CN116516404A - Preparation of molybdenum-doped nickel-cobalt Prussian blue analogue with binary composite structure and application of molybdenum-doped nickel-cobalt Prussian blue analogue in electrocatalytic oxidation of urea - Google Patents
Preparation of molybdenum-doped nickel-cobalt Prussian blue analogue with binary composite structure and application of molybdenum-doped nickel-cobalt Prussian blue analogue in electrocatalytic oxidation of urea Download PDFInfo
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- CN116516404A CN116516404A CN202310738092.2A CN202310738092A CN116516404A CN 116516404 A CN116516404 A CN 116516404A CN 202310738092 A CN202310738092 A CN 202310738092A CN 116516404 A CN116516404 A CN 116516404A
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- -1 nickel-cobalt Prussian blue analogue Chemical class 0.000 title claims abstract description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004202 carbamide Substances 0.000 title claims abstract description 34
- 239000011218 binary composite Substances 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 239000006260 foam Substances 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 37
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 229910003266 NiCo Inorganic materials 0.000 description 42
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000001075 voltammogram Methods 0.000 description 10
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 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
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method of a molybdenum-doped nickel-cobalt Prussian blue analogue with a binary composite structure and application of the molybdenum-doped nickel-cobalt Prussian blue analogue in electrocatalytic oxidation of urea. The invention adopts a simple hydrothermal method, and uses foam nickel as a nickel source and a conductive substrate to prepare the molybdenum-doped nickel cobalt Prussian blue analog electrocatalyst which grows on the foam nickel in situ. The structure of the catalyst consists of a plate-shaped structure at the bottom and rounded corner cubes with the surfaces interspersed, and the special structure can not only increase the active sites of the catalyst and improve the overall performance of the catalyst, but also is beneficial to enhancing the overall stability of the catalyst. Doping of heteroatom molybdenum enables the nickel cobalt prepared by the invention to be commonLu Shilan analog catalyst and commercial RuO 2 and/NF shows higher catalytic performance for urea oxidation reaction.
Description
Technical Field
The invention belongs to the field of electrocatalytic decomposition of urea-assisted water, and particularly relates to preparation of a molybdenum-doped nickel-cobalt Prussian blue analogue with a binary composite structure and application of the molybdenum-doped nickel-cobalt Prussian blue analogue in electrocatalytic oxidation of urea.
Background
The energy crisis and environmental pollution make the development of clean and efficient new energy systems urgent. Hydrogen molecules have a very high energy density compared to other fuels, and the products after combustion are only pollution-free water and are therefore considered as one of the most promising energy sources. Hydrogen production by water splitting (H) 2 ) Is an environmentally friendly method, however, hydrogen production efficiency is severely limited due to the thermodynamically slow Oxygen Evolution Reaction (OER) at the anode, which results in high energy loss and expensive production costs for water electrolysis. Therefore, development of high-performance electrocatalysts and replacement of anodic oxidation reactions are urgently required to reduce the driving voltage and promote practical applications thereof.
In electrochemical bulk water electrolysis plants, urea Oxidation (UOR) is considered a very promising alternative to anode OER because it requires a much lower cell voltage (0.37V) than OER (1.23V), which helps to save energy and increase the efficiency of hydrogen production. Meanwhile, urea electrolysis based on UOR is also one way to achieve purification of urea-containing wastewater. Urea-assisted water splitting involves two half reactions:
anode (UOR): CO (NH) 2 ) 2 +6OH - →N 2 +5H 2 O+CO 2 +6e - (1)
Cathode (HER): 6H 2 O+6e - →3H 2 +6OH - (2)
However, due to 6e - The kinetics of the transfer process, UOR, are relatively slow. Therefore, it is necessary to develop an effective catalyst to promote urea-assisted water decomposition.
So far, noble metal-based catalysts, such as ruthenium dioxide and iridium dioxide, have shown effective catalytic performance for OER and UOR, but their large-scale practical use is hampered by their high cost and rarity on earth. Recently, various nickel-based catalysts have been considered as more promising candidate materials for UOR. Prussian Blue (PB) and its analogues (PBAs) are very promising coordination polymers in this respect, with adjustable composition and open framework. However, their inherent electrochemical activity and conductivity are poor, impeding the catalytic activity of the overall water decomposition. Heteroatom doping engineering is an effective strategy to further increase the activity of electrocatalysts by adjusting the electronic structure, increasing the number of active sites and optimizing the formation of intermediates. For example, xu et al report the in situ growth of dendritic Mo-doped Ni on nickel foam 3 S 2 Nanometer forest catalyst, which can obtain 10mA cm with voltage of 1.45V -2 Urea assists in water decomposition and exhibits good durability. The electronic structure is regulated by precisely controlling Mo doping, a well-defined dendritic nano structure is formed, the absorption energy of surface reactant molecules can be optimized, and the exposure of rich active sites is promoted. Therefore, optimizing the structure and active site of the catalyst is critical to improving the electrocatalytic performance.
Disclosure of Invention
The invention provides a binary composite structure molybdenum doped nickel cobalt Prussian blue analogue (Mo-NiCo PBA/NF) grown on foam nickel in situ, which is used as a catalyst to realize efficient urea oxidation reaction.
The invention adopts a simple hydrothermal method, and uses foam nickel as a nickel source and a conductive substrate to prepare the molybdenum-doped nickel cobalt Prussian blue analog electrocatalyst which grows on the foam nickel in situ. The catalyst structure consists of plate structure at the bottom and rounded corner cube with surface decoration, and the special structure can increase active site of catalyst and raise its performanceIts overall performance also contributes to the stability of the catalyst. The doping of heteroatom Mo enables the Mo-NiCoPBA/NF nano catalyst prepared by the invention to be in combination with commercial RuO 2 and/NF shows higher catalytic performance for urea oxidation reaction.
The preparation method of the molybdenum-doped nickel-cobalt Prussian blue analogue with the binary composite structure comprises the following steps:
step 1: placing a certain amount of surfactant dextran-20, citric acid monohydrate and molybdenum salt into a beaker, adding 300mL of deionized water for dissolution, and marking as a solution A;
step 2: weigh a certain amount of K 3 [Co(CN) 6 ]Adding 200mL of deionized water into a beaker for dissolution, and marking as a solution B;
step 3: dropwise adding the solution A into the solution B under stirring, and uniformly mixing;
step 4: transferring 30mL of the mixed solution into a 40mL Teflon-lined autoclave with a pre-treated foamed nickel inside, and maintaining the temperature at 60-100 ℃ for 10-14 hours; and naturally cooling to room temperature after the reaction is finished, washing for a plurality of times by deionized water, and drying in an oven to finally obtain the binary composite structure molybdenum doped nickel cobalt Prussian blue analogue Mo-NiCo PBA/NF. The pretreated foam nickel electrode serves as both a nickel source and a conductive substrate.
In step 1, the molar amount of dextran-20 was 0.1mmol and the molar amount of citric acid monohydrate was 2.1mmol.
In the step 1, the molybdenum salt is Na 2 MoO 4 ·2H 2 The molar amount of O is 0.01 to 0.1mmol, preferably 0.05mmol.
In step 2, K 3 [Co(CN) 6 ]The molar amount of (2) was 0.5mmol.
In step 4, the pretreated foam nickel is obtained by the following method: cutting a foam nickel electrode with proper size, ultrasonically cleaning the foam nickel electrode with dilute hydrochloric acid solution, acetone and deionized water in advance, and drying the foam nickel electrode in an oven for standby.
The invention relates to an application of a binary composite structure molybdenum doped nickel cobalt Prussian blue analogue, which takes the binary composite structure molybdenum doped nickel cobalt Prussian blue analogue as a catalyst to realize the electrocatalytic oxidation reaction of urea under alkaline conditions.
Specifically, a standard three-electrode system is used, wherein Mo-NiCo PBA/NF (1.0 cm multiplied by 1.0 cm) grown in situ is directly used as a working electrode, a platinum sheet electrode is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode. The urea oxidation performance of Mo-NiCo PBA/NF catalysts was tested in alkaline electrolyte and Mo-NiCo PBA/NF was used as anode electrocatalyst and commercial Pt/C supported on foamed nickel was used as cathode electrocatalyst in urea-assisted full hydrolysis unit. Linear sweep voltammetric testing was performed at a sweep rate of 5mV/s over a potential range of 0.2V-1.0V (vs. Hg/HgO electrode) and was compatible with commercial RuO 2 Comparison was made to explore the variation in electrocatalytic properties; and at 10mAcm -2 Stability testing was performed for 50h at constant current density.
The alkaline electrolyte is 1mol/LKOH solution, KOH and CO (NH) 2 ) 2 The molar ratio of (2) was 1:0.33.
The beneficial effects of the invention are as follows:
the molybdenum doped nickel-cobalt Prussian blue analogue urea oxidation catalyst with the binary composite structure, which grows on the foam nickel in situ, is synthesized by adopting a simple hydrothermal method, and provides a simple and convenient method for synthesizing the Prussian blue analogue. The invention adopts the foam nickel as the nickel source directly, does not add nickel salt additionally, and adds molybdenum salt for heteroatom doping, thereby optimizing the electronic structure and further showing excellent catalytic performance. The synergistic effect among different metal centers is beneficial to improving the activity of nickel sites and accelerating the complete oxidation of urea. The catalyst of the present invention exhibits excellent catalytic performance in practical electrochemical water decomposition devices.
Drawings
The technical solution of the present invention will be further described with reference to the accompanying drawings and examples, and it should be noted that these drawings are not limited to the scope of the present invention, but serve as an explanation of the technical solution of the present invention.
Fig. 1 is an X-ray diffraction pattern (XRD) of the nickel cobalt prussian blue analog catalyst prepared in example 1.
Fig. 2 is an X-ray photoelectron spectrum (XPS) of a nickel cobalt prussian blue analog catalyst prepared in example 1.
FIG. 3 is a nickel cobalt Prussian blue analog catalyst prepared in example 1 and commercial RuO supported on nickel foam 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear sweep voltammogram in mixed solution.
FIG. 4 is a Tafel slope plot of the nickel cobalt Prussian blue analog catalyst prepared in example 1.
Fig. 5 is a Scanning Electron Microscope (SEM) image of a molybdenum-doped nickel cobalt prussian blue analog catalyst of binary composite structure prepared in example 2.
Fig. 6 is an X-ray diffraction pattern (XRD) of a molybdenum-doped nickel cobalt prussian blue analog catalyst of binary composite structure prepared in example 2.
Fig. 7 is an X-ray photoelectron spectrum (XPS) of a molybdenum-doped nickel cobalt prussian blue analog catalyst of binary composite structure prepared in example 2, and the inset is a partial enlarged view at 225-244 eV.
FIG. 8 is a molybdenum doped nickel cobalt Prussian blue analog catalyst of binary composite structure prepared in example 2 and commercial RuO supported on nickel foam 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear sweep voltammogram in mixed solution.
Fig. 9 is a Tafel slope plot of a binary composite structure molybdenum doped nickel cobalt prussian blue analog catalyst prepared in example 2.
FIG. 10 shows a molybdenum doped nickel cobalt Prussian blue analog catalyst of binary composite structure prepared in example 2 at 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 In the mixed solution, 10mAcm -2 A timing voltage graph of constant current density operation of (a).
FIG. 11 shows a binary composite structure molybdenum doped nickel cobalt Prussian blue analog catalyst prepared in example 2 and commercial Pt/C/NF supported on foam nickel used as anode and cathode respectively to make urea assisted perhydrolysis cell at 1mol/LKOH+0.33mol/L CO (NH 2 ) 2 Wires in a mixed solutionThe voltammogram was scanned sexually.
FIG. 12 shows a binary composite structure molybdenum doped nickel cobalt Prussian blue analog catalyst prepared in example 2 and commercial Pt/C/NF supported on foam nickel used as anode and cathode respectively to make urea assisted perhydrolysis cell at 1mol/LKOH+0.33mol/L CO (NH 2 ) 2 In the mixed solution, 10mAcm -2 A timing voltage graph of constant current density operation of (a).
FIG. 13 is a molybdenum doped nickel cobalt Prussian blue analog catalyst of binary composite structure prepared in example 3 and commercial RuO supported on nickel foam 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear sweep voltammogram in mixed solution.
Fig. 14 is a Tafel slope plot of a binary composite structure molybdenum doped nickel cobalt prussian blue analog catalyst prepared in example 3.
FIG. 15 is a schematic representation of a binary composite molybdenum doped NiCo Prussian blue analog catalyst prepared in example 4 and commercial RuO supported on foam Nickel 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear sweep voltammogram in mixed solution.
Fig. 16 is a Tafel slope plot of a binary composite structured molybdenum doped nickel cobalt prussian blue analog catalyst prepared in example 4.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, and it should be noted that the following specific descriptions of examples are only for illustrating the synthesis, characterization and performance of the catalyst, and should not be construed as limiting the invention, and those examples not directly mentioned herein may still be obtained by combining these technical solutions.
Example 1:
the present example prepared a nickel cobalt Prussian blue analog catalyst grown in situ on a foamed nickel, comprising the steps of:
1. a piece of NF (2.0 cm. Times.3.0 cm) was sonicated in 3mol/L dilute hydrochloric acid solution, acetone and deionized water for 15 minutes each.
2. 0.1mmol dextran-20, 2.1mmol citric acid monohydrate were dissolved in 300ml deionized water (solution A).
3. The mixed solution was added dropwise to 200mL containing 0.5mmol K 3 [Co(CN) 6 ](solution B).
4. 30mL of the mixed solution was transferred to a 40mL polytetrafluoroethylene-lined autoclave with a piece of pretreated NF and maintained at 80℃for 10 hours to obtain the final NiCo PBA/NF electrocatalyst.
FIG. 1 is an XRD pattern of NiCo PBA/NF electrocatalyst prepared in example 1, from which it can be seen that XRD diffraction peaks of the samples correspond to Ni 3 (Co(CN) 6 ) 2 (H 2 O) 12 (PDF # 89-3738) indicating successful synthesis of nickel cobalt prussian blue analogues.
Fig. 2 is an XPS diagram of the NiCo PBA/NF electrocatalyst prepared in example 1, from which it can be seen that Ni, co, C, N, O element is present in the catalyst, corresponding to the XRD diagram, illustrating the successful synthesis of the nickel cobalt prussian blue analogues.
FIG. 3 is a NiCo PBA/NF electrocatalyst prepared in example 1 and commercial RuO supported on nickel foam 2 (commercial RuO) 2 /NF) at 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear scan voltammograms in mixed solutions, as can be seen with and commercial RuO 2 The NiCo PBA/NF electrocatalyst prepared in example 1 had a lower starting potential than that of the catalyst, driving 100mAcm -2 Requires only a voltage of 1.38V, compared to commercial RuO 2 the/NF was 140mV lower, indicating that the NiCo PBA/NF electrocatalyst prepared in example 1 had better urea oxidation performance.
FIG. 4 is a Tafel plot of the NiCo PBA/NF electrocatalyst prepared in example 1, showing that the Mo-NiCo PBA/NF catalyst has a smaller Tafel slope (18.81 mV dec -1 ) Indicating a faster reaction kinetics.
Example 2:
the preparation method of the molybdenum-doped nickel-cobalt Prussian blue analog catalyst with a binary composite structure grown on foam nickel in situ comprises the following steps:
1. a piece of NF (2.0 cm. Times.3.0 cm) was sonicated in 3mol/L dilute hydrochloric acid solution, acetone and deionized water for 15 minutes each.
2. 0.1mmol dextran-20, 2.1mmol citric acid monohydrate and 0.05mmol Na 2 MoO 4 ·2H 2 O was dissolved in 300ml deionized water (solution A).
3. The mixed solution was added dropwise to 200mL containing 0.5mmol K 3 [Co(CN) 6 ](solution B).
4. 30mL of the mixed solution was transferred to a 40mL polytetrafluoroethylene-lined autoclave with a piece of pretreated NF and maintained at 80℃for 10 hours to obtain the final Mo-NiCo PBA/NF electrocatalyst.
FIG. 5 is an SEM image of a Mo-NiCo PBA/NF electrocatalyst prepared in example 2, where it can be seen that the structure of the Mo-NiCo PBA/NF consisted of a bottom plate-like structure with rounded corner cubes interspersed with surfaces.
FIG. 6 is an XRD pattern of the Mo-NiCo PBA/NF electrocatalyst prepared in example 2, from which it can be seen that the XRD diffraction peaks of the samples correspond to Ni 3 (Co(CN) 6 ) 2 (H 2 O) 12 (PDF # 89-3738) shows that the successful synthesis of the nickel cobalt Prussian blue analogues, and meanwhile, the introduction of trace molybdenum elements can be found that the main crystal structure of the nickel cobalt Prussian blue analogues is not changed in the reaction process.
Fig. 7 is an XPS diagram of the Mo-NiCo PBA/NF electrocatalyst prepared in example 2, from which it can be seen that molybdenum element is present in the catalyst, combined with an XRD diagram, indicating that we have successfully prepared a molybdenum doped nickel cobalt prussian blue analogue catalyst.
FIG. 8 is a Mo-NiCo PBA/NF electrocatalyst and commercial RuO prepared in example 2 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear scan voltammograms in mixed solutions, as can be seen with and commercial RuO 2 Compared with/NF, the Mo-NiCo PBA/NF electrocatalyst prepared in example 2 has higher current density and drives 100mAcm -2 Requires only a voltage of 1.34V, compared to the commercial RuO 2 NF low 180mV, shows that the Mo-NiCo PBA/NF electrocatalyst prepared in example 2 has better electrocatalysis performance in urea oxidation.
FIG. 9 is a Tafel plot of the Mo-NiCo PBA/NF electrocatalyst prepared in example 2, it can be seen that the Mo-NiCo PBA/NF catalyst has a smaller Tafel slope (15.59 mV dec -1 ) Indicating a faster reaction kinetics.
FIG. 10 is a schematic diagram of a Mo-NiCo PBA/NF electrocatalyst prepared in example 2 at 1mol/LKOH+0.33mol/LCO (NH 2 ) 2 The timing voltage graph in the mixed solution shows that the Mo-NiCo PBA/NF electrocatalyst prepared in example 2 is 10mAcm -2 The constant current density of the catalyst can stably run for more than 50 hours, and the voltage is not obviously increased, which indicates that the catalyst has higher stability in the electrocatalytic oxidation process.
FIG. 11 shows the Mo-NiCo PBA/NF electrocatalyst and commercial Pt/C/NF prepared in example 2 as an anode and cathode respectively, urea-assisted perhydrolysis cell at 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear sweep voltammogram in the mixed solution. The Mo-NiCo PBA/NF electrocatalyst prepared in example 2 and a commercial Pt/C/NF cell were run at 50mA cm -2 The voltage is only 1.44V, compared with the commercial RuO 2 The electrolysis cell composed of/NF and commercial Pt/C/NF was 120mV lower, demonstrating that the Mo-NiCo PBA/NF electrocatalyst prepared in example 2 can be effectively used for energy-saving hydrogen production in urea-assisted electrolyzed water systems.
FIG. 12 is a graph showing the timing voltage of a full hydrolysis cell with urea assistance for anode and cathode composition, respectively, using the Mo-NiCo PBA/NF electrocatalyst and commercial Pt/C/NF prepared in example 2, which can be seen at 10mAcm -2 Can be stably operated for more than 27 hours at a constant current density, and the voltage is not remarkably increased, which indicates that the electrolyte has excellent stability in a urea-assisted full hydrolysis electrolytic cell.
Example 3:
Mo-NiCo PBA/NF electrocatalyst prepared according to the procedure described in example 2, except that the other conditions were unchanged, na alone 2 MoO 4 ·2H 2 The molar amount of O was changed to 0.025mmol.
FIG. 13 is a Mo-NiCo PBA/NF electrocatalyst and commercial RuO prepared in example 3 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear scan voltammograms in mixed solutions, as can be seen from the figures, with commercial RuO 2 Compared with/NF, the Mo-NiCo PBA/NF electrocatalyst has lower initial potential and drives 100mAcm -2 Requires only a voltage of 1.36V, compared to commercial RuO 2 The NF was 160mV lower, indicating that the Mo-NiCo PBA/NF electrocatalyst prepared in example 3 had better urea oxidation performance.
FIG. 14 is a Tafel plot of the Mo-NiCo PBA/NF electrocatalyst prepared in example 3, it can be seen that the Mo-NiCo PBA/NF catalyst has a smaller Tafel slope (18.79 mV dec -1 ) Indicating a faster reaction kinetics.
Example 4:
Mo-NiCo PBA/NF electrocatalyst prepared according to the procedure described in example 2, except that the other conditions were unchanged, na alone 2 MoO 4 ·2H 2 The molar amount of O was changed to 0.1mmol.
FIG. 15 is a Mo-NiCo PBA/NF electrocatalyst and commercial RuO prepared in example 4 2 NF was varied between 1mol/LKOH+0.33mol/L CO (NH) 2 ) 2 Linear scan voltammograms in mixed solutions, as can be seen from the figures, with commercial RuO 2 Compared with/NF, the Mo-NiCo PBA/NF electrocatalyst has lower initial potential and drives 100mAcm -2 Requires only a voltage of 1.36V, compared to commercial RuO 2 The NF was 160mV lower, indicating that the Mo-NiCo PBA/NF electrocatalyst prepared in example 4 had better urea oxidation performance.
FIG. 16 is a Tafel plot of the Mo-NiCo PBA/NF electrocatalyst prepared in example 3, it can be seen that the Mo-NiCo PBA/NF catalyst has a smaller Tafel slope (17.74 mV dec -1 ) Indicating a faster reaction kinetics.
By analyzing the above examples, the results of example 1 and examples 2, 3 and 4 show that the doping of molybdenum salt can effectively enhance the catalytic performance of the urea oxidation reaction of the nickel cobalt Prussian blue analogues and improve the kinetic rate of the urea oxidation reaction. From the results of example 2 and examples 3 and 4, we found thatThe doping amount of the molybdenum salt has an influence on the urea electro-oxidation performance of the nickel cobalt Prussian blue analogue, and 0.05mmol of Na is doped 2 MoO 4 ·2H 2 O is most preferred, example 2 has optimal catalytic performance, driving 100mAcm -2 The voltage required for the large current density of (c) is the lowest, and the tafel slope is also the smallest.
Claims (8)
1. The preparation method of the molybdenum-doped nickel-cobalt Prussian blue analogue with the binary composite structure is characterized by comprising the following steps of:
preparing a molybdenum-doped nickel-cobalt Prussian blue analogue by using a hydrothermal method and using foam nickel as a nickel source and a conductive substrate and growing the foam nickel in situ; the structure of the molybdenum doped nickel-cobalt Prussian blue analogue consists of a plate-shaped structure at the bottom and a rounded corner cube with the surface decorated; the method specifically comprises the following steps:
step 1: placing the surfactant dextran-20, citric acid monohydrate and molybdenum salt into a beaker, adding deionized water for dissolution, and marking as a solution A;
step 2: weigh K 3 [Co(CN) 6 ]Adding deionized water into a beaker for dissolution, and marking as a solution B;
step 3: dropwise adding the solution A into the solution B under stirring, and uniformly mixing;
step 4: transferring the mixed solution obtained in the step 3 into a Teflon-lined autoclave with a pretreated foam nickel, and keeping the temperature at 60-100 ℃ for 10-14 hours; and naturally cooling to room temperature after the reaction is finished, washing with deionized water, and drying in an oven to finally obtain the molybdenum-doped nickel-cobalt Prussian blue analogue Mo-NiCoPBA/NF with the binary composite structure.
2. The method of manufacturing according to claim 1, characterized in that:
in step 1, the molar amount of dextran-20 was 0.1mmol and the molar amount of citric acid monohydrate was 2.1mmol.
3. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the molybdenum salt is Na 2 MoO 4 ·2H 2 O, the molar amount of which is 0.01-0.1 mmol.
4. The method of manufacturing according to claim 1, characterized in that:
in step 2, K 3 [Co(CN) 6 ]The molar amount of (2) was 0.5mmol.
5. The method of manufacturing according to claim 1, characterized in that:
in step 4, the pretreated foam nickel is obtained by the following method: cutting a foam nickel electrode, ultrasonically cleaning the foam nickel electrode with dilute hydrochloric acid solution, acetone and deionized water in advance, and drying the foam nickel electrode in an oven for standby.
6. The application of the molybdenum-doped nickel-cobalt Prussian blue analogues with the binary composite structures prepared by the preparation method according to any one of claims 1 to 5 is characterized in that:
the binary composite structure molybdenum doped nickel cobalt Prussian blue analogue is used as a catalyst, and the electrocatalytic oxidation reaction of urea is realized under an alkaline condition.
7. The use according to claim 6, characterized in that:
the three-electrode system is used, the molybdenum doped nickel-cobalt Prussian blue analogue is directly used as a working electrode, a platinum sheet electrode is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and the catalytic oxidation of urea is carried out in alkaline electrolyte.
8. The use according to claim 7, characterized in that:
the alkaline electrolyte is 1mol/LKOH solution, KOH and CO (NH) 2 ) 2 The molar ratio of (2) was 1:0.33.
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