CN110385119A - A kind of method that catalyst of transition metal oxide defect active site is constructed in situ - Google Patents
A kind of method that catalyst of transition metal oxide defect active site is constructed in situ Download PDFInfo
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- CN110385119A CN110385119A CN201910603019.8A CN201910603019A CN110385119A CN 110385119 A CN110385119 A CN 110385119A CN 201910603019 A CN201910603019 A CN 201910603019A CN 110385119 A CN110385119 A CN 110385119A
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- metal oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 25
- 230000007547 defect Effects 0.000 title claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 42
- 239000011593 sulfur Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- -1 Transition metal salt Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 27
- 239000011572 manganese Substances 0.000 description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 150000002696 manganese Chemical class 0.000 description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B01J35/33—
-
- 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
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Quick in situ constructs defect active site in catalyst of transition metal oxide method that the present invention relates to a kind of belongs to the electro-catalysis analysis oxygen field during electrolysis water, solves the problems such as existing method of modifying process is complicated, at high cost, stability is poor.The method of the present invention the following steps are included: S1, sulfur-bearing transition metal oxide precursor body preparation, the synthesis of S2, sulfur-bearing modified transition metal oxide catalyst.The active advantage high, stability is good of catalyst of transition metal oxide of richness defect active site prepared by the present invention, operating method is simple and convenient, is easy to control and low in cost, can be widely applied to electrolysis water and other electrochemical catalysis fields.
Description
Technical field
The present invention relates to the electro-catalysis during electrolysis water to analyse oxygen field, specifically a kind of catalyst of transition metal oxide
The method that defect active site is constructed in situ.
Background technique
Limited fossil fuel and associated environmental pollution have become hinder one of human social development it is urgent
Problem.Scientist all over the world is making great efforts to explore substitution clean energy technology.Hydrogen is efficient with it, cleans, is sustainable
Feature receives more and more attention, and wherein electrolysis water is a kind of easy, clean hydrogen manufacturing approach.But during electrolysis water
This slow problem of oxygen evolution reaction (OER) dynamics has become the bottleneck of electrolytic hydrogen production large-scale commercial application.Currently, activity compared with
High OER catalyst is metal oxide containing precious metals such as IrO2And Ru02.Find at low cost, simple process, catalytic activity height, stability
High OER catalyst is the research hotspot in electrochemistry direction.
It is well known that the influence of the catalytic activity of catalyst largely receptor 1 activity site density.Therefore, it constructs and to the greatest extent may be used
Active site more than energy is the effective ways for improving catalyst water dispersible energy.Since non-noble transition metal has reserves rich
The features such as rich, low in cost, unique d orbital electron structure, the application that transition metal oxide is catalyzed in the field OER obtain
Extensive concern.The catalysis of OER transition metal oxide can be improved by being doped modification by using hetero atoms such as sulphur, phosphorus, selenium, boron
The catalytic activity and stability of agent, but all there is the problems such as process is complicated in these method of modifying.
Summary of the invention
In view of this, the present invention provides a kind of defect active site original position structures for catalyst of transition metal oxide
Building method has catalytic performance height using the modified transition metal oxide catalyst of this method preparation, stable in catalytic performance
Feature, and this method preparation process is simple and easy to control, modification is at low cost.
The present invention provides a kind of methods that catalyst of transition metal oxide defect active site is constructed in situ, including with
Lower step:
The preparation of S1, sulfur-bearing transition metal oxide precursor body:
Transition metal salt is dissolved in organic solvent, the small organic molecule that sulfur-bearing is added is mixed；Then by it
It is placed in reaction kettle at 160-200 DEG C and reacts, products therefrom is collected by centrifugation, and sulfur-bearing transition metal oxide precursor body is made；
The synthesis of S2, sulfur-bearing modified transition metal oxide catalyst:
It the step S1 presoma prepared is placed in Muffle furnace high temperature sintering oxidation obtains sulfur-bearing transition metal oxide and urge
Agent.
The method of the present invention uses high temperature by the way that transition metal inorganic salts and sulfur-bearing small organic molecule are dissolved in organic solvent
Solvent thermal reaction can quickly obtain Transition Metal Sulfur coordination polymer, realize the introducing of hetero atom sulphur.
Further, in step sl, the transition metal salt is Mn2+And Co2+The mixture of ionic metal salt.
Further, in step sl, the organic solvent is one or more of DMF and acetone.
Further, in step sl, the sulfur-bearing small organic molecule is 5-sodium sulfo isophthalate, isophthalic diformazan
One or more of acid -5- sulfonic acid and xylene monosulfonic acid.
Further, in step s 2, the condition of Muffle furnace high temperature sintering oxidation are as follows: temperature is 500-700 DEG C, is kept
10-30min。
Compared with prior art, technical solution of the present invention has the advantage that as follows: the method for the present invention passes through mistake
It crosses metal salt uniformly to mix with the small organic molecule of sulfur-bearing, then makes sulfur doping in transition metal polymerization object by simple solvent thermal method
In presoma；By high-temperature oxydation, substitution and reciprocation occur for a large amount of oxygen atoms and sulphur to produce active sites abundant
Point.For the method for the present invention while introducing hetero-atoms S, precursor polymer skeleton, which is carbonized, can assist in effective structure of three phase boundary
It builds.The sulphur atom of introducing and a large amount of oxygen atom, which mutually replace, creates a large amount of active site, makes the height with catalytic activity
The ratio of valence transition metal and active oxygen is substantially increased.Compared with the complicated modifying process such as existing phosphatization, boronation, side of the present invention
Method has the advantages that easy, cheap.
Detailed description of the invention
Attached drawing is only used for showing the purpose of specific embodiment, and is not to be construed as limiting the invention.
Fig. 1 (a) and Fig. 1 (b) is respectively the original manganese/cobalt oxide catalyst and addition 5-SSIPA for being not added with 5-SSIPA
Sulfur-bearing modified manganese/cobalt oxide catalyst SEM electron microscope；
Fig. 2 is sulfur-bearing modified manganese/cobalt oxide catalyst TEM transmission plot (resolution ratio 200nm)；
Fig. 3 (a), Fig. 3 (b), Fig. 3 (c) and Fig. 3 (d) be respectively sulfur-bearing modified manganese/cobalt oxide catalyst Mn, Co, C,
The EDX of tetra- kinds of atoms of S schemes；
Fig. 4 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst X-ray diffractogram；
Fig. 5 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst LSV polarization curve；
Fig. 6 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst 20mA/cm2Work nearby
The chronoa mperometric plot figure of 5.5h.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
The embodiment of the invention discloses a kind of introducing sulfur-bearing organisms, and OER catalyst performance is carried out in a manner of hydro-thermal reaction
The method of promotion:
The organic matter of transition metal salt and sulfur-bearing is uniformly mixed, was mixing sulfur doping with simple water-heat process
It crosses among metal precursor；By high-temperature oxydation, a large amount of oxygen atoms occur to replace with sulphur and reciprocation is abundant to produce
Active site；While introducing hetero-atoms S, good electron conduction possessed by the carbon source in sulfur-bearing organism can be assisted
The building of three phase boundary, to further promote the catalytic performance of catalyst.
Embodiment 1
A specific embodiment of the invention includes following experimental procedure:
(1) sulfur-bearing manganese/cobalt mixed oxide presoma preparation: by 0.264mmol MnSO4·H2O's and 0.258mmol
Co(NO3)2·6H2O is dissolved in 40mL DMF and 40mL acetone, is added 0.8mmol 5-sodium sulfo isophthalate (5-SSIPA)
It is mixed.
Then it places it in autoclave, reacts 4h at 160 DEG C；Turned later in supercentrifuge with 8000r/min
Speed keeps 5min, obtains sulfur-bearing manganese/cobalt mixed oxide presoma.
(2) sulfur-bearing modified manganese/cobalt mixed oxide particle synthesis: before sulfur-bearing manganese/cobalt mixed oxide in step (1)
It drives body to be placed in Muffle furnace, is warming up to 500 DEG C with 5 DEG C/min, and kept for 10 minutes；Sulfur-bearing is obtained after then cooling to room temperature to change
Property manganese/cobalt mixed oxide particle, sulfur-bearing modified manganese/cobalt oxide catalyst of defect active site is constructed in obtained original position.
In control experiment, it is not added with 5-sodium sulfo isophthalate (5-SSIPA), remaining step is identical, is made original
Manganese/cobalt oxide catalyst.
The relevant characterization data of embodiment 1 are as follows:
Fig. 1 (a) and Fig. 1 (b) is respectively the original manganese/cobalt oxide catalyst and addition 5-SSIPA for being not added with 5-SSIPA
Sulfur-bearing modified manganese/cobalt oxide catalyst SEM electron microscope, from Fig. 1 (a) and Fig. 1 (b) it can be seen that
Compared with original manganese/cobalt oxide catalyst, sulfur-bearing modified manganese/cobalt oxide catalyst particle is integrally more tended to
Flakey, catalyst edge are superimposed in the form of sheets, and this sclay texture makes that catalyst can be made to expose more catalytic activity
Site.
Fig. 2 is sulfur-bearing modified manganese/cobalt oxide catalyst TEM transmission plot (resolution ratio 200nm):
It can be seen that more apparent lattice fringe from TEM image, this illustrate plus sulphur modification after grain size number compared with
Greatly, crystallization degree is more preferable.This good crystallization degree exposes more crystal faces, is conducive to the promotion of catalytic performance.
Fig. 3 (a), Fig. 3 (b), Fig. 3 (c) and Fig. 3 (d) be respectively sulfur-bearing modified manganese/cobalt oxide catalyst Mn, Co, C,
The EDX of tetra- kinds of atoms of S schemes, as can be seen from the figure:
Tetra- kinds of atoms of Mn, Co, C, S show good dispersibility, illustrate the introducing of hetero atom sulphur in the embodiment of the present invention 1
Mode is effective.
Fig. 4 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst X-ray diffractogram
(XRD):
It can significantly find out that the diffraction peak shape for two kinds of catalyst for adding sulphur modification or sulphur modification being not added is quite similar in figure,
And belong to MnCo2O4Crystal structure, this illustrates that the introducing of hetero atom S does not cause the variation of crystal structure.
Fig. 5 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst LSV polarization curve:
In figure as can be seen that under identical voltage, sulphur modification manganese/cobalt oxide catalyst shows higher catalysis and lives
Property, the current density for being catalyzed OER is higher.
Fig. 6 is original manganese/cobalt oxide catalyst and sulfur-bearing modified manganese/cobalt oxide catalyst 20mA/cm2Work nearby
The chronoa mperometric plot figure of 5.5h:
It can be seen that original manganese/cobalt oxide catalyst nearby just started significantly to decay at first hour in figure, and contain
Sulphur modification manganese/cobalt oxide catalyst still remains biggish current density in 5h.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of method that catalyst of transition metal oxide defect active site is constructed in situ, which is characterized in that including following
Step:
The preparation of S1, sulfur-bearing transition metal oxide precursor body:
Transition metal salt is dissolved in organic solvent, the small organic molecule that sulfur-bearing is added is mixed；Then it places it in
It is reacted at 160-200 DEG C in reaction kettle, products therefrom is collected by centrifugation, and sulfur-bearing transition metal oxide precursor body is made；
The synthesis of S2, sulfur-bearing modified transition metal oxide catalyst:
The step S1 presoma prepared is placed in Muffle furnace high temperature sintering oxidation and obtains sulfur-bearing catalyst of transition metal oxide.
2. the method that a kind of catalyst of transition metal oxide defect active site according to claim 1 is constructed in situ,
It is characterized in that, in step sl, the transition metal salt is Mn2+And Co2+The mixture of ionic metal salt.
3. the method that a kind of catalyst of transition metal oxide defect active site according to claim 2 is constructed in situ,
It is characterized in that, in step sl, the organic solvent is one or more of DMF and acetone.
4. the method that a kind of catalyst of transition metal oxide defect active site according to claim 3 is constructed in situ,
It is characterized in that, in step sl, the sulfur-bearing small organic molecule is 5-sodium sulfo isophthalate, M-phthalic acid -5- sulphur
One or more of acid and xylene monosulfonic acid.
5. a kind of catalyst of transition metal oxide defect active site according to claim 1-4 is constructed in situ
Method, which is characterized in that in step s 2, the condition of Muffle furnace high temperature sintering oxidation are as follows: temperature be 500-700 DEG C, protect
Hold 10-30min.
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| CN110947392B (en) * | 2019-11-20 | 2022-09-30 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing formic acid by electrochemical reduction of carbon dioxide and preparation method thereof |
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