CN112473673B - Nickel-based methane catalyst and preparation method and application thereof - Google Patents
Nickel-based methane catalyst and preparation method and application thereof Download PDFInfo
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- CN112473673B CN112473673B CN202011376266.8A CN202011376266A CN112473673B CN 112473673 B CN112473673 B CN 112473673B CN 202011376266 A CN202011376266 A CN 202011376266A CN 112473673 B CN112473673 B CN 112473673B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 98
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- -1 nickel salt ethanol-oleylamine Chemical compound 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/416—Systems
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Abstract
The invention belongs to the field of electrochemistry, and particularly relates to a nickel-based methane catalyst, and a preparation method and application thereof. The specific technical scheme is as follows: the foamed nickel is loaded with only monoatomic nickel. The invention provides a novel nickel-based catalyst, which not only effectively avoids the problem that the nano-catalyst is easy to generate carbon deposition and deactivate, but also avoids the problem that a nickel single atom is easy to unstably deactivate under the condition that an additive is not required to be additionally used; the obtained nickel-based catalyst has stable and reliable performance and high cycle efficiency. The nickel monoatomic in-situ growth is carried out on the foamed nickel, the nickel monoatomic in-situ growth and the foamed nickel are tightly combined, and no adhesive is added; the foam nickel and the monatomic nickel have a coordinating effect, and the problems of catalyst poisoning and agglomeration are avoided; thereby further improving the activity and stability of the catalyst and being widely applied to the field of electrochemical catalysis.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a nickel-based methane catalyst, and a preparation method and application thereof.
Background
Methane sensors have been an important research topic in modern industrial and technical fields. The rapid development of various catalysts makes it possible to realize rapid detection of methane at lower temperatures or normal temperature and pressure. Of the many catalysts, metal catalysts remain the mainstream for methane sensor applications. Compared with the noble metal catalyst, the nickel-based catalyst has the advantages of high reaction activity, abundant reserves, low price and the like, and has the possibility of replacing the noble metal catalyst. Therefore, the method plays an important role in the research of methane catalytic detection. However, the nickel-based catalyst or the nickel nanoparticle catalyst in the prior art generally has the problem of deactivation due to carbon deposition.
The deactivation of the nano nickel-based catalyst mainly comes from carbon deposition of the catalyst. The existing research shows that: the carrier and the catalytic active component are closely related to carbon deposition; if a nickel monoatomic compound is used as the catalytically active component, the carbon deposition is significantly reduced. However, the thermal stability of the nickel monoatomic layer is poor, and the nickel monoatomic layer is easy to sinter and is deactivated; in some cases, it is necessary to add a component such as cerium oxide to stabilize a single atom and improve the stability of the catalyst.
The method has important practical significance if a new nickel-based catalyst which does not need additional components, resists carbon deposition and has high stability can be provided.
Disclosure of Invention
The invention aims to provide a novel nickel-based catalyst and apply the catalyst to a methane sensor.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a nickel-based catalyst is supported on foamed nickel and only monatomic nickel is supported.
Correspondingly, the preparation method of the nickel-based catalyst comprises the following steps:
(1) adding ethanol and oleylamine into a nickel nitrate aqueous solution, and stirring to obtain a nickel salt ethanol-oleylamine solution; vertically inserting foamed nickel into a nickel salt ethanol-oleylamine solution, and reacting for 5-12 h at 80-150 ℃;
(2) and after the reaction is finished, naturally cooling to room temperature, taking out the foamed nickel, washing with water, and drying to obtain the required nickel-based catalyst.
Preferably, the nickel salt is nickel nitrate.
Preferably, before step (1), the nickel foam is pretreated as follows:
soaking the foamed nickel in a hydrochloric acid aqueous solution, then washing with water, then ultrasonically cleaning in an ammonia aqueous solution, then washing with water, and drying for 2 hours.
Preferably, the mass concentration of the hydrochloric acid aqueous solution is 0.5-5.0%.
Preferably, the mass fraction of the nickel nitrate aqueous solution is 0.01-1.0%.
Preferably, the nickel nitrate aqueous solution is 5-20 mL corresponding to 1-10 mL of ethanol and 0.1-2 mL of oleylamine.
Correspondingly, the nickel-based catalyst is applied to the preparation of the electrode.
Accordingly, a methane sensor comprising said electrode.
Correspondingly, the preparation method of the methane sensor takes silver/silver chloride as a reference electrode, a platinum wire as a counter electrode and the nickel-based catalyst as a working electrode.
The invention has the following beneficial effects:
the invention provides a novel nickel-based catalyst and a preparation method thereof. The nickel-based catalyst directly grows the nickel monoatomic atom on the foamed nickel in situ, thereby not only effectively avoiding the problem that the nano catalyst is easy to generate carbon deposition and inactivate, but also avoiding the problem that the nickel monoatomic atom is easy to unstably inactivate under the condition of not additionally using an additive; the obtained nickel-based catalyst has stable and reliable performance and high cycle efficiency.
In addition, the nickel monoatomic in-situ growth is carried out on the foamed nickel, the nickel monoatomic in-situ growth and the foamed nickel are tightly combined, and no adhesive is added; the foam nickel and the monatomic nickel have a coordinating effect, and the problems of catalyst poisoning and agglomeration are avoided; thereby further improving the activity and stability of the catalyst and being widely applied to the field of electrochemical catalysis.
Drawings
FIG. 1 is a SEM representation of nickel plate prepared by the present invention;
FIG. 2 is a TEM representation of a nickel plate prepared by the invention;
fig. 3 is a plot of the chronoamperometric current of methane on a modified nickel electrode.
Detailed Description
The invention provides a novel nickel-based catalyst, which specifically comprises the following components in percentage by weight: and loading monatomic nickel on the foamed nickel to prepare the nickel sheet. The nickel sheet can be used for manufacturing electrodes and further applied to various electrochemical sensors including methane sensors.
The preparation process of the nickel sheet specifically comprises the following steps:
1. foam nickel pretreatment: cutting the foamed nickel into a required shape, soaking in a hydrochloric acid aqueous solution with the mass concentration of 0.5-5.0% for 1-5 min, and then cleaning with deionized water. Then carrying out ultrasonic treatment in an ammonia water solution with the mass concentration of 1.0-15.0% for 10-30 min, and then cleaning with deionized water. And drying for 2 hours at the temperature of 50-100 ℃ after cleaning to obtain the foamed nickel substrate.
2. Preparing a nickel sheet with foamed nickel loaded with nickel monoatomic by a hydrothermal method: putting 5-20 mL of nickel nitrate water solution with the mass fraction of 0.01-1.0% into a 100mL beaker (any nickel salt soluble in ethanol can be used in the place), then adding 1-10 mL of ethanol and 0.1-2 mL of oleylamine, and stirring for 10-30 min to obtain the nickel nitrate ethanol-oleylamine solution. Transferring the nickel nitrate ethanol-oleylamine solution into a 50mL hydrothermal reaction kettle, vertically putting the pretreated foamed nickel into the reaction kettle filled with the nickel nitrate ethanol-oleylamine solution, and reacting for 5-12 h at the temperature of 80-150 ℃; within this reaction time range, the monatomic loading is proportional to the reaction time.
And after the reaction is finished, naturally cooling to room temperature, opening the hydrothermal reaction kettle, and taking out the foam nickel sheet. And repeatedly washing the foam nickel sheet with deionized water, ultrasonically cleaning the foam nickel sheet with deionized water for 10min, and finally drying the foam nickel sheet with nitrogen to obtain the foam nickel sheet loaded with the monatomic nickel. The nickel sheet can be directly used as an electrode.
The use method of the nickel sheet as the electrode of the methane sensor comprises the following steps: a conventional three-electrode system is used. Silver/silver chloride is used as a reference electrode, a platinum wire is used as a counter electrode (cathode), the nickel sheet is used as a working electrode, and an environment-friendly high-stability ionic liquid (1-butyl-3-methylimidazolium salt [ bmim ]) is adopted]、[CF3 SO3]、[bmim]ClEtc.) as the electrolyte.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Examples
1. Foam nickel pretreatment: cutting the foamed nickel into cuboids with the thickness of 1cm multiplied by 4cm multiplied by 0.5mm, soaking in 2.0% hydrochloric acid aqueous solution for 5min, cleaning with deionized water, then carrying out ultrasonic treatment in 5.0% ammonia aqueous solution for 30min, cleaning with deionized water, and drying at 80 ℃ for 2h to obtain the foamed nickel substrate.
2. Preparing a nickel-loaded foam monoatomic electrode by a hydrothermal method: 20mL of a 0.5% nickel nitrate aqueous solution was placed in a 100mL beaker, and then 10mL of a mixture of ethanol and 1mL of oleylamine was added thereto and stirred for 30 min. And then transferring the nickel foam into a 50mL polytetrafluoroethylene hydrothermal reaction kettle, vertically putting the nickel foam pretreated in the step 1 into the reaction kettle filled with the nickel nitrate ethanol-oleylamine solution, and reacting for 10 hours at the temperature of 120 ℃. And then naturally cooling to room temperature, opening the hydrothermal reaction kettle, taking out the foamed nickel sheet, repeatedly washing with deionized water, ultrasonically cleaning with deionized water for 10min, and finally drying with nitrogen to obtain the foamed nickel sheet loaded with the monatomic nickel.
SEM characteristics of the prepared nickel plate are shown in figure 1, and TEM characteristics are shown in figure 2.
3. After the preparation is finished, the traditional three-electrode system is randomly adopted to prepare the methane electrochemical sensor. Taking silver/silver chloride as a reference electrode, a platinum wire as a counter electrode, the foam nickel sheet as a working electrode and 1-butyl-3-methylimidazolium salt [ bmim ] as an electrolyte; the detection of methane is realized within the electrochemical window of-0.5V-1.5V. The results of the detection are shown in FIG. 3. In FIG. 3, a to f represent the methane concentrations: time-current curves of 0.5%, 3%, 6%, 9%, 12%, 16% (methane/nitrogen, v/v). As can be seen from fig. 3: the methane sensor has short response time to methane, high detection speed and wide detection range, and under different methane concentrations, the peak current of an oxidation peak is increased along with the increase of the methane concentration, and the concentration is in direct proportion to the peak current.
And the cycle life of the nickel sheet electrode material is measured within the range of-0.5V to 1.5V, the cycle is carried out for 5000 times, and the cycle efficiency is 98.5 percent.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes, modifications, alterations, and substitutions which may be made by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (9)
1. A nickel-based catalyst characterized by: the foam nickel is loaded with only monoatomic nickel; the preparation method of the nickel-based catalyst comprises the following steps:
(1) adding ethanol and oleylamine into the nickel salt aqueous solution, and stirring to obtain a nickel salt ethanol-oleylamine solution; vertically inserting foamed nickel into a nickel salt ethanol-oleylamine solution, and reacting for 5-12 h at 80-150 ℃;
(2) and after the reaction is finished, naturally cooling to room temperature, taking out the foamed nickel, washing with water, and drying to obtain the required nickel-based catalyst.
2. The nickel-based catalyst of claim 1, wherein: the nickel salt is nickel nitrate.
3. The nickel-based catalyst of claim 1, wherein: before the step (1), the foamed nickel is pretreated as follows:
soaking the foamed nickel in a hydrochloric acid aqueous solution, then washing with water, then ultrasonically cleaning in an ammonia aqueous solution, then washing with water, and drying for 2 hours.
4. The nickel-based catalyst according to claim 3, characterized in that: the mass concentration of the hydrochloric acid aqueous solution is 0.5-5.0%.
5. The nickel-based catalyst of claim 2, wherein: the mass fraction of the nickel nitrate aqueous solution is 0.01-1.0%.
6. The nickel-based catalyst according to claim 5, wherein: 5-20 mL of nickel nitrate aqueous solution corresponding to 1-10 mL of ethanol and 0.1-2 mL of oleylamine.
7. Use of the nickel-based catalyst according to any of claims 1 to 6 for the preparation of electrodes.
8. A methane sensor comprising the electrode of claim 7.
9. A method for producing the methane sensor according to claim 8, wherein: silver/silver chloride is used as a reference electrode, a platinum wire is used as a counter electrode, and the nickel-based catalyst is used as a working electrode.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051414A1 (en) * | 2000-01-07 | 2001-07-19 | Conoco, Inc. | Bulk nickel alloy catalysts and process for production of syngas |
| CN103311535A (en) * | 2013-06-21 | 2013-09-18 | 兰州大学 | Three-dimensional honeycomb-shaped Ni(OH)2 battery material as well as preparation method and application thereof |
| CN106887610A (en) * | 2017-05-04 | 2017-06-23 | 西安科技大学 | A kind of load Ir nano composite materials and its application in lithium air battery positive electrode in situ of nickel foam |
| CN109225257A (en) * | 2018-10-16 | 2019-01-18 | 中国科学技术大学先进技术研究院 | A kind of monatomic catalyst of support type and preparation method thereof |
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2020
- 2020-11-30 CN CN202011376266.8A patent/CN112473673B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051414A1 (en) * | 2000-01-07 | 2001-07-19 | Conoco, Inc. | Bulk nickel alloy catalysts and process for production of syngas |
| CN103311535A (en) * | 2013-06-21 | 2013-09-18 | 兰州大学 | Three-dimensional honeycomb-shaped Ni(OH)2 battery material as well as preparation method and application thereof |
| CN106887610A (en) * | 2017-05-04 | 2017-06-23 | 西安科技大学 | A kind of load Ir nano composite materials and its application in lithium air battery positive electrode in situ of nickel foam |
| CN109225257A (en) * | 2018-10-16 | 2019-01-18 | 中国科学技术大学先进技术研究院 | A kind of monatomic catalyst of support type and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Pd-Ni 双金属复合物修饰泡沫镍电极对水中4-氯酚的电化学脱氯;宋爽;《化工学报》;20090630;第60卷(第6期);第1555页第1.2节，第1556页第2.2节 * |
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