CN112279306B - Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof - Google Patents
Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof Download PDFInfo
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Abstract
The invention belongs to the field of nano, particularly belongs to the application of nano materials in renewable energy technology, and more particularly relates to an optimization method of layered sulfide nanocrystals and an optimized Sn-S-Co nanocrystal composite material. The performance of the composite material is excellent and superior to that of IrO2 which is commercially available at present through detection, and the composite material has important guiding significance for the technical development of renewable energy sources.
Description
Technical Field
The invention belongs to the field of nano, particularly belongs to the application of nano materials in renewable energy technology, and more particularly relates to an optimization method of sulfide nanocrystals, Sn-S-Co nanocrystals and optimized products thereof.
Background
In the last few years, with the increasing energy crisis, there is an urgent need for new clean fuels to replace fossil fuels.
Water splitting has attracted increasing attention as a means of producing hydrogen fuel. Water oxidation, also known as Oxygen Evolution Reaction (OER), is an important half-reaction in electrocatalytic water splitting, plays a crucial role in electrochemical reactions occurring in different energy storage and conversion systems, and the complex multi-step proton-coupled electron transport processes, such as splitting of oxyhydrogen bonds and formation of oxyhydrogen bonds, lead to the slow kinetics effect of OER. Therefore, by making an effective electrocatalyst, lowering its overpotential to accelerate OER rate and reduce energy input is essential.
RuO to date2And IrO2These Ru/Ir-based materials are considered to be the most effective, most powerful OER electrocatalysts. However, the scarcity and high cost of noble metals limits their applications. Therefore, there is an urgent need to develop an efficient, low-cost, highly available, highly durable OER electrocatalyst to replace the noble metal-based materials.
Literature studies have shown that metal sulfides are one of the most important layered non-noble metals, the hexagonal system SnS2Because of its abundance, non-toxicity, low cost, and good stability, it has been widely studied in lithium batteries, sodium ion batteries, and supercapacitors.
The layered non-noble metal sulfides and composites thereof exhibit excellent OER activity due to their high conductivity, abundant active sites and environmental friendliness. Layered metal sulfide electrocatalysts have unlimited potential in the OER field.
Therefore, in the development process of renewable energy technology, the development of efficient and cheap alloy nanocrystals has important significance for the electrocatalyst of the OER.
Disclosure of Invention
One of the technical problems to be solved by the invention is to optimize the sulfide nanocrystalline and improve the electrocatalytic efficiency of the sulfide nanocrystalline composite material used as a catalyst for OER.
The invention aims to solve another problem of providing a novel sulfide nanocrystalline composite material with high electrocatalytic efficiency, and optimizing the material to ensure that the material has high electrocatalytic efficiency.
In order to solve the technical problem, the invention discloses an optimization method of sulfide nanocrystals, wherein the sulfide nanocrystals are layered nanocrystals, the optimization method is to carry out controllable phosphorization on the sulfide nanocrystals, and the optimization method specifically comprises the following steps:
s1: dissolving the dried sulfide nano-crystal,
s2: and heating the sulfide nanocrystalline to 230 +/-5 ℃, adding a phosphating agent, and preserving heat to obtain a solution containing the optimized sulfide nanocrystalline.
Further preferably, the method further comprises the step of S3: and obtaining an optimized sulfide nanocrystalline product through dispersion, sedimentation and separation.
More preferably, the method further comprises the step of S4: and (4) drying in vacuum to obtain a dried sulfide nanocrystalline product.
As a preferable technical solution, in step S1, the sulfide nanocrystal is dried at a low temperature and then dissolved.
Further preferably, the low-temperature drying is drying at 50 ± 2 ℃ or lower.
As a preferable technical solution, in step S2, the temperature of the sulfide nanocrystal is raised in a sand bath.
Preferably, in step S2, the temperature is uniformly increased to 230 +/-5 ℃ at a temperature increasing rate of 5 ℃ min-1。
Further preferably, the keeping temperature time in step S2 is 30 minutes.
As a preferred technical scheme, the phosphating agent is tri-n-octyl phosphine.
More preferably, the addition amount of the phosphating agent is 3 to 10 mL. More preferably, the amount of the phosphating agent added is 5 mL.
In a preferred embodiment, the sedimentation in step S3 uses a mixed solution of n-heptane and absolute ethanol, and the mixing molar ratio of n-heptane to absolute ethanol is 3: 1.
Meanwhile, the invention also discloses a novel sulfide nanocrystalline composite material Sn-S-Co with a layered structure, wherein the Sn-S-Co nanocrystalline is a layered nanocrystal.
Meanwhile, the invention also discloses a preparation method of the Sn-S-Co layered nanocrystal, which comprises the following steps:
a1: thiourea (CS (NH)2)2)、SnCl2·2H2O、CoCl2·6H2O in H2O is in;
a2: heating the oil bath to 120 ℃;
a3: keeping the temperature for reaction until a crystal film appears;
a4: and (4) drying the crystal film to obtain the Sn-S-Co layered nanocrystal.
Preferably, the drying is low-temperature drying, and the low-temperature drying is drying at the temperature of 50 +/-2 ℃.
Preferably, the CS (NH)2)2，SnCl2·2H2O，CoCl2·6H2The molar ratio of O is 5: 0.75: 0.25.
furthermore, the invention also discloses an optimized sulfide nanocrystal composite material Sn-S-Co, wherein the Sn-S-Co nanocrystal is a polycrystalline surface laminar nanocrystal.
Meanwhile, the invention further discloses a preparation method of the sulfide nanocrystalline composite material Sn-S-Co with the sheet structure, which comprises two parts of preparation of Sn-S-Co layered nanocrystals and controllable phosphorization of the sulfide nanocrystals, and specifically comprises the following steps:
b1: thiourea (CS (NH)2)2)、SnCl2·2H2O、CoCl2·6H2O in H2O is in;
b2: heating the oil bath to 120 ℃;
b3: keeping the temperature for reaction until a crystal film appears;
b4: drying the crystal film to obtain Sn-S-Co layered nanocrystals;
b5: dissolving the dried Sn-S-Co nanocrystalline,
b6: and heating the Sn-S-Co nanocrystalline to 230 +/-5 ℃, adding a phosphating agent, and preserving heat to obtain a solution containing the optimized Sn-S-Co nanocrystalline.
Preferably, the CS (NH)2)2，SnCl2·2H2O，CoCl2·6H2The molar ratio of O is 5: 0.75: 0.25.
further preferably, the drying in B4 is low-temperature drying, and further preferably, the low-temperature drying is performed preferably at 50 ± 2 ℃ or lower.
In a preferred embodiment, in the step B5, the sulfide nanocrystal is dissolved by a dodecylamine (DDA) solution.
Further preferably, the temperature of the sulfide nanocrystals is raised in a sand bath in step B6.
As a preferable technical scheme, in the step B6, the temperature is uniformly increased to 230 +/-5 ℃, and the temperature increase rate is 5 ℃ min-1。
It is further preferred that the holding time in step B6 is 30 minutes.
As a preferred technical scheme, the phosphating agent is tri-n-octyl phosphine (TOP).
More preferably, the addition amount of the phosphating agent is 3 to 10 mL. More preferably, the amount of the phosphating agent added is 5 mL.
Further preferably, the method also comprises the following steps of B7: and performing dispersion sedimentation and centrifugal separation to obtain a product, and performing vacuum drying to obtain the product containing the Sn-S-Co nanosheet.
It is further preferred that a mixed solution of n-heptane and absolute ethanol is used for the sedimentation, and the mixing molar ratio of n-heptane to absolute ethanol is 3: 1.
Finally, the invention further discloses the application of the Sn-S-Co nanocrystalline in the preparation of a fuel cell catalyst and the application of the optimized Sn-S-Co nanocrystalline in the preparation of the fuel cell catalyst.
The controllable phosphorization optimization method disclosed by the invention can obviously improve the crystal form of the sulfide nanocrystal, thereby obviously improving the OER performance of the material and further improving the OER application of the material as a catalyst in a high-efficiency catalytic fuel cell. The performance of the composite material is excellent through detection, is far superior to that of IrO2 sold on the market at present, and has important guiding significance for the technical development of renewable energy sources.
Meanwhile, the synthesis method of the Sn-S-Co alloy nanocrystalline disclosed by the invention is simple, the Sn-S-Co alloy nanocrystalline can be synthesized only by a simple solid-liquid phase solvothermal method, and the Sn-S-Co alloy nanocrystalline has higher OER application value after being optimally synthesized by combining controllable phosphorization. Meets the requirement of industrial production and is suitable for batch production.
Drawings
FIG. 1 is a TEM image of Sn-S-Co-1, Sn-S-Co-2, Sn-S-Co-3 and Sn-S-Co-4 synthesized in the present invention;
FIG. 2 is an XRD pattern of Sn-S-Co-1, Sn-S-Co-2, Sn-S-Co-3 and Sn-S-Co-4 synthesized in the present invention;
FIG. 3 is a linear sweep voltammogram of an OER test of a Sn-S-Co composite synthesized according to the present invention;
FIG. 4 is a dual capacitance test chart of OER test of the Sn-S-Co composite material synthesized by the present invention;
FIG. 5 is a resistance plot of OER testing of the synthesized Sn-S-Co composite material of the present invention.
Detailed Description
In order that the invention may be better understood, we now provide further explanation of the invention with reference to specific examples.
Example 1
Thiourea (CS (NH)2)2)，SnCl2·2H2O，CoCl2·6H2O in H2And O, raising the temperature of the oil bath to 120 ℃ until a crystal film appears, and putting the crystal film into a drying oven to be dried at the temperature lower than 50 ℃. Sn-S-Co-0 is obtained.
Example 2
Obtaining Sn-S-Co-0 according to the method in the embodiment 1, then dissolving the Sn-S-Co-0 in a dodecylamine (DDA) solution, heating the solution in a sand bath to 230 ℃, adding 3-10mL of TOP, preserving the heat for 30min to obtain a product containing Sn-S-Co, and finishing the reaction. When the sand bath is naturally cooled to 48 ℃, adding a proper amount of n-heptane and absolute ethyl alcohol for dispersion, and centrifugally separating solids. The solid was washed to give a black product which was dried overnight under vacuum in a vacuum oven and used for analytical characterization.
In this example, products of different TOP addition amounts are respectively marked with different numbers.
Wherein:
when the adding amount of TOP is 3mL, the product is marked as Sn-S-Co-1;
when the adding amount of TOP is 5mL, the product is marked as Sn-S-Co-2;
when the adding amount of TOP is 8mL, the product is marked as Sn-S-Co-3;
when TOP was added at 10mL, the product was labeled Sn-S-Co-4.
The obtained product was characterized and analyzed by Transmission Electron Microscope (TEM) and X-ray single crystal diffraction (XRD) tests, and the results are shown in fig. 1 and fig. 2.
According to the figure 1, the Sn-S-Co composite material is a two-dimensional layered nano structure, and the diffraction projection color of the Sn-S-Co nano crystal optimized by the phosphating agent is lightened through a transmission electron microscope, which shows that the Sn-S-Co nano crystal has a thinner structure trend. Meanwhile, according to the crystal morphology in the TEM image, the optimized nanocrystal has better dispersibility.
Meanwhile, as can be seen from fig. 2, with the addition of the phosphating agent, the number of diffraction peaks is increased, the peak width is narrowed, and the peak height is enhanced, so that the crystal face formed on the surface of the sample is increased.
Example 3
The electrochemical properties of the sample are tested by cyclic voltammetry and polarization curve method in a three-electrode system, and the specific process is as follows:
the electrochemical experiments were carried out on an AUTOLAB-PGSTAT302N type electrochemical workstation, using a standard three-electrode test system, the corresponding working electrode being a glassy carbon electrode modified with the samples obtained herein, the counter electrode being a platinum sheet, and the reference electrode being mercury/silver mercuric oxide (Hg/HgO). All potentials herein are relative to Hg/HgO. The electrolyte is 0.1mol/L KOH solution. All electrochemical tests were performed at 25 ℃. At each experiment, all modified electrodes were tested in 0.1mol/L KOH solution.
The preparation method of the sample modified electrode comprises the following steps:
(1) and (3) preparing a sample solution, namely weighing 5mg of Sn-S-Co composite material sample into a centrifugal tube, adding 250 microliters of ethanol and 50 microliters of 1% Nafion, performing ultrasonic dispersion, adding 700 microliters of deionized water, and performing ultrasonic dispersion.
(2) Grinding an electrode: before each experiment, the glassy carbon electrode is lightly wiped by using wet lens wiping paper before grinding, and then is washed clean by using deionized water. And (3) adding the aluminum oxide polishing powder on the chamois, dropwise adding deionized water, wetting a small amount, and dispersing. Standing the electrode on the chamois leather, holding to horizontally grind the chamois leather until the surface is bright (the moving direction is in a shape of 'O' or '8', so that the surface of the electrode is uniformly ground).
(3) And (3) washing the ground electrode, removing surface particles, respectively and sequentially carrying out ultrasonic cleaning for about 30s by using water-ethanol-water until the alumina powder is completely removed, washing with water, and drying by using nitrogen. Then detecting the electrode, and if the scanning oxidation reduction peak potential difference delta V is not consistent with 80mV, operating again until the electrode is qualified.
(4) Dropping a sample: after the sample (5mg/mL) is dispersed by ultrasonic, 10 microliter of sample solution is dripped on the dry electrode, and the sample solution is put into an electrochemical special oven to be dried and taken out.
Before OER test, high-purity O is firstly introduced into the solution2For 30min to remove dissolved other gases in the solution and continue to pass O during the experiment2To maintain O of the solution2And (4) atmosphere. LSV is also at O2And (3) performing in an atmosphere.
The linear sweep voltammetry test chart of the Sn-S-Co nanosheet composite material is shown in FIG. 3, and FIG. 3 shows that after controllable phosphating, the OER performance of the Sn-S-Co nanosheet is obviously improved, and the catalytic activity of the composite material obtained by the invention in OER is superior to that of commercial IrO2The catalyst has higher catalytic activity after controllable phosphorization optimization.
Double-electric-layer capacitance measurement of Sn-S-Co nanosheet composite materialThe results of the tests and the calculation of the active area are shown in FIG. 4, where FIG. 4 includes the results of different sweep rates (1 mV. multidot.s)-1To 15 mV. s-1) The ordinate of the double-electric-layer capacitance test chart of each sample is current density which can be simply distinguished from the ordinate, and the product Sn-S-Co-2 can test larger current density within a unit voltage range. The active area calculated from the double layer capacitance diagram shows that the calculated active area of the product Sn-S-Co-2 is the largest and is 186mF cm-2. This result is consistent with the linear sweep voltammetry test results.
The impedance test result of the Sn-S-Co nanosheet composite material is shown in FIG. 5, and the smaller the radius of the circle formed by the impedance spectrum is, the smaller the impedance of the sample is, the faster the electron moves and the faster the reaction is. FIG. 5 shows that the impedance after Sn-S-Co phosphating was lower than that of the unphosphorized sample, and it can be confirmed that the phosphating indeed contributes to the improvement of the sample in performance for the OER test.
What has been described above is a specific embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (12)
1. The optimization method of the sulfide nanocrystal is a layered nanocrystal and is characterized in that the optimization method is to carry out controllable phosphorization on the sulfide nanocrystal, and specifically comprises the following steps:
s1: taking the dried sulfide nanocrystalline and dissolving the sulfide nanocrystalline by a dodecylamine solution;
s2: heating the sulfide nanocrystalline to 230 +/-5 ℃, adding a phosphating agent, and preserving heat to obtain a solution containing the optimized sulfide nanocrystalline;
the Sn-S-Co layered nanocrystal is prepared by the following steps:
a1: mixing thiourea with SnCl2•2H2O、CoCl2•6H2O in H2O is in;
a2: heating the oil bath to 120 ℃;
a3: keeping the temperature for reaction until a crystal film appears;
a4: drying the crystal film to obtain Sn-S-Co layered nanocrystals;
the phosphating agent is tri-n-octyl phosphine; the addition amount of the phosphating agent is 3-10 mL.
2. The optimization method of the sulfide nanocrystal, according to claim 1, further comprising S3, wherein the optimized sulfide nanocrystal product is obtained through dispersion, sedimentation and separation.
3. The method for optimizing sulfide nanocrystals, as recited in claim 2, further comprising the step of S4: and (4) drying in vacuum to obtain a dried sulfide nanocrystalline product.
4. The method for optimizing sulfide nanocrystals, as recited in claim 1, wherein in step S1, the sulfide nanocrystals are dried at a low temperature and then dissolved.
5. The method of claim 4, wherein the low temperature baking is performed at 50 ± 2 ℃ or lower.
6. The method for optimizing sulfide nanocrystals, according to claim 1, wherein the temperature of the sulfide nanocrystals is raised in a sand bath in step S2.
7. The optimization method of the sulfide nanocrystal according to claim 1, wherein in step S2, the temperature is raised to 230 ± 5 ℃ at a constant speed, and the temperature raising rate is 5 ℃ min "1.
8. The method for optimizing sulfide nanocrystal according to claim 1, wherein the holding time in step S2 is 30 minutes.
9. The method for optimizing sulfide nanocrystals, as recited in claim 1, wherein the amount of the phosphating agent added is 5 mL.
10. The method for optimizing sulfide nanocrystals, according to claim 2, wherein the step S3 of settling uses a mixed solution of n-heptane and absolute ethanol, and the mixing molar ratio of n-heptane to absolute ethanol is 3: 1.
11. The method of optimizing sulfide nanocrystals according to claim 1, wherein CS (NH)2)2，SnCl2•2H2O，CoCl2•6H2The molar ratio of O is 5: 0.75: 0.25.
12. the method for optimizing sulfide nanocrystals, as recited in claim 4, wherein the baking in the preparation of the Sn-S-Co layered nanocrystals is performed at a low temperature, which is 50 ± 2 ℃ or lower.
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| CN202011134054.9A CN112279306B (en) | 2020-10-21 | 2020-10-21 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| PCT/CN2020/134205 WO2022082944A1 (en) | 2020-10-21 | 2020-12-07 | Optimization method for sulfide nanocrystals, and sn-s-co nanocrystals and optimization product of sn-s-co nanocrystals |
| ZA2022/02231A ZA202202231B (en) | 2020-10-21 | 2022-02-22 | Optimization method of sulfide nanocrystals and sn-s-co nanocrystals and optimized products thereof |
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| WO2022082944A1 (en) | 2022-04-28 |
| CN112279306A (en) | 2021-01-29 |
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