CN110237868B - Supported ultra-small Prussian blue analogue and preparation method and application thereof - Google Patents
Supported ultra-small Prussian blue analogue and preparation method and application thereof Download PDFInfo
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Abstract
A load type ultra-small Prussian blue analogue, a preparation method and an application thereof belong to the technical field of functional nano materials. The preparation method comprises the following steps: 1) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; 2) and dispersing the turbid solution of the graphene supported ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, and mixing and reacting to obtain the graphene supported ultra-small Prussian blue analogue after graphene reduction. The method can realize the synthesis of the graphene-loaded ultra-small Prussian blue analogue and the synthesis of the ultra-small Prussian blue analogue. The supported ultra-small Prussian blue analogue prepared by the method is a composite structure of the Prussian blue analogue and graphene, and can improve the electric energy of the catalyst.
Description
Technical Field
The invention belongs to the technical field of functional nano materials, and particularly relates to a supported ultrasmall Prussian blue analogue and a preparation method and application thereof.
Background
Chemical nitrogen fixation refers to the synthesis of ammonia gas from nitrogen by a chemical reduction method to obtain a series of downstream nitrogen-containing products. The chemical nitrogen fixation method comprises thermal catalysis, photocatalysis, electrocatalysis nitrogen fixation and the like. At present, the nitrogen fixation method widely used in industry is the Haber method, and the iron catalyst is used as the catalyst to catalyze N at high temperature (about 500 ℃) and high pressure (10 MPa-30 MPa)2And H2The reaction produces ammonia gas. The haber process of synthesizing ammonia needs harsh conditions of high temperature, high pressure and other conditions, and the synthesis of ammonia needs hydrogen from water gas reforming and consumes great amount of energy. According to statistics, the energy consumed by the synthetic ammonia industry every year accounts for about 2% -3% of the total energy consumption of the whole world; in addition, the demand of chemical fertilizers is huge in the world, and the huge energy consumption brings about very serious environmental pollution. Therefore, the development of a new environment-friendly and efficient method for synthesizing ammonia is a key way for solving the energy crisis and environmental pollution. Meanwhile, the global environment faces the greenhouse effect, fossil fuels are increasingly exhausted, and the combustion of ammonia gas does not produce CO2And the greenhouse gases are considered as clean energy sources of the next generation.
The electrochemical catalysis ammonia synthesis reaction is a novel nitrogen fixation method which is developed at present, and N is catalyzed by electrochemistry2And protons in the solvent are converted to ammonia gas. The electrochemical catalysis has the advantages that the surface of the electrode can provide a plurality of high-activity electrons, and the rate of the nitrogen fixation reaction is effectively improved. And the hydrogen atoms in the nitrogen fixation reaction come from protons in the solvent, so that the use of hydrogen as a hydrogen source is avoided, and the energy utilization efficiency is higher and safer. The bond energy of N is up to 940.95 kJ mol-1To achieve activation of nitrogen molecules requires more active electrons, which can be easily achieved by potential adjustment in electrochemical catalysis. Despite such numerous advantages of the electrochemically catalyzed ammonia synthesis reaction, there are many problems faced in the ammonia synthesis reaction at this stage. Firstly, the activity of nitrogen fixation reaction is generally lower, the optimal performance of electrochemical catalysis ammonia synthesis reaction is that carbon-loaded bismuth nano-particles are used as a catalyst, and the ammonia generation activity reaches 3400 mu g mg-1 h-1Doping carbon with nitrogenThe load monatomic ruthenium is used as the catalyst and can realize 120 mug mg-1 h-1However, the activity of ammonia formation on the transition metal surface is generally less than 30 mug mg-1 h-1Although bismuth and ruthenium have high activities, they are rare elements and are expensive. Moreover, on the surface of the cathode, besides the reduction reaction of the nitrogen, a hydrogen evolution reaction also exists, the hydrogen evolution reduces the Faraday efficiency of the nitrogen fixation reaction, and the activation energy of the nitrogen reduction is far greater than that of the hydrogen evolution, so that the Faraday efficiency of the nitrogen fixation reaction at the present stage is low and is generally lower than 10%. Also, in addition to simple metal catalysts, the conductivity of transition metal-based catalysts is generally low, leading to an increase in the overpotential for the nitrogen fixation reaction, and therefore the need to catalyze the nitrogen reduction at a lower potential, which further exacerbates the hydrogen evolution reaction, reducing the activity of the nitrogen fixation reaction as a whole.
For nitrogen fixation reactions, activation of nitrogen molecules requires two key issues to be addressed. Firstly, how to effectively adsorb nitrogen molecules on the surface of the catalyst, the nitrogen molecules are nonpolar molecules and have low solubility in an aqueous solution, so that the key problem of improving the adsorption capacity of the nitrogen molecules on the surface of the catalyst is to improve the activity of nitrogen fixation reaction. The bond energy of the di-and N.ident.N bonds is high and activation of the nitrogen molecule requires that the bond length of N.ident.N be elongated as much as possible. Both of these key problems can be achieved by forming heteronuclear diatomic catalytic centers. The existing theoretical simulation research shows that heteronuclear diatoms change the original electronic structure due to different electronegativities of two atoms, when nitrogen molecules are adsorbed to the surface of a catalyst, the two nitrogen atoms are respectively adsorbed to the surfaces of different metal atoms, and the ability of electrons on a d orbit of a transition metal atom to enter an opposite bond orbit of the nitrogen molecules is different, so that the number of effective electrons received by each nitrogen atom is different, and finally, nonpolar nitrogen molecules are changed into polar molecules, thereby promoting the adsorption and activation of the nitrogen molecules on the surface of the catalyst.
The Prussian blue structure is Fe2+And Fe3+A framework structure formed by the alternative coordination of ions and cyanide radicals, wherein Fe2+Can be covered byMetal ion (Mn)2+，Cu2+，Zn2+，Ni2+，Co2+) A prussian blue analogue is formed. Prussian blue analogue can easily realize transition metal element doping to form Fe/M (M = Mn)2+，Cu2+，Zn2+，Ni2+，Co2+) The atomic ratio is 1: 1. This provides a good platform for us to study the effect of different heteronuclear atomic ratios on nitrogen molecule adsorption. And compared with noble metal ruthenium or bismuth catalysts, the Prussian blue structure formed by the transition metal elements has much lower cost and has good prospect in industrial application. At present, the application of the Prussian blue structure in the nitrogen fixation reaction is not reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a load type ultra-small Prussian blue analogue, and a preparation method and an application technical scheme thereof.
The preparation method of the supported ultrasmall Prussian blue analogue is characterized by comprising the following steps:
1) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue;
2) and dispersing the turbid solution of the graphene supported ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, and mixing and reacting to obtain the graphene supported ultra-small Prussian blue analogue after graphene reduction.
The preparation method of the supported ultrasmall prussian blue analogue is characterized in that the weight ratio of the trivalent metal compound, the divalent metal source compound, the first solvent, the ligand and the graphene in the step 1) is (1-50): (1-20): (100-5000): (1-100): 1, preferably (5-25): (5-10): (1000-4000): (10-60): 1, more preferably 5: 5: 3800: 10: 1.
the preparation method of the supported ultrasmall Prussian blue analogue is characterized in that the reaction conditions in the step 1) are as follows: the reaction temperature is 10-180 ℃, the reaction time is 1-7 days, preferably the reaction temperature is 20-160 ℃, the reaction time is 1-5 days, more preferably the reaction temperature is 30-100 ℃, and the reaction time is 2-4 days.
The preparation method of the supported ultrasmall prussian blue analogue is characterized in that in the step 1), a trivalent metal compound and a divalent metal compound are selected to contain transition metal ions, preferably the trivalent metal compound is a compound containing ferricyanide, the divalent metal compound is a compound containing nickel ions and cobalt ions, a ligand is a compound containing ethylene diamine tetraacetic acid, more preferably the trivalent metal compound is one of sodium ferricyanide, manganese ferricyanide and potassium ferricyanide, the divalent metal compound is one of nickel chloride, nickel nitrate, nickel sulfate, cobalt chloride and cobalt nitrate, and the ligand is ethylenediaminetetraacetic acid and disodium ethylenediaminetetraacetate.
The preparation method of the supported ultrasmall prussian blue analogue is characterized in that the first solvent in the steps 1) and 2) is water or ethanol.
The preparation method of the supported ultrasmall prussian blue analogue is characterized in that the reducing agent in the step 2) is at least one of ascorbic acid and salts thereof or citric acid and salts thereof.
The preparation method of the supported ultrasmall prussian blue analogue is characterized in that the weight ratio of the graphene supported ultrasmall prussian blue analogue, the first solvent, the reducing agent and the alkaline medicine in the step 2) is (1000-5000): (10000 to 100000): (100-500): 1, preferably (2000-4000): (40000-70000): (150-350): 1, more preferably 2500: 50000: 150: 1.
the preparation method of the supported ultrasmall Prussian blue analogue is characterized in that the reaction conditions in the step 2) are as follows: the reaction temperature is 10-180 ℃, the reaction time is 100-200 minutes, the reaction temperature is 30-160 ℃, the reaction time is 120-180 minutes, the reaction temperature is 60-140 ℃ and the reaction time is 150-180 minutes.
The load type ultra-small Prussian blue analogue.
The supported ultrasmall Prussian blue analogue is applied as a catalyst in synthesizing ammonia by electrochemically catalyzing nitrogen.
The trivalent metal compound adopted by the invention is a cyanide-containing compound, and the cyanide-containing compound can provide-C = N-in the Prussian blue analogue and is easier to synthesize; the divalent metal compound adopted by the invention is a compound containing nickel ions and cobalt ions, the compound containing nickel ions and cobalt ions provides the point position of the divalent metal in the graphene-loaded ultra-small Prussian blue analogue, and the divalent metal compound has a similar electronic structure with divalent iron, so that a cubic structure is favorably formed; the ligand compound adopts a compound containing ethylene diamine tetraacetic acid, and the compound containing ethylene diamine tetraacetic acid forms a complex with metal ions in the growth process of the graphene-loaded ultra-small Prussian blue analogue, so that the overall structure of the Prussian blue analogue is influenced, and smaller Prussian blue analogue nanocrystals are favorably formed; the adsorbent adopts graphene, the graphene loaded ultra-small Prussian blue analogue is not conductive, and the conductivity of the graphene makes the graphene possible to be applied in electrochemical application.
The invention has the following beneficial effects:
(1) the method can realize the synthesis of the graphene-loaded ultra-small Prussian blue analogue and the synthesis of the ultra-small Prussian blue analogue. Moreover, the method provided by the invention has the advantages of simple process and mild reaction conditions, and can realize the large-scale production of the catalyst;
(2) the graphene-loaded ultra-small Prussian blue analogue prepared by the method has an ultra-small size, and can provide more catalytic sites compared with a large-size Prussian blue analogue structure;
(3) the graphene-loaded ultra-small Prussian blue analogue prepared by the method has a basic structure of a Prussian blue structure doped with transition metal, the Prussian blue doped with the transition metal can provide a heteronuclear diatomic catalytic center, and the catalytic activity can be effectively improved by the synergetic catalysis of the heteronuclear metal;
(4) the supported ultrasmall Prussian blue analogue prepared by the method is a composite structure of the Prussian blue analogue and graphene, and can improve the electric energy of a catalyst;
(5) the graphene-supported ultra-small Prussian blue analogue prepared by the method can widely meet the requirements of catalysis, such as the reaction for synthesizing ammonia by electrochemically catalyzing nitrogen, and the like, and the graphene-supported ultra-small Prussian blue analogue obtained by the method has higher catalytic activity in the reaction for synthesizing ammonia by electrochemically catalyzing nitrogen.
Drawings
Fig. 1 is a transmission electron microscope photograph of the graphene-supported ultrasmall prussian blue analog obtained in step a) of example 4 of the present invention, with a scale of 40 nm;
fig. 2 is a transmission electron microscope photograph of the graphene-supported ultrasmall prussian blue analog obtained in step b) of example 4 of the present invention, with a scale of 40 nm;
fig. 3 is a size distribution diagram of a graphene-supported ultrasmall prussian blue analog structure prepared in embodiment 4 of the present invention;
fig. 4 is an X-ray photoelectron spectrum of the graphene supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention;
fig. 5 is an i-t curve of the graphene supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention;
fig. 6 is an ammonia production activity curve of the graphene-supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention;
fig. 7 is a faraday efficiency curve of the graphene supported ultra-small prussian blue analog catalyst prepared in example 4 of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, all the equipments and materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound to the first solvent to the ligand to the graphene is 5: 5: 4000: 10: 1; the reaction conditions are as follows: the reaction temperature is 100 ℃, and the reaction time is 2 days;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain a graphene-loaded ultra-small Prussian blue analogue after graphene reduction; the weight ratio of the graphene-loaded ultra-small Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 4000: 50000: 150: 1; the reaction conditions are as follows: the reaction temperature is 100 ℃, and the reaction time is 150 minutes;
c) and dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is potassium ferricyanide, and the divalent metal compound is nickel chloride; the ligand solution is 0.6mol/L disodium ethylene diamine tetraacetate solution; the reducing agent is ascorbic acid; the first solvent is ethanol; the alkaline solution is sodium hydroxide solution with PH = 9.
Example 2
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound, the first solvent, the ligand and the graphene is 1: 5: 1000: 10: 1; the reaction conditions are as follows: the reaction temperature is 10 ℃, and the reaction time is 7 days;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain a graphene-loaded ultra-small Prussian blue analogue after graphene reduction; the weight ratio of the graphene-loaded ultra-small Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 5000: 50000: 200: 1; the reaction conditions are as follows: the reaction temperature is 10 ℃, and the reaction time is 200 minutes;
c) and dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is potassium ferricyanide, and the divalent metal compound is cobalt sulfate; the ligand solution is 0.9mol/L disodium ethylene diamine tetraacetate solution; the reducing agent is ascorbic acid; the first solvent is water; the alkaline solution is sodium hydroxide solution with PH = 9.
Example 3
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound, the first solvent, the ligand and the graphene is 10: 9: 5000: 10: 1; the reaction conditions are as follows: the reaction temperature is 180 ℃, and the reaction time is 1 day;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain the graphene-loaded ultra-small Prussian blue analogue after graphene reduction. The weight ratio of the graphene-loaded ultra-small Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 10000: 50000: 150: 1; the reaction conditions are as follows: the reaction temperature is 180 ℃, and the reaction time is 100 minutes;
c) and dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is ruthenium chloride, and the divalent metal compound is potassium ferrocyanide; the ligand solution is 0.1mol/L EDTA solution; the reducing agent is ascorbic acid; the first solvent is water; the alkaline solution is a sodium hydroxide solution with PH = 12.
Example 4
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound, the first solvent, the ligand and the graphene is 5: 5: 3800: 10: 1; the reaction conditions are as follows: the reaction temperature is 30 ℃, and the reaction time is 3 days;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain a graphene-loaded ultra-small Prussian blue analogue after graphene reduction; the weight ratio of the graphene-loaded ultrasmall Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 2500: 50000: 150: 1; the reaction conditions are as follows: the reaction temperature is 110 ℃, and the reaction time is 180 minutes;
c) and dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is sodium ferricyanide, and the divalent metal compound is nickel chloride; the ligand solution is 0.014mol/L disodium ethylene diamine tetraacetate solution; the reducing agent is ascorbic acid; the first solvent is water; the alkaline solution is a sodium hydroxide solution with PH = 12.
Example 5
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound, the first solvent, the ligand and the graphene is 9: 7: 3800: 10: 1; the reaction conditions are as follows: the reaction temperature is 80 ℃, and the reaction time is 5 days;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain a graphene-loaded ultra-small Prussian blue analogue after graphene reduction; the weight ratio of the graphene-loaded ultrasmall Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 2500: 100000: 150: 1; the reaction conditions are as follows: the reaction temperature is 70 ℃, and the reaction time is 120 minutes;
c) and dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is sodium ferricyanide, and the divalent metal compound is nickel sulfate; the ligand solution is 0.014mol/L disodium ethylene diamine tetraacetate solution; the reducing agent is citric acid; the first solvent is water; the alkaline solution is a sodium hydroxide solution with PH = 12.
Example 6
The preparation method of the graphene-loaded ultrasmall Prussian blue analogue specifically comprises the following steps:
a) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; the weight ratio of the trivalent metal compound to the divalent metal source compound, the first solvent, the ligand and the graphene is 5: 5: 3800: 10: 1; the reaction conditions are as follows: the reaction temperature is 160 ℃, and the reaction time is 3 days;
b) dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, mixing and reacting to obtain a graphene-loaded ultra-small Prussian blue analogue after graphene reduction; the weight ratio of the graphene-loaded ultrasmall Prussian blue analogue to the first solvent to the reducing agent to the alkaline medicine is 2500: 80000: 150: 1; the reaction conditions are as follows: the reaction temperature is 120 ℃, and the reaction time is 150 minutes
c) And dispersing the graphene-loaded ultra-small Prussian blue analogue in a first solvent to obtain the dispersed graphene-loaded ultra-small Prussian blue analogue.
Wherein the trivalent metal compound is sodium ferricyanide, and the divalent metal compound is cobalt chloride; the ligand solution is 0.1mol/L disodium ethylene diamine tetraacetate solution; the reducing agent is ascorbic acid; the first solvent is water; the alkaline solution is a sodium hydroxide solution with PH = 12.
Example 7
And (3) performance testing:
1. and (3) morphology testing:
observing the surface morphology of the graphene-supported ultrasmall prussian blue analogue prepared in the step a) in the embodiment 4 by using a transmission electron microscope.
Observing the surface morphology of the graphene-loaded ultra-small Prussian blue analogue prepared in the step b) in the embodiment 4 by using a transmission electron microscope.
As can be seen from fig. 1, it can be seen from the transmission photograph that the graphene-supported ultrasmall prussian blue analog prepared by the method is a hollow structure, which illustrates that a structure specific to prussian blue is formed, thereby illustrating the effective synthesis of prussian blue analog.
As can be seen from fig. 1, it can be seen from the transmission photograph that the graphene-supported ultra-small prussian blue analog prepared by the method is a nanocrystal, which indicates that the size of the prussian blue analog is effectively controlled by the ligand solution.
As can be seen from fig. 2, it can be seen from the transmission photograph that the graphene-supported ultrasmall prussian blue analog prepared by the method is a nanocrystal, which illustrates that a divalent metal ion and a trivalent metal ion can form the graphene-supported ultrasmall prussian blue analog.
As can be seen from fig. 2, it can be seen from the transmission photographs that the reduction of graphene does not affect the graphene-supported ultramini prussian blue analog prepared by us.
In addition, the size of the graphene supported ultra-small prussian blue analogue prepared by the embodiment is about 15nm, which can be obtained from fig. 1, fig. 2 and fig. 3.
2. And (3) testing the performance of the electrochemical catalytic nitrogen reduction ammonia:
dispersing 5 mg of the graphene-supported ultra-small prussian blue analogue obtained by reducing the graphene oxide obtained in the embodiment 4 in 0.9 ml of methanol and 0.1 ml of a NaFion reagent, and performing ultrasonic treatment for 30 minutes to obtain catalyst slurry; taking 125 microliters of slurry to uniformly drop on the surface of the polished electrode, wherein the area of the electrode is 0.19625 square centimeters; the used electrochemical workstation is Chenghua electrochemical workstation, and the rotating disc test system adopts equipment produced by American Pine company; continuously introducing nitrogen into a sulfuric acid solution with the pH =1, and making an i-t curve under the condition of nitrogen saturation; nitrogen saturated sulfuric acid solution PH =1 at different potentials was tested for i-t curve, ammonia production efficiency curve, and faradaic curve. Fig. 3 is a size distribution diagram of the graphene-supported ultrasmall prussian blue analog particles prepared in example 4; fig. 4 is an X-ray photoelectron spectrum of the graphene supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention; fig. 5 is an i-t curve of the graphene supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention under an acidic condition; fig. 6 is an ammonia production efficiency curve of the graphene-supported ultrasmall prussian blue analog catalyst prepared in example 4 of the present invention; fig. 7 is a faraday curve of the graphene supported ultra-small prussian blue analog catalyst prepared in example 4 of the present invention.
As can be seen from FIG. 4, the X-ray photoelectron spectrum characterizes the composition of five elements, C, N, O, Fe and Ni.
As can be seen from FIG. 5, the i-t curve has an obvious catalytic effect in the range of 0 to-0.3V, and the faradaic efficiency is calculated by fitting the electrochemical active area of the nanomaterial to obtain FIG. 7.
As can be seen from FIG. 6, the ammonia production efficiency curve has a significant efficiency improvement in the range of 0 to-0.3V.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (5)
1. The application of the supported ultrasmall prussian blue analogue as a catalyst in synthesizing ammonia by electrochemically catalyzing nitrogen is characterized in that the supported ultrasmall prussian blue analogue is prepared by the following steps:
1) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue;
the trivalent metal compound is one of sodium ferricyanide, manganese ferricyanide and potassium ferricyanide, the divalent metal compound is one of nickel chloride, nickel nitrate, nickel sulfate, cobalt chloride and cobalt nitrate, and the ligand is ethylenediaminetetraacetic acid and disodium ethylenediaminetetraacetate;
the weight ratio of the trivalent metal compound, the divalent metal source compound, the first solvent, the ligand and the graphene is (1-50): (1-20): (100-5000): (1-100): 1;
2) and dispersing the turbid solution of the graphene supported ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, and mixing and reacting to obtain the graphene supported ultra-small Prussian blue analogue after graphene reduction.
2. The use according to claim 1, wherein the reaction conditions in step 1) are: the reaction temperature is 10-180 ℃, and the reaction time is 1-7 days.
3. The use according to claim 1, wherein the first solvent in steps 1) and 2) is water or ethanol.
4. The use of claim 1, wherein the reducing agent in step 2) is at least one of ascorbic acid and its salts or citric acid and its salts.
5. The use according to claim 1, wherein the reaction conditions in step 2) are: the reaction temperature is 10-180 ℃, and the reaction time is 100-200 minutes.
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