CN110813293A - Preparation method and application of Cu NPs-rGO electrocatalyst - Google Patents
Preparation method and application of Cu NPs-rGO electrocatalyst Download PDFInfo
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
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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
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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
Abstract
The invention belongs to the field of new nano materials, and particularly relates to a preparation method and application of a Cu NPs-rGO electrocatalyst, wherein two-dimensional reduced graphene oxide loaded zero-valent copper nanoparticles (Cu NPs-rGO) are synthesized by a hydrothermal method and hydrogen-argon mixed gas annealing treatment, and compared with a copper oxide catalyst, the zero-valent copper catalyst is easier to form a feedback pi bond, so that nitrogen is easier to adsorb and activate, the catalytic activity is improved, and the preparation method is simple and easy to implement‑ 1mgcat.‑1) And faraday efficiency (15.32%).
Description
Technical Field
The invention belongs to the field of new nano materials, and particularly relates to a preparation method and application of a Cu NPs-rGO electrocatalyst.
Background
Ammonia is an important industrial raw material and plays an irreplaceable role in the fields of agriculture, plastics, medicine, textile industry and the like. Because of the low liquefaction pressure of ammonia, the ideal hydrogen storage medium and the absence of carbon, etc., have been widely used. Currently, the industrial production of ammonia relies mainly on the conventional Haber-Bosch process, in which nitrogen and hydrogen are co-catalyzed by a heterogeneous catalyst at high pressure (150-300 atm) and high temperature (300-500 ℃ C.). However, this process consumes over 1% of the total global fossil energy annually, and results in carbon dioxide emissions of 300 million metric tons. Thus, there is a need for an economical, sustainable alternative. The realization of artificial nitrogen fixation from nitrogen and water by electrochemical catalysis under environmental conditions is an effective method for realizing clean, carbon-free and sustainable development, and has great potential, thus becoming a good choice for replacing the traditional Haber-Bosch process. However, an electrocatalyst for efficient nitrogen reduction is the most important part. The noble metal catalyst has the advantages of good conductivity, more active crystal faces, easy combination with reactants and the like, thereby showing excellent nitrogen reduction performance, but the practical application of the noble metal catalyst is limited by resource shortage, high cost and low Faraday efficiency. Therefore, it remains a great challenge to develop low-cost and earth-resource-rich electrocatalysts.
Copper is a cheap transition metal, and the unique physical and chemical properties of copper arouse great research interest. Copper-based materials can undergo a variety of reactions due to the wide range of valence states of copper. Generally, the feedback pi-bonding between metal and nitrogen weakens the N ≡ N bond, and plays a crucial role in the fixation and activation of nitrogen. Thus, the feedback pi-bonds are more easily formed for zero-valent copper catalysts than for copper oxide catalysts. On the other hand, the development of copper-based catalysts has been the most challenging to synthesize cheap zero-valent copper nanoparticle nano-particles with high activity, stability and oxidation resistance. In general, immobilization of copper nanoparticles on a substrate is an effective method. In recent years, Graphene Oxide (GO) has attracted much attention as an excellent catalyst carrier with characteristics of high specific surface area, good conductivity and strong nanoparticle coupling ability.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu NPs-rGO electro-catalyst, and the prepared Cu NPs-rGO electro-catalyst is applied to electro-catalysis artificial nitrogen fixation for preparing ammonia gas, and has the advantages of high efficiency and high selectivity.
The preparation method of the Cu NPs-rGO electrocatalyst comprises the following steps:
(1) mixing CuAc2·H2Dissolving O and graphene oxide in water to prepare a mixed solution, and carrying out ultrasonic treatment on the mixed solution;
(2) transferring the mixed solution into an oven for hydrothermal reaction under the conditions of 175 ℃ and 180 ℃ for 2-2.5 hours, centrifuging the product after the hydrothermal reaction, and washing the product with water to obtain a solid product;
(3) freeze-drying the obtained solid product in a freeze dryer, taking out and grinding to obtain powder;
(4) and (3) placing the ground powder in a tube furnace, introducing atmosphere, and annealing at the temperature of 490-510 ℃ for 3-3.5h to obtain the finished product of the Cu NPs-rGO.
CuAc2·H2The mass ratio of O to graphene oxide is 4-5: 1.
the atmosphere is a mixture of argon and hydrogen.
And dissolving the prepared Cu NPs-rGO finished product and a Nafion solution in an ethanol solution, placing the solution in an ultrasonic machine for ultrasonic treatment, dripping the ultrasonic solution on the surface of carbon paper, and airing at room temperature to obtain the working electrode.
The freeze-drying time is 20-24 hours.
The prepared Cu NPs-rGO has the following structure: and the surface of the rGO is uniformly loaded with zero-valent copper nanoparticles.
As a preferable technical scheme, the preparation method of the Cu NPs-rGO electrocatalyst specifically comprises the following steps:
mixing 1.0mmol CuAc2·H2Dissolving O and 50mg of graphene oxide in 35mL of water, placing the water in an ultrasonic machine for ultrasonic treatment for 1 hour, transferring the obtained liquid to a 50mL reaction kettle, placing the reaction kettle in an oven at 180 ℃ for hydrothermal reaction for 2 hours, taking the reaction kettle out after cooling to room temperature, centrifuging the reacted liquid, and washing the liquid with water for three times to remove unreacted CuAc2·H2And O, freeze-drying the solid obtained by centrifugation in a freeze dryer for 24 hours, finally grinding the solid, placing the ground solid in a tubular furnace, introducing mixed gas of hydrogen and argon, and annealing at 500 ℃ for 3 hours to obtain the Cu NPs-rGO.
The Cu NPs-rGO electrocatalyst disclosed by the invention is applied to preparation of ammonia gas by electrocatalysis artificial nitrogen fixation as a nitrogen reduction electrocatalyst, and the Cu NPs-rGO electrocatalyst is loaded on carbon paper to serve as a working electrode during application.
The preparation method of the working electrode comprises the following steps: dissolving 10mg of Cu NPs-rGO electrocatalyst and 40 mu L of Nafion solution with the concentration of 5 wt% in 960mL of mixed solution, wherein the mixed solution contains 640 mu L of ethanol and 320 mu L of water, placing the mixed solution in an ultrasonic machine for ultrasonic treatment for 1 hour to obtain a uniform solution, then dripping 10 mu L of the solution on clean carbon paper with the area of 1 x 1cm, and naturally airing the solution at room temperature to obtain the working electrode.
In the invention, the Cu NPs-rGO electrocatalyst prepared by using the two-dimensional layered graphene to load the zero-valent copper nanoparticles has a very large specific surface area, good conductivity and strong coupling with the nanoparticles, so that the graphene and the copper nanoparticles are compounded, the copper nanoparticles can be effectively prevented from agglomerating, more copper active sites are exposed, and the conductivity of the copper nanoparticles can be further enhanced. The exposed active sites can adsorb and activate nitrogen molecules more easily, and the good conductivity can reduce the impedance in the reaction process, thereby being beneficial to the electro-catalytic nitrogen reduction reaction, and improving the Faraday efficiency and the ammonia production rate.
Compared with the prior art, the invention has the following beneficial effects.
(1) The preparation method is simple and easy to operate, the two-dimensional reduced graphene oxide loaded zero-valent copper nanoparticles (Cu NPs-rGO) are synthesized by a hydrothermal method and hydrogen-argon mixed gas annealing treatment, and compared with a copper oxide catalyst, the zero-valent copper catalyst is easier to form feedback pi bonds, so that nitrogen is easier to adsorb and activate, and the catalytic activity is improved;
(2) according to the invention, the reductive graphene oxide is used as a substrate, so that the conductivity of the material can be further enhanced, copper nanoparticles and stable elemental copper can be better dispersed, and the prepared Cu NPs-rGO catalyst has a higher ammonia production rate (24.58 mu g h) under a potential of-0.4V-1mgcat.-1) And faraday efficiency (15.32%).
Drawings
In FIG. 1, a is an X-ray diffraction pattern of a Cu NPs-rGO nano-catalyst; b is a scanning electron microscope image of the Cu NPs-rGO nano catalyst; c is a transmission electron microscope image of the Cu NPs-rGO nano catalyst; d is a high-resolution transmission electron microscope image of the Cu NPs-rGO nano catalyst; e-g are respectively a mapping chart of Cu, C and O elements of the Cu NPs-rGO nano catalyst;
in FIG. 2, a is a general X-ray photoelectron spectroscopy diagram of the Cu NPs-rGO nano-catalyst; b is a high-resolution X-ray photoelectron spectrum of a Cu element in a Cu NPs-rGO nano catalyst; c is an Auger spectrogram of Cu; d is a high-resolution X-ray photoelectron spectrum of a C element in a Cu NPs-rGO nano catalyst; e is a high-resolution X-ray photoelectron spectrum of O element in the Cu NPs-rGO nano catalyst; f is a Raman spectrogram of the CuNPs-rGO nano catalyst and the rGO;
in FIG. 3, a is a schematic diagram of a nitrogen reduction test; b is an instant current diagram of the Cu NPs-rGO nano catalyst under each potential; c is an ultraviolet absorption diagram of the Cu NPs-rGO nano catalyst under each potential; d is a graph of ammonia production rate and Faraday efficiency of the Cu NPs-rGO nano catalyst under each potential; e is the ammonia yield of different electrodes; f is the ammonia production rate when different copper nanoparticles are loaded;
in FIG. 4, a is a cycle test chart of the Cu NPs-rGO nano-catalyst at-0.4V; b is long-time i-t of the Cu NPs-rGO nano catalyst;
FIG. 5 is a graph of the ultraviolet absorption curve of hydrazine hydrate detected after Cu NPs-rGO nano-catalyst testing.
The Cu NPs-rGO nanocatalysts in FIGS. 1-5 were prepared as in example 1.
Detailed Description
The invention is further illustrated by the following examples and figures of the specification.
Example 1
The preparation method of the Cu NPs-rGO electrocatalyst comprises the following steps: mixing 1.0mmol CuAc2·H2Dissolving O and 50mg of graphene oxide in 35mL of water, placing the mixture in an ultrasonic machine for ultrasonic treatment for 1 hour, and then carrying out ultrasonic treatment on the obtained solutionTransferring the obtained product into a 50mL reaction kettle, placing the reaction kettle in an oven with the temperature of 180 ℃ for hydrothermal reaction for 2 hours, cooling to room temperature after reaction, taking the reaction kettle out, centrifuging the reacted liquid, and washing with water for three times to remove unreacted CuAc2·H2And O, freeze-drying the solid obtained by centrifugation in a freeze dryer for 24 hours, grinding the solid obtained by freeze-drying, placing the ground solid in a tubular furnace, introducing a hydrogen-argon mixed gas, and annealing at 500 ℃ for 3 hours to obtain a finished product of the Cu NPs-rGO electrocatalyst.
In FIG. 1 a is an X-ray diffraction pattern from which it can be observed that the diffraction peak at 26.3 ° is derived from rGO, and the three strong diffraction peaks at 43.2 °, 50.4 ° and 74.1 ° correspond to the (111), (200), (220) crystal planes of elemental copper, respectively; scanning electron microscopy (fig. 1b) and TEM (fig. 1c) images of Cu NPs-rGO nanocatalysts demonstrate that copper nanoparticles are uniformly distributed on rGO; in addition, a high-resolution transmission electron microscope image (figure 1d) of the Cu NPs-rGO nano catalyst shows clear lattice stripes, the distance between planes is 0.210nm, and the clear lattice stripes correspond to (111) crystal faces of a copper simple substance; transmission electron microscope X-ray element mapping images (fig. 1e-g) show that the Cu, C, O elements are uniformly distributed in the catalyst;
as shown in FIG. 2a, the existence of Cu, C and O elements is further verified by X-ray photoelectron spectroscopy; in the Cu2p region (FIG. 2b), peaks appearing at 934.1eV and 944.1eV are derived from copper oxide, oxidation of the copper simple substance in air is inevitable, and a peak at 932.5eV is Cu0Or Cu+This is due to the effect of particle size and surface coverage on the binding energy; to distinguish Cu0Or Cu+We performed auger spectroscopy tests, as shown in fig. 2c, with peak positions centered at 568.0eV, indicating Cu0 in the catalyst; as shown in fig. 2d, the peak at 284.7eV corresponds to C ═ C bonds; in addition, at the other three signals 285.8eV, 287.8eV and 289.0eV respectively, corresponding to C-C, C ═ O, -COO-bonds respectively; in the O1s region (fig. 2e), there are two peaks at 531.6eV and 533.4eV corresponding to C ═ O and C — O bonds; in FIG. 2f, the Raman spectrum uses the intensity ratio of the D peak to the G peak (ID/IG) to study the GO change, and the ID/IG value (1.08) of the CuNPs-rGO nano-catalyst is greater than that of GO (0.95), indicating that GO is successfully reducedIs rGO;
example 2
The preparation method of the Cu NPs-rGO nano catalyst electrode comprises the following steps: 10mg of the Cu NPs-rGO electrocatalyst prepared in example 1 and 5 wt% Nafion solution are dissolved in 960mL of mixed solution, wherein the 960mL of mixed solution contains 640mL of ethanol and 320mL of water, the mixed solution is placed in a sonic machine for ultrasonic treatment for 1 hour to obtain a uniform solution, then 10 mu L of the solution is dripped on clean carbon paper with the area of 1 x 1cm, and the clean carbon paper is naturally dried at room temperature to obtain a working electrode.
As described above, the homemade Cu NPs-rGO nano-catalyst is deposited on carbon paper to prepare the working electrode (Cu NPs-rGO/CP, load capacity: 0.1 mg-cm-2) And performing electrochemical test on the working electrode.
As shown in FIG. 3a at 0.5M LiClO4Performing nitrogen reduction reaction test in water solution, separating with H-type electrolytic cell with Nafion 117 membrane, blowing ultrahigh pure nitrogen as feed gas into cathode chamber for 30 min before electrolysis, and collecting NH product3And possibly product N2H4Respectively adopting indoxyl blue spectrophotometry and a watt-Krispt method to carry out determination; chronoamperometric measurements as shown in FIG. 3b were conducted at different potentials from-0.2V to-0.7V for 7200 s; then collecting the obtained electrolyte, and developing the color by indoxyl blue; FIG. 3c is the relevant UV-VIS absorption spectrum with the highest absorbance at a potential of-0.4V; FIG. 3d shows NH at different potentials3Yield (V)NH3) And Faraday Efficiency (FE), the results show that VNH3And FE both increased with increasing concentration to a negative potential of-0.4V, and subsequently, VNH3Decreases simultaneously with FEs due to the influence of the hydrogen evolution reaction of the competing reaction; when the voltage is-0.4V, the ammonia production rate of the electrocatalyst is 24.58 mu g h-1mgcat. -1The Faraday efficiency can reach 15.32%; FIG. 5 shows that there is no N in this process2H4The generation shows that the Cu NPs-rGO nano catalyst has excellent selectivity; as shown in FIG. 3e, copper nanoparticles, reduced graphene oxide and carbon paper have little catalytic activity compared to Cu NPs-rGO nanocatalysts(ii) a FIG. 3f shows that when 0.5, 1.0, 1.5, 2.0mM CuAc was added for the hydrothermal reaction2·H2When O is required, 1.0mM CuAc is added2·H2O exhibits the best catalytic performance.
Stability is an important factor for the catalyst. As shown in fig. 4a and 4b, the Cu NPs-rGO nanocatalyst still exhibited very high catalytic activity after 6 cycles and 30 hours of i-t testing, indicating that the catalyst had excellent stability and durability.
As can be seen from the graph of fig. 5, no by-product production was detected, demonstrating the selectivity of the catalyst.
Claims (10)
1. A preparation method of a Cu NPs-rGO electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing CuAc2·H2Dissolving O and graphene oxide in water to prepare a mixed solution, and carrying out ultrasonic treatment on the mixed solution;
(2) transferring the mixed solution into an oven for hydrothermal reaction under the conditions of 175 ℃ and 180 ℃ for 2-2.5 hours, centrifuging the product after the hydrothermal reaction, and washing the product with water to obtain a solid product;
(3) freeze-drying the obtained solid product in a freeze dryer, taking out and grinding to obtain powder;
(4) and (3) placing the ground powder in a tube furnace, introducing atmosphere, and annealing at the temperature of 490-510 ℃ for 3-3.5h to obtain the finished product of the Cu NPs-rGO.
2. The method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: CuAc2·H2The mass ratio of O to graphene oxide is 4-5: 1.
3. the method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: the atmosphere is a mixture of argon and hydrogen.
4. The method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: and dissolving the prepared CuNPs-rGO finished product and a Nafion solution in an ethanol solution, placing the solution in an ultrasonic machine for ultrasonic treatment, dripping the ultrasonic solution on the surface of carbon paper, and airing at room temperature to obtain the working electrode.
5. The method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: the freeze-drying time is 20-24 hours.
6. The method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: the prepared CuNPs-rGO has the following structure: and the surface of the rGO is uniformly loaded with zero-valent copper nanoparticles.
7. The method of preparing a Cu NPs-rGO electrocatalyst according to claim 1, characterized in that: the preparation method specifically comprises the following steps:
mixing 1.0mM CuAc2·H2Dissolving O and 50mg of graphene oxide in 35mL of water, placing the water in an ultrasonic machine for ultrasonic treatment for 1 hour, transferring the obtained liquid to a 50mL reaction kettle, placing the reaction kettle in an oven at 180 ℃ for hydrothermal reaction for 2 hours, taking the reaction kettle out after cooling to room temperature, centrifuging the reacted liquid, and washing the liquid with water for three times to remove unreacted CuAc2·H2And O, freeze-drying the solid obtained by centrifugation in a freeze dryer for 24 hours, finally grinding the solid, placing the ground solid in a tubular furnace, introducing mixed gas of hydrogen and argon, and annealing at 500 ℃ for 3 hours to obtain the CuNPs-rGO electrocatalyst.
8. Use of the prepared Cu NPs-rGO electrocatalyst according to claim 1, wherein: the application of the electrocatalyst used for nitrogen reduction in preparing ammonia gas by electrocatalysis of artificial nitrogen fixation.
9. Use of the Cu NPs-rGO electrocatalyst according to claim 8, characterized in that: the Cu NPs-rGO electrocatalyst is loaded on carbon paper and is used as a working electrode in the preparation of ammonia gas by electrocatalysis artificial nitrogen fixation.
10. Use of the Cu NPs-rGO electrocatalyst according to claim 9, characterized in that: the preparation method of the working electrode comprises the following steps: 10mg of CuNPs-rGO electrocatalyst and 40. mu.L of 5 wt% Nafion solution were dissolved in 960mL of a mixed solution containing 640mL of ethanol and 320mL of water, and the solution was sonicated in a sonicator for 1 hour to obtain a uniform solution, and then 10. mu.L of the above solution was dropped on clean carbon paper having an area of 1X 1cm, and naturally dried at room temperature.
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| CN113201758A (en) * | 2021-04-08 | 2021-08-03 | 哈尔滨理工大学 | FeS2Preparation method and application of @ GO nitrogen fixation catalyst |
| CN113981481A (en) * | 2021-09-27 | 2022-01-28 | 西安电子科技大学 | Preparation method and application of copper nanoparticle-loaded one-dimensional carbon-based nano material |
| CN114293217A (en) * | 2022-01-05 | 2022-04-08 | 陕西科技大学 | Preparation method of reduced graphene oxide composite metal nano array catalyst |
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