CN110565113A - Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution - Google Patents

Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution Download PDF

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CN110565113A
CN110565113A CN201910773071.8A CN201910773071A CN110565113A CN 110565113 A CN110565113 A CN 110565113A CN 201910773071 A CN201910773071 A CN 201910773071A CN 110565113 A CN110565113 A CN 110565113A
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hydrogen evolution
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蔡金华
钟凡
黄俭根
陈海辉
黄智鹏
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Jinggangshan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

A process for preparing the composite electrocatalytic material used for alkaline electrocatalytic hydrogen evolution features that a layer of Ni (OH) is grown on the carbon fibre paper2A nanosheet structure; vacuum plating an oxide layer coated with titanium on the surface of the titanium substrate; then putting the mixture in a muffle furnace with the temperature of 360 ℃ in the air atmosphere for annealing and crystallization to obtain TiO2‑Ni(OH)2@ CFP composite structural material; the TiO is2‑Ni(OH)2And controlling different coating time of the @ CFP under a vacuum condition, and annealing and crystallizing in an air atmosphere to obtain the composite electro-catalytic material coated at different time. The CFP is used as a substrate material of the catalyst, so that the surface area of the composite electrode is increased, mass transfer is facilitated, and the electrochemical activity of the electrode is improved; simultaneous hydrothermal growth of Ni (OH) on a substrate material2Reducing the cost and enabling Ni (OH)2The catalyst is more firmly combined with the substrate material, and the catalyst is uniformly distributed, so that the stability of the catalyst is improved. The invention introduces TiO2Plays a great role in improving the catalytic performance of the catalyst and reducing the hydrogen evolution overpotential; the electrocatalytic hydrogen evolution activity is obviously improved.

Description

Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution
Technical Field
The invention relates to a preparation method of a composite electro-catalytic material for alkaline electro-catalytic hydrogen evolution, belonging to the technical field of electro-catalysis.
Background
The excessive consumption of fossil resources and the consequent environmental pollution problems have forced the urgent need to develop and utilize renewable clean energy sources that can replace fossil fuels. Hydrogen energy is considered as the most promising clean energy source in the 21 st century, as a new clean, efficient, safe and sustainable energy source. The hydrogen production by water electrolysis is an effective way to solve the current dilemma. However, the existence of overpotential in the water electrolysis process leads to high energy consumption of water electrolysis, so we need to develop a highly active hydrogen evolution reaction catalyst to reduce overpotential of water decomposition reaction, thereby improving energy conversion efficiency. Ideally, the electrolysis water should produce hydrogen at low cost and high yield, but this is not favorable for large-scale industrial application since the most efficient electrocatalysts for producing hydrogen efficiently are still dominated by scarce and expensive noble metal-based materials (e.g., Pt for HER) at present. Therefore, development of an electrolytic water catalyst having a low overpotential and abundant reserves on earth is urgently required to improve reaction kinetics and water electrolysis efficiency. Most of the HER electrocatalysts are currently more effective under acidic conditions than alkaline conditions, and since the lower efficiency of the HER process of the electrocatalyst in alkaline media is related to the slow dissociation process of water on the surface of the electrocatalyst, but when the water electrolysis is carried out in an alkaline electrolytic cell, the alkaline electrolyte has the advantages of easy availability and long-lasting performance, however, the related research on promoting the dissociation of water in the alkaline electrolyte is increased, but the performance of the synthesized composite material is still unsatisfactory, and the difference is still large compared with the precious metal-based electrocatalyst, so the development of the high-performance electrocatalyst is still a great challenge.
The nickel-based layered hydroxide has controllable composition and structure, and researchers continuously prove that the activity of the electrolytic water is improved to a certain extent after other materials are compounded, and the nickel-based layered hydroxide obtained at presentThe nickel-based layered hydroxide has poor electrocatalytic hydrogen evolution performance, poor product stability, short service cycle, poor conductivity, difficult recovery, high cost of preparation raw materials, great environmental pollution in the preparation process and the like. The electrocatalyst with excellent performance has moderate hydrogen ion adsorption capacity and TiO2Can promote the adsorption and the dissociation of water molecules on the surface, and hydrogen intermediates generated by dissociation can be transported to the surface of the electrocatalyst from the surface of the titanium oxide through the overflow effect, thereby improving the hydrogen evolution catalytic activity of the loading system.
Disclosure of Invention
The invention aims to prepare a catalyst suitable for hydrogen evolution reaction in alkaline electrolyte, improve the catalytic performance of the catalyst and ensure that hydrogen is produced by electrolysis quickly and efficiently, and provides a preparation method of a composite electro-catalytic material for alkaline electro-catalytic hydrogen evolution.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a composite electro-catalytic material for alkaline electro-catalytic hydrogen evolution is provided, wherein the composite electro-catalytic material prepared by the method is TiO2-Ni(OH)2@ CFP composite structural material.
The preparation method of the composite structure material comprises the following steps: firstly growing a layer of Ni (OH) on the carbon fiber paper2A nanosheet structure; then vacuum plating a titanium-coated oxide layer on the surface of the titanium-coated Ni (OH) to obtain the titanium dioxide-coated Ni (OH)2.nH2O a nanosheet electrocatalyst precursor; then putting the mixture in a muffle furnace at a certain temperature in air atmosphere for annealing and crystallization to obtain TiO2-Ni(OH)2@ CFP composite structural material; the TiO is2-Ni(OH)2@ CFP under vacuum condition, controlling different coating time, annealing and crystallizing in air atmosphere to obtain composite electrocatalytic material coated with film for different time, which is TiO2-Ni(OH)2@ CFP-XXX, where XXX ═ 20, 40, 80, or 120 minutes.
TiO2-Ni(OH)2@CFP-20，TiO2-Ni(OH)2@CFP-40，TiO2-Ni(OH)2@CFP-80，TiO2-Ni(OH)2@ CFP-120 is respectively notMeanwhile, the electric catalyst is compounded by coating a film at the same time.
the TiO is2-Ni(OH)2The material with the @ CFP composite structure is in a layered structure shape, and the primary structure of the material is Ni (OH)2nanometer flake with thickness of 20-40 nm.
The TiO is2-Ni(OH)2The preparation method of the @ CFP-XXX composite electro-catalytic material comprises the following steps:
(1) Preparation of Ni (OH) on carbon fiber paper2.nH2O-nanoflakes
0.725 g of Ni (NO)3)2·6H2O, 0.185 g NH4F and 0.625 g CO (NH)2)2Adding into 40 ml water, stirring rapidly to dissolve completely, stirring for 10min to obtain mixed solution, and mixing with 3 × 2cm water2The carbon fiber paper is horizontally placed at the bottom of a reaction kettle, the mixed solution is added, the reaction is carried out for 12 hours at the temperature of 130 ℃, the reaction is cooled to room temperature after the reaction is finished, the reaction product is washed by deionized water and absolute ethyl alcohol and dried for 6 hours at the temperature of 80 ℃, and light green Ni (OH) is obtained2.nH2The O nano-sheets are uniformly covered on the surface of the foamed nickel;
(2) Titanium dioxide coated Ni (OH)2.nH2O-nanoflakes
Taking the light green Ni (OH) covered film synthesized in the step (1)2.nH2Placing the O nano-sheets into a vacuum coating machine, spraying sublimation plating solution, and adjusting the spraying time to be 20 minutes, 40 minutes, 80 minutes and 120 minutes respectively; after the reaction is finished, vacuum drying is carried out for 6h at the temperature of 60 ℃ to obtain Ni (OH) coated with titanium dioxide2.nH2O a nanosheet electrocatalyst precursor;
(3) Taking Ni (OH) coated with titanium dioxide loaded in the step (2)2.nH2Placing an O nano-flake electrocatalyst precursor carbon fiber paper sample in a muffle furnace for annealing and crystallization to obtain TiO2-Ni(OH)2@ CFP-XXX composite catalytic material.
The Ni (NO)3)2·6H2O，NH4F and CO (NH)2)2The molar ratio of (A) to (B) is 1: 2: 5.
in the step (1), the reaction is carried out in a reaction kettle with a capacity of 100 ml and a polytetrafluoroethylene lining, and the filling degree is 50-60% by volume.
In the step (2), the sublimation plating solution is tetrabutyl titanate and distilled water, and the vacuum degree is 30 Pa; and the butyl titanate and the distilled water are alternately sublimated.
In the step (3), in the annealing and crystallization process, the annealing temperature is 360 ℃, the heat preservation time is 2 hours, and the heating rate is 5 ℃/min-1。
The composite structure electrocatalyst prepared by the method is at 20mA/cm-2The overpotential under the current density of (2) is 335mV, and the electrocatalytic activity is good; after 45 hours of electrocatalysis, the catalytic activity is still maintained to be more than 90 percent.
The titanium dioxide coated Ni (OH)2.nH2Annealing and crystallizing the O nano flake electrocatalyst precursor at 360 ℃ in air atmosphere; amorphous TiO after annealing2Crystallization is anatase type which can improve catalytic performance, and the nickel hydroxide of the precursor containing crystal water is transformed into nickel hydroxide after dehydration.
Compared with the prior art, the invention has the following advantages:
(1) The preparation method of the electrocatalytic material adopts a hydrothermal method and a vacuum sublimation coating method to prepare TiO2-Ni(OH)2@ CFP, not only the preparation condition is easy to control, but also Ni (OH)2 is loaded on CFP in a nanometer flake shape, thus improving the surface area of the electrode material and promoting the electrocatalytic activity of the electrode; the vacuum coating method is used, so that the coating is uniform and firm, and the coating thickness is controllable;
(2) the CFP is used as a substrate material of the catalyst, and the surface area of the composite electrode is increased due to the characteristic of the net-shaped structure of the CFP, so that the mass transfer is facilitated, and the electrochemical activity of the electrode is improved; simultaneous hydrothermal growth of Ni (OH) on a substrate material2Reducing the cost and enabling Ni (OH)2The catalyst is more firmly combined with the substrate material, and the catalyst is uniformly distributed, so that the stability of the catalyst is improved.
(3) The invention introduces TiO2Plays a great role in improving the catalytic performance of the catalyst and reducing the hydrogen evolution overpotential, and is attributed to the TiO2D electronic phase between Ni andThe interaction changes the Ni electronic structure, and simultaneously enhances the absorption of the catalyst to water molecules, thereby realizing the remarkable improvement of the electrocatalytic hydrogen evolution activity.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample of a composite electrocatalyst prepared according to the method of the example;
FIG. 2 is an SEM image and an EDS elemental map of samples prepared according to the methods of comparative example and example;
Wherein, FIG. 2(a) is a scanning electron microscope of low magnification, FIGS. 2(b-c) is a scanning electron microscope of high magnification, FIGS. 2(d-g) is an SEM image and an EDX elemental map, FIG. 2(e) is an oxygen element, FIG. 2(f) is a nickel element, FIG. 2(g) is a titanium element, and FIG. 2(h) is an EDS elemental analysis diagram;
FIG. 3 is a graph of overpotential curves for samples prepared according to the methods of comparative example and example;
FIG. 4 is a Nyquist plot for samples prepared according to the methods of comparative example and example;
FIG. 5 is a stability test of samples prepared according to the methods of comparative example and example;
Fig. 6 is a flow chart of the preparation of a composite electrocatalyst for alkaline electrocatalytic hydrogen evolution.
Detailed Description
The specific implementation steps of the present invention are shown in fig. 6.
The raw material used in this example is Ni (NO)3)2，NH4F，CO(NH2)2。
Weigh 0.725 grams of Ni (NO)3)2·6H2O, 0.185 g NH4F and 0.625 g CO (NH)2)2Rapidly stirring until completely dissolved, continuously stirring for 10min to obtain a mixed solution, mixing and dissolving in 40 ml of water;
Then taking a piece of Carbon Fiber Paper (CFP) and cutting the CFP into 2 multiplied by 3cm2The blocks are respectively and sequentially ultrasonically cleaned in acetone, ethanol and water for 15min, taken out, dried and weighed;
The solution was poured into a 50mL reaction vessel, and a piece of the washed solution was added thereto at 2X 3cm2CFP, sealed reactor maintenanceReacting for 12h at the temperature of 130 ℃, washing with deionized water and absolute ethyl alcohol, drying for 6h at the temperature of 80 ℃, and weighing the mass of the precursor loaded on the carbon fiber paper;
Covering the mixture synthesized in the above step with light green Ni (OH)2.nH2Placing the O nano-sheets into a vacuum coating machine, wherein the sublimation plating solution is butyl titanate, and the spraying time is respectively adjusted to be 20 minutes, 40 minutes, 80 minutes and 120 minutes; after the reaction is finished, vacuum drying is carried out for 6h at the temperature of 60 ℃ to obtain Ni (OH) coated with titanium dioxide2.nH2O a nanosheet electrocatalyst precursor;
Taking the synthesized Ni (OH) loaded with titanium dioxide coating2.nH2and (3) placing the O nano-sheet carbon fiber paper sample in a muffle furnace for annealing crystallization at 360 ℃, wherein the annealing time is 2 hours, and weighing and measuring the load capacity.
for the samples obtained in the examples, diffraction data were measured by an X-ray diffraction method, as shown in FIG. 1. Wherein the plot of figure 1 is diffraction data obtained from testing a sample of the prepared composite electrocatalyst. The vertical lines in fig. 1 are standard card data.
As can be seen from fig. 1, the samples were indexed with a space group of P-3m1, a lattice constant of a-b-3.126,α ═ β ═ 90 °, γ ═ 120 °. No change in lattice constant and no hetero-phase, indicating TiO2The crystal phase is not shown in the small amount of the compound.
for the samples obtained in the examples, the samples were examined for their new appearance by SEM scanning, and elemental composition data were obtained by energy dispersive X-ray spectroscopy (EDS), as shown in fig. 2.
FIG. 2 shows TiO2-Ni(OH)2@ CFP nanoflakes are homogeneously deposited on the surface of the CFP, where the thickness of the monolithic nanosheets is about 20-30 nm. Energy dispersive X-ray spectroscopy (EDS) confirmed that the light is in TiO2-Ni(OH)2In @ CFP, Ni, Ti, and O are present.
The overpotential curves of the comparative example and the example sample are shown in fig. 3.
usually, a voltage of-20 mA/cm is used2The overpotentials at time were compared. Apparently, is coated with TiO2Over potential absolute value ratio of samples of the layer to unplated TiO2The layer is much smaller than the overpotential absolute value of the sample. Unplated TiO 22The overpotential of hydrogen evolution of the layer sample under the alkaline condition exceeds 500mV, and TiO is plated2The lowest absolute value of the overpotential of the electrocatalyst sample after 80 minutes of the layer is reduced to 335mV, and the electrocatalyst sample has the optimal hydrogen evolution performance.
the Nyquist curves for the comparative and example samples are shown in fig. 4.
The half circle in the low frequency range is related to the faradaic process (HER) occurring at the electrocatalyst surface. The corresponding resistance component is the charge transfer resistance (R)ct)。
RctIs often used to assess the kinetic processes of HER, in general RctThe smaller, the faster the HER process. Apparently, in Ni (OH)2Coating the nano-sheet with TiO2After RctThis is a decrease which indicates that TiO2-Ni(OH)2@ CFP nanosheets have the fastest electron transfer capability in hydrogen evolution reactions.
electrocatalytic performance test of the material:
the electrochemical test adopts a three-electrode system, and is tested by a CHI-614D electrochemical analyzer workstation, the CFP loaded with the catalyst is used as a working electrode, a carbon rod electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. The electrolyte for electrochemical test was a 1mol/L KOH solution, and argon gas was introduced into the solution for 10min before the test to remove air from the electrolyte.
The experimental results show that: the current density can reach 20mA/cm when the overpotential for the electro-catalytic hydrogen evolution is 335mV-2。
Stability test:
the electrochemical test adopts a three-electrode system, and is tested by a CHI-614D electrochemical analyzer workstation, the CFP loaded with the catalyst is used as a working electrode, a carbon rod electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. The electrolyte for electrochemical test is 1mol/L KOH solution, argon is introduced into the solution for 10min before the test to remove air in the electrolyte, and the constant voltage is kept at 750mV in the stability test. The product has good stability, the current density is reduced by no more than 5 percent within 40 hours under the constant voltage of 750mV, and the structure is stable without collapse.

Claims (9)

1. The preparation method of the composite electro-catalytic material for alkaline electro-catalytic hydrogen evolution is characterized in that the composite electro-catalytic material prepared by the method is TiO2-Ni(OH)2@ CFP composite structural material,
The preparation method of the composite structure material comprises the following steps: growing a layer of Ni (OH) on the carbon fiber paper2A nanosheet structure; vacuum plating a titanium-coated oxide layer on the surface to obtain titanium dioxide-coated Ni (OH)2.nH2O a nanosheet electrocatalyst precursor; then putting the mixture in a muffle furnace with a certain temperature in air atmosphere for annealing and crystallization to obtain TiO2-Ni(OH)2@ CFP composite structural material; the TiO is2-Ni(OH)2@ CFP under vacuum condition, controlling different coating time, annealing and crystallizing in air atmosphere to obtain composite electrocatalytic material coated with film for different time, which is TiO2-Ni(OH)2@ CFP-XXX, where XXX ═ 20, 40, 80, or 120 minutes;
TiO2-Ni(OH)2@CFP-20，TiO2-Ni(OH)2@CFP-40，TiO2-Ni(OH)2@CFP-80，TiO2-Ni(OH)2@ CFP-120 is composite electrocatalyst for filming at different time.
2. The method for preparing the composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution according to claim 1, wherein the TiO is2-Ni(OH)2The material with the @ CFP composite structure is in a layered structure shape, and the primary structure of the material is Ni (OH)2nanometer flake with thickness of 20-40 nm.
3. The method for preparing the composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution according to claim 2, wherein the TiO is2-Ni(OH)2The preparation method of the @ CFP-XXX composite electro-catalytic material comprises the following stepsThe following:
(1) preparation of Ni (OH) on carbon fiber paper2.nH2O-nanoflakes
0.725 g of Ni (NO)3)2·6H2O, 0.185 g NH4F and 0.625 g CO (NH)2)2Adding into 40 ml water, stirring rapidly to dissolve completely, stirring for 10min to obtain mixed solution, and mixing with 3 × 2cm water2The carbon fiber paper is horizontally placed at the bottom of a reaction kettle, the mixed solution is added, the reaction is carried out for 12 hours at the temperature of 130 ℃, the reaction is cooled to room temperature after the reaction is finished, the reaction product is washed by deionized water and absolute ethyl alcohol and dried for 6 hours at the temperature of 80 ℃, and light green Ni (OH) is obtained2.nH2The O nano-sheets are uniformly covered on the surface of the foamed nickel;
(2) Titanium dioxide coated Ni (OH)2.nH2o-nanoflakes
taking the light green Ni (OH) covered film synthesized in the step (1)2.nH2Placing the O nano-sheets into a vacuum coating machine, spraying sublimation plating solution, and adjusting the spraying time to be 20 minutes, 40 minutes, 80 minutes and 120 minutes respectively; after the reaction is finished, vacuum drying is carried out for 6h at the temperature of 60 ℃ to obtain Ni (OH) coated with titanium dioxide2.nH2O a nanosheet electrocatalyst precursor;
(3) taking Ni (OH) coated with titanium dioxide loaded in the step (2)2.nH2o nano flake electro-catalyst precursor, putting the precursor into a muffle furnace for annealing and crystallization to obtain TiO2-Ni(OH)2@ CFP-XXX composite catalytic material.
4. The method for preparing a composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution according to claim 3, wherein said Ni (NO) is added3)2·6H2O，NH4F and CO (NH)2)2The molar ratio of (A) to (B) is 1: 2: 5.
5. The method for preparing the composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution according to claim 3, wherein in the step (1), the reaction is performed in a reaction kettle with a capacity of 100 ml and a polytetrafluoroethylene lining, and the filling degree is 50-60% by volume.
6. The method for preparing the composite electro-catalytic material for alkaline electro-catalytic hydrogen evolution according to claim 3, wherein in the step (2), the sublimation plating solution is butyl titanate and distilled water, and the vacuum degree is 30 Pa; and the butyl titanate and the distilled water are alternately sublimated.
7. the method for preparing the composite electro-catalytic material for the alkaline electro-catalytic hydrogen evolution according to the claim 3, wherein in the step (3), in the annealing and crystallization process, the annealing temperature is 360 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min-1。
8. The method for preparing the composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution as set forth in claim 2, wherein the composite electrocatalytic material prepared by the method is at 20mA/cm-2The overpotential under the current density of (2) is 335mV, and the electrocatalytic activity is good; after 45 hours of electrocatalysis, the catalytic activity is still maintained to be more than 90 percent.
9. the method for preparing a composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution according to claim 3, wherein said titanium dioxide coated Ni (OH)2.nH2Annealing and crystallizing the O nano flake electrocatalyst precursor at 360 ℃ in air atmosphere; amorphous TiO after annealing2Crystallization is anatase type which can improve catalytic performance, and the nickel hydroxide of the precursor containing crystal water is transformed into nickel hydroxide after dehydration.
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