CN109734134B - Preparation and application of coral-like structure ferroferric oxide nano material - Google Patents
Preparation and application of coral-like structure ferroferric oxide nano material Download PDFInfo
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Abstract
The invention provides a kind of coralStructure Fe3O4The preparation of the nano material is that orange peel is taken as a reducing agent and a template, water is taken as a solvent, and Fe (NO) is taken as3)3∙9H2O is an iron source and is prepared by a two-step impregnation-calcination method. The specific preparation method comprises the following steps: cleaning pericarpium Citri Tangerinae, naturally air drying, pulverizing, and soaking in Fe (NO)3)3∙9H2Leaching solid matters out of the O aqueous solution for 6-12 h, and naturally drying to obtain the Fe-adsorbed Fe3+Calcining the precursor material at 250-650 ℃ for 2.0-2.5 h to obtain the Fe with the coral-like structure3O4And (3) nano materials. The material has both electrocatalytic activity and magnetic performance, and has good electrocatalytic oxygen evolution performance when being used as an electrocatalyst for water electrolysis reaction.
Description
Technical Field
The invention relates to Fe3O4Nano material, especially coral-like Fe3O4A preparation method of a nano material is mainly used as an electrocatalyst for an electrolytic water reaction, and belongs to the technical field of nano materials and electrocatalysis.
Background
With the increase of population and the development of science and technology, the energy consumption of the current society is more serious. The exploitation of fossil fuels by people already brings crisis to the lives of people, and the emission of wastes (combustion products) also brings serious problems to the earth. Hydrogen, as a green and renewable energy source, is expected to alleviate the pressure of energy crisis and environmental pollution. The water electrolysis process comprises the hydrogen evolution reaction at the cathode and the oxygen evolution reaction at the anode. Since the oxygen evolution reaction involves a complicated four-electron redox process, a high overpotential is generated during the reaction, resulting in low energy conversion efficiency. At present, electrocatalysts of excellent performance are based on noble metals, such as IrO, used in oxygen evolution reactions2And RuO2Catalyst and Pt used in hydrogen evolution reaction. These noble metals are expensive and limit their widespread use. Therefore, development of an inexpensive transition metal oxide as an electrocatalyst with high catalytic activity and high stability has been receiving much attention.
SpinelOxide Fe3O4The nano particles are considered as materials with broad prospects in many fields due to the fact that iron sources of the nano particles are rich in earth, the cost of the nano particles is low, the nano particles are environment-friendly and easy to synthesize. Fe3O4Nanoparticles have attracted much attention due to their excellent electrical conductivity, magnetic properties and high electrocatalytic activity. At present, a plurality of methods for preparing the nano metal oxide exist, such as a solvent method, a ball milling method, a coprecipitation method, a microemulsion method and the like. However, the above method is complicated in operation, uses numerous chemical reagents (such as alkaline reagents, reducing agents, surfactants, etc.), is high in cost, pollutes the environment, and thus has limited mass production-application. The invention provides a novel low-cost and environment-friendly preparation method, namely a dipping-calcining method for preparing metal oxide. Iron source (Fe (NO) is removed in the preparation process3)3∙9H2O) and Orange Peel (OP), a solvent-water, and no other additives (such as an alkaline reagent or a surfactant and the like) are required to be added, the preparation method is simple, the cost is low, the environment is protected, the waste resources can be recycled, and the green chemical concept is met.
Oranges are distributed in regions in the south of the Yangtze river. Orange peel mainly contains cellulose, lignin and other components. However, a large amount of orange peel is discarded as waste every year, which not only wastes resources, but also causes environmental pollution. If orange peel is used as a reducing agent and a template to prepare the material, the material can be endowed with special appearance and excellent performance, and the reutilization of waste resources can be realized, so that the method has important practical significance.
Disclosure of Invention
The invention aims at preparing Fe in the prior art3O4The problem of the nano particles is to provide a coral-like structure Fe3O4A method for preparing nano material.
One, coral-like structure Fe3O4Preparation of nanomaterials
The invention relates to multifunctional coral-like structure Fe3O4The preparation of nano material is using orange peel as reducing agent and template, water as solvent and Fe (B), (B) and (C)NO3)3∙9H2O is an iron source and is prepared by a two-step impregnation-calcination method. The specific preparation method comprises the following steps: cleaning pericarpium Citri Tangerinae, naturally air drying, pulverizing, and soaking in Fe (NO)3)3∙9H2Leaching solid matters out of the O aqueous solution for 6-12 h, and naturally drying to obtain the Fe-adsorbed Fe3+Precursor material (labeled as Fe)3+OP), calcining the precursor material at 250-650 ℃ for 2.0-2.5 h to obtain the Fe with the coral-like structure3O4And (3) nano materials.
OP and Fe (NO)3)3∙9H2The mass ratio of O is 0.1:1 to 1:1 (preferably 0.77: 1).
II, Fe3O4Characterization of nanostructured materials
The structure and the like of the sample prepared by the invention are characterized by using the technologies such as XRD, SEM, TEM and the like.
FIG. 1a shows OP and Fe (NO)3)3∙9H2Fe as precursor material obtained when the mass ratio of O is 0.77: 1.003+XRD patterns of samples (sequentially marked as CT-250, CT-350, CT-450, CT-550 and CT-600) obtained by calcining/OP at 250, 350, 450, 550 and 600 ℃ for 2h respectively. Diffraction peak and Fe in XRD spectrogram3O4Andγ-Fe2O3the standard cards (JCPDS 19-0629 and JCPDS 39-1346) are basically consistent. As can also be seen from fig. 1 a: as the calcination temperature was increased from 250 ℃ to 600 ℃, the diffraction peak intensity of the sample showed a tendency to increase and the half-width decrease, i.e., the higher the calcination temperature, the better the crystallinity of the sample. To further determine the composition of the phases in the material (because of Fe)3O4Andγ-Fe2O3with similar XRD pattern), 32-40 timesoThe characteristic diffraction peak between the two is locally amplified (see figure 1 b), and the comparison shows that the characteristic diffraction peak can be better compared with Fe3O4Standard cards (JCPDS 19-0629) are agreed upon, which states that in the appropriate amounts of OP (OP and Fe (NO)3)3∙9H2O mass ratio of 0.77: 1.00), the iron oxide in the obtained sample is Fe3O4。
Sample OP-0.000 (No addition)Addition of OP) and samples OP-2.500 (OP with Fe (NO)3)3∙9H2Mass ratio of O0.77: 1.00) comparison of color and magnetic properties: at a calcination temperature of 450 ℃ without addition of OPoSample OP-0.000 is iron rust red Fe under C2O3Is non-magnetic; while 2.500g of OP was added, the calcination temperature was 450 deg.CoSample OP-2.500 (i.e., sample CT-450) obtained from C was brown and strongly magnetic. The result shows that the addition of OP can not only endow the material with special shape (see SEM of a sample), but also play the role of a reducing agent to partially react with Fe3+Reduction of Fe2+So that the iron salt (Fe (NO) is generated from a single valence state (+ 3 valence state)3)3∙9H2O) production of Fe3O4It becomes possible. And the preparation process does not add any alkaline reagent, so OP can also be used as an oxygen donor.
FIG. 2 is an SEM image of CT-450 of sample with different magnification. As can be seen from the low power SEM images, the samples had coral-like structures ("dendrites"); from the high power SEM, it can be seen that the sample coral-like structure is assembled from very thin nanosheets (see TEM of sample). The results show that: the OP gives the sample a specific 3D topography.
FIG. 3 shows TEM images of different multiples of-600, CT-450 for sample. From the TEM of sample CT-450, it can be seen that the sample is a very thin nanosheet assembled from nanoparticles having a size less than 10 nm (fig. 3 a), and the nanoparticles are relatively uniform in size. In contrast to CT-450, sample CT-600 (fig. 3 b) is a small aggregate formed by a small number of slightly larger sized particles (average size about 11 nm), which should be related to the large momentum of the gas generated by the intense combustion of OP at relatively high temperatures. From the lattice fringes in the high power TEM of samples CT-450 and-600 (FIG. 3c, d): the sample CT-450 exhibited significantly poorer crystalline properties than CT-600 (consistent with XRD results for this sample), and it was also found that there was significant distortion, i.e., lattice distortion, of the lattice fringes of the CT-450 microcrystals (at the interface).
III, coral-like structure Fe3O4Electrocatalytic oxygen evolution performance and magnetic performance of nano-structure material
Preparation of a working electrode: dispersing 10 mg of a sample prepared by the method in 1mL of a mixed solvent of distilled water and ethanol (the volume ratio of the water to the ethanol is 1: 1), and performing ultrasonic treatment for 15min to prepare a uniform dispersion liquid; dripping the dispersion liquid onto a glassy carbon electrode with the diameter of 5 mm by using a liquid transfer machine and naturally airing; and (3) dropwise adding 2uLNafion solution (serving as an adhesive), and naturally airing to obtain the working electrode.
The influence of the calcination temperature (250-650 ℃) and the amount of the template (0.000-2.500 g) on the oxygen evolution performance and the magnetic performance of the sample is examined below.
1. Influence of calcination temperature (250-650 ℃) on oxygen evolution performance of sample
FIG. 4 is the LSV curve (sweep rate of 0.01V s) for samples CT-250, -350, -450, -550, and-650-1And the electrolyte is 1M NaOH). From FIG. 4, it can be seen that the oxygen evolution performance of the samples CT-250-650 is very different.
FIG. 5 is an overpotential diagram of samples CT-250 to 650. As can be seen from FIG. 5, the current density was 10 mA cm-2When the overpotential of CT-250, -350, -450, -550 and-650 is 348, 224, 188, 257 and 492mV (vs. RHE), namely the overpotential (188 mV) of CT-450 is the lowest, and the best electrocatalytic oxygen evolution performance is achieved. Synthetic Fe by Shan Han et al3O4Film in 1M NaOH electrolyte at a current density of 10 mA cm-2When the overpotential exceeds 500 mV (vs. RHE); preparation of Fe by XiaoFeng Sun et al solvothermal method3O4The iron source is ferric chloride, the solvent is ethylene glycol (reducing agent), and sodium acetate is added as an auxiliary stabilizer. Working electrode prepared by sample on foamed nickel when current density is 20 mA cm-2The overpotential was 314 mV (vs. RHE). Therefore, compared with the similar nano materials, the sample prepared by the invention has obvious advantages in the aspect of electrocatalytic oxidation.
Combined with the XRD, SEM and TEM characterization results of the series of samples, the comprehensive analysis shows that: fe produced by the invention3O4The electrocatalytic performance of the material should be related to a plurality of factors such as the morphology, the composition, the crystallization performance and the like of the material; active component Fe in material3O4A certain degree of structural distortion is beneficial to OH-The adsorption-activation of (a), the specific 3D morphology of the material and the right amount of carbon therein should facilitate the transfer of charges. In addition, the preparation method is simple to operate, green and environment-friendly, and does not need to add any other additives (such as alkaline reagents or surfactants and the like), so that the method is low in cost and green and environment-friendly, and can realize the reutilization of waste resources.
2. Magnetic property of sample OP-0.000 and CT-450-600 materials
FIG. 6 shows the magnetic properties of samples OP-0.000, -2.500 and CT-450, 550, 600. It can be seen that: (1) the template OP had a significant effect on the composition and magnetic properties of the resulting sample, when no OP was added, the resulting material OP-0.000 was rust red and was non-magnetic, i.e., the sample wasα-Fe2O3(ii) a When adding proper amount of OP (OP and Fe (NO)3)3∙9H2The mass ratio of O is 0.77: 1.00), the obtained material OP-2.500 (namely CT-450) has strong magnetism, and the magnetic strength is 28.63 emu/g. (2) The calcination temperature has certain influence on the magnetic property of the obtained sample, and when the calcination temperature is increased from 450 ℃ to 600 ℃, the magnetic strength of the sample is increased from 28.63 emu/g to 39.27 emu/g. The change trend of the magnetic strength of the series of samples CT-450-600 along with the calcining temperature is consistent with the change trend of the crystallization performance of the samples along with the calcining temperature, namely the better the crystallization performance is, the better the magnetic performance is!
In summary, the present invention uses Fe (NO)3)3∙9H2O is a single iron source, the treated orange peel powder is used as a template, a reducing agent and an oxygen supplying agent, water is used as a solvent, and the coral-like structure Fe is prepared by adopting an impregnation-calcination two-step method3O4The nano-structure material has excellent electro-catalytic oxygen evolution performance and magnetic performance, and has important application value in the field of electro-catalytic oxygen evolution. In addition, no other additive is needed in the preparation process, the method is simple and convenient, the cost is low, the environment is protected, and waste resources can be fully utilized.
Drawings
FIG. 1 shows XRD patterns (a, b) of samples CT-250 to 600.
FIG. 2 is an SEM image of sample CT-450 (a, b).
FIG. 3 is a TEM image (a, c) of sample CT-450 and a TEM image (b, d) of sample CT-600.
FIG. 4 shows LSV curves of CT-250 to 650 samples.
FIG. 5 is an overpotential diagram of samples CT-250 to 650.
FIG. 6 shows the magnetic properties of samples OP-0.000, CT-450, -550, and-600.
Detailed Description
The following examples illustrate the preparation of Fe according to the invention3O4The method of preparation of the nanostructured material is further illustrated.
Example 1
3.2320g Fe (NO)3)3·9H2O dissolved in 30 mL H2And adding 2.500g of OP into the O, soaking for 12 h, draining solids, naturally airing at room temperature, and calcining at 250 ℃ for 2h to obtain a sample CT-250.
The sample was calcined at 700 ℃ for 2h and the carbon content of the material was calculated to be 28.2% from the mass change before and after calcination.
Sample CT-250 at a current density of 10 mA cm-2The overpotential was 348 mV (vs. RHE). The saturation magnetization was 8.52 emu/g.
Example 2
The calcination temperature was 350 ℃ and the other conditions were the same as in example 1, to obtain sample CT-350. The carbon content in the sample was 13.4%. The sample material was measured at a current density of 10 mA cm-2The overpotential was 224 mV (vs. RHE). The saturation magnetization was 15.64 emu/g.
Example 3
The calcination temperature was 450 ℃ and the other conditions were the same as in example 1, to obtain sample CT-450. The carbon content in the sample was 6.5%. The sample material was measured at a current density of 10 mA cm-2The overpotential was 188mV (vs. RHE), and the saturation magnetization was 28.63 emu/g.
Example 4
The calcination temperature was 550 ℃ and the other conditions were the same as in example 1, to obtain sample CT-550. The carbon content in the sample is5.6 percent. The sample material was measured at a current density of 10 mA cm-2The overpotential was 257 mV (vs. RHE), and the saturation magnetization was 33.62 emu/g.
Example 5
The calcination temperature was 600 ℃ and the other conditions were the same as in example 1, to obtain sample CT-600. The carbon content in the sample was 4.7%. The sample material was measured at a current density of 10 mA cm-2The overpotential was 290 mV (vs. RHE), and the saturation magnetization was 39.27 emu/g.
Example 6
The calcination temperature was 650 ℃ and the other conditions were the same as in example 1, to obtain sample CT-650. The carbon content in the sample was 4.5%. The sample material was measured at a current density of 10 mA cm-2When the overpotential is 492mV (vs. RHE).
Claims (3)
1. Coral-like structure Fe3O4The preparation method of the nanometer material comprises cleaning pericarpium Citri Tangerinae, naturally air drying, pulverizing, and soaking in Fe (NO)3)3∙9H2In an aqueous O solution, Fe3+Adsorbing onto pericarpium Citri Tangerinae; leaching out solid matter and naturally drying to obtain the Fe adsorbed3+The precursor material is calcined at high temperature to obtain the Fe with the coral-like structure3O4A nanomaterial; the dried orange peel powder is in Fe (NO)3)3∙9H2Soaking in the O aqueous solution for 6-12 h; the calcination temperature is 250-650 ℃, and the calcination time is 2.0-2.5 h.
2. The coral-like structure of claim 1, wherein Fe is3O4The preparation method of the nano material is characterized by comprising the following steps: orange peel dry powder and Fe (NO)3)3∙9H2The mass ratio of O is 0.1: 1-1: 1.
3. The coral-like structure Fe prepared by the process as set forth in claim 13O4The nano material is used as an electrocatalyst for water electrolysis reaction.
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