CN117210849A - Electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater and preparation method thereof - Google Patents

Electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater and preparation method thereof Download PDF

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CN117210849A
CN117210849A CN202310962213.1A CN202310962213A CN117210849A CN 117210849 A CN117210849 A CN 117210849A CN 202310962213 A CN202310962213 A CN 202310962213A CN 117210849 A CN117210849 A CN 117210849A
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formaldehyde
electrode material
electrode
foam
hydrogen
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符显珠
叶淳懿
骆静利
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Shenzhen University
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Shenzhen University
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Abstract

The invention discloses an electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing waste water and a preparation method thereof, wherein the preparation method comprises the following steps: soaking a PU foam substrate in an activating agent for activation treatment, taking out the PU foam substrate, and then immersing the PU foam substrate in electroless copper plating solution for plating to obtain an electroless copper plating foam material, which is named as PU@Cu; electrochemical oxidation and reduction treatment are carried out on the electroless copper foam material, and PU@Cu/Cu of a nanowire array structure is obtained, namely the electrode material for producing hydrogen by electrolysis of wastewater and removing dirt at the same time. The PU@Cu/Cu prepared by the method shows stronger electrocatalytic formaldehyde oxidation performance, and reaches 10mA cm in test ‑2 Overpotential reduction required for current density0.2V. Compared with the electrolytic water without formaldehyde, the PU@Cu/Cu overpotential is reduced by 1.49V; when the PU@Cu/Cu is used for removing formaldehyde in the electroless copper plating waste liquid, the electrocatalytic reaction and the electroless plating reaction can occur simultaneously, so that the formaldehyde removal efficiency is greatly improved, and 99.9% of formaldehyde is removed after 50 minutes.

Description

Electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater and preparation method thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to an electrode material for producing hydrogen by electrolyzing waste water and removing dirt at the same time and a preparation method thereof.
Background
Hydrogen is an important raw material for the ammonia synthesis industry and is considered as a promising clean energy carrier due to its high energy density. Currently, hydrogen is produced from fossil fuels mainly using low cost means, but this production is not environmentally friendly and sustainable. The use of renewable clean energy sources for electrolysis of water is expected to be a main way of producing hydrogen in the future, but more electric energy is consumed, and the problem of excessive cost still exists at present. Electrolysis of water produces Hydrogen (HER) at the cathode and low value Oxygen (OER) at the anode, which if mixed inadvertently would present an explosion risk and present a safety concern. In addition, OER thermodynamics and kinetics are slow, limiting hydrogen evolution from the cathode, resulting in high energy consumption.
On the other hand, the fresh water resource is limited, and the wastewater needs to be purified, for example, the wastewater can be electrolyzed to produce hydrogen and simultaneously decontaminated, so that multiple purposes can be achieved.
Disclosure of Invention
The invention aims to provide an electrode material for hydrogen production by electrolysis of wastewater and simultaneous decontamination and a preparation method thereof, and solves the problem of high hydrogen production energy consumption by electrolysis of water.
The technical scheme of the invention is as follows:
the preparation method of the electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing waste water comprises the following steps:
soaking a PU foam substrate in an activating agent for activation treatment, taking out the PU foam substrate, and then immersing the PU foam substrate in electroless copper plating solution for plating to obtain an electroless copper plating foam material, which is named as PU@Cu;
taking the electroless copper foam material as a working electrode, and performing electrochemical oxidation treatment to obtain PU@Cu/Cu (OH) 2 An array electrode;
taking out the PU@Cu/Cu (OH) 2 And (3) after the array electrode is subjected to cleaning treatment, carrying out reduction treatment to obtain the nano array porous copper electrode material, namely PU@Cu/Cu, namely the electrode material for producing hydrogen by electrolyzing wastewater and removing dirt at the same time.
The preparation method of the electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing waste water comprises the steps of preparing the electroless copper plating solution from sodium hydroxide, potassium sodium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylenediamine tetraacetate, potassium ferrocyanide trihydrate and formaldehyde. The predetermined temperature is 20-80 ℃.
The invention relates to an electrode material for producing hydrogen and removing formaldehyde by electrolyzing chemical plating wastewater, which is prepared by adopting the preparation method of the electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing wastewater.
The beneficial effects are that: according to the invention, an electroless copper plating mode is used, a PU foam is used as a base material to prepare an electroless copper plating foam material (PU@Cu), further electrochemical oxidation and reduction are carried out on the electroless copper plating foam material to obtain a nano array porous copper electrode material (PU@Cu/Cu), and an electric double layer method proves that the PU@Cu/Cu has three times of the electrochemical active surface area of the PU@Cu. Compared with PU@Cu, the PU@Cu/Cu shows stronger electrocatalytic formaldehyde oxidation performance, and reaches 10mA cm in test -2 The overpotential required for the current density is reduced by 0.2V. Compared with the formaldehyde-free electrolyzed water, the PU@Cu/Cu overpotential is reduced by 1.49V, and the product analysis proves that the anode product is changed from low-value oxygen to high-value hydrogen and formic acid. The invention also uses foam nickel as a cathode to construct a low-cost noble metal-free electrolytic cell device, and tests show that the electrolytic cell device is 100mA cm -2 When the current density is carried out, the energy consumption of the device is only 35 percent of the theoretical energy consumption of the electrolyzed water. Finally, the performance of PU@Cu/Cu on removing formaldehyde in sewage is tested by using KOH/HCHO electrolyte and electroless copper plating solution respectively. Wherein, when formaldehyde in the electroless copper plating waste liquid is removed, the electrocatalytic reaction and the electroless plating reaction can occur simultaneously, thereby greatly improving the formaldehyde removal efficiency and removing 99.9% of formaldehyde after 50 minutes.
Drawings
FIG. 1 is a flow chart of a method for preparing an electrode material for producing hydrogen and simultaneously decontaminating by electrolyzing wastewater.
A is a PU foam metallographic microscope image in FIG. 2; b is a metallographic microscope image of PU@Cu; c is an SEM image of PU@Cu; d and e are PU@Cu/Cu (OH) 2 Under different magnificationSEM images of (2); f is PU@Cu/Cu (OH) 2 A TEM image of (a); g and h are SEM images of PU@Cu/Cu at different magnifications; i is a TEM image of PU@Cu/Cu.
In FIG. 3, a is the LSV curve of PU@Cu/Cu, PU@Cu and commercial nickel foam in 0.5M KOH+0.1M HCHO, b is the LSV curve of PU@Cu/Cu with and without 0.1M HCHO, c is the I-T curve of PU@Cu/Cu at 0.5V vs. RHE for 5 hours, and d is the LSV curve of PU@Cu/Cu with and without 0.1M HCOOK.
FIG. 4 a is a graph of PU@Cu/Cu at 5, 20, 40, 60, 80, 100mV s -1 And b is PU@Cu at 5, 20, 40, 60, 80, 100mV s -1 D is an electric double layer capacitance comparison graph of PU@Cu/Cu and PU@Cu obtained after the CV curve is processed.
In fig. 5, a is an anode liquid phase ion chromatographic curve and a formate ion faraday efficiency, b is anode hydrogen "faraday efficiency", and c is a theoretical calculation comparison of collecting cathode and anode hydrogen by a water and gas drainage method.
Fig. 6 a is a schematic diagram of bipolar hydrogen production electrolyzer device, b is an electrolyzer device test LSV curve, c is a graph of energy consumption required to produce hydrogen per cubic meter using the device and is compared with theoretical energy consumption.
In FIG. 7, a is the formaldehyde content of 0.5M KOH+0.1M HCHO electrolyte before and after the test, the upper right-hand corner illustration is the I-T curve during the test, and the background is the ion chromatographic curve; b is the formaldehyde content in the plating solution before and after the test, and the upper right corner inset is the I-T curve during the test.
Detailed Description
The invention provides an electrode material for producing hydrogen by electrolyzing waste water and removing dirt at the same time and a preparation method thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
FIG. 1 is a flow chart of a preparation method of an electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing waste water, which comprises the following steps:
s10, providing electroless copper plating solution;
s20, soaking the PU foam substrate in an activating agent for activation treatment, taking out the PU foam substrate, and then immersing the PU foam substrate in electroless copper plating solution for plating to obtain an electroless copper plating foam material, namely PU@Cu;
s30, performing electrochemical oxidation treatment on the electroless copper foam material at the position of the electrode with the potential of 0V vs. Hg/HgO by taking the electroless copper foam material as a working electrode, a platinum sheet electrode as a counter electrode and an Hg/HgO electrode as a reference electrode and NaOH as an electrolyte to obtain PU@Cu/Cu (OH) 2 An array electrode;
s40, taking out the PU@Cu/Cu (OH) 2 After the array electrode is cleaned, PU@Cu/Cu (OH) is adopted 2 The array electrode is used as a working electrode, the platinum sheet electrode is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, KOH is used as electrolyte, and the PU@Cu/Cu (OH) is applied to the position of the electrode with the potential of-3V vs 2 The array electrode is subjected to reduction treatment to prepare the nano array porous copper electrode material which is named as PU@Cu/Cu, namely the electrode material for producing hydrogen by electrolyzing waste water and removing dirt at the same time.
According to the invention, an electroless copper plating mode is used, a PU foam is used as a base material to prepare an electroless copper plating foam material (PU@Cu), further electrochemical oxidation and reduction are carried out on the electroless copper plating foam material to obtain a nano array porous copper electrode material (PU@Cu/Cu), and an electric double layer method proves that the PU@Cu/Cu has three times of the electrochemical active surface area of the PU@Cu. Compared with PU@Cu, the PU@Cu/Cu shows stronger electrocatalytic formaldehyde oxidation performance, and reaches 10mA cm in test -2 The overpotential required for the current density is reduced by 0.2V. Compared with the formaldehyde-free electrolyzed water, the PU@Cu/Cu overpotential is reduced by 1.49V, and the product analysis proves that the anode product is changed from low-value oxygen to high-value hydrogen and formic acid. The invention also uses foam nickel as a cathode to construct a low-cost noble metal-free electrolytic cell device, and tests show that the electrolytic cell device is 100mA cm -2 When the current density is carried out, the energy consumption of the device is only 35 percent of the theoretical energy consumption of the electrolyzed water. Finally, the performance of PU@Cu/Cu on removing formaldehyde in sewage is tested by using KOH/HCHO electrolyte and electroless copper plating solution respectively. Wherein, when formaldehyde in the electroless copper plating solution is removed, electrocatalytic reaction is carried outThe chemical plating reaction and the chemical plating reaction can be carried out simultaneously, so that the formaldehyde removal efficiency is greatly improved, and 99.9% of formaldehyde is removed after 50 minutes.
The nano-array porous copper electrode material is used for electrocatalytic formaldehyde oxidation reaction, the reaction is coupled with electrolyzed water, and product analysis shows that the invention obtains a bipolar hydrogen-producing high-efficiency hydrogen production system, and meanwhile, the liquid phase product of the anode is also high-value formic acid; electrochemical tests prove that when the system generates 1m3 of hydrogen, the required energy consumption is only 35% of the theoretical energy consumption of the electrolyzed water. In addition, the invention also explores the use of the nanowire array porous foam copper electrode for removing formaldehyde in formaldehyde-containing wastewater, and the result proves that the nanowire array porous foam copper electrode can effectively purify formaldehyde in the formaldehyde-containing wastewater. This shows that the invention not only improves the hydrogen production efficiency, but also promotes the conversion from formaldehyde-containing wastewater to formate with high added value, and improves the economic benefit.
Compared with other preparation methods and other activators, the pure copper activator provided by the invention uses deionized water as a solvent in preparation, does not use toxic and harmful chemicals, has a low reaction temperature, and greatly reduces the preparation cost and pollution of the pure copper activator; PVP (polyvinylpyrrolidone) added in the preparation process plays a main role in stabilizing; CTAB (cetyltrimethylammonium bromide) is used as a surfactant, so that the stability is achieved, and meanwhile, the wettability of nano particles can be ensured, and the nano particles can grow uniformly; the added lactic acid is used for adjusting the pH value, so that the reaction solution is in an acidic environment, and sodium hypophosphite can be assisted to reduce copper ions.
In some embodiments, the predetermined temperature is 70-80 ℃, but is not limited thereto. As an example, the predetermined temperature may be 70 ℃, 72 ℃, 75 ℃, 77 ℃, 80 ℃, or the like.
In some embodiments, the electroless copper plating solution includes sodium hydroxide, potassium sodium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylenediamine tetraacetate, potassium ferrocyanide trihydrate, and formaldehyde.
In some embodiments, an electrode material for producing hydrogen and removing dirt from electrolytic wastewater is also provided, and the electrode material for producing hydrogen and removing dirt from electrolytic wastewater is prepared by the preparation method of the electrode material.
The invention is further illustrated by the following examples:
example 1
A preparation method of a nano-array porous copper electrode material PU@Cu/Cu, as shown in figure 2,
preparing a chemical plating foam copper electrode material PU@Cu: cleaning PU foam with deionized water, soaking in a pure copper activator for activation at room temperature for 10 minutes, taking out the activation solution which is washed by the deionized water and is removed from the surface, immersing the PU foam in an electroless copper plating solution at 55 ℃ for plating, and setting the plating time to be 1 hour to obtain an electroless copper foam material (porous copper electrode) which is marked as PU@Cu, wherein the formula of the electroless copper plating solution is shown in table 1;
TABLE 1 electroless plating solution formulation
Composition of the components Concentration of
Sodium hydroxide 2-8g L -1
Potassium sodium tartrate tetrahydrate 3-10g L -1
Copper sulfate pentahydrate 1-15g L -1
Ethylene diamine tetraacetic acid disodium salt 3-15g L -1
Potassium ferrocyanide trihydrate 0.1-1g L -1
Formaldehyde 10-100mL L -1
Preparation of nano-array porous copper electrode material PU@Cu/Cu: taking PU@Cu as a working electrode, and taking 0.3M NaOH as electrolyte to perform electrochemical oxidation for 10-600 seconds to obtain PU@Cu/Cu (OH) 2 Array electrodes. After the electrode was removed and rinsed with deionized water, PU@Cu/Cu (OH) was replaced in 0.5M KOH 2 Reducing for 0.1-1 hour to obtain the nano array porous copper electrode material PU@Cu/Cu.
As shown in fig. 2 a and b, the PU foam skeleton is covered with a bright copper coating after electroless plating, and SEM images of fig. 2 c demonstrate the integrity and uniformity of the coating, and pu@cu obtained after electroless copper plating for 1 hour meets the requirements for preparation in the next step. After electrochemical oxidation is carried out on PU@Cu, the surface of the copper plating layer is oxidized and a copper hydroxide array with a nanowire structure grows, so that PU@Cu/Cu (OH) is obtained 2 The electrode, as shown in fig. 2 d, was like grass under low-power SEM. From PU@Cu/Cu (OH) 2 High magnification SEM and TEM images of the electrodes (e, f in fig. 2) can see that the array is made up of elongated smooth nanowires with widths of about 40-60 nm. Reduction PU@Cu/Cu (OH) 2 The electrode obtained is PU@Cu/Cu electrode, and g-i in FIG. 2 shows high-power SEM and TEM images of the electrode, so that smooth nano wires become rugged nano rods after reduction, and the width of the nano rods is about 40-60 nm, therefore, the PU@Cu/Cu surface in the g in FIG. 2 is compared with the PU@Cu/Cu (OH) 2 Coarser.
The electrocatalytic formaldehyde oxidation at low potential is a key to bipolar hydrogen production, so this example evaluates the performance of the prepared material in electrocatalytic formaldehyde oxidation under 0.5M KOH alkaline conditions. As shown in fig. 3 a, this example compares the formaldehyde oxidation properties of pu@cu/Cu, pu@cu with commercial nickel foam in an electrolyte containing 0.1M formaldehyde. It can clearly be seen that commercial nickel foam is only largeThe oxidation performance of formaldehyde can be shown at a high potential of 1.2Vvs. RHE, and the oxidation of formaldehyde can be carried out at a low potential of less than 0.6V vs. RHE by PU@Cu/Cu and PU@Cu. Wherein PU@Cu/Cu has optimal performance (10 mA cm -2 @0.12V vs. RHE), PU@Cu times (10 mA cm -2 @0.32V vs. RHE) and the maximum current density of PU@Cu cannot exceed 34mA cm -2 . In fig. 5 b is shown the LSV curve of pu@cu/Cu in both the containing and the formaldehyde free electrolyte. When formaldehyde is not contained, PU@Cu/Cu catalyzes OER reaction to reach 10mA cm -2 The current density required potential is 1.61v vs. rhe, the product is low value oxygen. After formaldehyde is added, PU@Cu/Cu catalyzes formaldehyde oxidation reaction to reach 10mA cm -2 The potential of the current density is only 0.12V vs. RHE, which is reduced by 1.49V, and the product is high-value formate and hydrogen. In the formaldehyde-containing electrolyte, the potential was 0.5v vs. rhe, and the stability test was performed for pu@cu/Cu for 5 hours (as shown in fig. 3 c). After the current density was decreased, 300. Mu.L of formaldehyde was added, the current density was recovered and decreased at a similar rate, indicating good stability of PU@Cu/Cu. To verify the selective oxidation of formaldehyde by pu@cu/Cu we tested the LSV curve of pu@cu/Cu at low potential in an electrolyte containing and not containing 0.1M potassium formate (as shown in fig. 3 d). We can clearly see that pu@cu/Cu has only a Cu oxidation peak at low potential, and there is no oxidation to potassium formate.
To investigate why PU@Cu/Cu, which has been subjected to electrochemical oxidation and reduction, performs better than PU@Cu, we compared their electrochemically active surface areas using the double layer method. As shown in fig. 4 a-c, the double layer capacitance of pu@cu/Cu is more than three times that of pu@cu, which is more than twice that of pu@cu, meaning that its ECSA is higher than that of pu@cu, which is why its performance is better than that of pu@cu.
To verify the liquid and gas phase products of the anode end of pu@cu/Cu in the catalytic formaldehyde oxidation process and calculate their faraday efficiencies, we quantitatively analyzed the liquid and gas phase products using ion chromatography and gas chromatography in a three electrode system of an H-shaped electrolytic cell. The ion chromatography time-signal curve for the anodic liquid phase test at 0.7vvs.rhe is shown in figure 5 a along with the calculated formate ion faraday efficiency. It can be seen that as the amount of electricity tested increases, the peak intensity corresponding to formate ions also increases. And the Faraday efficiency of formate ions under three electric quantities is 100% on average through calculation, which proves that formate ions are the only liquid-phase product of the anode end of PU@Cu/Cu in the catalytic formaldehyde oxidation process. It is noted that it has been reported that aldehydes generate the corresponding acid under alkaline conditions by non-faradic processes, and that we have subtracted the concentration of formic acid generated by the non-faradic effect when calculated in the figure by testing the formic acid generated during the same time without applying current. As shown in fig. 5 b, we tested the "faraday efficiencies" of hydrogen generation at the anode at multiple potentials, all very close to 100%, confirming that the gas phase product at the anode end is hydrogen. In addition, we also collected the gas of both the cathode and the anode by using the water and gas drainage method (as shown in fig. 5 c), and can see that the volumes of the hydrogen generated by the cathode and the anode are similar, and the theoretical curve (formula 5.3) calculated when the faraday efficiency is assumed to be 100% is fit, which indicates that the faraday efficiency of the hydrogen generated by both the cathode and the anode is 100%. In fact, the anode generates hydrogen without the participation of electrons, so that in the system, the total Faraday efficiency of bipolar hydrogen generation reaches 200%.
Theoretical hydrogen generation occurs at a faraday efficiency of 100%:
n[mole] theoretically produced ＝Q/(n×F)(5.3)
noble metals, represented by Pt, are easily oxidized to carbon dioxide completely when aldehydes are oxidized, whereas in this experiment, pu@cu/Cu electrocatalytically oxidize formaldehyde to formic acid with electron selectivity up to 100% and no carbon dioxide is generated. Meanwhile, in aldehyde oxidation at a high potential, H atoms in aldehyde groups tend to be oxidized into water molecules, rather than being released as hydrogen gas as in the present experiment. In this reaction path, HCHO is first hydrated to CH 2 (OH) 2 And dissociate into CH 2 (OH)O - Anion, further absorbs energy and dehydrogenates to CH (OH) O - Intermediate, finally oxidized to HCOOH. This is followed by oxidation of formic acid to form on the Cu (111) crystal faceCarbon dioxide requires a free energy of up to 0.41eV, so this reaction does not occur when formaldehyde oxidation at low potential is carried out on pu@cu. The free energy required to combine two hydrogen atoms into hydrogen is lower than that required to oxidize the hydrogen atoms to water. In summary, PU@Cu/Cu is a suitable material for electrocatalytic oxidation of formaldehyde to high value chemicals formic acid and hydrogen.
As shown in fig. 6 a, the low-potential formaldehyde oxidation is combined with a cathode HER, and the PU@Cu/Cu is taken as an anode, and commercial foam nickel is taken as a cathode, so that the low-cost bipolar hydrogen production electrolytic cell device without noble metal is formed. Unlike the traditional electrolyzer which only produces hydrogen at the cathode, the electrolyzer system produces hydrogen at the cathode and anode simultaneously, thus solving the problem that the traditional electrolyzed water needs to separate anode oxygen. Meanwhile, formate produced by the anode is also a high-value chemical and widely used in leather, pesticides, medicines, dyes and rubber industries. FIG. 6 b shows the formaldehyde oxidation polarization curve after the cell is assembled, notably, the initial voltage of bipolar hydrogen is below 0.1V, achieving 100mA cm -2 The current density of (2) only needs 0.66V, which is far lower than the voltage of the traditional formaldehyde electrooxidation coupling hydrogen production system. In addition, we also compare bipolar hydrogen production systems with traditional electrolyzed water production of 1m 3 The energy consumption required for hydrogen (as shown in figure 6 c). Production of 1m by traditional electrolyzed water 3 The hydrogen at least needs 2.94 kW.h electricity, and our bipolar hydrogen production system realizes 100mA cm -2 The current density of the catalyst is only about 0.79 kW.h, and the energy consumption is reduced by more than 75 percent.
Formaldehyde is a common pollutant in industrial wastewater and is harmful to human bodies and the environment. The low potential oxidation of formaldehyde by pu@cu/Cu can convert it to valuable formic acid and hydrogen. If the process can be carried out in industrial wastewater, the industrial wastewater is changed into valuable. To explore whether this concept is viable, we characterized the performance of pu@cu/Cu for formaldehyde removal in solution. As shown in fig. 7 a, we first tested in a conventional 50ml 0.5M KOH/0.1M HCHO electrolyte, with pu@cu/Cu for the anode, platinum sheet electrode for the cathode, hg/HgO electrode for the reference electrode, test potential 0.7v vs. rhe. From the I-T curve, it can be seen that after about 46 minutes (2760 s) the current drops off, where we take the electrolyte for ion chromatography testing. From the above analysis, it is clear that oxidation of formaldehyde in this environment will all be converted to formic acid, so we can estimate the residual formaldehyde content of the solution from the formic acid content. The test results showed that PU@Cu/Cu removed about 60% of the formaldehyde in the electrolyte over a period of 46 minutes. To get closer to the actual production environment, we used electroless copper plating waste solution (52.375 mL) containing formaldehyde to simulate industrial formaldehyde-containing waste water. In the test, PU@Cu/Cu is used for the anode, PU@Cu is used for the cathode, hg/HgO is used as a reference electrode, and the test potential is 0V vs. Meanwhile, the characterization method of the formaldehyde content is changed into an acetylacetone spectrophotometry method. The electroless copper plating solution after 50 minutes of I-T test was taken to check the formaldehyde concentration, and as can be seen in FIG. 7 b, the system removed almost all of the formaldehyde from the solution over a period of 50 minutes. It is notable that the electroless copper plating reaction on the anode material PU@Cu/Cu and the cathode material PU@Cu also occurs simultaneously, and the electroless copper plating reaction is also removing formaldehyde, in addition to the reaction of PU@Cu/Cu electrocatalytic formaldehyde oxidation. The method is a high-value system for removing formaldehyde to generate hydrogen and formic acid through multiple reactions, and electroplating and electroless copper plating are carried out on cathode materials, so that the method has certain application potential in the future.
In summary, the invention prepares the foam copper material PU@Cu by taking PU foam as a base material, and carries out further electrochemical oxidation and reduction on the foam copper material PU@Cu to obtain PU@Cu/Cu with a nanowire array structure, and the electric double layer method proves that the PU@Cu/Cu has three times of electrochemical active surface area of the PU@Cu. Compared with PU@Cu, the PU@Cu/Cu shows stronger electrocatalytic formaldehyde oxidation performance, and reaches 10mA cm in test -2 The overpotential required for the current density is reduced by 0.2V. Compared with the formaldehyde-free electrolyzed water, the PU@Cu/Cu overpotential is reduced by 1.49V, and the product analysis proves that the anode product is changed from low-value oxygen to high-value hydrogen and formic acid. The invention also uses foam nickel as a cathode to construct a low-cost noble metal-free electrolytic cell device, and tests show that the electrolytic cell device is 100mA cm -2 The energy consumption of the device can be only 25% of the theoretical energy consumption of the electrolyzed water when the current density is carried out. Finally, the inventionThe performance of PU@Cu/Cu for removing formaldehyde in sewage was tested by using KOH/HCHO electrolyte and electroless copper plating solution respectively. Wherein, when formaldehyde in the electroless copper plating waste liquid is removed, the electrocatalytic reaction and the electroless plating reaction can occur simultaneously, thereby greatly improving the formaldehyde removal efficiency and removing 99.9 percent of formaldehyde after 50 minutes
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (5)

1. The preparation method of the electrode material for producing hydrogen and removing dirt simultaneously by electrolyzing waste water is characterized by comprising the following steps:
soaking a PU foam substrate in an electroless plating activating agent for activating treatment, taking out the PU foam substrate, and then immersing the PU foam substrate in electroless copper plating solution for plating to obtain an electroless plating foam copper material, which is marked as PU@Cu;
electrochemical oxidation treatment is carried out by taking the electroless copper foam material as a working electrode to obtain PU@Cu/Cu (OH) 2 An array electrode;
taking out the PU@Cu/Cu (OH) 2 The array electrode is subjected to reduction treatment after being cleaned, and the nano array porous copper electrode material is marked as PU@Cu/Cu, namely the electrode material for producing hydrogen by electrolyzing waste water and removing dirt at the same time.
2. The method for producing an electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater according to claim 1, wherein the electroless copper plating solution comprises sodium hydroxide, potassium sodium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylenediamine tetraacetate, potassium ferrocyanide trihydrate and formaldehyde.
3. The method for producing an electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater according to claim 2, wherein the predetermined temperature is 20 to 80 ℃.
4. The method for preparing the electrode material for producing hydrogen and removing pollution simultaneously by electrolyzing waste water as claimed in claim 1, wherein the PU@Cu is treated to obtain the nano copper array electrode.
5. An electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater, which is characterized by being prepared by the method for preparing the electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater according to any one of claims 1 to 3.
CN202310962213.1A 2023-08-01 2023-08-01 Electrode material for hydrogen production and simultaneous decontamination by electrolysis of wastewater and preparation method thereof Pending CN117210849A (en)

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