A modified iron-based metal catalyst and its preparation method

Abstract

The present invention belongs to the field of catalyst technology, and specifically relates to a modified iron-based metal catalyst and a preparation method thereof. The catalyst of the present invention is an iron-based metal with inactive metal atoms deposited on the surface, wherein the inactive metal atoms are deposited on the surface of the iron-based metal in a diffusely distributed manner, and the average deposition thickness of the inactive metal atoms is less than 50 nm. The present invention innovatively proposes a catalyst for modifying iron-based metals using trace inactive metal elements. Based on the strong reactivity between iron-based metals and inactive metal ions, a nanometer-scale atomic layer structure can be constructed on the surface of the iron-based metal, which significantly improves the catalytic activity of the catalyst, and the reaction is simple and easy. The modified iron-based metal catalyst prepared by the present invention has the dual advantages of low cost and high performance, and has good application prospects in the field of catalysts.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a modified iron-based metal catalyst and a preparation method thereof. Background Art

[0002] Iron-based metal materials are widely used in daily life and production due to their low cost and excellent magnetic and mechanical properties. In recent years, the performance and potential applications of iron-based metal materials, including iron-based amorphous alloys, in chemical catalysis have garnered widespread attention. Improving the catalytic activity of iron-based metal materials is crucial for expanding their application areas and meeting the market's strong demand for low-cost catalysts.

[0003] At present, alloying is the main method for modifying iron-based metal materials. For example, adding a certain amount of Co or Ni elements to iron-based magnetic alloys can improve their soft magnetic properties; adding more than 10% Cr elements to steel can significantly improve its corrosion resistance. In the field of catalysts, researchers have found that adding 4wt% Co elements to iron-based amorphous alloys can improve their catalytic performance in Fenton-like reactions (New J.Chem., 2019, 43, 6126-6135), increasing their apparent rate constant by 38%. However, the Co element needs to be added during the smelting stage, and the complex process and high addition content significantly increase its cost. At present, the alloying process of iron-based metals is usually achieved during the material smelting stage by adding alloying elements with a mass fraction between 1% and 20%, so that they are evenly distributed in the alloy matrix, thereby regulating the physical and chemical properties of the alloy.

[0004] However, alloying as a modification method not only has high process and material costs, but can also significantly weaken the material's ability to form amorphous materials, especially in amorphous alloys. This makes it difficult to achieve the desired alloy design performance requirements. In addition, because most chemical reactions occur at the interface, atoms within the alloy are often unable to effectively participate in the reaction, resulting in low utilization of alloying elements and a waste of resources.

[0005] Surface modification is an efficient and cost-effective alternative strategy. Currently, surface modification of iron-based materials is primarily achieved by forming a coating with a thickness of 10 to 50 microns on their surface, such as copper or nickel plating. However, because these surface coatings completely cover the substrate surface, they are often used to protect the iron-based material from corrosion rather than to enhance its reactivity. Therefore, how to modify the surface of iron-based metal materials to improve their catalytic performance is of great significance to meet the market demand for low-cost, highly active catalysts. Summary of the Invention

[0006] In response to the problems of high cost, great limitations and unsatisfactory catalytic performance improvement in the alloying modification of traditional iron-based metal materials, the present invention innovatively proposes a method for modifying the catalytic performance of iron-based alloys using trace inactive metal elements. Based on the strong reactivity of surface atoms of iron-based metals with inactive metal ions, a very small amount of inactive metal elements is deposited on the surface of the iron-based metal to construct a nanoscale atomic layer, which changes the atomic composition of the surface of the iron-based metal. These trace inactive metal atoms are dispersed on the surface of the iron-based metal, which can not only enhance the catalytic activity of the iron-based metal, but also cooperate with the iron-based metal to participate in catalytic reactions, thereby significantly enhancing the catalytic effect on chemical reactions. The modified iron-based metal catalyst prepared by the present invention has the dual advantages of low cost and high performance, and has good application prospects in the field of catalysts.

[0007] Based on the above purpose, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a modified iron-based metal catalyst, which is an iron-based metal with inactive metal atoms deposited on the surface; wherein the inactive metal atoms are deposited on the iron-based metal surface in a diffusely distributed manner; and the average deposition thickness of the inactive metal atoms is <50 nm.

[0009] In response to the problems of poor catalytic performance of traditional iron-based metal materials and high cost and limitations of alloying modification methods, the present invention deposits inactive metal atoms with a thickness of nanometer level on the surface of the iron-based metal material. The catalytic performance of the resulting modified iron-based metal catalyst is significantly improved. This is because the deposited inactive elements can directly intervene in the catalytic reaction, activate the iron-based metal through the galvanic cell effect, and cooperate with the iron metal to participate in the catalytic reaction, thereby comprehensively improving the catalytic performance of the modified iron-based metal catalyst.

[0010] The modified iron-based metal catalyst is in powder or filament form. This type of modified iron-based metal catalyst has a relatively large specific surface area, which is more conducive to improving the catalytic effect on chemical reactions.

[0011] Preferably, the mass ratio of the inactive metal atoms to the iron-based metal is 0.001% to 0.8%:1.

[0012] Experiments have found that depositing a very small amount of inactive metal atoms on the surface of iron-based metals can significantly improve their catalytic activity.

[0013] Preferably, when the iron-based metal is an iron-based amorphous alloy, the mass ratio of the inactive metal atoms to the iron-based amorphous alloy is 0.05% to 0.5%:1, preferably 0.05% to 0.3%:1, and preferably 0.1% to 0.3%:1.

[0014] Experiments have found that within the range of trace deposition of inactive metal atoms, as the amount of inactive metal atom deposition increases, the apparent rate constant of the modified iron-based metal catalyst in catalytic degradation of dyes first increases and then tends to stabilize. Inactive metal atoms have a relatively better catalytic effect within the above-mentioned deposition range.

[0015] Preferably, the iron-based amorphous alloy is at least one of a FeB-based amorphous alloy and a FeC-based amorphous alloy;

[0016] Among them, FeB-based amorphous alloys include but are not limited to FeB amorphous alloys, FeSiB amorphous alloys, FePB amorphous alloys, FeBCSiCr amorphous alloys, and FeSiBNbCu amorphous alloys;

[0017] FeC-based amorphous alloys include but are not limited to FeCB amorphous alloys, FeCP amorphous alloys, FeCBP amorphous alloys, and FeCBSiP amorphous alloys.

[0018] Preferably, when the iron-based metal is a crystalline iron-based metal, the mass ratio of the inactive metal atoms to the crystalline iron-based metal is 0.02% to 0.2%:1.

[0019] Experiments have found that depositing inactive metal atoms on the surface of crystalline iron-based metals such as pure iron powder can significantly improve their catalytic performance. The apparent rate constant of the modified iron-based metal catalyst in catalytic degradation of dyes first increases and then tends to stabilize. Inactive metal atoms have a relatively better catalytic effect within the above-mentioned deposition range.

[0020] Preferably, the crystalline iron-based metal is at least one of crystalline pure iron, iron-silicon alloy, iron-aluminum alloy, iron-carbon alloy, iron-boron alloy, iron-phosphorus alloy and other iron-based metals.

[0021] Preferably, the inactive metal atom is at least one of Cu, Ni, Ga, In, Sn, Ag, Ru, Rh, Pd, Pt, and Au.

[0022] In a second aspect, the present invention provides a method for preparing a modified iron-based metal catalyst, comprising the following steps:

[0023] The iron-based metal powder is mixed with an aqueous solution of inactive metal ions to react, so that the inactive metal atoms are deposited on the surface of the iron-based metal to obtain a modified iron-based metal catalyst;

[0024] The weight ratio of the inactive metal ions to the iron-based metal powder is 0.001% to 0.8%:1.

[0025] The present invention cleverly utilizes the strong reactivity between iron-based metals and inactive metal ions. By simply mixing iron-based metal powder with an aqueous solution of inactive metal ions, a nanometer-thick inactive metal atomic layer can be generated on the surface of the iron-based metal without adding additives. The inactive metal layer can activate the iron-based metal through the galvanic cell effect and can also cooperate with the iron metal to participate in catalytic reactions, thereby greatly improving the catalytic activity of the iron-based metal material at an extremely low cost.

[0026] By analyzing the absorption spectra of inactive metal ions in the solution before and after the reaction, it was found that there were almost no free inactive metal ions in the solution after the reaction, indicating that the inactive metal ions can be completely deposited on the surface of the iron-based metal in this reaction. Therefore, by adjusting the relative content of inactive metal ions and iron-based metals in the reaction raw materials, the amount of inactive metal ions deposited on the surface of the iron-based metal can be controlled.

[0027] In addition, the present invention uses powdered iron-based metal as a reaction raw material, which has a relatively large specific surface area and increases the carrying capacity of inactive metal ions.

[0028] Preferably, the aqueous solution of inactive metal ions contains Cu 2+ 、Ni 2+ 、Ga 3+ 、In 3+ 、Sn 2+ 、Ag + 、Ru 2+ 、Ru 3+ , Rh 3+ 、Pd 2+ , Pt 2+ 、Au 3+ An aqueous solution of at least one metal ion.

[0029] Preferably, the aqueous solution of inactive metal ions includes an aqueous solution of copper sulfate, an aqueous solution of copper chloride, an aqueous solution of copper nitrate, an aqueous solution of nickel sulfate, an aqueous solution of nickel chloride, an aqueous solution of gallium chloride, an aqueous solution of indium chloride, an aqueous solution of stannous chloride, an aqueous solution of silver chloride, an aqueous solution of silver nitrate, an aqueous solution of silver sulfate, an aqueous solution of ruthenium sulfate, an aqueous solution of ruthenium chloride, an aqueous solution of ruthenium nitrate, an aqueous solution of rhodium sulfate, an aqueous solution of rhodium chloride, an aqueous solution of rhodium nitrate, an aqueous solution of palladium sulfate, an aqueous solution of palladium chloride, an aqueous solution of palladium nitrate, an aqueous solution of chloroplatinic acid, an aqueous solution of platinum nitrate, an aqueous solution of gold chloride, and an aqueous solution of potassium aurous cyanide.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) Based on the strong reactivity between iron-based metals and inactive metal ions, the present invention constructs a nanometer-thick and diffusely distributed inactive metal atomic layer on the surface of the iron-based metal. The deposited inactive elements can directly intervene in the catalytic reaction, activate the iron-based metal through the galvanic cell effect, and cooperate with the iron metal to participate in the catalytic reaction, thereby comprehensively improving the catalytic performance of the modified iron-based metal catalyst.

[0032] (2) The present invention reacts powdered or filamentous iron-based metal with an aqueous solution of inactive metal ions to obtain a modified iron-based metal catalyst with a controllable amount of inactive metal atom deposition. The preparation process is extremely simple and the reaction is stable, which greatly reduces the cost of modifying iron-based metal materials.

[0033] (3) The iron-based metal of the present invention can be an iron-based amorphous alloy or a crystalline iron-based metal. After inactive metal atoms are deposited on its surface, its catalytic activity can be improved. Relatively speaking, the modified iron-based amorphous alloy catalyst has better catalytic performance than the modified crystalline iron-based metal.

[0034] In summary, the present invention is based on the strong reactivity between iron-based metals and inactive metal ions. Through a simple reaction between the iron-based metals and an aqueous solution of inactive metal ions, the controllable deposition of inactive metal atoms on the surface of the iron-based metal can be achieved. This modification process is extremely simple and easy, and greatly improves the catalytic performance of the modified iron-based metal catalyst at a low cost; the amount of inactive metal is controlled at an extremely low level, which effectively ensures the low cost and high benefit characteristics of the modification method, and shows good application prospects in the field of catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Comparison of the performance of FeSiBNbCu amorphous powder deposited with 0.03wt% copper atoms in catalytic Fenton-like reactions;

[0036] Figure 2 Comparison of the performance of FeSiBNbCu amorphous powder deposited with 0.06wt% copper atoms in catalytic Fenton-like reactions;

[0037] Figure 3 Comparison of the performance of FeSiBNbCu amorphous powder deposited with 0.25wt% copper atoms in catalytic Fenton-like reactions;

[0038] Figure 4 The effect of Cu atom deposition on the catalytic performance of FeSiBNbCu amorphous;

[0039] Figure 5 Comparison of XRD patterns of FeSiBNbCu amorphous powder deposited with 0.5wt% copper atoms and original amorphous powder;

[0040] Figure 6Cu2p XPS spectrum of FeSiB amorphous powder deposited with 0.03wt% copper atoms;

[0041] Figure 7 Comparison of the catalytic performance of FeSiB amorphous alloy after depositing trace amounts of Cu atoms and Ag atoms with that of the original amorphous alloy;

[0042] Figure 8 The effect of Cu atom deposition on the catalytic performance of modified pure iron;

[0043] Figure 9 The absorption spectrum of copper ions changes before and after the reaction of copper sulfate solution containing 0.3 mg copper ions with 1 g iron powder;

[0044] Figure 10 This is the XRD pattern of the modified powder in Example 16. DETAILED DESCRIPTION

[0045] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention will be further described below with reference to specific examples. Those skilled in the art will appreciate that the specific examples described herein are intended only to illustrate the present invention and are not intended to limit the present invention. The experimental methods used in the examples are conventional methods unless otherwise specified; the materials and reagents used are commercially available unless otherwise specified.

[0046] Example 1

[0047] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0048] 0.2 g of FeSiBNbCu amorphous powder was mixed with 2 mL of an 80 mg / L copper sulfate aqueous solution (containing 0.06 mg of copper ions) and shaken for 30 seconds. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder with 0.06 mg of copper deposited on its surface, which was the modified iron-based metal catalyst. The mass ratio of Cu to the iron-based amorphous (FeSiBNbCu) in the modified iron-based metal catalyst prepared in this example was 0.03%:1.

[0049] The modified iron-based metal catalyst powder prepared in this example was subjected to a Fenton-like oxidation experiment. A Fenton-like oxidation experiment was also conducted using 0.2 g of pristine iron-based amorphous (FeSiBNbCu) powder as a control. The reaction medium was 200 mL of a solution containing 1 mmol / L hydrogen peroxide and 20 mg / L azo dye, and the pH was 3.0. The experiments were conducted at room temperature with mechanical stirring.

[0050] The normalized concentration-time curves of the modified iron-based metal catalyst powder prepared in this example and the original iron-based amorphous powder for catalytic degradation of azo dyes are shown in FIG. Figure 1 As shown in Figure 2, the catalytic performance of the Fe-based amorphous material is significantly improved after trace Cu deposition. This performance improvement is due to two factors: first, the deposited Cu atoms are distributed on the surface of the Fe-based amorphous material, activating the iron atoms; second, the surface Cu ions can synergistically catalyze the reaction.

[0051] Example 2

[0052] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0053] 0.2 g of FeSiBNbCu amorphous powder was mixed with 2 mL of a 150 mg / L copper sulfate aqueous solution (containing 0.12 mg of copper ions) and shaken for 30 seconds. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder with 0.12 mg of copper deposited on the surface, which is the modified iron-based metal catalyst. The mass ratio of Cu to the iron-based amorphous (FeSiBNbCu) in the modified iron-based metal catalyst prepared in this example was 0.06%:1.

[0054] Take equal amounts of the modified iron-based metal catalyst prepared in this example and the original iron-based amorphous powder (FeSiBNbCu) and refer to the Fenton-like oxidation experiment in Example 1 to obtain the normalized concentration-time curves of the two powders for catalytic degradation of azo dyes, as shown in FIG. Figure 2 As shown in Figure 2, the catalytic performance of the iron-based amorphous material is significantly improved after a trace amount of Cu deposition, and the effect of the modified iron-based metal catalyst at a reaction time of 2 minutes exceeds that of the original iron-based amorphous powder at a reaction time of 4 minutes.

[0055] Depend on Figure 1 、 Figure 2 By comparison, it can be seen that the catalytic effect of the modified iron-based metal catalyst prepared in this example is better than that of the catalyst prepared in Example 1.

[0056] Example 3

[0057] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0058] 0.2 g of FeSiBNbCu amorphous powder was mixed with 2 mL of a 640 mg / L copper sulfate aqueous solution (containing 0.5 mg of copper ions) and shaken for 30 seconds. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder with 0.5 mg of copper deposited on its surface, which was the modified iron-based metal catalyst. The mass ratio of Cu to the iron-based amorphous (FeSiBNbCu) in the modified iron-based metal catalyst prepared in this example was 0.25%:1.

[0059] Take equal amounts of the modified iron-based metal catalyst prepared in this example and the original iron-based amorphous powder (FeSiBNbCu) and refer to the Fenton-like oxidation experiment in Example 1 to obtain the normalized concentration-time curves of the two powders for catalytic degradation of azo dyes, as shown in FIG. Figure 3 It can be seen that the catalytic performance of the iron-based amorphous material is further improved after a trace amount of Cu deposition.

[0060] Examples 4 to 6

[0061] The preparation method of the modified iron-based metal catalyst was referred to in Example 1, with the only difference being the mass of copper ions in the copper sulfate aqueous solution, as shown in Table 1. The parts not described in the preparation method were the same as those in Example 1.

[0062] Table 1 Composition of modified iron-based amorphous powders of Examples 4 to 6

[0063] Example Iron-based amorphous quality Copper atomic mass Mass ratio of copper to iron-based amorphous Example 4 0.2g 0.03mg 0.015％:1 Example 5 0.2g 0.24mg 0.12％:1 Example 6 0.2g 1mg 0.5％:1

[0064] Referring to the Fenton-like catalytic reaction test method described in Example 1, the effect of the amount of Cu atom deposition on the catalytic performance of the catalyst powder was analyzed using an equal amount of original iron-based amorphous as a control. Figure 4 As shown in the figure, it can be seen that depositing a small amount of Cu atoms can significantly improve the catalytic performance of iron-based amorphous materials. Within the test range, the catalytic performance of the alloy continues to rise with the increase of Cu deposition.

[0065] The XRD patterns of FeSiBNbCu amorphous powder deposited with 0.5wt% copper atoms (Example 6) and the original Fe-based amorphous alloy powder (FeSiBNbCu) are as follows: Figure 5 As shown in the figure, there is no significant difference in the XRD patterns of the two alloys, and no characteristic peaks of Cu are detected in the amorphous powder containing deposited Cu. This is due to the low Cu content, which prevents the formation of a macroscopic Cu layer. This result indirectly indicates that the formed Cu is nanostructured.

[0066] Example 7

[0067] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0068] 1 g of FeSiB amorphous powder was mixed with a copper sulfate aqueous solution containing 0.3 mg of copper ions. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder containing 0.3 mg of copper, which was the modified iron-based metal catalyst. The mass ratio of Cu to the iron-based amorphous in the modified iron-based metal catalyst prepared in this example was 0.03%:1.

[0069] The XPS spectrum of the modified iron-based metal catalyst powder prepared in this example is as follows: Figure 6 As shown, the test shows a strong Cu signal on the FeSiB amorphous surface. Analysis of the spectrum reveals that when the Cu atomic deposition is only 0.03wt%, the Cu to Fe content ratio within the nanometer depth of the FeSiB amorphous surface exceeds 25%. This means that 0.3mg of copper atoms are widely distributed on the surface of the Fe-based amorphous powder. This also explains the significant improvement in the performance of the modified Fe-based amorphous powder achieved in this invention.

[0070] Based on the copper density and the amount of copper deposited, the average depth of the deposited Cu atomic layer is estimated to be approximately 2.5 nm. This indicates that the strong reactivity of copper ions with the iron-based amorphous material allows the Cu atoms to form a dispersed nanolayer on the surface of the iron-based amorphous material. This unique structure significantly improves the catalytic performance of the alloy. It also demonstrates the feasibility of using iron-based amorphous alloys as metal catalyst supports.

[0071] Example 8

[0072] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0073] 1g of FeSiB amorphous powder was mixed with an aqueous copper sulfate solution containing 3mg of copper ions. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder containing 3mg of copper atoms, which was the modified iron-based metal catalyst. The mass ratio of Cu to the iron-based amorphous alloy in the modified iron-based metal catalyst prepared in this example was 0.3%:1.

[0074] Example 9

[0075] This embodiment provides a modified iron-based metal catalyst, and its preparation method is as follows:

[0076] 1 g of FeSiB amorphous powder was mixed with an aqueous silver nitrate solution containing 3 mg of silver ions. After sufficient reaction, the precipitated product was collected, washed with alcohol, and dried to obtain an iron-based amorphous powder containing 3 mg of silver atoms, which was the modified iron-based metal catalyst. The mass ratio of Ag to the iron-based amorphous alloy (FeSiB) in the modified iron-based metal catalyst prepared in this example was 0.3%:1.

[0077] Take equal amounts of 1g of FeSiB amorphous powder, modified iron-based metal catalyst powders of Example 8 and Example 9, and carry out Fenton-like catalytic tests under neutral conditions according to the Fenton-like oxidation experimental method in Example 1. The apparent rate constants of the reactions of different catalysts are as follows: Figure 7As shown in Figure 2, under neutral conditions, the catalytic performance of Examples 8 and 9 is significantly improved compared to the original iron-based amorphous alloy (FeSiB). This shows that the catalytic performance of the iron-based amorphous alloy after deposition of Cu and Ag is greatly improved. The reason for the stronger catalytic performance after deposition of Cu atoms may be that Cu atoms can jointly catalyze the Fenton-like reaction with Fe atoms, while Ag atoms can only enhance the reaction by enhancing the catalytic activity of Fe atoms.

[0078] Examples 10 to 16

[0079] Referring to the preparation method of the modified iron-based metal catalyst in Example 1, the difference is that in Examples 10 to 16, pure iron powder is used instead of the iron-based amorphous alloy powder to react with the copper sulfate solution. The specific method is as follows:

[0080] 1 g of pure iron powder was mixed with 2 mL of copper sulfate aqueous solution containing different amounts of copper ions for reaction. The remaining preparation methods were the same as those in Example 1. The parameters involved in Examples 10 to 16 are shown in Table 2.

[0081] Table 2 Composition of modified iron powder catalyst in Examples 10 to 16

[0082] Example Pure iron powder quality Copper atomic mass Copper to iron powder mass ratio Example 10 1g 0.05mg 0.005％:1 Example 11 1g 0.1mg 0.01％:1 Example 12 1g 0.3mg 0.03％:1 Example 13 1g 0.6mg 0.06％:1 Example 14 1g 1.2mg 0.12％:1 Example 15 1g 2.5mg 0.25％:1 Example 16 1g 5mg 0.5％:1

[0083] Referring to the Fenton-like oxidation test method in Example 1, with an equal amount of pure iron powder as a control, the effect of the amount of Cu atom deposition on the apparent rate constant of the modified iron-based metal catalyst when catalyzing the Fenton-like reaction was analyzed. Figure 8 As shown in the figure, it can be seen that the deposition of trace copper atoms greatly improves the catalytic performance of pure iron. Considering the cost and catalytic performance improvement effect, a copper atomic deposition amount of 0.02% to 0.2% is more suitable.

[0084] The changes in the absorption spectrum of copper ions in the copper sulfate solution before and after the reaction of Example 12 were detected, and the results were as follows: Figure 9 As shown, it can be seen that the trace amount of copper ions basically disappears after the reaction, thus confirming that the copper element is completely deposited on the surface of the iron powder after the reaction.

[0085] XPS analysis of the modified powder in Example 16 revealed that a mere 0.5% Cu atoms accounted for 41% of the nanoscale metal atoms on the iron powder surface. This suggests that the Cu atoms were deposited in a largely dispersed manner on the iron powder surface. This suggests that the average depth of the copper atoms is estimated to be 25 nm, far less than the conventional copper plating thickness (10 to 50 μm).

[0086] The XRD pattern of the modified powder in Example 16 is as follows: Figure 10As shown, no obvious Cu crystalline diffraction peaks were observed. This result further confirms the XPS test results, which show that due to the highly dispersed distribution and shallow depth of Cu atoms on the iron powder surface, they are highly diluted in XRD tests (detection depth ≥ 10μm). This result also indirectly indicates that the formed Cu is a nanostructure.

Claims

1. A modified iron-based metal Fenton catalyst, characterized in that: The catalyst is an iron-based metal with inactive metal atoms deposited on the surface; the inactive metal atoms are deposited on the surface of the iron-based metal in a dispersed manner; the average deposition thickness of the inactive metal atoms is less than 50 nm; the iron-based metal is an iron-based amorphous alloy, and the inactive metal atoms are at least one of Cu, Ag, and Au; the mass ratio of the inactive metal atoms to the iron-based metal is 0.001% to 0.8%:1; The preparation method of the modified iron-based metal Fenton catalyst comprises the steps of mixing iron-based metal powder with an aqueous solution of inactive metal ions to react, so that the inactive metal atoms are deposited on the surface of the iron-based metal to obtain the modified iron-based metal Fenton catalyst.

2. The modified iron-based metal Fenton catalyst according to claim 1, characterized in that The mass ratio of the inactive metal atoms to the iron-based amorphous alloy is 0.05% to 0.5%:

1.

3. The modified iron-based metal Fenton catalyst according to claim 2, characterized in that The iron-based amorphous alloy is at least one of a FeB-based amorphous alloy and a FeC-based amorphous alloy; The FeB series amorphous alloys include FeB amorphous alloys, FeSiB amorphous alloys, FePB amorphous alloys, FeBCSiCr amorphous alloys and FeSiBNbCu amorphous alloys; The FeC-based amorphous alloys include FeCB amorphous alloys, FeCP amorphous alloys, FeCBP amorphous alloys and FeCBSiP amorphous alloys.

4. The method for preparing the modified iron-based metal Fenton catalyst according to any one of claims 1 to 3, characterized in that: The steps include: The iron-based metal powder is mixed with an aqueous solution of inactive metal ions to react, so that the inactive metal atoms are deposited on the surface of the iron-based metal to obtain a modified iron-based metal catalyst; The weight ratio of the inactive metal ions to the iron-based metal powder is 0.001% to 0.8%:

1.

5. The preparation method according to claim 4, characterized in that The aqueous solution of the inactive metal ions contains Cu 2 + 、Ag + 、Au 3+ An aqueous solution of at least one metal ion.

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