CN110479332A - Porous flake phosphating sludge/carbon composite material and preparation method - Google Patents
Porous flake phosphating sludge/carbon composite material and preparation method Download PDFInfo
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- CN110479332A CN110479332A CN201910597759.5A CN201910597759A CN110479332A CN 110479332 A CN110479332 A CN 110479332A CN 201910597759 A CN201910597759 A CN 201910597759A CN 110479332 A CN110479332 A CN 110479332A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 94
- 239000010802 sludge Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 84
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 42
- 239000011733 molybdenum Substances 0.000 claims abstract description 42
- 239000011780 sodium chloride Substances 0.000 claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000012545 processing Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000003913 materials processing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000003670 easy-to-clean Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to materials processing technology fields, and in particular to a kind of composite material and preparation method of porous flake phosphating sludge/carbon, the preparation method include the following steps: to provide molybdenum source, phosphorus source, carbon source and sodium chloride；The molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in aqueous solvent, mixed solution is obtained；The mixed solution is dried, precursor powder is obtained；The precursor powder is subjected to calcination processing, then cleaning treatment, obtains porous flake phosphating sludge/carbon composite material.Preparation method of the invention can obtain phosphating sludge/carbon composite of high-purity, two-dimensional sheet, and whole preparation process is safe and reliable, and process conditions are simple and easy to control, production cost is low, be suitable for industrialization large-scale production；Obtained porous flake phosphating sludge/carbon composite has the characteristics that phosphating sludge partial size is small, with high purity, effective ratio area is big, and shows the good catalytic activity of similar platinum, can be widely applied to catalytic field.
Description
Technical field
The invention belongs to materials processing technology fields, and in particular to a kind of composite material of porous flake phosphating sludge/carbon and
Preparation method.
Background technique
The noble metals such as platinum are due to being therefore widely used in petrochemical industry, organic synthesis, fuel electricity with catalytic effect
In the catalytic process in the fields such as pond, automobile and electronics industry, still, on the one hand reserves are few on earth for such noble metal,
And constantly reducing, on the other hand the price is very expensive, and application cost is high.Just because of this, people always search for alternative
The new catalytic material of the noble metal catalysts such as platinum.
In numerous new catalytic materials, phosphating sludge (MoP) is due to its good chemically and thermally mechanical stability, outstanding
Corrosion resistance and good conductivity, attract the extensive interest of people.Especially phosphating sludge is being shown with platinum class seemingly
Electronic structure and after having a significant catalysis characteristics (Energy Environ.Sci., 2014,7,2624-2629), phosphating sludge
Just it is considered as partially or completely substituting the potential material of noble metal platinum, therefore has broad application prospects.
Currently, the conventional preparation techniques of phosphating sludge are by molybdenum oxide and hydrogen phosphide (PH3) or phosphate thermal decomposition production
Raw hydrogen phosphide reacts synthesis under the high temperature conditions.But the phosphating sludge particle size that this method is prepared is big, and specific surface area is small, purity
It is low, limit the catalytic activity of phosphating sludge.For the specific surface area for improving phosphating sludge, scientific research personnel develops some preparation Gao Bibiao
The method of area phosphating sludge, such as the gas phase reaction of volatile metal compounds, vapor-phase reactant such as PH3Equal to solid phase metal oxide
The reaction of object, but these methods, the technological parameter for needing to control is more, and reaction process is complex.For another example, Publication No.
The Chinese invention patent of CN108654659A provides a kind of phosphating sludge/graphene composite nano material and preparation method thereof, the system
Preparation Method needs to use nitrogen protection gas and is reacted in micro-wave oven, is easy to be mixed into air impact product in the synthesis process
Quality.For another example the Chinese invention patent of Publication No. CN108588713A discloses a kind of CVD and prepares two-dimentional phosphatization molybdenum film
Metal molybdenum foil substrate is placed in vacuum reaction furnace by preparation method, this method, and metal molybdenum foil base is made under certain reaction temperature
Bottom is reacted with carrier gas, obtains two-dimentional phosphatization molybdenum film, and it is inconvenient that the phosphatization molybdenum film that this method obtains is removed from substrate, can apply
Field is limited.
Therefore, the prior art has much room for improvement.
Summary of the invention
The purpose of the present invention is to provide a kind of composite material and preparation methods of porous flake phosphating sludge/carbon, it is intended to
Solve the low technical problem of the catalytic activity for hydrogen evolution of existing phosphating sludge.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of preparation method of the composite material of porous flake phosphating sludge/carbon, including walks as follows
It is rapid:
Molybdenum source, phosphorus source, carbon source and sodium chloride are provided；
The molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in aqueous solvent, mixed solution is obtained；
The mixed solution is dried, precursor powder is obtained；
The precursor powder is subjected to calcination processing, then cleaning treatment, obtains porous flake phosphating sludge/carbon and answer
Condensation material.
Another aspect of the present invention provides a kind of composite material of porous flake phosphating sludge/carbon, by of the invention above-mentioned porous
The preparation method of sheet phosphating sludge/carbon composite material is made.
The preparation method of porous flake phosphating sludge provided by the invention/carbon (MoP/C) composite material, with molybdenum source, phosphorus source,
Carbon source and sodium chloride are raw material, are dissolved in after obtaining mixed solution in aqueous solvent, make solvent volatilize to obtain through being dried
Precursor powder will form phosphating sludge/carbon solid of sodium chloride package, then cleaned place after precursor powder calcining
Reason removal sodium chloride, to obtain nanometer phosphating sludge/carbon composite of porous flake；During the preparation process, sodium chloride due to
Its excellent chemically and thermally mechanical stability will not influence phosphating sludge product in high temperature sintered and cooling recrystallization process
It is formed, and plays the role of pore creating material and orientation template, while removal easy to clean, therefore, preparation method energy of the invention
Phosphating sludge/carbon composite of high-purity, two-dimensional sheet is obtained, whole preparation process is safe and reliable, and process conditions are simply easy
Control, production cost are low, are suitable for industrialization large-scale production.Finally, porous flake phosphating sludge/carbon which obtains is compound
Material has the characteristics that phosphating sludge partial size is small, with high purity, effective ratio area is big, and the good catalysis for showing similar platinum is living
Property, it can be widely applied to catalytic field.
Detailed description of the invention
Phosphating sludge/carbon composite X-ray powder diffraction that Fig. 1 is 1-3 of the embodiment of the present invention and prepared by comparative example
(XRD) curve graph；
Fig. 2 is phosphating sludge/carbon composite scanning electron microscope (SEM) and electronics prepared by the embodiment of the present invention 1
Scattering energy spectrum (EDS mapping) figure；
Fig. 3 is phosphating sludge/carbon composite scanning electron microscope (SEM) figure prepared by the embodiment of the present invention 2；
Fig. 4 is phosphating sludge/carbon composite scanning electron microscope (SEM) figure prepared by the embodiment of the present invention 3；
Fig. 5 is phosphating sludge/carbon composite scanning electron microscope (SEM) figure of comparative example of the present invention preparation；
Fig. 6 is phosphating sludge/carbon composite transmission electron microscope (TEM) figure prepared by the embodiment of the present invention 1；
Fig. 7 is the N of the embodiment of the present invention 1 and comparative example2Adsorption desorption curve；Wherein, a is embodiment 1, and b is comparative example；
Phosphating sludge/carbon composite that Fig. 8 is 1-3 of the embodiment of the present invention and prepared by comparative example is anti-as the liberation of hydrogen of catalyst
Answer polarization curve comparison diagram.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
On the one hand, the embodiment of the invention provides a kind of preparation method of the composite material of porous flake phosphating sludge/carbon, packets
Include following steps:
S01: molybdenum source, phosphorus source, carbon source and sodium chloride are provided；
S02: the molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in aqueous solvent, mixed solution is obtained；
S03: the mixed solution is dried, precursor powder is obtained；
S04: the precursor powder is subjected to calcination processing, then cleaning treatment, obtains porous flake phosphating sludge/carbon
Composite material.
The preparation method of the composite material of porous flake phosphating sludge/carbon provided in an embodiment of the present invention, with molybdenum source, phosphorus source,
Carbon source and sodium chloride are raw material, are dissolved in after obtaining mixed solution in aqueous solvent, make solvent volatilize to obtain through being dried
Precursor powder will form phosphating sludge/carbon solid of sodium chloride package, then cleaned place after precursor powder calcining
Reason removal sodium chloride, to obtain nanometer phosphating sludge/carbon composite of porous flake；During the preparation process, sodium chloride due to
Its excellent chemically and thermally mechanical stability will not influence phosphating sludge product in high temperature sintered and cooling recrystallization process
It is formed, and plays the role of pore creating material and orientation template, while removal easy to clean, therefore, the preparation of the embodiment of the present invention
Method can obtain phosphating sludge/carbon composite of high-purity, two-dimensional sheet, and whole preparation process is safe and reliable, process conditions
It is simple and easy to control, production cost is low, be suitable for industrialization large-scale production.
In one embodiment, the molybdenum source in above-mentioned steps S01 is the molybdenum source of water-soluble solvent, and the molybdenum source selected is answered
It can be dissolved in simultaneously in identical solvent when with carbon source and phosphorus source.Specifically, the molybdenum source be Ammonium Molybdate Tetrahydrate, sodium molybdate,
At least one of potassium molybdate, zinc molybdate and molybdic acid；Phosphorus source is ammonium dihydrogen phosphate, sodium dihydrogen phosphate, dibastic sodium phosphate and phosphorus
At least one of acid dihydride potassium；The carbon source is at least one of dicyan diamino and melamine；The aqueous solvent is simultaneously
Molybdenum source, phosphorus source and carbon source can be dissolved, such as deionized water or distilled water.And sodium chloride is porous flake phosphatization in preparation process
Molybdenum/carbon composite material is formed by template.
In one embodiment, the molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in the mistake of aqueous solvent in above-mentioned steps S02
Cheng Zhong, the molybdenum source, phosphorus source, carbon source and sodium chloride mass ratio be 1:1:10:(10~100)；In the proportional region, not only
Sodium chloride can be allowed to play good template action, and porous flake phosphating sludge/carbon composite can be formed well.In
In specific embodiment, the molybdenum source, phosphorus source, carbon source and sodium chloride mass ratio be 1:1:10:10 or the molybdenum source, phosphorus source,
The mass ratio of carbon source and sodium chloride is 1:1:10:30 or the molybdenum source, phosphorus source, carbon source and sodium chloride mass ratio be 1:1:
10:80 or the molybdenum source, phosphorus source, carbon source and sodium chloride mass ratio be 1:1:10:100.
More specifically, the abundant dissolution in order to realize molybdenum source, it can be using stirring, ultrasonic treatment.In one embodiment, will
It includes: that water first is added in the molybdenum source, phosphorus source and carbon source that the molybdenum source, phosphorus source, carbon source and sodium chloride, which are dissolved in the step in solvent,
In solvent, it is stirred by ultrasonic 10~30min (molybdenum source, phosphorus source and carbon source are substantially completely dissolved in aqueous solvent at this time), adds chlorine
Change sodium and continue 2~10h of stirring, to form the mixed solution sufficiently dissolved.
In one embodiment, the drying process in above-mentioned steps S03 is freeze-drying process.Specifically, described cold
Freezing the step of being dried includes: that the mixed solution is first freezed to 20~28h under conditions of -20~-50 DEG C, then will
Product vacuum after frost is freeze-dried 64~80h.It can preferably recrystallize to form porous two-dimensional sheet structure under this condition.
Precursor powder can be obtained in grinding after freeze-drying process.
In one embodiment, the temperature of the calcination processing in above-mentioned steps S04 is 700~1000 DEG C；The calcination processing
Time be 1~5h；Preferably, during calcination processing, temperature is heated up with the heating rate of 1~10 DEG C/min.And institute
It states calcination processing to carry out in an inert atmosphere, inert atmosphere is generally nitrogen or argon gas.
It in one embodiment, include: to use the product after the calcination processing the step of cleaning treatment in above-mentioned steps S04
Water filters 1~5 time.Phosphating sludge/carbon surface of solids package sodium chloride can be cleaned well so specifically to be filtered with water
The method that can be suction filtration or centrifugal filtration or ultrasound filtration, (using silver nitrate to washing until sodium chloride is cleaned completely
Chloride ion is detected in water afterwards).
It preferably, further include vacuum drying after the cleaning treatment the step of.Specifically, described vacuum drying
Temperature is 40~80 DEG C；The vacuum drying time be 6~for 24 hours.It in this way can be by phosphating sludge/carbon composite after cleaning
Middle moisture is sufficiently dry.
The preparation method of the composite material of above-mentioned porous flake phosphating sludge/carbon provided in an embodiment of the present invention, using it is low at
Originally, sodium chloride that is environmental-friendly and facilitating removal is template, PH of the whole process without severe toxicity3Equal gases generate, and can get super
Thin sheet phosphating sludge/carbon composite, entire production process is safe and reliable, and process conditions are simple and easy to control, production cost is low, fits
In industrialization large-scale production.Corresponding performance detection is carried out to the final product of acquisition, specifically includes XRD, SEM, EDS, BET
There is phosphating sludge partial size small (average diameter 10nm), purity with TEM characterization and the test of electrochemistry Hydrogen Evolution Performance, the composite material
High, the features such as effective ratio area is big, and the catalytic activity of similar platinum is shown, therefore can be widely applied to liberation of hydrogen plus hydrogen, hydrogen
The catalytic fields such as solution, hydrogen reduction, carrier.
On the other hand, the embodiment of the present invention also provides a kind of composite material of porous flake phosphating sludge/carbon, the composite material
It is made by the preparation method of the composite material of above-mentioned porous flake phosphating sludge/carbon of the embodiment of the present invention.
The porous flake phosphatization that the preparation method of porous flake phosphating sludge/carbon composite material of the embodiment of the present invention obtains
Molybdenum/carbon composite has the characteristics that phosphating sludge partial size is small, with high purity, effective ratio area is big, and shows the good of similar platinum
Good catalytic activity, can be widely applied to catalytic field.
Specifically, the composite material of the porous flake phosphating sludge/carbon is used for liberation of hydrogen catalyst.In one embodiment, should
Phosphating sludge average diameter of particles in composite material is 10nm.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
A kind of preparation method of porous flake phosphating sludge/carbon composite, comprising the following steps:
(1) 100mg Ammonium Molybdate Tetrahydrate, 100mg ammonium dihydrogen phosphate, 1000mg dicyan diamino are dissolved in 50mL deionization by
In water, stirring, ultrasound continue stir about 30 minutes to being completely dissolved, obtain the first mixed solution；
(2) sodium chloride of 3000mg is added in the solution that is obtained to step (1), stirs to being completely dissolved, continues stirring 3
Hour, obtain the second mixed solution；
(3) the second mixed solution is put into -30 DEG C of refrigerator cabinet freezer and freezes 24 hours by, then by the production after frost
Object is placed in vacuum freeze drier, is freeze-dried 72 hours, and dry solid powder is obtained, and is ground 10 minutes；
(4) precursor after drying is placed in nitrogen atmosphere and carries out calcination processing by, and the heating rate of calcining is 5 DEG C/
Min is warming up to 900 DEG C, and the calcining at constant temperature 3h at 900 DEG C, subsequent natural cooling.
(5) takes out solid after cooling, is washed 4 times with the method for suction filtration, ultrasound to product.Product is collected, and true
70 DEG C drying 12 hours in empty drying box.
Embodiment 2
A kind of preparation method of porous flake phosphating sludge/carbon composite, comprising the following steps:
(1) 100mg Ammonium Molybdate Tetrahydrate, 100mg ammonium dihydrogen phosphate, 1000mg dicyan diamino are dissolved in 50mL deionization by
In water, stirring, ultrasound continue stir about 30 minutes to being completely dissolved, obtain the first mixed solution；
(2) sodium chloride of 1000mg is added in the solution that is obtained to step (1), stirs to being completely dissolved, continues stirring 3
Hour, obtain the second mixed solution；
(3) the second mixed solution is put into -30 DEG C of refrigerator cabinet freezer and freezes 24 hours by, then by the production after frost
Object is placed in vacuum freeze drier, is freeze-dried 72 hours, and dry solid powder is obtained, and is ground 10 minutes；
(4) precursor after drying is placed in nitrogen atmosphere and carries out calcination processing by, and the heating rate of calcining is 5 DEG C/
Min is warming up to 900 DEG C, and the calcining at constant temperature 3h at 900 DEG C, subsequent natural cooling.
(5) takes out solid after cooling, is washed 4 times with the method for suction filtration, ultrasound to product.Product is collected, and true
70 DEG C drying 12 hours in empty drying box.
Embodiment 3
A kind of preparation method of porous flake phosphating sludge/carbon composite, comprising the following steps:
(1) 100mg Ammonium Molybdate Tetrahydrate, 100mg ammonium dihydrogen phosphate, 1000mg dicyan diamino are dissolved in 50mL deionization by
In water, stirring, ultrasound continue stir about 30 minutes to being completely dissolved, obtain the first mixed solution；
(2) sodium chloride of 8000mg is added in the solution that is obtained to step (1), stirs to being completely dissolved, continues stirring 3
Hour, obtain the second mixed solution；
(3) the second mixed solution is put into -30 DEG C of refrigerator cabinet freezer and freezes 24 hours by, then by the production after frost
Object is placed in vacuum freeze drier, is freeze-dried 72 hours, and dry solid powder is obtained, and is ground 10 minutes；
(4) precursor after drying is placed in nitrogen atmosphere and carries out calcination processing by, and the heating rate of calcining is 5 DEG C/
Min is warming up to 900 DEG C, and the calcining at constant temperature 3h at 900 DEG C, subsequent natural cooling.
(5) takes out solid after cooling, is washed 4 times with the method for suction filtration, ultrasound to product.Product is collected, and true
70 DEG C drying 12 hours in empty drying box.
Comparative example
A kind of preparation method of phosphating sludge/carbon composite (sodium chloride template is not added), comprising the following steps:
(1) 100mg Ammonium Molybdate Tetrahydrate, 100mg ammonium dihydrogen phosphate, 1000mg dicyan diamino are dissolved in 50mL deionization by
In water, stirring, ultrasound continue stir about 30 minutes to being completely dissolved, obtain mixed solution；
(2) mixed solution is put into -30 DEG C of refrigerator cabinet freezer and freezes 24 hours by, then puts the product after frost
It sets in vacuum freeze drier, is freeze-dried 72 hours, obtain dry solid powder, grind 10 minutes；
(3) precursor after drying is placed in nitrogen atmosphere and carries out calcination processing by, and the heating rate of calcining is 5 DEG C/
Min, is warming up to 900 DEG C, and the calcining at constant temperature 3h at 900 DEG C, and subsequent natural cooling obtains target product.
Performance test
Corresponding performance detection is carried out to the final product that embodiment 1-3 and comparative example obtain, specifically include XRD, SEM,
EDS and TEM characterization and the test of electrochemistry Hydrogen Evolution Performance.
(1) XRD is tested
The final product of acquisition is tested according to the standard that conventional XRD is tested, test result is as shown in Fig. 1.
As can be known from Fig. 1, compared with phosphating sludge standard diffraction peak map PDF#24-0771 it is found that the embodiment of the present invention 1,
2,3 and comparative example synthesis phosphating sludge XRD diffraction maximum can be corresponding with standard spectrum, on the one hand prove the embodiment of the present invention 1 obtain
The final product obtained is the phosphatization molybdenum material of high-purity, on the other hand also illustrates that sodium chloride will not influence phosphating sludge in synthesis process
Object phase.
(2) SEM is tested
According to the mode of operation that conventional SEM is scanned, SEM sweep test carried out to the final product of embodiment 1, and to its into
Row EDS test, specific test result such as Fig. 2.SEM sweep test, specific test result are carried out to the final product of embodiment 2
Such as Fig. 3.SEM sweep test, specific test result such as Fig. 4 are carried out to the final product of embodiment 3.Meanwhile most to comparative example
Final product carries out SEM sweep test, test result Fig. 5.
From the SEM of Fig. 2 figure it is found that the final product that the preparation method of the embodiment of the present invention 1 obtains is the phosphorus of porous flake
Change molybdenum/carbon composite, can be seen that molybdenum, phosphorus, carbon are uniformly distributed from EDS result, illustrate that phosphating sludge particle uniform load exists
In carbon substrate.From Fig. 3 and Fig. 4 it is found that the NaCl of different quality is added, to 3 phosphating sludges of embodiment 2 and example/carbon material pattern
It is affected with structure, finally influences its catalytic performance.As can be seen from Figure 5, comparative example is added without sodium chloride mould in the synthesis process
Plate, obtained product reunite sintering seriously, have very with the product morphology of sodium chloride template and structure are added in embodiment 1,2 and 3
Big difference illustrates that sodium chloride template plays key effect during synthesizing phosphating sludge/carbon composite of porous flake.
(3) TEM is tested
Fig. 6 is phosphating sludge/carbon TEM figure prepared by embodiment 1, be can be seen that from TEM figure, phosphating sludge average diameter of particles is big
About 10nm, it is more uniform be covered with super-thin sheet-shaped it is carbon-based on, further demonstrate the embodiment of the present invention 1 preparation phosphatization
Molybdenum/carbon composite contains a large amount of two-dimensional sheet structure.
(4) BET is tested
Fig. 7 is the N of embodiment 1 and comparative example2Adsorption desorption curve, from Fig. 7 a it is found that the specific surface area of embodiment 1 is
175.9m2 g-1, the specific surface area of Fig. 7 b display comparative example is 69.7m2 g-1.Therefore, it is added in MoP/C synthesis process
NaCl can dramatically increase the specific surface area of obtained product, be conducive to the active site for increasing catalyst, and then improve catalysis and live
Property.
(5) catalytic hydrogen evolution is tested
Conventionally, porous flake phosphating sludge/carbon composite that embodiment 1,2,3 and comparative example obtain is used for
Acid evolving hydrogen reaction, and its polarization curve is tested, it is specific that test results are shown in figure 8.
As it can be observed in the picture that when current density is 10mA cm-2When, overpotential is only 0.126V, illustrates that the embodiment of the present invention 1 obtains
Porous flake phosphating sludge/carbon composite the Hydrogen Evolution Performance obtained is more than existing base metal evolving hydrogen reaction catalyst, performance
The catalytic performance similar with noble metal catalyst out.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of the composite material of porous flake phosphating sludge/carbon, which comprises the steps of:
Molybdenum source, phosphorus source, carbon source and sodium chloride are provided；
The molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in aqueous solvent, mixed solution is obtained；
The mixed solution is dried, precursor powder is obtained；
The precursor powder is subjected to calcination processing, then cleaning treatment, obtains porous flake phosphating sludge/carbon composite wood
Material.
2. the preparation method of the composite material of porous flake phosphating sludge/carbon as described in claim 1, which is characterized in that described
Being dried is freeze-drying process.
3. the preparation method of the composite material of porous flake phosphating sludge/carbon as claimed in claim 2, which is characterized in that described
The step of freeze-drying process includes: that the mixed solution is first freezed to 20~28h under conditions of -20~-50 DEG C, then will
Product vacuum after frost is freeze-dried 64~80h.
4. the preparation method of the composite material of porous flake phosphating sludge/carbon as described in claim 1, which is characterized in that described
The temperature of calcination processing is 700~1000 DEG C；And/or
The time of the calcination processing is 1~5h；And/or
The heating rate of the calcination processing is 1~10 DEG C/min；And/or
The calcination processing carries out in an inert atmosphere.
5. the preparation method of the composite material of porous flake phosphating sludge/carbon as described in claim 1, which is characterized in that by institute
It states in the step of molybdenum source, phosphorus source, carbon source and sodium chloride are dissolved in aqueous solvent, the mass ratio of the molybdenum source, phosphorus source, carbon source and sodium chloride
For 1:1:10:(10~100)；And/or
It includes: first by the molybdenum source, phosphorus source and carbon that the molybdenum source, phosphorus source, carbon source and sodium chloride, which are dissolved in the step in aqueous solvent,
Source is added in aqueous solvent, and 10~30min is stirred by ultrasonic, adds sodium chloride and continues 2~10h of stirring；And/or
The step of cleaning treatment includes: to filter the water of the product after the calcination processing 1~5 time.
6. the preparation method of the composite material of porous flake phosphating sludge/carbon as described in any one in claim 1-5, feature exist
In the molybdenum source is at least one of Ammonium Molybdate Tetrahydrate, sodium molybdate, potassium molybdate, zinc molybdate and molybdic acid；And/or
Phosphorus source is at least one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, dibastic sodium phosphate and potassium dihydrogen phosphate；And/or
The carbon source is at least one of dicyan diamino and melamine.
7. the preparation method of the composite material of porous flake phosphating sludge/carbon as described in any one in claim 1-5, feature exist
In, the cleaning treatment the step of after, further include vacuum drying.
8. the preparation method of the composite material of porous flake phosphating sludge/carbon as claimed in claim 7, which is characterized in that described
Vacuum drying temperature is 40~80 DEG C；And/or
The vacuum drying time be 6~for 24 hours.
9. a kind of composite material of porous flake phosphating sludge/carbon, which is characterized in that described in any item more by claim 1-8
The preparation method of hole sheet phosphating sludge/carbon composite material is made.
10. the composite material of porous flake phosphating sludge/carbon as claimed in claim 9, which is characterized in that the porous flake phosphorus
Change molybdenum/carbon composite material and is used for catalyst.
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| CN111304783A (en) * | 2020-02-19 | 2020-06-19 | 东华大学 | Molybdenum phosphide/carbon nanofiber composite material and preparation method and application thereof |
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| CN113457656A (en) * | 2021-06-25 | 2021-10-01 | 中北大学 | Molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme, preparation method and application |
| CN113457656B (en) * | 2021-06-25 | 2023-01-31 | 中北大学 | Molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme, preparation method and application |
| CN113584502A (en) * | 2021-07-28 | 2021-11-02 | 青岛科技大学 | Preparation and application of molybdenum phosphide-ruthenium phosphide bimetal phosphide |
| CN113584502B (en) * | 2021-07-28 | 2022-07-01 | 青岛科技大学 | Preparation and application of molybdenum phosphide-ruthenium phosphide bimetal phosphide |
| CN115874138A (en) * | 2021-09-27 | 2023-03-31 | 中国科学院福建物质结构研究所 | Molybdenum-based composite material and preparation and application thereof |
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