CN111054418A - Oxygen/hydrogen evolution two-dimensional cobalt monoxide @ cobalt diselenide @ nitrogen doped carbon nanotube/graphene dual-functional composite catalyst - Google Patents
Oxygen/hydrogen evolution two-dimensional cobalt monoxide @ cobalt diselenide @ nitrogen doped carbon nanotube/graphene dual-functional composite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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- B01J35/40—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
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- 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
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Abstract
The invention discloses an oxygen/hydrogen evolution two-dimensional cobalt monoxide @ cobalt diselenide @ nitrogen doped carbon nanotube/graphene bifunctional composite catalyst; the catalyst is formed by loading cobalt monoxide nano-particles, cobalt diselenide nano-particles and nitrogen-doped carbon nano-tubes on a two-dimensional graphene sheet; the preparation method comprises the steps of mixing cobalt salt, a nitrogen-containing organic micromolecule compound and graphene oxide through a liquid phase, drying, placing in a protective atmosphere, carrying out two-stage roasting treatment, and carrying out partial selenization treatment on a roasted product and selenium powder at a high temperature in the protective atmosphere to obtain the selenium-containing composite material; the preparation process is simple, low in cost and beneficial to industrial production; the obtained composite catalyst is applied to the electric decomposition process of water, has the characteristics of high activity and good stability, and shows good application prospect.
Description
Technical Field
The invention relates to an Oxygen Evolution (OER) and Hydrogen Evolution (HER) bifunctional composite catalyst, and a preparation method and an application method thereof, in particular to a high-performance oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe composite catalyst2A @ N-CNTs/rGO bifunctional composite catalyst and a preparation method thereof, and also relates to CoO @ CoSe2An application of a @ N-CNTs/rGO bifunctional composite catalyst in electrolytic water belongs to the technical field of electrocatalysis.
Background
Hydrogen energy is considered to be one of the most promising new clean energy sources because of its high energy density, its oxidation products being water only and it can be recycled. The electro-decomposition of water by taking water as a raw material is a zero-emission hydrogen production process without any pollutant release, the process flow and equipment are simple, the operation is easy, and the potential of large-scale application is realized. The process of electro-decomposing water includes an anodic Oxygen Evolution Reaction (OER) and a cathodic Hydrogen Evolution Reaction (HER). However, the electrolysis efficiency is very low due to the presence of unavoidable overpotentials and kinetic retardation, and must be improved by using a high-efficiency catalyst. At present, a precious metal Ru/Ir-based material is the most efficient OER catalyst; noble Pt-based materials are the best HER catalysts. However, the rare earth reserves, high price and stability to be improved of the noble metals greatly hinder the large-scale popularization and application of hydrogen production by water electrolysis. Therefore, the development of non-noble metal OER and HER catalysts with abundant earth reserves, low price, high activity and long durability is the key of wide commercial popularization and application of hydrogen production by water electrolysis, and has strategic significance on the conversion and storage of clean energy and environmental protection. Especially, the development of a catalyst capable of simultaneously and effectively catalyzing OER and HER has important significance for simplifying the process and equipment of a hydrogen production process, reducing the cost and improving the electrolysis efficiency. Because of the significant differences in the OER and HER mechanisms, there are significant challenges in the manufacturing processes and mechanisms to develop such bifunctional catalysts. In addition, at present, the structures related to the functional materials loaded by the graphene and the carbon nano tubes are almost three-dimensional net structures. The material of the three-dimensional network structure is not favorable for the transmission of electrons as an electrocatalyst relative to the two-dimensional structure.
Disclosure of Invention
Aiming at the defects that in the prior art, functional materials commonly loaded by graphene and carbon nano tubes are almost all three-dimensional network structures as electrocatalysts and are used as oxygen evolution/hydrogen evolution bifunctional electrocatalysts, the invention aims to provide a catalyst prepared from CoO @ CoSe2Two-dimensional CoO @ CoSe structure formed by jointly loading nanoparticles and nitrogen-doped carbon nanotubes (N-CNTs) on two-dimensional graphene sheets (rGO) and having excellent comprehensive catalytic performance of oxygen evolution and hydrogen evolution2@ N-CNTs/rGO bifunctional composite catalyst.
The second purpose of the invention is to provide a high-performance oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is simple and low in cost, and meets the application requirements of industrial production.
It is a third object of the present invention to provide the high performance oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is applied to electrolytic water, and has the characteristics of high activity, good stability and the like.
In order to realize the technical purpose, the invention provides an oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is formed by loading cobalt monoxide nanoparticles, cobalt diselenide nanoparticles and nitrogen-doped carbon nanotubes on a two-dimensional graphene sheet together.
The invention relates to oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The main active components in the @ N-CNTs/rGO bifunctional composite catalyst are CoO nano-particles and CoSe2The composite material is composed of two components of nano particles, the synergistic effect between the two components is obvious, the electronic structure modulation of the composite material is facilitated by the compounding of the two components, and the two active components are dispersed and loaded on the surface of the two-dimensional graphene sheet in the form of nano particles, so that defects and active point positions are increased, and the catalytic activity and stability of the composite material are improved. While the nitrogen doped carbon nanotube will partially CoO and CoSe during the formation process2The encapsulation of the nanoparticles in their tubes effectively reduces the agglomeration of these nanoparticles, on the other handHas high conductivity, and can improve CoO and CoSe2Poor conductivity. Meanwhile, the nitrogen-doped carbon nano tube can improve the stability of the composite material by utilizing the coordination effect between heteroatom nitrogen and metal ions. And the two-dimensional graphene has a large specific surface, so that CoO @ CoSe can be formed2The nano particles and the nitrogen-doped carbon nano tubes are dispersed and stably loaded, the agglomeration of the nano particles is further reduced, the two-dimensional plane structure of the graphene is favorable for the transfer of electrons, and the oxygen evolution and hydrogen evolution two-dimensional CoO @ CoSe are greatly promoted2The comprehensive performance of the @ N-CNTs/rGO bifunctional composite catalyst is improved.
In the preferable scheme, part of the cobalt monoxide nano-particles and the cobalt diselenide nano-particles are encapsulated in the nitrogen-doped carbon nano-tubes, so that the dispersion stability of the cobalt monoxide nano-particles and the cobalt diselenide nano-particles can be improved.
In a preferred embodiment, the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst comprises the following components in percentage by mass: 45% -65% of cobalt monoxide nano-particles and cobalt diselenide nano-particles; 5% -15% of nitrogen-doped carbon nanotubes; 20% -40% of graphene sheets. In a more preferred embodiment, the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst comprises the following components in percentage by mass: 50% -60% of cobalt monoxide nano-particles and cobalt diselenide nano-particles; 8% -12% of nitrogen-doped carbon nanotubes; 28% -38% of graphene sheets.
Preferably, the molar ratio of the cobalt monoxide nano particles to the cobalt diselenide nano particles is (4-13) to (3-11). More preferably, the molar ratio of the cobalt monoxide nanoparticles to the cobalt diselenide nanoparticles is (6-10) to (5-9).
In a preferred embodiment, the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The content of nitrogen in the @ N-CNTs/rGO bifunctional composite catalyst is 2-8% by mass. In a more preferred embodiment, the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The content of nitrogen in the @ N-CNTs/rGO bifunctional composite catalyst is 3-6% by mass.
The invention also provides oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe2@ N-CNTs/rGO bifunctional composite catalystA method for preparing an agent, comprising the steps of: 1) mixing cobalt salt, a nitrogen-containing organic small molecular compound and graphene oxide in a liquid phase, evaporating a solvent and drying to obtain mixed powder; 2) placing the mixed powder in a protective atmosphere, performing first-stage roasting treatment at the temperature of 500-600 ℃, and then heating to the temperature of 700-900 ℃ for second-stage roasting to obtain a precursor; 3) and placing the precursor and the selenium powder in a protective atmosphere, and performing partial selenization treatment at the temperature of 400-600 ℃ to obtain the selenium-rich material.
The invention is used for preparing oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe2The key point in the process of the @ N-CNTs/rGO bifunctional composite catalyst is that a process combining two-stage roasting and partial selenization is adopted. The first roasting at a relatively low temperature in a protective atmosphere can fully utilize nitrogen in the nitrogen-containing organic micromolecules to capture cobalt ions as much as possible, and then the second high-temperature roasting enables the nitrogen-containing organic micromolecules to generate nitrogen-doped carbon nanotubes in situ and encapsulate partial nanoparticles of cobalt-containing compounds, and the nanoparticles are dispersed and loaded on two-dimensional graphene sheets in situ. The second-stage high-temperature roasting can also ensure that the cobalt oxide is thermally reduced into metal cobalt, and the graphene oxide is thermally reduced into reduced graphene to obtain a precursor (CoO/Co @ N-CNTs/rGO); then placing the precursor and a proper amount of selenium powder in a protective atmosphere to perform partial selenization at high temperature to obtain CoO @ CoSe2@ N-CNTs/rGO composite catalyst.
In a preferred embodiment, the nitrogen-containing organic small molecule compound includes at least one of urea, melamine, cyanuric chloride, cyanamide, and dicyandiamide. The nitrogen-containing organic matters are nitrogen-rich organic micromolecule compounds which can be used as raw materials of nitrogen-doped carbon and can be used as complexing agents of cobalt salt in the high-temperature solid-phase reaction process, so that the coordination complexing and the dispersion of cobalt are realized, and the nano particles of the cobalt compound are formed.
In a preferred embodiment, the cobalt salt is a water-soluble cobalt salt. Such as cobalt nitrate, cobalt acetate, cobalt chloride and the like.
In a preferred scheme, the mass ratio of the cobalt salt, the nitrogen-containing organic small molecular compound and the graphene oxide is (2-4): (12-16): (1-2).
In a preferable scheme, the first-stage roasting treatment time is 0.5-4 h; more preferably 1-3 hours. The temperature of the first stage calcination treatment is preferably 530 ℃ to 580 ℃.
In a preferable scheme, the second-stage roasting treatment time is 0.5-4 h; more preferably 1-3 hours. The temperature of the second stage roasting treatment is preferably 750-850 ℃.
In the preferred scheme, the mass ratio of the precursor to the selenium powder is (3-6) to (40-60).
In a preferable scheme, the time of the partial selenylation treatment is 0.5-4 h; more preferably 1-3 hours. The temperature of the selenization process is more preferably 450-550 ℃.
The invention also provides oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe2A preparation method of a @ N-CNTs/rGO bifunctional composite catalyst is applied as an electrolytic water oxygen evolution or hydrogen evolution catalyst.
The invention relates to oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst comprises the following steps: dissolving cobalt salt and a nitrogen-containing organic micromolecule compound in 100mL of GO suspension liquid (the mass ratio of the cobalt salt to the nitrogen-containing organic micromolecule compound to the graphene oxide is (2-4): 12-16): 1-2)]Sonicate for 30min, then stir the resulting mixture at 80 ℃ for 24h, evaporate the water by rotary distiller, and vacuum dry at 60 ℃ overnight. And then heating the obtained solid mixture to 500-plus-600 ℃ at the speed of 5 ℃/min under the protection of nitrogen, preserving the heat for 0.5-4 h, heating to 700-plus-900 ℃ and preserving the heat for 2h, and naturally cooling under the protection of nitrogen to obtain CoO/Co @ N-CNTs/rGO. The mass ratio of CoO/Co @ N-CNTs/rGO to selenium powder [ CoO/Co @ N-CNTs/rGO ] to selenium powder is (3-6): (40-60)]Respectively placing the ceramic boat at the downstream end and the upstream end of the ceramic boat, heating the ceramic boat to 400-600 ℃ at the speed of 10 ℃/min under the protection of nitrogen, preserving the heat for 0.5 to 4 hours, and naturally cooling the ceramic boat under the protection of nitrogen to obtain the ceramic boat.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the invention relates to oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is prepared from high-activity CoO and CoSe2Two kinds of nano particles, N-doped carbon nano tube with large specific surface area and high conductivity and graphiteThe alkene material is compounded, and the substances have obvious synergistic interaction, so that the compound shows high catalytic activity.
2. The invention relates to oxygen and hydrogen evolution two-dimensional CoO @ CoSe2The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is simple, low in cost and beneficial to industrial production.
3. The invention relates to oxygen and hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is generated through in-situ reaction, and CoO and CoSe are2Nanoparticles and encapsulated portions of CoO and CoSe2The N-doped carbon nano tube of the nano particle is uniformly and stably loaded on a two-dimensional graphene sheet material with large specific surface area, the physical and chemical stability is good, and CoO @ CoSe2The two-dimensional planar structure of @ N-CNTs/rGO is beneficial to the transfer of electrons.
4. The invention relates to oxygen and hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is applied to electrolytic water, has the characteristics of high activity and good stability, and shows a good application prospect.
Drawings
FIG. 1 shows CoO @ CoSe in examples 1-32@N-CNTs/rGO-500、CoO@CoSe2@ N-CNTs/rGO-450 and CoO @ CoSe2@ N-CNTs/rGO-550 catalyst (a) LSV plot in oxygen-saturated 1MKOH solution and at a scan rate of 5mV/s, (b) Current Density of 10mA/cm2The overpotential required for the reaction is η, (c) Tafel curve chart, (e) 0.5M H saturated in nitrogen2SO4LSV chart at 5mV/s of solution and scanning speed, (f) Current Density of 10mA/cm2The desired overpotential η and (g) Tafel plot.
FIG. 2 shows CoO @ CoSe in example 1 and comparative examples 3 to 52@N-CNTs/rGO-500、CoO@CoSe2@ N-CNTs, CoO @ N-CNTs/rGO and CoSe2XRD pattern of @ N-CNTs/rGO composite catalyst; indicating successful preparation of each composite.
FIG. 3 shows CoO @ CoSe in example 12The (a) SEM images, (b and c) TEM images and (d) HRTEM images of @ N-CNTs/rGO-500; the SEM picture shows that CoO @ CoSe2The @ N-CNTs/rGO-500 presents a two-dimensional planar structure; TEM and HRTEM images showCoO and CoSe2The spherical particles with the particle size of 20-100 nm are partially encapsulated in bamboo-shaped carbon nanotubes, and the carbon nanotubes are dispersed on two-dimensional graphene sheet layers together.
FIG. 4 shows CoO @ CoSe in example 1, comparative example 1 and comparative examples 3 to 52@N-CNTs/rGO-500、RuO2、CoO@CoSe2@ N-CNTs, CoO @ N-CNTs/rGO and CoSe2@ N-CNTs/rGO catalyst (a) LSV plot in oxygen saturated 1M KOH solution and at a scan rate of 5mV/s, (b) Current Density of 10mA/cm2The overpotential η required for the treatment and (c) Tafel plot, (d) CoO @ CoSe in example 12@ N-CNTs/rGO-500 and RuO in comparative example 12Respectively at a current density of 10mA/cm2A timing current chart under the corresponding overpotential; the figure shows CoO @ CoSe in all of the above catalysts2@ N-CNTs/rGO-500 having the lowest OER onset potential at a current density of 10mA/cm2The lowest overpotential η and the smallest Tafel slope indicate CoO @ CoSe2The @ N-CNTs/rGO-500 has the highest catalytic activity and the most suitable catalytic kinetics, and the synergistic effect among the components is obvious; at the same time, CoO @ CoSe2@ N-CNTs/rGO-500 having a specific RuO ratio2Better stability.
FIG. 5 shows CoO @ CoSe in example 1 and comparative examples 2 to 52@N-CNTs/rGO-500、20wt％Pt/C、CoO@CoSe2@ N-CNTs, CoO @ N-CNTs/rGO and CoSe2@ N-CNTs/rGO catalyst (a) 0.5M H saturated with nitrogen2SO4LSV chart at 5mV/s of solution and scanning speed, (b) Current Density of 10mA/cm2The overpotential η required for the treatment and (c) Tafel plot, (d) CoO @ CoSe in example 12@ N-CNTs/rGO-500 and 20 wt% Pt/C in comparative example 1 at a current density of 10mA/cm, respectively2A timing current chart under the corresponding overpotential; relative to CoO @ CoSe is shown in the figure2@ N-CNTs, CoO @ N-CNTs/rGO and CoSe2@N-CNTs/rGO，CoO@CoSe2@ N-CNTs/rGO-500 has the lowest HER onset potential at a current density of 10mA/cm2The lowest overpotential η and the smallest Tafel slope indicate CoO @ CoSe2@ N-CNTs/rGO-500 has the highest catalytic activity and the most suitable catalytic kineticsThe synergistic effect among the components is obvious; CoO @ CoSe relative to 20 wt% Pt/C2The catalytic activity and catalytic kinetics of @ N-CNTs/rGO-500 are still different, but CoO @ CoSe2The stability of @ N-CNTs/rGO-500 is far better than that of 20 wt% Pt/C.
Detailed Description
The following examples are given to illustrate the present invention in more detail, but do not limit the scope of the claims of the present invention.
Example 1
CoO@CoSe2Preparation of @ N-CNTs/rGO-500
GO is prepared by adopting a modified Hummers method. Weighing 1g of flake graphite and 20g of NaCl, mixing, grinding for 15min, and washing away NaCl by using deionized water in a vacuum filtration mode. Vacuum drying wet graphite powder at 60 deg.C for 30min, transferring to 250mL round bottom flask, adding 23mL concentrated sulfuric acid, magnetically stirring for 24h, heating to 35 deg.C, adding 0.5g NaNO under stirring3. After 5min, the suspension was transferred to an ice bath and 3g KMnO were added very slowly with stirring4And controlling the temperature of the system to be lower than 20 ℃, heating the system for 120min at 35 ℃ under the condition of stirring, slowly adding 46mL of deionized water, heating the system to 98 ℃, and stirring the mixture for 30 min. After the mixture was cooled to room temperature and stirring was continued for 30min, 140mL of deionized water and 10mL of 30 wt% H were added2O2. And centrifuging the precipitate, washing the precipitate for 5 times by using a 5 wt% HCl solution and deionized water respectively, and then dispersing the precipitate in 1500mL of absolute ethanol for ultrasonic treatment for 60min to obtain a brownish black GO suspension.
238mg of cobalt nitrate hexahydrate and 1g of dicyandiamide were dissolved in 100mL of a suspension of GO (1g/mL), sonicated for 30min, and the resulting mixture was stirred at 80 ℃ for 24h, evaporated to dryness by a rotary distiller, and dried under vacuum at 60 ℃ overnight. And then heating the obtained solid mixture to 550 ℃ at the speed of 5 ℃/min under the protection of nitrogen, preserving heat for 2h, heating to 800 ℃ again, preserving heat for 2h, and naturally cooling under the protection of nitrogen to obtain CoO/Co @ N-CNTs/rGO. Respectively placing 40mg of CoO/Co @ N-CNTs/rGO and 500mg of selenium powder at the downstream end and the upstream end of a porcelain boat, heating to 500 ℃ at a speed of 10 ℃/min under the protection of nitrogen, preserving heat for 2h, and naturally cooling under the protection of nitrogen to obtain CoO @ CoSe2@N-CNTs/rGO-500。
X-ray diffraction techniques (XRD, Empyrean, Cu K α,
) Performing phase and crystal structure characterization on the product; observing the morphology of the surface of the product by a scanning electron microscope (SEM, Quanta 250 FEG); and (3) performing Transmission Electron Microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) characterization on the product through a transmission electron microscope (JEOL JEM-2100), and observing the microscopic morphology of the product.
The electrochemical performance of the samples was tested by the CHI660E electrochemical workstation in a three-electrode system at room temperature. Preparation of a working electrode: weighing 4mg of sample powder to be detected, dispersing the sample powder in 1mL of mixed solution of deionized water, ethanol and 5% Nafion solution (the volume ratio is 0.45:0.5:0.05), and carrying out ultrasonic treatment for 30min to uniformly disperse the sample in the matrix solution. Drawing 5 mu L of suspension liquid by using a pipette, dripping the suspension liquid on a glassy carbon electrode with the diameter of 3mm, and drying the suspension liquid at room temperature for later use (the loading amount of the catalyst is 0.28 mg/cm)2). During the OER performance test of the sample, the platinum electrode is used as a counter electrode, and Hg/HgO is used as a reference electrode. The OER activity of the samples was evaluated using Linear Sweep Voltammetry (LSV) with an oxygen saturated 1M KOH solution at a sweep rate of 5 mV/s. OER stability test is at 10mA/cm2And operating for 24h under the corresponding constant potential, and observing the current attenuation condition. In the process of testing HER performance of a sample, the graphite rod is used as a counter electrode, and Ag/AgCl is used as a reference electrode. Evaluation of HER Activity of samples Using the LSV method, the electrolyte was 0.5M H saturated with nitrogen2SO4The solution was scanned at a rate of 5 mV/s. HER stability test is at 10mA/cm2And operating for 24h under the corresponding constant potential, and observing the current attenuation condition. The LSV test data for both OER and HER are IR compensated.
CoO@CoSe2The onset potential of the @ N-CNTs/GO complex as an OER catalyst is 1.410V (vs. RHE). At a current density of 10mA/cm2Desired overpotential η of 250mV (vs. RHE) with Tafel slope of 68mV/dec in stability evaluation, the current density dropped only 4% over a 24h test at a constant potential of 1.48V (vs. RHE)bit-0.052V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 220mV (vs. RHE) and the Tafel slope was 53mV/dec in the stability evaluation, the current density dropped only 17% over a 24h test at a constant potential of-0.22V (vs. RHE).
Example 2
By CoO @ CoSe2@ N-CNTs/rGO-450 is an OER and HER bifunctional catalyst.
Following the procedure of example 1 at CoO @ CoSe2The CoO @ CoSe is prepared at the selenization temperature of 450 ℃ in the preparation process of @ N-CNTs/rGO-5002@N-CNTs/rGO-450。
The catalytic performance was evaluated in the same manner as in example 1.
CoO@CoSe2The onset potential of @ N-CNTs/rGO-450 as an OER catalyst was 1.426V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 293mV (vs. RHE). Tafel slope was 69 mV/dec.
CoO@CoSe2The initial potential of @ N-CNTs/rGO-450 as a HER catalyst is close to 0(vs. At a current density of 10mA/cm2The desired overpotential η is 253mV (vs. RHE). the Tafel slope is 90 mV/dec.
Example 3
By CoO @ CoSe2@ N-CNTs/rGO-550 is an OER and HER bifunctional catalyst.
Following the procedure of example 1 at CoO @ CoSe2The CoO @ CoSe is prepared at the selenization temperature of 550 ℃ in the process of preparing @ N-CNTs/rGO-5502@N-CNTs/rGO-550。
The catalytic performance was evaluated in the same manner as in example 1.
CoO@CoSe2The onset potential of @ N-CNTs/rGO-550 as OER catalyst was 1.415V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 279mV (vs. RHE). the Tafel slope was 70 mV/dec.
CoO@CoSe2The initial potential of @ N-CNTs/rGO-550 as a HER catalyst was-0.089V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 257mV (vs. RHE). Tafel slope was 54 mV/dec.
Comparative example 1
In commercial RuO2Is an OER catalyst.
The catalytic performance was evaluated in the same manner as in example 1.
RuO2The initial potential as an OER catalyst was 1.468V (vs. At a current density of 10mA/cm2The desired overpotential η was 310mV (vs. RHE) and the Tafel slope was 71mV/dec in the stability evaluation, the current density dropped 49% over a 12h test at a constant potential of 1.54V (vs. RHE).
Comparative example 2
Commercial 20 wt% Pt/C was used as the HER catalyst.
The catalytic performance was evaluated in the same manner as in example 1.
The initial potential of 20 wt% Pt/C as a HER catalyst was close to 0V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 35mV (vs. RHE) and the Tafel slope was 39mV/dec in the stability evaluation, the current density dropped by 78% over a 12h test at a constant potential of-0.035V (vs. RHE).
Comparative example 3
By CoO @ CoSe2@ N-CNTs are OER and HER bifunctional catalysts.
Following the procedure of example 1 at CoO @ CoSe2During the preparation process of @ N-CNTs/rGO-500, 100mL deionized water is used for replacing 100mL GO suspension to prepare CoO @ CoSe2@N-CNTs。
The catalytic performance was evaluated in the same manner as in example 1.
CoO@CoSe2The initial potential of @ N-CNTs as OER catalyst was 1.508V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 345mV (vs. RHE). Tafel slope was 83 mV/dec.
CoO@CoSe2The initial potential of @ N-CNTs as HER catalyst was-0.242V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 452mV (vs. RHE). the Tafel slope was 146 mV/dec.
Comparative example 4
CoO @ N-CNTs/rGO is used as an OER and HER bifunctional catalyst.
Following the procedure of example 1CoO@CoSe2And CoO @ N-CNTs/rGO is prepared without adding selenium powder in the selenizing stage in the preparation process of @ N-CNTs/rGO-500.
The catalytic performance was evaluated in the same manner as in example 1.
CoO @ N-CNTs/rGO as OER catalyst has an initial potential of 1.513V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 369mV (vs. RHE). Tafel slope was 84 mV/dec.
CoO @ N-CNTs/rGO as HER catalyst has an initial potential of-0.109V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η is 240mV (vs. RHE). the Tafel slope is 103 mV/dec.
Comparative example 5
By CoSe2@ N-CNTs/rGO is an OER and HER bifunctional catalyst.
Following the procedure of example 1 at CoO @ CoSe2In the selenizing stage in the preparation process of @ N-CNTs/rGO-500, CoO/Co @ N-CNTs/rGO and selenium powder are not respectively placed at the downstream end and the upstream end of a porcelain boat, but are mixed to prepare CoSe2@N-CNTs/rGO。
The catalytic performance was evaluated in the same manner as in example 1.
CoSe2The onset potential of @ N-CNTs/rGO as OER catalyst was 1.425V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 340mV (vs. RHE). Tafel slope was 107 mV/dec.
CoSe2The initial potential of @ N-CNTs/rGO as a HER catalyst was-0.059V (vs. RHE). At a current density of 10mA/cm2The desired overpotential η was 231mV (vs. RHE). Tafel slope was 66 mV/dec.
Claims (10)
1. Oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst is characterized in that: the graphene material is formed by loading cobalt monoxide nano-particles, cobalt diselenide nano-particles and nitrogen-doped carbon nano-tubes on a two-dimensional graphene sheet together.
2. Oxygen/hydrogen evolution two-dimensional CoO @ CoSe according to claim 12@ N-CNTs/rGO bifunctionalA composite catalyst characterized by:
the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst comprises the following components in percentage by mass:
45% -65% of cobalt monoxide nano-particles and cobalt diselenide nano-particles;
5% -15% of nitrogen-doped carbon nanotubes;
20% -40% of graphene sheets;
the molar ratio of the cobalt monoxide nano particles to the cobalt diselenide nano particles is (4-13) to (3-11);
the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The content of nitrogen in the @ N-CNTs/rGO bifunctional composite catalyst is 2-8% by mass;
a portion of the cobalt monoxide nanoparticles and cobalt diselenide nanoparticles were encapsulated within the nitrogen-doped carbon nanotubes.
3. Oxygen/hydrogen evolution two-dimensional CoO @ CoSe according to claim 1 or 22The @ N-CNTs/rGO bifunctional composite catalyst is characterized in that:
the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The @ N-CNTs/rGO bifunctional composite catalyst comprises the following components in percentage by mass:
50% -60% of cobalt monoxide nano-particles and cobalt diselenide nano-particles;
8% -12% of nitrogen-doped carbon nanotubes;
28% -38% of graphene sheets;
the molar ratio of the cobalt monoxide nano particles to the cobalt diselenide nano particles is (6-10) to (5-9);
the oxygen/hydrogen evolution two-dimensional CoO @ CoSe2The content of nitrogen in the @ N-CNTs/rGO bifunctional composite catalyst is 3-6% by mass.
4. Oxygen evolution/hydrogen evolution two-dimensional CoO @ CoSe as set forth in any one of claims 1 to 32The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of: the method comprises the following steps:
1) mixing cobalt salt, a nitrogen-containing organic small molecular compound and graphene oxide in a liquid phase, evaporating a solvent and drying to obtain mixed powder;
2) placing the mixed powder in a protective atmosphere, performing first-stage roasting treatment at the temperature of 500-600 ℃, and then heating to the temperature of 700-900 ℃ for second-stage roasting to obtain a precursor;
3) and placing the precursor and the selenium powder in a protective atmosphere, and performing partial selenization treatment at the temperature of 400-600 ℃ to obtain the selenium-rich material.
5. The oxygen/hydrogen evolution two-dimensional CoO @ CoSe of claim 42The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of:
the nitrogen-containing organic small molecular compound comprises at least one of urea, melamine, cyanuric chloride, cyanamide and dicyandiamide;
the cobalt salt is water-soluble cobalt salt.
6. An oxygen/hydrogen evolution two-dimensional CoO @ CoSe according to claim 4 or 52The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of: the mass ratio of the cobalt salt, the nitrogen-containing organic micromolecule compound and the graphene oxide is (2-4): (12-16): 1-2).
7. The oxygen/hydrogen evolution two-dimensional CoO @ CoSe of claim 42The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of:
the first stage roasting treatment time is 0.5-4 h;
the second stage roasting treatment time is 0.5-4 h.
8. The oxygen/hydrogen evolution two-dimensional CoO @ CoSe of claim 42The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of: the mass ratio of the precursor to the selenium powder is (3-6) to (40-60).
9. The oxygen/hydrogen evolution two-dimensional CoO @ CoSe of claim 42@ N-CNTs/rGO bifunctional composite catalysisThe preparation method of the agent is characterized in that: the time of the partial selenization treatment is 0.5-4 h.
10. An oxygen/hydrogen evolution two-dimensional CoO @ CoSe as claimed in any one of claims 1 to 32The preparation method of the @ N-CNTs/rGO bifunctional composite catalyst is characterized by comprising the following steps of: the catalyst is applied as a catalyst for oxygen evolution or hydrogen evolution of electrolyzed water.
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