate tetrahydrate and
0.1739 gram of ferrous acetate, which is dissolved in 30 ml deionized waters, obtains solution a；Weigh 0.5944 gram of 2,5- dihydroxy terephthaldehyde
Acid is dissolved in 30 milliliters of tetrahydrofurans and obtains solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is sufficiently stirred for
It is transferred to afterwards in the autoclave with polytetrafluoro liner, 110 DEG C are reacted 48 hours, product are centrifuged, and use deionization
Water is cleaned three times with ethanol, you can obtain many metal MOF-74 presomas of different metal ratio.
2) 1.0 grams of steps 1 are weighed) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
400 DEG C are heated to 1 DEG C of heating rate per minute to calcine 3 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.1 gram of step 2) in intermediate and 2.0 grams of sodium hypophosphite be respectively placed in the two ends of corundum porcelain boat, will
Porcelain boat is put into tube furnace, is passed through the air in 100 milliliters every point of nitrogen purge tube furnace；With 5 DEG C of heating speed per minute
Rate is heated to 300 DEG C, and is incubated 2 hours at this temperature (nitrogen during this persistently using 100 milliliters every point is purged),
Can much metal phosphide nano tube catalysts.
Embodiment 14
1) preparation of MOF-74 presomas：Weigh 0.6719 gram of four acetate hydrate cobalt and 0.0747 gram of nickel acetate tetrahydrate is molten
Solution a is obtained in 30 ml deionized waters；Weigh 0.5944 gram of 2,5- dihydric para-phthalic acid and be dissolved in 30 milliliters of tetrahydrochysene furans
Mutter and obtain solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is transferred to in polytetrafluoro after being sufficiently stirred for
In the autoclave of lining, 110 DEG C are reacted 48 hours, and product is centrifuged, and clean with deionized water and ethanol three times, i.e.,
Many metal MOF-74 presomas of different metal ratio can be obtained.
2) weigh 0.5 gram of step 1) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
350 DEG C are heated to 1 DEG C of heating rate per minute to calcine 2 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) weigh 0.05 gram of step 2) in intermediate and 1.0 grams of ammonium hypophosphite be respectively placed in the two ends of corundum porcelain boat,
Porcelain boat is put into tube furnace, the air in 100 milliliters every point of argon gas emptying tube furnace is passed through；With 5 DEG C of heatings per minute
Speed is heated to 300 DEG C, and is incubated 2 hours at this temperature (inert gas purge is persistently used during being somebody's turn to do), you can
Many metal phosphide nano tube catalysts.
Embodiment 15
A kind of method of many metal phosphide nano tube catalysts of low temperature preparation, including step are as follows：
1) preparation of MOF-74 presomas：Weigh 0.2488 gram of four acetate hydrate cobalt, 0.2491 gram of nickel acetate tetrahydrate and
0.1739 gram of ferrous acetate, which is dissolved in 30 ml deionized waters, obtains solution a；Weigh 0.5944 gram of 2,5- dihydroxy terephthaldehyde
Acid is dissolved in 30 milliliters of tetrahydrofurans and obtains solution b；It is 1 by volume by solution a and solution b:1 ratio mixing, is sufficiently stirred for
It is transferred to afterwards in the autoclave with polytetrafluoro liner, 110 DEG C are reacted 48 hours, product are centrifuged, and use deionization
Water is cleaned three times with ethanol, you can obtain many metal MOF-74 presomas of different metal ratio.
2) 1.0 grams of steps 1 are weighed) in MOF-74 presomas, be placed in corundum porcelain boat, porcelain boat be put into tube furnace,
400 DEG C are heated to 1 DEG C of heating rate per minute to calcine 3 hours, obtain poly-metal deoxide intermediate under air atmosphere；
3) intermediate and 2.0 grams of ammonium hypophosphite in weighing 0.1 gram 2) are respectively placed in the two ends of corundum porcelain boat, by porcelain boat
It is put into tube furnace, is passed through the air in 30 milliliters every point of nitrogen purge tube furnace；With 5 DEG C of heating rate heating per minute
To 300 DEG C, and 2 hours are incubated at this temperature (nitrogen during this persistently using 30 milliliters every point is purged), i.e., much
Metal phosphide nano tube catalyst.
Claims (10)
1. a kind of equally distributed many metal phosphide nano tube catalysts of catalytic center, many metal phosphide catalysts have
Hollow nanotube structure, is the equally distributed composite of catalytic center using carbon as support.
2. a kind of preparation method of the equally distributed many metal phosphide nano tube catalysts of catalytic center, including step are as follows：
1) preparation of MOF-74 presomas：
Claim mixed metal salt to be dissolved in deionized water, obtain solution a；Weigh 2,5-Dihydroxyterephthalic acid and be dissolved in tetrahydrofuran
Obtain solution b；It is sufficiently stirred for being warming up to 105-120 DEG C after solution a is mixed with solution b to react 6-72 hours, product is centrifuged
Cleaned after separation, obtain many metal MOF-74 presomas；
2) many metal MOF-74 presomas are placed in corundum porcelain boat, be then placed in tube furnace, be warming up to 250-500 DEG C of calcining
0.5-12 hours, obtain poly-metal deoxide intermediate；
3) poly-metal deoxide intermediate and hypophosphites are respectively placed in the two ends of corundum porcelain boat, are put into tube furnace, lazy
Property atmosphere in be warming up to 250-400 DEG C be incubated 0.5-12 hours, obtain many metal phosphide nano tube catalysts.
3. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 1)
Described in metal salt of the mixed metal salt selected from cobalt, nickel, iron, zinc or manganese in any two kinds or any two or more mixed
Close；Described cobalt, nickel, iron, the metal salt of zinc or manganese are cobalt, nitrate, acetate hydrate, the sulfate of nickel, iron, zinc or manganese
Or chloride.
4. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that described
Mixed metal salt is that the mol ratio of cobalt and nickel in cobalt, the mixture of the acetate hydrate of nickel, mixture is 1:0.1~10；It is excellent
Choosing, described mixed metal salt is the mixing of four acetate hydrate cobalts and nickel acetate tetrahydrate.
5. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 1)
In, the mass volume ratio of mixed metal salt and deionized water is：(0.1-10)：(15-600), unit：G/mL, further preferably
, the mass volume ratio of mixed metal salt and deionized water is：(0.1-1)：(15-60), unit：G/mL, it is further preferred that
Mixed metal salt and the mass volume ratio of deionized water are：(0.4-0.8)：(15-40), unit：g/mL.
6. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 1)
In, the mass volume ratio of 2,5-Dihydroxyterephthalic acid and tetrahydrofuran is：(0.297-11.89)：(15-600), unit：
G/mL, it is further preferred that the mass volume ratio of 2,5-Dihydroxyterephthalic acid and tetrahydrofuran is：(0.297-1.000)：
(15-60), unit：G/mL, it is further preferred that the mass volume ratio of 2,5-Dihydroxyterephthalic acid and tetrahydrofuran is：
(0.297-0.600)：(15-40), unit：g/mL.
7. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 1)
In, solution a is with the solution b volume ratios mixed：(1-2)：(1-2)；Step 1) in, reaction temperature is：105-110 DEG C, reaction
Time is 22-24h, is cleaned successively with deionized water, ethanol after centrifugation, each to clean three times.
8. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 2)
In, heating rate is 1~5 DEG C/min；Step 2) calcining heat be 300~400 DEG C, calcining the reason time be 1~3 hour.
9. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step 3)
The hypophosphites is sodium hypophosphite or ammonium hypophosphite, and the mass ratio of poly-metal deoxide intermediate and hypophosphites is (0.01-
30)：(0.05~900), it is preferred that the mass ratio of poly-metal deoxide intermediate and hypophosphites is (0.01-10)：(0.05
~90), it is preferred that the mass ratio of poly-metal deoxide intermediate and hypophosphites is (0.01-1)：(0.05~9), it is preferred that
The mass ratio of poly-metal deoxide intermediate and hypophosphites is (0.01-0.1)：(0.05~2).
10. the preparation method of many metal phosphide nano tube catalysts according to claim 2, it is characterised in that step
3) inert atmosphere is argon gas, nitrogen or helium in；Inert gas flow velocity is 1~500mL/min；It is further preferred that described lazy
Property gas flow rate be 20~100mL/min；Heating rate is 1~20 DEG C/min, it is preferred that heating rate is 5~10 DEG C/min；
Heat treatment temperature is 250~350 DEG C, and heat treatment time is 1~3 hour.
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