CN111921552A - Transition metal nitrogen-doped phosphide catalyst and preparation method and application thereof - Google Patents
Transition metal nitrogen-doped phosphide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 54
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006262 metallic foam Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 13
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 30
- 239000010411 electrocatalyst Substances 0.000 description 13
- 239000006260 foam Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- -1 salt ions Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a transition metal nitrogen-doped phosphide catalyst, a preparation method thereof and application of the transition metal nitrogen-doped phosphide catalyst as a hydrogen production catalyst or an oxygen production catalyst. The preparation method comprises the following steps: (1) adding transition metal foam into deionized water, then carrying out hydrothermal reaction at 160-250 ℃, and washing and drying after the reaction is finished to obtain a transition metal hydroxide catalyst; (2) placing the obtained transition metal hydroxide catalyst and red phosphorus at two different positions in the same tubular furnace, heating to 400-700 ℃ under protective atmosphere, vacuumizing at the temperature until the air pressure in the tubular furnace is 5-100 Pa, then adjusting the power of a radio frequency power supply to be 50-200W, performing glow discharge on the gas in the tubular furnace to generate plasma for assisting phosphorization, and cooling to obtain a transition metal nitrogen-doped phosphide catalyst; the protective atmosphere is nitrogen or a mixed gas of nitrogen and rare gas.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a transition metal nitrogen-doped phosphide catalyst and a preparation method and application thereof.
Background
In recent years, many researchers have paid attention to transition metal phosphide because of its excellent electrochemical catalytic performance. However, in the conventional preparation method of the precursor, metal salt is added for hydrothermal reaction and is loaded on the transition metal foam, so that the stability of the electrocatalyst is poor. In addition, if the method is popularized in industrial production on a large scale, the residual metal salt ions will cause environmental pollution. In addition, the catalytic performance of the currently reported transition metal phosphide catalysts is still worse than that of the same supported platinum carbon.
Patent specification No. CN 109208028A discloses a method for producing nitrogen and phosphorus compounds with improved water-splitting performance, and although nitriding or phosphating treatment in a tube furnace is disclosed, it is not clear how to nitride or phosphide. In the art, the nitriding method is generally carried out by calcination under an ammonia atmosphere. And the above patent art does not disclose how to simultaneously implement nitrogen doping and phosphating.
The patent specification with publication number CN 107478699A discloses a preparation method and application of a foam transition metal phosphide-supported noble metal, wherein the phosphorization method comprises the steps of respectively placing red phosphorus powder and foam transition metal with an oxide layer removed on the surface on two sides of a porcelain boat, placing the porcelain boat in the center of a tubular annealing furnace, and adopting one or a mixture of nitrogen and argon as protective gas. The method uses nitrogen as protective gas, only can carry out phosphorization, and cannot fully utilize nitrogen to realize simultaneous nitridation.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a transition metal nitrogen-doped phosphide catalyst, which comprises the steps of taking deionized water as a reaction liquid under the condition of not adding metal salt, growing an electrocatalyst on transition metal foam in situ, and preparing the nitrogen-doped phosphide catalyst by the aid of plasma. The in-situ hydrothermal method is combined with the plasma-assisted phosphating method, so that the catalytic stability and catalytic activity of the electrocatalyst are improved, the preparation cost of the electrocatalyst is reduced, and the environmental pollution is reduced.
A preparation method of a transition metal nitrogen-doped phosphide catalyst comprises the following steps:
(1) adding transition metal foam into deionized water, then carrying out hydrothermal reaction at 160-250 ℃, and washing and drying after the reaction is finished to obtain a transition metal hydroxide catalyst;
(2) placing the obtained transition metal hydroxide catalyst and red phosphorus at two different positions in the same tubular furnace, heating to 400-700 ℃ under protective atmosphere, vacuumizing at the temperature until the air pressure in the tubular furnace is 5-100 Pa, then adjusting the power of a radio frequency power supply to be 50-200W, performing glow discharge on the gas in the tubular furnace to generate plasma for assisting phosphorization, and cooling to obtain a transition metal nitrogen-doped phosphide catalyst;
the protective atmosphere is nitrogen or a mixed gas of nitrogen and rare gas.
The invention provides an environment-friendly in-situ preparation method capable of improving the stability and the electrocatalysis performance of an electrocatalyst. According to the method, transition metal foam is used as a metal source, hydrothermal reaction is carried out in deionized water, and the hydroxide electrocatalyst is prepared in situ, so that the stability of the electrocatalyst is improved, and the preparation cost and the environmental pollution of the catalyst are reduced. And then, on the basis of preparing phosphide in the traditional nitrogen-containing gas protective atmosphere, adding a radio frequency power supply on a quartz tube of the tube furnace for nitrogen-doped phosphating. The invention fully utilizes the protective gas nitrogen, simultaneously realizes the introduction of phosphorus and nitrogen elements, and greatly improves the electrocatalytic performance of the electrocatalyst.
In the step (1), the transition metal foam is preferably made of at least one transition metal of Ni, Fe, Co, Cu, and Ti, and more preferably made of at least two transition metals of Ni, Fe, Co, Cu, and Ti.
In the step (1), the volume ratio of the transition metal foam to the deionized water is preferably 1: 10-40, and more preferably 1: 15-35.
In the step (1), the time of the hydrothermal reaction is preferably 6-72 hours, and more preferably 12-60 hours.
Preferably, in the step (1), the drying temperature is 40-70 ℃ and the drying time is 2-24 h.
Preferably, the ratio of the volume of the transition metal foam in step (1) to the mass of red phosphorus in step (2) is 1cm3:0.1～2g。
Preferably, in the step (2), the temperature is raised to 400 to 650 ℃ in a protective atmosphere, and the tube furnace is evacuated at the temperature until the air pressure in the tube furnace is 5 to 100 Pa.
Preferably, in the step (2), the time for generating plasma-assisted phosphating by glow discharge is 1-4 h.
In the preparation method, the transition metal foam is not only used as a base material, but also used as a source of transition metal elements, so that the catalyst forms a stable integrated structure, thereby showing super-strong catalytic stability. In addition, the nitrogen-doped phosphide electrocatalyst is prepared by a plasma-assisted method, so that the temperature and time required by phosphorization are reduced, the reaction activity of the protective atmosphere is increased, the utilization rate of the protective atmosphere is increased, the doping of nitrogen is introduced, the active sites and the electron transmission capability of the electrocatalyst are increased, and the electrocatalysis performance of the electrode material is obviously improved.
The invention also provides the transition metal nitrogen-doped phosphide catalyst prepared by the preparation method.
The invention also provides the application of the transition metal nitrogen-doped phosphide catalyst as a hydrogen production catalyst or an oxygen production catalyst.
The invention adopts a two-step method to prepare the catalyst in situ. Firstly, under the condition of not adding metal salt, taking multiphase transition metal foam as a metal source, and carrying out hydrothermal preparation on a catalyst hydroxide precursor by using pure water, so that the stability of the catalyst is fundamentally improved; secondly, the N is contained by plasma assistance2Synchronous phosphorus nitridation of the catalyst is realized in the atmosphere, so that the electrochemical performance of the catalyst is greatly improved. The method not only generates the sub-glow plasma, but also has no pollution to the environment in the whole process, and is a resource-saving, energy-saving and environment-friendly preparation process. The invention can effectively solve the problem that the residual metal salt ions in the traditional catalyst preparation process cause certain degree to the environmentPollution, poor catalyst stability and the like, reduces the preparation cost of the catalyst, and provides a new approach and a new technology for preparing the heterogeneous transition metal catalyst with ultra-stable electrocatalytic activity by in-situ engineering.
Compared with the prior art, the invention has the main advantages that: the invention prepares the transition metal electrocatalyst in situ by an environment-friendly hydrothermal method, and then prepares the nitrogen-doped phosphide electrocatalyst material by the aid of plasma. The nitrogen-doped phosphide electrocatalyst material prepared by the invention shows excellent HER catalytic activity due to good electrocatalytic water decomposition performance, the initial overpotential is 0mV and is 10 mA/cm-2Has an overpotential of less than 28mV at 400mA cm-2Is less than 190 mV. The activity of the transition metal nitrogen doped phosphide catalyst of the present invention was even better than that of the commercial Pt/C catalyst. The result shows that the heterogeneous transition metal nitrogen-doped phosphide catalyst can be used as a high-efficiency non-noble metal hydrogen production catalyst, and simultaneously shows good OER catalytic activity at 100mA cm-2And 400mA cm-2The overpotential at the current density of (a) is less than 350mV and 400mV, respectively. The activity of the transition metal nitrogen-doped phosphide catalyst is superior to that of RuO2A catalyst. This indicates that the heterogeneous transition metal nitrogen-doped phosphide of the present invention can be used as an efficient oxygen-producing catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of N-doped NiCoFeP obtained in example 1;
FIG. 2 is a N1s XPS plot of N-doped NiCoFeP obtained in example 1;
FIG. 3 is a graph of hydrogen evolution performance for different catalysts;
FIG. 4 is a graph of oxygen evolution performance for different catalysts;
FIG. 5 is a polarization curve diagram of the nitrogen-doped nickel-cobalt iron phosphide obtained in example 1 for full water splitting at two electrodes.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The preparation method of the transition metal nitrogen-doped phosphide catalyst in the following example comprises the following steps:
(1) firstly, ultrasonically cleaning cut transition metal foam with acetone, respectively cleaning with ethanol and deionized water for three times, and drying in a vacuum drying oven to obtain the pretreated transition metal foam.
(2) Transferring the treated metal foam and weighed deionized water into a Teflon high-pressure reaction kettle together for hydrothermal reaction. And after the reaction is finished, taking out the sample, respectively washing the sample with ethanol and deionized water for three times, and then putting the sample into a vacuum drying oven for drying.
(3) And placing the dried sample on a porcelain boat along the direction of air flow, and placing the porcelain boat at the downstream of the tube furnace. And weighing red phosphorus, paving the red phosphorus at the bottom of another porcelain boat, and placing the red phosphorus at the upstream of the tube furnace. A temperature rise control program is set.
(4) Introducing N at a flow rate of 10-50 sccm2Gas is exhausted for 10-30 min to exhaust the air in the tube furnace;
(5) raising the temperature in the tubular furnace cavity to the reaction temperature at a heating rate of 4-5 ℃/min;
(6) after the temperature is raised to the reaction temperature, the reaction temperature is kept unchanged, the pressure in the tubular furnace cavity is controlled, the radio frequency power supply is turned on, the gas in the tubular furnace is subjected to glow discharge to generate plasma by adjusting the power, and the synchronous nitrogen-doped phosphating of the catalyst is realized. Then naturally cooling along with the furnace to obtain the transition metal nitrogen-doped phosphide.
Example 1
Firstly, ultrasonically cleaning cut foam nickel-cobalt-iron with the size of 1cm multiplied by 1cm by acetone, respectively cleaning the foam nickel-cobalt-iron with ethanol and deionized water for three times, and putting the foam nickel-cobalt-iron into a vacuum drying oven for drying to obtain the pretreated transition metal foam.
And step two, transferring the treated metal foam and 35mL of deionized water into a Teflon high-pressure reaction kettle together, and carrying out hydrothermal reaction at 200 ℃ for 24 hours. And after the reaction is finished, taking out the sample, respectively washing the sample with ethanol and deionized water for three times, and then putting the sample into a vacuum drying oven for drying.
And step three, placing the dried sample on a porcelain boat along the direction of air flow, and placing the porcelain boat at the downstream of the tube furnace. Then 0.2g of red phosphorus is weighed and spread at the bottom of another porcelain boat and placed at the upstream of the tube furnace. A temperature rise control program is set.
Step four, introducing N2The gas was purged for 10min at a flow rate of 20sccm to purge the air from the tube furnace.
Step five, raising the temperature in the cavity of the tubular furnace to 550 ℃ at a heating rate of 5 ℃/min;
and step six, after the temperature is raised to the reaction temperature, maintaining the reaction temperature unchanged, vacuumizing to control the pressure in the cavity of the tubular furnace to reach 5Pa, turning on a radio frequency power supply, performing glow discharge on the gas in the tubular furnace to generate plasma by adjusting the power, wherein the power of the radio frequency power supply is 100W, so that the synchronous nitrogen-doping and phosphorization of the catalyst are realized, and the time of the nitrogen-doping and phosphorization treatment is 2 hours. And then naturally cooling along with the furnace to obtain the nickel-cobalt-iron nitrogen-doped phosphide.
Fig. 1 shows a scanning electron microscope photograph of the nifp prepared in this example, from which it is clear that the nifp grows uniformly on the metal foam and has a sheet structure.
Fig. 2 is an N1s XPS diagram of the ni-fe-ni doped phosphide of the present example, from which it can be seen that two peaks near 399.1eV and 400.1eV are metal bonded nitrogen (M-N) and pyrrole nitrogen (Pyrrolic-N), respectively, indicating that the simultaneous N doped phosphide was successfully performed by plasma assistance.
Comparative example 1
The difference from the embodiment 1 is that no vacuum pumping is performed, no radio frequency power supply is used for glow discharge to generate plasma, the temperature is raised to 550 ℃ in the step five times, the step is maintained for 2 hours, and then the nickel cobalt iron phosphide is obtained after natural cooling along with the furnace.
The preparation method of the Pt/C/foam nickel-cobalt-iron composite catalyst (Pt/C or Pt/C catalyst for short) is similar to the preparation method of Pt/C/NF electrodes disclosed by the concept Performance of high efficiency Ni-Fe Oxyhydroxide @ NiFe Alloy Nanowire catalysts for Large Current Density Water spraying (DOI: 10.1039/C9ee02388g), and the difference is only that the foam carriers are different.
RuO2Foam nickel cobalt iron composite catalyst (RuO for short)2Catalyst) was prepared according to the following general practice of theoretical Ni-Fe Oxyhydroxide @ NiFe Alloy Nanowire arrays electrolytes for Large Current sensitivity Water spraying (DOI: 10.1039/c9ee02388g) IrO2NF electrolytes preparation method, the difference is only that RuO is used2And foam nickel cobalt iron to respectively replace IrO2And nickel foam.
Figure 3 shows the hydrogen evolution performance of different catalysts tested for nickel-cobalt-iron nitrogen-doped phosphide catalyzed HER performance in a 1.0M KOH solution at room temperature using a classical three-electrode system. Foam nickel cobalt iron and Pt/C were also used as comparative samples. At 5mV s-1Polarization curves for the foamed nickel cobalt iron, the nickel cobalt iron phosphide of comparative example 1, the nickel cobalt iron nitrogen-doped phosphide of example 1 and the Pt/C catalyst were obtained at the sweep rate of (a). As can be seen from the figure, the HER activity of the foamed nickel-cobalt-iron is poor, while the nickel-cobalt-iron phosphide and the nickel-cobalt-iron nitrogen-doped phosphide show excellent HER catalytic activity, especially the nickel-cobalt-iron nitrogen-doped phosphide prepared by the aid of plasma at 10mA cm-2And 400mA cm-2The overpotential at the current density of (a) is 27mV and 185mV, respectively. The activity of the nickel-cobalt-iron nitrogen-doped phosphide catalyst is even better than that of the Pt/C catalyst. The result shows that the catalytic performance of the catalyst is greatly improved by the aid of the plasma to assist nitrogen-doped phosphorization, and the nickel-cobalt-iron nitrogen-doped phosphide can be used as a high-efficiency non-noble metal hydrogen production catalyst.
Figure 4 shows the oxygen evolution performance of different catalysts, which were also tested in a 1.0M KOH solution at room temperature using a classical three electrode system for nickel-cobalt-iron nitrogen-doped phosphide catalyzed OER. FIG. 4 shows s at 5mV-1Sweeping speed of foam nickel cobalt iron, comparative example 1 nickel cobalt iron phosphide, example 1 nickel cobalt iron nitrogen-doped phosphide and RuO2Polarization curve of the catalyst, from which it can be seen that nickel foamThe cobalt iron has poor OER activity, the nickel cobalt iron phosphide and the nickel cobalt iron nitrogen-doped phosphide have excellent OER catalytic activity, and particularly the nickel cobalt iron nitrogen-doped phosphide prepared by the aid of plasma has 100mA cm-2And 400mA cm-2The overpotential at the current density of (a) is 310mV and 390mV, respectively. The activity of the nickel-cobalt-iron nitrogen-doped phosphide is superior to that of RuO2A catalyst. This indicates that nickel-cobalt-iron nitrogen-doped phosphide can be used as an oxygen-generating catalyst.
To be closer to practical use, we assembled a two-electrode electrolytic water device using the ni-fe-ni doped npp of example 1 as the anode and cathode, respectively. FIG. 5 shows the polarization curve of two-electrode total water splitting at a current density of 10mA cm-2The applied voltage is only 1.57V, and the results show that the nickel-cobalt-iron nitrogen-doped phosphide has practical value in full water decomposition.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a transition metal nitrogen-doped phosphide catalyst is characterized by comprising the following steps:
(1) adding transition metal foam into deionized water, then carrying out hydrothermal reaction at 160-250 ℃, and washing and drying after the reaction is finished to obtain a transition metal hydroxide catalyst;
(2) placing the obtained transition metal hydroxide catalyst and red phosphorus at two different positions in the same tubular furnace, heating to 400-700 ℃ under protective atmosphere, vacuumizing at the temperature until the air pressure in the tubular furnace is 5-100 Pa, then adjusting the power of a radio frequency power supply to be 50-200W, performing glow discharge on the gas in the tubular furnace to generate plasma for assisting phosphorization, and cooling to obtain a transition metal nitrogen-doped phosphide catalyst;
the protective atmosphere is nitrogen or a mixed gas of nitrogen and rare gas.
2. The production method according to claim 1, wherein in the step (1), the transition metal foam is composed of at least one transition metal of Ni, Fe, Co, Cu, Ti.
3. The preparation method according to claim 1, wherein in the step (1), the volume ratio of the transition metal foam to the deionized water is 1: 10-40.
4. The preparation method according to claim 1, wherein in the step (1), the hydrothermal reaction time is 6-72 h.
5. The method according to claim 1, wherein the drying in step (1) is carried out at a temperature of 40 to 70 ℃ for 2 to 24 hours.
6. The method according to claim 1, wherein the ratio of the volume of the transition metal foam in step (1) to the mass of the red phosphorus in step (2) is 1cm3:0.1～2g。
7. The preparation method according to claim 1, wherein in the step (2), the time for generating plasma-assisted phosphating by glow discharge is 1-4 h.
8. The transition metal nitrogen-doped phosphide catalyst prepared by the preparation method of any one of claims 1 to 7.
9. Use of the transition metal nitrogen-doped phosphide catalyst of claim 8 as a hydrogen-producing catalyst or an oxygen-producing catalyst.
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