CN112023959A - Junction type NiP2Electrocatalyst and preparation method and application thereof - Google Patents
Junction type NiP2Electrocatalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
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- 230000003197 catalytic effect Effects 0.000 abstract description 21
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002064 nanoplatelet Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- 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
-
- 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
-
- 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 junction type NiP2An electrocatalyst, a preparation method and application thereof, belonging to the technical field of electrocatalysts. The junction type NiP2The electrocatalyst includes an electrically conductive substrate and a NiP grown in-situ on the electrically conductive substrate2Catalyst of said NiP2The catalyst comprises monoclinic phase NiP2And cubic phase NiP2. The invention adopts vacuum tube sealing and high-temperature sintering to construct phosphorus-rich phase nickel phosphide nanosheets, and the electrocatalyst has m-phase NiP2And c-phase NiP2The formed unique heterojunction structure successfully solves the problems of interface resistance and interface gaps of the composite catalyst formed among different substances, and can optimize interface electronic arrangement and promote the Volmer reaction, so that the hydrogen evolution catalyst has excellent hydrogen evolution catalytic performance and structural stability.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular toRelates to a junction type NiP2An electrocatalyst, a method of making and use thereof.
Background
Environmental pollution and energy crisis caused by the dependence on fossil energy have attracted much attention globally. The search for efficient, sustainable, clean and pollution-free alternative energy becomes a hotspot and difficulty in the research field of new energy at present. Among a plurality of new energy systems, the hydrogen energy is an extremely excellent substitute, the calorific value of the hydrogen energy can reach 143kJ/g, which is about 3 times of gasoline, 3.9 times of alcohol and 4.5 times of coke, and the hydrogen energy is considered as an ideal substitute energy for fundamentally solving global problems of energy, environment and the like. At present, the hydrogen preparation method in industry mainly uses fossil fuel to prepare hydrogen (about 65% of total yield), but the method cannot fundamentally abandon the consumption of fossil energy. With the research in the electrochemical field, water electrolysis is gradually becoming an important method for producing high-purity hydrogen, and compared with the traditional hydrogen production method, the hydrogen production by water electrolysis can effectively reduce the pollution of fossil energy consumption to the environment, and meanwhile, because the reactant is only water, the produced hydrogen is also the purest. The water electrolysis is composed of two half reactions of a Hydrogen Evolution Reaction (HER) at the cathode and an Oxygen Evolution Reaction (OER) at the anode. Since the catalytic activity of a common electrode is generally low, the required applied voltage is far higher than the decomposition voltage of water (1.23V), so that the energy consumption of water electrolysis is too high, and the cost is greatly increased.
To solve this problem, it is usually necessary to support a catalyst on the surface of the electrode with high efficiency so that the reaction can generate a large current at a low overpotential. The catalysts currently used are mainly platinum group noble metal materials, for example Pt/C for the hydrogen evolution reaction and RuO for the oxygen evolution reaction2And the like. They have low overpotential and excellent reaction kinetic behavior in the electrolytic water reaction process, however, precious metals such as Pt are low in reserves on the earth and expensive, and limit the large-scale application of them in the actual industry.
In recent years, some non-noble metals have been used as hydrogen evolution catalysts, such as transition metal phosphides (CoP, Ni)2P、Ni5P4Etc.), sulfides (MoS)2、NiS2Etc.), selenides (NiSe)2、FeSe2Etc.), particularly transition metal phosphides, are considered to be one of the powerful substitutes for platinum-based noble metal catalysts due to their characteristics such as abundant crystal structure, more surface unsaturated active sites, etc. The transition metal phosphide catalyst prepared by a plurality of methods still has larger overpotential, and the performance has a certain gap with noble metal platinum, which seriously restricts the popularization and development of the transition metal phosphide catalyst.
In order to meet the requirements of practical application, some regulation strategies need to be adopted to further improve the catalytic activity and stability of the transition metal phosphide. Common regulatory strategies include: nano material, element doping, heterojunction construction and the like. Wherein, the construction of heterojunction is an effective means for improving the water electrolysis rate, and the combination of excellent hydrogen evolution catalyst and strong hydroxyl absorbent (common Layered Double Hydroxides (LDHs) or metal oxides) can greatly improve the water electrolysis rate, such as MoS2/TiO2NTs catalyst, Ni3Se4NiO catalyst, ruthenium/MoO2And (4) a nano-junction catalyst. However, this strategy has the following problems: firstly, a large interface resistance exists between the hydrogen evolution catalyst and the layered double hydroxide hydroxyl absorbent, so that the catalytic activity is limited; secondly, the larger gap between the hydrogen evolution catalyst and the hydroxyl absorbent will lead to the recombination of the hydrogen ions and hydroxyl ions generated in the electrolyte. Due to the above two problems, the catalytic activity of the composite catalyst combining a hydrogen evolution catalyst with a hydroxyl absorbent is severely limited. Therefore, a novel hydrogen evolution catalyst with a compact heterogeneous interface is constructed, so that the cost of the catalyst can be reduced, and the catalytic activity can be obviously improved.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a junction type NiP2Electrocatalyst, by constructing phosphorus-rich phase nickel phosphide NiP2The nano-sheet ensures good catalytic activity and stability, and the electrocatalyst has m-phase NiP2And c-phase NiP2The formed unique heterojunction structure is successfully solvedThe problems of interface resistance and interface gaps are solved, the electronic arrangement of the interface can be optimized, and the Volmer reaction is promoted, so that the hydrogen evolution catalyst has excellent hydrogen evolution catalytic performance and structural stability.
In order to achieve the purpose, the invention is realized by the following technology:
junction type NiP2Electrocatalyst comprising an electrically conductive substrate and NiP grown in situ on said electrically conductive substrate2Catalyst of said NiP2The catalyst comprises monoclinic phase (m-phase) NiP2And cubic phase NiP2(phase c).
Further, the m phase accounts for 7% of the total crystal phase, and the c phase accounts for 93% of the total crystal phase.
Further, the conductive substrate is a carbon cloth.
The second purpose of the invention is to provide the junction type NiP2The preparation method of the electrocatalyst adopts vacuum tube sealing sintering, can easily obtain high-phosphorus compounds, and effectively adjusts NiP by adjusting the phosphating temperature2M-phase NiP in nanosheet2And c-phase NiP2In order to obtain a crystalline phase ratio superior to that of a single-phase NiP2And nickel-rich phase nickel phosphide, and also provides a novel phase engineering strategy for later electrocatalyst design.
In order to achieve the purpose, the invention is realized by the following technology:
junction type NiP2A method of preparing an electrocatalyst, comprising the steps of:
s1 growing Ni (OH) on the conductive substrate in situ2A crystal layer containing Ni (OH)2The conductive substrate of (1);
s2, loading Ni (OH) on the substrate2The conductive substrate is mixed with red phosphorus, the temperature is raised to 650 plus 750 ℃ under the vacuum condition, the heat is preserved, the high-temperature phosphating reaction is carried out, and the mixture is cooled to the room temperature after the reaction is finished, so as to obtain the load NiP2The conductive substrate of (1);
s3, taking out the load NiP2The conductive substrate is washed and dried to obtain the phase-bonded NiP2Electro-catalyst。
Further, in step S2, the temperature rise rate is 1-10 ℃/min, and the heat preservation time is 5-10 h.
Further, in step S2, the red phosphorus is ground.
Further, step S1 specifically includes the following steps:
s11, cleaning the conductive substrate to obtain the conductive substrate with a clean surface;
s12, sequentially adding nickel salt, urea and ammonium fluoride into deionized water to obtain a reaction solution;
and S13, immersing the conductive substrate into the reaction liquid obtained in the step S12, carrying out hydrothermal reaction, taking out the conductive substrate after the reaction is finished, and cleaning and drying the conductive substrate to obtain a precursor.
Further, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate and nickel chloride.
Further, in step S12, the molar ratio of the nickel salt, the urea, and the ammonium fluoride is 2: 10: 5.
further, in step S13, the temperature of the hydrothermal reaction is 100-160 ℃, and the reaction time is 6-12 h.
The third purpose of the invention is to provide the junction type NiP2Application of an electrocatalyst in preparation of hydrogen by electrolyzing water.
Compared with the prior art, the invention has the following advantages:
1. vacuum tube sealing and high-temperature sintering are adopted to construct phosphorus-rich phase nickel phosphide nanosheets, and the electrocatalyst has m-phase NiP2And c-phase NiP2The formed unique heterojunction structure successfully solves the problems of interface resistance and interface gaps of the composite catalyst formed among different substances, and can optimize interface electronic arrangement and promote the Volmer reaction, so that the hydrogen evolution catalyst has excellent hydrogen evolution catalytic performance and structural stability.
2. In-situ growth of NiP directly on carbon cloth2The contact of the nanosheets, the catalyst and the conductive substrate is tighter, the nanosheets can be directly used as HER electrodes without further treatment, and the method is beneficial to large-scale industrial application.
3. The Ni element and the P element required by the electrocatalyst are rich elements, the chemical property is stable, the raw material source is wide, the price is low, and the cost for preparing hydrogen by electrolyzing water can be greatly reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a combination type NiP2Schematic diagram of electrocatalyst preparation flow;
FIG. 2 shows a NiP junction2M-phase and c-phase transformation processes in the electrocatalyst;
FIG. 3 shows the phase-bonded type NiP prepared at 600 ℃ in example 12SEM images of the nanoplatelets;
FIG. 4 shows the phase-bonded NiP prepared at 650 ℃ in example 22SEM images of the nanoplatelets;
FIG. 5 shows the phase-bonded NiP prepared at 650 ℃ in example 22A high-resolution Transmission Electron Microscope (TEM) image of the nanosheets, wherein an inset image is a Selected Area Electron Diffraction (SAED) image, and the length of a ruler is 51/nm;
FIG. 6 shows the phase-bonded NiP prepared at 700 ℃ in example 32SEM images of the nanoplatelets;
FIG. 7 shows the phase-bonded NiP prepared at 750 ℃ in example 42SEM images of the nanoplatelets;
FIG. 8 is an X-ray diffraction (XRD) pattern of electrocatalysts prepared in examples 1-4 at different temperatures;
FIG. 9 is a hydrogen evolution polarization curve (LSV) of the electrocatalysts of examples 1-4 in a 1M KOH solution;
FIG. 10 is an Electrochemical Impedance Spectroscopy (EIS) of the electrocatalysts of examples 1-4;
FIG. 11 is a plot of the m-phase and c-phase example versus the catalytic properties of the electrocatalysts of examples 1-4;
FIG. 12 shows a junction type NiP2Stability test pattern of electrocatalyst.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In addition, the terms "comprising," "including," "containing," and "having" are intended to be non-limiting, i.e., that other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents are commercially available unless otherwise specified.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in the present invention are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The invention aims to provide a junction type NiP2Electrocatalyst, by constructing phosphorus-rich phase nickel phosphide NiP2The nano-sheet ensures good catalytic activity and stability, and the electrocatalyst has m-phase NiP2And c-phase NiP2The formed unique heterojunction structure successfully solves the problems of interface resistance and interface gaps, can optimize interface electron arrangement and promote the Volmer reaction, and therefore has excellent hydrogen evolution catalytic performance and structural stability.
Junction type NiP2Electrocatalyst comprising an electrically conductive substrate and NiP grown in situ on said electrically conductive substrate2Catalyst of said NiP2The catalyst comprises monoclinic phase (m-phase) NiP2And cubic phase NiP2(phase c). Specifically, a plurality of crystal phases may be present in any ratio, and the m phase accounts for the entire crystal phasesThe c phase accounts for 0 to 100 percent of the total crystal phase, and the m phase and the c phase account for 100 percent of the total sum.
NiP grown in-situ on conductive substrate2The catalyst is of a sheet structure, has a larger specific surface area, can provide more active sites for hydrogen evolution reaction, and greatly increases the transmission and diffusion of electrolyte. Furthermore, NiP2Is a phosphorus-rich phase nickel phosphide compared with a nickel-rich phase nickel phosphide (Ni)3P、Ni5P2、Ni12P5、Ni2P、Ni5P4) And monophosphorous nickel phosphide (NiP), which has higher phosphorus content, higher theoretical specific capacity and better catalytic activity; at the same time, it is compared with another phosphorus-rich phase nickel phosphide NiP which cannot exist stably3And the stability is higher.
Further make NiP2The catalyst has two crystal phase structures, namely monoclinic phase (m phase) and cubic phase (c phase), compared with single-phase NiP2The catalyst and the composite phase catalyst have the following advantages:
first, the m phase and the c phase have a plurality of crystal phases with different crystal axis directions, obvious crystal boundaries exist, a heterojunction structure can be formed, and a composite phase NiP2The arrangement of electrons can be optimized at the interface, particularly the energy level structures of the two are different, the electrons can migrate from m phase to c phase and are enriched at Ni position of the c phase, thereby being beneficial to H in the solution+Resulting in the reduction of electrons to hydrogen.
Second, the formation of heterojunctions may facilitate the Volmer reaction, which, as a determining step of the basic HER rate, will provide sufficient reactant, i.e. H, for the subsequent steps+。
Third, after the heterojunction is formed, the Gibbs free energy of hydrogen adsorption at the interface of the m-phase and the c-phase is superior to that of single-phase NiP2。
In addition, compared with the existing common heterojunction structure formed by two different substances (such as a hydrogen evolution catalyst and a hydroxyl absorbent), the heterojunction structure formed by the same catalyst has double matching relation of energy level matching and lattice matching, the problem that the grain boundary between different substances has large thermal stress on the grain boundary is solved, the binding force between the heterojunction structures is strong, the interface gap and the interface resistance are reduced, the charge transfer resistance is small, and the electrocatalytic activity is high.
The proper number of the heterojunctions has excellent rectification effect, can overcome the defect that electron holes are easy to recombine in the catalysis process when the heterojunctions are used in the electrocatalytic hydrolysis reaction, and can further improve the performance of the electrocatalyst, so that preferably, the m phase accounts for 3-17% of the total crystal phase, and the c phase accounts for 83-97% of the total crystal phase; more preferably, the m phase accounts for 5-10% of the total crystalline phase, and the c phase accounts for 90-95% of the total crystalline phase; further preferably, the m phase accounts for 7% of the total crystal phase, and the c phase accounts for 93% of the total crystal phase.
Optionally, the conductive substrate is a carbon cloth. Compared with other conductive substrates, such as carbon paper, carbon felt, foamed nickel and the like, the carbon cloth has good conductivity and stable structure, has a three-dimensional support structure, can effectively improve the conductivity of the electrocatalyst as a carrier, and can prevent a load NiP (nickel phosphide) by using the three-dimensional support structure2The aggregation of the catalyst nanocrystal improves the stability; more importantly, the carbon cloth and the NiP2The catalyst has good lattice matching degree and is beneficial to NiP2The catalyst grows on the surface of the conductive substrate in an epitaxial manner, so that the NiP is improved2The compactness and the strength of the combination of the catalyst and the conductive substrate do not need additional bonding, thereby being beneficial to obtaining a high-stability structure and improving the electrocatalytic activity.
The invention also provides the NiP with the junction type2The preparation method of the electrocatalyst is the second aim of the invention, the high-phosphorus compound can be easily obtained by adopting vacuum tube-sealing sintering, and the NiP can be effectively adjusted by adjusting the phosphating temperature2M-phase NiP in nanosheet2And c-phase NiP2In order to obtain a crystalline phase ratio superior to that of a single-phase NiP2And nickel-rich phase nickel phosphide, and also provides a novel phase engineering strategy for later electrocatalyst design.
The junction type NiP is shown in FIG. 12A method of preparing an electrocatalyst, comprising the steps of:
s1 growing Ni (OH) on the conductive substrate in situ2A crystal layer containing Ni (OH)2The conductive substrate of (1) is a combined NiP2A precursor of an electrocatalyst;
s2, loading Ni (OH) on the substrate2The conductive substrate is mixed with red phosphorus, the temperature is raised to 650 plus 750 ℃ under the vacuum condition, the heat is preserved, the high-temperature phosphating reaction is carried out, and the mixture is cooled to the room temperature after the reaction is finished, so as to obtain the load NiP2The conductive substrate of (1);
s3, taking out the load NiP2The conductive substrate is washed and dried to obtain the phase-bonded NiP2An electrocatalyst. The washing method may be, for example, washing with ethanol and deionized water for several times, and the drying method may be forced air drying or natural drying.
Adopt above-mentioned technical scheme: firstly, a nickel hydroxide crystal layer grows on a conductive substrate through a hydrothermal process to obtain a precursor, and then red phosphorus powder is used as a phosphorus source to carry out high-temperature phosphorization on the precursor mixed with red phosphorus under a vacuum condition so as to convert nickel hydroxide into NiP in situ2Nanosheets, NiP2The nano-sheets are supported on the conductive substrate in a disorderly manner to form a three-dimensional self-supporting structure in the shape of a silver ear, so that the specific surface area of the electrocatalyst is greatly increased, the contact area between the electrocatalyst and electrolyte and the number of catalytic active sites are increased, and the catalytic performance is improved. In addition, the NiP containing m phase is obtained by vacuum tube sealing and high-temperature sintering2And c-phase NiP2The performance of the electrocatalyst is superior to that of single-phase NiP2And a hydrogen evolution electrocatalyst for nickel-rich phase nickel phosphide.
Since the m phase is a high temperature phase and the c phase is a low temperature phase, when the temperature is transited from low temperature to high temperature, the phase transition occurs naturally, and the transition process between the c phase and the m phase is shown in fig. 2. Meanwhile, NiP with phase change occurs at the same time of heat preservation due to different temperatures2The proportion is different, therefore, the phase combination type NiP with different crystal phase proportions can be obtained by controlling the heat preservation temperature2An electrocatalyst.
The specific operation of step S2 is: cutting the precursor into a rectangle of 1 × 3cm,putting the mixture into the bottom of a quartz tube, simultaneously taking red phosphorus powder and pouring the red phosphorus powder into the bottom of the quartz tube, and then pumping the vacuum degree in the quartz tube to 10-4Pa below, sealing the tube opening with a quartz column, maintaining the vacuum degree in the tube, placing the sealed quartz tube into a box-type furnace, heating the furnace to 600-750 ℃ at a constant heating rate, preserving the temperature for a period of time, and naturally cooling to room temperature to obtain the NiP-loaded material2The conductive substrate of (1).
In step S2, excess red phosphorus is used to ensure NiP in the final electrocatalyst2The purity of the nanoparticles is high.
Preferably, in step S2, the temperature rising rate is 1-10 ℃/min, and the heat preservation time is 5-10 h. The temperature rise rate can fully activate the reaction substrate and improve the phosphorization rate. In addition, m-phase NiP with good crystallinity can be obtained within the heat preservation time2And c-phase NiP2. If the phosphating time is short, red phosphorus fails to react with Ni (OH)2React well and result in the formation of NiP2Less, the catalytic activity will be weaker. With prolonged phosphating time, NiP2The amount of produced will be more and more, and the catalytic activity of the electrocatalyst will become stronger and stronger. However, if the phosphating time is too long, not only NiP will be present2And some side reactions may occur, leading to NiP by introducing other nickel-containing phosphides2The purity of (2) is reduced and the catalytic activity is weakened.
Preferably, in step S2, the red phosphorus is subjected to a grinding process. Specifically, the red phosphorus block is ground in a glove box for one hour to obtain fine red phosphorus powder for later use. The fine red phosphorus powder is obtained by grinding, and the reaction activity of the red phosphorus powder can be properly increased.
Preferably, the step S1 specifically includes the following steps:
s11, cleaning the conductive substrate to obtain the conductive substrate with a clean surface;
s12, sequentially adding nickel salt, urea and ammonium fluoride into deionized water to obtain a reaction solution;
and S13, immersing the conductive substrate into the reaction liquid obtained in the step S12, carrying out hydrothermal reaction, taking out the conductive substrate after the reaction is finished, and cleaning and drying the conductive substrate to obtain a precursor.
The kind of nickel salt is not particularly limited in the present invention, and Ni (OH) can be efficiently formed2That is, in some embodiments, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, and nickel chloride. Urea is used as a pH regulator to make the pH of the reaction solution alkaline so as to ensure that Ni (OH) is generated2. Ammonium fluoride as surfactant to control Ni (OH)2Morphology to produce uniformly dispersed, uniformly sized Ni (OH)2And (3) a crystal layer.
It should be understood that, although the sequence of step S11 and step S12 is limited in the embodiment of the present invention, the sequence is limited only for descriptive purposes, and the two steps are not in a substantial sequential relationship. That is, step S11 may be performed first, and then step S12 may be performed; or, step S12 is performed first, and then step S11 is performed; or the step S11 is performed simultaneously with the step S12.
Preferably, in step S12, the molar ratio of the nickel salt, the urea and the ammonium fluoride is 2: 10: 5.
preferably, in step S13, the temperature of the hydrothermal reaction is 100-160 ℃, and the reaction time is 6-12 h. The specific operation is as follows: and (3) placing the conductive substrate into a Teflon lining, slowly adding the reaction liquid obtained in the step S12, then placing the Teflon lining into a reaction kettle, and reacting for 6-12h at the temperature of 100-160 ℃.
The third purpose of the invention is to provide the junction type NiP2Application of an electrocatalyst in preparation of hydrogen by electrolyzing water. The junction type NiP2Application of electrocatalyst and above-mentioned phase combination type NiP2The advantages of electrocatalysts over the prior art are the same and are not described in detail here.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
Example 1
The above-mentioned junction type NiP2ElectrocatalysisThe preparation method of the reagent comprises the following steps:
s1 growing Ni (OH) on the conductive substrate in situ2A crystal layer containing Ni (OH)2The conductive substrate of (1) is a combined NiP2A precursor of an electrocatalyst;
step S1 specifically includes the following steps:
s11, cutting the carbon cloth into rectangles of 3 x 3cm, respectively ultrasonically cleaning the rectangles with acetone, ethanol and deionized water for 20min, and drying the rectangles in vacuum for later use;
s12, adding 2mM Ni (NO)3)2·6H2O、10mM(NH2)2CO and 5mM NH4Sequentially dissolving F in 40mL of deionized water, and stirring for 30min to obtain a reaction solution;
s13, putting the carbon cloth into a Teflon lining, slowly adding the reaction liquid obtained in the step S12, putting the Teflon lining into a reaction kettle, and reacting for 6h at 100 ℃ to obtain the material loaded with Ni (OH)2After the temperature is reduced to room temperature, taking out the carbon cloth, respectively washing the carbon cloth with alcohol and deionized water for three times, and carrying out vacuum drying to obtain a precursor;
s2, cutting the precursor into a rectangle of 1 × 3cm, placing the rectangle at the bottom of a quartz tube, pouring 30mg of red phosphorus powder at the same time into the bottom of the quartz tube, and then pumping the vacuum degree in the quartz tube to 10-4Sealing the pipe orifice with a quartz column under Pa, maintaining the vacuum degree in the pipe, placing the sealed quartz pipe into a box-type furnace, heating the furnace to 600 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5h, and naturally cooling to room temperature to obtain the NiP-loaded material2The conductive substrate of (1);
s3, taking out the load NiP2The conductive substrate is washed and dried to obtain the phase-bonded NiP2Electrocatalyst, phase-bonded NiP obtained in example 12SEM of the nanoplatelet array is shown in figure 3.
Example 2
Example 2 is essentially the same as example 1, except that: in step S2, the furnace temperature was raised to 650 ℃ at a temperature rise rate of 3 ℃/min, and the junction-type NiP obtained in example 2 was used2SEM of the nanosheet array is shown in FIG. 4, high resolution transmissionA mirror image (TEM) is shown in FIG. 5.
Example 3
Example 3 is essentially the same as example 1, except that: in step S2, the furnace temperature was raised to 700 ℃ at a temperature raising rate of 3 ℃/min, and the phase-bonded type NiP obtained in example 3 was used2SEM of the nanoplatelet array is shown in figure 6.
Example 4
Example 4 is essentially the same as example 1, except that: in step S2, the furnace temperature was raised to 750 ℃ at a temperature raising rate of 3 ℃/min, and the phase-junction type NiP obtained in example 4 was used2SEM of the nanoplatelet array is shown in figure 7.
The XRD data of the electrocatalysts obtained in examples 1-4 are shown in figure 8. As can be seen in FIG. 8, the sample prepared at 600 ℃ is pure c-phase NiP2With increasing phosphating temperature, m-phase NiP2The proportion of (A) is gradually increased to obtain pure m-phase NiP at 750 DEG C2. The above results indicate that NiP2The proportion of the m phase and the c phase can be regulated and controlled by changing the phosphating temperature, so that the NiP with different phase ratios can be obtained2Nanosheets.
Junction NiP2The method for testing the alkaline HER performance of the nanosheets comprises the following steps:
1) preparing an electrode: the electrocatalysts of examples 1-4 were cut into a rectangular shape of 1X 2cm as a working electrode;
2) solution preparation: KOH with the concentration of 1M is adopted as electrolyte, and the alkaline HER performance is tested;
3) electrochemical performance of the test electrode: a three-electrode system was used, the working electrode was the electrocatalyst of examples 1-4, the counter electrode was a high purity graphite rod, and the reference electrode was the Hg/HgO electrode. First three electrodes were immersed in 1M KOH, phase-bound NiP2The immersion area of the electrocatalyst in the electrolyte was 1X 1cm2The sample was activated using cyclic voltammetric scans using an electrochemical workstation, scanning ranging from-0.9 to-1.5V vs. hg/HgO, scanning rate of 2mV/s, for a total of 1000 cycles.
The samples were then tested for hydrogen evolution polarization curve (LSV) data ranging from-0.9 to-1.6V vs. Hg/HgO with a scan rate of 2mV/s, knotsAs shown in FIG. 9, when the current density reached 10mAcm-2The overpotentials for examples 1-4 were 181mV, 134mV, 175mV, and 263mV vs. RHE, respectively.
Then, EIS data of the sample were measured, with a test voltage of-1.08V vs. Hg/HgO and a frequency range of 0.01-106Hz, the results are shown in FIG. 10, and the charge transfer resistances of examples 1 to 4 were 45.1. omega., 17.4. omega., 38.8. omega., and 63.6. omega., respectively. The electrochemical performance test result shows that the combined type NiP2The HER performance of the electrocatalyst has close relation with the crystal phase proportion, and the catalytic performance of the electrocatalyst can be optimized by adjusting the proportion of different phases.
The relationship between the catalytic properties of the electrocatalysts of examples 1 to 4 and the m-phase and c-phase examples is shown in fig. 11, and it can be seen from fig. 11 that the electrocatalysts prepared at a phosphating temperature of 650 c had the best electrochemical performance and the highest catalytic activity when the m-phase accounted for 7% and the c-phase accounted for 93% of the total crystalline phase.
Stability test, using the alkaline HER Performance test method, the test results are shown in FIG. 12, 10mAcm after 1000CV cycles-2The overpotential increased by only 4 mV. At the same time, 50mAcm-2After 14 hours of testing under the current density condition, the property is not obviously attenuated, which indicates the phase junction type NiP2The electrocatalyst has good stability.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. Junction type NiP2An electrocatalyst, comprising an electrically conductive substrate and NiP grown in situ on said electrically conductive substrate2Catalyst of said NiP2The catalyst comprises monoclinic phase NiP2And cubic phase NiP2。
2. The combination NiP of claim 12Electro-catalystCharacterized in that the monoclinic phase NiP2The cubic phase NiP accounts for 7 percent of the total crystal phase2The proportion of the total crystal phase was 93%.
3. The combination NiP of claim 12The electrocatalyst is characterized in that the conductive substrate is carbon cloth.
4. Junction type NiP2The preparation method of the electrocatalyst is characterized by comprising the following steps of:
s1 growing Ni (OH) on the conductive substrate in situ2A crystal layer containing Ni (OH)2The conductive substrate of (1);
s2, loading Ni (OH) on the substrate2The conductive substrate is mixed with red phosphorus, the temperature is raised to 650 plus 750 ℃ under the vacuum condition, the heat is preserved, the high-temperature phosphating reaction is carried out, and the mixture is cooled to the room temperature after the reaction is finished, so as to obtain the load NiP2The conductive substrate of (1);
s3, taking out the load NiP2The conductive substrate is washed and dried to obtain the phase-bonded NiP2An electrocatalyst.
5. The method according to claim 4, wherein in step S2, the temperature rise rate is 1-10 ℃/min, and the holding time is 5-10 h.
6. The manufacturing method according to claim 4, wherein in step S2, the red phosphorus is subjected to grinding treatment.
7. The method according to claim 4, wherein step S1 specifically comprises the steps of:
s11, cleaning the conductive substrate to obtain the conductive substrate with a clean surface;
s12, sequentially adding nickel salt, urea and ammonium fluoride into deionized water to obtain a reaction solution;
and S13, immersing the conductive substrate into the reaction liquid obtained in the step S12, carrying out hydrothermal reaction, taking out the conductive substrate after the reaction is finished, and cleaning and drying the conductive substrate to obtain a precursor.
8. The method according to claim 7, wherein in step S12, the molar ratio of the nickel salt to the urea to the ammonium fluoride is 2: 10: 5.
9. the method as claimed in claim 7, wherein the hydrothermal reaction is performed at a temperature of 100 ℃ and 160 ℃ for 6-12h in step S13.
10. A binder type NiP according to any one of claims 1 to 32Application of an electrocatalyst in preparation of hydrogen by electrolyzing water.
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