CN113134361A - Ag/alpha-Co (OH)2Preparation method of oxygen evolution catalyst - Google Patents
Ag/alpha-Co (OH)2Preparation method of oxygen evolution catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000002064 nanoplatelet Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 4
- 229960004011 methenamine Drugs 0.000 claims 2
- 229960002668 sodium chloride Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 12
- 239000002114 nanocomposite Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H01M4/00—Electrodes
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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)2A preparation method and application of the oxygen evolution catalyst. The invention prepares a transition metal oxygen evolution catalyst by a simple photochemical deposition method, and the catalytic material generates a surface plasma resonance effect under the laser irradiation due to the introduction of noble metal Ag, so that the electro-catalytic 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 laser with different powers. Ag/alpha-Co (OH)2-3% at 10mA cm‑2The overpotential is 278mV at the current density of (3). When green laser is irradiated, 5Under the light intensity of 00mW and 1000mW, the overpotential is respectively reduced to 269mV and 243 mV. The catalyst of the invention can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal-air cells or electrolysis of water.
Description
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 particularly relates to Ag/alpha-Co (OH)2A method for preparing a nanocomposite.
Background
The development and application of new energy and energy transfer technologies can solve the problems of increasingly severe environmental pollution and increasingly high energy demand to a great extent. Among the numerous methods, electrolyzed water has received much attention as a promising renewable clean energy technology. The water splitting reaction can be divided into two half-reactions, namely the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER). However, the Oxygen Evolution Reaction (OER) is a slow kinetic process during electron transport, which may increase the energy consumption of the electrolysis of water, thereby reducing the overall efficiency. In order to improve the energy conversion efficiency, the search for efficient, low-cost, environmentally friendly OER catalysts is urgently needed. Ruthenium dioxide (RuO) due to lower overpotential and Tafel slope in alkaline environment2) And iridium dioxide (IrO)2) Becoming the conventional commercial OER catalyst recognized at present. However, the scarcity, poor stability and high manufacturing cost of the noble metal greatly limit the large-scale production and application of the noble metal.
In recent years, due to the advantages of low cost, rich rare earth, and the like, the development and design of transition metal-based OER electrocatalysts have received much attention.
Disclosure of Invention
The present invention aims to overcome the disadvantages of the prior art and to solve the above problems. Therefore, the preparation method and the application of the oxygen evolution electrocatalyst with rich raw materials, low price and simple preparation process are provided.
The invention achieves the above purpose through the following detailed technical scheme:
Ag/alpha-Co (OH)2The preparation method of the oxygen evolution catalyst comprises the following steps:
(1) according to the ratioThe cobalt chloride hexahydrate, the sodium chloride and the hexamethylenetetramine are sequentially dissolved in a mixed solution of deionized water and ethanol, and then the mixed solution is stirred and heated in an oil bath; heating to produce a suspension containing green particles, centrifuging to collect the solid product, washing, air drying at room temperature to obtain the final product alpha-Co (OH)2；
(2) The alpha-Co (OH) prepared in the step (1)2Ultrasonically dispersing in deionized water, and then adding Ag (NH)3)2OH solution was added dropwise to the dispersed alpha-Co (OH)2Stirring in suspension under shading condition, irradiating under xenon lamp illumination condition, centrifuging and collecting the product after reaction, washing with water and ethanol, freeze drying, and taking out to obtain Ag-loaded alpha-Co (OH)2。
In the step (1), the amount of cobalt chloride hexahydrate, sodium chloride and hexamethylenetetramine is 1:5:6, wherein the concentration of the cobalt chloride hexahydrate is 0.005-0.015 mol/L.
In the step (1), the volume ratio of the deionized water to the ethanol is 9:1 in the mixed solution of the deionized water and the ethanol.
In the step (1), the reaction solution is heated to 70-100 ℃ in an oil bath under magnetic stirring for 1-3 h.
In the step (1), the product is collected and centrifuged at 7000rpm for 2min, and washed with deionized water and absolute ethanol for multiple times.
In step (2), Ag (NH)3)2The OH solution is prepared by slowly dripping diluted ammonia water solution to prepare silver nitrate aqueous solution into Ag (NH)3)2And (3) preparing an OH solution.
In the step (2), the stirring time is 5-60min under the shading condition, and the irradiation is 30min under the condition of 300W xenon lamp illumination.
In step (2), Ag (NH)3)2OH solution and alpha-Co (OH)2The volume ratio of the suspension was 79.5 μ L: 40 mL; wherein, Ag (NH)3)2The concentration of the OH solution was 10 mg. mL-1, alpha-Co (OH)2The concentration of the suspension was 1.25 g/L.
The invention has the beneficial effects that:
(1) the invention prepares a transition metal oxygen evolution catalyst Ag/alpha-Co (OH) by a simple photochemical deposition method2A nanocomposite; and due to the introduction of noble metal Ag, the catalytic material generates a surface plasma resonance effect (LSPR) under the irradiation of laser, so that the performance of the electrocatalytic oxygen evolution reaction is further improved.
(2) As an oxygen evolution reaction electrocatalytic material, the excellent performance is shown to have lower overpotential and smaller Tafel slope, and the current density is 10mA cm in general-2Overpotential of time is used as a measure. Ag/alpha-Co (OH) prepared by the method of the invention2The catalyst has excellent OER activity. The current density was 10mA cm-2The overpotential is 293mV, the Tafel slope is only 55mV dec-1And has better stability than the prior commercial IrO2The catalyst can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal-air cells and water electrolysis.
(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 and the design of the novel composite electrocatalyst under low-power laser treatment.
(4) The preparation method has simple steps, convenient operation and low cost.
Drawings
FIG. 1Ag/α -Co (OH)2FESEM images of the nanocomposites;
FIG. 2. alpha. -Co (OH)2Nanosheets and Ag/alpha-Co (OH)2XRD spectrum of nanocomposite;
FIG. 3 series Ag/alpha-Co (OH)2LSV spectra of the nanocomposite in 1M KOH solution;
FIG. 4 series a-Co (OH)2The nanocomposites were subjected to different conditions (a-dark, b-500, c-700 and d-1000mW laser irradiation) at 10mA cm-2Lower LSV map.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the described embodiments are only a part of the embodiments of the present invention, and are not limited. All other embodiments obtained on the basis of the following should be considered to fall within the scope of protection of the present invention.
Example 1:
(1)α-Co(OH)2synthesis of nanoplatelets
In a typical procedure, CoCl2·6H2O, NaCl and Hexamethylenetetramine (HMT) were dissolved in sequence in 200 mL of a 9:1 mixture of deionized water and ethanol in volume ratio to give final concentrations of 10, 50 and 60mM, respectively. The reaction solution was then heated to 90 ℃ in an oil bath with stirring. After heating for about 1h, a suspension containing green particles was produced. The solid product was collected by centrifugation at 7000rpm for 2min and washed several times with deionized water and absolute ethanol. The final product was air-dried at room temperature.
(2)Ag/α-Co(OH)2Synthesis of nanocomposites
50mg of the above-prepared alpha-Co (OH)2The sample was dispersed in deionized water (40mL) and sonicated for 5 min. An aqueous silver nitrate solution (79.5. mu.L, 10mg mL) was added slowly dropwise to the diluted aqueous ammonia solution-1) Ag (NH) configured to 1mL3)2OH solution, then 1mL of prepared Ag (NH)3)2OH solution was added dropwise to the dispersed alpha-Co (OH)2In suspension. Stirring for 30min under shading conditions, and then irradiating for 30min under 300W xenon lamp illumination. The obtained product is collected by centrifugation, washed by water and ethanol and taken out after being frozen and dried for 24h, and the Ag-loaded alpha-Co (OH) can be obtained2Catalyst, noted Ag/alpha-Co (OH)2-1％。
And (3) characterization and analysis:
the resulting Ag/alpha-Co (OH)2Scanning electron micrographs of-1% composite catalyst are shown in figure 1. As can be seen from the scanning results shown in FIG. 1, alpha-Co (OH)2the/Ag nano structure consists of spherical silver clusters and flaky units, the thickness of the nanosheet is about 10nm, the width of the nanosheet is 2-3 microns, and the nanosheet is an ultrathin 2D nano structure. The surface of the nano-sheet is not smoothAnd some Ag nanoclusters with an average diameter of 60-100nm are distributed. Ag nanoclusters and alpha-Co (OH)2And without any voids, which would facilitate the rapid transfer of "hot electrons".
By para-alpha-Co (OH)2Analysis of X-ray diffraction spectrogram 2 of the monomer catalyst can show that the catalyst is pure alpha-Co (OH)2Nanosheets and alpha-Co (OH)2The spectrum of the/Ag nanocomposite can be indexed as standard card alpha-Co (OH)2(JCPDS No.97-017-2037) and a face-centered cubic phase (f.c.c.) Ag (JCPDS No. 04-0783). The XRD pattern showed peaks at 11.0,22.1,33.7,37.9,44.9,53.7,58.7,59.9 and 60.4 °, corresponding to α -Co (OH)2The (003), (006), (012), (105), (018), (0111), (110), (113) and (1013) planes of (A) and the literature reports of alpha-Co (OH)2And (4) the same. The intense, distinct diffraction peaks indicate alpha-Co (OH)2Has higher crystallinity and well-arranged layered structure. alpha-Co (OH)2Can be attributed to hydrolysis of HMT to alpha-Co (OH)2Is caused by nucleation and slow growth rate. 38.1, 44.3, 64.4 and 77.5 ° correspond to the (111), (200), (220) and (311) crystal planes of f.c.c. Ag, respectively, indicating that Ag of f.c.c. structure is reduced during the light irradiation. As the content of Ag nanoclusters in the final product increases, the corresponding Ag diffraction peak also gradually increases.
And (3) performance testing:
preparing Ag/alpha-Co (OH) with different Ag loading contents by the same method2Catalyst for comparison.
All performance tests were performed on a CHI 760E electrochemical workstation equipped with a typical three-electrode system, and the electrocatalyst materials were tested for oxygen evolution performance in a 1mol/L potassium hydroxide solution in electrolyte. Wherein, a platinum wire electrode is adopted as a counter electrode, and an Hg/HgO electrode is adopted as a reference electrode. 4mg of the prepared electrocatalyst powder was weighed and dispersed in 970ul of a mixed solution of anhydrous ethanol and 30ul of 5 wt% Nafion. After ultrasonic dispersion for 30min, 10ul of catalyst slurry is dripped to a glassy carbon electrode with the thickness of 3mm by using a micro sample injection needle and dried to be used as a working electrode. At a scan rate of 5mV s-1Linear Sweep Voltammetry (LSV) curves under shading conditions, with 95% iR compensation applied. As shown in FIG. 3, when the current density was 10mA/cm2Prepared Ag/alpha-Co (OH)2Overpotential of-1% catalyst is reduced to 305mV, whereas α -Co (OH)2The overpotential of the monomer catalyst is 318mV, which shows that the oxygen evolution performance is obviously improved. In conclusion, Ag/alpha-Co (OH) with different Ag loading contents is successfully prepared by the method2The catalyst has excellent catalytic activity for oxygen evolution reaction.
Under laser irradiation (532 nm green laser at 500, 700 and 1000 mW) at 5mV s-1The LSV curve was tested for scan rate. The iR compensation was not performed in this test. As shown in FIG. 4a, alpha-Co (OH) was irradiated with 500, 700 and 1000mW of laser light2The catalytic performance of the monomeric catalyst is not significantly enhanced, and the slight enhancement of the current density may be due to the photothermal effect. As shown in fig. 4 b-c, the overpotentials of these catalysts decreased significantly with increasing Ag loading concentration. Ag/alpha-Co (OH) under 500mW laser irradiation2The overpotential of 1% catalyst was 299mV and the laser intensity was adjusted to 1000mW, with a further reduction of the overpotential to 273 mV. (FIG. 4 b). This property is significantly better than that of alpha-Co (OH) without laser irradiation2Ag-1% (306 mV). Indicating that the "plasmonic antenna" grafted transition metal hydroxide can achieve efficient OER reaction under illumination. This positive effect may be due to the fact that the LSPR excited Ag nanocluster surface generated "hot holes" limit Con+The outer electrons of (2) promote electrons from alpha-Co (OH)2Transfer to Ag nanoclusters
Example 2:
Ag/alpha-Co (OH) with different Ag loading content2The catalyst was prepared essentially as in example 1, except that: aqueous silver nitrate solution (238.5. mu.L, 10mg mL)-1) Ag (NH) configured to 1mL3)2OH solution, and the rest steps are the same; further, characterization analysis and performance test are carried out on the composite material, and the aim of the invention can be achieved in example 2.
Example 3:
different Ag loading containsAmount of Ag/alpha-Co (OH)2The catalyst was prepared essentially as in example 1, except that: aqueous silver nitrate solution (397.5. mu.L, 10mg mL)-1) Ag (NH) configured to 1mL3)2OH solution, and the rest steps are the same; further, characterization analysis and performance test are carried out on the product, and the aim of the invention can be achieved in example 3.
And (3) testing results: Ag/alpha-Co (OH) with different Ag loading contents is prepared by changing the concentration of the added silver-ammonia solution2And the catalyst is subjected to X-ray diffraction, and the result of an electron scanning microscope shows that the Ag nanoclusters are successfully loaded. It was subjected to a linear voltammetric sweep test, as shown in FIG. 3, example 2 shows that when the current density was 10mA/cm-2Prepared Ag supported Ag/alpha-Co (OH)2The overpotential of the catalyst was reduced to 278mV, and example 3 shows that when the current density was 10mA/cm-2Prepared Ag supported Ag/alpha-Co (OH)2The overpotential of the catalyst was reduced to 295 mV. Thus, it can be seen that Ag/α -Co (OH) of different Ag loading contents2The OER performance of the catalyst is all in alpha-Co (OH)2The method is greatly improved on the basis of the monomer catalyst, which is probably due to the increase of the conductivity of the Ag loaded composite material and the effective adjustment of the electronic structure of the composite material. The interlayer space channels allow for the insertion and rapid transport of water and ions. These water and ions act as quasi-electrolytes, facilitating the exchange of reactants and products, thereby increasing the number of active sites. Meanwhile, the Ag nanocluster is loaded, so that the conductivity of the catalyst is further improved, and the electron transfer rate is increased. As the loading of Ag varies, it exhibits different overpotentials indicating that the more the loading of Ag is, the better the loading is, and the best the electrocatalyst performance is only achieved 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. It was subjected to linear voltammetric sweep tests under laser irradiation (532 nm green laser at 500, 700 and 1000 mW) as shown in fig. 4. In the absence of Ag nanoclusters, alpha-Co (OH)2The nanoplatelets show poor OER electrocatalytic performance under laser irradiation (fig. 4 a). In that500. The catalytic performance of the catalyst is not obviously enhanced under the laser irradiation of 700 and 1000mw, and the slight enhancement of the current density is probably caused by the photothermal effect. As shown in FIGS. 4 b-d, the overpotentials of these catalysts decreased significantly with increasing Ag loading concentration, and example 2 shows that when the current density was 10mA/cm-2Prepared Ag supported Ag/alpha-Co (OH)2The 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 243 mV. (FIG. 4 c). This property is significantly better than that of alpha-Co (OH) without laser irradiation (288mV)2Ag-3 percent. Example 3 shows that when the current density is 10mA/cm-2Prepared Ag supported Ag/alpha-Co (OH)2The overpotential of the catalyst under the irradiation of 500mW laser is only 290 mV. The laser intensity was adjusted to 1000mW and its overpotential was further reduced to 250 mV. The experimental results show that the transition metal hydroxide grafted by the plasma antenna can realize high-efficiency OER reaction under illumination. This positive effect may be due to the fact that the LSPR excited Ag nanocluster surface generated "hot holes" limit Con+The outer electrons of (2) promote electrons from alpha-Co (OH)2Transfer to Ag nanoclusters
According to the results, the method avoids complex preparation process, and successfully prepares Ag/alpha-Co (OH) loaded with Ag with higher electro-catalysis oxygen evolution performance at lower temperature and under simple and convenient preparation method2The catalyst effectively overcomes the defects of complicated preparation and poor oxygen evolution performance of the transition metal-based electro-catalytic material, and provides a new idea for a means of improving the catalytic performance by adjusting an electronic structure by anions. In addition, Ag supported Ag/alpha-Co (OH) prepared by the method2The catalyst can also be applied to the fields of metal-air batteries, novel capacitors, novel energy sources and the like.
The present invention has been described in detail by way of example, and specific features of the above embodiments may be modified and combined in any suitable way without departing from the spirit of the present invention, which should also be regarded as disclosed in the present invention.
The invention is not the best known technology. The practice and equipment employed in the present invention are, unless otherwise indicated, those conventional in the art; the reagents and materials used are commercially available.
Claims (10)
1. Ag/alpha-Co (OH)2The preparation method of the oxygen evolution catalyst is characterized by comprising the following steps:
(1) dissolving cobalt chloride hexahydrate, sodium chloride and hexamethylenetetramine in a mixed solution of deionized water and ethanol in sequence according to a proportion, and then stirring and heating the mixed solution in an oil bath; heating to produce a suspension containing green particles, centrifuging to collect the solid product, washing, air drying at room temperature to obtain the final product alpha-Co (OH)2；
(2) The alpha-Co (OH) prepared in the step (1)2Ultrasonically dispersing in deionized water, and then adding Ag (NH)3)2OH solution was added dropwise to the dispersed alpha-Co (OH)2Stirring in suspension under shading condition, irradiating under xenon lamp illumination condition, centrifuging and collecting the product after reaction, washing with water and ethanol, freeze drying, and taking out to obtain Ag-loaded alpha-Co (OH)2。
2. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (1), the amount of cobalt chloride hexahydrate, sodium chloride and hexamethylene tetramine is 1:5:6, wherein the concentration of the cobalt chloride hexahydrate is 0.005-0.015 mol/L.
3. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (1), the volume ratio of deionized water to ethanol is 9:1 in the mixed solution of the deionized water and the ethanol.
4. Ag/α -Co (OH) according to claim 12A process for the preparation of an oxygen evolution catalyst, characterized in thatIn the step (1), the reaction solution is heated to 70-100 ℃ in an oil bath under magnetic stirring for 1-3 h.
5. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (1), the product is collected and centrifuged at 7000rpm for 2min, and the product is washed by deionized water and absolute ethyl alcohol for multiple times.
6. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (2), Ag (NH)3)2The OH solution is prepared by slowly dripping diluted ammonia water solution to prepare silver nitrate aqueous solution into Ag (NH)3)2And (3) preparing an OH solution.
7. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (2), the stirring time is 5-60min under the shading condition, and the irradiation is carried out for 30min under the condition of 300W xenon lamp illumination.
8. Ag/α -Co (OH) according to claim 12The preparation method of the oxygen evolution catalyst is characterized in that in the step (2), Ag (NH)3)2OH solution and alpha-Co (OH)2The volume ratio of the suspension was 79.5 μ L: 40 mL; wherein, Ag (NH)3)2The concentration of the OH solution was 10 mg/mL-1，α-Co(OH)2The concentration of the suspension was 1.25 g/L.
9. Ag/alpha-Co (OH)2The oxygen evolution catalyst is characterized by being prepared by the preparation method according to any one of claims 1 to 8, wherein the Ag/alpha-Co (OH)2Oxygen evolution catalyst, presenting spherical silver clusters and lamellar units, Ag nanoclusters with average diameter of 60-100nm well dispersed in alpha-Co (OH)2The surface of the nanoplatelets.
10. Combining the Ag/α -Co (OH) of claim 92Use of an oxygen evolution catalyst as an electrocatalyst for the field of renewable fuel cells, rechargeable metal-air cells or electrolysis of water.
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