CN114934223B - Nano porous high-entropy alloy with efficient azo dye degradation performance and preparation method thereof - Google Patents
Nano porous high-entropy alloy with efficient azo dye degradation performance and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano-porous high-entropy alloy with efficient azo dye degradation performance and a preparation method thereof, wherein the chemical composition of the nano-porous high-entropy alloy is Fe a Co b Ni c Al d Si e Wherein a is more than or equal to 20 and less than or equal to 35, B is more than or equal to 30 and less than or equal to 40,7 and less than or equal to 40,2 and less than or equal to d is more than or equal to 20,2 and less than or equal to e is less than or equal to 12, mainly comprises a B2 phase, and contains a BCC phase and an amorphous phase with a volume fraction not higher than 20%; the nano-porous structure with nano-scale pores and ligament bicontinuous has the average pore size of 40-60 nm and the average ligament thickness of 60-80 nm; has high-efficiency degradation to direct blue 6 azo dyeThe performance and the magnetism are also realized, and the recycling is easy when in use; the nano-porous high-entropy alloy can be prepared from FeCoNiAlSiB high-entropy alloy precursor strips by an electrochemical dealloying method under an acidic condition. The technical scheme of the invention solves the problems of low degradation efficiency, poor stability, complex preparation process and the like of the existing material for degrading azo dyes.
Description
Technical Field
The invention relates to the technical field of environment functional materials, in particular to a nano porous high-entropy alloy with efficient azo dye degradation performance and a preparation method thereof.
Background
With the continuous acceleration of the industrialization process in China, the dye industry develops rapidly, and the discharge amount of dye wastewater is increasing day by day, which becomes one of the important sources of water pollution. The azo dye is used in the largest amount in textile industry, the azo double bond has high stability, and the degradation treatment is difficult to carry out by microorganisms in nature. The azo dye-containing wastewater is discharged into a water body, so that not only can the ecosystem of the water body be damaged, but also toxic and harmful substances can enter a food chain, and the health of a human body is threatened. Therefore, it is of great significance to develop materials capable of efficiently degrading azo dyes.
At present, the treatment methods for azo dye-containing wastewater mainly comprise a physical method, a microbial degradation method and the like, but the methods have the defects of low efficiency, high cost and the like. In recent years, due to the unique disordered atomic arrangement structure characteristics and thermodynamic metastable state characteristics of the amorphous alloy and the strong reducibility of zero-valent iron (ZVI), the amorphous alloy is widely concerned in the field of azo dye degradation, and a plurality of series of amorphous alloys with good azo dye degradation performance and derivatives thereof are developed. For example, zeng et al found that Fe 76 B 12 Si 9 Y 3 The degradation efficiency of the amorphous alloy to methyl orange in strong acid and near neutral environment is higher than that of crystalline ZVI powder and other iron-based amorphous alloys [ Scientific Reports,2016,6]. Chen et al will (Fe) 73.5 Si 13.5 B 9 Nb 3 Cu 1 ) 91.5 Ni 8.5 The amorphous alloy strip is annealed at 700 ℃ for 300s to prepare a multiphase nanocrystalline alloy strip with distributed nanocrystals in an amorphous matrix, and by virtue of selective corrosion of the multiphase nanocrystalline alloy strip in a degradation process, the degradation efficiency of the multiphase nanocrystalline alloy strip on methyl orange is far higher than that of an amorphous alloy with the same components [ Intermetallics,2017,90]. However, the existing amorphous alloy still has the defects of low degradation efficiency, poor stability, strict requirements on the use environment and the like.
The high-entropy alloy is a novel material developed in recent years and consists of five or more elements with (nearly) equal atomic ratios. A high entropy value promotes the formation of a solid solution phase; a large degree of mismatch of atomic sizes easily causes lattice distortion; the "delayed diffusion effect" makes the high-entropy alloy thermodynamically metastable, which is consistent with amorphous alloys, so that the high-entropy alloy also has excellent degradation performance. At present, the research objects of the high-entropy alloy for degrading azo dyes are basically high-entropy alloy powder. For example, lv et al found that AlCoCrTiZn high-entropy alloy powder has a significant effect of degrading direct blue 6 azo dyes, and compared with iron-based amorphous powder and other materials, the activation energy is lower and the reaction is easier to proceed [ Scientific Reports,2016, 6. However, the high-entropy powder developed at present has poor stability, is difficult to store and transport, and has limited practicability. The degradation performance of other types of high-entropy alloys except powder on azo dyes is not reported.
The nano porous metal and alloy consists of nano-sized pores and metal pore walls (ligaments), has a three-dimensional pore and ligament double-communicated net structure, and is a novel functional material. The dealloying method is a common process for preparing the nano porous alloy, and has the advantages of simple operation, short preparation flow and relatively low cost. The nano porous alloy has the characteristics of high specific surface area, high surface energy and the like, and is expected to be widely applied to the fields of energy, sensing, catalysis and the like. Deng et al convert Fe 72 Si 2 B 20 Nb 6 Etching the amorphous alloy strip by 40mi in HF solution with the concentration of 20%And n, obtaining the nano-porous alloy with the pore diameter of between 50 and 100 nm. The specific surface area of the nanoporous alloy strips was increased by 25-fold compared to the original amorphous strips, and the degradation time for direct blue 15 was reduced by half [ chemisphere, 2017,174]。
The nano-porous high-entropy alloy may have more excellent azo dye degradation performance by combining the characteristics of multi-component components of the high-entropy alloy and the characteristics of the nano-porous alloy such as high specific surface area. However, no report is available about the degradation performance of the nanoporous high-entropy alloy and the azo dyes thereof. Therefore, the development of the nano-porous high-entropy alloy and the expansion of the application of the nano-porous high-entropy alloy in the field of wastewater degradation are of great significance.
Disclosure of Invention
Aiming at the problems of low degradation efficiency, poor stability, complex preparation process and the like of the existing material for degrading azo dyes, the invention combines the multicomponent synergistic effect of the high-entropy alloy with the advantages of high specific surface area and reticular channel of the nano-porous alloy, utilizes a simple dealloying process, takes FeCoNiAlSiB series high-entropy alloy strips as precursors, and prepares FeCoNiAlSi series nano-porous high-entropy alloy in an acid environment by an electrochemical method, thereby providing the nano-porous high-entropy alloy with high-efficiency azo dye degradation performance and the preparation method thereof.
The technical means adopted by the invention are as follows:
a nano-porous high-entropy alloy with efficient azo dye degradation performance has a chemical composition of Fe a Co b Ni c Al d Si e Wherein a, b, c, d and e respectively represent the atom percentage content of the corresponding elements, and satisfy: a is more than or equal to 20 and less than or equal to 35, b is more than or equal to 30 and less than or equal to 40,7 and less than or equal to 40,2 and less than or equal to d and less than or equal to 20,2 and less than or equal to e and less than or equal to 12, and a + b + c + d + e =100;
mainly consists of a B2 phase and contains no more than 20% of BCC phase and amorphous phase by volume fraction;
the nano-porous structure with nano-scale pores and ligament bicontinuous has the average pore size of 40-60 nm and the average ligament thickness of 60-80 nm;
under the conditions that the pH value is 3 and the temperature is 25 ℃, more than 80% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L is removed by 0.05g of the nano-porous high-entropy alloy within 30 min;
the saturation magnetization is 92-105 emu/g;
with the composition formula being Fe f Co g Ni h Al i Si j B k The high-entropy alloy strip is used as a precursor, wherein f, g, h, i, j and k respectively represent the atomic percentage content of corresponding elements, and the following conditions are met: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to 30,5 and less than or equal to i is more than or equal to 35,5 and less than or equal to j is more than or equal to 20,0 and less than or equal to k is less than or equal to 20, and f + g + h + i + j + k =100, and dealloying is carried out on the precursor alloy strip in an acid solution through an electrochemical method to prepare the nano-porous high-entropy alloy.
Further, the alloy also contains B element with the content of not more than 5 atomic percent.
Further, the chemical composition is Fe 32 Co 35 Ni 15 Al 6 Si 12 (ii) a Using Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 The high-entropy alloy precursor is prepared in an acid solution by an electrochemical dealloying method; the average pore size is 50nm and the average ligament thickness is 60nm; under the conditions that the pH value is 3 and the temperature is 25 ℃,0.05g of the nano-porous high-entropy alloy removes over 95% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L within 30 min; the saturation magnetization was 103emu/g.
The invention also provides a preparation method of the nano porous high-entropy alloy with efficient azo dye degradation performance, which specifically comprises the following steps:
step one, preparing a precursor alloy strip
Selecting Fe, co, ni, al, si and B raw materials with the purity not lower than 99% in mass fraction, weighing and proportioning according to the component proportion of the high-entropy alloy precursor, and smelting the weighed raw materials in a non-consumable vacuum arc furnace or an induction smelting furnace in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components; crushing the master alloy ingot, then putting the crushed master alloy ingot into a quartz tube, and preparing a high-entropy alloy strip which is 1-5 mm wide, 20-30 mu m thick and has a BCC and B2 mixed phase structure in an argon or nitrogen atmosphere by adopting single-roller melt-spun equipment; the width and the thickness of the alloy strip can be adjusted by changing the rotating speed of a copper roller of single-roller melt-spinning equipment and the size of a nozzle of a quartz tube, wherein the rotating speed of the copper roller is controlled to be 35-40 m/s, and the size of the nozzle is a circular hole with the diameter of 1-2 mm or a rectangular hole with the width of 1mm and the length of 3-5 mm;
step two, preparing the nano porous high-entropy alloy
Taking the high-entropy alloy strip prepared in the step one as a working electrode, ag/AgCl as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electrochemical reaction on the counter electrode in the presence of H + In an acid solution with the concentration of 0.1-1 mol/L and the temperature of 25 ℃, an electrochemical workstation is used for carrying out dealloying treatment on the precursor alloy strip under the constant potential of-0.1V; repeatedly cleaning the dealloyed nanoporous alloy with deionized water for three times, and placing the dealloyed nanoporous alloy in a vacuum drying oven for drying treatment to finally obtain the nanoporous high-entropy alloy; the chemical composition, the average pore diameter and the average ligament thickness of the nano-porous high-entropy alloy can be changed by changing the components of a precursor alloy and H of an acid solution used for dealloying + Concentration and dealloying potential.
Further, the high-entropy alloy precursor in the step one has a component formula of Fe f Co g Ni h Al i Si j B k Wherein f, g, h, i, j and k respectively represent the atom percentage content of the corresponding elements, and satisfy: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to h is less than or equal to 30,5 and less than or equal to i and less than or equal to 35,5 and less than or equal to j and less than or equal to 20,0 and less than or equal to 20, and f + g + h + i + j + k =100.
Compared with the prior art, the invention has the following advantages:
1. the nano-porous high-entropy alloy provided by the invention combines the multi-component synergistic effect and the delayed diffusion effect of the high-entropy alloy and the advantages of the high specific surface area and the reticular structure of the nano-porous structure, has excellent degradation performance on azo dyes, and can degrade over 95% of direct blue 6 within 30 min.
2. The nano-porous high-entropy alloy provided by the invention does not contain precious metals and toxic elements, and is low in raw material cost and environment-friendly.
3. The preparation process of the nano-porous high-entropy alloy provided by the invention is simpleThe method has the advantages of simple process, short flow, easy control of operation conditions, and realization of the alloying components of the precursor and the dealloying solution H + The regulation of concentration and dealloying potential can realize the regulation of chemical composition and nano-porous structure of alloy, so that the degradation performance can be effectively regulated.
4. The nano-porous high-entropy alloy provided by the invention has soft magnetism and is easy to recycle in practical application.
Based on the reason, the nano porous high-entropy alloy with efficient azo dye degradation performance can be used for degrading azo dyes such as direct blue 6 and has popularization value in the field of environment functional materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 X-ray diffraction (XRD) spectra of the precursor strip and the dealloyed nanoporous high entropy alloy (example 1).
FIG. 2 is Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 Differential Scanning Calorimetry (DSC) curve of nanoporous high entropy alloy (example 1) after strip dealloying.
FIG. 3 is Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 Scanning Electron Microscope (SEM) image of the surface of the nano-porous high-entropy alloy (example 1) after strip dealloying.
FIG. 4 is Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 Ultraviolet-visible absorption (UV-vis) spectra of strip dealloyed nanoporous high entropy alloy (example 1) for degradation of direct blue 6 solution for different times。
FIG. 5 is Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 Hysteresis loop of the nano-porous high entropy alloy after strip dealloying (example 1).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
The invention provides a nano porous high-entropy alloy with efficient azo dye degradation performance, and the chemical composition of the nano porous high-entropy alloy is Fe a Co b Ni c Al d Si e Wherein a, b, c, d and e respectively represent the atom percentage content of the corresponding elements, and satisfy: a is more than or equal to 20 and less than or equal to 35, b is more than or equal to 30 and less than or equal to 40,7 and less than or equal to 40,2 and less than or equal to d and less than or equal to 20,2 and less than or equal to e and less than or equal to 12, and a + b + c + d + e =100;
mainly consists of a B2 phase and contains a BCC phase and an amorphous phase with a volume fraction not higher than 20%;
the nano-porous structure with nano-scale pores and ligament bicontinuous has the average pore size of 40-60 nm and the average ligament thickness of 60-80 nm;
the nano-porous high-entropy alloy has high-efficiency degradation performance on direct blue 6 azo dyes, and can remove over 80% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L within 30min by 0.05g of the nano-porous high-entropy alloy under the conditions that the pH value is 3 and the temperature is 25 ℃;
the magnetic material has magnetism, and the saturation magnetization is 92-105 emu/g;
can be prepared by dealloying a high-entropy alloy strip, namely adopting the composition formula of Fe f Co g Ni h Al i Si j B k The high-entropy alloy strip is used as a precursor, wherein f, g, h, i, j and k respectively represent the atomic percentage content of corresponding elements, and the following conditions are met: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to 30,5 and less than or equal to i is more than or equal to 35,5 and less than or equal to j is more than or equal to 20,0 and less than or equal to 20, and f + g + h + i + j + k =100, dealloying the precursor alloy strip in an acid solution by an electrochemical method, and preparing the nano-porous high-entropy alloy.
Further, the alloy also contains B element with the content of not more than 5 atomic percent.
Further, the chemical composition is Fe 32 Co 35 Ni 15 Al 6 Si 12 (ii) a Using Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 The high-entropy alloy precursor is prepared in an acid solution by an electrochemical dealloying method; the average pore diameter is 50nm, and the average ligament thickness is 60nm; under the conditions that the pH value is 3 and the temperature is 25 ℃, more than 95% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L is removed by 0.05g of the nano-porous high-entropy alloy within 30 min; the saturation magnetization was 103emu/g.
The invention also provides a preparation method of the nano porous high-entropy alloy with efficient azo dye degradation performance, which specifically comprises the following steps:
step one, preparing a precursor alloy strip
Selecting Fe, co, ni, al, si and B raw materials with the purity not lower than 99 mass percent, weighing and proportioning according to the component proportion of the high-entropy alloy precursor, and smelting the weighed raw materials in a non-consumable vacuum arc furnace or an induction smelting furnace in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components; crushing the master alloy ingot, then putting the crushed master alloy ingot into a quartz tube, and preparing a high-entropy alloy strip which is 1-5 mm wide, 20-30 mu m thick and has a BCC and B2 mixed phase structure in an argon or nitrogen atmosphere by adopting single-roller melt-spun equipment; the width and the thickness of the alloy strip can be adjusted by changing the rotating speed of a copper roller of single-roller melt-spinning equipment and the size of a nozzle of a quartz tube, wherein the rotating speed of the copper roller is controlled to be 35-40 m/s, and the size of the nozzle is a circular hole with the diameter of 1-2 mm or a rectangular hole with the width of 1mm and the length of 3-5 mm;
step two, preparing the nano porous high-entropy alloy
Taking the high-entropy alloy strip prepared in the step one as a working electrode, ag/AgCl as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electrochemical reaction on the counter electrode in the presence of H + In an acid solution with the concentration of 0.1-1 mol/L and the temperature of 25 ℃, an electrochemical workstation is used for carrying out dealloying treatment on the precursor alloy strip under the constant potential of-0.1V; repeatedly cleaning the dealloyed nanoporous alloy with deionized water for three times, and placing the dealloyed nanoporous alloy in a vacuum drying oven for drying treatment to finally obtain the nanoporous high-entropy alloy; the chemical composition, the average pore diameter and the average ligament thickness of the nano-porous high-entropy alloy can be changed by changing the components of a precursor alloy and H of an acid solution used for dealloying + Concentration and dealloying potential.
Further, the high-entropy alloy precursor in the step one has a component formula of Fe f Co g Ni h Al i Si j B k Wherein f, g, h, i, j and k respectively represent the atom percentage content of the corresponding elements, and satisfy: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to h is less than or equal to 30,5 and less than or equal to i and less than or equal to 35,5 and less than or equal to j and less than or equal to 20,0 and less than or equal to 20, and f + g + h + i + j + k =100.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The following detailed description of the embodiments of the invention refers to the accompanying drawings. For ease of explanation, the various embodiments are described herein using precursor alloy compositions as the primary terms:
example 1: fe 35 Co 25 Ni 10 Al 10 Si 15 B 5
Step one, preparing a precursor alloy strip
Selecting Fe, co, ni, al, si and B raw materials with the purity not lower than 99% in mass fraction, weighing and proportioning the raw materials according to the component proportion of a precursor alloy, and smelting the weighed raw materials in a non-consumable vacuum arc furnace in an argon atmosphere to obtain a master alloy ingot with uniform components; crushing the master alloy ingot, then putting the crushed master alloy ingot into a quartz tube with a nozzle size of 3mm multiplied by 1mm, and preparing a high-entropy alloy strip with the width of 3mm and the thickness of 30 mu m by adopting single-roller melt-spun equipment under the argon atmosphere at the surface linear velocity of a copper roller of 35 m/s;
characterizing the microstructure of the high-entropy alloy strip by XRD; as shown in fig. 1, XRD results showed that the high-entropy alloy ribbon was composed of BCC phase and B2 phase structures;
step two, preparing the nano porous high-entropy alloy
Taking the high-entropy alloy strip prepared in the step one as a working electrode, ag/AgCl as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electrochemical reaction on the working electrode and the counter electrode in the presence of hydrogen + Dealloying the precursor alloy in an acid solution with the concentration of 0.1mol/L and the temperature of 25 ℃ by using an electrochemical workstation at a constant potential of-0.02V; and repeatedly cleaning the dealloyed nanoporous alloy with deionized water for three times, and placing the dealloyed nanoporous alloy in a vacuum drying oven for drying treatment to finally obtain the nanoporous high-entropy alloy.
The microstructure is characterized by XRD, and as shown in figure 1, the alloy after dealloying consists of a B2 phase and a BCC phase; the thermal performance was analyzed by DSC, and as shown in FIG. 2, the DSC curve showed a distinct exothermic peak, indicating that the strip of dealloyed alloy contained an amorphous phase. Since the content of the amorphous phase is small, no diffuse peak of the amorphous phase is observed in the XRD spectrum of fig. 1. And observing the appearance by adopting SEM (scanning Electron microscope), as shown in figure 3, the alloy after the alloy is removed consists of gaps and ligaments, has a uniformly distributed three-dimensional double-communicated nano porous structure, and has an average pore diameter of 50nm and an average ligament thickness of 60nm. Measuring the chemical composition of the nano-porous alloy as Fe by adopting an energy spectrum analyzer (EDS) 32 Co 35 Ni 15 Al 6 Si 12 。
The degradation performance of the nano-porous high-entropy alloy on direct blue 6 dye is tested in an acid environment with the pH =3 and the temperature of 25 ℃: controlling the temperature of the direct blue 6 solution to be kept at 25 ℃ by a water bath method, shearing 50mg of nano porous sample, adding the cut sample into 50mL of direct blue 6 solution with the concentration of 200mg/L, and fully contacting the sample with the dye solution by a stirrer; and filtering the solution degraded at different time by a 0.22-0.45 mu m filter membrane, and detecting the absorbance of the solution by using an ultraviolet-visible spectrophotometer to obtain the concentration of the residual direct blue 6 in the reaction solution. As shown in fig. 4, before the degradation was not started (0 min), the absorption peak of the curve appeared at 574nm, which represents the chromophoric group of-N = N-bond in the direct blue 6 molecule, and the intensity of the absorption peak gradually decreased with the increase of the degradation time, indicating that the-N = N-bond is broken, the dye was degraded at 81% at 10min, and the absorption peak at 574nm disappeared at 30min, indicating that the degradation efficiency of the direct blue 6 solution was over 95%.
Magnetic properties were measured using a Vibrating Sample Magnetometer (VSM), and as shown in FIG. 5, the nanoporous high entropy alloy has typical soft magnetic properties with a saturation magnetization of 103emu/g.
The precursor components, the dealloying solution used, the nanoporous high-entropy alloy components, and the main morphology and performance characteristics thereof are listed in the attached table 1.
Example 2: fe 40 Co 20 Ni 10 Al 10 Si 15 B 5
The preparation, structure and morphology characterization and performance test methods of the precursor alloy and the nano-porous alloy are the same as those of the embodiment 1, and only the differences are that: step one, preparing a high-entropy alloy strip with the width of 5mm and the thickness of 28 mu m under the conditions that the nozzle size of a quartz tube is 5mm multiplied by 1mm and the surface linear velocity of a copper roller is 36 m/s. The constant potential adopted by dealloying is 0.05V. The average pore diameter of the nano-porous high-entropy alloy prepared after dealloying is 53nm, the average ligament thickness is 75nm, and the chemical composition is Fe 34 Co 30 Ni 18 Al 7 Si 11 . The degradation efficiency to direct blue 6 within 30min was 93%. The saturation magnetization was 105emu/g. Specific data are listed in attached table 1.
Example 3: fe 30 Co 30 Ni 10 Al 10 Si 15 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: and (3) preparing a high-entropy alloy strip with the width of 3mm and the thickness of 28 microns by using the protective gas used in the first step as a nitrogen atmosphere under the condition that the surface linear speed of the copper roller is 36 m/s.The constant potential adopted by dealloying is-0.05V. The average pore diameter of the nano-porous alloy prepared after dealloying is 48nm, the average ligament thickness is 64nm, and the chemical composition is Fe 28 Co 40 Ni 15 Al 6 Si 11 . The degradation efficiency to direct blue 6 within 30min was 87%. The saturation magnetization was 100emu/g. Specific data are listed in attached table 1.
Example 4: fe 25 Co 25 Ni 20 Al 10 Si 15 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 3mm and the thickness of 27 mu m under the condition that the surface linear speed of a copper roller is 36 m/s. The constant potential adopted by dealloying is 0.06V. The average pore diameter of the nano-porous alloy prepared after dealloying is 47nm, the average ligament thickness is 62nm, and the chemical composition is Fe 23 Co 32 Ni 26 Al 9 Si 10 . The degradation efficiency to direct blue 6 within 30min was 83%. The saturation magnetization was 95emu/g. Specific data are listed in attached table 1.
Example 5: fe 25 Co 25 Ni 25 Al 10 Si 10 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 3mm and the thickness of 29 mu m under the condition that the surface linear speed of a copper roller is 35 m/s. The constant potential adopted by dealloying is-0.07V. The average pore diameter of the nano-porous alloy prepared after dealloying is 46nm, the average ligament thickness is 61nm, and the chemical composition is Fe 23 Co 32 Ni 33 Al 5 Si 7 . The degradation efficiency for direct blue 6 within 30min was 82%. The saturation magnetization was 96emu/g. Specific data are listed in attached table 1.
Example 6: fe 25 Co 25 Ni 30 Al 10 Si 5 B 5
Precursor alloy and nano-porousThe alloy preparation, structure and morphology characterization and performance testing methods are similar to those of example 1, except that: step one, preparing a high-entropy alloy strip with the width of 2mm and the thickness of 27 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 2mm and the surface linear speed of a copper roller is 36 m/s. The constant potential adopted by dealloying is-0.08V. The average pore diameter of the nano-porous alloy prepared after dealloying is 40nm, the average ligament thickness is 60nm, and the chemical composition is Fe 22 Co 34 Ni 40 Al 2 Si 2 . The degradation efficiency to direct blue 6 within 30min was 80%. The saturation magnetization was 97emu/g. Specific data are listed in attached table 1.
Example 7: fe 25 Co 25 Ni 5 Al 35 Si 5 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 2mm and the thickness of 25 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 2mm and the surface linear speed of a copper roller is 37 m/s. The constant potential adopted by dealloying is-0.01V. The average pore diameter of the nano-porous alloy prepared after dealloying is 56nm, the average ligament thickness is 77nm, and the chemical composition is Fe 35 Co 35 Ni 7 Al 20 Si 3 . The degradation efficiency to direct blue 6 within 30min was 90%. The saturation magnetization was 92emu/g. Specific data are listed in attached table 1.
Example 8: fe 25 Co 25 Ni 10 Al 30 Si 5 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 1mm and the thickness of 23 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 1mm and the surface linear speed of a copper roller is 38 m/s. The constant potential adopted by dealloying is-0.08V. The average pore diameter of the nano-porous alloy prepared after dealloying is 54nm, the average ligament thickness is 76nm, and the chemical composition is Fe 35 Co 35 Ni 14 Al 11 Si 3 . The degradation efficiency for direct blue 6 within 30min was 93%. The saturation magnetization was 94emu/g. Specific data are listed in attached table 1.
Example 9: fe 25 Co 25 Ni 10 Al 20 Si 15 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of the embodiment 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 1mm and the thickness of 20 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 1mm and the surface linear speed of a copper roller is 40 m/s. The constant potential adopted by dealloying is-0.07V. The average pore diameter of the nano-porous alloy prepared after dealloying is 53nm, the average ligament thickness is 75nm, and the chemical composition is Fe 34 Co 34 Ni 14 Al 9 Si 9 . The degradation efficiency to direct blue 6 within 30min was 91%. The saturation magnetization was 93emu/g. Specific data are listed in attached table 1.
Example 10: fe 25 Co 25 Ni 10 Al 5 Si 20 B 15
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 3mm and the thickness of 23 mu m under the condition that the surface linear speed of a copper roller is 38 m/s. The constant potential used for dealloying is 0.08V. The average pore diameter of the nano-porous alloy prepared after dealloying is 55nm, the average ligament thickness is 75nm, and the chemical composition is Fe 33 Co 38 Ni 16 Al 3 Si 8 B 2 . The degradation efficiency to direct blue 6 within 30min was 90%. The saturation magnetization was 92emu/g. Specific data are listed in attached table 1.
Example 11: fe 25 Co 25 Ni 10 Al 10 Si 10 B 20
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: in the first step, the mother alloy ingot adopts inductionThe melting furnace is prepared under nitrogen atmosphere. Preparing a high-entropy alloy strip with the width of 1mm and the thickness of 30 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 1mm, the surface linear speed of a copper roller is 36m/s and nitrogen atmosphere. The constant potential adopted by dealloying is 0.1V. The average pore diameter of the nano-porous alloy prepared after dealloying is 57nm, the average ligament thickness is 79nm, and the chemical composition is Fe 27 Co 38 Ni 15 Al 7 Si 8 B 5 . The degradation efficiency to direct blue 6 within 30min was 88%. The saturation magnetization was 92emu/g. Specific data are listed in attached table 1.
Example 12: fe 35 Co 25 Ni 10 Al 10 Si 20
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of the embodiment 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 1mm and the thickness of 25 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 1mm and the surface linear speed of a copper roller is 37 m/s. The constant potential used for dealloying is 0.03V. The average pore diameter of the nano-porous alloy prepared after dealloying is 60nm, the average ligament thickness is 80nm, and the chemical composition is Fe 30 Co 40 Ni 16 Al 6 Si 8 . The degradation efficiency to direct blue 6 within 30min was 88%. The saturation magnetization was 94emu/g. Specific data are listed in attached table 1.
Example 13: fe 35 Co 20 Ni 10 Al 15 Si 15 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of the embodiment 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 3mm and the thickness of 27 mu m under the condition that the surface linear speed of a copper roller is 36 m/s. The solution adopted for dealloying is H + The sulfuric acid solution with the concentration of 0.5mol/L and the constant potential of 0.01V. The average pore diameter of the nano-porous alloy prepared after dealloying is 57nm, the average ligament thickness is 75nm, and the chemical composition is Fe 29 Co 36 Ni 18 Al 6 Si 11 . Direct blue within 30minThe degradation efficiency of 6 was 89%. The saturation magnetization was 93emu/g. Specific data are listed in attached table 1.
Example 14: fe 25 Co 25 Ni 15 Al 5 Si 15 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 4mm and the thickness of 27 mu m under the conditions that the nozzle size of a quartz tube is 4mm multiplied by 1mm and the surface linear velocity of a copper roller is 36 m/s. The solution adopted for dealloying is H + The concentration of the hydrochloric acid solution is 0.1mol/L, and the constant potential is-0.01V. The average pore diameter of the nano-porous alloy prepared after dealloying is 51nm, the average ligament thickness is 69nm, and the chemical composition is Fe 20 Co 40 Ni 27 Al 4 Si 9 . The degradation efficiency for direct blue 6 within 30min was 82%. The saturation magnetization was 94emu/g. Specific data are listed in attached table 1.
Example 15: fe 35 Co 25 Ni 5 Al 20 Si 10 B 5
The preparation, structure and morphology characterization and performance testing methods of the precursor alloy and the nanoporous alloy are similar to those of example 1, and the differences are only that: step one, preparing a high-entropy alloy strip with the width of 1mm and the thickness of 29 mu m under the conditions that the size of a nozzle of a quartz tube is a circular hole with the diameter of 1mm and the surface linear speed of a copper roller is 35 m/s. The solution adopted for dealloying is H + The constant potential of the sulfuric acid solution with the concentration of 1mol/L is 0.04V. The average pore diameter of the nano-porous alloy prepared after dealloying is 59nm, the average ligament thickness is 78nm, and the chemical composition is Fe 32 Co 40 Ni 10 Al 11 Si 7 . The degradation efficiency to direct blue 6 within 30min was 92%. The saturation magnetization was 95emu/g. Specific data are listed in attached table 1.
Comparative examples 1 and 2: selected from the references [ Scientific Reports,2016, 34213]. The high-entropy alloy powder samples of AlCoCrFeNi and CoCrFeMnNi with equal atomic ratio are synthesized by a mechanical alloying method, and the grain diameters of the powder are respectively 6.5 μm and 7.2 μm. Degradation tests were carried out on 10mL of direct blue 6 at a concentration of 200mg/L at a temperature of 25 ℃ using 0.1g of powder. The result shows that the degradation efficiency of the AlCoCrFeNi powder to the direct blue 6 is 75% in 40min, and the degradation efficiency of the CoCrFeMnNi powder to the direct blue 6 is 70% in 40 min. The specific data statistics are shown in attached table 1. It can be seen that comparative examples 1 and 2 have longer degradation time for direct blue 6 than examples 1 to 15 of the present invention, and the degradation efficiency is also low.
Comparative example 3: selected from references [ Journal of Alloys and Compounds,2019,815]. Is (FeCoNi) 78 Si 13 B 9 High entropy amorphous strips. A degradation test was carried out using 1g alloy strips at a temperature of 35 ℃ on 40mL of Orange II solution at a concentration of 40 mg/L. The result shows that the degradation efficiency of the amorphous strip on Orange II within 70min is only 33.3 percent, and the amorphous strip is only physically adsorbed and has no chemical reaction. It can be seen that comparative example 3 has longer degradation time for azo dyes than examples 1 to 15 of the present invention, and the degradation efficiency is much lower than that of the examples of the present invention.
TABLE 1 precursor composition, electrolyte concentration, nanoporous alloy composition, average pore size, average ligament thickness, and degradation efficiency of different times for direct blue 6 azo dyes and saturation magnetization of nanoporous Fe-Co-Ni-Al-Si-B high entropy alloys disclosed in the present invention
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. Efficient azo dyeThe nano porous high-entropy alloy with degradation performance is characterized in that the chemical composition is Fe a Co b Ni c Al d Si e Wherein a, b, c, d and e respectively represent the atom percentage content of the corresponding elements, and satisfy: a is more than or equal to 20 and less than or equal to 35, b is more than or equal to 30 and less than or equal to 40,7 and less than or equal to 40,2 and less than or equal to d and less than or equal to 20,2 and less than or equal to e and less than or equal to 12, and a + b + c + d + e =100;
mainly consists of a B2 phase and contains a BCC phase and an amorphous phase with a volume fraction not higher than 20%;
the nano-porous structure with nano-scale pores and double continuous ligaments has the average pore size of 40-60 nm and the average ligament thickness of 60-80 nm;
under the conditions that the pH value is 3 and the temperature is 25 ℃, more than 80% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L is removed by 0.05g of the nano-porous high-entropy alloy within 30 min;
the saturation magnetization is 92-105 emu/g;
with the composition formula being Fe f Co g Ni h Al i Si j B k The high-entropy alloy strip as a precursor, wherein f, g, h, i, j and k respectively represent the atomic percentage content of corresponding elements, and the atomic percentage content satisfies the following conditions: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to 30,5 and less than or equal to i is more than or equal to 35,5 and less than or equal to j is more than or equal to 20,0 and less than or equal to 20, and f + g + h + i + j + k =100, dealloying the precursor alloy strip in an acid solution by an electrochemical method, and preparing the nano-porous high-entropy alloy.
2. The nanoporous high-entropy alloy with high-efficiency azo dye degradation performance according to claim 1, further comprising a B element in an amount of not more than 5 atomic%.
3. The nanoporous high-entropy alloy with efficient azo-dye degradation properties according to claim 1, wherein the chemical composition is Fe 32 Co 35 Ni 15 Al 6 Si 12 (ii) a Using Fe 35 Co 25 Ni 10 Al 10 Si 15 B 5 High-entropy alloy precursor in acid solutionThe alloy is prepared by an electrochemical dealloying method; the average pore size is 50nm and the average ligament thickness is 60nm; under the conditions that the pH value is 3 and the temperature is 25 ℃,0.05g of the nano-porous high-entropy alloy removes over 95% of direct blue 6 solution with the volume of 50mL and the initial concentration of 200mg/L within 30 min; the saturation magnetization was 103emu/g.
4. A preparation method of a nano porous high-entropy alloy with efficient azo dye degradation performance is characterized by comprising the following steps:
step one, preparing a precursor alloy strip
Selecting Fe, co, ni, al, si and B raw materials with the purity not lower than 99 mass percent, weighing and proportioning according to the component proportion of the high-entropy alloy precursor, and smelting the weighed raw materials in a non-consumable vacuum arc furnace or an induction smelting furnace in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components; crushing a master alloy ingot, putting the crushed master alloy ingot into a quartz tube, and preparing a high-entropy alloy strip with the width of 1-5 mm, the thickness of 20-30 mu m and a mixed phase structure of BCC and B2 in an argon or nitrogen atmosphere by adopting single-roller melt-spinning equipment; the width and the thickness of the alloy strip can be adjusted by changing the rotating speed of a copper roller of single-roller melt-spinning equipment and the size of a nozzle of a quartz tube, wherein the rotating speed of the copper roller is controlled to be 35-40 m/s, and the size of the nozzle is a circular hole with the diameter of 1-2 mm or a rectangular hole with the width of 1mm and the length of 3-5 mm;
step two, preparing the nano porous high-entropy alloy
Taking the high-entropy alloy strip prepared in the step one as a working electrode, ag/AgCl as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electrochemical reaction on the counter electrode in the presence of H + In an acid solution with the concentration of 0.1-1 mol/L and the temperature of 25 ℃, an electrochemical workstation is used for carrying out dealloying treatment on the precursor alloy strip under the constant potential of-0.1V; repeatedly cleaning the dealloyed nanoporous alloy with deionized water for three times, and placing the dealloyed nanoporous alloy in a vacuum drying oven for drying treatment to finally obtain the nanoporous high-entropy alloy; the chemical composition, the average pore diameter and the average ligament thickness of the nano porous high-entropy alloy can be changed by changing the components of a precursor alloy and H of an acid solution used for dealloying + Concentration and dealloying potential.
5. The preparation method of the nanoporous high-entropy alloy with high-efficiency azo dye degradation performance according to claim 4, wherein the precursor of the high-entropy alloy in the step one has a composition formula of Fe f Co g Ni h Al i Si j B k Wherein f, g, h, i, j and k respectively represent the atom percentage content of the corresponding elements, and satisfy: f is more than or equal to 25 and less than or equal to 40, g is more than or equal to 20 and less than or equal to 30,5 and less than or equal to h is less than or equal to 30,5 and less than or equal to i and less than or equal to 35,5 and less than or equal to j and less than or equal to 20,0 and less than or equal to 20, and f + g + h + i + j + k =100.
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