CN116732564A - CF (compact flash) m @Ni x Fe y Preparation method of P composite material and application of P composite material in catalyzing urea electrooxidation - Google Patents
CF (compact flash) m @Ni x Fe y Preparation method of P composite material and application of P composite material in catalyzing urea electrooxidation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000004202 carbamide Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000006056 electrooxidation reaction Methods 0.000 title abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 239000006260 foam Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910018104 Ni-P Inorganic materials 0.000 claims description 12
- 229910018536 Ni—P Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 241000080590 Niso Species 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- LHLROOPJPUYVKD-UHFFFAOYSA-N iron phosphanylidynenickel Chemical compound [Fe].[Ni]#P LHLROOPJPUYVKD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002070 nanowire Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000001075 voltammogram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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Abstract
The invention discloses a CF m @Ni x Fe y A preparation method of a P composite material and application thereof in catalyzing urea electro-oxidation reaction belong to the fields of composite material preparation and electro-catalysis. The invention uses foamy copper as a support body and adopts chemical oxidation, reduction and electrodeposition methodsSelf-supporting CF is prepared m @Ni x Fe y -P electrode material; the physical stability and the electrical conductivity of the electrode material are obviously improved by the in-situ growth mode of the self-supporting electrode; chemical oxidation and reduction enable the surface of copper Foam (Cu Foam, CF) to grow a special nanowire structure and simultaneously enable the copper Foam to have excellent conductivity; the nickel-iron-phosphorus complex formed by electrodeposition has a large specific surface area and rich active sites. In addition, the composite material shows excellent urea electrooxidation catalytic activity due to the synergistic effect among Ni, fe and P. CF (compact flash) m @Ni x Fe y The P composite material has special morphology structure, rich active sites and excellent electrocatalytic performance.
Description
Technical Field
The invention relates to a CF m @Ni x Fe y A preparation method of a P composite material and application thereof in catalyzing urea electro-oxidation reaction belong to the fields of composite material preparation and electro-catalysis.
Background
The urea electrooxidation reaction (Urea Oxidation Reaction, UOR) is applied to various fields such as fuel cells, electrolytic hydrogen production, wastewater treatment and the like, and has good prospect. In the actual electrooxidation reaction process, kinetics are slow due to its complex electron transfer process. The preparation of the efficient catalyst for the urea electrooxidation reaction has important significance.
Nickel-based catalysts have received considerable attention from researchers in recent years because of their low cost and their ability to effectively catalyze the electro-oxidation reaction of urea, but their catalytic activity has yet to be further improved. The structure and composition of the catalyst have a significant impact on its catalytic properties. The doping of phosphorus element in the nickel-based catalyst can improve the electro-oxidation performance of the catalyst for catalyzing urea. Rui Ding et al (Rui Ding, xudeng Li, wei Shi, qialei Xu, luo Wang, haixia Jiang, zeng Yang, enhui Liu. Mesoporous Ni-P nanocatalysts for alkaline urea electrooxidation [ J ]]Electrochimica Acta, 2016, 222:455-462.) produced stainless steel mesh-supported Ni-P composites exhibiting superior urea electrooxidation catalytic activity over pure Ni. But this electricityOrganic binders are needed in the preparation process of the electrode, which reduces the conductivity of the prepared material, and is easy to cause a catalytic activity dead zone, and has adverse effects on the catalytic process. Gautam Das et al (Gautam Das, robel Mehari Tesfaye, yusunWon, hyon Hee Yoon. NiO-Fe 2 O 3 based graphene aerogel as urea electrooxidation catalyst[J]Electrochimica Acta, 2017, 237:171-176.) NiO-Fe with polyvinyl alcohol as structural scaffold was prepared 2 O 3 Base graphene aerogel (NiO-Fe) 2 O 3 rGO/PVA) composite catalytic material having a specific three-dimensional structure and NiO-Fe 2 O 3 the/rGO/PVA shows more excellent urea electro-oxidation catalytic activity than the NiO/rGO/PVA. However, graphene is used in the prepared electrode, the preparation process is complex, the price is high, and the catalytic activity of the electrode still needs to be improved.
Disclosure of Invention
The invention aims to provide a modified foam copper supported nickel-based composite material (CF) m @Ni x Fe y P) and a preparation method, the composite material is used for catalyzing UOR, and the electrocatalytic reaction performance is improved.
According to the invention, firstly, the foamy copper is subjected to modification treatment, so that the foamy copper has a special morphology structure, the charge transmission and the active material loading are facilitated, and then, the final electrode is prepared by a simple electrodeposition method. Wherein, the addition of P is beneficial to improving the electronic structure of nickel and the stability of the electrode, and the addition of Fe is beneficial to the generation of electrode surface active substances in the reaction process.
The invention provides a CF m @Ni x Fe y The preparation method of the P composite material comprises the following specific preparation steps:
(1) Washing 10 mm ×10 mm CF (copper foam) square pieces with distilled water, ultrasonic treating in acetone solution for 10 min, washing with distilled water, soaking in 3.0 mol ‧ dm -3 Ultrasonic treatment is carried out in HCl solution for 5 min, and finally, the solution is fully washed for standby;
(2) Immersing the CF treated in step (1) in 50 mL containing 2 mol ‧ dm -3 NaOH and 0.1 mol ‧ dm -3 (NH 4 ) 2 S 2 O 8 Is subjected to chemical oxidation, is dried under vacuum at 70 ℃ for 3 h, is calcined in a muffle furnace at 200 ℃ for 1 h, and is finally soaked in 0.1 mol ‧ dm -3 NaBH of (B) 4 Chemical reduction is carried out in the solution to obtain CF m An electrode;
(3) CF obtained in step (2) m The electrode is a working electrode, and CF is prepared in a three-electrode system m @Ni electrode, CF m @Ni-P electrode and CF m @Ni x Fe y -a P electrode.
The CF mentioned above m @Ni x Fe y In the P electrode material, CF m For modified copper foam, m represents "modified"; the ratio of x to y is 15:1-1:5.
In particular, in conventional three-electrode systems, CF is prepared by electrochemical deposition by potentiostatic methods m @ Ni electrode: wherein the working electrode is CF m The reference electrode is Ag/AgCl (saturated KCl), the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O and 0.1 mol ‧ dm -3 C 6 H 5 Na 3 O mixed solution to prepare CF m An @ Ni electrode.
Specifically, CF is prepared m @ Ni-P electrode: CF (compact flash) m Preparation method of @ Ni-P electrode and CF m Similar to @ Ni, the deposition solution was changed to 0.1 mol ‧ dm only -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.0143~0.3000 mol‧dm -3 NaH 2 PO 4 And 0.2 mol ‧ dm -3 (NH 4 ) 2 SO 4 Is a mixed solution of (a) and (b).
Specifically, CF m @Ni x Fe y Preparation method of P electrode and CF m Similar to @ Ni, the deposition solution was changed to 0.1 mol ‧ dm only -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.033 mol‧dm -3 NaH 2 PO 4 、0.2 mol‧dm -3 (NH 4 ) 2 SO 4 And 0.067 to 0.500 mol ‧ dm -3 FeSO 4 ‧7H 2 Mixed solution of O.
The preparation method is further described as follows:
the step (2) is used for preparing CF m In the process of the electrode, the oxidation time is 0.5-2.5 h, and the reduction time is 0.5-2.5 h.
Step (3) preparation of CF m In the process of the @ Ni electrode, the deposition potential is-0.5 to-2.5V, and the deposition time is 300 to 1500 s.
The essence of the invention is to modify the foamy copper and prepare CF by using the electrodeposition method m @Ni x Fe y -P composite material applied as high performance catalyst for catalyzing UOR.
The specific process of the application is as follows: by CF m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 1.0-5.0 mol ‧ dm -3 KOH and 0.1 to 0.5 mol ‧ dm -3 Performing linear sweep voltammetric test in urea mixed solution at 298.15-338.15K, sweep range of 0-0.8V and sweep rate of 5 mV s -1 。
The invention has the beneficial effects that:
(1) The foam copper is used as a support body, so that the conductive material has the advantages of high conductivity and high porosity;
(2) The copper foam is modified, so that the electrode forms a special morphology structure and has larger specific surface area;
(3) The invention uses no organic binder and uses the electrodeposition method to load Ni on the foamy copper x Fe y The P complex is in amorphous form and, due to the synergistic effect between the different elements, the composite exhibits excellent electrocatalytic activity towards UOR; in addition, nickel-based materials are low in price and low in cost.
Drawings
FIG. 1 is a CF prepared in example 1 m @Ni、CF m @Ni-P and CF m @Ni x Fe y Linear sweep voltammogram of P electrode.
FIG. 2 is a CF prepared in example 2 m @Ni x Fe y The P electrode was at 4 mol ‧ dm -3 KOH and 0.1 mol ‧ dm -3 Linear sweep voltammogram in urea solution.
FIG. 3 is a CF prepared in example 3 and example 4 m @Ni x Fe y Linear sweep voltammogram of P electrode at different temperatures.
FIG. 4 is a CF prepared in example 5 m @Ni x Fe y -timed current profile of P electrode.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
(1) Cutting copper foam into square pieces of 10 mm ×10 mm, washing with distilled water, and ultrasonic treating in acetone solution for 10 min to remove impurities on the surface; washing with distilled water, soaking in 3.0 mol ‧ dm -3 The HCl solution is treated by ultrasonic for 5 min to remove oxide, and finally, the mixture is washed fully for standby.
(2) Immersing the pretreated CF into 50 mL containing 2 mol ‧ dm -3 NaOH and 0.1 mol ‧ dm -3 (NH 4 ) 2 S 2 O 8 1.5 h in the above-mentioned process, washing and drying under vacuum at 70 ℃ for 3 h, placing the dried material in a muffle furnace, calcining at 200 ℃ for 1 h, and soaking in 0.1 mol ‧ dm of 50 mL -3 NaBH of (B) 4 2 h in solution to give CF m An electrode.
（3）CF m The @ Ni electrode was prepared in a conventional three electrode system by electrochemical deposition by potentiostatic method. Wherein the working electrode is CF m The reference electrode is Ag/AgCl (saturated KCl), the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O and 0.1 mol ‧ dm -3 C 6 H 5 Na 3 O 7 Is a mixture of (3)Solution, electrode CF is prepared m @ Ni. Wherein the deposition potential is-2V and the deposition time is 900 s.
CF m Preparation method of @ Ni-P electrode and CF m Similar to @ Ni, the electrodeposition solution was replaced with 0.1 mol ‧ dm only -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.033 mol‧dm -3 NaH 2 PO 4 And 0.2 mol ‧ dm -3 (NH 4 ) 2 SO 4 The rest conditions are unchanged, and the electrode CF is prepared m @Ni-P。
CF m @Ni x Fe y Preparation method of P electrode and CF m Similar to @ Ni, the electrodeposition solution was replaced with 0.1 mol ‧ dm only -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.033 mol‧dm -3 NaH 2 PO 4 、0.2 mol‧dm -3 (NH 4 ) 2 SO 4 And 0.02 mol ‧ dm -3 FeSO 4 ·7H 2 O mixed solution, and the rest conditions are unchanged, thus preparing the electrode CF m @Ni x Fe y -P。
(4) By CF m An @ Ni electrode is used as a working electrode, an Ag/AgCl (saturated KCl) electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and the reaction time is 3 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 Performing linear sweep voltammetric test in urea mixed solution at 298.15-K deg.f, sweep range of 0-0.8-V and sweep rate of 5 mV s -1 . When the potential is 0.8. 0.8V, the oxidation current density can reach 332.1. 332.1 mA ‧ cm -2 。
By CF m The @ Ni-P electrode is used as a working electrode, the Ag/AgCl (saturated KCl) electrode is used as a reference electrode, the carbon rod is used as a counter electrode, and the reaction time is 3 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 Performing linear sweep voltammetric test in urea mixed solution at 298.15-K deg.f, sweep range of 0-0.8-V and sweep rate of 5 mV s -1 . When the potential is 0.8. 0.8V, the oxidation current density can reach 658.9 mA ‧ cm -2 。
By CF m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 3 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 Performing linear sweep voltammetric test in urea mixed solution at 298.15-K deg.f, sweep range of 0-0.8-V and sweep rate of 5 mV s -1 . When the potential is 0.8. 0.8V, the oxidation current density can reach 760.8 mA ‧ cm -2 。
FIG. 1 shows the corresponding CF in example 1 m @Ni、CF m @Ni-P and CF m @Ni x Fe y Linear sweep voltammogram of the P electrode, CF, from the figure m @Ni x Fe y The oxidation current density generated by the P electrode is higher than that of the other electrodes, indicating CF m @Ni x Fe y P has a more advantageous catalytic activity towards UOR.
Example 2
(1) Cutting copper foam into square pieces of 10 mm ×10 mm, washing with distilled water, and ultrasonic treating in acetone solution for 10 min to remove impurities on the surface; washing with distilled water, soaking in 3.0 mol ‧ dm -3 And carrying out ultrasonic treatment on the HCl solution for 5 min to remove oxides, and finally, fully washing with distilled water for standby.
(2) Immersing the pretreated CF into 50 mL containing 2 mol ‧ dm -3 NaOH and 0.1 mol ‧ dm -3 (NH 4 ) 2 S 2 O 8 1.5 h in the above-mentioned process, washing and drying under vacuum at 70 ℃ for 3 h, placing the dried material in a muffle furnace, calcining at 200 ℃ for 1 h, and soaking in 0.1 mol ‧ dm of 50 mL -3 NaBH of (B) 4 2 h in solution to give CF m An electrode.
（3）CF m @Ni x Fe y The P-electrode is prepared in a conventional three-electrode system by electrochemical deposition by potentiostatic method. Wherein the working electrode is CF m The reference electrode is Ag/AgCl (saturated KCl), the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.033 mol‧dm -3 NaH 2 PO 4 、0.2 mol‧dm -3 (NH 4 ) 2 SO 4 And 0.02 mol ‧ dm -3 FeSO 4 ·7H 2 O, preparing an electrode CF m @Ni x Fe y -P. Wherein the deposition potential is-2V and the deposition time is 900 s.
(4) By CF m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 4 mol ‧ dm -3 KOH and 0.1 mol ‧ dm -3 The urea solution is subjected to linear sweep voltammetric test at 298.15 and K, the sweep range is 0-0.8V, and the sweep rate is 5 mV s -1 At a potential of 0.8V, the oxidation current density can reach 674.1 mA ‧ cm -2 。
FIG. 2 is a CF in example 2 m @Ni x Fe y The P electrode was at 4 mol ‧ dm -3 KOH and 0.1 mol ‧ dm -3 Linear sweep voltammogram in urea solution.
Example 3
CF prepared in example 2 m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 4 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 Performing linear sweep voltammetry test in urea mixed solution with a sweep range of 0-0.8V and a sweep rate of 5 mV s -1 The test temperature was 298.15. 298.15K. When the potential is 0.8. 0.8V, the oxidation current density can reach 840.8 mA ‧ cm -2 。
Example 4
CF prepared as in example 2 m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 4 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 Performing linear sweep voltammetry test in urea mixed solution with a sweep range of 0-0.8V and a sweep rate of 5 mV s -1 The test temperature was 338.15K.When the potential is 0.8. 0.8V, the oxidation current density can reach 1025.1 mA ‧ cm -2 。
FIG. 3 shows CF in example 3 and example 4 m @Ni x Fe y Linear sweep voltammograms for the P-electrode at test temperatures 298.15K (curve a) and 338.15K (curve b). The higher oxidation current density at the reaction temperature of 338.15K indicates that an increase in reaction temperature is beneficial for improving UOR performance.
Example 5
In CF prepared in example 2 m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl (saturated KCl) electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 4 mol ‧ dm -3 KOH and 0.3 mol ‧ dm -3 The timing current test was performed in urea mixed solution at 298.15. 298.15K and test potentials of 0.4, 0.5, 0.6 and 0.7. 0.7V, respectively.
FIG. 4 is a CF in example 5 m @Ni x Fe y The timed current curves of the P-electrode at different potentials, it can be seen that the corresponding oxidation current densities remain relatively stable at the 0.4, 0.5, 0.6 and 0.7V test potentials.
Claims (9)
1. CF (compact flash) m @Ni x Fe y -a process for the preparation of a P composite, characterized in that it comprises the following steps:
(1) Washing 10 mm ×10 mm copper foam CF square pieces with distilled water, ultrasonic treating in acetone solution for 10 min, washing with distilled water, soaking in 3.0 mol ‧ dm -3 Ultrasonic treatment is carried out in HCl solution for 5 min, and finally, the solution is fully washed for standby;
(2) Immersing the CF treated in step (1) in 50 mL containing 2 mol ‧ dm -3 NaOH and 0.1 mol ‧ dm -3 (NH 4 ) 2 S 2 O 8 Is subjected to chemical oxidation, is dried under vacuum at 70 ℃ for 3 h, is calcined in a muffle furnace at 200 ℃ for 1 h, and is finally soaked in 0.1 mol ‧ dm -3 NaBH of (B) 4 Chemical reduction is carried out in the solution to obtain CF m Electrode；
(3) CF obtained in step (2) m The electrode is a working electrode, and CF is prepared in a three-electrode system m @Ni electrode, CF m @Ni-P electrode or CF m @Ni x Fe y -a P electrode; wherein the ratio of x to y is 15:1-1:5.
2. The CF of claim 1 m @Ni x Fe y -a process for the preparation of a P composite, characterized in that: step (2) preparation of CF m In the process of the electrode, the oxidation time is 0.5-2.5 h, and the reduction time is 0.5-2.5 h.
3. The CF of claim 1 m @Ni x Fe y -a process for the preparation of a P composite, characterized in that: step (3) preparation of CF m In the process of the @ Ni electrode, the deposition potential is-0.5 to-2.5V, and the deposition time is 300 to 1500 s.
4. The CF of claim 1 m @Ni x Fe y -a process for the preparation of a P composite, characterized in that: preparation of CF by electrochemical deposition by potentiostatic method in three-electrode system m @ Ni electrode: wherein the working electrode is CF m The reference electrode is Ag/AgCl, the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O and 0.1 mol ‧ dm -3 C 6 H 5 Na 3 O mixed solution to prepare CF m An @ Ni electrode.
5. The CF of claim 1 m @Ni x Fe y -a process for the preparation of a P composite, characterized in that: preparation of CF by electrochemical deposition by potentiostatic method in three-electrode system m @ Ni-P electrode: wherein the working electrode is CF m The reference electrode is Ag/AgCl, the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.0143~0.3000 mol‧dm -3 NaH 2 PO 4 And 0.2 mol ‧ dm -3 (NH 4 ) 2 SO 4 Is a mixed solution of (a) and (b).
6. The CF of claim 1 m @Ni x Fe y -a process for the preparation of a P composite, characterized in that: preparation of CF by electrochemical deposition by potentiostatic method in three-electrode system m @Ni x Fe y -P electrode: wherein the working electrode is CF m The reference electrode is Ag/AgCl, the counter electrode is Pt sheet electrode, and the deposition solution is 0.1 mol ‧ dm -3 NiSO 4 ‧6H 2 O、0.1 mol‧dm -3 C 6 H 5 Na 3 O 7 、0.033 mol‧dm -3 NaH 2 PO 4 、0.2 mol‧dm -3 (NH 4 ) 2 SO 4 And 0.067 to 0.500 mol ‧ dm -3 FeSO 4 ‧7H 2 Mixed solution of O.
7. A CF produced by the production method of claim 6 m @Ni x Fe y -P composite material.
8. A CF as claimed in claim 7 m @Ni x Fe y The P composite is applied as a high-performance catalyst for catalyzing UOR.
9. The application according to claim 8, characterized in that the specific application procedure is: by CF m @Ni x Fe y The P electrode is a working electrode, the Ag/AgCl electrode is a reference electrode, the carbon rod is a counter electrode, and the reaction time is 1.0-5.0 mol ‧ dm -3 KOH and 0.1 to 0.5 mol ‧ dm -3 Performing linear sweep voltammetric test in urea mixed solution at 298.15-338.15K, sweep range of 0-0.8V and sweep rate of 5 mV s -1 。
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