CN105056961B - Perovskite composite catalyst that amorphous non-noble metal hydroxide for oxygen evolution reaction is modified and preparation method thereof - Google Patents
Perovskite composite catalyst that amorphous non-noble metal hydroxide for oxygen evolution reaction is modified and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 22
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 64
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910002449 CoO3−δ Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 13
- 239000006259 organic additive Substances 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229930013930 alkaloid Natural products 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 11
- 230000002079 cooperative effect Effects 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 primary alconol Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 206010058490 Hyperoxia Diseases 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000222 hyperoxic effect Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910002741 Ba0.5Sr0.5Co0.8Fe0.2O3-δ Inorganic materials 0.000 description 1
- 229910002742 Ba0.5Sr0.5Co0.8Fe0.2O3−δ Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000009841 combustion method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- Y02E60/50—Fuel cells
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- Catalysts (AREA)
Abstract
The invention discloses perovskite composite catalyst of the modification of the amorphous non-noble metal hydroxide for oxygen evolution reaction and preparation method thereof, the composite catalyst is made up of material of main part and decorative material, material of main part is perofskite type oxide, and decorative material is amorphous non-noble metal hydroxide.The chemical composition of amorphous non-noble metal hydroxide decorative material is MxA1‑x(OH)y, wherein M and A are selected from transition metal, and 0≤x≤1,2≤y≤3；Material of main part is A ordering double negative properties, and molecular formula is Ln0.5Ba0.5CoO3‑δ.There is cooperative effect in the composite catalyst between hydroxide decorative material and perovskite main body, not only its catalytic activity is greatly improved than bulk catalyst, and pass through long-time electrochemical property test, composite catalyst can keep catalytic activity and stable appearance.
Description
Technical field
The invention belongs to the regenerative fuel cell of high-energy-density density and metal-air battery field, and in particular to Yi Zhongyong
Composite catalyst of perovskite and preparation method thereof is modified in the amorphous non-noble metal hydroxide of oxygen evolution reaction.
Background technology
The energy is the power of the national economic development, is the basis of national sustainable development.But with greatly developing for industry
The continuous improvement lived with people, the mankind increasingly increase the demand of the energy.However, exceedingly developing and being made using fossil energy
Into lack of energy and serious environmental pollution.It is development and utilization economy, clean new in order to realize the sustainable development of the mankind
The energy is the theme of 21 century world energy sources science and technology.At present, fuel cell and metal-air battery have energy efficiency high and
Advantages of environment protection, thus it is very noticeable.Electrochemistry hydrolytic hydrogen production in energy storage and field of energy conversion, such as metal-
There is important effect in the application such as air cell, regenerative fuel cell.
In electrochemistry hydrolysis hydrogen preparation field, the oxygen evolution reaction (OER) on anode is more difficult than the evolving hydrogen reaction on negative electrode
A lot.In order to improve the electrochemical efficiency of electrolysis water, find the Oxygen anodic evolution catalyst of superior performance to reduce sun as much as possible
Overpotential is reacted in pole, is the hot issue for being electrolysed wate research.Noble metal Ru or Ir and its oxide urging for oxygen evolution reaction
Change activity very high.But these noble metal catalysts all limit it due to too high cost, relatively low reserves and stability problem
Large-scale application.Many researchers be directed to exploitation it is cheap, can efficiently replace or part precious metal catalyst
Agent.Transition metal oxide particularly has ABO3The perovskite material of type structure is because cost is low, resistance to oxidation, hyperoxia are separated out
(OER) the advantages of catalytic activity, as the most possible OER elctro-catalysts for replacing or partly replacing noble metal.ABO3In account for
It is rare earth or alkali metal according to A, B are transition metal.The Yang Shao-Horn professors of the Massachusetts Institute of Technology
Propose the OER performances of perofskite type oxide and the electronics filling situation and metal ion of the transition metal ions in its structure
It is relevant with the covalency of oxygen.Current cobalt-based perovskite oxide catalyst material（Such as：Ba0.5Sr0.5Co0.8Fe0.2O3-δ
(BSCF)）, good catalysis oxygen evolution activity is shown, but BSCF suctions out catalytic process in oxygen to occur amorphous turn on surface
Change, cause its long-time stability poor.
Researcher has found double calcium titanium-type oxides than similar high times of perovskite oxide long-time stability.Yang
A series of professor Shao-Horn (Ln by Experimental Comparison0.5Ba0.5)CoO3-δ（Ln=Pr, Sm, Gd and Ho）The double calcium of type
The performance of titanium ore material, wherein (Pr0.5Ba0.5)CoO3-δ（PBC）The activity and stability shown is superior to BSCF.However, double
Perovskite material such as PBC needs more than 900oC to synthesize, and too high synthesis temperature causes such catalyst particle size
Excessive, particle diameter distribution is uneven, causes mass activity too low.To in order to improve the effective rate of utilization of catalyst material, selection height is urged
The decorative material for changing activity is modified its surface to increase catalytic activity, while the microscopic appearance of controlled modification material, is obtained
To high-ratio surface decorative layer.Therefore, the microscopic appearance of selection face finish material and the control decorative material is to make such pair of calcium
The key of titanium ore oxide catalyst successful application.
In recent years, many researchers' discovery transition metal oxides and hydroxide show good in alkaline medium
Oxygen evolution reaction activity, but there is presently no double perovskite materials are repaiied using them as catalyst outer layer decorative material
The research of decorations.Therefore high-specific surface area, high activity and high stability composite catalyst are prepared, and explores decorative material and main body
Cooperative effect between material is the key technology target of the present invention.
The content of the invention
It is an object of the invention to provide the calcium that a kind of amorphous non-noble metal hydroxide for oxygen evolution reaction is modified
There is cooperative effect between hydroxide decorative material and perovskite main body in titanium ore composite catalyst, the composite catalyst, not only
Its catalytic activity is greatly improved than bulk catalyst, and passes through long-time electrochemical property test, and composite catalyst can be kept
Catalytic activity and stable appearance；
Another object of the present invention is to provide to prepare the perovskite of above-mentioned amorphous non-noble metal hydroxide modification and answer
Close catalyst preparation method, by controlling the species and proportional quantity of organic additive and alkali in preparation process, obtain high activity,
The perovskite composite catalyst of the amorphous non-noble metal hydroxide modification of high porosity, and cause decorative material with nanometer chi
The very little surface for being evenly distributed on perovskite bulk catalyst, not only further improves its oxygen catalytic activity, and can be for a long time
Stable operation.
The perovskite composite catalyst that amorphous non-noble metal hydroxide for oxygen evolution reaction is modified, the composite catalyzing
Agent is made up of material of main part and decorative material, and material of main part is perofskite type oxide, and decorative material is amorphous base metal
Hydroxide.
The decorative material is hydroxide MxA1-x(OH)y, wherein M and A be selected from transiting group metal elements, 0≤x≤1,
2≤y≤3.M and A is selected from least one of Mn, Fe, Mg, Co, Ni and Cu.
Perofskite type oxide material of main part is A ordering double negative properties, and molecular formula is
Ln0.5Ba0.5CoO3-δ, wherein Ln is the combination of one or both of La, Pr, Nd, Sm, Gd and Y and the arbitrary proportion of the above.
For the preparation method of the base metal amorphous hydroxide catalyst of oxygen evolution reaction, by the nitre containing transition metal
Hydrochlorate is configured to the salting liquid of transparent and homogeneous through fully dissolving, and material of main part is then added into solution and is stirred together for, then
Add alkali and organic additive so that the transition metal ions in solution is evenly distributed to material of main part with the form of hydroxide
The surface of catalyst, by ageing, cleaning, filtering, dry and baking, prepares amorphous non-noble metal hydroxide modification
Perovskite composite catalyst.
Organic additive can be at least one of water-soluble substanceses such as the tertiary alcohol, primary alconol, secondary alcohol, glucose, citric acid,
The preferably tert-butyl alcohol or glucose, it is therefore an objective to make the distribution of the metal ion component of each in solution than more uniform, can impregnate altogether
It is deposited in bulk catalyst surface.
Mole total amount of alkali used is 1 ~ 4 times of nitrate anion mole total amount in nitrate.
Described alkali be KOH, ammoniacal liquor and urea mixture, wherein the scope of alkali mole total amount shared by every kind of alkali be 10 ~
50%, preferably KOH, ammoniacal liquor, urea in molar ratio 1 ~ 3:1~3:1 ~ 3 mixing.
The quality of organic additive is the 5% ~ 20% of main body quality of materials.
The stoving temperature of the composite catalyst is 100~300oC, and the time is 2 ~ 10 hours, and heating rate is 1 ~ 5 oC/
min。
The material of main part of composite catalyst includes but is not limited to perovskite material in the present invention, and perovskite material can be
Structure of double perovskite Ln0.5Ba0.5CoO3-δ, wherein Ln is any of one or both of La, Pr, Nd, Sm, Gd and Y and the above
The combination of ratio, 0≤δ≤3, its preparation method refers to document Alexis Grimaud, Kevin J. May,
Christopher E. Carlton, Yueh-Lin Lee, Marcel Risch, Wesley T. Hong, Jigang
Zhou & Yang Shao-Horn. Double perovskites as a family of highly active
Catalysts for oxygen evolution in alkaline solution, Nature Communications,
DOI: 10.1038/ncomms3439, 2013。(Pr0.5Ba0.5)CoO3-δ(PBC) it is wherein than more typical perovskite material
Material.
In the prior art, double negative property such as PBC ratio surface is very small, and catalytic efficiency is low.In order to carry
The effective rate of utilization of high catalyst material, is modified its surface to increase catalyst effective active area, at the same choose with
Catalyst body material has the high activated catalyst of cooperative effect.Therefore, selection face finish material and the control modification material
The microstructure and pattern of material are the keys that such double-perovskite oxide catalyst is applied successfully.
The technique effect of the present invention：
Metal salt is wrapped in double-perovskite powder surface using infusion process by the present invention, by the addition of organic additive,
The processes such as alkali process, cleaning, filtering and dry and low temperature calcination are formed on double-perovskite bulk catalyst surface to be uniformly distributed
Nanometer hydroxide particle, change preparation process in organic additive and alkali species and proportional quantity, obtain with hyperoxia analyse
Go out the perovskite composite catalyst of the amorphous non-noble metal hydroxide modification of activity, the electro-chemical activity of the composite catalyst
Height, stable circulation performance is good.Due to there is cooperative effect between decorative material and material of main part, this composite catalyst catalysis is lived
Property greatly improved than bulk catalyst, and pass through long-time electrochemical property test, catalyst keeps catalytic activity and shape for a long time
Looks stability, can be widely applied to various fuel cell electrodes.
Brief description of the drawings
Fig. 1 is the amorphous state Fe of the embodiment of the present invention 10.75Ni0.25(OH)2Modify the scanning electron microscopy of PBC catalyst
Structure.
Fig. 2 is the amorphous state Fe of the embodiment of the present invention 10.75Ni0.25(OH)2Modify the transmission electron microscopy of PBC catalyst
Structure chart.
Fig. 3 is the X of the catalyst and pure PBC powder of amorphous hydroxide modification prepared by the embodiment of the present invention 1 and 2
X ray diffraction collection of illustrative plates comparison diagram.
Fig. 4 is the amorphous Fe for preparing in the embodiment of the present invention 10.75Ni0.25(OH)2Modify PBC catalyst and crystalline state
Fe0.75Ni0.25(OH)2Modification and pure PBC OER curve comparison figures.（Curve is marked in figure numeral and catalyst type
Corresponding, Fig. 7 and 8 is similarly）
Fig. 5 is the indefiniteness state Fe of the embodiment of the present invention 10.75Ni0.25(OH)2Modify the OER long-time stables of PBC catalyst
Performance curve.
Fig. 6 is the amorphous state Ni (OH) of the embodiment of the present invention 22Modify the scanning electron microscopy structure of PBC catalyst.
Fig. 7 is the amorphous Ni (OH) for preparing in the embodiment of the present invention 22PBC catalyst is modified to modify with NiO and pure
PBC OER curve comparison figures.
Fig. 8 is the amorphous state Fe for preparing in the embodiment of the present invention 1 and 20.75Ni0.25(OH)2With Ni (OH)2Modification
The OER curve comparison figures of PBC catalyst and pure PBC.
Fig. 9 is amorphous state Ni (OH) in the embodiment of the present invention 22The OER long-time stables performance for modifying PBC catalyst is bent
Line.
Figure 10 be the catalyst of the indefiniteness state hydroxide modification prepared in the embodiment of the present invention 1 and 2 with the beginning of pure PBC
Beginning Tafel curve comparison figure.
The catalyst of indefiniteness state hydroxide modifications of the Figure 11 to be prepared in the embodiment of the present invention 1 and 2 is passed through with pure PBC
Stable Tafel curve comparison figures after long time test.
Embodiment
Typical double perovskite materials (Pr is used in following examples of the present invention0.5Ba0.5)CoO3-δ(PBC) it is modification pair
As the synthesis of the material uses sol-gel process or combustion method, and it is small to pass through calcining 3-8 under higher temperature, such as 800 ~ 1000oC
When obtain structure of double perovskite.Specific preparation method bibliography Alexis Grimaud, Kevin J. May,
Christopher E. Carlton, Yueh-Lin Lee, Marcel Risch, Wesley T. Hong, Jigang
Zhou & Yang Shao-Horn. Double perovskites as a family of highly active
Catalysts for oxygen evolution in alkaline solution, Nature Communications,
DOI: 10.1038/ncomms3439, 2013.In order to illustrate amorphous hydroxide as the high catalytic activity of decorative material,
It is crystallization Fe that the embodiment of the present invention, which gives decorative material,0.75Ni0.25(OH)2, oxide Fe0.75Ni0.25O and NiO catalyst
Catalytic activity result, and with the amorphous Fe in example below0.75Ni0.25(OH)2With Ni (OH)2Contrasted, characterized each
Catalyst modification PBC is planted as the microstructure, phase structure and its oxygen of OER catalysis materials and separates out catalytic activity.
Specific embodiment is following but is not limited to these embodiments：
Embodiment 1
Amorphous Fe0.75Ni0.25(OH)2Modify the preparation of PBC catalyst
It is 3 by mol ratio:1 ferric nitrate, nickel nitrate are dissolved into distilled water, and wherein nickel nitrate takes 0.25mmol, is placed in
The dissolving in favor of salting liquid is stirred on magnetic stirring apparatus, after nitrate fully dissolves, is added while stirring into solution
904 mg PBC powders and the 124 mg tert-butyl alcohols simultaneously continue stirring, and the modified catalyst quality prepared is about the 10 of PBC powders
wt%.By double in nitrate ion mole（Mole total amount of alkali is 5.5 mmol）Excessive mixed base（In the present embodiment,
KOH, ammoniacal liquor and urea mole are respectively 1.5 mmol, 2 mmol and 2 mmol in mixed base）Weigh and be dissolved in distilled water
In, fully it is added to after dissolving in the beaker of lasting stirring, it is molten from its salt that the iron and nickel ion in solution will generate hydroxide
The surface of perovskite particle is separated out and is attached in liquid.Mixture is aged 10 h, filtered 5 times using sand core funnel, by solution
In K ions, ammonia radical ion etc. cleaned up from precipitation, by drying and bakeing 5 h in 150 oC, wherein bakeing from 50 o
The programming rate that C is warming up to 150 oC is 2 oC/min, obtains amorphous Fe0.75Ni0.25(OH)2The catalyst of modification.It is amorphous
Fe0.75Ni0.25(OH)2Modify PBC catalyst scanning electron and transmission electron microscopy structure difference as illustrated in fig. 1 and 2, PBC surfaces
Cover the microscopic appearance not only short texture, and being distributed in the form of sheets of decorative material.Using X ray diffracting spectrum analysis of catalyst
Phase structure is not as shown in figure 3, the PBC phase structures of hydroxide modification have notable difference with pure PBC, and which demonstrate this implementation
Hydroxide decorative material prepared by example is amorphous state.Fig. 4 gives amorphous Fe0.75Ni0.25(OH)2Modify PBC catalyst
Oxygen is separated out and crystalline state Fe0.75Ni0.25(OH)2Modify PBC catalyst chemical property comparison diagrams, it can be seen that crystalline state and nothing
The state that shapes Fe0.75Ni0.25(OH)2The electro-chemical activity of modification PBC catalyst is above pure PBC, but amorphous state
Fe0.75Ni0.25(OH)2PBC oxygen reduction catalytic activity is modified compared with crystalline state Fe0.75Ni0.25(OH)2The material of modification is high, this
Microscopic appearance with amorphous state phase structure and uniqueness is inseparable.Fig. 5 is amorphous Fe0.75Ni0.25(OH)2Modify PBC catalysis
Agent oxygen separates out stability test result, it is seen that by 50 loop tests, catalytic activity does not substantially decay；Figure 10 and figure
11 are the initial Tafel curves with after stabilization of its test, and its slope is respectively 0.019 and 0.017, is superior to pure PBC materials
Material 0.085 and 0.075, while it can be found that with the extension of testing time, the activity of three kinds of catalyst increases.
Embodiment 2
Amorphous state Ni (OH)2Modify the preparation of PBC catalyst
From embodiment 1 except different from decorative material, only with nickel impregnation PBC powders in the present embodiment, remaining
Building-up process is same as Example 1 with means of testing.The phase structure result of the catalyst is included in Fig. 3, with pure PBC without bright
Significant difference is other, it was demonstrated that Ni (OH)2Decorative layer is amorphous state.Fig. 6 is Ni (OH)2Modify the scanning electron microscopy structure of PBC catalyst
Figure, with amorphous Fe0.75Ni0.25(OH)2Modify PBC similar, decorative material open structure in the form of sheets；Given in Fig. 7,8 and 9
Its oxygen separates out chemical property and stability, it is seen that its catalytic activity compared with the PBC that pure PBC and corresponding oxide are modified,
Greatly improve, but performance is slightly below amorphous Fe0.75Ni0.25(OH)2Modify PBC catalyst；In addition, its stable circulation performance
Well, by 50 loop tests, performance is without obvious decay；Figure 10 and Figure 11 give amorphous state Ni (OH)2Modification PBC is urged
Tafel curves after agent test is initial and stable, the Tafel slope of a curves after test is initial and stable are respectively 0.026
With 0.028, it is seen then that although performance is better than pure PBC, than amorphous state Fe0.75Ni0.25(OH)2Modify PBC catalyst
Activity is slightly worse, and the Tafel slope of curve values after performance test stabilization are increased slightly.
Claims (9)
1. the perovskite composite catalyst that the amorphous non-noble metal hydroxide for oxygen evolution reaction is modified, it is characterised in that
The composite catalyst is made up of material of main part and decorative material, and material of main part is perofskite type oxide, and decorative material is without fixed
Shape non-noble metal hydroxide；The chemical composition of described amorphous non-noble metal hydroxide decorative material is MxA1-x(OH)y,
Wherein M and A are selected from transition metal, and 0≤x≤1,2≤y≤3.
2. the perovskite that the amorphous non-noble metal hydroxide according to claim 1 for oxygen evolution reaction is modified is combined
Catalyst, it is characterised in that perofskite type oxide material of main part is A ordering double negative properties, molecular formula is
Ln0.5Ba0.5CoO3-δ, wherein Ln is the combination of one or both of La, Pr, Nd, Sm, Gd and Y and the arbitrary proportion of the above.
3. the perovskite that the amorphous non-noble metal hydroxide according to claim 1 for oxygen evolution reaction is modified is combined
Catalyst, it is characterised in that M and A is selected from least one of Mn, Fe, Mg, Co, Ni and Cu.
4. the perovskite composite catalyzing that the amorphous non-noble metal hydroxide for oxygen evolution reaction described in claim 1 is modified
The preparation method of agent, it is characterised in that the nitrate containing transition metal is configured to homogeneous salting liquid through fully dissolving, then
Add and material of main part and be stirred together for into solution, be subsequently added alkali and organic additive so that transition metal in solution from
Son is evenly distributed to the surface of material of main part catalyst with the form of hydroxide, by ageing, cleaning, filters, dries and dries
Roasting, prepares the perovskite composite catalyst of amorphous non-noble metal hydroxide modification.
5. preparation method according to claim 4, it is characterised in that described organic additive is the tertiary alcohol, primary alconol, secondary
At least one of alcohol, glucose or citric acid.
6. preparation method according to claim 4, it is characterised in that mole total amount of alkali used is nitrate anion in nitrate
1 ~ 4 times of mole total amount.
7. preparation method according to claim 4, it is characterised in that the quality of organic additive is main body quality of materials
5%~20%。
8. preparation method according to claim 4, it is characterised in that the stoving temperature of the composite catalyst is 100~
300oC, the time is 2 ~ 10 hours, and heating rate is 1 ~ 5 oC/min.
9. preparation method according to claim 6, it is characterised in that described alkali is KOH, ammoniacal liquor and urea mixing
Thing, wherein the scope that the mole of every kind of alkali accounts for mixing alkaloids mole total amount is 10 ~ 50%.
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