CN111777102A - Metal oxide-based bifunctional water decomposition nano material and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a metal oxide-based bifunctional water decomposition nano material and a preparation method thereof. The invention selects commercial current collector as substrate, prepares nanometer material precursor containing two or more than two kinds of metal ions by chemical coprecipitation method, and then obtains corresponding metal oxide nanometer material by thermal conversion method by utilizing different thermal decomposition properties of different metal precursors. The material prepared by the invention can integrate the metal oxide with stronger H adsorption capacity into a material system with excellent electrocatalytic oxygen production property, so that the material finally has the capacity of simultaneously catalyzing and decomposing water to generate hydrogen and oxygen, thereby achieving the purpose of completely decomposing water in an alkaline environment. The material prepared by the invention has strong binding force with a current collector, regular and ordered structure, excellent conductivity, good mechanical and chemical stability, simple process, low energy consumption, safety and reliability, is convenient for large-scale preparation, and is beneficial to popularization and application.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a metal oxide-based bifunctional water decomposition nano material and a preparation method thereof.
Background
The bifunctional water decomposing material can catalyze and decompose water to generate hydrogen and oxygen at the same time, is environment-friendly, can greatly save cost and improve electrochemical conversion efficiency, and is widely concerned by people.
The preparation method of the existing bifunctional water decomposing material mainly comprises the following steps: the method comprises the following steps of (1) simply and mechanically mixing materials with excellent hydrogen evolution property and materials with oxygen generation property by simple ultrasonic or stirring. The disadvantages are that: low catalytic activity, poor structural order, lack of control of the material on a nanometer scale, and the like. ② growing in situ, which is to grow the material with oxygen generating property on the surface of the material with hydrogen generating property or to grow the material with hydrogen generating property on the surface of the material with oxygen generating property. The disadvantages of this method are mainly: the poor binding force between two materials easily causes the separation of hydrogen evolution or oxygen production materials, so that the catalytic activity of the materials is reduced, the service life is shortened, and the further practical application is not facilitated. Surface modification is to introduce other elements by surface doping to improve the catalytic activity center of the material, but has the disadvantages of poor stability of the material, low content of doped elements and the like, and is difficult to produce in batches.
Therefore, the practical and effective method is provided for preparing the bifunctional metal oxide nano material with high catalytic activity and stable structure, and the method has very important theoretical and practical significance in basic scientific research and application of electrocatalytic water decomposition technology.
Disclosure of Invention
The invention aims to provide a metal oxide-based bifunctional water decomposition nano material with high catalytic activity and stable structure and a preparation method thereof, aiming at the problem of low hydrogen evolution efficiency of metal oxide catalysis.
The preparation method of the metal oxide-based bifunctional water decomposition nano material provided by the invention utilizes an in-situ thermal conversion method to prepare the metal oxide nano material with excellent hydrogen evolution property and oxygen generation property. The method has the advantages of convenient operation, low cost, easy control, mass production and the like; and the metal oxide nano material has the excellent performances of regular structure, good orderliness, stable structure, high catalytic activity and the like. Has potential commercial application value in the field of preparing hydrogen by electrocatalytic decomposition of water.
The invention provides a preparation method of a water nanometer material based on metal oxide dual-function decomposition, which comprises the steps of taking transition metal salt as a raw material, firstly preparing transition metal hydroxide, and then carrying out thermal decomposition on the metal hydroxide through an in-situ thermal conversion process to obtain the metal oxide nanometer material with excellent hydrogen evolution and oxygen generation properties. The method comprises the following specific steps:
(1) preparation of Metal hydroxide precursor
Before growing the material, the substrate is pretreated, namely the substrate is put into dilute acid solution and deionized water for cleaning to remove impurities on the surface, and then inert gas is used for blow drying for standby. Adding two or more different metal salts and alkaline salts into deionized water according to a ratio, and performing ultrasonic treatment for 1-200 min to obtain a mixed solution; then putting the substrate into the mixed solution, and carrying out ultrasonic treatment for 1-200 min; putting the mixed solution and the substrate into a reaction kettle, and reacting for 1-24 h at 100-200 ℃; naturally cooling after the reaction is finished, taking out the substrate, washing the substrate for a plurality of times by using deionized water and ethanol, and drying (putting the substrate into a vacuum box) to obtain a metal hydroxide precursor;
(2) preparation of metal oxides
Heating the metal hydroxide precursor prepared in the step (1) to 200-600 ℃ at a heating rate of 0.5-50 ℃/min, and adding an inert gas (such as N)2and/Ar) performing heat treatment for 1-5 hours to obtain the metal oxide nano material with the property of dual-function water decomposition.
In step (1) of the present invention, the molar ratio of the two different metal salts is: 1, (0.1-10), and the preferable molar ratio is as follows: 1, (0.5-2); the molar ratio of the three different metal salts is: 1, (0.1-10) and (0.1-10), wherein the preferable molar ratio is as follows: 1 (0.5-2) and (0.5-2), and so on. Typically, two, three or four different metal salts are employed.
In step (1) of the present invention, the different metal salts are respectively selected from two or more of copper salt, cobalt salt, nickel salt, iron salt or vanadium salt, and must contain copper salt. Among them, the copper salts are copper nitrate, copper acetate, copper chloride, etc., the cobalt salts are cobalt nitrate, cobalt acetate, cobalt chloride, etc., the nickel salts are nickel nitrate, nickel acetate, nickel chloride, etc., and the iron salts are ferric nitrate, ferric acetate, ferric chloride, etc.
In the step (1), the substrate is one or more of commercial nickel foam, copper foam, titanium sheet, stainless steel sheet or FTO. Preferably, nickel foam, copper foam, titanium sheet.
In the step (1), the alkaline salt is one or more of urea, ammonia water, sodium hydroxide, potassium bicarbonate, ammonium bicarbonate or sodium bicarbonate.
In the step (2), the heat treatment temperature is preferably 300-500 ℃ and the heat treatment time is preferably 2-4 hours.
The material prepared by the invention can integrate the metal oxide with stronger H adsorption capacity into a material system with excellent electrocatalytic oxygen production property, so that the material finally has the capacity of simultaneously catalyzing and decomposing water to generate hydrogen and oxygen, thereby achieving the purpose of completely decomposing water in an alkaline environment. The material prepared by the invention has strong binding force with a current collector, regular and ordered structure, excellent conductivity and good mechanical and chemical stability, and can be applied to the fields of energy storage and conversion, environmental protection and the like. The method has the advantages of simple process, low energy consumption, safety, reliability, convenience for large-scale preparation and contribution to popularization and application.
The method has the advantages that:
1. the invention adopts the procedures of chemical coprecipitation, in-situ thermal conversion and the like, has simple process and convenient operation, is beneficial to large-scale production and is convenient to popularize and apply;
2. the process of the invention is easy to regulate and control, and the control of the components and the structure can be realized by simply changing the combination of adding the metal salt; therefore, the invention can be widely applied to the preparation of various transition metal oxide-based functional materials;
3. the invention adopts cheap transition metal elements, has low cost and is easy to realize large-scale production;
4. the metal oxide nano material prepared by the method has controllable components and good mechanical stability, can better realize the synergistic effect among different components of the nano material compared with simple mechanical mixing, and is more convenient for the metal oxide nano material to realize functional application.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the copper-cobalt-based metal oxide bifunctional decomposed water nanomaterial prepared in example 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the copper-cobalt-based metal oxide bifunctional decomposed water nanomaterial prepared in example 1: a and b are common TEM pictures; and c is a high-resolution TEM picture.
FIG. 3 is a diagram of hydrogen evolution (a) and oxygen production (b) properties of the copper-cobalt-based metal oxide bifunctional decomposition water nanomaterial prepared in example 1.
Fig. 4 is a diagram illustrating the performance of the copper-cobalt-based metal oxide bifunctional decomposition water nanomaterial prepared in example 1. Wherein, (a) is the full water decomposition performance under a two-electrode system, and (b) is the circulation stability.
Detailed Description
The technical solution of the present invention is further described below with reference to the specific embodiments.
Example 1:
a preparation method of a catalyst for double-function water decomposition based on metal oxide comprises the following specific steps:
(a) preparation of Metal hydroxide precursor
And (3) putting the commercial foam nickel substrate into a dilute acid solution and deionized water for cleaning to remove impurities on the surface, and finally blowing the commercial foam nickel substrate by inert gas for later use. 1.0 mmol of Co (NO)3)2、0.5mmol Cu(NO3)26 mmol of urea is dissolved in 40 mL of deionized water solution, and the mixture is stirred for 15 min to obtain a dispersion mixed solution. And then putting the cleaned foam nickel substrate into a high-temperature hydrothermal reaction kettle. Adding the dispersion solution into a high-temperature hydrothermal reaction kettle with a foamed nickel substrate, and reacting for 6 hours at 120 ℃. And naturally cooling after the reaction is finished, taking out the substrate on which the metal hydroxide precursor grows out, washing the substrate for a plurality of times by using deionized water and ethanol, and then putting the substrate into a vacuum drying oven for drying to obtain the copper-cobalt metal hydroxide precursor.
(b) Preparation of metal oxides
Heating the precursor of the copper-cobalt metal hydroxide prepared in the step at the temperature rise rate of 5 ℃/min in an inert atmosphere (N)2Ar) heat treatment, wherein the heat treatment temperature is 300 ℃, and the heat treatment time is 2 hours. And naturally cooling to obtain the copper-cobalt-based oxide nano material with the bifunctional water decomposition property.
The copper-cobalt-based oxide material obtained by the preparation process described in example 1 was selected for Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) observation (fig. 1-2), electrocatalytic hydrogen evolution and oxygen production performance test (fig. 3), and bifunctional total decomposition water property test (fig. 4).
From the analysis of the test results, the copper-cobalt-based oxide material obtained by the preparation process described in example 1 is a very regular one-dimensional nanowire array structure, each nanowire is composed of many fine Cu2O, CoO and CuCo2O4The nano particles are piled up. The formation of different phases can create more grain boundaries, increasing the exposure of the active sites of the material. Furthermore, it is inferred that the method of the present invention can prepare a one-dimensional nanowire array formed by stacking different metal oxide phases. Meanwhile, the one-dimensional nanowire structure has excellent mechanical and chemical stability. Other methods have difficulty achieving such regulation. Under a three-electrode system, the copper-cobalt-based oxide material can start a hydrogen evolution reaction under the overpotential of 85 mV, and 10 mA cm can be obtained by only needing 140 mV of overpotential-2The current density of (1). When used as an oxygen generating material, the starting overpotential is 250 mV. On two electrode bodiesUnder the condition that the copper-cobalt-based oxide nano material is used as a positive electrode and a negative electrode to simultaneously catalyze and decompose water for hydrogen evolution and oxygen generation, the electrolytic cell can obtain 10 mA cm under the voltage of 1.61V-2And exhibits excellent cycle stability at a voltage of 1.7V.
Example 2:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in the step (a), Co (NO)3)2.6H2O and Cu (NO)3)2.6H2The molar ratio of O is 1: 0.1; the hydrothermal reaction temperature is 100 ℃, and the reaction time is 1 h; in the step (b), the high-temperature heat treatment temperature is 300 ℃, the heating rate is 0.5 ℃/min, and the reaction time is 2 h. The copper-cobalt-based oxide nano material prepared in the embodiment is subjected to a full water decomposition reaction to obtain 10 mA cm-2The voltage of 1.65V is required for the current density of (2).
Example 3:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in the step (a), Co (NO)3)2.6H2O and Cu (NO)3)2.6H2The molar ratio of O is 1: 10; the hydrothermal reaction temperature is 200 ℃, and the reaction time is 24 hours; in the step (b), the high-temperature heat treatment temperature is 600 ℃, the heating rate is 50 ℃/min, and the reaction time is 5 h. The copper-cobalt-based oxide nano material prepared in the embodiment is subjected to a full water decomposition reaction to obtain 10 mA cm-2The voltage of 1.82V is required for the current density of (2).
Example 4:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in the step (a), Ni (NO)3)2.6H2O and Cu (NO)3)2.6H2The molar ratio of O is 1: 0.5; in the step (b), the high-temperature heat treatment temperature is 350 ℃, the heating rate is 5 ℃/min, and the reaction time is 3 h. The copper-nickel-based oxide nano material prepared by the embodiment is subjected to full decompositionIn the water reaction, 10 mA cm was obtained-2The voltage of 1.67V is required for the current density of (2).
Example 5:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in step (a), FeCl3And CuCl2In a molar ratio of 1: 0.5; the hydrothermal reaction temperature is 120 ℃, and the reaction time is 10 hours; in the step (b), the high-temperature heat treatment temperature is 400 ℃, the heating rate is 5 ℃/min, and the reaction time is 3 h. The Cu-Fe-based oxide nano material prepared in the embodiment is subjected to a full water decomposition reaction to obtain 10 mA cm-2The voltage of 1.75V is required for the current density of (2).
Example 6:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in the step (a), a metal salt CoCl2、VCl3And CuCl2In a molar ratio of 1:0.5: 0.5; the hydrothermal reaction temperature is 180 ℃, and the reaction time is 5 hours; in the step (b), the high-temperature heat treatment temperature is 350 ℃, the heating rate is 10 ℃/min, and the reaction time is 3 h. The Cu-Co-V-based oxide nano material prepared by the embodiment is subjected to a full water decomposition reaction to obtain 10 mA cm-2The voltage of 1.66V is required for the current density of (2).
Example 7:
a preparation method of a catalyst for bifunctional water decomposition based on metal oxide, which is the same as in example 1, wherein:
in the step (a), Co (NO) as a metal salt3)2、Ni(NO3)2And Cu (NO)3)2In a molar ratio of 1:0.5: 0.2; the substrate is a stainless steel sheet; the hydrothermal reaction temperature is 150 ℃, and the reaction time is 6 hours; in the step (b), the high-temperature heat treatment temperature is 350 ℃, the heating rate is 10 ℃/min, and the reaction time is 3 h. The Cu-Co-Ni-based oxide nano material prepared in the embodiment is subjected to a full water decomposition reaction to obtain 10 mA cm-2The voltage of 1.63V is required for the current density of (2).
Claims (7)
1. A preparation method for a metal oxide based double-function decomposed water nanometer material is characterized in that transition group metal salt is used as a raw material, transition group metal hydroxide is firstly prepared, and then the metal hydroxide is subjected to thermal decomposition through an in-situ thermal conversion process to obtain the metal oxide nanometer material with excellent hydrogen evolution and oxygen generation properties; the method comprises the following specific steps:
(1) preparation of Metal hydroxide precursor
Pretreating the substrate to remove impurities on the surface; adding two or more different metal salts and alkaline salts into deionized water according to a ratio, and performing ultrasonic treatment for 1-200 min to obtain a mixed solution; then putting the substrate into the mixed solution, and carrying out ultrasonic treatment for 1-200 min; putting the mixed solution and the substrate into a reaction kettle, and reacting for 1-24 h at 100-200 ℃; naturally cooling after the reaction is finished, taking out the substrate, washing the substrate for a plurality of times by using deionized water and ethanol, and drying to obtain a metal hydroxide precursor;
(2) preparation of metal oxides
And (2) heating the metal hydroxide precursor prepared in the step (1) to 200-600 ℃ at a heating rate of 0.5-50 ℃/min, and carrying out heat treatment for 1-5 hours in an inert gas atmosphere to obtain the metal oxide nano material with the dual-function water decomposition property.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the two different metal salts is: 1, (0.1-10); the molar ratio of the three different metal salts is: 1 (0.1-10) and (0.1-10), and so on.
3. The method according to any one of claims 1 to 2, wherein the two different metal salts in step (1) are selected from two or more of cobalt salt, copper salt, nickel salt, iron salt and vanadium salt, respectively, and must contain copper salt.
4. The method according to claim 3, wherein the substrate in step (1) is one or more of foamed nickel, foamed copper, titanium sheet, stainless steel sheet or FTO.
5. The method according to any one of claims 1 to 3, wherein the basic salt in step (1) is one or more of urea, ammonia water, sodium hydroxide, potassium bicarbonate, ammonium bicarbonate or sodium bicarbonate.
6. The method according to claim 1, wherein the heat treatment temperature in the step (2) is 300 to 500 ℃ and the heat treatment time is 1 to 8 hours.
7. A metal oxide-based bifunctional decomposed water nanomaterial obtained by the preparation method of any one of claims 1 to 6.
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| CN114291849A (en) * | 2021-12-24 | 2022-04-08 | 盐城工学院 | Preparation method and application of Fe oxide nano material |
| CN114314674A (en) * | 2021-12-24 | 2022-04-12 | 盐城工学院 | Preparation method of Fe oxide nano material applied to dechlorination of wastewater |
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