CN114164445A - V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-electrolysis water-electric catalyst - Google Patents
V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-electrolysis water-electric catalyst Download PDFInfo
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-hydrolysis water-electric catalyst. Firstly, growing a V-doped Ni Fe precursor on a nitrogen-doped graphene tube carrier by a hydrothermal method, then heating the V-doped Ni Fe precursor to 470 ℃ in a tube furnace, introducing ammonia gas, and nitriding for 2 hours to obtain V-doped Ni grown on the nitrogen-doped graphene tube in situ3Electrocatalysts composed of FeN and Ni nanoparticles, i.e. V-Ni3FeN/Ni @ N-GTs. Based on V doping to Ni3Effective regulation of the electronic structure of Ni, Fe in FeN, V-Ni3Heterojunction interface-induced charge rearrangement of FeN and Ni, and good conductivity of nitrogen-doped graphene tube carrierThe electrocatalyst shows excellent electrocatalytic activity and stability in hydrogen evolution reaction and oxygen evolution reaction in an alkaline medium; simultaneously used as an anode catalyst and a cathode catalyst for catalyzing the total hydrolysis reaction, and the cell voltage of only 1.55V can reach 10mA cm‑2And exhibits excellent stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-electrolysis water-electric catalyst and preparation and application thereof.
Background
Hydrogen energy is widely considered as a sustainable alternative energy by virtue of the advantages of high mass specific energy density and no carbon emission, and can solve the environmental problem caused by consumption of traditional fossil energy. Electrocatalytic cracking of water is an effective way to obtain clean hydrogen fuel, involving two half-reactions: cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), both of which depend on efficient electrocatalysts. To date, Pt-and Ir/Ru-oxide based catalysts have remained considered ideal electrocatalysts for HER and OER. However, their large-scale commercial use is hampered by the expensive cost and low reserves. A full electrolysis water electrocatalyst capable of having both HER and OER functions in the same electrolyte will reduce the cost of electrocatalytic cracking of water. In recent years, researchers have developed some non-noble metal based bifunctional electrocatalysts, mainly transition metal phosphides, sulfides, carbides, nitrides, etc. Among them, transition metal nitrides are becoming ideal materials for full-electrolysis hydro-catalysts by virtue of their low resistance, wide d-band, excellent corrosion resistance and good mechanical strength.
Because the surface electronic structure of the catalyst is a main factor influencing the catalytic activity of the catalyst, effective strategies can be adopted to optimize the electronic structure of the catalyst and improve the catalytic activity of the catalyst. First, heteroatom doping has been identified as an effective strategy to modulate the electronic structure of the procatalyst. Introduction of heteroatoms of different electronegativities into the transition metal nitride lattice can induce redistribution of electron density, with precisionThe electronic structure of the main catalyst is regulated and controlled, so that the adsorption and desorption behaviors of the intermediate in the reaction process are optimized, and the activity of the catalyst is further improved. In addition, the heterojunction structure formed by materials with different work functions can induce the charge to be rearranged at a heterogeneous interface to form a relatively stable local electrophilic/nucleophilic region, and can meet the requirement of an ideal hydrogen evolution and oxygen evolution bifunctional electrocatalyst on charge distribution. Finally, in order to improve the overall conductivity of the transition metal nitride, the introduction of a carbon material with excellent conductivity as a skeleton is an effective method, and simultaneously, the agglomeration of active ingredients in the catalytic process can be avoided, and the exposed active sites are increased, so that the hydrogen evolution and oxygen evolution activities are improved. In summary, the doping and heterojunction strategies are combined, the nitrogen-doped graphene tube is used as a carrier through hydrothermal and nitridation methods, and V-doped Ni grown on the nitrogen-doped graphene tube in situ is prepared3Full-hydrolysis hydro-electric catalysts composed of FeN and Ni nanoparticles, i.e. V-Ni3FeN/Ni @ N-GTs. The catalyst shows high-efficiency and stable electrocatalytic activity for hydrogen evolution and oxygen evolution reactions in an alkaline medium. And, with V-Ni3FeN/Ni @ N-GTs are simultaneously used as cathode and anode catalysts to carry out total water decomposition to generate 10mA cm-2Only 1.55V cell voltage is required for the current density of (2), and excellent stability is exhibited.
Disclosure of Invention
The invention aims to provide a method for constructing V-Ni based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-hydrolysis water-electric catalyst. The specific invention content is as follows:
1. v-doped Ni in-situ grown on a nitrogen-doped graphene tube is obtained by taking the nitrogen-doped graphene tube as a carrier through hydrothermal and nitridation methods3Full-hydrolysis electrocatalyst V-Ni formed by FeN and Ni nanoparticles3FeN/Ni @ N-GTs prepared by the following method:
(1) weighing 4mmol of NH4F，8mmol CH4N2O and 0.08-0.15 mmol of Na3VO4Dissolving in 70mL of distilled water, weighing 2mmol of nickel nitrate and ferric nitrate according to the molar ratio of 5:1, dissolving in the solution, transferring to a reaction kettle,simultaneously immersing a nitrogen-doped graphene tube growing on a graphite sheet into a reaction kettle for hydrothermal reaction at the reaction temperature of 120 ℃ for 6 hours, and then washing and drying the product to obtain a V-doped NiFe precursor loaded on the nitrogen-doped graphene tube;
(2) putting the product obtained in the step (1) into a tube furnace, heating to 470 ℃ in an argon atmosphere, closing argon, introducing ammonia gas at the set temperature for 2 hours, and cooling to room temperature to obtain the full-electrolysis water electrocatalyst V-Ni3FeN/Ni@N-GTs。
2. The full-hydrolysis water catalyst V-Ni3The FeN/Ni @ N-GTs has excellent electro-catalytic performance in an alkaline medium, and can reach 10mA cm only with a cell voltage of 1.55V as a full-electrolysis water catalyst-2And exhibits excellent stability.
The invention discloses V-Ni constructed based on doping and heterojunction strategies3Compared with the prior art, the FeN/Ni @ N-GTs full-electrolysis water-electric catalyst has the advantages that:
(1) introducing hetero atom V into electrocatalyst to regulate and control host material Ni precisely3The electronic structures of Ni and Fe in FeN are adopted, so that the adsorption and desorption behaviors of the intermediate in the reaction process are optimized, and the activity of the catalyst is improved;
(2) doping Ni with V3The heterojunction formed by FeN and Ni nanoparticles can induce the charge to be rearranged at a heterogeneous interface, so that a relatively stable local electrophilic/nucleophilic region is formed, and the catalytic activity of hydrogen evolution/oxygen evolution is respectively improved;
(3) the nitrogen-doped graphene tube with excellent conductivity is introduced as a carrier, so that the overall conductivity of the catalyst can be improved, the agglomeration of active ingredients in the catalytic process can be avoided, and the exposed active sites are increased, thereby improving the hydrogen evolution and oxygen evolution performances.
Drawings
FIG. 1 shows the total hydrolysis catalyst V-Ni prepared in example 13SEM pictures of FeN/Ni @ N-GTs, (a)2 μm, (b)500 nm;
FIG. 2 shows the total hydrolysis catalyst V-Ni prepared in example 13FeN/Ni@N-GTsTem (a) and hrtem (b) photographs;
FIG. 3 shows the total hydrolysis catalyst V-Ni prepared in example 13An XRD spectrogram of FeN/Ni @ N-GTs;
FIG. 4 shows the total hydrolysis catalyst V-Ni prepared in example 13XPS spectra of FeN/Ni @ N-GTs, (a) V2 p spectra, (b) Ni 2p spectra, (c) Fe 2p spectra;
FIG. 5 shows the electrocatalyst V-Ni prepared in example 13A hydrogen evolution reaction performance diagram of electrocatalytic decomposition of water by FeN/Ni @ N-GTs in a 1mol/L KOH solution, (a) an LSV curve diagram (iR correction), (b) a Tafel slope diagram, and (c) a stability test diagram;
FIG. 6 shows the electrocatalyst V-Ni prepared in example 13An oxygen evolution reaction performance diagram of electrocatalytic decomposition of water by FeN/Ni @ N-GTs in a 1mol/L KOH solution, (a) an LSV curve diagram (iR correction), (b) a Tafel slope diagram, and (c) a stability test diagram;
FIG. 7 shows the electrocatalyst V-Ni prepared in example 13The FeN/Ni @ N-GTs are simultaneously used as cathode and anode catalysts and applied to a performance chart of electrocatalytic full-hydrolysis, (a) an LSV curve chart (iR correction), and (b) a stability test chart.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which, however, should not be construed as limiting the scope of the present invention in any way.
Example 1
The full hydrolysis hydro-catalyst V-Ni described in this example3The preparation method of FeN/Ni @ N-GTs comprises the following steps:
(1) 0.108mmol of Na was weighed3VO4、4mmol NH4F and 8mmol CH4N2Dissolving O in 70mL of distilled water, weighing 2mmol of nickel nitrate and ferric nitrate according to the molar ratio of 5:1, dissolving in the solution, transferring to a reaction kettle (100mL), simultaneously immersing a nitrogen-doped graphene tube growing on a graphite sheet into the reaction kettle, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 6h, washing, and drying the product to obtain a V-doped NiFe precursor loaded on the nitrogen-doped graphene tube;
(2) putting the product of the step (1) into a tube furnaceHeating to 470 ℃ at the temperature of 5 ℃/min in Ar atmosphere, closing argon, introducing ammonia gas for 2 hours at the temperature, and cooling to room temperature to obtain the full-hydrolysis water catalyst V-Ni3FeN/Ni@N-GTs。
SEM photographs of the full-hydrolysis water catalyst with different magnifications are shown in figures 1(a) and (b) in the attached drawing of the specification, and it can be seen that the carrier material is in a uniform tubular shape with the diameter of 200-250 nm and V-Ni3The FeN/Ni is granular and is uniformly anchored on the surface of the nitrogen-doped graphene tube, and the particle size is 10-30 nm. The TEM and HRTEM photographs are shown in FIGS. 2(a) and (b) in the drawings, and V-Ni is clearly shown in FIG. 2(a)3The granular structure of FeN/Ni, from FIG. 2(b), clearly shows two different interplanar spacing d stripes, wherein the lattice stripe with d value of 0.203nm corresponds to the (111) plane of metallic Ni, and the lattice stripe with d value of 0.266nm corresponds to Ni3The (110) face of FeN, which confirms V-Ni in the product3And (3) successfully preparing the FeN/Ni heterojunction. Its XRD pattern is shown in FIG. 3, and is located at 41.3 deg., 48.0 deg., 70.3 deg. and 85.2 deg. characteristic peaks, and Ni3The (111), (200), (220) and (311) crystal planes of FeN are coincident (JCPDF #50-1434), and the characteristic peaks at 44.3 DEG, 51.6 DEG and 76.1 DEG are assigned to the (111), (200) and (311) crystal planes of Ni (JCPDF #04-0850), which confirms that Ni in the product3FeN coexists with Ni. The XPS spectrum of FIG. 4 shows the surface composition and chemical valence of the full-hydrolysis electrocatalyst, and it can be seen from the V spectrum of FIG. 4(a) that the V element is successfully doped into Ni3In FeN, as can be seen from the Ni 2p spectrum of FIG. 4(b) and the Fe 2p spectrum of FIG. 4(c), compared with undoped Ni3FeN, Ni after doping3The d-band centers of Ni and Fe in FeN are shifted to low energy direction, which shows that the doping of V element effectively adjusts Ni3The electronic structure of FeN.
The electrocatalytic performance test of the product adopts a three-electrode system loaded with the V-Ni3The graphite sheet of the FeN/Ni @ N-GTs electrocatalyst is used as a working electrode, a Pt electrode (oxygen evolution reaction) and a graphite electrode (hydrogen evolution reaction) are used as counter electrodes, a Hg/HgO electrode is used as a reference electrode, 1mol/L KOH aqueous solution is used as electrolyte, and the CHI 760E electrochemical workstation is used for the hydrogen evolution reaction and the oxygen evolution reaction of the productThe catalytic activity and stability were tested. FIGS. 5(a), (b) and (c) are the electrocatalysts V-Ni prepared in this example3Performance diagram of FeN/Ni @ N-GTs for electrocatalytic hydrogen evolution reaction by decomposing water with catalysis, and as can be seen from the diagram, the current density of the catalyst is 10mA cm-2When the overpotential for the hydrogen evolution reaction is 66mV, the Tafel slope is 88mV dec-1And at 10mAcm-2The current density can be kept for 35 hours without obvious change, which shows that the hydrogen evolution catalyst has good hydrogen evolution stability; FIGS. 6(a), (b) and (c) are the electrocatalysts V-Ni prepared in this example3Performance diagram of FeN/Ni @ N-GTs for electrocatalytic decomposition of water for oxygen evolution reaction, and as can be seen from the diagram, the current density of the catalyst is 10mA cm-2When the overpotential for the oxygen evolution reaction is 252mV, the Tafel slope is 29mV dec-1And at 10mA cm-2The current density can be maintained for 35 hours without obvious change, which shows that the catalyst has good oxygen evolution stability.
Graphite flakes supporting the product of example 1 were used as both anode and cathode, a two-electrode system electrolytic cell was constructed, and 1mol/L KOH aqueous solution was used as electrolyte, and the catalytic activity and stability of the above-mentioned electrode for catalyzing full hydrolysis were tested using CHI 660E electrochemical workstation, as shown in FIGS. 7(a), (b), in which the electrocatalyst V-Ni prepared in this example was used3The FeN/Ni @ N-GTs have excellent electrocatalytic full-hydrolytic performance and generate 10mA cm-2The catalytic activity of the catalyst is basically kept unchanged and the catalyst shows excellent stability when the cell voltage of 1.55V is passed through a current stability test for counting 35 hours.
Claims (4)
1. V-Ni constructed based on doping and heterojunction strategies3The FeN/Ni @ N-GTs full-electrolysis water-electric catalyst is characterized in that V-doped Ni grown on a nitrogen-doped graphene tube in situ is obtained by a hydrothermal and nitridation method3The full-hydrolysis water electric catalyst composed of FeN and Ni nano-particles is characterized by being prepared by the following method:
(1) weighing 4mmol of NH4F，8mmol CH4N2O and a proper amount of Na3VO4Dissolved in 70mL of distilled waterWeighing 2mmol of nickel nitrate and ferric nitrate according to a molar ratio of 5:1, dissolving the nickel nitrate and the ferric nitrate in the solution, transferring the solution to a reaction kettle, simultaneously immersing a nitrogen-doped graphene tube growing on a graphite sheet into the reaction kettle for hydrothermal reaction at the reaction temperature of 120 ℃ for 6 hours, and then washing and drying a product to obtain a V-doped NiFe precursor loaded on the nitrogen-doped graphene tube;
(2) putting the product obtained in the step (1) into a tubular furnace, heating the tubular furnace to a set temperature in an argon atmosphere, closing argon, introducing ammonia gas at the set temperature for a certain time, and cooling the tubular furnace to room temperature to obtain the full-electrolysis water electrocatalyst V-Ni3FeN/Ni@N-GTs。
2. The fully hydrolyzed hydro-electric catalyst V-Ni as set forth in claim 13FeN/Ni @ N-GTs, characterized in that Na is used in step (1)3VO4The dosage is 0.08-0.15 mmol.
3. The fully hydrolyzed hydro-electric catalyst V-Ni as set forth in claim 13The FeN/Ni @ N-GTs is characterized in that the heating rate in the step (2) is 5 ℃/min, the set temperature is 470 ℃, and the ammonia gas introduction time is 2 h.
4. The fully hydrolyzed hydro-electric catalyst V-Ni as set forth in claim 13The FeN/Ni @ N-GTs is characterized in that the electrocatalyst shows excellent electrocatalytic performance in an alkaline medium, and can reach 10mA cm only with a cell voltage of 1.55V as a full-electrolysis water electrocatalyst-2And exhibits excellent stability.
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| CN114606512A (en) * | 2022-03-30 | 2022-06-10 | 青岛科技大学 | Ru-doped W4.6N4Particle @ nitrogen-doped graphene tube hydrogen evolution electrocatalyst |
| CN114752946A (en) * | 2022-04-11 | 2022-07-15 | 四川大学 | Preparation method of electrocatalytic water electrolysis bipolar plate |
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| CN114752946A (en) * | 2022-04-11 | 2022-07-15 | 四川大学 | Preparation method of electrocatalytic water electrolysis bipolar plate |
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