Self-supporting three-metal CC (at) M-trimental / PBA material and preparation method thereof

Abstract

The invention discloses a self-supporting three-metal CC (at) M-trimetal / PBA (poly (butylene succinate))) material and a preparation method thereof. The method comprises the following steps: growing a CC (at) PS micron array on a conductive substrate by using polystyrene microspheres, then obtaining a CC (at) PS-trimental nano array through an electro-deposition method, then obtaining CC (at) PS-trimental / PBA through a soaking method, and finally dissolving a polystyrene microsphere template. The material is a self-supporting electrode with unique macroporous characteristics, and the surface of the material is provided with a square PBA substance. The method provided by the invention is simple and safe, and the obtained product is high in specific surface area, good in structural stability, good in conductivity and high in charge mass transfer speed, shows excellent catalytic activity in electro-catalytic hydrolysis, and has a good application prospect.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic material preparation, and particularly to a self-supporting trimetallic CC@M-trimental / PBA material and its preparation method. Background Technology

[0002] Hydrogen, due to its high energy density, simple process, clean and pollution-free combustion products, and convenient transportation and storage, is considered an ideal alternative energy source to traditional fossil fuels and has attracted widespread attention from researchers. Currently, water electrolysis is considered an ideal method for the continuous production of hydrogen. Water electrolysis involves two half-reactions: the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) (Hua Li, Zhenyao Du, Shuiqiang Chen, Haihua Yang, and Kewen Tang, ACS Applied Energy Materials 20236(4), 2178-2186). Compared with the hydrogen evolution reaction, the oxygen evolution reaction involves a more complex process and therefore exhibits slow kinetic characteristics. In order to effectively improve the kinetics of the oxygen evolution reaction, oxygen evolution electrocatalysts are often used in the water electrolysis process. Currently, RuO2 and IrO2 are recognized as highly efficient OER electrocatalysts, but their large-scale industrial application is greatly limited due to factors such as small reserves, high price, and instability. Therefore, the development of efficient non-precious metal catalysts is of great significance for the application of water electrolysis.

[0003] In recent years, Prussian blue analogues (PBAs), as a typical metal-organic framework material, have become a research hotspot for OER electrocatalysts due to their advantages such as tunable chemical structure, abundant pore structure, and ease of preparation (Z. Chen, B. Fei, M. Hou, X. Yan, M. Chen, H. Qing, R. Wu, NanoEnergy. 2020, 68, 104371.). Furthermore, PBAs possess more coordinating ions and valence states, resulting in extremely high metal active centers and self-controllable morphologies. Direct growth of PBAs on conductive surfaces can significantly enhance the electrocatalytic activity and conductivity of OERs. Electrochemical deposition is also considered a rapid, efficient, and environmentally friendly method for material preparation. It can not only immobilize metal ions on a substrate but also control their size by adjusting the electrodeposition conditions. However, materials prepared by this method often have insufficient exposure of active sites. Therefore, to further improve the performance of existing materials in electrocatalytic hydrolysis, it is necessary to overcome the aforementioned bottlenecks. Summary of the Invention

[0004] To address the problems of existing methods, the present invention aims to provide a method for preparing a self-supporting trimetallic CC@M-trimental / PBA material.

[0005] The objective of this invention is achieved through the following technical solution.

[0006] The preparation method of the self-supporting trimetallic CC@M-trimental / PBA material includes the following steps:

[0007] (1) The conductive substrate (1×1cm) 2 After activation, the particles were placed in a polystyrene microsphere solution and allowed to stand for 24 hours for adsorption. They were then washed 5-6 times with ethanol and ultrapure water and dried at 60°C to obtain CC@PS.

[0008] (2) Dissolve two or three metal salts in deionized water and disperse them by ultrasonication to obtain a mixed solution;

[0009] (3) The CC@PS material obtained in step (1) is added to a deionized aqueous solution containing three metal salts, and electrodeposition is performed in a three-electrode system. After washing and drying, CC@PS-trimental material can be obtained.

[0010] (4) Take 20 ml of 0.6M PBA and immerse the CC@PS-trimental / PBA material obtained in step (3) upside down. After washing and drying, CC@PS-trimental / PBA is obtained.

[0011] (5) Take the CC@PS-trimental / PBA material obtained in step (4) and immerse it in toluene solution to dissolve PS. After washing and drying, CC@M-trimental / PBA is obtained.

[0012] Preferably, the conductive substrate in step (1) is carbon cloth.

[0013] Preferably, the two or three metal salts mentioned in step (2) are selected from Co(NO3)2·6H2O, Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Fe(NO3)3·9H2O, Zn(NO3)2·6H2O, Na2MoO4, MgSO4·7H2O and NaWO4 for the reaction.

[0014] Preferably, the electrodeposition voltage in step (3) is -2.5-1V and the electrodeposition time is 1200s.

[0015] Preferably, the concentration of the two or three metal salt solutions in step (3) is 0.06M.

[0016] Preferably, in the three electrodes described in step (3), the reference electrode is an Ag / AgCl electrode, the counter electrode is a carbon rod, and the working electrode is a PS@CC material.

[0017] Preferably, the soaking time for PBA in step (4) is 1 hour.

[0018] Preferably, the PS dissolution time in step (5) is 24 hours.

[0019] A nanosheet Ni-Fe-Co microarray material with polystyrene as a template, prepared by the above-described method, has an abundant porous structure. The type and thickness of the nanosheets on it can be adjusted according to the composition of the metal salt solution and the electrodeposition parameters.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] (1) The open and ordered porosity of CC@M-trimental / PBA not only ensures uniform and sufficient contact between the catalyst and the electrolyte, thus achieving good mass transfer, but also helps the electrolyte to penetrate deeply into the core-shell interface and fully react at the active sites at the boundary.

[0022] (2) Using CC@PS as a precursor, due to the limitation of the PS microsphere template, the outer layer of grown nanosheets becomes smaller and thinner, which can also prevent product aggregation.

[0023] (3) The material has the advantages of large specific surface area, regular shape, controllable material size and stable performance, which is conducive to shortening the mass transfer distance, improving the utilization rate of internal active sites and increasing the exposed catalytic active sites. Attached Figure Description

[0024] Figure 1 Scanning electron microscope image of CC@M-Ni3Fe1Co1 / PBA material with a three-dimensional multi-level nanosheet structure prepared in Example 2 of this invention.

[0025] Figure 2 The image shows the XRD (X-ray diffraction) pattern of the CC@M-Ni3Fe1Co1 / PBA material with a three-dimensional multi-level nanosheet structure prepared in Example 2 of this invention.

[0026] Figure 3 , Figure 4 , Figure 5 , Figure 6 The image shows the XPS (X-ray photoelectron spectroscopy) pattern of CC@M-Ni3Fe1Co1 / PBA prepared in Example 2 of this invention.

[0027] Figure 7This is a graph showing the catalytic performance evaluation of the CC@M-Ni3Fe1Co1 / PBA material with a nanoporous structure prepared in Example 2 of the present invention for electrocatalytic hydrolysis. Detailed Implementation

[0028] The specific implementation of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the implementation of the present invention is not limited thereto.

[0029] Example 1

[0030] Take 1×1cm 2 After carbon cloth is activated with 0.5 mol / L H2SO4, it is washed and dried, and then vertically immersed in polystyrene microsphere solutions of 100-200 nm, 200-300 nm, 300-400 nm, and 400-500 nm. After standing for 24 h, the carbon cloth is washed and dried in an oven at 60 °C to obtain CC@PS materials of different sizes.

[0031] Example 2

[0032] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, the Ag / AgCl electrode as the reference electrode, and the carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.5234 g), Fe(NO3)3·9H2O (0.2484 g), and Co(NO3)3·6H2O (0.1746 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was porous.

[0033] CC@M-Ni3Fe1Co1 / PBA material with nanosheet structure.

[0034] Figure 1 The SEM (scanning electron microscope) image of the CC@M-Ni3Fe1Co1 / PBA material with a three-dimensional nanosheet structure prepared for this embodiment shows that porous NiFeCo nanosheets are uniformly and vertically grown on the carbon cloth. Figure 2 The XRD pattern of CC@M-Ni3Fe1Co1 / PBA shows that the diffraction peaks of NiFeCo at 15.06° and 35.23° correspond to the (111) and (400) crystal planes of NiFeCo (PDF#01-073-4399), respectively, indicating that we have successfully prepared CC@M-Ni3Fe1Co1 / PBA. Figure 3 , Figure 4 , Figure 5 , Figure 6 The XPS plot shows XPS peaks at 708.78 eV and 721.58 eV corresponding to Fe 2p. 3 / 2 and Fe 2p 1 / 2 The characteristic peaks indicate the presence of Fe. 3+ The XPS spectra of Ni 2p show XPS peaks at 856.58 eV and 873.98 eV corresponding to Ni 2p. 3 / 2 and Ni 2p 1 / 2 The characteristic peaks indicate the presence of Ni in CC@M-Ni3Fe1Co1 / PBA. 2+ The XPS spectra of Co 2p show XPS peaks at 786.08 eV and 797.68 eV corresponding to Co 2p. 3 / 2 and Co2p 1 / 2 The characteristic peaks indicate the presence of Co in CC@M-Ni3Fe1Co1 / PBA. 2+ ; Figure 7 This is a graph evaluating the catalytic performance of the sample in the electrocatalytic hydrolysis reaction (reaction conditions: 1×1cm). 2 The catalyst, with a scan rate of 5 mV / s, 90% compensation, and 50 mL of KOH (1 M) aqueous solution as the electrolyte, shows that the catalyst can achieve 10 mA cm⁻¹ at a voltage of 1.438 V. -2 The current density. The structure and catalytic performance of CC@M-trimental / PBA prepared in other examples are basically similar to those in this example.

[0035] Example 3

[0036] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.1745 g), Fe(NO3)3·9H2O (0.7452 g), and Co(NO3)3·6H2O (0.1746 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Ni1Fe3Co1 / PBA material with a porous nanosheet structure.

[0037] Example 4

[0038] Take 1×1cm 2In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.1745 g), Fe(NO3)3·9H2O (0.2484 g), and Co(NO3)2·6H2O (0.5238 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Ni1Fe1Co3 / PBA material with a porous nanosheet structure.

[0039] Example 5

[0040] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing 0.6543 g of Ni(NO3)2·6H2O and 0.3105 g of Fe(NO3)3·9H2O. Under a three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Ni3Fe1 / PBA material with a three-dimensional porous nanosheet structure.

[0041] Example 6

[0042] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.5234 g), Zn(NO3)2·6H2O (0.1785 g), and Co(NO3)2·6H2O (0.1746 g). Under a three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Co1Ni3Zn1 / PBA material with a three-dimensional porous nanosheet structure.

[0043] Example 7

[0044] Take 1×1cm 2In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.5234 g), Cu(NO3)2·3H2O (0.1450 g), and Co(NO3)2·6H2O (0.1746 g). Under a three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Co1Ni3Cu1 / PBA material with a three-dimensional porous nanosheet structure.

[0045] Example 8

[0046] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.5234 g), NaWO4 (0.1763 g), and Co(NO3)2·6H2O (0.1746 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Co1Ni3W1 / PBA material with a three-dimensional porous nanosheet structure.

[0047] Example 9

[0048] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode clamp as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Ni(NO3)2·6H2O (0.5234 g), Na2MoO4 (0.09716 g), and Fe(NO3)2·9H2O (0.2484 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Fe1Ni3Mo1 / PBA material with a three-dimensional multi-level nanosheet structure.

[0049] Example 10

[0050] Take 1×1cm 2In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing 0.6543 g of Ni(NO3)2·6H2O and 0.1214 g of Na2MoO4. Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Ni3Mo1 / PBA material with a three-dimensional multi-level nanosheet structure.

[0051] Example 11

[0052] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing 0.218 g of Ni(NO3)2·6H2O and 0.3643 g of Na2MoO4. Under this three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Ni1Mo3 / PBA material with a three-dimensional multi-level nanosheet structure.

[0053] Example 12

[0054] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing Fe(NO3)3·9H2O (0.9315 g) and Co(NO3)2·6H2O (0.1746 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Co1Fe3 / PBA material with a three-dimensional porous nanosheet structure.

[0055] Example 13

[0056] Take 1×1cm 2 In Example 1, the CC@PS clamp is used as the working electrode on the Pt electrode clamp, and the Ag / AgCl electrode...

[0057] The reference electrode and the working electrode were both placed in a 50 mL solution of deionized water containing Fe(NO3)3·9H2O (0.9315 g) and MgSO4·7H2O (0.1479 g). Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Mg1Fe3 / PBA material with a three-dimensional porous nanosheet structure.

[0058] Example 14

[0059] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode. All electrodes were placed in a 50 mL solution of deionized water containing 0.5234 g of Ni(NO3)2·6H2O and 0.2183 g of Co(NO3)2·6H2O. Under a three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean and dried in an oven at 60 °C. The resulting sample was the CC@M-Co1Ni3 / PBA material with a three-dimensional porous nanosheet structure.

[0060] Example 15

[0061] Take 1×1cm 2 In Example 1, the CC@PS electrode was clamped onto a Pt electrode holder as the working electrode, an Ag / AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in a 50 mL solution of Co(NO3)2·6H2O (0.4365 g) and deionized water. Under the three-electrode system, a voltage of -2.5 V vs. SCE was applied, and the electrodeposition time was 1200 s. After deposition, the carbon cloth was rinsed clean, dried in an oven at 60 °C, and then vertically immersed in 0.0328 g of 2-methylimidazole. After standing for 12 h, the resulting sample was the CC@M-Co(OH)2-ZiF67 material with a three-dimensional multi-level nanosheet structure.

Claims

1. A self-supporting trimetallic CC@M-trimental / PBA material of the formula: 1 and a method for its preparation, characterized in that, Comprising the following steps: (1) The conductive substrate (1x1cm 2 ) was activated, then placed in a polystyrene microsphere solution and allowed to stand for 24h. It was washed with ethanol and ultrapure water for 5-6 times, and dried at 60°C to obtain CC@PS. (2) Dissolve two or three metal salts in deionized water and ultrasonically disperse to obtain a mixed solution; (3) Add the CC@PS material obtained in step (1) to the deionized aqueous solution with two or three metal salts, and perform electrodeposition under a three-electrode system, and after washing and drying, the CC@PS-trimental material is obtained; (4) Take 0.6M PBA 20ml and immerse the CC@PS-trimental material obtained in step (3) upside down, and after washing and drying, the CC@PS-trimental / PBA is obtained. (5) Take the CC@PS-trimental / PBA material obtained in step (4) and immerse it in a toluene solution to dissolve the PS, and after washing and drying, the CC@M-trimental / PBA is obtained.

2. The production method according to claim 1, characterized by, The conductive substrate in step (1) is carbon cloth.

3. The preparation method according to claim 1, characterized in that, The electrodeposition voltage in step (3) is -2.5-1V, and the electrodeposition time is 1200s.

4. The method of claim 1, wherein, The two or three metal salts in step (3) are Co(NO3)2·6H2O, Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Fe(NO3)3·9H2O, Zn(NO3)2·6H2O, Na2MoO4, MgSO4·7H2O, and NaWO4, and two or three of them are selected for reaction.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the three metal salts in step (3) is (3-1-1):(1-3-1):(1-1-3), and the salt solution concentration is 0.06M.

6. The method of claim 1, wherein, In the three-electrode system in step (3), the reference electrode is Ag / AgCl electrode, the counter electrode is carbon rod, and the working electrode is CC@PS material.

7. The preparation method according to claim 1, characterized in that, The soaking PBA time in step (4) is 1h.

8. The method of claim 1, wherein, The PS dissolving time in step (5) is 24h.

9. A self-supporting three-metal CC@M-trimental / PBA material prepared by the preparation method of any one of claims 1-8.

Images