CN114908374A - Copper-cerium hydroxide electrocatalyst prepared by in-situ dynamic reconstruction, method and application - Google Patents
Copper-cerium hydroxide electrocatalyst prepared by in-situ dynamic reconstruction, method and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a copper-cerium hydroxide electrocatalyst by in-situ dynamic reconstruction, which comprises the following steps of: a. putting the copper substrate in ethanol, ultrasonically cleaning, and drying in vacuum; b. depositing cerium hydroxide on a copper substrate by adopting an electrodeposition method; c. reconstituting the cerium hydroxide-deposited copper substrate in situ in an electrolyte to have a substantial amount of Cu-Ce (OH) x A catalyst at the interface site. The preparation method is simple and easy to implement, and can realize large-scale production. The electrocatalyst prepared by the method of the invention shows excellent catalytic performance in nitrate radical reduction reaction, and has high catalytic activity, ammonia selectivity and stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a copper-cerium hydroxide electrocatalyst prepared by in-situ dynamic reconstruction, a method and application thereof.
Background
Human activities have created an imbalance in the global nitrogen cycle over the past decades. FossilCombustion of fuels, overuse of fertilizers, and discharge of nitrogen-rich industrial wastewater can produce large amounts of nitrogen oxides, resulting in increased nitrate concentrations in surface and ground water. Nitrate contamination can have many adverse effects on ecosystem and human health. Therefore, it is necessary to remove and reuse the excess nitrate in the water to restore the nitrogen cycle. Currently, a variety of techniques are available for removing nitrates from water, such as reverse osmosis, ion exchange, biological denitrification, catalysis, and photocatalytic reduction. However, these solutions have several limitations, including high cost, the need for secondary treatment, and slow kinetics. Electrocatalytic nitrate reduction (NO) 3 - RR) can convert NO using electrons as a green reducing agent 3 - Conversion to valuable ammonia (NH) 3 ) It can be used as fertilizer, chemical raw material and fuel. Electrocatalytic technology represents a promising technology for the reduction of nitrate to ammonia.
Various catalysts, including metals, metal oxides, metal phosphides and other compounds have been developed for NO 3 - And (3) RR. Of the catalysts studied, copper-based materials have very high catalytic performance, especially in alkaline solutions (e.g., 1mol/L KOH). However, under neutral conditions, the activity and selectivity of ammonia synthesis are still insufficient due to unfavorable catalyst interfaces. NO 3 - RR process is slow in kinetics with eight electron transfers, and side reactions typically occur due to the scaling of reaction intermediates. To date, achieving high activity, selectivity, and efficiency ammonia synthesis simultaneously in neutral systems remains a significant challenge. Previous studies have focused on doping, alloying, crystal plane conditioning and defect introduction to improve NO 3 - Performance of the RR. The preparation process of the catalyst related to the methods usually needs conditions such as high temperature, solvent heat and the like, the preparation method is complex, the cost is high, most of products are powder catalysts, and industrial production is difficult to realize.
The literature (Energy Environmental Science 2021,14, 4989-.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a copper-cerium hydroxide electrocatalyst prepared by in-situ dynamic reconstruction, a method and application thereof.
In the invention, Cu-Ce (OH) is constructed on a copper substrate by adopting an electrochemical deposition method x A catalyst. In electrodeposition processes, higher valent copper species such as Cu 2 Cl(OH) 3 ,Cu 2 O and Ce (OH) x Are deposited together on the surface of the copper substrate. Cu by in situ dynamic restructuring in electrochemical reactions 2 Cl(OH) 3 And Cu 2 O is reduced to metallic copper and is fragmented, forming a large amount of Cu-Ce (OH) x A heterogeneous interface.
A method for preparing a copper-cerium hydroxide electrocatalyst through in-situ dynamic reconstruction comprises the following steps: a. putting the copper substrate in ethanol, ultrasonically cleaning, and vacuum drying; b. depositing cerium hydroxide on a copper substrate in a cerium salt solution by an electrodeposition method; c. reconstituting the cerium hydroxide-deposited copper substrate in situ in an electrolyte solution to have a substantial amount of Cu-Ce (OH) x A catalyst at the interface site.
Further, in the preparation method of the copper-cerium hydroxide electrocatalyst, the copper substrate used in the step a comprises one of copper foam, a copper sheet and a copper mesh.
In the preparation method of the copper-cerium hydroxide electrocatalyst, the cerium salt solution used in the electrodeposition in the step b is a mixed solution of cerium nitrate and other electrolytes, such as potassium chloride or sodium chloride.
In the preparation method of the copper-cerium hydroxide electrocatalyst, the concentration of a cerium nitrate solution used in the electrodeposition in the step b is 5-100mmol/L, and the concentration of potassium chloride or sodium chloride is 50-500 mmol/L.
Wherein, the preparation method of the copper-cerium hydroxide electrocatalyst comprises the following stepsThe electro-deposition in the step b adopts a constant current mode, and the current density is 0.5-5.0mA/cm 2 The deposition time is 5-70 min.
In the preparation method of the copper-cerium hydroxide electrocatalyst, the electrolyte used for in-situ reconstruction in the step c is 0.1mol/L potassium sulfate solution or sodium sulfate solution, and the electrolyte contains 50-500 mg/L potassium nitrate or sodium nitrate.
In the preparation method of the copper-cerium hydroxide electrocatalyst, a constant potential electrolysis mode is adopted in the in-situ reconstruction in the step c, the potential is-1.1 to-1.5V vs. Ag/AgCl, and the electrolysis time is 0.5 to 3 hours.
The invention has the beneficial effects that:
the method has the advantages of low price of raw materials, no need of high temperature or solvothermal process, obtaining of the self-supporting electrocatalyst through electrodeposition-in-situ reconstruction, no need of adhesive, and reconstruction of the obtained Cu-Ce (OH) x The electrocatalyst has a large number of interface sites and excellent nitrate radical reduction catalytic performance in 100mg/L potassium nitrate (in NO) 3 - Calculated from-N) NO 3 - The conversion rate of (3) is up to 100.0%, NH 3 Selectivity 97.8%, NH 3 The faraday efficiency was 99.2%. The method is simple and convenient to operate and easy to realize industrial production.
Drawings
FIG. 1 is the copper-cerium hydroxide (Cu-Ce (OH) prepared by in situ dynamic reconstitution in example 1 x ) Scanning electron micrographs of the electrocatalyst at different magnifications.
FIG. 2 is a graph showing nitrate conversion ratios in nitrate reduction reactions of catalysts obtained in examples 1 to 3 and comparative examples 1 to 2.
FIG. 3 is a graph showing the ammonia selectivity in the nitrate reduction reaction of the catalysts obtained in examples 1 to 3 and comparative examples 1 to 2.
FIG. 4 is a graph showing ammonia process efficiencies in nitrate reduction reactions of catalysts obtained in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
The present invention will be further illustrated by the following specific examples. The following examples are only for more clearly illustrating the technical solution of the present invention, but the practice and protection of the present invention are not limited thereto.
Example 1
A method for preparing a copper-cerium hydroxide electrocatalyst through in-situ dynamic reconstruction comprises the following steps:
1) and (4) electrodeposition. The copper foam was cut into pieces of 3X 1cm in size and ultrasonically cleaned in ethanol for 15 min. Rinsed several times with deionized water and ethanol and dried under vacuum at room temperature. Electrodeposition was then carried out using the CHI660E electrochemical workstation. The foamy copper electrode, the graphite rod electrode and the Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The electrodeposition solution contains 100mmol/L KCl and 25mmol/L Ce (NO) 3 ) 3 . At 1.5mA/cm 2 Is kept for 30min for deposition at the current density of (2). After deposition was complete, the working electrode was rinsed several times with deionized water and dried in air.
2) And (4) in-situ reconstruction. Subjecting the electrode obtained by electrodeposition in 1) to NO 3 - In situ reconstruction was performed under RR conditions. In situ reconstitution was performed in H-cells separated by Nafion 117 cation exchange membranes. The experiment was performed using a three-electrode system. The working electrode was the electrode obtained by electrodeposition in 1). An Ag/AgCl electrode (containing saturated KCl) and a Pt plate were used as a reference electrode and a counter electrode, respectively. 25mL of 0.1mol/L K 2 SO 4 Solution (containing 100mg L) -1 KNO 3 By NO 3 - Calculated as N) is added as an electrolyte to the cathode and anode chambers. Degassing for 5min with argon bubbling to remove dissolved N 2 And O 2 Thereafter, in situ reconstitution was performed at-1.2V (vs. Ag/AgCl) for 2h in potentiostatic mode. The in-situ reconstructed sample is analyzed by a scanning electron microscope, and a large amount of Cu-Ce (OH) can be seen to be formed x An interface, as shown in FIG. 1.
Example 2
A method for preparing a copper-cerium hydroxide electrocatalyst through in-situ dynamic reconstruction comprises the following steps:
1) and (4) electrodeposition. The copper sheet was cut into pieces of 3X 1cm in size and ultrasonically cleaned in ethanol for 15 min. Rinsed several times with deionized water and ethanol and dried under vacuum at room temperature. Then, useCHI660E electrochemical station for electrodeposition. The copper sheet electrode, the graphite rod electrode and the Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The electrodeposition solution contained 200mmol/L NaCl and 50mmol/L Ce (NO) 3 ) 3 . At 3mA/cm 2 Is kept for 5min for deposition. After deposition was complete, the working electrode was rinsed several times with deionized water and dried in air.
2) And (4) in-situ reconstruction. Subjecting the electrode obtained by electrodeposition in 1) to NO 3 - In situ reconstruction was performed under RR conditions. In situ reconstitution was performed in H-cells separated by Nafion 117 cation exchange membranes. The experiment was performed using a three-electrode system. The working electrode was the electrode obtained by electrodeposition in 1). An Ag/AgCl electrode (containing saturated KCl) and a Pt plate were used as a reference electrode and a counter electrode, respectively. 25mL of 0.1mol/L K 2 SO 4 Solution (containing 50mg L) -1 KNO 3 By NO 3 - Calculated as N) is added as an electrolyte to the cathode and anode chambers. Degassing for 5min with argon bubbling to remove dissolved N 2 And O 2 Thereafter, in situ reconstitution was performed at-1.5V (vs. Ag/AgCl) for 0.5h in potentiostatic mode.
Example 3
A method for preparing a copper-cerium hydroxide electrocatalyst through in-situ dynamic reconstruction comprises the following steps:
1) and (4) electrodeposition. The copper mesh was cut into pieces of 3 × 1cm in size and ultrasonically cleaned in ethanol for 15 min. Rinsed several times with deionized water and ethanol and dried under vacuum at room temperature. Electrodeposition was then carried out using the CHI660E electrochemical workstation. The copper mesh electrode, the graphite rod electrode and the Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The electrodeposition solution contains 500mmol/L KCl and 100mmol/L Ce (NO) 3 ) 3 . At 5mA/cm 2 The current density of (2) was maintained for 70min for deposition. After deposition was complete, the working electrode was rinsed several times with deionized water and dried in air.
2) And (4) in-situ reconstruction. Subjecting the electrode obtained by electrodeposition in 1) to NO 3 - In situ reconstruction was performed under RR conditions. In situ in H-cell separated by Nafion 117 cation exchange membraneAnd (6) reconstructing. The experiment was performed using a three-electrode system. The working electrode was the electrode obtained by electrodeposition in 1). An Ag/AgCl electrode (containing saturated KCl) and a Pt plate were used as a reference electrode and a counter electrode, respectively. 25mL of 0.1mol/L Na 2 SO 4 Solution (containing 500mg L) -1 NaNO 3 By NO 3 - Calculated as N) is added as an electrolyte to the cathode and anode chambers. Degassing for 5min with argon bubbling to remove dissolved N 2 And O 2 Thereafter, in situ reconstitution was performed at-1.1V (vs. Ag/AgCl) for 3h in potentiostatic mode.
Comparative example 1
Copper foam without electrodeposited cerium hydroxide.
Comparative example 2
Only the electrodeposition, not in situ reconstructed electrodes, was performed. The copper foam was cut into pieces of 3X 1cm in size and ultrasonically cleaned in ethanol for 15 min. Then, it was washed several times with deionized water and ethanol, and dried in a vacuum oven at room temperature. Electrodeposition was then performed using the CHI660E electrochemical workstation. The foamy copper electrode, the graphite rod electrode and the Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The electrodeposition solution contains 100mmol/L KCl and 25mmol/L Ce (NO) 3 ) 3 . Depositing at 1.5mA/cm 2 Is maintained at the current density of (3) for 30 min. After deposition was complete, the working electrode was rinsed several times with deionized water and dried in air.
The electrocatalytic nitrate reduction experiments on the catalysts obtained in comparative examples 1-2 and examples 1-3 showed that the catalysts obtained had nitrate conversions of 48.1%, 97.8%, 100.0%, 98.0%, 100.0%, ammonia selectivities of 11.5%, 47.0%, 97.8%, 93.0%, 89.9%, and ammonia process efficiencies of 39.6%, 72.8%, 99.2%, 95.2%, and 91.9%, respectively, and the results are shown in fig. 2-4. The results show that the prepared catalyst has obviously improved nitrate conversion rate, ammonia selectivity and ammonia process efficiency after the method is used, and the effectiveness of the method is shown.
Claims (10)
1. A method for preparing a copper-cerium hydroxide electrocatalyst through in-situ dynamic reconstruction is characterized by comprising the following steps:
a. putting the copper substrate in ethanol, ultrasonically cleaning, and vacuum drying;
b. depositing cerium hydroxide on a copper substrate in a cerium salt solution by an electrodeposition method;
c. reconstituting the cerium hydroxide-deposited copper substrate in situ in an electrolyte solution to have a substantial amount of Cu-Ce (OH) x A catalyst at the interface site.
2. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 1, wherein the copper substrate used in step a comprises one of copper foam, copper sheet, and copper mesh.
3. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 1, wherein the cerium salt solution used in the electrodeposition in the step b is a mixed solution of cerium nitrate and other electrolytes, such as potassium chloride or sodium chloride.
4. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 3, wherein the concentration of the cerium salt solution is 5-100mmol/L, and the concentration of the potassium chloride or sodium chloride is 50-500 mmol/L.
5. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 1, wherein the electro-deposition in step b adopts a constant current mode, and the current density is 0.5-5.0mA/cm 2 The deposition time is 5-70 min.
6. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 1, wherein the electrolyte used for in-situ reconstitution in step c is potassium sulfate solution or sodium sulfate solution.
7. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 6, wherein the electrolyte contains 50-500 mg/L potassium nitrate solution or sodium nitrate solution.
8. The method for preparing the copper-cerium hydroxide electrocatalyst according to claim 1, wherein the in-situ reconstruction in step c adopts a constant potential electrolysis mode, the potential is-1.1 to-1.5V vs. ag/AgCl, and the electrolysis time is 0.5 to 3 hours.
9. A copper-cerium hydroxide electrocatalyst prepared according to the method of any one of claims 1 to 8.
10. Use of a copper-cerium hydroxide electrocatalyst according to claim 9 for electrocatalytic nitrate reduction reactions.
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| CN116732568A (en) * | 2023-08-11 | 2023-09-12 | 内蒙古大学 | Cerium doped Cu for electrocatalytic reduction of nitrate into ammonia 2+1 O/Cu 3 VO 4 Process for preparing catalyst |
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| TW200944477A (en) * | 2008-04-21 | 2009-11-01 | Chuin-Tih Yeh | Precipitation method for preparation of CuO/CeO2 catalysts |
| CN108927163A (en) * | 2018-07-13 | 2018-12-04 | 浙江大学 | It is a kind of using cerium oxide as the preparation method of the supported copper oxide catalyst of carrier |
| JP2021030180A (en) * | 2019-08-28 | 2021-03-01 | 時空化学株式会社 | Production method of voc removal catalyst, voc removal catalyst, and voc removal method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200944477A (en) * | 2008-04-21 | 2009-11-01 | Chuin-Tih Yeh | Precipitation method for preparation of CuO/CeO2 catalysts |
| CN108927163A (en) * | 2018-07-13 | 2018-12-04 | 浙江大学 | It is a kind of using cerium oxide as the preparation method of the supported copper oxide catalyst of carrier |
| JP2021030180A (en) * | 2019-08-28 | 2021-03-01 | 時空化学株式会社 | Production method of voc removal catalyst, voc removal catalyst, and voc removal method |
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| P. BOCCHETTA等: ""From ceria nanotubes to nanowires through electrogeneration"" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116732568A (en) * | 2023-08-11 | 2023-09-12 | 内蒙古大学 | Cerium doped Cu for electrocatalytic reduction of nitrate into ammonia 2+1 O/Cu 3 VO 4 Process for preparing catalyst |
| CN116732568B (en) * | 2023-08-11 | 2023-11-07 | 内蒙古大学 | Cerium doped Cu for electrocatalytic reduction of nitrate into ammonia 2+1 O/Cu 3 VO 4 Process for preparing catalyst |
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