CN117165999A - Silver-loaded manganese-based metal oxide catalyst and preparation method and application thereof - Google Patents
Silver-loaded manganese-based metal oxide catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemistry, and discloses a manganese-based metal oxide catalyst loaded with silver, a preparation method and application thereof, wherein the catalyst comprises silver particle nanorods loaded with manganese-based metal oxide, and the atomic content of Ag in the silver particle nanorods is more than zero and less than or equal to 14.7%. According to the invention, silver particles are loaded on the manganese monoxide nanorod, so that divalent Mn ions are promoted to be in-situ converted into high-activity trivalent Mn ions in the oxygen precipitation process, and the dissolution process of Mn ions in an acidic solution is inhibited.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a silver-loaded manganese-based metal oxide catalyst, and a preparation method and application thereof.
Background
The energy crisis and environmental problems are becoming increasingly severe forcing us to explore renewable, environmentally friendly energy conversion and storage technologies. Among them, acidic electrolyzed water hydrogen production has the characteristics of large theoretical current density and high gas purity, and is considered as one of the most attractive sustainable technologies. The reaction of the acid solution to hydrolyze the hydrogen production anode side is an Oxygen Evolution Reaction (OER), i.e. the water is split at the anode side to produce oxygen. At present, noble metal catalyst materials based on Ir and Ru show good electrochemical performance of oxygen precipitation of acidic aqueous solutions, but the high price and scarcity limit the wide application thereof. Accordingly, efforts have been made to design low-cost, high-activity and long-term-stability non-noble metal acid aqueous solution oxygen evolution catalysts.
The manganese-based metal oxide catalyst has a relatively broad application prospect due to low cost, low toxicity and rich Mn valence state change. Currently, most manganese-based metal oxide catalysts are studied to optimize for tetravalent manganese dioxide. However, in an acidic environment, there is a large gap between the performance of most manganese-based oxides and noble metal catalysts. At 10mA/cm 2 An electrolysis voltage of 1.7V to 2.0V is required at a current density of (c), and it is difficult to achieve efficient catalysis. In addition, due to acid corrosion and disproportionation reaction of manganese ions, the manganese-based metal oxide catalyst is obviously deactivated when running for 50 hours under the actual working condition, so that the actual cost of producing hydrogen by electrolyzing water is excessive. Therefore, in order to improve the electrolytic efficiency of acidic water electrolysis hydrogen production and reduce the operation cost, it is necessary to develop a high-performance low-overpotential manganese-based oxide acidic aqueous solution oxygen precipitation catalyst.
Disclosure of Invention
In order to meet the above defects or improvement demands of the prior art, the invention provides a silver-loaded manganese-based metal oxide catalyst, a preparation method and application thereof, which promote in-situ conversion of divalent Mn ions into high-activity trivalent Mn ions in an oxygen precipitation process and inhibit the dissolution process of Mn ions in an acidic solution by loading silver particles on a manganese monoxide nanorod.
To achieve the above object, according to one aspect of the present invention, there is provided a silver-supported manganese-based metal oxide catalyst comprising manganese-based metal oxide-supported silver particle nanorods, the silver particle nanorods having an atomic content of Ag of greater than zero and equal to or less than 14.7%.
Further, the length of the silver particle nano rod is 0.5-5 mu m, and the width is 10-800 nm.
The invention also provides a preparation method of the silver-supported manganese-based metal oxide catalyst, which comprises the following steps: dissolving potassium permanganate, manganese sulfate monohydrate and silver nitrate in deionized water, mixing to obtain a mixed solution, heating the mixed solution at 100-200 ℃ for 10-14 hours, and washing to obtain the catalyst.
Further, the concentration of potassium permanganate in the mixed solution is 0.05mol/L to 0.5mol/L.
Further, the concentration of the manganese sulfate monohydrate in the mixed solution is 0.01mol/L to 0.1mol/L.
Further, the concentration of silver nitrate in the mixed solution is 0.002 mol/L-0.05 mol/L.
Further, the mixed solution was heated at 160 ℃ for 12 hours to generate the catalyst in situ.
The invention also provides an application of the silver-loaded manganese-based metal oxide catalyst in the electrolysis of an acidic aqueous solution.
In general, compared with the prior art, the silver-loaded manganese-based metal oxide catalyst and the preparation method and application thereof have the following main beneficial effects:
1. the catalyst provided by the invention can promote the in-situ conversion of divalent Mn ions into high-activity trivalent Mn ions under low potential in the oxygen precipitation process, and can greatly reduce the dissolution of Mn in an acidic solution caused by gasification reaction of trivalent Mn ions due to the load of Ag, so that the catalyst has better catalytic activity and stability when being used as an acidic aqueous solution oxygen precipitation electrocatalyst.
2. The catalyst microstructure provided by the invention is a nano rod with a larger specific surface area, can expose more active sites and can be used as a transmission channel of ions, and has excellent catalytic performance as a water decomposition electrocatalyst.
3. The components and the surface electronic structure of the catalyst provided by the invention can be regulated and controlled by controlling the precursor feeding ratio, so that the atomic content of Ag in the catalyst can be accurately controlled, and the catalyst is favorable for obtaining a non-noble metal catalyst with high performance.
4. The catalyst provided by the invention has better catalytic activity and stability as an acidic aqueous solution oxygen precipitation electrocatalyst, has excellent catalytic activity when oxygen precipitation reaction is carried out in acidic aqueous solution, and has a current density of 10mA/cm 2 The voltage is lower than 1.42V at a current density of 50mA/cm 2 When the voltage is lower than 1.60V, the voltage is far lower than the electrolysis voltage required by the existing non-noble metal catalyst.
5. When the manganese monoxide-loaded silver particle nano-rod catalyst and the commercial Pt/C catalyst (the mass fraction of Pt is 20%) are used as the anode and the cathode in the proton exchange membrane electrolytic cell, the manganese monoxide-loaded silver particle nano-rod catalyst at the anode has a large specific surface area, rich active sites and in-situ conversion of the valence state of Mn atoms, so that the manganese monoxide-loaded silver particle nano-rod catalyst has excellent catalytic activity and has the current density of 10mA/cm 2 When the catalyst is used, the electrolysis voltage of the proton exchange membrane electrolyzer is less than 1.5V, and the proton exchange membrane electrolyzer can stably run for more than 160 hours and is superior to most of the existing catalysts.
Drawings
FIG. 1A is a manganese-based metal oxide-supported silver particle (MnAg) prepared in example 1 of the present invention x O) transmission electron microscopy pictures of the catalyst;
FIG. 1B is a manganese-based metal oxide-supported silver particle (MnAg) prepared in example 2 of the present invention x O) transmission electron microscopy pictures of catalysts, wherein x is greater than 0 and equal to or less than 14.7%;
FIG. 1C is a block diagram of example 3 of the present inventionPrepared manganese-based metal oxide-supported silver particles (MnAg x O) transmission electron microscopy pictures of the catalyst;
FIG. 1D is a transmission electron microscope photograph of a pure manganese monoxide (MnO) catalyst prepared in comparative example 1 of the present invention;
FIG. 1E is a manganese-based metal oxide-supported silver particle (MnAg) prepared in example 4 of the present invention x O) transmission electron microscopy pictures of the catalyst;
FIG. 1F shows manganese-based metal oxide-supported silver particles (MnAg) prepared in example 5 of the present invention x O) transmission electron microscopy pictures of the catalyst;
FIG. 2 is a manganese-based metal oxide-supported silver particle (MnAg) prepared in example 1 of the present invention x O) high resolution transmission electron microscopy pictures of the catalyst;
FIG. 3A is a schematic diagram showing manganese-based metal oxide-supported silver particles (MnAg) prepared in examples 1, 2 and 3 and comparative example 1 according to the present invention x O) X-ray diffraction pattern of the catalyst;
FIG. 3B is a schematic diagram of manganese-based metal oxide-supported silver particles (MnAg) prepared in examples 4 and 5 of the present invention x O) X-ray diffraction pattern of the catalyst;
FIG. 4A is a schematic illustration of manganese-based metal oxide-supported silver particles (MnAg) in catalytic performance test example 1 of the present invention x O) a polarization profile of the catalyst oxygen evolution process;
FIG. 4B is a graph showing the polarization of the oxygen evolution process of a pure manganese monoxide (MnO) catalyst of comparative example 1 for the catalytic performance test of the present invention;
FIG. 5 shows the manganese-based metal oxide-supported silver particles (MnAg x O) stability profile of the catalyst, wherein the test current density is 10mA/cm 2 。
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a silver-loaded manganese-based metal oxide catalyst, a preparation method and application thereof, wherein components and surface microcosmic morphology of a manganese-based metal oxide loaded silver particle catalyst are controlled, and loaded silver particles are utilized to promote in-situ conversion of divalent manganese ions into high-activity trivalent manganese ions in an oxygen precipitation process and inhibit dissolution of manganese ions in an acidic solution, so that catalytic performance is improved, overpotential is reduced, and the technical problems of poor catalytic performance, high overpotential and low stability of the existing oxygen precipitation catalyst for the acidic aqueous solution are solved.
The invention provides a silver-supported manganese-based metal oxide catalyst comprising manganese-based metal oxide-supported silver particle nanorods. The atomic content of Ag in the silver particle nano rod is more than zero and less than or equal to 14.7%.
The length of the silver particle nano rod is 0.5-5 mu m, and the width is 10-800 nm.
The invention also provides a preparation method of the silver-loaded manganese-based metal oxide catalyst, which comprises the following steps: dissolving potassium permanganate, manganese sulfate monohydrate and silver nitrate in deionized water, heating at 100-200 ℃ for 10-14 hours, and washing to obtain the catalyst.
The concentration of potassium permanganate in deionized water in which potassium permanganate, manganese sulfate monohydrate and silver nitrate are dissolved is 0.05mol/L to 0.5mol/L, the concentration of manganese sulfate monohydrate is 0.01mol/L to 0.1mol/L, and the concentration of silver nitrate is 0.002mol/L to 0.05mol/L.
The mass of the potassium permanganate in the deionized water dissolved with the potassium permanganate, the manganese sulfate monohydrate and the silver nitrate is 0.05-0.5 mol/L, and 500mg of the potassium permanganate is dissolved in 32ml of deionized water.
Further, the mass of the manganese sulfate monohydrate in the deionized water dissolved with the potassium permanganate, the manganese sulfate monohydrate and the silver nitrate is 0.01-0.1 mol/L, and the manganese sulfate monohydrate is 210mg dissolved in 32ml of deionized water.
Further, the mass of the silver nitrate in the deionized water dissolved with the potassium permanganate, the manganese sulfate monohydrate and the silver nitrate is 0.002-0.05 mol/L, and 75mg of the silver nitrate is dissolved in 32ml of deionized water.
Further, the heating at 100-200 ℃ for 10-14 hours is heating at 160 ℃ for 12 hours to generate MnAg in situ x O nano-rods.
The invention also provides an application of the silver-supported manganese-based metal oxide catalyst in the electrolysis of an acidic aqueous solution, and the catalyst is used as an anode in the electrolysis of the acidic aqueous solution.
The invention is described in further detail below with respect to a few specific examples.
Example 1
The embodiment provides a preparation method of a silver-supported manganese-based metal oxide catalyst, which specifically comprises the following steps:
500mg of potassium permanganate, 210mg of manganese sulfate monohydrate and 75mg of silver nitrate were weighed separately by analytical days and added to 32ml of deionized water solution, followed by stirring for 10 minutes, so that the potassium permanganate, manganese sulfate monohydrate and silver nitrate were uniformly dispersed in the deionized water solution.
Pouring the uniformly stirred mixed solution into a polytetrafluoroethylene liner of a 100ml reaction kettle, sealing the reaction kettle, placing the reaction kettle in a blast oven, preserving heat for 12 hours at 160 ℃, and growing in situ to obtain nano rod-shaped MnAg x O catalytic material.
After the temperature of the reaction kettle is reduced to room temperature, the inner container of the reaction kettle is taken out, and the suspension in the inner container is led into a 50ml centrifuge tube and centrifuged for 5 minutes by a centrifuge. Subsequently, the supernatant is led into a waste liquid barrel to obtain solid MnAg x And (3) an O catalyst. Sequentially cleaning MnAg with deionized water, ethanol and deionized water x O catalyst, removing residual precursor on the surface of the material, so as to obtain pure MnAg x O catalytic material. Drying in a vacuum oven at 80 ℃ to obtain nano rod-shaped MnAg x O catalyst, designated MnAg 0.05 O。
For MnAg 0.05 O performs performance characterization:
observation of MnAg with a Transmission Electron microscope (Tecnai G2) 0.05 The morphology of the O sample is shown in figure 1A, and the O sample is a nano rod which is uniformly distributed, the length is 1-2 mu m, and the width is 50-150 nm.
Viewing MnAg with a high resolution transmission electron microscope (Talos F200X) 0.05 O sample, as shown in FIG. 2, mnAg 0.05 The Ag simple substance particles on the O sample are attached to the MnO nano rod, which shows that the MnAg 0.05 The O sample has obvious phase separation structure.
Testing MnAg with an X-ray diffractometer (DMAX-2400X) 0.05 O sample with X-ray spectrum shown in FIG. 3A, mnAg 0.05 The O material presents lattice diffraction peaks of MnO and Ag, which indicates MnAg 0.05 The O material exhibits a split phase structure of MnO and Ag.
Examples 2 to 3, comparative example 1
Examples 2-3 and comparative example 1 provide a MnAg x The preparation method of the O nanorod catalyst was the same as that of example 1, except that the mass of silver nitrate added to 32ml of deionized water solution was different, and the effect of the addition amount of silver nitrate was shown as in table 1.
TABLE 1 silver nitrate addition in preparation of manganese-based Metal oxide Supported silver particle catalyst
Wherein, for the MnAg provided in example 2 and example 3 x The O nanorod catalyst was observed by a transmission electron microscope (Tecnai G2), and the results are shown in FIG. 1B and FIG. 1C. The product samples of example 2 and example 3 were tested with an X-ray diffractometer (DMAX-2400X) and the results are shown in FIG. 3A. XRD tests detected that examples 2 and 3 showed MnO and Ag peaks, exhibiting a phase-separated structure. Example 2 and example 3 are respectively designated as MnAg 0.03 O and MnAg 0.15 O。
With respect to the product characterization of comparative example 1, see specifically fig. 1D, a sample of the product of comparative example 1 was observed with a transmission electron microscope (Tecnai G2) and the morphology of the sample was shown in fig. 1D as uniformly distributed nanoparticles ranging in size from 500m to 600nm. The product sample of comparative example 1 was tested by an X-ray diffractometer (DMAX-2400X) and only the MnO peak was detected as a result of the test, and exhibited a pure MnO structure, and comparative example 1 was designated as MnO.
It can be seen that too small an atomic content of Ag results in MnAg x O catalysts have difficulty forming elongated nanorods with large specific surface areas, thereby affecting the catalytic activity of the material. When the content of Ag atoms is excessive, a large amount of material is aggregated on the manganese monoxide nanorods due to aggregation of silver simple substances, clusters of large particles are formed, exposure of active sites of the material is affected, and catalytic activity of the material is affected.
Examples 4 to 5
Examples 4 to 5 provide a MnAg x The preparation method of the O nano rod catalyst is the same as that of the example 1, except that the mixed solution is poured into a reaction kettle and then placed in a blast oven to be subjected to different heat preservation temperatures and times, and the heat preservation temperatures and times are different for MnAg x The effect of the O catalyst is shown in table 2.
TABLE 2 examples 4-5MnAg x O catalyst preparation method parameters and morphology
As can be seen from the results in Table 2, the above-mentioned holding temperature and holding time do not significantly affect the in-situ formation of MnAg x Microscopic morphology of O. Heating for 10-14 hours at 100-200 ℃ to obtain MnAg by in-situ growth x O nanorod catalyst.
The catalyst samples prepared in examples 4-5 were observed by transmission electron microscopy (Tecnai G2) and the morphology was shown in fig. 1E and 1F. The phase structures of examples 4 to 5 were tested by an X-ray diffractometer (DMAX-2400X), and the test results are shown in FIG. 3B, which shows that examples 4 to 5 each exhibit a phase-separated structure, showing diffraction peaks of MnO and Ag. Examples 4 and 5 are respectively designated as MnAg 0.05 O-1 and MnAg 0.05 O-2。
Catalytic performance test example 1
MnAg prepared by the preparation method provided in example 1 of the present invention was tested in an acidic solution using an electrochemical workstation (CHI 760D) 0.05 Oxygen evolution catalytic performance of O material (i.e., silver particle catalyst supported on nanorod-shaped manganese-based metal oxide), wherein the acidic solution was formulated with 98% concentrated sulfuric acid and deionized water, the catalytic performance was as shown in FIG. 4A, which compared with commercial iridium dioxide electrode material, mnAg was found 0.05 The oxygen evolution catalytic activity of the O material is superior to that of the commercial iridium dioxide existing at present.
Catalytic performance test comparative example 1
The MnO material (i.e., the nanoparticulate pure manganese monoxide catalyst) prepared by the preparation method provided in comparative example 1 of the present invention was tested for oxygen evolution catalysis using an electrochemical workstation (CHI 760D) in an acidic solution, wherein the acidic solution was formulated using 98% concentrated sulfuric acid with deionized water. The catalytic performance of the catalyst is shown in fig. 4B, and compared with the silver particle catalyst loaded by the nano rod-shaped manganese-based metal oxide, the catalytic activity of oxygen precipitation of the pure MnO material can be found to be lower than that of the silver particle catalyst loaded by the nano rod-shaped manganese-based metal oxide.
Analysis shows that the nano rod-shaped MnAg 0.05 The O catalyst, due to its extremely large specific surface area and abundant active sites, can provide a large number of adsorption sites for the incorporation of O, OOH in the oxygen evolution reaction. Meanwhile, the doping of Ag substances can promote the in-situ conversion of divalent Mn ions into high-activity trivalent Mn ions in the oxygen precipitation process, so that the reactivity of the material is improved.
Application examples
Respectively taking MnAg 0.05 O electrode materials (i.e., nano rod-shaped manganese-based metal oxide loaded silver particles) and commercial Pt/C electrode materials (mass fraction of Pt is 20%) are used as anode and cathode catalytic materials for full hydrolysis of an acidic solution, and are assembled into membrane electrodes and placed in a proton exchange membrane electrolyzer for testing. Wherein the acidic solution is prepared by using deionized water as raw material and passing through nafion membraneIs a proton donor. 10mA cm was performed in a blue electric testing platform (C3001B) -2 Stability test at current density. As shown in FIG. 5, the temperature was set at 10mA cm -2 MnAg at current density 0.05 The potential of the O electrode is 1.45V relative to that of the standard electrode, and the material can stably work for more than 160 hours under the high current working density so as to meet the requirement of industrial production.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A silver-supported manganese-based metal oxide catalyst characterized by:
the catalyst comprises silver particle nano rods loaded by manganese-based metal oxide, wherein the atomic content of Ag in the silver particle nano rods is more than zero and less than or equal to 14.7%.
2. The silver-supported manganese-based metal oxide catalyst according to claim 1, wherein: the length of the silver particle nano rod is 0.5-5 mu m, and the width is 10-800 nm.
3. A method for preparing the silver-supported manganese-based metal oxide catalyst according to any one of claims 1 to 2, characterized in that the method comprises the steps of: dissolving potassium permanganate, manganese sulfate monohydrate and silver nitrate in deionized water, mixing to obtain a mixed solution, heating the mixed solution at 100-200 ℃ for 10-14 hours, and washing to obtain the catalyst.
4. A method for preparing a silver-supported manganese-based metal oxide catalyst according to claim 3, wherein: the concentration of potassium permanganate in the mixed solution is 0.05 mol/L-0.5 mol/L.
5. A method of preparing a silver-supported manganese-based metal oxide catalyst according to claim 3, wherein: the concentration of the manganese sulfate monohydrate in the mixed solution is 0.01 mol/L-0.1 mol/L.
6. A method of preparing a silver-supported manganese-based metal oxide catalyst according to claim 3, wherein: the concentration of the silver nitrate in the mixed solution is 0.002 mol/L-0.05 mol/L.
7. A method of preparing a silver-supported manganese-based metal oxide catalyst according to claim 3, wherein: the mixed solution was heated at 160 ℃ for 12 hours to generate the catalyst in situ.
8. Use of a silver-loaded manganese-based metal oxide catalyst according to any one of claims 1-2 in the electrolysis of an acidic aqueous solution.
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