CN110433860A - A kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material and preparation method thereof - Google Patents
A kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material and preparation method thereof Download PDFInfo
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- CN110433860A CN110433860A CN201910626729.2A CN201910626729A CN110433860A CN 110433860 A CN110433860 A CN 110433860A CN 201910626729 A CN201910626729 A CN 201910626729A CN 110433860 A CN110433860 A CN 110433860A
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- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 75
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical class NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000013384 organic framework Substances 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 150000002500 ions Chemical class 0.000 description 10
- 239000013110 organic ligand Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- 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
-
- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
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Abstract
A kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material and preparation method thereof, belongs to catalysis material preparation technical field.The method comprises the following steps: the reaction solution that preparation pH value is 3.2: by phosphomolybdic acid, copper salt and 4- amino -4H-1,2,4- triazoles are dissolved into deionized water, stir 3h under normal temperature conditions, pH value is adjusted to 3.2 with sodium hydroxide solution and hydrochloric acid solution again, obtains reaction solution；Reaction solution is added in the reaction kettle of polytetrafluoroethylene (PTFE), is reacted 4 days at a temperature of 160 DEG C, cooled to room temperature obtains red octahedral crystal, as three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material.Advantages of the present invention are as follows: polyacid Base Metal organic framework materials easily form interpenetrating structure in the synthesis process, and catalysis material structure novel prepared by the present invention, fine and close, active site is more, are beneficial to improve electro-catalysis hydrolysis Hydrogen Evolution Performance.
Description
Technical field
The invention belongs to catalysis material preparation technical fields, and in particular to it is a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline state urge
Change material and preparation method thereof.
Background technique
With the increasingly consumption and the continuous aggravation of Environment pollution of fossil fuel, hydrogen is as a kind of clean renewable
The energy enters everybody eyes.The preparation method of hydrogen is varied, and studying more two methods at present is electro-catalysis
Aquatic products hydrogen and photocatalysis aquatic products hydrogen.The principle of Photocatalyzed Hydrogen Production is that catalyst by ultraviolet excitation generates electrons and holes, photoproduction
Electronics by external circuit be transferred to on electrode to by H2O is reduced into H2, and hole on catalyst electrode by H2O is oxidized to
O2.It is the H in solution that electro-catalysis, which produces hydrogen,+It is combined with the active site of catalyst and generates H2Process.Compared with Photocatalyzed Hydrogen Production
Electro-catalysis, which produces hydrogen, has the characteristics that preparation process is simple, product purity is high, environmentally protective, but traditional electro-catalysis produces hydrogen catalysis
Agent is expensive Pt noble metal catalyst, is not suitable for the large-scale production of factory, thus develop it is a kind of cheap,
Environmentally protective efficient liberation of hydrogen catalyst remains current a major challenge.
Summary of the invention
The problem of the purpose of the present invention is to solve existing production hydrogen catalyst higher costs, provides that a kind of three-dimensional is non-to pass through
Phosphomolybdic acid base copper crystalline catalysis material and preparation method thereof is worn, the catalysis material has good electro-catalysis H2-producing capacity.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material, the molecular formula of the catalysis material are CuI 5
[HPMoVI 9MoV 3O40][C2N4H4]6, wherein C2N4H4For 4- amino -4H-1,2,4- triazoles, crystallographic system is trigonal system, space
Group be P-31c, cell parameter be α=90 °, β=90 °, γ=120 °, Z=2.
A kind of preparation method of above-mentioned three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material, the method step is such as
Under:
Step 1: the reaction solution that preparation pH value is 3.2: by phosphomolybdic acid, copper salt and 4- amino -4H-1,2,4- tri-
Nitrogen azoles is dissolved into deionized water, stirs 3h under normal temperature conditions, then adjusted pH value with sodium hydroxide solution and hydrochloric acid solution
To 3.2, reaction solution is obtained；
Step 2: reaction solution is added in the reaction kettle of polytetrafluoroethylene (PTFE), reacted 4 days at a temperature of 160 DEG C, it is naturally cold
But to room temperature, red octahedral crystal is obtained, as three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material.
The present invention compared with the existing technology have the beneficial effect that polyacid Base Metal organic framework materials are easy in the synthesis process
Interpenetrating structure is formed, catalysis material structure novel prepared by the present invention, fine and close, active site is more, is beneficial to improve electro-catalysis water
Solve Hydrogen Evolution Performance.
Detailed description of the invention
Fig. 1 is the pattern schematic diagram of catalysis material prepared by the present invention under the microscope；
Fig. 2 be catalysis material prepared by the present invention dissymmetrical structure schematic diagram, wherein 1-C, 2-N, 3-P, 4-O, 5-Mo,
6-Cu；
Fig. 3 is the Cu ion of the different coordination environments of catalysis material prepared by the present invention, and is coordinated therewith respectively
N1, N2 atom and O8, i.e. metal-organic framework schematic diagram；
Fig. 4 is the coordination structure schematic diagram of single polyacid and organic ligand in catalysis material prepared by the present invention；
Fig. 5 is the coordination structure schematic diagram of single organic ligand and polyacid in catalysis material prepared by the present invention；
Fig. 6 is that the three-dimensional structure of catalysis material prepared by the present invention constitutes figure, wherein (a) is single polyacid molecule,
(b) it is metal organic frame, (c) is [PMoVI 9MoV 3O40]-The one-dimensional chain structure that anion and metal organic frame are constituted, (d)
It is (e) tomograph of compound for the two-dimensional layered structure of compound, (f) is three-dimensional knot of the compound on c-axis direction
Composition；
Fig. 7 is the infrared spectrogram of catalysis material prepared by the present invention；
Fig. 8 is that the PXRD of catalysis material prepared by the present invention schemes, wherein 1- experiment test map, 2- software simulate map；
Fig. 9 is cyclic voltammogram of the catalysis material prepared by the present invention under different scanning speed；
Figure 10 is the linear sweep voltammetry figure of catalysis material prepared by the present invention；
Figure 11 is the electrochemical AC impedance figure of catalysis material prepared by the present invention.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover within the protection scope of the present invention.
Polyacid, i.e. polyoxometallate (polyoxometalates, POMs) are a kind of inorganic multi-metal oxygen cluster compounds,
It is the metal-oxygen cluster class compound formed and being connect with oxygen atom by early transition metal ion (such as: V, Mo, W etc.), presses
It can be divided into isopolyacid and heteropoly acid (center hetero atom has P, B, Al, Co etc.) according to element composition, had based on its structure uniform
Nano-scale, composed structure adjustability and unique physicochemical property, have in research fields such as absorption, catalysis, biology, photoelectricity
Be widely applied.It is recycled since polyacid is dissolved in after water is unfavorable for reaction as catalyst, so polyacid sill causes extensively
General concern.The specific surface area of polyacid catalyst not only can be improved in catalysis material prepared by the present invention, can also realize that polyacid is being divided
Monodisperse in sub- level, realizes the homogeneous catalytic reaction of heterogeneous catalysis.Meanwhile transition metal atoms are due to its outermost layer
The d track of electronic shell is also easy to produce hole, is suitble to the absorption of hydrogen atom, and nitrogen azole compounds steric hindrance is small, and coordination site is more, coordination
Mode is flexible and changeable, the coordination structure of diversified high dimension easy to form, so selecting copper salt and 4- amino -4H-
1,2,4- triazole participates in reaction.
The preparation method of polyacid sill is varied, including room temperature filtration method, hydrothermal synthesis method and chemical deposition etc.
Refer to Deng, hydrothermal synthesis method and utilizes substance chemistry in aqueous solution under the conditions of temperature is 100~1000 DEG C, pressure is 1MPa~1GPa
React carried out synthesis.Under subcritical and supercritical water heat condition, since reaction is in molecular level, reactivity is improved,
Thus hydro-thermal reaction can substitute certain high temperature solid state reactions.Again due to the homogeneous nucleation and nonhomogen-ous nucleation mechanism of hydro-thermal reaction
It is different from the flooding mechanism of solid phase reaction, thus noval chemical compound and new material that other methods can not be prepared can be createed.It
The advantages of be products therefrom purity is high, good dispersion, granularity are easy to control, thus the present invention use hydrothermal synthesis method.
Specific embodiment 1: present embodiment record is a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material
Material, the molecular formula of the catalysis material are CuI 5[HPMoVI 9MoV 3O40][C2N4H4]6, wherein C2N4H4For 4- amino -4H-1,2,
4- triazole, crystallographic system are trigonal system, space group P-31c, and cell parameter is α=90 °, β=90 °, γ=120 °, Z=2.A, b, c are lattice parameters, indicate three sides of structure cell
Length, i.e. axial length.α, β, γ are shaft angles.Z indicates the number of asymmetric cell in structure cell.
Specific embodiment 2: three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in a kind of specific embodiment one
The preparation method of material, the method comprises the following steps:
Step 1: the reaction solution that preparation pH value is 3.2: by phosphomolybdic acid, copper salt and 4- amino -4H-1,2,4- tri-
Nitrogen azoles is dissolved into deionized water, stirs 3h under normal temperature conditions, then adjusted pH value with sodium hydroxide solution and hydrochloric acid solution
To 3.2, reaction solution is obtained；
Step 2: reaction solution is added in the reaction kettle of polytetrafluoroethylene (PTFE), reacted 4 days at a temperature of 160 DEG C, it is naturally cold
But to room temperature, red octahedral crystal is obtained, as three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material.
Catalysis material of the invention is by Keggin-type phosphomolybdic acid, 4- amino -4H-1,2,4- triazoles and copper salt
It is synthesized according to certain molar ratio by one step hydro thermal method, the result shows that, there is novel structure by single crystal X-ray diffraction
The 3 D stereo non-through structure of feature.It is directed to the redox property of polyacid simultaneously, in 0.5M H2SO4With 100mV/ in solution
The scanning speed of s has carried out the research of electro-catalysis H2-producing capacity to the catalysis material, the results showed that current density be -10mA
cm-2When corresponding potential be 0.593V.Powder x-ray diffraction the result shows that, pass through the synthetic method of step 1 and step 2, survey
The X-ray diffraction peak of examination and the single crystal X-ray diffraction peak of simulation are almost the same, show a large amount of monocrystal material purity of synthesis very
It is high.Electro-catalysis hydrolysis test shows that the catalysis material of preparation has certain Hydrogen Evolution Performance.
There are independent copper ions in two crystallography in the asymmetric cell structure of crystal prepared by the present invention, wherein
Cu1 ion be four-coordination, respectively with two [PMoVI 9MoV 3O40]-End oxygen atom O8 atom and two organic ligands in polyacid
4- amino -4H-1, the N1 Atomic coordinate in 2,4- triazoles, Cu2 ion are three-fold coordination, with organic ligand 4- amino -4H-1,
N2 Atomic coordinate in 2,4- triazoles.There are 6 oxygen atoms to participate in coordination in each polyacid molecule, and in each organic ligand
There are two nitrogen-atoms to participate in coordination.The one-dimentional structure of the crystal is by [a PMoVI 9MoV 3O40]-Polyoxoanion and 3 Cu1
Ion is connected and is formed, and Cu1 ion is in conplane [PMo with other againVI 9MoV 3O40]-Polyoxoanion connection, is constituted
Two-dimensional structure, so with the [PMo on third directionVI 9MoV 3O40]-Polyoxoanion is connected to form three-dimensional structure.
Specific embodiment 3: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the copper salt is copper chloride or copper nitrate.
Specific embodiment 4: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the molar ratio of the phosphomolybdic acid and copper salt is 0.1:0.4~0.9.
Specific embodiment 5: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the amount of the substance of the phosphomolybdic acid and the volume ratio of distilled water are 0.1mmol:10mL.
Specific embodiment 6: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the phosphomolybdic acid and 4- amino -4H-1, the molar ratio of 2,4- triazoles are 0.1:0.1.
Specific embodiment 7: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the phosphomolybdic acid is Keggin-type phosphomolybdic acid.
Specific embodiment 8: a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in specific embodiment two
The preparation method of material, in step 1, the concentration of hydrochloric acid solution is 0.1mol/L~2mol/L, the concentration of sodium hydroxide solution
For 0.1mol/L~2mol/L.
Specific embodiment 9: a kind of three-dimensional non-through of specific embodiment two to eight any specific embodiment preparation
The application of phosphomolybdic acid base copper crystalline catalysis material, the glass-carbon electrode modified through three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material
As elctro-catalyst in 0.5M H2SO4There is electro-catalysis H2-producing capacity in solution.
Embodiment 1:
A kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material, is completed by the following steps:
One, the reaction solution that preparation pH value is 3.2: 0.1mmol phosphomolybdic acid, 0.4~0.9mmol copper salt are dissolved into
In 10ml deionized water, then 0.1mol 4- amino -4H-1 is added into solution, 2,4- triazole organic ligands are reacted
Liquid: the pH value of reaction solution is adjusted to using 0.1mol/L~2mol/LHCl solution and 0.1mol/L~2mol/LNaOH solution
3.2, obtain the reaction solution that pH value is 3.2；
Two, the reaction solution that pH value is 3.2 is added in ptfe autoclave, is reacted 4 days at a temperature of 160 DEG C,
Cooled to room temperature obtains red octahedral crystal, sees Fig. 1, as three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material.
The X- single crystal diffraction structure elucidation number of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material manufactured in the present embodiment
According to being shown in Table 1, instrument is the ApexII single crystal diffractometer of Brooker company.
Table 1
aR1=∑ ║ Fo│─│Fc║/∑│Fo│,bwR2=∑ [w (Fo 2─Fc 2)2]/∑[w(Fo 2)2]1/2
By table 1 it is found that the chemical formula of the three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material of preparation is CuI 5
[HPMoVI 9MoV 3O40][C2N4H4]6, molecular formula H25C12N24O40PCu5Mo12, Cu chemical valence is+1 valence.As shown in Fig. 2, X- is penetrated
Line single crystal diffraction analysis shows, CuI 5[HPMoVI 9MoV 3O40][C2N4H4]6Dissymmetrical structure unit by one
[PMoVI 9MoV 3O40]-Polyoxoanion, 5 copper ions, 6 4- amino -4H-1,2,4- triazole organic ligands are constituted.Wherein
Cu1 ion exists in the form of four-coordination, respectively with the O8 atom in polyacid and the N1 Atomic coordinate in organic ligand, Cu2
Ion exists in the form of three-fold coordination, is coordinated with the N2 atom in organic ligand；Meanwhile Cu-O key bond distance isCu-N key bond distance isAll these bond distances are in reasonable range.Each metal
There are 5 copper ions, i.e. three Cu1 ions and two Cu2 ions in organic framework, if centered on Cu2 ion, three
Cu1 ion is spatially in 120 ° of angle respectively, sees Fig. 3.[PMoVI 9MoV 3O40]-Polyoxoanion and 31 ions of Ni metal
Alternating constitutes one-dimensional chain structure, sees Fig. 4.[PMoVI 9MoV 3O40]-By two positioned at same between polyoxoanion chain
Cu1 ion in plane is respectively connected with composition two-dimensional layered structure, sees Fig. 5.Between layers in the same way be located at
Third Cu1 ion on third direction connects and then constitutes tridimensional network, sees Fig. 6.Fig. 7 is urging for the preparation of embodiment 1
The infrared spectrogram for changing material, in 1058,974,863,793,619 ν (P-O), ν (Mo=Ot), ν as (Mo-Ob-Mo) and ν as
(Mo-Oc-Mo) stretching vibration；In 1680cm-1Vibration peak, belong to C=N double bond stretching vibration peak in organic ligand, in addition,
Vibration peak is in 3440cm-1Belong to the flexible peak of vibration of hydrone in compound.Fig. 8 is catalysis material prepared by embodiment 1
Powder x-ray diffraction figure, the analogue data that the measurement data and software of gained crystalline material are obtained according to normal structure weigh substantially
It closes, it was demonstrated that experiment gained crystalline material is parsed structure, and purity is higher.Fig. 9 is catalysis prepared by embodiment 1
The glass-carbon electrode of material modification is in 0.5M H2SO4The cyclic voltammogram under different scanning speed in solution, scanning range be-
0.1~0.6V, scanning speed be respectively 10mV/s, 20mV/s, 30mV/s, 40mV/s, 50mV/s, 60mV/s, 70mV/s,
80mV/s, 90mV/s, 100mV/s, and being continuously increased with scanning speed, the abscissa of three pairs of redox peaks is substantially not
Become, peak area uniformly increases, and illustrates that oxidation-reduction process has good invertibity, the average spike potential of three pairs of redox peaks
Respectively E (I)=- 0.020V, E (II)=0.204V, E (III)=0.354V.Figure 10 is catalysis material prepared by embodiment 1
The glass-carbon electrode of modification is in 0.5M H2SO4Linear Circulation voltammogram when scanning speed is 50mV/s in solution, as seen from the figure: In
Current density is -10mA/cm-2When corresponding overpotential be 0.593V.Figure 11 is catalysis material modification prepared by embodiment 1
Glass-carbon electrode is in 0.5M H2SO4The electrochemical AC impedance figure tested after multiple cyclic voltammetric in solution.
Claims (9)
1. a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material, it is characterised in that: the molecular formula of the catalysis material is
CuI 5[HPMoVI 9MoV 3O40][C2N4H4]6, wherein C2N4H4For 4- amino -4H-1,2,4- triazoles, crystallographic system is trigonal system,
Space group is P-31c, and cell parameter is α=90 °, β=90 °, γ=120 °, Z=2.
2. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material described in claim 1, feature exist
In: the method comprises the following steps:
Step 1: the reaction solution that preparation pH value is 3.2: by phosphomolybdic acid, copper salt and 4- amino -4H-1,2,4- triazoles
It is dissolved into deionized water, stirs 3h under normal temperature conditions, then be adjusted to pH value with sodium hydroxide solution and hydrochloric acid solution
3.2, obtain reaction solution；
Step 2: reaction solution is added in the reaction kettle of polytetrafluoroethylene (PTFE), reacts 4 days, naturally cool at a temperature of 160 DEG C
Room temperature is to get to three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material.
3. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the copper salt is copper chloride or copper nitrate.
4. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the molar ratio of the phosphomolybdic acid and copper salt is 0.1:0.4~0.9.
5. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the amount of the substance of the phosphomolybdic acid and the volume ratio of distilled water are 0.1mmol:10mL.
6. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the phosphomolybdic acid and 4- amino -4H-1, the molar ratio of 2,4- triazoles are 0.1:0.1.
7. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the phosphomolybdic acid is Keggin-type phosphomolybdic acid.
8. a kind of preparation method of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material according to claim 2, special
Sign is: in step 1, the concentration of hydrochloric acid solution is 0.1mol/L~2mol/L, and the concentration of sodium hydroxide solution is
0.1mol/L~2mol/L.
9. a kind of three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material of claim 2~8 any claim preparation is answered
With, it is characterised in that: the glass-carbon electrode modified through three-dimensional non-through phosphomolybdic acid base copper crystalline catalysis material exists as elctro-catalyst
0.5M H2SO4There is electro-catalysis H2-producing capacity in solution.
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