CN113026032A - Ruthenium atom-level loaded manganese oxide catalyst and preparation method and application thereof - Google Patents
Ruthenium atom-level loaded manganese oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN113026032A CN113026032A CN202110262336.5A CN202110262336A CN113026032A CN 113026032 A CN113026032 A CN 113026032A CN 202110262336 A CN202110262336 A CN 202110262336A CN 113026032 A CN113026032 A CN 113026032A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 72
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000002378 acidificating effect Effects 0.000 claims abstract description 30
- 239000012265 solid product Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000002070 nanowire Substances 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 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 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明提供一种钌原子级负载的氧化锰催化剂及其制备方法和应用。该制备方法包括以下步骤：1)将混合溶液进行水热反应后，过滤、洗涤、干燥，获得固体产物；混合溶液包括锰盐、氧化剂、孔道填充剂和水；2)将固体产物和钌盐在溶剂水中进行反应，过滤、洗涤、干燥、焙烧、冷却，获得催化剂。通过该制备方法获得钌原子级负载的氧化锰催化剂，将原子级均匀分散的钌元素组分锚定在酸性介质稳定的氧化锰纳米线外表面，有效提高钌金属活性位点的分散效果，优化活性位点的电荷分布结构，提高活性位点的本征活性和稳定性，作为酸性电解质条件下电解水制氢电解池阳极材料，应用于酸性条件下电解水制氢电解池中，具有优异的酸性析氧反应催化活性和稳定性。The present invention provides a ruthenium atom-level supported manganese oxide catalyst, a preparation method and application thereof. The preparation method includes the following steps: 1) after the mixed solution is subjected to a hydrothermal reaction, filtered, washed and dried to obtain a solid product; the mixed solution includes a manganese salt, an oxidant, a pore filler and water; 2) the solid product and the ruthenium salt are combined The reaction is carried out in solvent water, filtered, washed, dried, calcined and cooled to obtain a catalyst. Through the preparation method, a ruthenium atomically supported manganese oxide catalyst is obtained, and the atomically uniformly dispersed ruthenium element components are anchored on the outer surface of the manganese oxide nanowires stabilized by an acidic medium, which effectively improves the dispersion effect of ruthenium metal active sites, and optimizes the The charge distribution structure of the active site improves the intrinsic activity and stability of the active site. As an anode material for electrolysis of water for hydrogen production under acidic electrolyte conditions, it is used in electrolysis of water for hydrogen production under acidic conditions. Catalytic activity and stability of acidic oxygen evolution reaction.
Description
Technical Field
The invention belongs to the technical field of nano materials and energy technology, relates to a ruthenium atomic-scale loaded manganese oxide catalyst, a preparation method and application thereof, and particularly relates to an acidic stable oxygen evolution reaction catalytic material, namely an anode material for hydrogen production by water electrolysis, a preparation method thereof and application thereof in the field of hydrogen production by water electrolysis.
Background
Renewable energy such as wind energy, tidal energy and solar energySource power generation has become the cheapest power generation technology in recent years. The conversion of renewable energy sources into "fuels" is an important renewable energy strategy to cope with the exhaustion of fossil fuels and climate change in the future. The hydrogen production by electrolyzing water by using renewable energy is one of the most feasible large-scale renewable energy storage and utilization technologies at present. Among the numerous water electrolysis technologies, Proton Exchange Membrane (PEM) water electrolysis technologies are of great interest. The electrocatalytic Oxygen Evolution Reaction (OER) is an important anodic half-reaction in this electrocatalytic energy conversion technology. However, OER is kinetically slow and requires an efficient oxygen evolution electrocatalyst to lower the reaction energy barrier and thus accelerate the reaction. Despite the extensive efforts to develop efficient and stable basic OER catalysts, little has been done in the development of acidic OER electrocatalysts. Because the electrocatalysis reaction in the acidic PEM electrolytic cell has the advantages of higher mass transfer speed, higher product purity, higher reaction efficiency and the like, the development of the high-efficiency acidic OER electrocatalyst has more important large-scale industrial application significance. To date, highly active and stable acidic OER electrocatalysts are still lacking, which greatly hinders the development of electrocatalytic energy conversion reactions in acidic media. At present, although RuO2The catalyst is an acidic oxygen evolution catalyst with the highest intrinsic activity, but the storage capacity is limited, the cost is high, and the utilization rate of the noble metal needs to be improved as much as possible in order to reduce the use amount of the noble metal and the cost of the catalyst. Increasing the active site density per unit area by maximizing the dispersion of the noble metal is the most effective method for reducing the noble metal materials and improving the utilization rate of the noble metal. A common strategy is to load noble metal nanoparticles on a corrosion-resistant conductive support with high specific surface area, such as RuO2(ii)/CNT and RuO2Gr, but the interaction force between the active component and the carrier in the system is relatively weak, the dispersion degree of the active sites is limited, the agglomeration is easy, and the activity and the stability of the catalyst are not ideal.
Manganese oxide is the most common acidic and stable transition metal oxide, has low cost, is environment-friendly and harmless to human bodies, and is known as the most potential high-stability non-noble metal acidic OER catalyst. And the manganese oxide can realize the secondary deposition of manganese ions on the surface of the manganese oxide through a self-repairing mechanism under the acidic electrolytic oxygen evolution reaction environment, and the tolerance capability and the performance stability of the manganese oxide in an acidic reaction system are greatly improved through the mechanism. However, due to the high OER reaction energy barrier of manganese oxide, a single manganese oxide nanomaterial cannot meet commercial requirements.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a ruthenium atom-grade supported manganese oxide catalyst, and a preparation method and application thereof, so as to solve the problems of few types, low activity and poor stability of the existing acidic OER catalyst. The ruthenium atomic-level loaded manganese oxide catalyst obtained by the preparation method can anchor the ruthenium element component uniformly dispersed at atomic level on the outer surface of the manganese oxide nanowire stable in an acidic medium, effectively improve the dispersion effect of ruthenium metal active sites, optimize the charge distribution structure of the active sites, improve the intrinsic activity and stability of the active sites, and stably operate for a long period in an acidic electrolyte environment so as to solve the problem of poor stability of an anode material in the acidic electrolyte environment, and has a long service life.
In order to achieve the above and other related objects, a first aspect of the present invention provides a method for preparing a ruthenium atom-scale supported manganese oxide catalyst, comprising the steps of:
1) carrying out hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a solid product; the mixed solution comprises manganese salt, an oxidant, a pore filler and solvent water;
2) and (3) reacting the solid product with ruthenium salt in solvent water, filtering, washing, drying, roasting and cooling to obtain the catalyst.
Preferably, step 1) further comprises at least one of the following technical features:
1a) the manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese nitrate and manganese chloride;
1b) the oxidant is persulfate;
1c) the pore filler is selected from at least one of potassium salt, sodium salt and ammonium salt;
1d) the molar ratio of the manganese salt to the oxidant is 0.5-2: 1, such as 0.5-0.99: 1. 0.99 to 1: 1. 1-1.02: 1 or 1.02-2: 1;
1e) the molar ratio of the manganese salt to the pore canal filler is 1: 2-5, such as 1: 2-3, 1: 3-3.05, 1: 3.05-3.07, 1: 3.07-5;
1f) in the mixed solution, the concentration of the oxidant is 0.1-2.0mol/l, such as 0.1-0.28mol/l, 0.28-0.6mol/l or 0.6-2.0 mol/l.
More preferably, at least one of the following technical characteristics is also included:
1b1) the feature 1b) is that the persulfate is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium persulfate;
1c1) in the feature 1c), the potassium salt is at least one selected from potassium sulfate, potassium acetate, potassium nitrate and potassium chloride;
1c2) in the feature 1c), the sodium salt is at least one selected from the group consisting of sodium sulfate, sodium acetate, sodium nitrate and sodium chloride;
1c3) in the feature 1c), the ammonium salt is at least one selected from the group consisting of ammonium sulfate, ammonium acetate, ammonium nitrate and ammonium chloride;
1d1) in feature 1d), the molar ratio of the manganese salt to the oxidizing agent is 0.5 to 1.5: 1;
1e1) characteristic 1e), the molar ratio of the manganese salt to the pore filler is 1: 2.5 to 3.5;
1f1) in feature 1f), the concentration of the oxidizing agent is 0.2 to 1.0 mol/l.
Preferably, step 1) further comprises at least one of the following technical features:
1h) the reaction temperature of the hydrothermal reaction is 100-180 ℃, such as 100-140 ℃ or 140-180 ℃;
1i) the reaction time of the hydrothermal reaction is 0.5-24h, such as 0.5-12h or 12-24 h;
1j) the hydrothermal reaction is carried out in a hydrothermal kettle;
1k) after the hydrothermal reaction, carrying out filtration treatment in a suction filtration mode;
1l) the washing is one or more times with deionized water and/or ethanol;
1m) the drying temperature is 60-100 ℃, such as 60-80 ℃ or 80-100 ℃;
1n) the drying time is 1-24h, such as 1-12h or 12-24 h.
Preferably, step 2) further comprises at least one of the following technical features:
2a) the solid product is in MnO2The ratio of the calculated molar amount to the molar amount of the ruthenium salt is 1: 1 to 50, such as 1: 1-3.21, 1: 3.21-6.43, 1: 6.43-12.85, 1: 12.85-25.71 or 1: 25.71-50;
2b) the concentration of the ruthenium salt is 1 to 15mol/L, such as 1 to 1.205mol/L, 1.205 to 2.41mol/L, 2.41 to 4.82mol/L, 4.82 to 9.64mol/L, or 9.64 to 15mol/L, based on the total amount of the solid product, the ruthenium salt, and the solvent water;
2c) the ruthenium salt is selected from one or more of ruthenium acetate, ruthenium nitrate and ruthenium chloride;
2d) the reaction time is 1-24h, such as 1-12h or 12-24 h;
2e) the reaction is a stirring reaction at room temperature; the room temperature is 20-30 ℃;
2f) the filtration mode is suction filtration;
2g) washing is carried out after the filtration, and the washing is carried out for one time or multiple times by adopting water;
2h) the drying temperature is 50-80 deg.C, such as 50-70 deg.C or 70-80 deg.C;
2i) the drying time is 2-24h, such as 2-12h or 12-24 h;
2j) the roasting temperature is 150-250 ℃, such as 150-200 ℃ or 200-250 ℃;
2k) the roasting time is 1-5 h;
2l) the roasting atmosphere is air atmosphere;
2m) the cooling is natural cooling to room temperature; the room temperature is 20-30 ℃;
2n) mixing the solid product and part of solvent water in an ultrasonic dispersion mode to obtain a first solution; mixing the ruthenium salt and the residual solvent water to obtain a second solution; and mixing the first solution and the second solution for reaction.
More preferably, at least one of the following technical characteristics is also included:
2a1) in feature 2a), the solid product is in the form of MnO2The ratio of the calculated molar amount to the molar amount of the ruthenium salt is 1: 3-30;
2b1) in the feature 2b), the concentration of the ruthenium salt is 2 to 20 mol/L;
2d1) in the characteristic 2d), the reaction time is 10-24 h;
2n1) feature 2n), the ultrasound time of the ultrasound dispersion is 10-60 min;
2n2) feature 2n), the ruthenium salt concentration of the second solution is 2 to 30mol/L, such as 2 to 2.41mol/L, 2.41 to 4.82mol/L, 4.82 to 9.64mol/L, 9.64 to 19.28mol/L, or 19.28 to 30 mol/L.
More preferably, at least one of the following technical characteristics is also included:
2j1) in the characteristic 2j), the roasting temperature is 150-230 ℃;
2k1) in the characteristic 2k), the roasting time is 1-3 h.
The invention provides a manganese oxide catalyst loaded on a ruthenium atom scale, which is prepared by the preparation method.
Preferably, the nano-wire comprises atomically dispersed ruthenium element multi-center active sites and manganese oxide nano-wires.
In a third aspect, the invention provides the use of the ruthenium atom-scale-supported manganese oxide catalyst as an anode material for an acidic aqueous solution electrolytic cell.
As mentioned above, the ruthenium atom-level supported manganese oxide catalyst, the preparation method and the application thereof provided by the invention have the following beneficial effects:
(1) according to the ruthenium atomic-level loaded manganese oxide catalyst, the ruthenium element components uniformly dispersed at the atomic level are anchored on the outer surface of the manganese oxide nanowire stable in an acidic medium, so that the dispersion effect of ruthenium metal active sites is effectively improved, the charge distribution structure of the active sites is optimized, and the intrinsic activity and stability of the active sites are improved.
(2) The ruthenium atom-level loaded manganese oxide catalyst can be used as a high-performance acidic oxygen evolution reaction electrocatalyst, can stably and efficiently perform Oxygen Evolution Reaction (OER) in an acidic electrolyte environment, can be used as an anode material for hydrogen production by water electrolysis, is used in a proton conduction polymer membrane electrolytic hydrogen production electrolytic cell, and solves the problems of few types, low performance and short service life of the existing acidic oxygen evolution catalyst.
Drawings
FIG. 1 shows Ru/MnO as described in examples and comparative examples2X-ray diffraction patterns 1a and 1b for catalysts, where FIG. 1a is the Ru/MnO described in the examples2X-ray diffraction Pattern of the catalyst, FIG. 1b shows Ru/MnO as described in example 4 and comparative examples 1# and 2#2X-ray diffraction pattern of the catalyst.
FIG. 2 shows the Ru/MnO in the scanning example of a scanning electron microscope2The resulting image of the catalyst.
FIG. 3 shows Ru/MnO in example 42Synchrotron radiation X-ray absorption fine structure spectrum of the catalyst.
FIG. 4 shows Ru/MnO2Oxygen evolution polarization curve results for the catalyst.
FIG. 5 shows Ru/MnO2The oxygen evolution catalytic performance of the catalyst is compared with that of the reported acidic OER catalyst.
FIG. 6 shows Ru/MnO2The catalyst (example 4) was used at a current density of 10mAcm-2Next, the long-cycle stability test results.
FIG. 7 shows Ru/MnO before and after electrocatalytic reaction for scanning by a high angle annular dark field scanning transmission electron microscope after spherical aberration correction2Images 7a, 7b obtained with the catalyst (example 4), where FIG. 7a is Ru/MnO2Electron microscope images before catalyst reaction; FIG. 7b shows Ru/MnO2Electron microscope images after catalyst reaction.
FIG. 8 shows Ru/MnO before and after the reaction2Catalyst energy scattering X-ray spectra 8a, 8b, where FIG. 8a is Ru/MnO2Energy scattering X-ray spectroscopy before catalyst reaction; FIG. 8b shows Ru/MnO2The energy after the catalyst reaction scatters the X-ray spectrum.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
0.02mol of manganese sulfate and 0.06mol of potassium sulfate are added into 70ml of ammonium persulfate aqueous solution with the concentration of 0.28mol/l, and a mixed solution is obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
15mmol of solid is producedThe substance A is dispersed in 20mL of deionized water by ultrasound, 20mL of RuCl with the concentration of 2.41mol/l is added in one time3The aqueous solution is vigorously stirred and reacts for 1 hour, the solution is filtered until solid precipitate is completely dried, a large amount of deionized water is adopted for washing for many times, the solid precipitate is dried for 12 hours at the temperature of 80 ℃, the solid precipitate is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and the solid precipitate is naturally cooled to room temperature to obtain Ru/MnO2Catalyst sample # 1.
Example 2
0.014mol of manganese nitrate and 0.043mol of potassium nitrate were added to 50ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and completely dissolved to obtain a mixed solution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
Ultrasonically dispersing 15mmol of solid product A in 20ml of deionized water, and adding 20ml of RuCl with the concentration of 4.82mol/l in one step3The aqueous solution is vigorously stirred and reacts for 1 hour, the solution is filtered until solid precipitate is completely dried, a large amount of deionized water is adopted for washing for many times, the solid precipitate is dried for 8 hours at the temperature of 80 ℃, the solid precipitate is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and the solid precipitate is naturally cooled to room temperature to obtain Ru/MnO2 Catalyst sample # 2.
Example 3
0.028mol of manganese nitrate and 0.086mol of potassium nitrate were added to 100ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and a mixed solution was obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
Ultrasonically dispersing 15mmol of solid product A in 20ml of deionized water, and adding 20ml of RuCl with the concentration of 9.64mol/l in one step3The aqueous solution is vigorously stirred and reacts for 1 hour, the solution is filtered until solid precipitate is completely dried, a large amount of deionized water is adopted for washing for many times, the solid precipitate is dried for 12 hours at 70 ℃, the solid precipitate is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and the solid precipitate is naturally cooled to room temperature to obtain Ru/MnO2 Catalyst sample # 3.
Example 4
0.021mol of manganese nitrate and 0.064mol of potassium nitrate were added to 75ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and the mixture was completely dissolved to obtain a mixed solution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion3The aqueous solution is vigorously stirred and reacts for 12 hours, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for a plurality of times, is dried for 12 hours at 80 ℃, is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO2 Catalyst sample # 4.
Example 5
0.028mol of manganese nitrate and 0.086mol of potassium nitrate were added to 14ml of an aqueous ammonium persulfate solution having a concentration of 2.0mol/l, and a mixed solution was obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion3The aqueous solution is vigorously stirred and reacts for 12 hours, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for a plurality of times, is dried for 12 hours at 80 ℃, is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO2 Catalyst sample # 5.
Example 6
0.028mol of manganese nitrate and 0.086mol of potassium sulfate are added into 47ml of 0.6mol/l ammonium persulfate aqueous solution, and a mixed solution is obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.
30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion3The aqueous solution is stirred vigorously to react for 12 hours, and then is filtered until the solid is precipitated completelyFully drying, washing with a large amount of deionized water for multiple times, drying at 80 deg.C for 12h, calcining at 200 deg.C in air atmosphere for 1h, and naturally cooling to room temperature to obtain Ru/MnO2Catalyst sample # 6.
Ru/MnO obtained in examples 1-62Catalyst samples # 1-6 were subjected to X-ray testing and the results are shown in figure 1. As can be seen from fig. 1a and 1b, the support in the catalyst is alpha-phase manganese oxide, and no characteristic peak corresponding to ruthenium and its oxide is found, which indicates that the ruthenium element of the sample prepared in the example is uniformly dispersed and no agglomeration occurs. From FIG. 1b, when MnO was changed2Nanowire preparation conditions, MnO2The peak intensity of the corresponding characteristic peak is obviously changed, which shows that the MnO is improved by the high manganese ion concentration2The crystallinity of (a).
Ru/MnO obtained in examples 1-42Catalyst samples # 1-4, were scanned by scanning electron microscopy and the results are shown in figure 2. As can be seen from fig. 2, the catalysts described in examples 1 to 4 are all of nanowire structure, and the surface roughness gradually increases with the increase of the loading amount of the ruthenium element, which indicates that the ruthenium element can be effectively loaded on the surface of the manganese oxide carrier through the cation exchange reaction.
Ru/MnO obtained in example 42And 4# catalyst sample, performing synchrotron radiation X-ray absorption spectrum fine structure analysis, and obtaining a test result shown in figure 3. From the fitting result of the curve of FIG. 3, Ru/MnO2In the catalyst, the coordination number of the Ru-O bond is 6, and the coordination number of the Ru-Ru bond is 2.7, which shows that the Ru active sites in the catalyst are of a multi-center atomic-level dispersed structure connected by the Ru-O bond, and the active sites can effectively cooperate with each other, thereby providing a structural basis for realizing the oxygen evolution reaction depending on an oxide path, and being beneficial to accelerating the promotion of the catalytic process of the oxygen evolution reaction on the premise of not influencing the stability of the material.
Ru/MnO obtained in examples 1 to 4 was measured2Catalyst samples 1-4# at 0.1M HClO4The oxygen evolution reaction in aqueous solution is catalytically active and the results are shown in fig. 4 and 5. As can be seen from FIGS. 4 and 5, the optimized Ru/MnO2The catalyst shows excellent OER catalytic performance of an acid electrolyte system, 10mAcm-2The overpotential is only 161mVIs superior to RuO2Catalysts, and other noble metal acidic OER catalysts have been reported.
Ru/MnO obtained in example 42And 4# catalyst sample, carrying out a constant current oxygen evolution reaction stability test, and the test result is shown in figure 6. As can be seen from FIG. 6, Ru/MnO2The catalyst can effectively carry out OER reaction for more than 100h, has no obvious performance attenuation, and fully proves the stability of the catalytic performance. Scanning of the Ru/MnO obtained in example 4 with a high angle annular dark field scanning transmission electron microscope after spherical aberration correction2The images of catalyst sample No. 4 before and after the stability test of oxygen evolution reaction are shown in FIG. 7. As can be seen from FIG. 7a, the Ru/MnO was prior to the OER reaction2Orderly arranged bright spots were observed on the surface of the catalyst, and Ru/MnO after the reaction was shown in FIG. 7b2The catalyst surface is enriched with more obvious ordered bright spots arranged in an array manner. As can be seen from the results of the energy scattering X-ray spectroscopy of fig. 8, the ordered bright spots in the sample before and after the reaction correspond to Ru atoms. The Ru element can be self-assembled to form an ordered array structure in the OER reaction process, and the single atomic layer and multi-center synergistic ruthenium atom structure is beneficial to the catalyst to efficiently and stably drive the electrolytic oxygen generation reaction to be carried out by depending on a metal oxide mechanism.
In conclusion, the invention provides a preparation method and application of a high-performance oxygen evolution reaction catalyst suitable for an acidic electrolyte system, and prepared Ru/MnO2The catalyst can be used as an anode material of an electrolytic cell for producing hydrogen by electrolyzing water, solves the problems of few types, low performance and short service life of the existing acidic electrolyte system oxygen evolution reaction catalyst, and prepares the Ru/MnO2The catalyst shows excellent oxygen evolution reaction activity and long-period stability under an acidic system, and is far superior to most of reported related catalysts. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
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