CN107790164A - Porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping and preparation method thereof - Google Patents
Porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping and preparation method thereof Download PDFInfo
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- CN107790164A CN107790164A CN201710947923.1A CN201710947923A CN107790164A CN 107790164 A CN107790164 A CN 107790164A CN 201710947923 A CN201710947923 A CN 201710947923A CN 107790164 A CN107790164 A CN 107790164A
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- carbon coating
- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000010949 copper Substances 0.000 title claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 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 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 7
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 7
- 230000033228 biological regulation Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 22
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 125000005842 heteroatom Chemical group 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000010953 base metal Substances 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 102100031478 C-type natriuretic peptide Human genes 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 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
- 239000002002 slurry Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- -1 Nie Chemical compound 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/50—
-
- B01J35/60—
-
- 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
- B01J37/06—Washing
-
- 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
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses porous carbon coating copper phosphide composite catalyst of a kind of nitrogen-phosphor codoping and preparation method thereof, it is related to composite catalyst and electro-catalysis technical field.The composite catalyst is with nitrogen phosphorus double heteroatoms mixed matching copper base metal organic framework materials（It is abbreviated as：Cu‑NPMOF）A kind of porous carbon coating copper phosphide electro-catalysis of compound nitrogen-phosphor codoping is prepared for for presoma and produces hydrogen catalyst, for efficient electrolysis aquatic products hydrogen.In 0.5 mol L‑1Sulfuric acid electrolyte in, when current density reaches 10 mA cm‑2When, its overpotential of hydrogen evolution is 89 mV, has relatively low liberation of hydrogen overpotential.And the catalyst remains to keep higher catalytic activity after multiple loop test, has stronger stability, has higher actual application value.
Description
Technical field
The present invention relates to composite catalyst and electro-catalysis technical field, and in particular to a kind of porous carbon coating of nitrogen-phosphor codoping
Copper phosphide composite catalyst and preparation method thereof.
Background technology
In global industry development, the today's society of fossil energy worsening shortages, hydrogen as a kind of high-energy-density and
The renewable energy source carrier of clean environment firendly, meet very much the following energy demand to globalize so as to receive worldwide internal medicine
The extensive concern of scholar.At present, ripe commercial liberation of hydrogen catalyst be mainly precious metal material (such as：Platinum etc.), but it is high
High cost and low reserves seriously limit the extensive use of such material.
It is widely used in dehydrogenation and adds the transition metal phosphide material of sulphur process due to good conductance and moderate
Hydrogen energy of adsorption and stronger ph stability receive the very big concern of catalysis production hydrogen field researcher, and near
There is within several years the research report of increasing such production hydrogen catalyst.But most of such liberation of hydrogen catalysis at present
Agent research is concentrated on the metallic elements such as iron, cobalt, Nie, Molybdenum.By comparison, copper is a kind of cheap, and earth's crust reserves are more
Add abundant transition metal, but the transition metal phosphide (Cu based on copper3P) material this aspect research also
It is fewer.In addition, porous carbon is wide because of advantages such as its unique loose structure, high conductivity, high-specific surface area and high stabilities
It is general to be applied to the research fields such as catalysis, adsorbing separation and energy storage.Porous carbon materials and transition metal phosphide nano particle
It is compound, can greatly enhance its catalytic performance further combined with the double dominant of the two, extend its application.
Metal-organic framework material (MOFs) be fast development in recent years a metal ion species and organic ligand by with
The crystalline state porous material that hyte dress is constructed.Due to the diversity of its structure, the controllability of construction unit and crystalline state MOFs materials
The uniform sequential distribution of each element in material, therefore, porous carbon is prepared by pyrolysis processing using MOFs as presoma or from template is sacrificed
Base compound material is increasingly subject to the concern of scientist.However, it has been reported that it is a large amount of using various MOFs as presoma prepare
In the research of catalysis material, selected MOF presomas are mainly：ZIF-8/ZIF-67, MOF-5, HKUST-1, MIL-101 etc.
The MOFs structures for assembling to obtain by single part and metal ion.Therefore, except pair it has been reported that using various conventional MOF before
Drive body to prepare outside composite catalyst progress more in-depth study exploration, by reasonably selecting by including more hetero atoms
(such as：Nitrogen phosphate and sulfur etc.) the MOFs that constructs of mixed ligand be presoma to prepare efficient compound production hydrogen catalyst be current
One extremely important research direction.
The content of the invention
It is an object of the invention to provide a kind of copper phosphide nanometer of new nitrogen-phosphor codoping porous carbon materials parcel
Particles dispersed type electro-catalysis production hydrogen catalyst is (referred to as：Cu3P@NPPC)；Another object is the preparation side for providing the catalyst
Method.
To realize the purpose of the present invention, the present invention from two kinds of parts of pyrazine and 1-hydroxy ethylidene-1,1-diphosphonic acid cheap and easy to get with
Nitrogen phosphorus double heteroatoms mixed matching copper base metal-organic framework materials that copper nitrate is constructed (are abbreviated as：Cu-NPMOF) it is presoma
A kind of compound electro-catalysis production hydrogen catalyst is prepared for, for efficient electrolysis aquatic products hydrogen.
The preparation method of the efficiently electro-catalysis production hydrogen catalyst is as follows：
(1) it is respectively that pyrazine, 1-hydroxy ethylidene-1,1-diphosphonic acid, soluble copper salt is soluble in water, add the pH value of alkali regulation solution
For 3-5,130-140 DEG C of isothermal reaction, after reaction terminates, turbid solution is obtained after system temperature is down to room temperature.
(2) turbid solution obtained in step (1) is filtered, it is neutral to be washed repeatedly with deionized water to filtrate, is obtained
Solid is required Cu-NPMOF presomas after drying.
(3) the Cu-NPMOF presomas obtained by step (2) are calcined under nitrogen atmosphere, black powder is obtained, through watery hydrochloric acid
Supersound washing, then it is centrifuged repeatedly washing for several times with deionized water and ethanol, solid powder is obtained after drying.
(4) black powder obtained in step (3) is mixed with sodium hypophosphite, forged under nitrogen atmosphere after being fully ground
Burn, gained black powder is washed with deionized, centrifuged, obtaining target product after drying.
The mol ratio of preferred pyrazine, copper nitrate and 1-hydroxy ethylidene-1,1-diphosphonic acid is 1 in step (1)：1：1.3, sodium hydroxide is adjusted
The pH value for saving solution is 3.
Step (3) heating rate is 10 DEG C/min, and the temperature of presoma calcining is 600-700 DEG C.
In step (4), the mass ratio that black powder and sodium hypophosphite are obtained in (3) is 1：8-12, preferably 1：10, calcining temperature
Spend for 200-300 DEG C, heating rate is 10 DEG C/min.
The soluble copper salt is any of copper nitrate, copper chloride, copper sulphate.
The alkali of the regulation pH value selects sodium hydroxide or potassium hydroxide.
Application of the composite as catalyst, mainly in terms of electrocatalytic decomposition aquatic products hydrogen.
Above-mentioned application process is as follows：The copper phosphide composite material loaded with prepared nitrogen-phosphor codoping porous carbon materials
Expect the catalyst as working electrode, the test of its catalytic hydrogen evolution reactivity worth is used for using three-electrode system.With silver-silver chloride
(Ag/AgCl) electrode be reference electrode, graphite rod be auxiliary electrode, 0.5mol L-1Aqueous sulfuric acid is electrolyte.
The invention has the advantages that：
The electrocatalytic hydrogen evolution material is with new nitrogen phosphorus double heteroatoms mixed matching copper base metal-organic framework materials (Cu-
NPMOF it is) presoma, the compound catalysis material of copper phosphide of the porous carbon coating of nitrogen-phosphor codoping prepared by carbonization, phosphatization
Material.Carbon-based framework has high specific surface area, with micropore, mesoporous, macropore and the multistage pore property deposited.These structural advantages can be with
Bigger contact area, the more avtive spots of exposure, there is provided more preferable mass transfer channel, while nitrogen, phosphorus etc. are provided for catalyst
Doping of the hetero atom in carbon matrix can increase the avtive spot of catalyst, improve the electric conductivity of catalyst so as to further carry
Rise its catalytic activity.With reference to the catalysis advantage of metal phosphide, the two effectively compound electricity for further improving material is urged
Change activity, there is important value and realistic meaning in electro-catalysis production hydrogen research field.
Brief description of the drawings
Fig. 1 is powder x-ray diffraction (PXRD) collection of illustrative plates and monocrystalline mould of Cu-NPMOF presomas synthesized in step (1)
Intend PXRD collection of illustrative plates comparison diagrams；Wherein, the 1 PXRD spectrums to be simulated by single crystal data；2 compose for the Cu-NPMOF of synthesis PXRD.
Fig. 2 is the catalyst Cu prepared by the present invention3P@NPPC powder x-ray diffraction (PXRD) phenogram, wherein 1 is
The Cu obtained by inorganic crystal data place3The PXRD spectrums that P standard cards are simulated；2 be the catalyst Cu prepared by the present invention3P@
NPPC PXRD spectrums.
Fig. 3 is the transmission electron microscope picture (a, b) of the catalyst amplification different multiples prepared by the present invention, and (c) is catalyst
Constituency element Surface scan (Mapping) electron microscope.
Fig. 4 is nitrogen adsorption isotherm of the catalyst at a temperature of 77K prepared by the present invention, and illustration is according to absorption etc.
The pore size distribution curve for the catalyst that warm line computation goes out.
Fig. 5 is the high-resolution-ration transmission electric-lens figure of the catalyst prepared by the present invention, in figure 1 be outer cladding carbon substrate layer, 2
For by the lattice diffraction fringe of the copper phosphide nano particle of carbon coating.
Fig. 6 is for the catalyst prepared by the present invention as working electrode active material in 0.5mol L-1Sulfuric acid solution center line
Property scanning polarization curve, wherein 1 be blank electrode polarization curve, 2 be catalyst of the present invention polarization curve.
Fig. 7 is the Tafel slope curve of the prepared catalyst of the present invention fitted by Fig. 6 polarization curves.
Fig. 8 is for the catalyst prepared by the present invention as working electrode active material in 0.5mol L-1Passed through in sulfuric acid solution
The linear scan polarization curve crossed before and after 3000 circle cyclic voltammetries, wherein sublinear scans polarization curve headed by 1,2 be this
Linear scan polarization curve after invention catalyst circulates 3000 times.
Embodiment
Below by example, the present invention is described further：
Embodiment 1：Synthesize the compound electro-catalysis production hydrogen catalyst of nitrogen-phosphor codoping porous carbon materials cladding copper phosphide.
(1) 0.52g Gerhardites and 0.55g 1-hydroxy ethylidene-1,1-diphosphonic acids and 0.16g pyrazines are dissolved in 20mL
In ionized water, the pH value that sodium hydroxide regulation system is added in above-mentioned solution is 3.Then it is stirred at reflux under the conditions of 140 DEG C
6h obtains blue turbid solution.It is filtered, filtrate is washed to as neutrality, and presoma (Cu-NPMOF) blueness is obtained after vacuum drying
Solid powder.The PXRD of presoma as shown in figure 1, prepared presoma have very strong diffraction maximum and with single crystal data mould
The PXRD peaks for intending obtaining almost fit like a glove, and show that prepared presoma has very high crystallinity and purity.
(2) blue solid powder will be obtained in 200mg steps (1) to be placed in quartz boat, quartz boat is placed on tube furnace
It is interior, first lead to nitrogen 30min and drain furnace air, then tube furnace is warming up to 650 with 10 DEG C/min speed under nitrogen atmosphere
DEG C, and in 650 DEG C of calcining at constant temperature 4h.Room temperature is naturally cooled to, obtained black porous solid is through watery hydrochloric acid supersound washing, then
Washing is centrifuged repeatedly with deionized water and ethanol for several times, and black solid powder is obtained after drying and grinding.
(3) by gained black solid powder in step (2) and sodium hypophosphite mixed grinding it is uniform after be placed in quartz boat, will
Quartz boat is placed in tube furnace, is first led to nitrogen 30min and is drained furnace air, then under nitrogen atmosphere tube furnace with 10 DEG C/
Min speed is warming up to 250 DEG C, and in 250 DEG C of calcining at constant temperature 2h.Room temperature is naturally cooled to, obtained dark gray solid is spent
Ionized water and ethanol are centrifuged repeatedly washing for several times, and final catalyst (Cu is obtained after drying and grinding3P@NPPC).(2) gained is black in
The mass ratio of color solid powder and sodium hypophosphite is 1：10.
(4) sign of nitrogen-phosphor codoping porous carbon materials cladding copper phosphide compound material：
The PXRD of prepared composite is as shown in Fig. 2 the characteristic peak of resulting materials characterizes card with JCPDS in collection of illustrative plates
No.71-2261 Cu3P is consistent, and belongs to hexagonal system structure.Transmission electron microscope and element Surface scan (Mapping) such as Fig. 3 institutes
Show, resulting materials are loose porous structure, and many nano particles are loaded in loose matrix.The bright institute of element Surface scan chart
Carbon, nitrogen, phosphorus, oxygen, copper in material is obtained to be evenly distributed.Nitrogen adsorption result is as shown in figure 4, show resulting materials with very high
Nitrogen adsorption capacity, specific surface area is larger, and has micropore, mesoporous, macropore and the multistage porous deposited.High-resolution-ration transmission electric-lens
As shown in figure 5, being loaded with copper phosphide nano particle in carbon matrix, and wrapped up by carbon-coating.
Embodiment 2：Nitrogen-phosphor codoping porous carbon materials of the present invention coat copper phosphide compound material as elctro-catalyst
Performance test.
The preparation of elctro-catalyst working electrode：
By 2mg Cu produced by the present invention3P@NPPC catalyst is added in 400uL ethanol and the mixed solution of 80uL deionized waters,
The Nafion solution that 20uL mass percents are 5% is added, finely dispersed catalyst slurry is obtained after ultrasonic disperse 30min.
5uL slurry drops are coated on glass-carbon electrode and are dried at room temperature for stand-by.Elctro-catalyst performance test uses three-electrode system, electricity
Solution liquid is 0.5mol L-1Sulfuric acid solution.Tester is Shanghai morning China CHI660E electrochemical workstations.
As shown in fig. 6, in 0.5mol L-1Sulfuric acid electrolyte in, be loaded with the electrode of catalyst have it is clearly electric
Catalytic hydrogen evolution property.Compared with blank electrode, significant effect enhancing.When current density reaches 10mA cm-2When, its liberation of hydrogen is excessively electric
Position is -89mV, has relatively low liberation of hydrogen overpotential.
As shown in fig. 7, the catalyst has relatively low Tafel slope (76mv/dec), show that there is faster electricity to urge for it
Change kinetics.And Tafel slope indicates the machine of the catalyst electrocatalytic hydrogen evolution between 40-120mv/dec
It is the ratedeterming step of the catalyst electrocatalytic hydrogen evolution to manage as Volmer-Heyrovsky mechanism, Heyrovsky steps.
As shown in figure 8, the catalyst is in 0.5mol L-1By the line before and after 3000 circle cyclic voltammetries in sulfuric acid solution
Property scanning polarization curve do not change obviously, show after multiple cyclic voltammetry the catalyst remain to keep compared with
High catalytic activity, there is stronger stability, there is higher actual application value.
Claims (8)
1. a kind of porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping, it is characterised in that make by the following method
It is standby to form：
（1）Respectively that pyrazine, 1-hydroxy ethylidene-1,1-diphosphonic acid, soluble copper salt is soluble in water, the pH value for adding alkali regulation solution is 3-
5,130 DEG C of -140 DEG C of isothermal reactions, after reaction terminates, turbid solution is obtained after system temperature is down to room temperature；
（2）By step（1）In obtained turbid solution filtering, it is neutral to be washed repeatedly with deionized water to filtrate, obtains solid
Cu-NPMOF presomas are obtained after drying；
（3）Under nitrogen atmosphere by step（2）The Cu-NPMOF presomas calcining of gained, obtains powder through watery hydrochloric acid supersound washing,
Then washing is centrifuged repeatedly with deionized water and ethanol, solid powder is obtained after drying；
（4）By step（3）In obtained powder mixed with sodium hypophosphite, calcined under nitrogen atmosphere after being fully ground, gained powder
End is washed with deionized, centrifuged, obtaining target product after drying.
2. the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as claimed in claim 1, it is characterised in that
Step（1）The mol ratio of middle pyrazine, soluble copper salt and 1-hydroxy ethylidene-1,1-diphosphonic acid is 1：1：1.3, the regulation pH value
Alkali selects sodium hydroxide or potassium hydroxide.
3. the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as claimed in claim 1, it is characterised in that step
Suddenly（3）Heating rate is 10 DEG C/min, and the temperature of presoma calcining is 600-700 DEG C；Step（4）Middle powder and sodium hypophosphite
Mass ratio be 1：8-12, heating rate are 10 DEG C/min, and calcining heat is 200-300 DEG C.
4. the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as described in one of claim 1-3, its
It is characterised by, the soluble copper salt selects a kind of in copper nitrate, copper chloride, copper sulphate.
5. preparing the method for the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping described in claim 1, it is special
Sign is, realizes by the following method：
（1）Respectively that pyrazine, 1-hydroxy ethylidene-1,1-diphosphonic acid, soluble copper salt is soluble in water, the pH value for adding alkali regulation solution is 3-
5,130 DEG C of -140 DEG C of isothermal reactions, after reaction terminates, turbid solution is obtained after system temperature is down to room temperature；
（2）By step（1）In obtained turbid solution filtering, it is neutral to be washed repeatedly with deionized water to filtrate, obtains solid
Cu-NPMOF presomas are obtained after drying；
（3）Under nitrogen atmosphere by step（2）The Cu-NPMOF presomas calcining of gained, obtains powder through watery hydrochloric acid supersound washing,
Then washing is centrifuged repeatedly with deionized water and ethanol, solid powder is obtained after drying；
（4）By step（3）In obtained powder mixed with sodium hypophosphite, calcined under nitrogen atmosphere after being fully ground, gained powder
End is washed with deionized, centrifuged, obtaining target product after drying.
6. the preparation method of the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as claimed in claim 5, its
It is characterised by, step（1）The mol ratio of middle pyrazine, soluble copper salt and 1-hydroxy ethylidene-1,1-diphosphonic acid selects 1：1：1.3, the regulation pH
The alkali of value selects sodium hydroxide or potassium hydroxide.
7. the preparation method of the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as claimed in claim 5, its
It is characterised by, step（3）Heating rate is 10 DEG C/min, and the temperature of presoma calcining is 600-700 DEG C；Step（4）Middle powder
The mass ratio of end and sodium hypophosphite is 1：8-12, heating rate are 10 DEG C/min, and calcining heat is 200-300 DEG C.
8. the system of the porous carbon coating copper phosphide composite catalyst of nitrogen-phosphor codoping as described in one of claim 5-7
Preparation Method, it is characterised in that the soluble copper salt selects a kind of in copper nitrate, copper chloride, copper sulphate.
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