CN115404515A - Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof - Google Patents

Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof Download PDF

Info

Publication number
CN115404515A
CN115404515A CN202211208891.0A CN202211208891A CN115404515A CN 115404515 A CN115404515 A CN 115404515A CN 202211208891 A CN202211208891 A CN 202211208891A CN 115404515 A CN115404515 A CN 115404515A
Authority
CN
China
Prior art keywords
ruthenium
manganese
carbon
salt
preparation
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.)
Pending
Application number
CN202211208891.0A
Other languages
Chinese (zh)
Inventor
王得丽
王双
黄晓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN202211208891.0A priority Critical patent/CN115404515A/en
Publication of CN115404515A publication Critical patent/CN115404515A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a carbon-loaded ruthenium-manganese compound, a preparation method and application thereof. The preparation method comprises the following steps: (1) Dispersing ruthenium salt, manganese salt and a carbon carrier in a solvent, heating and ultrasonically treating until the solvent is evaporated to dryness, so that the ruthenium salt and the manganese salt are adsorbed on the carbon carrier to obtain intermediate solid powder; (2) And carrying out thermal reduction on the intermediate solid powder in a reducing atmosphere, so that ruthenium salt and manganese salt are decomposed and reduced to obtain the carbon-supported ruthenium-manganese alloy. By introducing the Mn-cheap metal manganese, the catalyst cost is reduced, the noble metal loading capacity is reduced, and the catalytic activity and stability of the Ru-based material are improved. The catalyst achieves the aim of good OER oxygen precipitation activity and stability, and overcomes the technical problems of over high consumption of noble metal, poor activity, poor stability and the like of the traditional acidic oxygen precipitation catalyst.

Description

Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon-supported ruthenium-manganese compound, and a preparation method and application thereof.
Background
Along with the increasing demand of fossil energy, a series of problems of environmental pollution, energy crisis and the like are caused, and researchers are forced to seek high-efficiency, clean and sustainable energy composition to optimizeCurrent energy architectures. Among them, hydrogen energy is considered as a clean energy with high energy density, zero pollution, and long-term storage, and is considered as a key ring for solving the problems of energy crisis, environmental pollution, and greenhouse effect. As an ideal technology for hydrogen production, the water electrolysis technology produces high-purity oxygen and hydrogen driven by electric energy without producing any by-products, and can be coupled with fuel cell technology to realize hydrogen circulation. At present, acidic proton exchange membrane electrolyzers (pempes) and alkaline electrolyzers (AWEs) have been scaled up for practical use. PEMWEs have higher operating current densities (2-3A cm maximum) than conventional AWEs -2 ) Greater energy power density, faster hydrogen production rates, higher purity hydrogen output, better ionic conductivity, and wider operating temperature and pressure ranges make pemves the best candidates for coupling with energy of the fluctuating input type. Currently, the main challenges facing the industrialization of the electrolytic water technology are the high energy barrier and slow kinetics of the anodic Oxygen Evolution Reaction (OER) and the stability of the anodic catalytic material in a strong acid environment. Therefore, the development of efficient and stable anode electrocatalysts is the key to commercialization of pempes.
For acidic water electrolysis, OER catalysts rely primarily on noble metal-based materials, and although some reports indicate that non-noble metal electrocatalysts have some OER activity in acids, they still face more severe stability problems than noble metal-based materials. So far, the acidic oxygen evolution reaction is still dominated by Ru-based and Ir-based noble metal electrocatalysts. Compared with an Ir-based material, the Ru-based material has higher oxygen evolution activity, higher abundance and far lower price than the Ir-based material. Therefore, the Ru-based material is considered to be the electrocatalyst with the most application prospect in the current acidic medium OER process. However, the stability of Ru-based catalysts remains a very challenging problem.
Disclosure of Invention
In view of the above defects or improvement requirements of the prior art, the present invention provides a carbon-supported ruthenium-manganese compound, a preparation method and applications thereof, which aim to reduce the noble metal loading amount, and improve the catalytic efficiency and stability of the catalyst, thereby solving the technical problem of acidic electrolyzed water.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a carbon-supported ruthenium manganese compound, comprising the steps of:
(1) Dispersing ruthenium salt, manganese salt and a carbon carrier in a solvent, heating and ultrasonically treating until the solvent is evaporated to dryness, so that the ruthenium salt and the manganese salt are adsorbed on the carbon carrier to obtain intermediate solid powder;
(2) And carrying out thermal reduction on the intermediate solid powder in a reducing atmosphere, so that ruthenium salt and manganese salt are decomposed and reduced to obtain the carbon-supported ruthenium-manganese alloy.
Preferably, the thermal reduction comprises a pre-sintering stage and a thermal reduction stage which are sequentially carried out, wherein the temperature of the pre-sintering stage is 200-500 ℃, the pre-sintering time is 0.5-2 h, the temperature rise rate of the pre-sintering stage is 5-10 ℃/min, the temperature of the thermal reduction stage is 900-1000 ℃, the heating time of the thermal reduction stage is 2-10 h, and the temperature rise rate of the thermal reduction stage is 5-10 ℃/min.
Preferably, the mass ratio of the ruthenium element in the intermediate solid powder is 5-45%.
Preferably, the atomic ratio of ruthenium to manganese in the carbon-supported ruthenium manganese alloy is 1: (1-9).
Preferably, the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate, ruthenocene, potassium ruthenate, ammonium ruthenate chloride, sodium ruthenate chloride and potassium ruthenate chloride; the manganese salt is at least one of manganese nitrate, manganese chloride, manganese acetate, manganese sulfate and manganese acetylacetonate.
Preferably, the carbon support is at least one of carbon black, graphene oxide, reduced graphene oxide, carbon nanotubes, carbon nanofibers, and carbon quantum dots.
Preferably, the reducing atmosphere in the step (2) comprises a mixed gas of hydrogen and argon with a hydrogen volume fraction of 2-50% or a mixed gas of hydrogen and nitrogen with a hydrogen volume fraction of 2-50%; the solvent is at least one of water, ethanol, methanol, acetone, acetonitrile or tetrahydrofuran.
Preferably, the ultrasonic time in the step (1) is 0.5 to 3 hours; the heating temperature in the step (1) is 45-75 ℃.
According to another aspect of the invention, a carbon-supported ruthenium-manganese compound is provided, wherein the ruthenium-manganese compound in the carbon-supported ruthenium-manganese compound is a ruthenium-manganese alloy.
According to another aspect of the invention, the application of the carbon-supported ruthenium-manganese compound is provided, which is used for an acidic oxygen evolution electrocatalytic reaction and a proton exchange membrane water electrolysis anode catalyst.
In general, at least the following advantages can be obtained by the above technical solution contemplated by the present invention compared to the prior art.
(1) By introducing the Mn-cheap metal manganese, the catalyst cost is reduced, the noble metal loading capacity is reduced, and the catalytic activity and stability of the Ru-based material are improved. The catalyst achieves the aim of good OER oxygen precipitation activity and stability, and overcomes the technical problems of over high consumption of noble metal, poor activity, poor stability and the like of the traditional acidic oxygen precipitation catalyst. The preparation method is simple, has low requirements on production equipment, is easy to obtain raw materials, and is beneficial to large-scale development of catalytic materials.
(2) The formation of the ruthenium-manganese alloy is realized by adopting the heat treatment for 2 times, and particularly, the thermal reduction comprises a pre-burning stage and a thermal reduction stage which are sequentially carried out, so that on one hand, the ruthenium salt is easy to be reduced and nucleated in the low-temperature pre-reduction process, and the self-catalytic action of the Ru nano particles is utilized to realize better alloying in the subsequent reduction process. On the other hand, mn is difficult to reduce, and is usually in an oxidation state in an indoor environment, and in the application, pure-phase ruthenium-manganese alloy can be obtained only at the temperature higher than 900 ℃ in a thermal reduction stage, and MnO impurities can be generated at low temperature. The formation of pure-phase ruthenium-manganese alloy is beneficial to improving the stability of the catalyst.
(3) In the application, when the carbon-loaded ruthenium-manganese alloy is applied, carbon cloth or carbon paper is abandoned as a substrate, and a corrosion-resistant titanium mesh is adopted as the substrate, so that the high-efficiency and stable self-supporting electrode is prepared.
Drawings
FIG. 1 shows RuMn at different temperatures in example 1 3 An X-ray diffraction (XRD) pattern of/C;
FIG. 2 shows RuMn as a ruthenium manganese alloy on carbon at 900 ℃ in example 1 3 X-ray diffraction (XRD) patterns of/C and the carbon-supported ruthenium elemental Ru/C;
FIG. 3 shows RuMn on carbon at different temperatures in example 3 3 LSV polarization curve of/C;
FIG. 4 is a test curve for acidic oxygen evolution in example 3;
FIG. 5 is a graph showing the test curve of the stability of acid oxygen evolution in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides a carbon-supported ruthenium-manganese alloy, and a preparation method thereof comprises the following steps:
the method comprises the following steps: uniformly dispersing Vulcan carbon in a ruthenium chloride and manganese acetate aqueous solution, and carrying out ultrasonic stirring for 30min;
step two: stirring the mixed solution obtained in the first step at 65 deg.C, ultrasonically evaporating to dryness to obtain intermediate solid powder (wherein the Ru loading is 20%, and the atomic ratio of Ru to Mn is 1:3), and adding the obtained Ru-Mn precursor into the mixed solution at 10% 2 Presintering for 2h under the condition of 300 ℃ in mixed atmosphere, and then performing high-temperature thermal reduction at 500 ℃, 700 ℃, 900 ℃ and 1000 ℃ respectively to obtain the carbon-supported ruthenium-manganese alloy, wherein the heating rate is 10 ℃/min.
Comparative example 1
The comparative example provides a carbon-supported ruthenium-manganese alloy, and the preparation method comprises the following steps:
the method comprises the following steps: uniformly dispersing Vulcan carbon in a ruthenium chloride aqueous solution, performing ultrasonic stirring for 30min, wherein the loading capacity of Ru is 20%;
step two: and (3) heating, stirring and ultrasonically treating the mixed solution obtained in the step one until the water solvent is evaporated to dryness to obtain intermediate solid powder (the mass fraction of Ru in the solid powder is 20%), and then placing the intermediate solid powder in a vacuum drying oven for vacuum drying. The milled precursor was 10% Ar/H 2 Heating for 2 hours at 500 ℃ in a mixed atmosphere to obtain a carbon-supported ruthenium simple substance, wherein the heating rate is 10 ℃/min;
example 3
The carbon-supported elemental ruthenium and the ruthenium-manganese alloy prepared in example 1 and comparative example 1 were subjected to an acidic oxygen evolution test, and 5mg of the ruthenium-manganese alloy catalyst powder was added to 1mL of an isopropyl alcohol/Nafion mixed solution to prepare an ink (wherein the mass fraction of Nafion is one thousandth). And (4) ultrasonically mixing the ink for 20 min. And (3) transferring 5uL of ink by using a liquid transfer gun, uniformly coating the ink on the electrode of the rotary ring disk, and naturally drying the ink. The rotating ring disk electrode loaded with the catalyst is used as a working electrode, the carbon rod is used as an auxiliary electrode, and the reversible hydrogen electrode is used as a reference electrode. 250-turn activation is carried out in 0.1mol/L perchloric acid solution at 1.2-1.4V, and the sweep rate is 200mV/s. The polarization curves were then tested in an oxygen-saturated 0.1mol/L perchloric acid solution at a sweep rate of 5mV/s and a rotational speed of 1600rpm/min in the range from 1.2 to 1.65V. In addition, the stability of the catalyst was tested in a 0.1mol/L perchloric acid solution saturated with oxygen using a constant current density of 10mA/cm 2 。
FIG. 1 shows RuMn at different temperatures in example 1 3 An X-ray diffraction (XRD) pattern of/C shows that manganese which is easy to oxidize is gradually reduced along with the increase of temperature, and the result proves the synthesis of the carbon-supported ruthenium-manganese alloy. It can be seen that when the temperature is lower than 900 ℃, the XRD peak of MnO appears, indicating the generation of impurities, while the 900 ℃ is followed by pure phase ru-mn alloy.
FIG. 2 shows RuMn as a carbon-supported Ru-Mn alloy at 900 ℃ in example 1 3 X-ray diffraction (XRD) patterns of/C and of Ru/C elemental ruthenium on carbon, the introduction of manganese caused the lattice of ruthenium to shrink, which indicates the successful preparation of Ru elemental ruthenium on carbonAnd (4) preparing. Ruthenium lattice shrinkage proves that alloying is successfully realized between ruthenium and manganese, and strong combination is favorable for adjusting the electronic structure of Ru to promote the promotion of catalytic activity and can improve the stability of Ru.
FIG. 3 shows RuMn on carbon at different temperatures in example 3 3 The LSV polarization curve of/C shows that the activity of the catalyst increases with increasing temperature, and the activity of the material peaks when the temperature reaches 900 ℃. With further increase in temperature, over-ripening leads to a decrease in catalyst activity.
Fig. 4 is a test curve of acidic oxygen evolution in example 3, and the result shows that the prepared carbon-supported ruthenium-manganese alloy catalyst has acidic oxygen evolution performance, and the introduction of manganese promotes the improvement of the catalytic activity of the material, and is even better than that of the carbon-supported ruthenium metal catalyst Ru/C.
Fig. 5 is an acidic oxygen evolution stability test curve of example 3, and the result shows that the stability of Ru can be significantly improved by introducing metal manganese.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a carbon-supported ruthenium-manganese compound is characterized by comprising the following steps:
(1) Dispersing ruthenium salt, manganese salt and a carbon carrier in a solvent, heating and ultrasonically treating until the solvent is evaporated to dryness, so that the ruthenium salt and the manganese salt are adsorbed on the carbon carrier to obtain intermediate solid powder;
(2) And carrying out thermal reduction on the intermediate solid powder in a reducing atmosphere, so that ruthenium salt and manganese salt are decomposed and reduced to obtain the carbon-supported ruthenium-manganese alloy.
2. The preparation method according to claim 1, wherein the thermal reduction comprises a pre-sintering stage and a thermal reduction stage which are sequentially performed, the temperature of the pre-sintering stage is 200 ℃ to 500 ℃, the pre-sintering time is 0.5 to 2 hours, the temperature rise rate of the pre-sintering stage is 5 to 10 ℃/min, the temperature of the thermal reduction stage is 900 to 1000 ℃, the heating time of the thermal reduction stage is 2 to 10 hours, and the temperature rise rate of the thermal reduction stage is 5 to 10 ℃/min.
3. The production method according to claim 1 or 2, wherein the mass ratio of the ruthenium element in the intermediate solid powder is 5% to 45%.
4. The method of claim 1, wherein the carbon-supported ruthenium manganese alloy has an atomic ratio of ruthenium to manganese of 1: (1-9).
5. The method according to claim 1, wherein the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate, ruthenocene, potassium ruthenate, ammonium ruthenate, sodium ruthenate chloride, potassium ruthenate chloride; the manganese salt is at least one of manganese nitrate, manganese chloride, manganese acetate, manganese sulfate and manganese acetylacetonate.
6. The method of claim 1, wherein the carbon support is at least one of carbon black, graphene oxide, reduced graphene oxide, carbon nanotubes, carbon nanofibers, and carbon quantum dots.
7. The method according to claim 1, wherein the reducing atmosphere in the step (2) comprises a mixed gas of hydrogen and argon gas having a hydrogen volume fraction of 2 to 50% or a mixed gas of hydrogen and nitrogen gas having a hydrogen volume fraction of 2 to 50%; the solvent is at least one of water, ethanol, methanol, acetone, acetonitrile or tetrahydrofuran.
8. The preparation method according to claim 1, wherein the ultrasound time in the step (1) is 0.5 to 3 hours; the heating temperature in the step (1) is 45-75 ℃.
9. The carbon-supported ruthenium-manganese compound prepared by the preparation method according to any one of claims 1 to 8, wherein the ruthenium-manganese compound in the carbon-supported ruthenium-manganese compound is a pure-phase ruthenium-manganese alloy.
10. Use of the carbon-supported ruthenium manganese compound according to claim 9 in an acidic oxygen evolution electrocatalytic reaction, proton exchange membrane electrolysis of water anode catalysts.
CN202211208891.0A 2022-09-30 2022-09-30 Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof Pending CN115404515A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211208891.0A CN115404515A (en) 2022-09-30 2022-09-30 Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211208891.0A CN115404515A (en) 2022-09-30 2022-09-30 Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115404515A true CN115404515A (en) 2022-11-29

Family

ID=84167640

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211208891.0A Pending CN115404515A (en) 2022-09-30 2022-09-30 Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115404515A (en)

Similar Documents

Publication Publication Date Title
CN113388847B (en) Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof
CN112103520B (en) Anode catalyst of alcohol fuel cell
CN113437314B (en) Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof
CN112968184B (en) Electrocatalyst with sandwich structure and preparation method and application thereof
CN111883785B (en) Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof
CN115548351A (en) Carbon nano tube confinement type fuel cell catalyst and preparation method and application thereof
CN114583191A (en) Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition
CN113363510A (en) Hydrogen oxidation and reduction dual-function catalytic electrode and preparation method thereof
Liu et al. Valence regulation of Ru/Mo2C heterojunction for efficient acidic overall water splitting
CN113398923A (en) Carbon-supported IrO2@ Ir heterojunction composite catalyst with strawberry-shaped structure and preparation method and application thereof
CN110354870B (en) Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst
CN109097788B (en) Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof
CN108306023B (en) BN/CuAg/CNT composite material and preparation method and application thereof
CN113981468B (en) Multi-dimensional nickel-cobalt-based sulfide heterojunction electrocatalytic composite material and preparation method thereof
CN112295581B (en) Electrocatalyst material and application thereof
CN115404515A (en) Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof
CN113668012A (en) Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof
CN113231107A (en) Carbon nanotube-coated vanadium nitride/iron carbide composite electrocatalyst and preparation method and application thereof
CN113241451A (en) Low-platinum alloy catalyst prepared by crystal face, preparation method thereof and application thereof in fuel cell
CN117564265B (en) Preparation method and application of porous carbon supported Ni nanoparticle catalyst
CN114649538B (en) Electro-catalyst for preparing hydrogen by methanol electrolysis and preparation method thereof
CN115652357B (en) Sulfur-doped yttrium ruthenate, preparation method thereof and oxygen evolution reaction electrode
CN114622242B (en) Ni/NiO nano heterojunction porous graphite carbon composite material and preparation method and application thereof
CN113224321B (en) Vanadium-doped carbon-coated iron carbide multifunctional composite electrocatalyst and preparation method and application thereof
CN113889633B (en) Alloy catalyst and preparation method and application thereof

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