CN110354848B - PtRu catalyst and preparation method and application thereof - Google Patents
PtRu catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN110354848B CN110354848B CN201910441507.3A CN201910441507A CN110354848B CN 110354848 B CN110354848 B CN 110354848B CN 201910441507 A CN201910441507 A CN 201910441507A CN 110354848 B CN110354848 B CN 110354848B
- Authority
- CN
- China
- Prior art keywords
- ptru catalyst
- ruo
- ruthenium
- substrate material
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910002849 PtRu Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 38
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims abstract description 9
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000002659 electrodeposit Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910021603 Ruthenium iodide Inorganic materials 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000007654 immersion Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- QYZBCWXZSYTIOY-UHFFFAOYSA-N Mercuric oxide Chemical compound [O-2].[Hg+2] QYZBCWXZSYTIOY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 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
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 229940074994 mercuric sulfate Drugs 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 phosphides Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of a PtRu catalyst, which comprises the following steps: s1, soaking the substrate material in ruthenium salt solution to load ruthenium on the substrate material, taking out the substrate material and drying; s2, placing the dried substrate material in a muffle furnace for calcination to obtain RuO2A precursor; s3 comparing RuO obtained in step S22The precursor is placed in a three-electrode electrolytic cell, and the electrolyte is sulfuric acid solution, Pt net, mercuric mercurous sulfate and obtained RuO2Precursors as counter, reference and working electrodes, RuO2The precursor electrodeposits Pt to obtain the PtRu catalyst. The preparation method of the PtRu catalyst disclosed by the invention is simple in synthesis method, and the prepared PtRu catalyst has good catalytic stability in acidic and alkaline electrolytes. The invention also discloses the PtRu catalyst and application thereof as an electrolytic water hydrogen evolution electrode.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a PtRu catalyst, a preparation method thereof and application thereof as an electrode for hydrogen evolution by water electrolysis.
Background
Due to the increasing severity of energy crisis and the environmental problems caused by traditional fossil energy, the search for new green energy becomes an urgent problem to be solved.
The hydrogen energy has no pollution to the environment due to the higher energy density, and is an ideal alternative energy source. In the process of preparing hydrogen, a method for preparing hydrogen by electrolyzing water is advocated. However, during the electrolysis of water, an excessively high overpotential causes a problem of high energy consumption, reducing energy conversion efficiency. Therefore, the development of a high-efficiency water electrolysis catalyst is of great significance.
At present, Pt-based catalysts remain ideal catalysts for electrolytic water reactions. However, the metal Pt is relatively deficient in nature and expensive, which limits the wide application of the Pt. Therefore, it is very important to develop an inexpensive, efficient and stable electrocatalyst for hydrogen evolution reaction. Although sulfides, selenides, phosphides, carbides, nitrides, and the like of transition metals such as molybdenum, tungsten, iron, cobalt, nickel, and the like are widely used in electrocatalytic hydrogen evolution reactions, these catalysts have far inferior performance to platinum-based catalysts, and are also inferior in stability in an acidic environment. Although ruthenium is also a precious metal, it is much less expensive than platinum, and the use of a small amount of ruthenium helps to obtain a cheap and efficient electrocatalyst. Most of ruthenium materials used for electrocatalytic hydrogen evolution reaction currently are metallic ruthenium and RuO2And RuPx nanoparticles, nanowires, and nanosheets are supported on different materials, such as graphene, carbon nitride, carbon nanotubes, TiO2 nanotube arrays, and the like. However, these materials cannot effectively exert electrocatalytic effect of the materials in hydrogen evolution reaction due to complicated synthesis method, large dosage and poor stability.
Disclosure of Invention
The invention aims to provide a preparation method of a PtRu catalyst, which is simple in synthesis method.
The preparation method of the PtRu catalyst disclosed by the invention adopts the technical scheme that:
a preparation method of the PtRu catalyst comprises the following steps:
s1, soaking the substrate material in ruthenium salt solution to load ruthenium on the substrate material, taking out the substrate material and drying;
s2, placing the dried substrate material in a muffle furnace for calcination to obtain RuO2A precursor;
s3 comparing RuO obtained in step S22The precursor is placed in a three-electrode electrolytic cell, and the electrolyte is sulfuric acid solution, Pt net, mercuric mercurous sulfate and obtained RuO2Precursors as counter, reference and working electrodes, RuO2The precursor electrodeposits Pt to obtain the PtRu catalyst.
Preferably, in step S1, the substrate material is carbon cloth, titanium foam, copper foam or nickel foam.
Preferably, in step S1, the ruthenium salt is ruthenium chloride, ruthenium iodide or ruthenium acetate.
Preferably, in the step S1, the concentration of the ruthenium salt solution is 0.001-5 mol/L.
Preferably, in step S1, the soaking time of the substrate material in the ruthenium salt solution is 1-120 min.
Preferably, in step S2, the calcination temperature of the dried substrate material in a muffle furnace is 200 to 600 ℃, and the calcination time is 5 to 120 min.
Preferably, in step S3, the concentration of the sulfuric acid solution is 0.01-5 mol/L.
Preferably, the mass ratio of Pt to Ru in the PtRu catalyst obtained in the step 3 is 0.01: 1-1: 1.
The preparation method of the PtRu catalyst disclosed by the invention has the beneficial effects that: the synthetic method is simple.
Another object of the present invention is to provide a PtRu catalyst, which is prepared by the above preparation method and has good catalytic stability in both acidic and alkaline electrolytes.
The invention also aims to disclose the application of the PtRu catalyst prepared by the preparation method as an electrolytic water hydrogen evolution electrode.
Drawings
FIG. 1 shows RuO prepared in example 12TEM images of the precursors;
fig. 2 is a TEM image of the PtRu catalyst prepared in example 1;
FIG. 3 shows PtRu catalysts prepared in examples 1 to 6 at 0.5M H2SO4A performance diagram of hydrogen evolution reaction in the electrolyte;
FIG. 4 is a graph showing the performance of the PtRu catalysts prepared in examples 1 to 6 in a hydrogen evolution reaction in a 1M KOH electrolyte;
FIG. 5 shows the PtRu catalyst prepared in example 4 at 0.5M H2SO4A stability performance diagram of hydrogen evolution reaction in the electrolyte;
fig. 6 is a graph showing the stability of the PtRu catalyst prepared in example 4 in the hydrogen evolution reaction in a 1M KOH electrolytic solution.
Detailed Description
The invention will be further elucidated and described with reference to the embodiments and drawings of the specification:
in the technical scheme, all the raw materials are commercially available.
Example 1:
(1) firstly, soaking the carbon cloth in 0.001mol/L ruthenium chloride aqueous solution for 1min, loading ruthenium chloride on the carbon cloth, and then drying at 60 ℃.
(2) Calcining the carbon cloth obtained in the step (1) in a muffle furnace, heating to 200 ℃ at a speed of 5 ℃/min, calcining in air for 5min, and obtaining a product after calcination, namely RuO2A precursor.
(3) And (3) placing the precursor obtained in the step (2) into a standard three-electrode electrolytic cell, wherein the electrolyte is a 0.01mol/L sulfuric acid solution. Pt net, mercury mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electro-depositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition timeThe mass ratio of Pt to Ru is 0.01: 1.
FIG. 1 shows RuO2The transmission electron microscope shows that the single nano-particles have the particle size of about 3nm and are uniformly dispersed. FIG. 2 is a schematic representation of a RuO2The transmission electron microscope image of the PtRu catalyst after Pt is deposited on the precursor shows that the particle size and the morphology are basically unchanged before and after electrodeposition and are uniformly dispersed on the carbon cloth substrate.
Example 2:
(1) firstly, soaking titanium foam in 5mol/L ruthenium chloride aqueous solution for 120min, loading ruthenium chloride on the titanium foam, and then drying at 70 ℃.
(2) Calcining the foamed titanium obtained in the step (1) in a muffle furnace, heating to 600 ℃ at a speed of 5 ℃/min, calcining in air for 120min, and obtaining a product after calcination, namely RuO2A precursor.
(3) The RuO obtained in the step (2)2The precursor is placed in a standard three-electrode electrolytic cell, and the electrolyte is a 5mol/L sulfuric acid solution. Pt net, mercury mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electrodepositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition time to ensure that the mass ratio of Pt to Ru is 1: 1.
Example 3:
(1) firstly, soaking foamed nickel in 0.1mol/L ruthenium iodide aqueous solution for 60min, loading ruthenium iodide on the foamed nickel, and then drying at 80 ℃.
(2) Calcining the foamed nickel obtained in the step (1) in a muffle furnace, heating to 400 ℃ at a speed of 5 ℃/min, calcining in air for 40min, and obtaining a product after calcination, namely RuO2A precursor.
(3) The RuO obtained in the step (2)2The precursor is placed in a standard three-electrode electrolytic cell, and the electrolyte is 1mol/L sulfuric acid solution. Pt net, mercury mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electrodepositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition time to ensure that the mass ratio of Pt to Ru is 0.1: 1.
Example 4:
(1) firstly, soaking the carbon cloth in 0.2mol/L ruthenium chloride aqueous solution for 40min, loading ruthenium chloride on the carbon cloth, and then drying at 60 ℃.
(2) Calcining the carbon cloth obtained in the step (1) in a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, calcining for 80min in air, wherein the calcined product is RuO2A precursor.
(3) The RuO obtained in the step (2)2The precursor is placed in a standard three-electrode electrolytic cell, and the electrolyte is 0.5mol/L sulfuric acid solution. Pt net, mercury mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electrodepositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition time to ensure that the mass ratio of Pt to Ru is 0.5: 1.
Example 5:
(1) firstly, soaking foamed nickel in 0.3mol/L ruthenium chloride aqueous solution for 100min, loading ruthenium chloride on the foamed nickel, and then drying at 80 ℃.
(2) Calcining the foamed nickel obtained in the step (1) in a muffle furnace, heating to 400 ℃ at a speed of 5 ℃/min, calcining for 80min in air, wherein the calcined product is RuO2A precursor.
(3) The RuO obtained in the step (2)2The precursor is placed in a standard three-electrode electrolytic cell, and the electrolyte is a 5mol/L sulfuric acid solution. Pt net, mercury mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electrodepositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition time to ensure that the mass ratio of Pt to Ru is 0.2: 1.
Example 6:
(1) firstly, soaking the copper foam in 0.5mol/L ruthenium acetate water solution for 120min, loading ruthenium acetate on the copper foam, and then drying at 80 ℃.
(2) Calcining the foamy copper obtained in the step (1) in a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, calcining in air for 100min, and obtaining a product after calcination, namely RuO2A precursor.
(3) The RuO obtained in the step (2)2The precursor is placed in a standard three-electrode electrolytic cell, and the electrolyte is a 2mol/L sulfuric acid solution. Pt net, mercuric mercurous sulfate electrode and RuO obtained in step (2)2Precursors as counter, reference and working electrodes, respectively, in RuO2In-situ electrodepositing Pt on the precursor to obtain the PtRu catalyst, and controlling the deposition time to ensure that the mass ratio of Pt to Ru is 0.8: 1.
The PtRu catalysts prepared in examples 1-6 were used as working electrodes, carbon rods as counter electrodes, mercuric sulfate mercurous electrodes and mercuric oxide electrodes as reference electrodes in acidic and alkaline electrolytes, respectively, and electrochemical performance tests were performed using Chenghua 760E electrochemical workstation. The linear scan plot of the hydrogen evolution reaction in the acid electrolyte is shown in fig. 3, where the catalytic performance prepared in example 4 is best. The linear scan plot of the hydrogen evolution reaction in the alkaline electrolyte is shown in fig. 4, where the catalyst prepared in example 4 performs best.
In the above tests, the hydrogen evolution stability test result of the PtRu catalyst obtained in example 4 in the acidic electrolyte is shown in fig. 5, and the hydrogen evolution stability test result in the alkaline electrolyte is shown in fig. 6, indicating that the catalyst has good catalytic stability in both the acidic electrolyte and the alkaline electrolyte.
Therefore, the PtRu catalyst prepared by the method can be applied to serving as an electrolytic water hydrogen evolution electrode.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a PtRu catalyst is characterized by comprising the following steps:
s1, soaking the substrate material in ruthenium salt solution to load ruthenium on the substrate material, taking out the substrate material and drying;
s2, placing the dried substrate material in a muffle furnace for calcination to obtain RuO2A precursor;
s3 comparing RuO obtained in step S22The precursor is placed in a three-electrode electrolytic cell, and the electrolyte is sulfuric acid solution, Pt net, mercuric mercurous sulfate and obtained RuO2Precursors as counter, reference and working electrodes, RuO2The precursor electrodeposits Pt to obtain the PtRu catalyst.
2. The method for producing a PtRu catalyst according to claim 1, wherein in step S1, the base material is carbon cloth, titanium foam, copper foam, or nickel foam.
3. The preparation method of the PtRu catalyst according to claim 1, wherein in step S1, the ruthenium salt is ruthenium chloride, ruthenium iodide or ruthenium acetate.
4. The method for producing a PtRu catalyst according to claim 1, wherein in step S1, the concentration of the ruthenium salt solution is 0.001 to 5 mol/L.
5. The method for preparing a PtRu catalyst according to claim 1, wherein in step S1, the immersion time of the base material in the ruthenium salt solution is 1 to 120 min.
6. The preparation method of the PtRu catalyst according to claim 1, wherein in step S2, the calcination temperature of the dried substrate material in a muffle furnace is 200-600 ℃, and the calcination time is 5-120 min.
7. The method for producing a PtRu catalyst according to claim 1, wherein in step S3, the concentration of the sulfuric acid solution is 0.01 to 5 mol/L.
8. The method of producing a PtRu catalyst according to claim 1, wherein the mass ratio of Pt to Ru in the PtRu catalyst obtained in step S3 is 0.01:1 to 1: 1.
9. A PtRu catalyst, characterized by being produced by the production method for a PtRu catalyst according to any one of claims 1 to 8.
10. Use of the PtRu catalyst prepared by the method for preparing a PtRu catalyst according to any one of claims 1 to 8 as a hydrogen evolution electrode in electrolytic water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910441507.3A CN110354848B (en) | 2019-05-24 | 2019-05-24 | PtRu catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910441507.3A CN110354848B (en) | 2019-05-24 | 2019-05-24 | PtRu catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110354848A CN110354848A (en) | 2019-10-22 |
| CN110354848B true CN110354848B (en) | 2021-05-07 |
Family
ID=68215275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910441507.3A Active CN110354848B (en) | 2019-05-24 | 2019-05-24 | PtRu catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110354848B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167442A (en) * | 2020-01-05 | 2020-05-19 | 复旦大学 | Ruthenium-iridium composite oxide material doped with hydrated metal and preparation method and application thereof |
| CN113684498B (en) * | 2021-08-05 | 2023-01-24 | 中国科学技术大学 | Preparation method and application of monatomic alloy catalyst |
| CN113603191B (en) * | 2021-08-23 | 2022-11-01 | 中国科学院生态环境研究中心 | Metal ruthenium-based electrode and preparation method and application thereof |
| CN116103693B (en) * | 2022-11-25 | 2023-09-12 | 东莞理工学院 | Hydrogen evolution electrode, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN116062722B (en) * | 2023-02-24 | 2024-08-06 | 海卓动力(北京)能源科技有限公司 | Catalyst and preparation method and application thereof |
| CN116083952B (en) * | 2023-03-28 | 2023-06-13 | 西南石油大学 | Cu (copper) alloy 3 Ti nano-sheet loaded Ti-doped CuO/Ru hydrogen evolution reaction catalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6086957A (en) * | 1999-05-28 | 2000-07-11 | Sandia Corporation | Method of producing solution-derived metal oxide thin films |
| CN101122040A (en) * | 2007-05-21 | 2008-02-13 | 哈尔滨工程大学 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
| CN102477564A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing SPE (solid polymer electrolyte) anodic oxygen evolution catalysts for water electrolysis |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
| CN104124071A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Ruthenium dioxide-based composite nano-material and preparation method thereof |
| CN109713330A (en) * | 2018-11-13 | 2019-05-03 | 厦门大学 | Fuel battery anode catalyst and preparation method thereof |
-
2019
- 2019-05-24 CN CN201910441507.3A patent/CN110354848B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6086957A (en) * | 1999-05-28 | 2000-07-11 | Sandia Corporation | Method of producing solution-derived metal oxide thin films |
| CN101122040A (en) * | 2007-05-21 | 2008-02-13 | 哈尔滨工程大学 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
| CN102477564A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing SPE (solid polymer electrolyte) anodic oxygen evolution catalysts for water electrolysis |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
| CN104124071A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Ruthenium dioxide-based composite nano-material and preparation method thereof |
| CN109713330A (en) * | 2018-11-13 | 2019-05-03 | 厦门大学 | Fuel battery anode catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Direct methanol oxidation at low overpotentials using Pt nanoparticles electrodeposited at ultrathin conductive RuO2 nanoskins;Jeremy J. Pietron等;《J. Mater. Chem.》;20120206;第22卷;5197–5204 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110354848A (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110354848B (en) | PtRu catalyst and preparation method and application thereof | |
| CN109659143B (en) | Nickel hydroxide/trinickel disulfide/foamed nickel compound and preparation method and application thereof | |
| CN110201697B (en) | Three-dimensional nitrogen-doped transition metal oxide/nickel sulfide composite catalyst, and preparation method and application thereof | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| CN107008461B (en) | Honeycomb macroporous structure transition metal-based catalyst electrode and preparation method and application thereof | |
| WO2020252820A1 (en) | Ferronickel catalytic material, preparation method therefor, and application thereof in preparing hydrogen from electrolyzed water and preparing liquid solar fuel | |
| CN110433829B (en) | MoO (MoO)2-NiSx/CC hydrogen evolution electrocatalyst and preparation method thereof | |
| CN108315758B (en) | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof | |
| CN115369422A (en) | Low-iridium electrolyzed water catalyst, and preparation method and application thereof | |
| CN114289043B (en) | Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst | |
| CN110841658A (en) | Preparation method of cobalt-based sulfide nanorod array | |
| CN110565113B (en) | Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution | |
| CN110629248A (en) | Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst | |
| CN110354870B (en) | Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst | |
| CN109012673B (en) | Preparation method and application of oxygen evolution catalyst | |
| CN109012683B (en) | Preparation method of cobalt molybdate hollow microsphere electrocatalyst | |
| CN115261915B (en) | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof | |
| CN113981468B (en) | Multi-dimensional nickel-cobalt-based sulfide heterojunction electrocatalytic composite material and preparation method thereof | |
| CN113174611B (en) | Self-supporting Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode and preparation method thereof | |
| CN114990615B (en) | Preparation method of molybdenum disulfide-cobalt sulfide@passivation layer composite material | |
| CN113802144A (en) | Preparation method and application of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst | |
| CN113802143A (en) | Preparation method and application of hierarchical pore covalent organic framework compound and metal composite hydrogen evolution catalyst | |
| CN112501645A (en) | Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof | |
| CN111957329A (en) | Preparation method of self-supporting Ni2P-WOx hydrogen evolution electrocatalyst | |
| CN110433818B (en) | Nickel molybdate-carbon composite nanosphere, preparation method and application of nickel molybdate-carbon composite nanosphere as electrolytic water hydrogen evolution catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |