CN115007169A - Catalyst for electrochemical oxidation reaction of ammonia, preparation method and application thereof - Google Patents
Catalyst for electrochemical oxidation reaction of ammonia, preparation method and application thereof Download PDFInfo
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- CN115007169A CN115007169A CN202210030550.2A CN202210030550A CN115007169A CN 115007169 A CN115007169 A CN 115007169A CN 202210030550 A CN202210030550 A CN 202210030550A CN 115007169 A CN115007169 A CN 115007169A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 47
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 97
- 229910002845 Pt–Ni Inorganic materials 0.000 claims description 46
- 239000006260 foam Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000002484 cyclic voltammetry Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- NTTJUFWCRRMIGF-UHFFFAOYSA-L [H]O[Ni]([Pt])O[H] Chemical compound [H]O[Ni]([Pt])O[H] NTTJUFWCRRMIGF-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 239000010411 electrocatalyst Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000002815 nickel Chemical class 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 12
- 235000019270 ammonium chloride Nutrition 0.000 description 10
- 238000010998 test method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a catalyst for the electrochemical oxidation reaction of ammonia, a preparation method and application thereof, belonging to the technical field of preparation of platinum-based electrocatalysts. The preparation method of the catalyst provided by the invention not only uses nickel salt and reduces the preparation cost of the catalyst, but also avoids the loading processes such as spraying of powder materials and the like by adopting a one-step in-situ growth method, and simultaneously improves the stability of the catalyst structure. The invention enriches and widens the preparation method and material types of the catalyst for the electrochemical oxidation reaction of ammonia.
Description
Technical Field
The invention belongs to the technical field of preparation of platinum-based electrocatalysts, and particularly relates to a catalyst for an electrochemical oxidation reaction of ammonia, a preparation method and application thereof.
Background
With the aggravation of global energy problems and environmental problems, the search for clean and efficient fossil fuel substitutes becomes a new research hotspot. Ammonia (NH) 3 ) The fuel is a promising fossil fuel substitute, has the outstanding advantages of high hydrogen storage capacity (17.7 wt%), high volume energy density, convenient transportation and storage, low production cost, easy liquefaction and the like, and further has wide attention in the field of energy. In addition, NH in the body of water 3 And NH 4 + The concentration exceeds the specified standard, thus causing water eutrophication, threatening the health of aquatic organisms and even causing harm to human bodies. Thus, NH in the water body is efficiently removed 3 And NH 4 + Also has important significance.
The electrochemical oxidation reaction of ammonia is one of the most important reactions to solve energy and environmental problems. It is a direct ammonia fuel cell, ammonia electrolysis, wastewater remediation, and anode reaction in electrochemical sensors. However, slow reaction kinetics become one of the challenges that limit its application. Platinum, a noble metal, is considered to be the best catalyst for the electrochemical oxidation reaction of ammonia, because of its advantages of low overpotential, weak binding force, and large current sensitivity. However, platinum reserves are low on the earth, which makes the platinum catalyst more expensive, and in order to solve this problem, scientists improve the catalytic activity of the catalyst, improve the utilization rate of platinum and reduce the cost of the platinum-based catalyst by methods such as morphology and size control, alloying and compounding.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for the electrochemical oxidation reaction of ammonia, a preparation method and application thereof.
The invention is realized by the following technical scheme:
a preparation method of a catalyst for the electrochemical oxidation reaction of ammonia specifically comprises the following steps:
the method comprises the following steps: cleaning the foamed nickel by taking the foamed nickel as a conductive substrate and a nickel source;
step two: adding chloroplatinic acid aqueous solution into deionized water, performing ultrasonic dispersion, putting the foamed nickel cleaned in the step (1) into the solution, transferring the solution into a reaction kettle for hydrothermal reaction, and preparing the platinum-nickel hydroxide (Pt-Ni (OH)) supported by the foamed nickel 2 -Ni foam)。
Further, the cleaning step in the first step is specifically that an organic reagent and a hydrochloric acid solution are adopted for ultrasonic cleaning in sequence, the ultrasonic cleaning time is 15 minutes each time, and finally deionized water is used for cleaning until the solution is neutral, and the solution is dried for standby; the organic reagent is one or more of toluene, acetone or ethanol.
Further, in the second step, the concentration of the chloroplatinic acid is 0.05-0.5mol/L, and the volume ratio of the deionized water to the chloroplatinic acid aqueous solution is 400: 1-40: 1.
further, the temperature of the hydrothermal reaction in the second step is 100-180 ℃, and the reaction time is 8-40 hours.
In another aspect, the present invention further provides an application of a catalyst for an electrochemical oxidation reaction of ammonia in an electrochemical oxidation reaction of ammonia, specifically as follows: platinum-nickel hydroxide supported on foamed nickel (Pt-Ni (OH)) using an electrochemical workstation 2 -Ni foam), platinum sheet (1.0cm × 1.0cm) and Saturated Calomel Electrode (SCE) were working, counter and reference electrodes, respectively; the Pt-Ni (OH) prepared by the method is prepared by taking a 1M KOH solution as an electrolyte and adopting Cyclic Voltammetry (CV) 2 -the catalytic ability of the Ni foam catalyst to perform the electrochemical oxidation reaction of ammonia.
Compared with the prior art, the invention has the following advantages:
1) the invention uses the foam nickel as the conductive substrate, and utilizes the three-dimensional structure thereof, thereby not only increasing Pt-Ni(OH) 2 The growth area of the catalyst and the specific surface area of the catalyst electrode can ensure that the catalyst is more fully contacted with the electrolyte, thus being beneficial to the diffusion rate of reactants and products;
2) the invention uses the foam nickel as the nickel source, thereby avoiding the use of other nickel salts and saving the preparation cost of the catalyst;
3) in the invention, Pt-Ni (OH) is prepared in situ by adopting one-step method 2 -Ni foam catalyst, compared to powder catalyst, Pt-Ni (OH) 2 The Ni foam grows on the surface of the Ni foam without a binder, is not easy to fall off and is more stable;
4) Pt-Ni (OH) prepared in the present invention 2 The catalyst is of a lamellar structure, so that the exposure of active sites is facilitated, and the catalytic activity is improved;
5) the invention successfully prepares the catalyst which can be directly used for the electrochemical oxidation reaction of ammonia, and provides reference for the design and preparation of the novel catalyst.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1: Pt-Ni (OH) in example 1 2 -Scanning Electron Microscopy (SEM) photographs, (b) Transmission Electron Microscopy (TEM) photographs and (c) transmission electron microscopy High Resolution (HRTEM) photographs of Ni foam samples;
FIG. 2: Pt-Ni (OH) prepared in example 1 2 -XRD and XPS spectra of Ni foam samples: (a) an XRD spectrum, (b) an XPS spectrum of O1s, (c) an XPS spectrum of Ni2p and (d) an XPS spectrum of Pt4 f;
FIG. 3: Pt-Ni (OH) in examples 1 to 3 2 CV curve of Ni foam catalyst at 0 and 0.1mol/L ammonium chloride concentration: (a) example 1, (b) example 2, (c) example 3;
FIG. 4 is a schematic view of: examples 4-7 Pt-Ni (OH) 2 CV curve of Ni foam catalyst at 0 and 0.1mol/L ammonium chloride concentration: (a) practice ofExample 4, (b) example 5, (c) example 6, (d) example 7;
FIG. 5: Pt-Ni (OH) in examples 8 to 9 2 CV curve of Ni foam catalyst at 0 and 0.1mol/L ammonium chloride concentration: (a) example 8, (b) example 9.
Detailed Description
The following embodiments are only used for illustrating the technical solutions of the present invention more clearly, and therefore, the following embodiments are only used as examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) cutting foamed nickel (Ni foam) into small blocks with the size of 1.0cm multiplied by 2.0cm, ultrasonically cleaning the small blocks by using organic reagents (toluene, acetone and ethanol) and hydrochloric acid solution, wherein the ultrasonic cleaning time is 15 minutes each time, finally cleaning the small blocks to be neutral by using deionized water, and drying the small blocks for later use;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), and the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally, reacting for 24 hours in a baking oven at 140 ℃, and washing the obtained Pt-Ni (OH)2-Ni foam with deionized water for later use;
Pt-Ni (OH) will be obtained 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test uses a three-electrode system, i.e. Pt-Ni (OH) 2 the-Ni foam is the working electrode, the platinum sheet (1.0 cm. times.1.0 cm) is the counter electrode, and the Saturated Calomel Electrode (SCE) is the reference electrode. The test method is cyclic voltammetry, the potential window is-1 to 0.2V (vs. SCE), and the scanning speed is 50 mV/s; a KOH solution of 1mol/L is used as a supporting electrolyte, and ammonium chloride of 0.1mol/L is used as an ammonia source. Before cyclic voltammetry testing, electricity was applied in a 1mol/L KOH solutionThe electrode is activated, and the number of scanning turns is 30.
The test result shows that: the catalyst prepared by the method of the invention has an oxidation peak current density of 22.81mA cm -2 。
Example 2
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 50. mu.L of chloroplatinic acid (0.1mol/L), the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally reacting for 24 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure was the same as in example 1; the test result shows that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of 2.47mA cm -2 。
Example 3
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 200. mu.L of chloroplatinic acid (0.1mol/L), the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally reacting for 24 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 -washing the Ni foam with deionized water for later use;
will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of ammonia of 11.18mA cm -2 。
Example 4
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), the Ni foam treated in a) was put into solution and transferred to a reaction vessel having a volume of 50 mL. Finally, reacting for 8 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of ammonia of 9.31mA cm -2 。
Example 5
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), and the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally reacting for 16 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of ammonia of 10.70mA cm -2 。
Example 6
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) toTo 35mL of deionized water, 100. mu.L of chloroplatinic acid (0.1mol/L) was added, and the Ni foam treated in a) was put into the solution and transferred to a 50 mL-volume reaction vessel. Finally, reacting for 32 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
Pt-Ni (OH) will be obtained 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of 8.39mA cm -2 。
Example 7
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), and the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally reacting for 40 hours in an oven at 140 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of 6.56mA cm -2 。
Example 8
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), and the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally, reacting for 24 hours in an oven at 100 ℃, and obtaining Pt-Ni (OH) 2 Flushing of-Ni foam with deionized waterWashing for later use
Will obtain Pt-Ni (OH) 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has the oxidation peak current density of 15.29mA cm -2 。
Example 9
The embodiment provides a preparation method of a catalyst for an electrochemical oxidation reaction of ammonia, which specifically comprises the following steps:
a) the cleaning process for the foamed nickel was as in example 1;
b) to 35mL of deionized water was added 100. mu.L of chloroplatinic acid (0.1mol/L), and the Ni foam treated in a) was put into solution and transferred to a 50mL reaction vessel. Finally reacting for 24 hours in an oven at 180 ℃, and obtaining Pt-Ni (OH) 2 Washing the-Ni foam with deionized water for later use;
Pt-Ni (OH) will be obtained 2 CC as catalyst for the catalytic activity test of the electrochemical oxidation reaction of ammonia. The test procedure is the same as that of example 1, and the test results show that: the test result shows that: the catalyst prepared by the method of the invention has an oxidation peak current density of 4.29mA cm -2 。
As shown in FIG. 1, from a of FIG. 1, Pt-Ni (OH) 2 The nanosheets formed on the surface of the Ni foam samples, but no platinum nanoparticles were observed, indicating that Pt-Ni (OH) 2 Together forming a nanoplate; from b of FIG. 1, it can be seen that Pt-Ni (OH) 2 Nanoplatelets, this result is in accordance with a of figure 1; FIG. 1 c is an HRTEM photograph showing two kinds of lattice fringes, which correspond to Ni (OH) 2 And Pt, which again demonstrates the formation of Pt-Ni (OH) 2 And (c) a complex.
In FIG. 2, a is Pt-Ni (OH) 2 XRD patterns of the-Ni foam samples, which can be seen to be respectively assigned to Ni (OH) 2 (001), (100) and (101) of (1) (JCPDS No. 14-0117). Illustrating the formation of Ni (OH) 2 Is beta type. But no diffraction peak of Pt is detected on the XRD pattern, which is probably stronger by foam nickelThe diffraction peak of (2) is masked. FIG. 2 b shows the result of fitting XPS spectra of O1s in Pt-Ni (OH)2-Ni foams. Two resolved peaks at binding energies of 531.3eV and 533.2eV, respectively, which can be attributed to OH - And metal-oxygen species. FIG. 2 c is a fit of Ni2p XPS spectra, with two peaks at binding energies 856.1eV and 873.8eV corresponding to Ni2p 3/2 And Ni2p 1/2 (ii) a Two peaks at the binding energies of 861.7eV and 879.8eV are respectively Ni2p 3/2 And Ni2p 1/2 The satellite peak of (2). The above results again show that Ni (OH) 2 Formed on the surface of the foamed nickel. XPS spectra of Pt (d in FIG. 2) shows two peaks corresponding to Pt4f 7/2 And Pt4f 5/2 . These two peaks can be further divided into three pairs of doublets: are located at 71.3eV and 74.7eV, 72.5eV and 75.7eV, 73.6eV and 76.9eV, and are respectively assigned to Pt 0 、Pt 2+ And Pt 4+ 。
FIG. 3 shows Pt-Ni (OH) in example 1 (a of FIG. 3), example 2 (b of FIG. 3) and example 3 (c of FIG. 3) under the conditions of a potential window of-1 to 0.2V and a scanning speed of 50mV/s 2 CV curves for the Ni foam catalyst at 0mol/L and 0.1mol/L ammonium chloride. It can be seen that a relatively clear oxidation peak appears upon addition of 0.1mol/L ammonium chloride, as illustrated in Pt-Ni (OH) 2 The oxidation reaction of ammonia takes place under the catalytic action of the-Ni foam catalyst.
FIG. 4 shows Pt-Ni (OH) in example 4 (a of FIG. 4), example 5 (b of FIG. 4), example 6 (c of FIG. 4) and example 7 (d of FIG. 4) under the conditions of a potential window of-1 to 0.2V and a scanning speed of 50mV/s 2 CV curves for the Ni foam catalyst at 0mol/L and 0.1mol/L ammonium chloride. It can be seen that a relatively clear oxidation peak appears upon addition of 0.1mol/L ammonium chloride, as illustrated in Pt-Ni (OH) 2 The oxidation reaction of ammonia occurs under the catalytic action of the Ni foam catalyst.
FIG. 5 shows Pt-Ni (OH) in example 8 (a in FIG. 5) and example 9 (b in FIG. 5) under the conditions of a potential window of-1 to 0.2V and a scanning speed of 50mV/s 2 CV curves for the Ni foam catalyst at 0mol/L and 0.1mol/L ammonium chloride. It can be seen that a relatively clear oxidation peak appears upon addition of 0.1mol/L ammonium chloride, as illustrated in Pt-Ni (OH) 2 The oxidation reaction of ammonia takes place under the catalytic action of the-Ni foam catalyst.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (6)
1. A preparation method of a catalyst for an electrochemical oxidation reaction of ammonia is characterized by comprising the following steps:
the method comprises the following steps: cleaning the foamed nickel by taking the foamed nickel as a conductive substrate and a nickel source;
step two: adding chloroplatinic acid aqueous solution into deionized water, performing ultrasonic dispersion, putting the foamed nickel cleaned in the step (1) into the solution, transferring the solution into a reaction kettle for hydrothermal reaction, and preparing the platinum-nickel hydroxide (Pt-Ni (OH)) supported by the foamed nickel 2 -Ni foam)。
2. The method for preparing the catalyst for the electrochemical oxidation reaction of ammonia according to claim 1, wherein the cleaning step in the first step is specifically ultrasonic cleaning with an organic reagent and a hydrochloric acid solution in sequence, each ultrasonic cleaning time is 15 minutes, and finally, the catalyst is cleaned to be neutral with deionized water and dried for later use; the organic reagent is one or more of toluene, acetone or ethanol.
3. The method of claim 1, wherein the concentration of chloroplatinic acid in step two is 0.05 to 0.5mol/L, and the volume ratio of the deionized water to the aqueous solution of chloroplatinic acid is in the range of 400: 1-40: 1.
4. the method according to claim 1, wherein the hydrothermal reaction is carried out at 100-180 ℃ for 8-40 hours.
5. A method for preparing a catalyst for the electrochemical oxidation of ammonia, characterized in that it is prepared by the method according to any one of claims 1 to 4.
6. The use of the catalyst prepared according to the method of claim 1 for the electrochemical oxidation of ammonia, in the electrochemical oxidation of ammonia, is characterized in that it comprises: platinum-nickel hydroxide supported on foamed nickel (Pt-Ni (OH)) using an electrochemical workstation 2 -Ni foam), platinum sheet (1.0cm × 1.0cm) and Saturated Calomel Electrode (SCE) were working, counter and reference electrodes, respectively; the Pt-Ni (OH) prepared by the method is prepared by taking a 1M KOH solution as an electrolyte and adopting Cyclic Voltammetry (CV) 2 -the catalytic ability of the Ni foam catalyst to perform the electrochemical oxidation reaction of ammonia.
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