CN108786825A - A kind of ceria base nano electro-catalytic liberation of hydrogen catalyst and preparation method thereof - Google Patents
A kind of ceria base nano electro-catalytic liberation of hydrogen catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 38
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010953 base metal Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 230000001052 transient effect Effects 0.000 claims abstract description 4
- 235000019441 ethanol Nutrition 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 28
- 125000005909 ethyl alcohol group Chemical group 0.000 description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 14
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 8
- 229960003512 nicotinic acid Drugs 0.000 description 8
- 235000001968 nicotinic acid Nutrition 0.000 description 8
- 239000011664 nicotinic acid Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 metals Ion Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
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- 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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- 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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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of ceria base nano electro-catalytic liberation of hydrogen catalyst, includes the transient metal doped ceria of porous nickel and load on it, wherein the transition metal is selected from Co2+、Ni2+At least one of, the transition metal is dispersed in the ceria；The preparation method of the catalyst, includes the following steps：With Ce3+With transition metal M be metal ion, isonicotinic acid is organic ligand, porous nickel is the cerium Base Metal organic frame containing transition metal M that carrier synthesizes porous nickel load, wherein the M is selected from Co2+、Ni2+At least one of；It is calcined the cerium Base Metal organic frame containing transition metal M of the porous nickel load to obtain the ceria base nano electro-catalytic liberation of hydrogen catalyst in air.Transition metal ions in the catalyst is dispersed in CeO2In matrix, while there is big specific surface area, there is high electrocatalytic hydrogen evolution activity.
Description
Technical field
The present invention relates to electrocatalytic hydrogen evolution technical field, specifically a kind of ceria base nano electro-catalytic liberation of hydrogen catalyst
And preparation method thereof.
Background technology
Hydrogen Energy is a kind of important energy in new energy system as a kind of efficient, clean, regenerative resource,
It can replace fossil fuel.Hydrogen Energy has the advantages that many uniquenesses, such as：It is resourceful, combustion heat value is high, clean environment firendly etc..
Water electrolysis hydrogen production technology is the method that application quite widely prepares hydrogen known to the current mankind, and the method for water electrolysis hydrogen production is just
It is to promote water that cell reaction occurs using the effect of additional power source to prepare hydrogen, it is simple with flow, pollution-free, recyclable
The advantages that utilization.But during water electrolysis hydrogen production, there are a big problems, that is, the excessive problem of energy expenditure, this system
The about technology more massive use.In order to solve this problem, electrolysis system could be reduced by effectively reducing overpotential of hydrogen evolution
Energy consumption during hydrogen.So cathode hydrogen evolution material of the research with high catalytic activity, low overpotential is urgently to solve at present
Certainly the problem of.Existing frequently-used catalyst is platinum-group noble metals catalyst, it is a kind of highest elctro-catalyst of liberation of hydrogen efficiency, energy
It is enough to realize evolving hydrogen reaction under the voltage of very close thermodynamical reaction electromotive force.But due to Precious Metals Resources rareness, price
Costliness, can not large-scale industrial production hydrogen.Therefore, scientists have been devoted to develop a kind of abundance, have it is efficient
The catalyst of electrocatalytic hydrogen evolution performance replace platinum-group noble metals.Ceria (CeO2) be it is a kind of have good electrical conductivity
Rare-earth oxide is the cubic fluorite structure with many octahedral voids, even if being formed under conditions of anoxic big
The Lacking oxygen of amount remains to keep cubic fluorite type crystal structure.This metastable oxide is exposed in oxidizing atmosphere, and is easy
It is oxidized to CeO2.Thus CeO2Have the function of superior storage and release oxygen and redox reaction ability.In addition, CeO2With
The strong interaction and adjustability of carried metal or metal oxide become its excellent performance of the carrier material of function admirable
Show the following aspects：Reinforce metal dispersion, promotes carrier anti-agglutinatting property, promotes Precious metal oxidation and reduction, high storage
Oxygen (OSC) is related to the migration etc. of structure oxygen.In addition, CeO2Cubic fluorite structure make other ions such as Cu2+、Co2+、Ni2+
Etc. CeO can be entered2Lattice, so as to improve CeO2Physicochemical property.These performances all make with CeO2Based on electrocatalysis material
With sizable advantage, can be widely used in electrocatalytic hydrogen evolution.
The prior art is mainly with previously prepared CeO2Nano material (including nanometer sheet, nanometer rods etc.), by adulterating
Metal or metal oxide etc. are crossed, to promote electrocatalytic hydrogen evolution performance.Defect and deficiency existing for such technology are doping metals
Ion bad dispersibility, local concentration are high, and specific surface area is smaller and is difficult to continuously regulate and control and influence electro catalytic activity.
Invention content
It is an object of the invention to solve above-mentioned problems of the prior art, a kind of ceria base nanometer electricity is provided
Catalytic hydrogen evolution catalyst and preparation method thereof, the catalyst have high electrocatalytic hydrogen evolution performance.
For achieving the above object, the technical solution adopted in the present invention is：
A kind of ceria base nano electro-catalytic liberation of hydrogen catalyst, the catalyst include porous nickel and load on it
Transient metal doped ceria, wherein the transition metal is selected from Co2+、Ni2+At least one of, the transition metal
It is dispersed in the ceria.
A kind of preparation method of the ceria base nano electro-catalytic liberation of hydrogen catalyst, includes the following steps：
(1) with Ce3+With transition metal M be metal ion, isonicotinic acid is organic ligand, porous nickel is carrier synthesis porous nickel
The cerium Base Metal organic frame containing transition metal M of load, wherein the M is selected from Co2+、Ni2+At least one of；
(2) the cerium Base Metal organic frame containing transition metal M of the porous nickel load is carried out calcining in air
To the ceria base nano electro-catalytic liberation of hydrogen catalyst.
Preferably, pass through the cerium base containing transition metal M of porous nickel load described in solvent structure in the step (1)
Metal organic frame.
Preferably, the solvent-thermal method is that porous nickel is placed in containing Ce3+, transition metal M and isonicotinic acid solution in,
120 DEG C carry out solvent thermal reaction and obtain the cerium Base Metal organic frame containing transition metal M of the porous nickel load.
Preferably, the solvent in the solution is ethyl alcohol.
Preferably, calcination temperature is 300 DEG C in the step (2), calcination time 2h.
The beneficial effects of the invention are as follows：Preparation method provided by the invention is that have with the cerium Base Metal of transition-containing metal ion
Machine frame (MOF) is presoma, and transient metal doped CeO is prepared through high temperature pyrolysis2Base nano electro-catalytic liberation of hydrogen catalyst,
Since MOF has metal ion spatially periodic arrangement, the diversity of finely dispersed characteristic and organic ligand, Yi Hui
Hair property, the regulatable characteristic of component content, so as to get catalyst in transition metal ions can evenly spread to CeO2Matrix
In, while increasing the specific surface area of the catalyst to improve its electrocatalytic hydrogen evolution activity；Transitional metal ion Co2+Or Ni2+
Introducing, CeO can be enhanced2The electric conductivity of matrix regulates and controls CeO2Electronic structure and improve its electrocatalytic hydrogen evolution activity；CeO2
Very strong interaction can be formed with transition metal ions, so as to improve the electrocatalytic hydrogen evolution performance of the catalyst；The present invention
Transition metal ions in the electrocatalytic hydrogen evolution catalyst is dispersed in CeO2In matrix, while there is big specific surface
Product has high electrocatalytic hydrogen evolution activity.
Description of the drawings
The institute Ce in Fig. 1 embodiments 10.5Co0.5O2-δThe linear polarization scanning curve graph of/NF.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In following embodiment, NF refers to porous nickel.
Embodiment 1
The preparation method of the ceria base nano electro-catalytic liberation of hydrogen catalyst, includes the following steps：
(1) by 0.76g Ce (NO3)3·9H2O、0.47g Co(NO3)2·6H2O, 0.209g isonicotinic acid be added to 50ml without
In water-ethanol, magnetic agitation to being completely dissolved, continue stir 30min, solution is transferred to be placed with a piece of porous nickel (1cm ×
In the reactor of 100ml Teflon- linings 1cm), places it in 120 DEG C of baking oven and react 12 hours, naturally cool to
After room temperature, taking out load has the porous nickel of MOF, is cleaned twice with deionized water and ethyl alcohol respectively, dries 6h in air and prepares
Obtain porous nickel load contains Co2+Cerium Base Metal organic frame Ce0.5Co0.5MOF/NF；
(2) by the Ce of above-mentioned preparation0.5Co0.5MOF/NF is placed in Muffle furnace, in air 300 DEG C calcining 2 hours after, it is cold
But to taking out after room temperature, the ceria base nano electro-catalytic liberation of hydrogen catalyst Ce is obtained0.5Co0.5O2-δ/NF。
Embodiment 2
The catalyst Ce is prepared using step same as Example 10.1Co0.9O2-δ/ NF, only described in step (1)
Co(NO3)2·6H2The addition of O is 4.19g.
Embodiment 3
The catalyst Ce is prepared using step same as Example 10.3Co0.7O2-δ/ NF, only described in step (1)
Co(NO3)2·6H2O additions are 1.09g.
Embodiment 4
The catalyst Ce is prepared using step same as Example 10.7Co0.3O2-δ/ NF, only described in step (1)
Co(NO3)2·6H2O additions are 0.20g.
Embodiment 5
The catalyst Ce is prepared using step same as Example 10.9Co0.1O2-δ/ NF, only described in step (1)
Co(NO3)2·6H2O additions are 0.052g.
Embodiment 6
The catalyst Ce is prepared using step same as Example 10.1Ni0.9O2-δ/ NF, be in step (1) only by
0.76g Ce(NO3)3·9H2O、4.19g Ni(NO3)2·6H2O, 0.209g isonicotinic acid is added in 50ml absolute ethyl alcohols.
Embodiment 7
The catalyst Ce is prepared using step same as Example 10.3Ni0.7O2-δ/ NF, be in step (1) only by
0.76g Ce(NO3)3·9H2O、1.09g Ni(NO3)2·6H2O, 0.209g isonicotinic acid is added in 50ml absolute ethyl alcohols.
Embodiment 8
The catalyst Ce is prepared using step same as Example 10.5Ni0.5O2-δ/ NF, be in step (1) only by
0.76g Ce(NO3)3·9H2O、0.47g Ni(NO3)2·6H2O, 0.209g isonicotinic acid is added in 50ml absolute ethyl alcohols.
Embodiment 9
The catalyst Ce is prepared using step same as Example 10.7Ni0.3O2-δ/ NF, be in step (1) only by
0.76g Ce(NO3)3·9H2O、0.20g Ni(NO3)2·6H2O, 0.209g isonicotinic acid is added in 50ml absolute ethyl alcohols.
Embodiment 10
The catalyst Ce is prepared using step same as Example 10.9Ni0.1O2-δ/ NF, be in step (1) only by
0.76g Ce(NO3)3·9H2O、0.052g Ni(NO3)2·6H2O, 0.209g isonicotinic acid is added in 50ml absolute ethyl alcohols.
Embodiment 11
The catalyst Ce is prepared using step same as Example 10.5Co0.125Ni0.375O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、0.12g Co(NO3)2·6H2O、0.35g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 12
The catalyst Ce is prepared using step same as Example 10.5Co0.25Ni0.25O2-δ/ NF, only step (1)
In be by 0.76g Ce (NO3)3·9H2O、0.235g Co(NO3)2·6H2O、0.235g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 13
The catalyst Ce is prepared using step same as Example 10.5Co0.375Ni0.125O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、0.35g Co(NO3)2·6H2O、0.12g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 14
The catalyst Ce is prepared using step same as Example 10.3Co0.175Ni0.525O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、0.27g Co(NO3)2·6H2O、0.82g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 15
The catalyst Ce is prepared using step same as Example 10.3Co0.35Ni0.35O2-δ/ NF, only step (1)
In be by 0.76g Ce (NO3)3·9H2O、0.545g Co(NO3)2·6H2O、0.545g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 16
The catalyst Ce is prepared using step same as Example 10.3Co0.525Ni0.175O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、0.82g Co(NO3)2·6H2O、0.27g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 17
The catalyst Ce is prepared using step same as Example 10.3Co0.225Ni0.675O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、1.05g Co(NO3)2·6H2O、3.14g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Embodiment 18
The catalyst Ce is prepared using step same as Example 10.3Co0.45Ni0.45O2-δ/ NF, only step (1)
In be by 0.76g Ce (NO3)3·9H2O、2.09g Co(NO3)2·6H2O、2.10g Ni(NO3)2·6H2O, the different cigarettes of 0.209g
Acid is added in 50ml absolute ethyl alcohols.
Embodiment 19
The catalyst Ce is prepared using step same as Example 10.3Co0.675Ni0.225O2-δ/ NF, only step
(1) it is by 0.76g Ce (NO in3)3·9H2O、3.14g Co(NO3)2·6H2O、1.05g Ni(NO3)2·6H2O, 0.209g is different
Niacin is added in 50ml absolute ethyl alcohols.
Test case
Using Shanghai Chen Hua CHI 660E electrochemical workstations come prepared by testing example 1
Ce0.5Co0.5O2-δThe electrocatalytic hydrogen evolution performance of/NF, all potential values are all converted to plus 1.068V relatively reversible
Hydrogen electrode (RHE) voltage.It is tested using three-electrode system, Ce0.5Co0.5O2-δ/ NF is working electrode, and graphite rod is pair
Electrode, saturated calomel electrode are reference electrode, and electrolyte used is the KOH solution of 1mol/L.Linear scan test parameter
Related setting it is as follows：Scanning range is 1mV from 0~-0.5V (vs.RHE), linear scanning velocity 5mV/s, sampling interval.
Fig. 1 gives Ce in embodiment 10.5Co0.5O2-δThe electrocatalytic hydrogen evolution performance of/NF, the results show that it starts liberation of hydrogen
Minimum take-off potential be about 127mV, be more than the current potential after, cathode current in 264mV rapidly rise reaches 10mAcm-2。
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (6)
1. a kind of ceria base nano electro-catalytic liberation of hydrogen catalyst, which is characterized in that the catalyst includes porous nickel and bears
It is loaded in transient metal doped ceria thereon, wherein the transition metal is selected from Co2+、Ni2+At least one of, institute
Transition metal is stated to be dispersed in the ceria.
2. a kind of preparation method of ceria base nano electro-catalytic liberation of hydrogen catalyst described in claim 1, which is characterized in that
Include the following steps：
(1) with Ce3+With transition metal M be metal ion, isonicotinic acid is organic ligand, porous nickel is that carrier synthesizes porous nickel load
The cerium Base Metal organic frame containing transition metal M, wherein the M be selected from Co2+、Ni2+At least one of；
(2) it is calcined the cerium Base Metal organic frame containing transition metal M of the porous nickel load to obtain institute in air
State ceria base nano electro-catalytic liberation of hydrogen catalyst.
3. the preparation method of ceria base nano electro-catalytic liberation of hydrogen catalyst according to claim 2, which is characterized in that
Pass through the cerium Base Metal organic frame containing transition metal M of porous nickel load described in solvent structure in the step (1).
4. the preparation method of ceria base nano electro-catalytic liberation of hydrogen catalyst according to claim 3, which is characterized in that
The solvent-thermal method is that porous nickel is placed in containing Ce3+, transition metal M and isonicotinic acid solution in, solvent heat is carried out at 120 DEG C
The cerium Base Metal organic frame containing transition metal M of the porous nickel load is obtained by the reaction.
5. the preparation method of ceria base nano electro-catalytic liberation of hydrogen catalyst according to claim 4, which is characterized in that
Solvent in the solution is ethyl alcohol.
6. the preparation method of ceria base nano electro-catalytic liberation of hydrogen catalyst according to claim 2, which is characterized in that
Calcination temperature is 300 DEG C in the step (2), calcination time 2h.
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