CN110433833B - Non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and preparation method thereof - Google Patents
Non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and preparation method thereof Download PDFInfo
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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Abstract
The invention belongs to the technical field of hydrogen production materials, and discloses a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and a preparation method thereof. The catalyst consists of a metal phosphide active phase, an oxide matrix phase and a carrier, wherein the metal phosphide active phase is dispersed and distributed on the surface of the oxide matrix phase in a fine nano-particle form, and the oxide matrix phase is loaded on the carrier. The invention separates out metal phosphide active phase through the phosphating reaction, and then combines with matrix oxide to construct a synergistic catalytic active site; meanwhile, the matrix oxide partially reduces the introduced oxygen vacancy, which is beneficial to improving the conductivity of the matrix material; in addition, a large number of nano holes are generated by dehydration or deamination of the precursor material in the heating process, so that the mass transfer performance of the catalyst is further improved while more active sites are provided. Thereby realizing the optimization of the intrinsic activity, the number of active sites and the conductivity. The comprehensive catalytic performance is close to that of a noble metal Pt catalyst.
Description
Technical Field
The invention belongs to the technical field of hydrogen production materials, and particularly relates to a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and a preparation method thereof.
Background
Hydrogen is a clean and efficient energy carrier, and the large-scale industrial application of the hydrogen is expected to fundamentally solve the global problems of energy shortage, environmental pollution and the like, so the development of the hydrogen energy utilization technology becomes the key point of the energy development strategy of all countries in the world. Promoting the industrial application of hydrogen energy requires constructing a complete hydrogen energy industrial chain including the links of hydrogen production, hydrogen storage, hydrogen fuel cells and the like, wherein the hydrogen production is a source. Among the existing hydrogen production methods, the electrolyzed water has the longest development history, but the coupling with the renewable energy sources can endow the electrolyzed water with brand new vitality. Water is dissociated by electric energy generated by primary energy sources such as solar energy, wind energy and the like, and chemical energy contained in the prepared hydrogen can be converted into electric energy again at a hydrogen terminal for the fuel cell. Therefore, the electrolyzed water provides a sustainable hydrogen production mode and a feasible scheme for the effective utilization of renewable energy sources. The electrolysis of water involves two half reactions of cathodic hydrogen evolution and anodic oxygen evolution, and the reduction of overpotential of the two reactions, namely the reduction of energy consumption of electrolysis reaction, is the core of the development of water electrolysis technology.
The noble metal platinum (Pt) has excellent hydrogen evolution reaction electrocatalytic activity and is known as the most representative cathode catalyst for the electrolysis of water, but the practical application of the noble metal platinum (Pt) is severely restricted by the overhigh material cost. In recent years, the development of efficient and inexpensive non-noble transition metal electrocatalysts has become a mainstream trend in water electrolysis technology. According to the literature report, compounds such as 3d transition metal sulfide, phosphide, nitride, carbide and the like have good hydrogen evolution reaction electrocatalytic activity, and the catalytic performance can be effectively improved by adopting modification strategies such as structural nanocrystallization and component modulation. However, in general, the non-noble transition metal electrocatalyst still generally has the defects of high overpotential of hydrogen evolution reaction, poor stability in long-term operation and the like, so the development of an advanced design concept of a cheap metal catalyst and a controllable synthesis method are still key problems to be solved in the process of promoting the practicability of the water electrolysis technology.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification. The catalyst has high intrinsic catalytic activity, abundant active sites and good conductivity, can efficiently and stably catalyze electrolysis water hydrogen evolution reaction under alkaline conditions, and has comprehensive catalytic performance close to that of a noble metal Pt catalyst.
Another object of the present invention is to provide a preparation method of the above non-noble metal hydrogen evolution electrocatalyst based on synergistic modification. The method has the advantages of easily available raw materials, simple operation and convenient mass production.
The purpose of the invention is realized by the following technical scheme:
a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification is composed of a metal phosphide active phase, an oxide matrix phase and a carrier, wherein the metal phosphide active phase is dispersed and distributed on the surface of the oxide matrix phase in a fine nanoparticle form, and the oxide matrix phase is loaded on the carrier.
Preferably, the metal phosphide active phase is phosphide of transition metal, and the oxide matrix phase is oxide of transition metal; the transition metal is at least one of Fe, Co, Ni, W, Mo and Mn.
Preferably, the particle size of the metal phosphide active phase is 5-15 nm.
Preferably, the oxide crystal lattice of the oxide matrix phase is rich in oxygen vacancies, the oxide matrix phase has a nano porous structure, and the size of the nano pores is 1-10 nm.
Preferably, the carrier is selected from a foamed metal, a metal mesh, an ion exchange resin, a molecular sieve or a porous carbon material; more preferably nickel foam.
The preparation method of the non-noble metal hydrogen evolution electrocatalyst based on synergistic modification comprises the following preparation steps:
adding a carrier material into an aqueous solution containing a transition metal salt and a precipitator, carrying out hydrothermal reaction at 90-180 ℃, growing a metal oxide precursor on the surface of the carrier material, cleaning and drying the metal oxide precursor, carrying out a phosphating reaction with a phosphorus source at 300-450 ℃ in an inert atmosphere, precipitating a metal phosphide active phase on the surface of the metal oxide in situ, and simultaneously obtaining an oxide matrix phase rich in oxygen vacancies and having a nano porous structure to obtain the non-noble metal hydrogen evolution electrocatalyst based on synergistic modification.
Preferably, the transition metal salt refers to at least one of halide, nitrate, sulfate, sulfamate, acetate or oxygen-containing or non-oxygen-containing acid salt of transition metal; the transition metal refers to Fe, Co, Ni, W, Mo or Mn.
Preferably, the precipitant is selected from at least one of urea, ammonia water, hexamethylenetetramine, dimethyl oxalate and diethyl oxalate; more preferably urea.
Preferably, the concentration of the transition metal salt is 0.01-0.2M, and the concentration of the precipitant is 0-0.3M.
Preferably, the hydrothermal reaction time is 4-20 h.
Preferably, the phosphorus source is sodium hypophosphite.
Preferably, the inert atmosphere refers to an argon atmosphere.
Preferably, the time of the phosphating reaction is 1-3 h.
The principle of the invention is as follows: for an electrocatalyst, the three elements that affect its apparent catalytic activity are: intrinsic activity, number of active sites, conductivity. The traditional electrocatalyst only focuses on one or two aspects, and the three elements of the catalyst provided by the invention are simultaneously optimized in the design idea, and a simple and easy preparation method is provided for realizing. Firstly, growing a metal oxide precursor which contains a catalyst active component and has a high specific surface area on the surface of a carrier material by adopting a hydrothermal method, and laying a material composition and structural foundation for synthesizing a high-performance catalyst; and then, selectively precipitating a metal phosphide active phase by regulating and controlling the treatment condition of the phosphating reaction, so that the metal phosphide active phase is dispersed and distributed on the surface of the oxide in a fine nanoparticle form, and realizing the in-situ compounding of two phases. The metal phosphide precipitated in situ and an oxide matrix are combined to construct a synergistic catalytic active site, wherein the oxide promotes the dissociation of water molecules, the metal phosphide phase provides a hydrogen atom composite desorption active site, and the intrinsic catalytic activity of the synergistic catalyst is obviously higher than that of a single-phase metal phosphide catalyst; metal atom separation or partial reduction of metal cations occurs in the phosphating process, so that oxygen vacancies are generated in oxide lattices, and the generation of a large number of lattice defects is helpful for improving the conductivity of the base material; in addition, the precursor material of the hydrothermal synthesis contains crystal water or ammonia radicals, and dehydration or deamination reaction generated in the heating process can cause generation of a large number of nano-pores, so that the specific surface area of the material is further increased, and more active sites are provided. In conclusion, the hydrogen evolution electrocatalyst provided by the invention has high intrinsic activity, abundant active sites and good conductivity.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention selectively separates out the metal phosphide active phase by regulating and controlling the treatment condition of the phosphating reaction, and then the metal phosphide active phase and the matrix oxide are combined to construct a synergistic catalytic active site; meanwhile, the matrix oxide partially reduces the introduced oxygen vacancy, which is beneficial to improving the conductivity of the matrix material; in addition, a large number of nano holes are generated by dehydration or deamination of the precursor material in the heating process, so that the mass transfer performance of the catalyst is further improved while more active sites are provided. Thereby realizing the optimization of the intrinsic activity, the number of active sites and the conductivity.
(2) The preparation method has the advantages of easily available raw materials, simple process and convenience for mass production.
(3) The non-noble metal hydrogen evolution electrocatalyst prepared by the invention can efficiently catalyze the water electrolysis hydrogen evolution reaction under the alkaline condition, has excellent stability and durability, and has comprehensive catalytic performance close to that of a noble metal Pt catalyst.
Drawings
FIG. 1 shows a hydrothermal sample (NH) obtained in example 1 of the present invention4)HNi2(OH)2(MoO4)2/NF (a) and phosphating sample Ni2-xMoxP/NiMoO4-yThe scanning electron microscope topography of/NF (b).
FIG. 2 is a diagram showing a hydrothermal sample (NH) obtained in example 1 of the present invention4)HNi2(OH)2(MoO4)2/NF (a), phosphating-treated sampleNi2-xMoxP/NiMoO4-yX-ray diffraction pattern of/NF and its heat-treated crystallized sample (b) at 500 ℃.
FIG. 3 shows a hydrothermal sample (NH) obtained in example 1 of the present invention4)HNi2(OH)2(MoO4)2(a) With phosphating sample Ni2-xMoxP/NiMoO4-y(b) A transmission electron microscope topography; phosphating sample Ni2-xMoxP/NiMoO4-yThe high-resolution electron microscope picture (c), the selected area electron diffraction picture (d) and the linear scanning energy spectrogram (e) are inserted as high-angle annular dark field scanning transmission electron microscope pictures.
FIG. 4 shows (NH) obtained in example 1 of the present invention4)HNi2(OH)2(MoO4)2/NF (hydrothermal sample) with Ni2-xMoxP/NiMoO4-yX-ray photoelectron spectrum of NF sample (phosphorized sample): (a) a Mo 3d spectrum; (b) a Ni 2p spectrum; (c) ni2- xMoxP/NiMoO4-yThe X-ray photoelectron spectrum of the NF sample in the P2P region; (d) (NH)4)HNi2(OH)2(MoO4)2/NF and Ni2-xMoxP/NiMoO4-yXPS spectra of O1 s for the/NF samples.
FIG. 5 shows Ni obtained in example 1 of the present invention2-xMoxP/NiMoO4-yThe polarization curves of hydrogen evolution reaction of the/NF and Pt/C/NF catalysts are compared.
FIG. 6 shows Ni obtained in example 1 of the present invention2-xMoxP/NiMoO4-y/NF with (NH)4)HNi2(OH)2(MoO4)2A relation graph (a) of capacitance current density and potential sweep rate of the NF sample under an open circuit potential; ni2-xMoxP/NiMoO4-y/NF and (NH)4)HNi2(OH)2(MoO4)2Graph (b) of the impedance spectroscopy test results of the NF samples at-0.05V (vs. reversible hydrogen electrode) potential.
FIG. 7 shows Ni obtained in example 1 of the present invention2-xMoxP/NiMoO4-yDurability test results of/NF catalysts (chronopotentiometry).
FIG. 8 shows Ni obtained in example 1 of the present invention2-xMoxP/NiMoO4-yThe shape and appearance of the NF catalyst after 80-hour durability test by a scanning electron microscope.
FIG. 9 shows a CoMoO sample of hydrothermal state obtained in example 2 of the present invention4·nH2O (a) and phosphating sample Co3P/CoMoO4(b) X-ray diffraction pattern of (a).
FIG. 10 shows a CoMoO sample of hydrothermal state obtained in example 2 of the present invention4·nH2O/NF (a) and phosphating heat treatment sample Co3P/CoMoO4Comparative image of the appearance of the scanning electron microscope of/NF (b).
FIG. 11 shows a CoMoO sample of hydrothermal state obtained in example 2 of the present invention4·nH2O (a) and phosphating Heat treatment sample Co3P/CoMoO4(b) The appearance of the transmission electron microscope is compared.
FIG. 12 shows Co obtained in example 2 of the present invention3P/CoMoO4Polarization curves for hydrogen evolution reaction for the/NF and Pt/C/NF catalysts are shown in FIG. (a) and at 10mA/cm2Stability test results at current density (b).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Using foam Nickel (NF) as carrier, its thickness is 1.85mm, and its surface density is 620 plus or minus 30g/m2The aperture is 0.20-0.80 mm. Foamed nickel (1X 4 cm)2) Ultrasonic cleaning with ethanol for 10 min and activating with 3M hydrochloric acid solution for 10 min, together with 30mL Ni (NO)3)2·6H2O(0.1M)、(NH4)6Mo7O24·4H2O(0.025M)、(NH2)2Placing CO (0.25M) deionized water solution in a hydrothermal kettle with volume of 50mL, treating at 150 deg.C for 18 hr, naturally cooling to room temperature, cleaning the obtained sample, and vacuum drying at room temperature for 1 hr to obtain hydrothermal sample (NH)4)HNi2(OH)2(MoO4)2/NF。
(2) Placing about 1g of sodium hypophosphite and a hydrothermal sample in a quartz boat at an interval of 1 cm, heating to 300 ℃ under argon atmosphere, raising the temperature at a rate of 2 ℃/min, carrying out constant temperature treatment for 3 hours, and cooling to room temperature to obtain the target catalyst Ni2-xMoxP/NiMoO4-y/NF。
In this example, the hydrothermal sample (NH) obtained in step (1)4)HNi2(OH)2(MoO4)2/NF (a) and the target catalyst Ni obtained in the step (2)2-xMoxP/NiMoO4-yThe SEM image of/NF (b) is shown in FIG. 1.
In this example, the hydrothermal sample (NH) obtained in step (1)4)HNi2(OH)2(MoO4)2/NF (a), the target catalyst Ni obtained in the step (2)2-xMoxP/NiMoO4-y/NF and target catalyst are crystallized by heat treatment at 500 ℃ to obtain sample Ni2-xMoxP/NiMoO4-yThe X-ray diffraction pattern of/NF-500 deg.C (b) is shown in FIG. 2.
FIG. 3 shows the hydrothermal sample (NH) obtained in step (1) of this example4)HNi2(OH)2(MoO4)2(a) With the target catalyst Ni2-xMoxP/NiMoO4-yTransmission electron microscopy topography of/NF (b); target catalyst Ni2-xMoxP/NiMoO4-yThe high-resolution electron microscope picture (c) of/NF, the selected area electron diffraction spectrum (d) and the linear scanning energy spectrum (e), and the insets are high-angle annular dark field scanning transmission electron microscope pictures.
FIG. 4 shows the hydrothermal sample (NH) obtained in step (1) of this example4)HNi2(OH)2(MoO4)2/NF and target catalyst Ni2-xMoxP/NiMoO4-yX-ray photoelectron spectrum of/NF: (a) a Mo 3d spectrum; (b) ni 2p spectrum. (c) Ni2-xMoxP/NiMoO4-yThe X-ray photoelectron spectrum of the NF sample in the P2P region. (d) (NH)4)HNi2(OH)2(MoO4)2/NF and Ni2- xMoxP/NiMoO4-yXPS spectra of O1 s of/NF samples.
Scanning electrodeObserving through a lens (a in figure 1), and finding that a large number of nano sheets grow on the surface of the foamed nickel through hydrothermal reaction treatment, and the nano sheets are self-assembled to form a 3D nano flower structure; according to XRD analysis (a in figure 2), the nano-sheet materials are (NH)4)HNi2(OH)2(MoO4)2A crystalline phase; the sample in the hydrothermal state is subjected to phosphating treatment at 300 ℃ for 3 hours, and the appearance of the sample is not obviously changed (b in figure 1).
The observation of a transmission electron microscope (a and b in fig. 3) further confirms the nanosheet structure of the hydrothermal sample and the phosphating target catalyst, and simultaneously discovers that a large number of newly generated nanoparticles and nanopores exist on the nanosheets of the phosphating sample, wherein the particle size of the nanoparticles is 5-15 nanometers, and the pore size of the nanoparticles is 1-10 nanometers; according to high resolution electron microscopy analysis (c in FIG. 3), the newly generated nanoparticles are Ni2A P nanocrystal phase around which a large amount of an amorphous phase is present; selective electron diffraction analysis confirmed Ni2Generation of P nanocrystalline and amorphous phases.
XRD analysis (b in FIG. 2) showed that the hydrothermal sample was phosphated at 300 ℃ for 3 hours (NH)4)HNi2(OH)2(MoO4)2Transformation of crystalline phase into unique nanocrystalline phase Ni2And P. However, when XRD was carefully analyzed, newly formed Ni was found2Diffraction peak of P to original Ni2The diffraction peak of P is slightly shifted to a lower angle, and Mo is detected by X-ray photoelectron spectroscopy (XPS, a in FIG. 4)0The results of the signals clearly show that Mo-doped Ni2Generating a P nanocrystalline phase; the linear scanning energy spectrum analysis (e in FIG. 3) further confirms Ni2-xMoxGeneration of P nanocrystal phase. NiMoO was detected from XRD results of phosphatized samples calcined at high temperature of 500 ℃ for 2h4The generation of a crystalline phase indicates that the amorphous phase in the phosphatized sample is NiMoO4Amorphous phase (b in fig. 2).
According to X-ray photoelectron spectroscopy (FIG. 4), the hydrothermal sample contained only Mo6+And Ni2+A signal; after 3 hours of phosphating at 300 ℃ additional Ni was present in the samples0、Mo0、Mo4+And Mo5+Signal, and P element in the phosphating sample is present0And POxA signal; watch withMeasuring Mo0、Ni0、P0Signal and Mo doped Ni2P production is consistent, observed POxProbably due to partial oxidation of the surface of the catalyst on exposure to air, while Mo is observed4+、Mo5+、Mo6+The signal indicates the matrix NiMoO4A large number of O vacancies are present, which is further confirmed by the XPS spectrum of O1 s.
The target catalyst Ni obtained in this example2-xMoxP/NiMoO4-yElectrocatalytic performance test of/NF:
the results of the hydrogen evolution reaction polarization curve test (FIG. 5) show that Ni2-xMoxP/NiMoO4-ythe/NF catalyst has excellent hydrogen evolution reaction electrocatalytic activity, and can reach 10mA/cm in 1.0M alkali liquor only by 36mV hydrogen evolution overpotential2The catalytic activity of the catalyst is close to that of a noble metal Pt/C catalyst.
In FIG. 6 a shows Ni2-xMoxP/NiMoO4-y/NF and (NH)4)HNi2(OH)2(MoO4)2Compared with a hydrothermal sample, the double-electric-layer capacitance of the sample obtained after phosphating at 300 ℃ for 3 hours is improved by nearly 30 times, namely the electrochemical specific surface area is improved by nearly 30 times, and the obvious improvement of the electrochemical specific surface area is due to dehydration and deamination reactions in the phosphating process; according to the impedance spectrum test result (b in FIG. 6), the charge transfer resistance of the reduced sample is greatly reduced compared with that of the hydrothermal sample, and is due to the metal characteristic Ni2-xMoxIn-situ precipitation of P phase and NiMoO4O vacancies in the matrix are generated.
FIG. 7 shows Ni2-xMoxP/NiMoO4-yStability test results of/NF catalyst by constant current measurement for 80 hours (10 mA/cm)2、50mA/cm 240 hours each at current density), the catalyst activity did not decline, indicating that the catalyst has good stability.
FIG. 8 shows Ni2-xMoxP/NiMoO4-yThe NF catalyst is tested for durability in 80 hoursThe result shows that the morphology and the characteristics of the hierarchical nano structure of the catalyst are not obviously changed, which indicates that the catalyst has good structural stability.
Example 2
(1) Using foam Nickel (NF) as carrier, its thickness is 1.85mm, and its surface density is 620 plus or minus 30g/m2The aperture is 0.20-0.80 mm. Foamed nickel (1X 4 cm)2) Ultrasonic cleaning with ethanol for 10 min, activating with 3M hydrochloric acid solution for 10 min, and mixing with 30mL of a solution containing Co (NO)3)2·6H2O(0.02M)、Na2MoO4·2H2Placing O (0.01M) deionized water solution in a hydrothermal kettle with volume of 50mL, treating at constant temperature of 150 deg.C for 6 hr, naturally cooling to room temperature, cleaning the obtained sample, and vacuum drying at room temperature for 1 hr to obtain hydrothermal CoMoO sample4·nH2O。
(2) Placing about 1g of sodium hypophosphite and a hydrothermal sample in a quartz boat at an interval of 1 cm, heating to 300 ℃ under argon atmosphere, raising the temperature at a rate of 2 ℃/min, carrying out constant temperature treatment for 3 hours, and cooling to room temperature to obtain the target catalyst Co3P/CoMoO4/NF。
This example was conducted using CoMoO as a hydrothermal sample obtained in step (1)4·nH2O (a) and the target catalyst Co obtained in the step (2)3P/CoMoO4The XRD pattern of/NF (b) is shown in FIG. 9. The results show that: CoMoO is generated in the hydrothermal reaction process4·nH2A crystalline phase O; phosphating at 300 ℃ for 3 hours, CoMoO4·nH2Transformation of O crystal phase into Co3P and CoMoO4A nanocrystalline phase.
This example was conducted using CoMoO as a hydrothermal sample obtained in step (1)4·nH2O (a) and the target catalyst Co obtained in the step (2)3P/CoMoO4The SEM image of/NF (b) is shown in FIG. 10. The results show that: in the hydrothermal reaction process, a large number of nano sheets grow on the surface of the foamed nickel, and partial nano sheets are self-assembled to form a 3D nano flower structure (a in FIG. 10); after 3 hours of phosphating at 300 ℃, no significant change in the morphology of the sample was seen (b in fig. 10).
This example was conducted using CoMoO as a hydrothermal sample obtained in step (1)4·nH2O (a) and the target catalyst Co obtained in the step (2)3P/CoMoO4FIG. 11 shows a transmission electron micrograph of/NF (b). The results show that: after the hydrothermal sample is subjected to phosphating treatment, a large number of nano holes with the aperture of about 8 nanometers are generated on the nano sheets.
The target catalyst Co obtained in this example3P/CoMoO4Electrocatalytic performance test of/NF:
the results of the hydrogen evolution reaction polarization curve test (a in FIG. 12) show that Co3P/CoMoO4the/NF catalyst has excellent hydrogen evolution reaction electrocatalytic activity, and can reach 10mA/cm in 1.0M alkali liquor only by the hydrogen evolution overpotential of 41mV2The catalytic activity of the catalyst is close to that of a noble metal Pt/C catalyst. At 10mA/cm2Testing at current density for 22 hours, Co3P/CoMoO4The activity of the/NF catalyst is not degraded, which shows that the catalyst has good stability (b in figure 12).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A non-noble metal hydrogen evolution electrocatalyst based on synergistic modification is characterized in that: the catalyst consists of a metal phosphide active phase, an oxide matrix phase and a carrier, wherein the metal phosphide active phase is dispersed and distributed on the surface of the oxide matrix phase in a fine nano-particle form, and the oxide matrix phase is loaded on the carrier;
the metal phosphide active phase is phosphide of transition metal, and the oxide matrix phase is oxide of transition metal; the transition metal is at least one of Fe, Co, Ni, W, Mo and Mn;
the oxide crystal lattice of the oxide matrix phase is rich in oxygen vacancies, and the oxide matrix phase has a nano porous structure;
the preparation method of the non-noble metal hydrogen evolution electrocatalyst based on synergistic modification comprises the following preparation steps:
adding a carrier material into an aqueous solution containing a transition metal salt and a precipitator, carrying out hydrothermal reaction at 90-180 ℃, growing a metal oxide precursor on the surface of the carrier material, cleaning and drying the metal oxide precursor, carrying out a phosphating reaction with a phosphorus source at 300-450 ℃ in an inert atmosphere, in-situ precipitating a metal phosphide active phase on the surface of the metal oxide, and simultaneously obtaining an oxide matrix phase rich in oxygen vacancies and having a nano porous structure to obtain a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification;
the catalyst has high intrinsic catalytic activity, abundant active sites and good conductivity, and can efficiently and stably catalyze the electrolytic water hydrogen evolution reaction under the alkaline condition;
the precipitant is selected from at least one of urea, ammonia water and hexamethylenetetramine.
2. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the particle size of the metal phosphide active phase is 5-15 nm.
3. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the size of the nano-pores is 1-10 nm.
4. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the carrier is selected from foamed metal, metal net, ion exchange resin, molecular sieve or porous carbon material.
5. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the transition metal salt is at least one of halide, nitrate, sulfate, sulfamate and acetate of transition metal or oxygen-containing or non-oxygen-containing acid salt of transition metal, and the concentration of the transition metal salt is 0.01-0.2M; the transition metal refers to Fe, Co, Ni, W, Mo or Mn.
6. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the concentration of the precipitant is more than 0 and less than or equal to 0.3M.
7. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the hydrothermal reaction time is 4-20 h, and the phosphating reaction time is 1-3 h.
8. The synergistically modified non-noble metal based hydrogen evolution electrocatalyst according to claim 1, wherein: the phosphorus source is sodium hypophosphite, and the inert atmosphere is argon atmosphere.
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| CN111701607A (en) * | 2020-06-15 | 2020-09-25 | 西北大学 | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof |
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| CN113699552B (en) * | 2021-08-26 | 2022-07-29 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN107502919A (en) * | 2017-08-16 | 2017-12-22 | 中国科学院长春应用化学研究所 | A kind of sulfur doping catalyst of phosphatizing nickel for Hydrogen evolving reaction and preparation method thereof |
| CN107999114A (en) * | 2017-12-19 | 2018-05-08 | 成都玖奇新材料科技有限公司 | Electrochemical reduction nitrogen ammonia non-precious metal catalyst |
| CN108083242A (en) * | 2017-12-15 | 2018-05-29 | 国家纳米科学中心 | The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water |
| CN109529844A (en) * | 2018-11-28 | 2019-03-29 | 北京工业大学 | The two-step synthesis method of finely dispersed Transition Metal Cluster Compounds elctro-catalyst |
| CN109797404A (en) * | 2019-01-26 | 2019-05-24 | 南开大学 | The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation |
-
2019
- 2019-08-14 CN CN201910746775.6A patent/CN110433833B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN107502919A (en) * | 2017-08-16 | 2017-12-22 | 中国科学院长春应用化学研究所 | A kind of sulfur doping catalyst of phosphatizing nickel for Hydrogen evolving reaction and preparation method thereof |
| CN108083242A (en) * | 2017-12-15 | 2018-05-29 | 国家纳米科学中心 | The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water |
| CN107999114A (en) * | 2017-12-19 | 2018-05-08 | 成都玖奇新材料科技有限公司 | Electrochemical reduction nitrogen ammonia non-precious metal catalyst |
| CN109529844A (en) * | 2018-11-28 | 2019-03-29 | 北京工业大学 | The two-step synthesis method of finely dispersed Transition Metal Cluster Compounds elctro-catalyst |
| CN109797404A (en) * | 2019-01-26 | 2019-05-24 | 南开大学 | The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation |
Non-Patent Citations (3)
| Title |
|---|
| 廖满生.磷化处理过渡金属钼酸盐电解水电极的研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2017, * |
| 磷化处理过渡金属钼酸盐电解水电极的研究;廖满生;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170315;第B014-1280页 * |
| 过渡金属磷化物的制备及电催产氢性能研究;王克伟;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190115;第B014-657页 * |
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