CN113832494A - Preparation method and application of transition/rare earth multi-metal co-doped phosphide - Google Patents
Preparation method and application of transition/rare earth multi-metal co-doped phosphide Download PDFInfo
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- CN113832494A CN113832494A CN202111145752.3A CN202111145752A CN113832494A CN 113832494 A CN113832494 A CN 113832494A CN 202111145752 A CN202111145752 A CN 202111145752A CN 113832494 A CN113832494 A CN 113832494A
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- 230000007704 transition Effects 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 239000002041 carbon nanotube Substances 0.000 claims description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 19
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- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 19
- PNYPSKHTTCTAMD-UHFFFAOYSA-K trichlorogadolinium;hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Gd+3] PNYPSKHTTCTAMD-UHFFFAOYSA-K 0.000 claims description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- ULJUVCOAZNLCJZ-UHFFFAOYSA-K trichloroterbium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Tb+3] ULJUVCOAZNLCJZ-UHFFFAOYSA-K 0.000 claims description 13
- BUQFCXABQYNXLP-UHFFFAOYSA-K trichloroholmium;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ho](Cl)Cl BUQFCXABQYNXLP-UHFFFAOYSA-K 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 238000003760 magnetic stirring Methods 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
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- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- 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 provides a preparation method and application of a transition/rare earth multi-metal co-doped phosphide, wherein the method comprises the following steps: dissolving soluble ferric salt, soluble nickel salt and hydrated rare earth chloride in water containing organic ligands, stirring, completely dissolving to form a solution, cooling, washing and centrifuging through a hydrothermal method, and drying to obtain a precursor; step two, mixing the precursor prepared in the step one with an organic nitrogen source compound, fully and uniformly grinding, placing the porcelain boat containing the material in a tube furnace, and calcining in a protective atmosphere environment to obtain FeNiRE-NCNTs; and step three, the FeNiRE-NCNTs prepared in the step two and the inorganic phosphorus source compound are respectively loaded in two porcelain boats and placed in a tube furnace for phosphorization, and finally, the FeNiRE-P-NCNTs, namely the transition/rare earth multi-metal co-doped phosphide is obtained. The electrocatalyst prepared by the preparation method has excellent hydrogen production performance by water electrolysis and excellent stability under an acidic condition.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, relates to a doped phosphide, and particularly relates to a preparation method and application of a transition/rare earth multi-metal co-doped phosphide.
Background
Hydrogen energy, as the most sustainable and renewable green energy, will play a very important role in carbon neutralization and road decoration. Among the numerous methods of producing hydrogen, the great potential for hydrogen production by electrolysis of water has been recognized as one of the most attractive energy storage technologies with its environmental friendliness. However, in fact, the most efficient catalysts in the hydrogen evolution from water electrolysis, such as platinum, are noble metals, have low reserves in the earth's crust and are expensive, and thus cannot be used industrially on a large scale. Therefore, the development of a catalyst for hydrogen production by electrolyzing water with non-noble metal, which has high stability and activity, low price and abundant reserves, is a necessary trend of historical development.
Rare earth MOFs (RE-MOFs) is a novel MOFs taking rare earth ions as nodes, wherein rare earth cations have rich energy level structures, and therefore the rare earth MOFs has huge application potential in the field of electrocatalysis. MOFs have been widely reported as precursors for the preparation of nitrogen-doped transition metal carbon materials due to their high specific surface area and controllable intrinsic nitrogen-containing organic ligands, a strategy that overcomes the conductivity problem of MOFs to some extent. However, MOFs-derived carbon-based materials generally exhibit microporous properties, low graphitization degree and metal nanoparticle agglomeration phenomena, which are detrimental to mass and electron transport in electrocatalytic processes. The key to effectively solve the problems is to construct a novel carbon nanotube/carbon-based material, and the structure not only helps to prevent the metal nanoparticles from agglomerating, but also can effectively increase the conductivity of the metal nanoparticles and accelerate charge transfer in the electrochemical process. In addition, doping of heteroatoms (such as phosphorus) can enhance the catalytic activity of the carbon matrix by changing electronegativity, charge distribution and electron transfer behavior to introduce more active sites, thereby further enhancing the catalytic performance. Therefore, it is of great significance to explore the phosphide with efficient hydrogen evolution performance by using transition/rare earth multi-metal MOFs as a precursor.
Although related reports have been made on MOF-derived metal phosphide, such as the reports in Chinese patent application No. 201910325365.4, No. 202110308913.X, etc., the problems of ultra-high overvoltage, poor stability, etc. can not meet the requirement of commercial hydrogen evolution catalysis. Therefore, phosphide derived from transition/rare earth multi-metal co-doped MOFs is expected to show a special synergistic effect or electronic interaction so as to achieve the purpose of having high-efficiency and long-term stable catalytic electrolysis water hydrogen evolution performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and application of a transition/rare earth multi-metal co-doped phosphide, so as to solve the technical problems that noble metals in the metal-doped phosphide in the prior art are expensive, and MOFs-derived phosphide is high in overpotential and poor in stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a transition/rare earth multi-metal co-doped phosphide comprises the following steps:
dissolving soluble ferric salt, soluble nickel salt and hydrated rare earth chloride in water containing an organic ligand, stirring, completely dissolving to form a solution, cooling, washing and centrifuging through a hydrothermal method, and drying to obtain a precursor;
step two, mixing the precursor prepared in the step one with an organic nitrogen source compound, fully and uniformly grinding, placing the porcelain boat containing the material in a tubular furnace, and calcining in a protective atmosphere environment to obtain the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube;
and step three, the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nano tube prepared in the step two and an inorganic phosphorus source compound are respectively packaged in two porcelain boats and placed in a tubular furnace for phosphorization, and finally the transition/rare earth multi-metal co-doped phosphide is obtained.
The invention also has the following technical characteristics:
in the first step, the soluble ferric salt is ferric chloride hexahydrate; the soluble nickel salt is nickel chloride hexahydrate; the hydrated rare earth chloride is gadolinium chloride hexahydrate, terbium chloride hexahydrate or holmium chloride hexahydrate; the organic ligand is trimesic acid; the molar ratio of the total amount of the soluble ferric salt, the soluble nickel salt and the hydrated rare earth chloride to the trimesic acid is 3: 2.
In the first step, the molar ratio of the soluble ferric salt to the soluble nickel salt to the hydrated rare earth chloride is 1:1 (0.5-2), 1:1 (0.5-2.5) or 1:1 (0.5-3).
In the first step, the stirring mode is magnetic stirring, and the magnetic stirring time is 20 min; in the hydrothermal method, the filling volume ratio of the lining of the high-pressure reaction kettle is 70-80%; the reaction temperature of the sealing reaction is 150 ℃, and the reaction time is 24 h; the cooling mode is natural cooling; the washing mode is that water and ethanol are alternately washed for 6-8 times; the specific condition of the centrifugation is 7000rpm centrifugation for 15 min; the drying mode is that the mixture is placed in a vacuum oven at 60 ℃ for drying for 12 hours.
In the second step, the organic nitrogen source compound is dicyanodiamine; the mass ratio of the precursor to the dicyanodiamide is 1 (0.5-1.5), and preferably, the mass ratio of the precursor to the dicyanodiamide is 1:1.
In the second step, the calcining temperature is 700-900 ℃, and the time is 1-3 h; the protective gas is nitrogen.
In the third step, the inorganic phosphorus source compound is sodium hypophosphite; the mass ratio of the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube to the sodium hypophosphite is 1 (5-15), and preferably, the mass ratio of the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube to the sodium hypophosphite is 1: 10.
In the third step, the temperature of the phosphorization is 300-400 ℃, and the time is 1-3 h;
in the third step, the ceramic boat containing inorganic phosphorus source compound is placed at the upper tuyere of the tube furnace which is communicated with protective atmosphere, the ceramic boat containing iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nano tube is placed at the lower tuyere of the combustion tube of the tube furnace, and the tail end of the tube furnace is connected with saturated copper sulfate solution to remove tail gas generated in the phosphating process.
The invention also protects the application of the transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide as a catalyst for hydrogen production by electrolyzing water.
Compared with the prior art, the invention has the following technical effects:
the electrocatalyst prepared by the preparation method has excellent performance of hydrogen production by electrolyzing water and excellent stability under acidic conditions. The transition/rare earth multi-metal phosphide with the carbon nanotube morphology obtained by the preparation method is expected to show a special synergistic effect or electronic interaction, so that a target product has good conductivity and more excellent hydrogen evolution performance.
The invention (II) comprehensively considers the economic cost, abundance and radioactivity influence of transition metal and rare earth metal, takes cheap and easily obtained ferric chloride hexahydrate, nickel chloride hexahydrate and hydrated rare earth chloride as metal sources and trimesic acid as an organic ligand to synthesize a series of precursors, and obtains a series of FeNiRE multi-metal co-doped phosphide catalysts by mixing with dicyanodiamine, fully grinding uniformly, pyrolyzing at high temperature and then phosphorizing at low temperature.
(III) the series of FeNiRE-P-NCNTs catalysts of the invention select cheap non-noble metals with abundant reserves as raw materials, not only save the cost, but also can realize high-efficient hydrogen evolution catalytic reaction under acidic conditions, and is a practical catalytic material with stable structure and excellent hydrogen evolution performance.
(IV) the data show that the optimized FeNiGd-P-NCNTs, FeNiTb-P-NCNTs and FeNiHo-P-NCNTs are 0.5M H2SO4Under the condition of (2), the current density is 10mA cm-2The overpotential for time was 63.3mV, 47.5mV and 99.8mV, respectively.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of the resulting objective products of examples 5, 10 and 15 of the present invention; wherein a is the SEM picture of the obtained target product of example 5, b is the SEM picture of the obtained target product of example 10, and c is the SEM picture of the obtained target product of example 15; in the figure, d is a TEM image of the obtained target product of example 5, in the figure, e is a TEM image of the obtained target product of example 10, and in the figure, f is a TEM image of the obtained target product of example 15.
FIG. 2 is an X-ray diffraction (XRD) pattern of the resulting target products of examples 5, 10 and 15 of the present invention.
FIG. 3(a) shows that the target product obtained in example 1-5 of the present invention is 0.5M H2SO4An electrocatalytic hydrogen evolution performance diagram in the electrolyte. FIG. 3(a) is an inset of a target product obtained by different FeNiGd three-metal co-doping ratios at a current density of 10mA cm-2Over potential histogram of time.
FIG. 3(b) is a graph showing that the target product obtained in examples 1 to 5 of the present invention is 0.5M H2SO4Stability test results in electrolyte. The inset in FIG. 3(b) is HER at a current density of 10mA cm-2The following time-counting current (i-t) curves.
FIG. 4(a) shows that the target product obtained in examples 6 to 12 of the present invention is 0.5M H2SO4And (b) an electrocatalytic hydrogen evolution performance diagram (a) in the electrolyte. The inset in FIG. 4(a) is the target product obtained by different FeNiTb three-metal co-doping ratios at a current density of 10mA cm-2Over potential histogram of time.
FIG. 4(b) is a graph showing that the target product obtained in examples 6 to 12 of the present invention is 0.5M H2SO4Stability test results in electrolyte. The inset in FIG. 4(b) is HER at a current density of 10mA cm-2The following i-t curve.
FIG. 5(a) shows that the target product obtained in examples 13 to 16 of the present invention is 0.5M H2SO4An electrocatalytic hydrogen evolution performance diagram in the electrolyte. FIG. 5(a) is an inset of the current density of 10mA cm of the target product obtained by different FeNiHo tri-metal co-doping ratios-2Over potential histogram of time.
FIG. 5(b) is a graph showing that the target product obtained in examples 13 to 16 of the present invention is 0.5M H2SO4Stability test results in electrolyte. The inset in FIG. 5(b) is HER at a current density of 10mA cm-2The following i-t curve.
The present invention will be explained in further detail with reference to examples.
Detailed Description
In the present invention, it is to be noted that:
FeNiRE-NCNTs refers to iron-nickel-rare earth three-metal co-doped nitrogen-doped carbon nanotubes.
FeNiRE-P-NCNTs refers to iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube phosphide.
HER refers to hydrogen evolution reactions.
η10Means that a current density of 10mA cm was reached-2The required overpotential value.
The specifications of the instruments and raw materials used in this example are as follows:
CHI660B electrochemical workstation, shanghai chenhua instruments ltd.
Electronic analytical balance, Shenyang Longteng electronic weighing apparatus, Inc.
pH meter, chemical series of Beijing university.
Ultrasonic cleaning machine, Ningbo Xinzhi Biotech GmbH.
Ferric chloride hexahydrate, national chemical group chemical reagent, shanxi ltd.
Nickel chloride hexahydrate, Shanghai Michelin Biochemical technology, Inc.
Gadolinium chloride hexahydrate, experimental science and technology ltd of the seian sea union.
Terbium chloride hexahydrate, experimental science and technology ltd of the seian sea union.
Holmium chloride hexahydrate, western aven chemical corps ltd.
Trimesic acid, Fuyu Fine chemical Co., Ltd, Tianjin.
Sulfuric acid, experimental science and technology limited of the western sea union.
Dicyanodiamine, national chemical reagent, Shaanxi, Inc.
Nafion, Sigma-Aldrich, co. at a mass concentration of 5%.
The water is double distilled water.
The test method comprises the following steps:
all electrochemical experiments were performed at room temperature using a CHI660B electrochemical workstation from Shanghai Chenghua instruments Inc. and a three-electrode system (platinum wire electrode as counter electrode, saturated glycerol as counter electrode)Mercury electrode as reference electrode) the target product obtained in this example was subjected to an electrochemical test, and high-purity nitrogen gas was introduced into the electrolyte for 30 minutes to reach a saturated state before the test was performed. In the case of iR compensation, the sweep rate is 0.005 V.s-1The resulting polarization curve data were calibrated to reversible hydrogen electrode potential (vs. rhe) according to the nernst equation E (vs. SCE) +0.2415+0.059 × pH, where 0.2415 is the standard electrode potential of a saturated calomel reference electrode at 25 ℃, and pH refers to the pH of the electrolyte. Overpotential (η) 0-ERHE. The stability of the catalyst is tested by an i-t method, and the test voltage is that the current density of each material is 10mA cm-2The voltage of time.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
this embodiment provides a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is performed according to the following steps:
step one, ferric chloride hexahydrate, nickel chloride hexahydrate and gadolinium chloride hexahydrate are sequentially dissolved in 75mL of deionized water containing 2.1g of trimesic acid according to the molar ratio of 1:1:0.5, and the molar ratio of the total amount of soluble ferric salt, soluble nickel salt and hydrated rare earth chloride to the trimesic acid is 3: 2.
And (3) after magnetic stirring for 20min, completely dissolving the solution to form a yellow solution, putting the yellow solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the high-pressure reaction kettle, reacting for 24h at 150 ℃, naturally cooling to room temperature, alternately washing for 6-8 times by using ethanol and water, centrifuging and drying to obtain a precursor.
And step two, mixing the precursor prepared in the step one with dicyandiamide according to the mass ratio of 1:1, fully grinding the mixture uniformly, placing the porcelain boat containing the material in a tube furnace, heating the porcelain boat to 800 ℃ at the heating rate of 5 ℃/min in a nitrogen environment, and calcining the porcelain boat for 2 hours to obtain FeNiGd-NCNTs.
And step three, the FeNiGd-NCNTs prepared in the step two and sodium hypophosphite are distributed into two porcelain boats according to the mass ratio of 1:10, the porcelain boats are placed into a tubular furnace, and phosphorization is carried out for 2 hours at 350 ℃, and finally the FeNiGd-P-NCNTs are obtained. Wherein the porcelain boat filled with sodium hypophosphite is arranged at the upper tuyere of a tube furnace which is communicated with nitrogen, the porcelain boat filled with materials is arranged at the lower tuyere of a combustion tube of the tube furnace, and the tail end of the tube furnace is connected with a saturated copper sulfate solution to remove tail gas generated in the phosphating process.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 2:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in step one of this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and gadolinium chloride hexahydrate was 1:1:1.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 3:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in step one of this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and gadolinium chloride hexahydrate was 1:1: 1.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 4:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in step one of this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and gadolinium chloride hexahydrate was 1:1:2.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 5:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in step one of this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and gadolinium chloride hexahydrate was 1:1: 2.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
As shown in fig. 1, a and d in fig. 1 are an SEM image and a TEM image of the target product obtained in example 5, respectively, and the catalyst has a sheet microsphere structure with entangled carbon nanotubes, forming a "rattan ball-shaped" coating structure with a large number of carbon nanotubes entangled.
As shown in fig. 2, the synthesized material in example 5 is a hybrid structure of nanoparticles such as carbon nanotubes, iron-nickel oxide, and iron nitride.
As shown in FIG. 3(a), the target product was obtained at a current density of 10mA cm-2The magnitude of the required overpotential values are ordered as follows: (FeNiGd)1:1:2-P-NCNTs(η10＝63.3mV)< (FeNiGd)1:1:1.5-P-NCNTs(η10＝79.8mV)<(FeNiGd)1:1:1-P-NCNTs(η10＝82.7mV) <(FeNiGd)1:1:2.5-P-NCNTs(η10＝107.8mV)<(FeNiGd)1:1:0.5-P-NCNTs(η10110.6 mV), the optimal proportion of FeNiGd co-doping is 1:1:2, and the results show that the hydrogen evolution performance of the optimized FeNiGd-P-NCNTs catalyst is obviously improved, especially (FeNiGd)1:1:2-P-NCNTs catalysisThe agent is added at 100mA cm-2Only 197.2mV overpotential is needed at high current densities, which is a practical industrial application that is advantageous for operation at high current densities.
The long-term stability is a key factor in practical application, as shown in FIG. 3(b), the LSV changes only negligibly after 8000 cycles of cyclic voltammetry scan, and the current density is 10mA cm-2Only 6.6mV change; next, at a current density of 10mA cm-2And 160mA cm-2After 48 hours and 53 hours of testing by a chronopotentiometry, the current density of FeNiGd-P-NCNTs is basically not attenuated, which shows that the catalyst has excellent stability.
It can be known from the above examples 1 to 5 that the hydrogen evolution performance of the FeNiGd-P-NCNTs of the invention is substantially affected by adjusting and controlling the ratio of the transition metal FeNi and the rare earth metal Gd, and particularly the hydrogen evolution performance of the catalytic material is greatly improved by the construction strategy of the transition/rare earth multi-metal co-doped carbon nanotube hybrid-phosphorization system adopted by the invention.
Example 6:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 1 with terbium chloride hydrate in equivalent amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1: 0.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 7:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 2 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 2 with terbium chloride hexahydrate in equivalent amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1:1.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 8:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 3 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 3 with terbium chloride hexahydrate in equivalent amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1: 1.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 9:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 4 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 4 with terbium chloride hexahydrate in equivalent amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1:2.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 10:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 5 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 5 with terbium chloride hexahydrate in equivalent amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1: 2.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
As shown in fig. 1, b and e in fig. 1 are SEM image and TEM image of the target product obtained in example 10, respectively, the catalyst presents a typical core-shell nano-sphere structure, and a large number of intertwined carbon nanotubes are grown on the nano-sphere.
Example 11:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 10 except that:
in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and terbium chloride hexahydrate was 1:1: 3.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
As can be seen from FIG. 4(a), as the ratio of the rare earth metal Tb increases, the hydrogen evolution performance increases first and then decreases, and when the FeNiTb co-doping ratio is 1:1:2.5, the current density is 10mA cm-2The hydrogen evolution overpotential is only 47.5mV, the initial potential is only-30.4 mV, and the current density is 100mA cm-2The required overpotential is only 164.6mV, which is very advantageous for practical industrial applications operating at high current densities. Shows that the reasonable adjustment of the co-doping proportion of Tb metal has larger electro-catalysis hydrogen evolution performance on the catalytic material.
As can be seen from FIG. 4(b), the LSV curve of the FeNiTb-P-NCNTs catalyst has only negligible change after 8000 cycles of cyclic voltammetry scan, and the current density is 10mA cm-2Only 3.3mV change; the current density is 150mA cm-2No attenuation of the current density after 93h of test by chronopotentiometry indicates that the catalyst has excellent stability.
It can be known from the above examples 6 to 11 that the hydrogen evolution performance of FeNiTb-P-NCNTs of the invention is substantially affected by adjusting and controlling the co-doping ratio of three metals of FeNiTb, and the optimized FeNiTb-P-NCNTs has a current density of 10mA cm-2The overpotential of hydrogen evolution is reduced by 60.7mV, which is 83.7mV lower than that of the FeNi-P-NCNTs catalyst. The results show that the construction strategy of the transition/rare earth multi-metal co-doped carbon nanotube hybrid-phosphorization system adopted by the invention greatly improves the hydrogen evolution performance of the catalytic material.
Example 12:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 1 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 1 with holmium chloride hexahydrate in equal amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and holmium chloride hexahydrate was 1:1: 0.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 13:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 2 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 2 with holmium chloride hexahydrate in equal amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and holmium chloride hexahydrate was 1:1:1.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 14:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 3 except that:
in step one of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 3 with holmium chloride hexahydrate in an equivalent amount.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and holmium chloride hexahydrate was 1:1: 1.5.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
Example 15:
this example shows a preparation method of a transition/rare earth multi-metal co-doped phosphide, which is substantially the same as that of example 4 except that:
in the first step of this example, the hydrated rare earth chloride was replaced from gadolinium chloride hexahydrate in example 4 with holmium chloride hexahydrate in equal amounts.
That is, in this example, the molar ratio of ferric chloride hexahydrate, nickel chloride hexahydrate, and holmium chloride hexahydrate was 1:1:2.
The transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide is applied to a catalyst for hydrogen production by water electrolysis.
As shown in FIG. 1, c and f in FIG. 1 are SEM image and TEM image of the target product obtained in example 15, respectively, the catalyst shows that the catalytic material shows a regular nanorod structure, and a large number of nanospheres and carbon nanotubes are grown on the nanorod structure as shown in the TEM image.
As can be seen from FIG. 5(a), as the proportion of the rare earth metal Ho increases, the hydrogen evolution performance thereof is steadily improved, and when the FeNiHo co-doping proportion is 1:1:2, the current density is 10mA cm-2The overpotential is only 99.8mV, the initial potential is only 37.2mV, and the current density is 100mA cm-2The required overpotential only needs 246.2 mV. The reasonable adjustment of the co-doping proportion of FeNiHo on the catalytic material promotes the improvement of the electrocatalytic hydrogen evolution performance, but the economic cost problem is considered, so that the optimal performance condition is that the metal proportion is 1:1:2.
As can be seen from fig. 5(b), the linear voltammogram after 8000 cycles of cyclic voltammograms shows: at a current density of 10mA cm-2The potential changes by only 2.5 mV; next, the current density was measured at 10mA cm by chronopotentiometry-2After 24h of the test, the current density of FeNiHo-P-NCNTs is basically not attenuated, which indicates that the catalyst has excellent stability.
It can be known from the above examples 12 to 15 that the hydrogen evolution performance of the FeNiGd-P-NCNTs of the invention is substantially affected by adjusting and controlling the co-doping ratio of three metals of FeNiHo, thereby showing that the hydrogen evolution performance of the catalytic material is greatly improved by the construction strategy of the transition/rare earth multi-metal co-doped carbon nanotube hybrid-phosphorization system adopted by the invention.
It can be known from the above embodiments 1 to 15 that the co-doping of the rare earth metal substantially improves the hydrogen evolution performance of the series of electrocatalysts, and the aim of adjusting the hydrogen evolution effect of the target product can be further achieved by regulating and controlling the proportion of the transition and the co-doping of the rare earth multi-metal. The research results show that the construction strategy of the transition/rare earth multi-metal co-doped carbon nanotube hybrid-phosphorization system has universality on the aspect of improving the hydrogen evolution performance of the catalytic material of different rare earth metals.
Claims (10)
1. The preparation method of the transition/rare earth multi-metal co-doped phosphide is characterized by comprising the following steps of:
dissolving soluble ferric salt, soluble nickel salt and hydrated rare earth chloride in water containing organic ligands, stirring, completely dissolving to form a solution, cooling, washing and centrifuging through a hydrothermal method, and drying to obtain a precursor;
step two, mixing the precursor prepared in the step one with an organic nitrogen source compound, fully and uniformly grinding, placing the porcelain boat containing the material in a tubular furnace, and calcining in a protective atmosphere environment to obtain the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube;
and step three, the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nano tube prepared in the step two and an inorganic phosphorus source compound are respectively packaged in two ceramic boats and placed in a tubular furnace for phosphorization, and finally the transition/rare earth multi-metal co-doped phosphide is obtained.
2. The method for preparing the transition/rare earth multi-metal co-doped phosphide as claimed in claim 1, wherein in the first step, the soluble iron salt is ferric chloride hexahydrate; the soluble nickel salt is nickel chloride hexahydrate; the hydrated rare earth chloride is gadolinium chloride hexahydrate, terbium chloride hexahydrate or holmium chloride hexahydrate; the organic ligand is trimesic acid; the molar ratio of the total amount of the soluble ferric salt, the soluble nickel salt and the hydrated rare earth chloride to the trimesic acid is 3: 2.
3. The preparation method of the transition/rare earth multi-metal co-doped phosphide of claim 1, wherein in the first step, the molar ratio of the soluble iron salt to the soluble nickel salt to the hydrated rare earth chloride is 1:1 (0.5-2), 1:1 (0.5-2.5) or 1:1 (0.5-3).
4. The method for preparing the transition/rare earth multi-metal co-doped phosphide as claimed in claim 1, wherein in the first step, the stirring mode is magnetic stirring, and the magnetic stirring time is 20 min; in the hydrothermal method, the filling volume ratio of the lining of the high-pressure reaction kettle is 70-80%; the reaction temperature of the sealing reaction is 150 ℃, and the reaction time is 24 h; the cooling mode is natural cooling; the washing mode is that water and ethanol are alternately washed for 6-8 times; the specific condition of the centrifugation is 7000rpm centrifugation for 15 min; the drying mode is that the mixture is placed in a vacuum oven at 60 ℃ for drying for 12 hours.
5. The method according to claim 1, wherein in the second step, the organic nitrogen source compound is dicyandiamide; the mass ratio of the precursor to the dicyanodiamine is 1 (0.5-1.5).
6. The preparation method of the transition/rare earth multi-metal co-doped phosphide as claimed in claim 1, wherein in the second step, the calcination temperature is 700-900 ℃ and the calcination time is 1-3 h; the protective gas is nitrogen.
7. The method for preparing the transition/rare earth multi-metal co-doped phosphide as claimed in claim 1, wherein in the third step, the inorganic phosphorus source compound is sodium hypophosphite; the mass ratio of the iron-nickel-rare earth tri-metal co-doped nitrogen-doped carbon nanotube to the sodium hypophosphite is 1 (5-15).
8. The preparation method of the transition/rare earth multi-metal co-doped phosphide of claim 1, wherein in the third step, the temperature of the phosphorization is 300-400 ℃, and the time is 1-3 h.
9. The method of claim 1, wherein in step three, the ceramic boat containing inorganic phosphorus source compound is placed at the upper tuyere of the tube furnace through which the protective atmosphere is introduced, the ceramic boat containing Fe-Ni-RE tri-metal co-doped nitrogen-doped carbon nanotubes is placed at the lower tuyere of the combustion tube of the tube furnace, and the end of the tube furnace is connected with saturated copper sulfate solution to remove the tail gas generated during the phosphating process.
10. Use of the transition/rare earth multi-metal co-doped phosphide prepared by the preparation method of the transition/rare earth multi-metal co-doped phosphide as defined in any one of claims 1 to 9 as a catalyst for hydrogen production by electrolysis of water.
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