CN106345465A - Application of three-dimensional macroporous molybdenum dioxide loaded palladium particle material to electrocatalysis material - Google Patents
Application of three-dimensional macroporous molybdenum dioxide loaded palladium particle material to electrocatalysis material Download PDFInfo
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- CN106345465A CN106345465A CN201610810337.8A CN201610810337A CN106345465A CN 106345465 A CN106345465 A CN 106345465A CN 201610810337 A CN201610810337 A CN 201610810337A CN 106345465 A CN106345465 A CN 106345465A
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- moo
- dimensional
- molybdenum dioxide
- aqueous solution
- pdcl
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 title claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000001119 stannous chloride Substances 0.000 claims description 9
- 235000011150 stannous chloride Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000009194 climbing Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- -1 bismuth vanadates Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UQJSLVWCKFZHFO-UHFFFAOYSA-N molybdenum(4+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Mo+4] UQJSLVWCKFZHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—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
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses application of three-dimensional macroporous molybdenum dioxide loaded palladium particle material to an electrocatalysis material. A mass ratio of molybdenum dioxide to palladium is 20:(0.06-0.6), molybdenum dioxide is 200-400nm in pore diameter, and palladium particles are 5-10nm. Polymethyl methacrylate microsphere colloidal crystal templates in ordered array are adopted for preparation of a three-dimensional macroporous molybdenum dioxide structure, and the palladium particles are loaded on the three-dimensional macroporous molybdenum dioxide structure. A synthesis method is low in implementation cost, convenient and simple in operation, low in pollution, high in efficiency and economical, and the material is structurally stable and has an electrocatalysis property.
Description
The present patent application is parent application " a kind of three-dimensional macroporous structure molybdenum dioxide supported palladium granular materialss and its synthesis side
The divisional application of method ", the applying date of parent application is on April 8th, 2015, Application No. 2015101622232.
Technical field
The present invention relates to a kind of novel nano-material and its synthetic method, more particularly, to a kind of three-dimensional macroporous structure titanium dioxide
Molybdenum supported palladium granular materialss and its synthetic method.
Background technology
Transition metal oxide mo02Belong to monoclinic system, there is the rutile crystalline structure of distortion, mo02It is to have high electricity
Conductance, high-melting-point, the transition metal oxide of high chemical stability, its efficient charge transmission makes it in catalyst, biography
The aspects such as sensor, electrochromic display device (ECD), recording materials, electric chemical super capacitor, li ion battery and field emmision material
Application prospect is extensive.Layer structure moo2There is low-resistivity, high electro-chemical activity and high stability, show good urging
Change performance, more and more extensive in catalysis material application aspect scope, and applied in electrocatalytic hydrogen evolution field.But by
May result in plastic deformation and hydraulic performance decline in irreversible volumetric expansion, it is therefore necessary to for further study in its structure.
In all of metal material, for electrocatalytic hydrogen evolution reaction, platinum group metal has the deposition potential of minimum.Load
A small amount of platinum-group noble metals granule can increase the number of active sites of reaction system, be unlikely to block three-dimensional macroporous structure again.
Content of the invention
It is an object of the invention to provide a kind of load pd particle three-dimensional macroporous structure moo2Material and its synthetic method, obtain
A kind of specific surface area is big, Stability Analysis of Structures and have the nanostructured of electrocatalysis characteristic, and the method has low cost, preparation process letter
Single feature.
The purpose of the present invention is achieved by following technical proposals:
A kind of three-dimensional macroporous structure molybdenum dioxide supported palladium granular materialss, moo2Mass ratio with pd is 20:(0.06-
0.6), the aperture of molybdenum dioxide is 200 400nm, and palladium granule is 5 10nm and is evenly distributed in the hole wall of molybdenum dioxide
On, and carry out as steps described below:
Step 1, three-dimensional macropore moo2The preparation of structure: by polymethyl methacrylate (pmma) the microsphere glue of ordered arrangement
Crystal template is placed in mocl5In aqueous solution, sucking filtration drying repeatedly after oxidation, then 640 650 under circulation protective gas atmosphere
DEG C heat treatment 1 2h, obtains the three-dimensional macropore moo that pore size is 200-400nm2, described mocl5Concentration of aqueous solution is
0.05m, from room temperature, 20 25 degrees Celsius rise to 640 650 DEG C, and the climbing speed of heating-up temperature is 58 DEG C/min, described
Protective gas atmosphere is argon, or helium, or nitrogen；
In step 1, polymethyl methacrylate (pmma) the microsphere glue crystal template of ordered arrangement enters according to prior art
Row preparation: (1) sadakane, m.；takahashi,c.；kato,n.；ogihara,h.；nodasaka,y.；doi,y.；
hinatsu,y.and ueda,w.three-dimensionally ordered macroporous(3dom)materials
of spinel-type mixed iron oxides.synthesis,structural characterization,and
formation mechanism of inverse opals with a skeleton
structure.bull.chem.soc.jpn.2007,80(4),677-685；(2)yuxi liu,hongxing dai,
jiguang deng,lei zhang,chak tong au three-dimensional ordered macroporous
bismuth vanadates:pmma-templating fabrication and excellent visible light-
driven photocatalytic performance for phenol degradation.nanoscale,2012,4,
2317–2325.
Step 2, in three-dimensional macropore moo2The load of pd granule: the three-dimensional macropore moo being obtained in step 1 is carried out on structure2
Put in the mixing suspension being made up of water, hydrochloric acid and stannous chloride, with magnetic stirrer 30 40 minutes, centrifuging and taking was sunk
Starch；Precipitate is put into pdcl2Aqueous solution magnetic stirrer 30 40 minutes, centrifugation taking precipitate is after drying
To load pd particle three-dimensional macroporous structure moo2；
In described step 2, in described mixing suspension, water, hydrochloric acid, the mass ratio of stannous chloride are 20:1:0.1,
Hydrochloric acid is the hydrochloride aqueous solution of 1 5mol/l；In described pdcl2Concentration of aqueous solution is pdcl2Quality (g) and aqueous solvent
Volume (ml) ratio is (0.1-1): 10；Described three-dimensional macropore moo2Quality (mg) and mixing suspension volume (ml) than being 1:
1.
Method of the present invention cost is low, easy and simple to handle, take shorter, compared with traditional preparation methods, mainly have with
Under several advantages: (1) can with effective control three-dimensional macropore moo2The pore size (2) of structure solves the feature of particle agglomeration,
Pd granule is made to be evenly distributed on three-dimensional macropore moo2In structure (as shown in Figures 2 and 3), molybdenum dioxide have (110), (101),
(220) crystal face, pd granule has (111), (200) and (220) crystal face；(3) response time greatly shortens, and simple to operate；(4)
Instead of noble metal pt with pd, greatly save preparation cost, be a kind of synthetic method of high-efficiency and economic.(5) use electrochemistry
Work station gamry reference 600 is tested, and the solution for test is ph=0, the h of 0.5m2so4Aqueous solution, is carried out
The speed of linear voltammetric scan is 50mv/s, the macropore moo of load pd granule2Electric current density significantly increase (as accompanying drawing 6 institute
Show), show that this material catalytic performance is greatly improved, can be used as elctro-catalyst.
Brief description
Fig. 1 is the three-dimensional macropore moo of the big small-bore of the independent 200nm of the present invention2100k times of sem pattern photo (fe-sem,
hitachi s-4800)；
Fig. 2 loads the three-dimensional macropore moo of pd granule for the present invention2100k times of sem pattern photo (fe-sem, hitachi
s-4800)；
Fig. 3 loads the three-dimensional macropore moo of pd granule for the present invention230k times of sem pattern photo (fe-sem, hitachi
s-4800)；
Fig. 4 loads the three-dimensional macropore moo of pd granule for the present invention2Tem pattern photo (tem, philips tecnai
g2f20)；
Fig. 5 loads the three-dimensional macropore moo of pd granule for the present invention2Xrd collection of illustrative plates (xrd, rigaku/dmax), wherein round
Point represents moo2Crystal face；Square represents the crystal face of pd,；
Fig. 6 is the linear voltammetric scan testing current figure line of material of the present invention, and wherein curve is prepared independent macropore
moo2Test figure line, curve be load pd granule macropore moo2The test figure line of complex, curve is commodity moo2's
Test figure line.
Specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, below embodiment of the present invention is made further
Ground describes in detail.
Carry out the system of polymethyl methacrylate (pmma) the microsphere glue crystal template of ordered arrangement first according to prior art
Standby, specifically: take 60-88ml deionized water, 5-16ml methyl methacrylate, be placed in magnetic force under circulation nitrogen protection and stir
Mix and be stirred on device 15 minutes, add 7.5-24ml persulfate aqueous solution (0.059-0.1888g containing potassium peroxydisulfate), fully
Stirring and dissolving.After stopping logical nitrogen, setting heating schedule is so as to being to slowly warm up to 70 DEG C and being incubated 1.5h.Then extremely cold, from
The heart, it is dried to obtain white solid.Extracting waste solid, after grinding to form fine powder, ratio and water according to mass ratio 1:40 are blended in
Together, simultaneously ultrasonic disperse makes it again become emulsion form for stirring.It is poured into beaker, be placed in and be dried at 50 DEG C in drying baker.Dry
Dry finish after the white solid thin slice of strip, as glue crystal template are occurred on sheet glass and walls of beaker.
Embodiment 1
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, rises to 650 DEG C from 20 DEG C under flowing argon gas atmosphere protection
2 hours of heat treatment, wherein heating rate are 5 DEG C/min, and then furnace cooling obtains the three-dimensional macropore that pore size is 200nm
moo2.
Gained moo2Put into 20ml water, hydrochloric acid, the mixing suspension of stannous chloride (mass ratio is 20:1:0.1) for 20 milligrams
In, hydrochloric acid is the hydrochloride aqueous solution of 1mol/l, with magnetic stirrer 30 minutes, is centrifuged taking precipitate.Precipitate is put
Enter pdcl2Solution (10ml water, 0.5g pdcl2), with magnetic stirrer 30 minutes, centrifuging and taking precipitated, and is born after being dried
Carry the three-dimensional macroporous structure moo of pd granule pore size 200nm2, pd granular size is 5nm, moo2Mass ratio with pd is 20:
0.3.
Embodiment 2
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, rises to 640 DEG C from 25 DEG C under flowing argon gas atmosphere protection
1.5 hours of heat treatment, wherein heating rate are about 8 DEG C/min.Then furnace cooling obtains the three-dimensional that pore size is 350nm
Macropore moo2.
Gained moo220 milligrams put into 20ml water, hydrochloric acid, protochloride mass ratio be (20:1:0.1) mixing suspension
In, hydrochloric acid is the hydrochloride aqueous solution of 3mol/l, and precipitate is put into pdcl2Solution (10ml water, 0.5g pdcl2), use magnetic force
Agitator stirs 30 minutes, and centrifuging and taking precipitates, and obtains loading the three-dimensional macroporous structure of pd granule pore size about 350nm after being dried
moo2, pd granular size is 8nm, moo2Mass ratio with pd is 20:0.3.
Embodiment 3
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, rises to 645 DEG C from 22 DEG C under flowing argon gas atmosphere protection
2 hours of heat treatment, wherein heating rate are about 8 DEG C/min.Then furnace cooling obtains pore size is the three-dimensional big of 400nm
Hole moo2.
Gained moo2Put into 20ml water, hydrochloric acid, the mixing suspension of stannous chloride (mass ratio is 20:1:0.1) for 20 milligrams
In, hydrochloric acid is the hydrochloride aqueous solution of 5mol/l, with magnetic stirrer 30 minutes, is centrifuged taking precipitate.Precipitate is put
Enter pdcl2Solution (10ml water, 0.5g pdcl2), with magnetic stirrer 30 minutes, centrifuging and taking precipitated, and is born after being dried
Carry the three-dimensional macroporous structure moo of pd granule pore size 400nm2, pd granular size is 10nm moo2Mass ratio with pd is 20:
0.3.
Embodiment 4
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, rises to 650 DEG C from 25 DEG C under flowing argon gas atmosphere protection
1 hour of heat treatment, wherein heating rate are about 8 DEG C/min.Then furnace cooling obtains pore size is the three-dimensional big of 200nm
Hole moo2.
Gained moo2Put into 20ml water, hydrochloric acid, the mixing suspension of stannous chloride (mass ratio is 20:1:0.1) for 20 milligrams
In, hydrochloric acid is the hydrochloride aqueous solution of 1mol/l, with magnetic stirrer 30 minutes, is centrifuged taking precipitate.Precipitate is put
Enter pdcl2Solution (10ml water, 0.1g pdcl2), with magnetic stirrer 30 minutes, centrifuging and taking precipitated, and is born after being dried
Carry the three-dimensional macroporous structure moo of pd granule pore size about 200nm2, pd granular size is 5nm, moo2Mass ratio with pd is
20:0.06.
Embodiment 5
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, from 20 DEG C of -650 DEG C of heat treatments under flowing argon gas atmosphere protection
2 hours, wherein heating rate are about 6 DEG C/min.Then furnace cooling obtains the three-dimensional macropore that pore size is 200nm
moo2.
Gained moo2Put into 20ml water, hydrochloric acid, the mixing suspension of stannous chloride (mass ratio is 20:1:0.1) for 20 milligrams
In, hydrochloric acid is the hydrochloride aqueous solution of 2mol/l, with magnetic stirrer 40 minutes, is centrifuged taking precipitate.Precipitate is put
Enter pdcl2Solution (10ml water, 1g pdcl2), with magnetic stirrer 30 minutes, centrifuging and taking precipitated, and is loaded after being dried
The three-dimensional macroporous structure moo of pd granule pore size about 200nm2, pd granular size is 10nm, moo2Mass ratio with pd is 20:
0.6.
Embodiment 6
2g template is taken to put into the mocl filling 10 milliliters of 0.05m5Beaker, beaker is put into 50 DEG C of couveuse, sealing
Good beaker prevents the volatilization of moisture, about two days time solution oxides, and multiple sucking filtration is simultaneously dried, and obtains the solid of blueness.By this
Solid is placed in crucible and puts in the heating furnace that can lead to protective atmosphere, from 20 DEG C of -640 DEG C of heat treatments under flowing argon gas atmosphere protection
2 hours, wherein heating rate are about 5 DEG C/min.Then furnace cooling obtains the three-dimensional macropore that pore size is 400nm
moo2.
Gained moo2Put into 20ml water, hydrochloric acid, the mixing suspension of stannous chloride (mass ratio is 20:1:0.1) for 20 milligrams
In, hydrochloric acid is the hydrochloride aqueous solution of 1mol/l, with magnetic stirrer 30 minutes, is centrifuged taking precipitate.Precipitate is put
Enter pdcl2Solution (10ml water, 1g pdcl2), with magnetic stirrer 30 minutes, centrifuging and taking precipitated, and is loaded after being dried
The three-dimensional macroporous structure moo of pd granule pore size about 400nm2, pd granular size is 10nm, moo2Mass ratio with pd is 20:
0.6.
Above the present invention is done with exemplary description it should illustrate, in the situation of the core without departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (3)
1. three-dimensional macroporous structure molybdenum dioxide supported palladium granular materialss as the application of electrocatalysis material it is characterised in that three
In dimension macroporous structure molybdenum dioxide supported palladium granular materialss, moo2Mass ratio with pd is 20:(0.06-0.6), molybdenum dioxide
Aperture is 200 400nm, and palladium granule is 5 10nm and is evenly distributed on the hole wall of molybdenum dioxide.Enter as steps described below
OK:
Step 1, three-dimensional macropore moo2The preparation of structure: the poly (methyl methacrylate) micro-sphere glue crystal template of ordered arrangement is placed in
mocl5In aqueous solution, sucking filtration drying repeatedly after oxidation, then 640 650 DEG C of heat treatments under circulation protective gas atmosphere
1 2h, obtains the three-dimensional macropore moo that pore size is 200-400nm2, described mocl5Concentration of aqueous solution is 0.05m, from room temperature
20 25 degrees Celsius rise to 640 650 DEG C, and the climbing speed of heating-up temperature is 58 DEG C/min, described protective gas atmosphere
For argon, or helium, or nitrogen.
Step 2, in three-dimensional macropore moo2The load of pd granule: the three-dimensional macropore moo being obtained in step 1 is carried out on structure2Put into
In the mixing suspension being made up of water, hydrochloric acid and stannous chloride, with magnetic stirrer 30 40 minutes, centrifuging and taking precipitates
Thing；Precipitate is put into pdcl2Aqueous solution magnetic stirrer 30 40 minutes, centrifugation taking precipitate obtains after drying
Load pd particle three-dimensional macroporous structure moo2；In described step 2, in described mixing suspension, water, hydrochloric acid, stannous chloride
Mass ratio be 20:1:0.1, hydrochloric acid is the hydrochloride aqueous solution of 1 5mol/l；In described pdcl2Concentration of aqueous solution is pdcl2
The volume ratio of quality and aqueous solvent be (0.1-1): 10；Described three-dimensional macropore moo2Quality and mixing suspension volume ratio
For 1:1.
2. three-dimensional macroporous structure molybdenum dioxide supported palladium granular materialss answering as electrocatalysis material according to claim 1
With it is characterised in that in described step 1, the poly (methyl methacrylate) micro-sphere glue crystal template of ordered arrangement is placed in mocl5
In aqueous solution, sucking filtration drying repeatedly after oxidation, then 645 650 DEG C of heat treatment 2h under circulation protective gas atmosphere.
3. three-dimensional macroporous structure molybdenum dioxide supported palladium granular materialss answering as electrocatalysis material according to claim 1
With it is characterised in that in described step 2, in described pdcl2Concentration of aqueous solution is pdcl2Quality and aqueous solvent volume ratio
For (0.5-1): 10.
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| CN201610810337.8A CN106345465B (en) | 2015-04-08 | 2015-04-08 | Application of the three-dimensional macroporous structure molybdenum dioxide supported palladium granular materials as electrocatalysis material |
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| CN106824189B (en) * | 2017-01-18 | 2019-04-26 | 中国科学技术大学 | A kind of preparation method and its usage of ruthenium-molybdenum dioxide nano junction |
| JPWO2022091915A1 (en) * | 2020-10-30 | 2022-05-05 | ||
| CN113584552B (en) * | 2021-07-30 | 2022-10-11 | 嘉兴学院 | Preparation method and application of nano composite film |
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| CN104841423A (en) | 2015-08-19 |
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