CN113134361B - Ag/alpha-Co (OH) 2 Preparation method of oxygen evolution catalyst - Google Patents

Ag/alpha-Co (OH) 2 Preparation method of oxygen evolution catalyst Download PDF

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CN113134361B
CN113134361B CN202110342027.9A CN202110342027A CN113134361B CN 113134361 B CN113134361 B CN 113134361B CN 202110342027 A CN202110342027 A CN 202110342027A CN 113134361 B CN113134361 B CN 113134361B
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CN113134361A (en
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吴静波
宁天雅
柯文韬
曹珈旖
尚子彬
张蓉仙
何苗苗
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
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    • 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
    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention belongs to the field of new energy materials and electrochemical catalysis, and discloses silver-loaded Ag/alpha-Co (OH) 2 A preparation method and application of oxygen evolution catalyst. The transition metal oxygen evolution catalyst is prepared by a simple photochemical deposition method, and the catalytic material generates a surface plasma resonance effect under the irradiation of laser due to the introduction of noble metal Ag, so that the electrocatalytic oxygen evolution reaction performance is further improved. The composite catalyst shows excellent OER catalytic performance in 1.0M KOH electrolyte under the irradiation of green lasers with different powers. Ag/alpha-Co (OH) 2 -3% at 10mA cm ‑2 The overpotential was 278mV at the current density of (c). When green laser is irradiated, the overpotential is respectively reduced to 269mV and 243mV under the light intensity of 500mW and 1000 mW. The catalyst of the invention can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal-air cells or electrolyzed water.

Description

Ag/alpha-Co (OH) 2 Preparation method of oxygen evolution catalyst
Technical Field
The invention belongs to the field of new energy materials and electrochemical catalysis, relates to a preparation method of a transition metal oxygen evolution catalyst, and in particular relates to Ag/alpha-Co (OH) 2 A method for preparing a nanocomposite.
Background
The development and application of new energy and energy transfer technology can solve the problems of increasingly serious environmental pollution and increasingly energy demand to a great extent. Among the many methods, electrolyzed water has received widespread attention as a promising renewable clean energy technology. Water decomposition reactionIt should be possible to divide into two half reactions, namely Hydrogen Evolution (HER) and Oxygen Evolution (OER). However, during electron transfer, oxygen Evolution Reaction (OER) is a slow kinetic process, which may increase the energy consumption of the electrolyzed water, thereby reducing the overall efficiency. In order to increase the energy conversion efficiency, there is an urgent need to find efficient, low cost, environmentally friendly OER catalysts. Ruthenium dioxide (RuO) due to lower overpotential and Tafel slope in alkaline environment 2 ) And iridium dioxide (IrO) 2 ) Becoming the currently accepted traditional commercial OER catalysts. But noble metals have the disadvantages of scarcity, poor stability and high manufacturing cost, and greatly limit the large-scale production and application of the noble metals.
In recent years, development and design of transition metal-based OER electrocatalysts have received extensive attention due to advantages of low cost, rare earth enrichment, and the like.
Disclosure of Invention
The present invention aims to overcome the disadvantages of the prior art and solve the above problems. Therefore, the preparation method and the application of the oxygen evolution electrocatalyst are provided, wherein the oxygen evolution electrocatalyst has rich raw materials, low price and simple preparation process.
The invention achieves the above object by the following detailed technical scheme:
Ag/alpha-Co (OH) 2 The preparation method of the oxygen evolution catalyst comprises the following steps:
(1) Sequentially dissolving cobalt chloride hexahydrate, sodium chloride and hexamethylenetetramine in a mixed solution of deionized water and ethanol according to a proportion, and stirring and heating the mixed solution in an oil bath; after heating a suspension containing green particles is produced, the solid product is collected by centrifugation, washed, air dried at room temperature and the final product α -Co (OH) 2 ；
(2) alpha-Co (OH) prepared in the step (1) 2 Ultrasonic dispersion in deionized water followed by addition of Ag (NH) 3 ) 2 The OH solution is dripped into the well dispersed alpha-Co (OH) 2 Stirring the suspension under the condition of shading, then irradiating under the condition of illumination of a xenon lamp, centrifugally collecting the product after the reaction is finished, washing with water and ethanol, freeze-drying and taking out to obtain the Ag-loaded alpha-Co (OH) 2 。
In the step (1), the mass quantity of the cobalt chloride hexahydrate, the sodium chloride and the hexamethylene tetramine is 1:5:6, wherein the concentration of the cobalt chloride hexahydrate is 0.005-0.015mol/L.
In the step (1), in the mixed solution of deionized water and ethanol, the volume ratio of the deionized water to the ethanol is 9:1.
In the step (1), the reaction solution is heated to 70-100 ℃ in an oil bath under magnetic stirring for 1-3 h.
In step (1), the product was collected by centrifugation at 7000rpm for 2min and washed with deionized water and absolute ethanol multiple times.
In step (2), ag (NH) 3 ) 2 The OH solution is prepared by slowly dripping diluted ammonia water solution to prepare Ag (NH) 3 ) 2 OH solution.
In the step (2), the stirring time under the shading condition is 5-60min, and the irradiation is carried out for 30min under the condition of 300W xenon lamp illumination.
In step (2), ag (NH) 3 ) 2 OH solution and alpha-Co (OH) 2 The volume ratio of the suspension was 79.5. Mu.L: 40mL; wherein Ag (NH) 3 ) 2 The concentration of the OH solution was 10mg mL-1, α -Co (OH) 2 The concentration of the suspension was 1.25g/L.
The beneficial effects of the invention are as follows:
(1) The invention prepares a transition metal oxygen evolution catalyst Ag/alpha-Co (OH) by a simple photochemical deposition method 2 A nanocomposite; and due to the introduction of noble metal Ag, the catalytic material generates a surface plasmon resonance effect (LSPR) under the irradiation of laser, so that the electrocatalytic oxygen evolution reaction performance is further improved.
(2) As an oxygen evolution reaction electrocatalytic material, the excellent performance is shown by low overpotential and small Tafel slope, and the current density is 10mA cm -2 The overpotential at that time is used as a measure. Ag/alpha-Co (OH) prepared by the method of the present invention 2 The catalyst has very excellent OER activity. The current density is 10mA cm -2 The overpotential at this time was 293mV and the Tafel slope was only 55mV dec -1 And has better stability than the IrO of the current commercial industry 2 Can be used as an electrocatalyst in the field of renewable fuel cells, rechargeable metal-air cells and electrolyzed water.
(3) A low power laser is applied to the OER reaction to further enhance the catalyst performance. The experiment can provide insight for the activation of the plasma induced electrocatalyst under the low-power laser treatment and the design of the novel composite electrocatalyst.
(4) The preparation method has the advantages of simple steps, convenient operation and low cost.
Drawings
FIG. 1 Ag/alpha-Co (OH) 2 FESEM images of nanocomposite;
FIG. 2 alpha-Co (OH) 2 Nanoplatelets and Ag/alpha-Co (OH) 2 XRD spectrum of the nanocomposite;
FIG. 3 series Ag/alpha-Co (OH) 2 LSV spectrum of the nanocomposite in 1M KOH solution;
FIG. 4 series alpha-Co (OH) 2 Nanocomposite material was irradiated with laser light at 10mA cm under different conditions (a-darkness, b-500, c-700 and d-1000 mW) -2 Lower LSV profile.
Detailed Description
In order to make the present invention better understood by those skilled in the art, the following description of the technical solutions of the embodiments of the present invention will be made in detail, with reference to the accompanying drawings of the embodiments of the present invention, which are only a part of the embodiments of the present invention, and are not limitative. All other embodiments based on the following are intended to fall within the scope of the present invention.
Example 1:
(1)α-Co(OH) 2 synthesis of nanoplatelets
In a typical procedure, coCl 2 ·6H 2 O, naCl and Hexamethylenetetramine (HMT) were dissolved in 200 mL of deionized water and ethanol in a 9:1 volume ratio to give final concentrations of 10, 50 and 60mM, respectively. The reaction solution was then heated to 90 ℃ with stirring in an oil bath. After heating for about 1h, a suspension containing green particles was produced. At 7000rpmThe solid product was collected by centrifugation for 2min and washed with deionized water and absolute ethanol multiple times. The final product was air dried at room temperature.
(2)Ag/α-Co(OH) 2 Synthesis of nanocomposite materials
50mg of the above-prepared alpha-Co (OH) 2 The sample was dispersed in deionized water (40 mL) and sonicated for 5min. Silver nitrate aqueous solution (79.5. Mu.L, 10mg mL) was added dropwise slowly with diluted aqueous ammonia solution -1 ) Ag (NH) configured to 1mL 3 ) 2 OH solution and then 1mL of prepared Ag (NH) 3 ) 2 The OH solution is dripped into the well dispersed alpha-Co (OH) 2 In suspension. Stirring under a shading condition for 30min, and then irradiating for 30min under a 300W xenon lamp irradiation condition. The obtained product is collected by centrifugation, washed by water and ethanol, and taken out after 24 hours of freeze drying, thus obtaining the Ag-loaded alpha-Co (OH) 2 Catalyst, noted Ag/alpha-Co (OH) 2 -1％。
Characterization analysis:
the obtained Ag/alpha-Co (OH) 2 A scanning electron micrograph of 1% composite catalyst is shown in figure 1. As can be seen from the scan results shown in FIG. 1, α -Co (OH) 2 The Ag nano structure consists of spherical silver clusters and lamellar units, the thickness of the nano sheet is about 10nm, and the width is 2-3 mu m, which shows that the nano sheet is an ultrathin 2D nano structure. The nanoplatelet surface is not smooth and some Ag nanoclusters with an average diameter of 60-100nm are distributed. Ag nanoclusters and alpha-Co (OH) 2 The bonding is tight without any gaps, which is beneficial for rapid transfer of "hot electrons".
By reacting alpha-Co (OH) 2 Analysis of the X-ray diffraction spectrum of the monomeric catalyst, FIG. 2, shows pure alpha-Co (OH) 2 Nanoplatelets and alpha-Co (OH) 2 The pattern of the Ag nanocomposite can be indexed as standard card α -Co (OH) 2 (JCPDS No. 97-017-2037) and face centered cubic (f.c.c.) Ag (JCPDS No. 04-0783). XRD patterns showed peaks of 11.0,22.1,33.7,37.9,44.9,53.7,58.7,59.9 and 60.4, corresponding to alpha-Co (OH), respectively 2 (0 00 3), (0 00 6), (0 1 2), (1 0 5), (0 1 8), (0 1 11), (1 1 0), (1 3) and (1 0 13) crystal planes,alpha-Co (OH) reported in literature 2 And are consistent. The strong and pronounced diffraction peaks indicate alpha-Co (OH) 2 Has higher crystallinity and good arrangement of lamellar structure. alpha-Co (OH) 2 Can be attributed to the hydrolysis of HMT to alpha-Co (OH) 2 Is caused by slow nucleation and growth rate. The (1 1 1), (2 0) and (3 1) crystal planes of f.c.c.ag are respectively corresponding to 38.1, 44.3, 64.4 and 77.5 °, indicating that the Ag of f.c.c. structure is reduced during the illumination process. As the content of Ag nanoclusters in the final product increases, the corresponding Ag diffraction peaks also gradually increase.
Performance test:
the Ag/alpha-Co (OH) with different Ag loading contents is prepared by the same method 2 The catalyst was used as a comparison.
All performance tests were performed on a CHI 760E electrochemical workstation equipped with a typical three-electrode system, with oxygen evolution performance testing of the electrocatalyst material in 1mol/L potassium hydroxide solution electrolyte. Wherein, a platinum wire electrode is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode. The prepared electrocatalyst powder 4mg was weighed out and dispersed into a mixed solution of 970ul absolute ethanol and 30ul 5wt% nafion. After ultrasonic dispersion for 30min, 10ul of catalyst slurry is dripped into a glassy carbon electrode with the thickness of 3mm by adopting a microsyringe needle to be dried, and the glassy carbon electrode is used as a working electrode. At a scan rate of 5mV s -1 Is applied with 95% iR compensation. As shown in FIG. 3, when the current density is 10mA/cm 2 Prepared Ag/alpha-Co (OH) 2 The overpotential of 1% of the catalyst was reduced to 305mV, whereas alpha-Co (OH) 2 The overpotential of the monomer catalyst is 318mV, which shows that the oxygen evolution performance is obviously improved. In conclusion, the method successfully prepares the Ag/alpha-Co (OH) with different Ag loading contents 2 The catalyst has excellent catalytic activity for oxygen evolution reaction.
Under laser irradiation (500, 700 and 1000mW of 532nm green laser) at 5mV s -1 The LSV curve was tested for scan rate. The current test did not compensate for iR. As shown in fig. 4a, under 500, 700 and 1000mW laser irradiation, α-Co(OH) 2 The catalytic performance of the monomeric catalyst is not significantly enhanced and the slight increase in current density may be due to the photo-thermal effect. As shown in fig. 4 b-c, the overpotential of these catalysts decreases significantly with increasing Ag loading concentration. Ag/alpha-Co (OH) under 500mW laser irradiation 2 The overpotential for 1% of the catalyst was 299mV and the laser intensity was adjusted to 1000mW, the overpotential being further reduced to 273mV. (FIG. 4 b). This property is significantly better than that of alpha-Co (OH) without laser irradiation 2 Ag-1% (306 mV). The transition metal hydroxide grafted by the plasma antenna can realize efficient OER reaction under illumination. This positive effect may be due to the "hot holes" generated by LSPR excitation of the Ag nanocluster surface limiting Co n+ Is promoted from alpha-Co (OH) 2 Transfer to Ag nanoclusters
Example 2:
Ag/alpha-Co (OH) with different Ag loading contents 2 The catalyst was prepared in essentially the same manner as in example 1, except that: silver nitrate aqueous solution (238.5. Mu.L, 10mg mL) -1 ) Ag (NH) configured to 1mL 3 ) 2 OH solution, the remaining steps being the same; further characterization analysis and performance testing were performed, and example 2 was able to achieve the objectives of the invention.
Example 3:
Ag/alpha-Co (OH) with different Ag loading contents 2 The catalyst was prepared in essentially the same manner as in example 1, except that: silver nitrate aqueous solution (397.5. Mu.L, 10mg mL) -1 ) Ag (NH) configured to 1mL 3 ) 2 OH solution, the remaining steps being the same; further characterization analysis and performance testing were performed, and example 3 was able to achieve the objectives of the invention.
Test results: ag/alpha-Co (OH) with different Ag loading contents is prepared by changing the concentration of the added silver ammonia solution 2 The catalyst is subjected to X-ray diffraction, and the result of an electron scanning microscope shows that the Ag nanocluster is successfully loaded. A linear voltammetric scan was performed as shown in FIG. 3, example 2 shows that when the current density was 10mA/cm -2 Ag-supported Ag/alpha-Co (OH)) 2 The overpotential of the catalyst was reduced to 278mV, example 3 shows that when the current density was 10mA/cm -2 Ag/alpha-Co (OH) supported by the prepared Ag 2 The overpotential of the catalyst was reduced to 295mV. From this, it can be seen that Ag/alpha-Co (OH) with different Ag loading contents 2 The OER performance of the catalyst is alpha-Co (OH) 2 The monomer catalyst is greatly improved on the basis of the monomer catalyst, which is probably due to the increase in conductivity after Ag is loaded and the effective adjustment of the electronic structure of the composite material. The interlayer space channels allow for insertion and rapid transport of water and ions. These water and ions act as quasi-electrolytes, facilitating the exchange of reactants and products and thus increasing the number of active sites. Meanwhile, the load of the Ag nanocluster further improves the conductivity of the catalyst and accelerates the electron transfer rate. With different Ag loadings, the different overpotential is presented, which indicates that the Ag loading content is not as high as possible, and the performance of the electrocatalyst is optimal only when the proper loading is achieved.
To study the Localized Surface Plasmon Resonance (LSPR) effect and the photo-induced OER effect, a 532nm laser source was applied. Under laser irradiation (500, 700 and 1000mW of 532nm green laser), a linear voltammetric scan test was performed as shown in FIG. 4. alpha-Co (OH) without Ag nanoclusters 2 The nanoplatelets exhibit poor OER electrocatalytic properties under laser irradiation (fig. 4 a). The catalytic performance of the catalyst was not significantly enhanced under 500, 700 and 1000mw laser irradiation, and the slight increase in current density was probably due to the photo-thermal effect. As shown in FIGS. 4 b-d, the overpotential of these catalysts decreases significantly with increasing Ag loading concentration, example 2 shows that when the current density is 10mA/cm -2 Ag/alpha-Co (OH) supported by the prepared Ag 2 The catalyst showed the highest OER performance with an overpotential of only 269mV under 500mW laser irradiation. The laser intensity was adjusted to 1000mW and its overpotential was further reduced to 243mV. (FIG. 4 c). This property is significantly better than that of alpha-Co (OH) without laser irradiation (288 mV) 2 Ag-3%. Example 3 shows that when the current density is 10mA/cm -2 Ag/alpha-Co (OH) supported by the prepared Ag 2 The catalyst was passed under 500mW laser irradiationThe potential was only 290mV. The laser intensity was adjusted to 1000mW and its overpotential was further reduced to 250mV. The experimental result shows that the transition metal hydroxide grafted by the plasma antenna can realize efficient OER reaction under illumination. This positive effect may be due to the "hot holes" generated by LSPR excitation of the Ag nanocluster surface limiting Co n+ Is promoted from alpha-Co (OH) 2 Transfer to Ag nanoclusters
According to the results, the method provided by the invention avoids complex preparation process, and successfully prepares Ag-loaded Ag/alpha-Co (OH) with higher electrocatalytic oxygen evolution performance at lower temperature and by a simple and easy preparation method 2 The catalyst effectively overcomes the defects of complicated preparation and poor oxygen evolution performance of the transition metal-based electrocatalytic material, and provides a new thought for means for improving the catalytic performance by regulating an electronic structure by anions. In addition, ag-loaded Ag/alpha-Co (OH) prepared by the method 2 The catalyst can also be applied to the fields of metal-air batteries, novel capacitors, novel energy sources and the like.
The foregoing description of the exemplary embodiments of the present invention shows that the specific features of the embodiments can be modified and combined in any suitable manner without departing from the spirit of the invention, and the invention is also considered as the disclosure of the present invention, and in order to avoid unnecessary repetition, any possible modification and combination will not be described in detail.
The invention is not a matter of the known technology. The practice and apparatus employed in the present invention are those conventional in the art unless otherwise indicated; the reagents and materials used were all commercially available.

Claims (8)

1.Ag/α-Co(OH) 2 Use of an oxygen evolution catalyst for renewable fuel cells, rechargeable metal-air cells or electrolyzed water, characterized in that the Ag/alpha-Co (OH) 2 Oxygen evolution catalyst, which presents spherical silver clusters and lamellar units, and Ag nanoclusters with average diameter of 60-100nm are well dispersed in alpha-Co (OH) 2 The surface of the nano-sheet, the preparation method thereof comprises the following steps of：
(1) Sequentially dissolving cobalt chloride hexahydrate, sodium chloride and hexamethylenetetramine in a mixed solution of deionized water and ethanol according to a proportion, and stirring and heating the mixed solution in an oil bath; after heating a suspension containing green particles is produced, the solid product is collected by centrifugation, washed, air dried at room temperature and the final product α -Co (OH) 2 ；
(2) alpha-Co (OH) prepared in the step (1) 2 Ultrasonic dispersion in deionized water followed by addition of Ag (NH) 3 ) 2 The OH solution is dripped into the well dispersed alpha-Co (OH) 2 Stirring the suspension under the condition of shading, then irradiating under the condition of illumination of a xenon lamp, centrifugally collecting the product after the reaction is finished, washing with water and ethanol, freeze-drying and taking out to obtain the Ag-loaded alpha-Co (OH) 2 。
2. The use according to claim 1, characterized in that in step (1) the amount of cobalt chloride hexahydrate, sodium chloride and hexamethylenetetramine is 1:5:6, wherein the concentration of cobalt chloride hexahydrate is 0.005-0.015mol/L.
3. The use according to claim 1, wherein in step (1) the volume ratio of deionized water to ethanol is 9:1 in the mixed solution of deionized water and ethanol.
4. The use according to claim 1, wherein in step (1), the reaction solution is heated to 70 to 100 ℃ in an oil bath under magnetic stirring for a period of 1 to 3 hours.
5. The use according to claim 1, characterized in that in step (1) the product is collected by centrifugation at 7000rpm for 2min and washed several times with deionized water and absolute ethanol.
6. The use according to claim 1, wherein in step (2), ag (NH) 3 ) 2 The OH solution is prepared by slowly dripping diluted ammonia water solutionSilver nitrate aqueous solution is prepared into Ag (NH) 3 ) 2 OH solution.
7. The use according to claim 1, wherein in step (2), the stirring time is 5 to 60min under a light-shielding condition, and the irradiation is performed for 30min under a 300w xenon lamp irradiation condition.
8. The use according to claim 1, wherein in step (2), ag (NH) 3 ) 2 OH solution and alpha-Co (OH) 2 The volume ratio of the suspension was 79.5. Mu.L: 40mL; wherein Ag (NH) 3 ) 2 The concentration of the OH solution was 10 mg/mL -1 ，α-Co(OH) 2 The concentration of the suspension was 1.25g/L.
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