CN113078329A - Ni with hollow yolk-eggshell structure2Preparation method and application of P/C nano composite material - Google Patents

Ni with hollow yolk-eggshell structure2Preparation method and application of P/C nano composite material Download PDF

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CN113078329A
CN113078329A CN202110320708.5A CN202110320708A CN113078329A CN 113078329 A CN113078329 A CN 113078329A CN 202110320708 A CN202110320708 A CN 202110320708A CN 113078329 A CN113078329 A CN 113078329A
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CN113078329B (en
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王春栋
李林峰
孙华传
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Huazhong University of Science and Technology
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Abstract

The invention discloses Ni with a hollow yolk-eggshell (yolk-shell) structure2A preparation method of a P/C nano composite material belongs to the technical field of electrocatalysis electrode material preparation, can be used for catalyzing urea electrooxidation (UOR) to generate hydrogen so as to change waste into valuable, and comprises the following two steps: firstly, mixing nickel nitrate hexahydrate, glycerol and isopropanol according to a certain proportion, stirring at room temperature, adding deionized water, and preparing the nickel glycerate yolk shell nanospheres by a hydrothermal method; secondly, the obtained nickel glycerate and sodium hypophosphite are subjected to chemical vapor deposition to obtain black powder Ni2P/C nanocomposites. The invention passes through the mouldMethod for preparing hollow yolk-eggshell nano-structure Ni by plate method2The P/C composite material shows excellent catalytic activity and stability in the urea electrooxidation reaction and lower cost, and has great commercialization potential.

Description

Ni with hollow yolk-eggshell structure2Preparation method and application of P/C nano composite material
Technical Field
The invention relates to the technical field of materials and electrochemical energy storage new energy, in particular to Ni with a hollow yolk-eggshell structure2Preparation method of P/C nano composite material and obtained Ni2The P/C nanocomposite canAs a highly efficient UOR catalyst.
Background
Hydrogen production from natural resources and industrial wastewater is considered to be one of the effective ways to alleviate serious energy crisis and increasingly serious environmental problems. Fuel cells and corresponding energy conversion technology are considered to be the most promising hydrogen production strategy because they are safe and effective in the transportation and storage of hydrogen, and in this regard, methanol fuel cells, ethanol fuel cells, urea fuel cells, and other devices that use low molecular weight organic substances as hydrogen-rich fuels have received much attention. The development of the electrochemical oxidation reaction of urea has recently increased the awareness of sustainable processes for the production of hydrogen, since urea can be used on an industrial scale as a promising fuel in direct urea fuel cells due to its non-toxic, non-flammable and affordable properties, on the other hand, urea is also a common and abundant pollutant from human/animal urine, fertilizer industry and other waste products, and urea in waste water is naturally converted into ammonia and continues to be oxidized into next hydrolytic pollutants (such as nitrite, nitrate and nitrogen oxide), and thus, harmful environmental problems caused by toxic and harmful substances produced by urea can also be successfully dealt with by the electrochemical oxidation reaction of urea.
In general, urea electrolysis (anode: CO (NH))2)2+6OH-→N2+5H2O+CO2+6e-, cathode 6H2O+6e-→3H2+6OH) appears to be significantly superior to water splitting (anodic: oxygen evolution reaction, cathodic: hydrogen evolution reaction) in hydrogen production because of the lower theoretical dynamic potential required (0.37V versus 1.23V), however, due to the 6e transfer process, the anodic urea oxidation reaction undergoes slow kinetics, limiting the overall performance of urea electrolysis. Although a significant ability of noble metal-based electrocatalysts (i.e. rhodium, iridium and palladium) to oxidize urea has recently been reported, the scarcity and high cost of noble metals makes their large-scale application impossible. Heretofore, non-previous metal-based catalysts, particularly nickel-based materials, have become more popular and highly active Urea Oxidation (UOR) catalysts. For example, it has been widely studied in the prior artOver Ni (OH)2，NiSe2，NiMoO4，NiLaO3。
In the nickel-based material, Ni2P is widely studied in the electrochemical field, such as oxygen evolution reactions, hydrogen evolution reactions, supercapacitors and hydrodeoxygenation, because of its abundant availability, low cost, high activity and excellent stability. In the case of UOR, it is well known that nickel phosphide may be oxidized to nickel oxyhydroxide during UOR as the primary active site for catalyzing urea oxidation. However, after the nickel oxyhydroxide is formed, the electrical conductivity of the electrode material is significantly reduced, causing a gradual deterioration of the UOR process, and in this respect, the nanostructure modulation by the carbon coating is considered to be one of the most effective methods to increase the electrical conductivity of the electrode material without changing the intrinsic catalytic mechanism. For example, nickel hydroxide-carbon nanotube composites prepared by a one-pot hydrothermal process exhibit significant electrochemical urea oxidation performance with a maximum peak current density of 98.5mA/cm2This can be attributed to the unique layered carbon nanotube conductive structure and high trivalent nickel species content. Furthermore, two-dimensional nickel/nickel oxide nanoplates coated with ultra-thin nitrogen doped carbon layers are reported to be well designed, contain many schottky heterointerfaces, and the catalyst shows a peak at 10mA/cm2The UOR potential of the lower 1.35V, due to the feasible cleavage of the urea molecule after self-driven charge redistribution at the heterointerface, inspired by these factors, will activate Ni2The advantages of P coupling to conductive carbon materials, and exposing many active sites, are highly desirable, but also challenging.
Disclosure of Invention
In view of the above-mentioned drawbacks or needs for improvement of the prior art, an object of the present invention is to provide Ni having a hollow yolk-eggshell (yolk-shell) structure2The preparation method of the P/C nano composite material is characterized in that the object aimed at by the preparation method and the whole process flow of the preparation method are controlled, the nickel-based material is taken as the object, and the carbon-doped phosphatized nickel-based structural substance is prepared on the nickel-based material in a deposition manner, so that the technical problems of complex preparation process, high cost, low efficiency and low stability of the obtained catalyst in the prior art are solvedThe catalytic performance, especially the hydrogen evolution catalytic performance, of the nickel-based catalyst can be improved. In addition, the invention preferably controls the amount of carbon and phosphorus modified on the nickel-based structural material, and can further ensure the improvement effect on the catalytic performance of the nickel-based catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
ni with hollow yolk-eggshell structure2The preparation method of the P/C nano composite material is characterized by comprising the following steps:
(1) preparing a yolk-shell nickel-glycine precursor: adding nickel nitrate hexahydrate into a Teflon container filled with glycerol and isopropanol in advance, stirring uniformly, adding deionized water into the mixed solution, stirring uniformly, transferring the container into a stainless steel autoclave for hydrothermal reaction, naturally cooling to room temperature, filtering, separating, washing, and drying at constant temperature to obtain a light green powder nickel-glycine precursor;
(2) preparation of Ni2P/C nanocomposite: respectively placing a nickel-glycine precursor and disodium hydrogen phosphate powder at the rear end and the front end of a tubular heating furnace, heating to 250-450 ℃ at the speed of 2 ℃/min in an inert gas environment, maintaining for 2-3 h, washing and drying to obtain black powdery Ni2P/C nanocomposites.
According to the invention, the carbon-doped nickel-based phosphide catalyst (such as perovskite oxide) can be used for preparing nickel-glycine by a simple hydrothermal method, and further annealing is carried out to obtain a carbon-doped nickel-based phosphide structure substance, so that the hydrogen evolution reaction capacity and stability of UOR are improved, and the method is simple and easy to operate, short in preparation period, environment-friendly and pollution-free, and can be used for replacing a noble metal catalyst to prepare an electrode material on a large scale.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the proportion of nickel nitrate hexahydrate, glycerol, isopropanol and deionized water in the step (1) is 0.6-0.7 mmol: 9-10 ml: 54-60 ml: 2-3 ml.
Preferably, in one of the above mentionedNi of empty yolk-eggshell structure2In the preparation method of the P/C nano composite material, the temperature of the hydrothermal reaction in the step (1) is 180-200 ℃, and the reaction time is 9-12 h.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the filtration and separation in the step (1) are to filter and separate precipitates through a micron nylon organic filter membrane.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the constant-temperature drying temperature in the step (1) is 60-70 ℃, and the time is 9-12 hours.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the mass ratio of the nickel-glycine precursor to the disodium hydrogen phosphate powder in the step (2) is 1: and 10, ensuring that the disodium hydrogen phosphate powder is sufficient to ensure sufficient phosphorization.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the annealing temperature in the step (2) is 350 ℃.
Preferably, Ni is in a hollow yolk-eggshell structure as described above2In the preparation method of the P/C nano composite material, the inert gas in the step (2) is argon.
The invention also discloses Ni with a hollow yolk-eggshell structure prepared by the method2P/C nanocomposites.
The invention also discloses Ni with a hollow yolk-eggshell structure prepared by the method2The application of the P/C nano composite material as the catalyst for hydrogen evolution by urea electrooxidation, the reaction process of the nickel-based material for catalyzing urea oxidation conforms to the indirect electrochemistry-chemistry (EC) mechanism and process (E: electrochemistry step; C: chemistry step) as follows:
electrochemical step:
6Ni(OH)2+6OH-→6NiOOH+6H2O+6e-
the chemical steps are as follows:
6Ni(OH)2+CO(NH2)2+H2O→6Ni(OH)2+N2+CO2。
according to the above technical solution, compared with the prior art, the present disclosure provides a Ni with a hollow yolk-eggshell structure2The preparation method and the application of the P/C nano composite material have the following beneficial effects:
(1) the invention adopts a hydrothermal method and a chemical vapor deposition technology to realize the preparation of the carbon-doped phosphorized nickel-based structural substance with a hollow yolk-eggshell structure, so as to further improve the hydrogen evolution capability of the substance in UOR, and preferably adopts an environment-friendly and low-cost nickel-based material as a precursor, compared with noble metals, the nickel-based material shows higher urea electrolytic oxidation current density in an alkaline medium, and the commercialization of the nickel is possible due to the abundant reserves and the low price of the nickel;
(2) the invention preferably controls the mol ratio of carbon element and phosphorus element in the nickel-based material by controlling the annealing temperature in the chemical vapor deposition method so as to adjust the UOR hydrogen evolution performance of the nickel-based material, the phosphorus source concentration controls the preparation of pure nickel phosphide, and the excessive or too small coating concentration of carbon is not favorable for adsorption and desorption in the hydrogen evolution intermediate step, thereby having a crucial influence on the improvement of the catalytic performance; and because the nickel-based material is easily oxidized into nickel oxyhydroxide in the UOR process, on one hand, the nickel oxyhydroxide is an active center for catalyzing urea oxidation, and on the other hand, the nickel oxyhydroxide reduces the conductivity of the material, which is harmful to the UOR process, and the carbon-doped phosphatized nickel-based catalyst prepared by the invention can well solve the problem, because the carbon can not only increase the conductivity of the catalyst material, but also does not change the inherent catalyst mechanism;
(3) the hydrothermal temperature for preparing the nickel-glycine is preferably 200 ℃, and when the annealing temperature is 350 ℃, the quality of the carbon layer is highest, the performance of the obtained carbon-doped nickel phosphide-based structural catalyst is the best, the UOR hydrogen evolution catalytic performance of the nickel-based material can be obviously improved by adopting a simple chemical vapor deposition method to realize carbon doping, the cost is greatly reduced, the commercial requirement is met, and the important value of the nickel-glycine in future application in a urea fuel cell using wastewater is highlighted.
In summary, the carbon-doped metal-phosphated nickel-based catalyst prepared by the simple chemical vapor deposition method is adopted to improve the hydrogen evolution reaction capability and stability in UOR, and correspondingly, the carbon-doped metal-phosphated nickel-based high-efficiency UOR hydrogen evolution catalyst and the preparation method thereof are provided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Ni of the present invention2A preparation schematic diagram of the P/C yolk shell nano-structure catalyst;
FIG. 2 shows Ni prepared in example 1 and example 2 of the present invention2XRD pattern of P/C-YS;
FIG. 3 shows Ni prepared in example 1 of the present invention2XPS plots of P/C-YS-350 and Ni-gly precursors;
FIG. 4 Ni prepared in example 12Raman spectrum of P/C-YS-350;
FIG. 5 shows Ni prepared in example 1 of the present invention2SEM picture of P/C-YS-350;
FIG. 6 shows Ni prepared in example 1 of the present invention2TEM image of P/C-YS-350;
FIG. 7 shows Ni prepared in example 22XRD pattern of P/C-YS-250;
FIGS. 8(a) (b) and (c) (d) shows Ni prepared in example 22SEM picture of P/C-YS-400/450;
FIG. 9 shows Ni prepared in example 1 of the present invention2LSV curves with iR compensation for P/C-YS-350 and Ni-gly precursors compared to commercial Pt/C;
FIG. 10 shows Ni prepared in example 1 of the present invention2LSV curve of P/C-YS-350 under different urea concentration;
FIG. 11 shows Ni prepared in example 1 of the present invention2P/C-YS-350 at 10mA/cm2Time-lapse potential measurement;
FIG. 12 shows Ni prepared in example 1 of the present invention2P/C-YS-350 at 10mA cm-2Digital photographs of a urea electrolytic cell in operation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides Ni with a hollow yolk-eggshell (yolk-shell) structure2The preparation method of the P/C nano composite material is characterized in that aiming at nickel-based structural substances, a hydrothermal method and a chemical vapor deposition technology are adopted to deposit and prepare the carbon-doped phosphated nickel-based structural substance catalyst on the nickel-based materials, so that the catalytic performance of the nickel-based catalyst is improved.
Example 1:
ni with hollow yolk-eggshell structure2The preparation method of the P/C nano composite material is realized according to the following steps:
(1) preparing a yolk-shell nickel-glycine precursor: adding 0.7mmol of Ni (NO)3)2·6H2O and 10mL of glycerin were added to a 100mL Teflon container previously filled with 60mL of isopropyl alcohol, stirred for 5 minutes, and then 2mL of deionized water was added to the above solution, which was then transferred to a stainless steel autoclave and kept in an electric oven at 200 ℃ for 12 hours, after naturally cooling to room temperature, the precipitate was separated by filtration through a 0.22 μm nylon organic filterWashing with ethanol for several times, and drying in an oven at 60 ℃ overnight to obtain a nickel-glycine precursor;
(2) preparation of Ni2P/C yolk-eggshell nanostructure: mixing the nickel-glycine (100mg) prepared in step (1) with NaH2PO2·H2O powder (1.0g) annealed in NaH2PO2·H2The O powder should be placed on the upstream side, the temperature is raised to 350 ℃ at a temperature raising rate of 2 ℃/min in an argon atmosphere and kept for another 2 hours, and the product is obtained after washing and drying.
Example 2:
this example is different from example 1 in that the temperature of the phosphating annealing was set to 250 ℃, 300 ℃, 400 ℃ and 450 ℃, and other parameters and concrete implementation steps were the same as those of example 1.
FIG. 1 is a scheme for preparing Ni2Flow diagram of P/C yolk shell nanostructured catalyst. Firstly, a nickel-glycine precursor with a yolk-eggshell structure is well designed and prepared by a one-pot template-free solvothermal method, and the forming mechanism of the yolk-eggshell nanostructure is mainly due to an ostwald curing process. Specifically, after nickel ions are combined with glycerol molecules, the solid nanospheres with rough surfaces are obtained, in the next stage of the solvothermal reaction, the inner cores are gradually separated from the nanosphere shells and continue to shrink, and gaps between the inner cores and the outer shells are formed along with the extension of the reaction time, so that a hollow yolk-eggshell structure is formed. Secondly, the nickel-glycine (Ni-gly) precursor is transferred to Ni after high-temperature phosphating treatment2In P/C-YS (see experimental part), the yolk-eggshell nanosphere structure is still maintained. For comparison, different annealing temperatures were performed to obtain Ni with different carbon contents2P/C-YS。
FIG. 2 shows Ni prepared in examples 1 and 22The XRD pattern of P/C-YS shows that a series of characteristic diffraction peaks positioned at 40.6 degrees, 44.6 degrees, 47.3 degrees, 54.2 degrees, 54.8 degrees, 66.2 degrees, 72.7 degrees and 74.8 degrees can be observed, and the characteristic diffraction peaks point to Ni2The (111), (201), (210), (300), (211), (202), (311) and (212) planes of the P hexagonal plane, and the weak and broad peaks at 25.7 ℃ are attributed to the (002) plane of graphitic carbon (JCPDS card No. 41-1487), confirming thatThe sample prepared is made of Ni2P and carbon. In contrast, in Ni2P/C-YS-400 and Ni2No significant diffraction peak was detected at 25.7 in the XRD pattern of P/C-YS-450, which is probably due to the transfer of carbon element of glyceric acid to hydrocarbon after volatilization at high temperature, resulting in low carbon content, confirming that the final product is not pure Ni when the phosphating temperature is 450 deg.C2P。
FIG. 3 shows Ni prepared in example 12XPS (X-ray diffraction) diagram of P/C-YS-350 and nickel-glycine precursor shows that the nickel-glycine prepared by the invention contains Ni, O and C elements, and Ni2The P/C-YS-350 also contains P element besides Ni, O, C and elements, which shows that the nickel phosphide-glycine is successfully prepared by the chemical vapor deposition method.
FIG. 4 shows Ni prepared in example 12Raman spectrum of P/C-YS-350. At 1334cm-1And 1584cm-1Two distinct peaks are identified, corresponding to the characteristic D and G bands of the carbonaceous material. The D-band (disordered phonon mode) is due to structural defects in the graphite plane, the G-band (graphite band) and SP in graphitic carbon2Bond E2gVibration mode dependent, the peak intensity ratio of the D-band to the G-band is typically used to identify the degree of disorder in the graphite structure, since the calculated inner diameter/inner diameter ratio is 1.005, which means that Ni is2The carbon layer in P/C-YS-350 is of high quality, and its high conductivity facilitates electron transfer during electrochemical reactions.
FIG. 5 shows Ni prepared in example 12SEM image of P/C-YS-350, from which Ni is clearly seen2P/C-YS-350 consists of an inner spherical core and an outer spherical shell surrounded by an outer layer.
FIG. 6 shows Ni prepared in example 12TEM image of P/C-YS-350, from which it can be seen that the present invention successfully prepares carbon-doped metal phosphide (Ni) with hollow yolk-eggshell nanostructure2P/C)。
FIG. 7 shows Ni prepared in example 22XRD pattern of P/C-YS-250. A strong diffraction peak at 10.1 deg. was observed, which correlates with the metal alkoxide of the nickel-glycine precursor. Furthermore, several unknown diffraction peaks indicate 250 ℃ for any phosphorusThe formation of the compound is not high enough.
FIGS. 8(a) (b) and (c) (d) are Ni prepared in example 2, respectively2P/C-YS-400、Ni2SEM image of P/C-YS-450. It can be seen from the figure that too high temperature causes a part of the hollow yolk-eggshell structure to be difficult to form, thereby reducing the catalytic active sites and specific surface area, and affecting the catalytic performance.
FIG. 9 shows Ni prepared in example 1 of the present invention2LSV curves with iR compensation for P/C-YS-350 and Ni-gly precursors compared to commercial Pt/C, from which Ni can be seen2The UOR activity of P/C-YS-350 exhibited the lowest potential and the highest current density (1.354V) in the above-mentioned materials, when the current density was 50mA/cm2The potentials of the Ni-gly precursor and Pt/C were 1.426V and 1.742V, respectively.
FIG. 10 shows Ni prepared in example 1 of the present invention2LSV curve of P/C-YS-350 at different urea concentrations, from which it can be seen that in the absence of urea, at 10mA/cm2The potential of (1) is 1.546V, and oxygen evolution reaction occurs. The current density recorded for 0.1mol/L urea was 151.5mA/cm2(ii) a In addition, under the natural diffusion condition of 1.45V (vs. RHE), when the concentration of urea is 0.33mol/L, the concentration is remarkably increased to 252.5mA/cm2. It can be seen from this that the gradient effect of urea concentration on UOR performance is significant, Ni2The P/C-YS-350 has the highest oxidation performance on urea in the electrolyte solution mixture of 1mol/L KOH and 0.33mol/L urea. The improvement of UOR performance benefits from Ni2P and C act synergistically with specific architectures. At the beginning, at a certain potential, when urea approaches Ni2OH on the surface of the P/C-YS sample-NH tending to break up urea molecules2Group, resulting in the transport of liberated electrons to NiOOH and the formation of H2O, in the next step, NH2The radicals are converted into nitrogen species adsorbed on the exposed nickel sites after the carbon-nitrogen bonds of the urea molecules are broken, nitrogen and carbon dioxide gas are generated, and the high-activity nickel oxide returns to Ni2+. Because the carbon additive acts as an electron acceptor, electrons can be transferred from the nickel site to the carbon site, which places the nickel in a higher valence state for further catalytic oxidation, and, at the same time, SP2Pi → pi of C-C bond in hybridizationThe transition occurs when the electron is captured by the C site; in addition, benefit from the yolk shell structure, Ni2P/C has many exposed active sites and unique electronic structure, giving high conductivity for fast electron transfer to the catalyst surface, reducing the carbon dioxide adsorption/desorption barrier for fast reaction kinetics, ultimately facilitating the UOR process.
FIG. 11 shows Ni prepared in example 12P/C-YS-350 is tested at a current density of 10mA/cm by a chronopotentiometry method2The stability performance shows that the material has good stability, excellent electrocatalytic performance and certain commercialization potential.
FIG. 12 shows a cross section of 10mA cm-2The digital photo of the urea electrolytic cell working at the time, in the urea auxiliary energy-saving integral decomposition cell, urea generates oxidation reaction at the anode to generate N2And CO2At the cathode, hydrogen evolution reaction takes place to produce H2The theoretical electrode potential of urea oxidation is 0.37V, which is far lower than the standard electrode potential of the whole water decomposition by 1.23V, and the energy utilization capability is high.
In addition, the invention also relates to Ni prepared in example 12P/C-YS-350 was compared to several UOR catalysts, and the results are shown in Table 1.
TABLE 1 comparative results
Figure BDA0002992714530000101
The comparison shows Ni of example 1 of the invention2P/C-YS-350 exhibits excellent UOR performance in the recently reported electrocatalysts.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. Ni with hollow yolk-eggshell structure2The preparation method of the P/C nano composite material is characterized by comprising the following steps:
(1) preparing a yolk-heel l nickel-glycine precursor: adding nickel nitrate hexahydrate into a Teflon container filled with glycerol and isopropanol in advance, stirring uniformly, adding deionized water into the mixed solution, stirring uniformly, transferring the container into a stainless steel autoclave for hydrothermal reaction, naturally cooling to room temperature, filtering, separating, washing, and drying at constant temperature to obtain a light green powder nickel-glycine precursor;
(2) preparation of Ni2P/C nanocomposite: respectively placing a nickel-glycine precursor and disodium hydrogen phosphate powder at the rear end and the front end of a tubular heating furnace, heating to 250-450 ℃ at the speed of 2 ℃/min in an inert gas environment, maintaining for 2-3 h, washing and drying to obtain black powdery Ni2P/C nanocomposites.
2. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the proportion of nickel nitrate hexahydrate, glycerol, isopropanol and deionized water in the step (1) is 0.6-0.7 mmol: 9-10 ml: 54-60 ml: 2-3 ml.
3. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the temperature of the hydrothermal reaction in the step (1) is 18 DEGThe reaction time is 9-12 h at 0-200 ℃.
4. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the filtration and separation in the step (1) are carried out by filtering and separating precipitates through a micron nylon organic filter membrane.
5. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the constant-temperature drying temperature in the step (1) is 60-70 ℃, and the time is 9-12 hours.
6. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the mass ratio of the nickel-glycine precursor to the disodium hydrogen phosphate powder in the step (2) is 1: 10.
7. ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the annealing treatment temperature in the step (2) is 350 ℃.
8. Ni with hollow yolk-shell structure according to claim 12The preparation method of the P/C nano composite material is characterized in that the inert atmosphere in the step (2) is argon.
9. Ni having a hollow yolk-shell structure, obtainable by a process according to any one of claims 1 to 82P/C nanocomposites.
10. Ni having a hollow yolk-shell structure, obtainable by a process according to any one of claims 1 to 82The P/C nano composite material is used as a catalyst for hydrogen evolution by urea electrooxidation.
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CN105964288A (en) * 2016-06-12 2016-09-28 常州大学 Method for preparing mesoporous carbon nitride loaded nano nickel phosphide
CN107142488A (en) * 2017-04-28 2017-09-08 南开大学 A kind of porous multiple casing nickel phosphide tiny balloon and its preparation method and application
CN108493426A (en) * 2018-04-13 2018-09-04 西北大学 A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery
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