CN114635153B - Defect-rich copper-based nano catalyst and preparation method and application thereof - Google Patents
Defect-rich copper-based nano catalyst and preparation method and application thereof Download PDFInfo
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- CN114635153B CN114635153B CN202210193406.0A CN202210193406A CN114635153B CN 114635153 B CN114635153 B CN 114635153B CN 202210193406 A CN202210193406 A CN 202210193406A CN 114635153 B CN114635153 B CN 114635153B
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Abstract
The invention discloses a copper-based nano catalyst rich in defects, and a preparation method and application thereof. Placing the Wide alloy in an acid solution dissolved with a corrosion inhibitor for standing reaction, washing, filtering and vacuum drying after the reaction to obtain the copper-based nano catalyst rich in defects. The catalyst can be applied to electrocatalytic reduction of carbon dioxide into high carbon compounds (C2+). The invention adopts a very simple and controllable preparation process, prepares the copper-based nano catalyst rich in a large number of defects such as vacancies, steps, dislocation and the like by dealloying through a one-step chemical etching method, and has excellent performance on electrochemical reduction of carbon dioxide into ethylene and ethanol, and the selectivity of a C2 product is higher than 60 percent.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a copper-based nano catalyst rich in defects, and a preparation method and application thereof.
Background
Since the industrial revolution, a large amount of fossil energy has been mined and utilized, which inevitably causes serious environmental problems and energy crisis. Among them, excessive emission of carbon dioxide forms a serious greenhouse effect, threatening future survival and development of human beings. The electrocatalytic carbon dioxide reduction technology can utilize renewable electric energy, and can be used for electrocatalytically reducing carbon dioxide captured from the atmosphere into a series of chemicals and fuels (carbon monoxide, methane, formic acid, ethylene, ethanol and the like) in a mild environment, so that carbon cycle closure is realized, the energy crisis and the greenhouse effect can be relieved, and intermittent renewable electric energy can be converted into chemical energy of carbon-containing compounds for storage and transportation. Electrochemical reduction of carbon dioxide can produce a variety of carbon products, two or more of which are considered multi-carbon compounds (c2+), which are considered high value-added products due to their high energy density, and have greater commercial value. Therefore, electrocatalytic reduction of carbon dioxide to specific multi-carbon compounds is considered as a very promising technological path.
Carbon dioxide is an extremely stable molecule, so the core technology for electrochemical reduction of carbon dioxide to high carbon compounds is the development of electrochemical catalysts with high activity and selectivity. Copper metal has been widely studied and paid attention to its unique catalytic properties due to its proper binding force to the reaction intermediates of high carbon compounds. At present, a great deal of copper-based materials such as oxidation-derived copper, alloy-type copper, doped copper, alloy copper and the like are prepared and studied. For example, a method for preparing carbon-containing compounds from carbon dioxide by electrocatalytic carbon dioxide of a copper alloy material is disclosed, and the amorphous copper alloy material can electrocatalytic carbon dioxide into alcohol or acid-type carbon products, but the material is not only carried out under high temperature conditions, but also needs to accurately control alloy components, and the overall preparation condition is complex. In the current research, the selectivity and activity of the electrocatalytic reduction of high carbon compounds by carbon dioxide are still a great challenge, and the high active reaction sites with universality and mature material development technology are not discovered.
Recently, studies have shown that defective sites in copper-based materials can promote adsorption of multi-carbon compounds, CO reaction intermediates, and reduce the activation energy of c—c coupling reactions, thereby having high selectivity and activity for multi-carbon compounds. For example, the Zheng Gengfeng group prepared grain boundary-rich cuprous oxide (Yang C, shen H, guan A, et al fast cooling induced grain-boundary-rich copper oxide for electrocatalytic carbon dioxide reduction to ethanol [ J ]. Journal of Colloid and Interface Science,2020, 570:375-381) by rapid cooling, which exhibited superior performance on high carbon compounds. However, the type of defects of the catalyst is mainly grain boundaries, the preparation process is also complicated, multiple steps such as oxidation, reduction, liquid nitrogen cooling and the like are involved, and large-scale preparation is difficult. Therefore, how to develop a high-performance copper-based catalyst which is stable, controllable, rich in defects and capable of being produced in large scale by using a simple preparation method is a problem to be solved in the field of carbon dioxide electrocatalytic reduction.
Disclosure of Invention
Based on the prior art, the invention aims to provide a copper-based nano catalyst rich in defects, and a preparation method and application thereof. The defect-rich copper-based nano-catalyst is prepared by an extremely simple and controllable process technology, and is used for efficiently and electrically catalyzing reduction of carbon dioxide into high-carbon compounds. The invention prepares the copper-based nano catalyst rich in a large number of defect sites (vacancies, steps and dislocation) by dealloying the crushed Wide alloy particles by using acid through a one-step chemical etching method. The catalyst shows excellent selectivity and activity to ethylene and ethanol in the electrochemical reduction reaction of carbon dioxide.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a method for preparing a copper-based nano catalyst rich in defects, comprising the following steps:
(1) Crushing the purchased Wildd alloy by a crusher, and screening the Wildd alloy particles with uniform granularity;
(2) Placing the screened Wide alloy particles with uniform granularity into an acid solution containing a corrosion inhibitor, and heating for reacting for a period of time;
(3) Washing the reacted particles, filtering, and drying in a vacuum environment to obtain the copper-based nano catalyst rich in defects.
Further, the Wilde alloy of step (1) is an aluminum-copper-zinc alloy.
Further, the mesh number of the particles of the Wilde alloy in the step (1) is 200-300 mesh.
Further, the acid solution in the step (2) is one or more of hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution and perchloric acid solution.
Further, the mass fraction of the acid solution in the step (2) is 5% -20%.
Further, the corrosion inhibitor in the step (2) is more than one of benzotriazole, methyl benzotriazole and mercaptobenzothiazole.
Further, the mass percentage of the corrosion inhibitor in the acid solution containing the corrosion inhibitor in the step (2) is 0.1% -1%.
Further, the temperature of the heating reaction in the step (2) is 30-80 ℃, and the time of the heating reaction in the step (2) is 1-12 hours.
The heating reaction time in the step (2) is 1-6 hours.
Further, the washing of the reacted particles in the step (3) is carried out by respectively washing with water and ethanol for 2 to 6 times.
Further, the washing of the reacted particles in the step (3) is performed three times by using water and ethanol respectively.
Further, the drying in the step (3) is carried out in a vacuum drying oven at 20-80 ℃ for 6-12h.
Further, the particles after the reaction in the step (3) are dried for 10 hours in a vacuum drying oven at 60 ℃ after washing and suction filtration.
The invention provides a copper-based nano catalyst rich in defects, which is prepared by the preparation method.
The invention also provides application of the copper-based nano catalyst rich in defects in electrocatalytic reduction of carbon dioxide into a high carbon compound (C2+).
Further, the copper-based nano catalyst rich in defects is dripped on a glassy carbon electrode to serve as a working electrode, silver-silver chloride serves as a reference electrode, a platinum sheet serves as a counter electrode, potassium bicarbonate solution serves as electrolyte, and electrocatalytic carbon dioxide reduction reaction is carried out in an H-type electrolytic cell.
Further, the potassium bicarbonate solution has a concentration of 0.1M.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes acid solution, corrosion inhibitor and Wide alloy as raw materials, and the copper-based nano catalyst rich in defects can be prepared by standing reaction. The preparation method is extremely simple, mild in reaction condition, strong in controllability and high in repeatability, and is beneficial to large-scale production.
(2) The copper-based nano catalyst prepared by the method contains a large number of vacancy, step, dislocation and other defect sites, and the copper-based nano catalyst rich in defects can be stored for a long time without special protection.
(3) The copper-based nano catalyst rich in defects, which is prepared by the invention, is beneficial to adsorbing a CO reaction intermediate, reduces the activation energy of C-C coupling reaction, and shows high performance for electrochemical reduction of carbon dioxide into high carbon compounds.
Drawings
FIG. 1 is an SEM characterization of the resulting 200-300 mesh particles of a Wilde alloy (P-AlCuZn).
FIG. 2 is an SEM characterization of a defect-rich copper-based nanocatalyst (DeCu-3W) obtained according to example 1.
FIG. 3 is a TEM characterization of a defect-rich copper-based nanocatalyst ((DeCu-3W)) obtained in example 1.
FIG. 4 is an SEM characterization of a less defective copper-based nanocatalyst (DeCu-3 WO) obtained from comparative example 1.
FIG. 5 is a TEM characterization of a less defective copper-based nanocatalyst (DeCu-3 WO) obtained from comparative example 1.
FIG. 6 is an XRD characterization of the obtained 200-300 mesh Wilde alloy (P-AlCuZn) particles, the defect-rich copper-based nanocatalyst (DeCu-3W) obtained in example 1, and the less defect copper-based nanocatalyst (DeCu-3 WO) obtained in comparative example 1.
FIG. 7 shows electrocatalytic CO enriched in defective copper-based nanocatalysts ((DeCu-3W)) obtained in example 1 2 Reduction product profile.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
A method for producing a first wick alloy particle (P-AlCuZn), the method comprising the steps of:
(1) Weighing 5g of the purchased Wide alloy, crushing for 10s in a crusher, and collecting crushed particles;
(2) And (3) sieving the particles in the step (1) sequentially by using a standard sample sieve, and screening out 200-300 meshes of Wide alloy particles (P-AlCuZn).
FIG. 1 is an SEM image of the obtained 200-300 mesh particles of the Wilde alloy (P-AlCuZn), and it can be seen from FIG. 1 that the particles of the Wilde alloy exhibit a smooth-surfaced, particulate shape.
Example 1
The present embodiment provides a method for preparing a defect-rich copper-based nano catalyst (DeCu-3W), the method comprising the steps of:
(1) Preparing a hydrochloric acid solution with the mass fraction of 10%, and dissolving benzotriazole in the hydrochloric acid solution to obtain a hydrochloric acid solution containing benzotriazole, wherein the mass fraction of benzotriazole in the hydrochloric acid solution containing benzotriazole is 0.3%;
(2) Weighing 0.25g of 200-300 mesh Wide alloy particles (P-AlCuZn), pouring the Wide alloy particles into the hydrochloric acid solution containing benzotriazole obtained in the step (1), and standing at 80 ℃ for reaction for 3 hours;
(3) Pouring out the residual solution after the reaction is stopped, washing three times by deionized water and absolute ethyl alcohol respectively, carrying out suction filtration, and placing the collected particles in a vacuum drying oven at 60 ℃ for drying for 10 hours to obtain the copper-based nano catalyst (DeCu-3W) rich in defects.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the defect-rich copper-based nanocatalyst (DeCu-3W) obtained in example 1, and it can be observed from FIG. 2 that the defect-rich copper-based nanocatalyst (DeCu-3W) exhibits oval nanoparticulate (about 250 nm) with surface spread over cracks. FIG. 3 is a Transmission Electron Microscope (TEM) image of the defect-rich copper-based nanocatalyst (DeCu-3W) obtained in example 1, and it can be seen from FIG. 3 that the surface of the obtained defect-rich copper-based nanocatalyst has a layer of Cu (OH) filled with crystal lattice 2 A thin layer having three crystal orientations, namely, (211), (012), (122) (see upper left corner of b in fig. 3), and having lattice defects such as steps, dislocations, etc. at the edge of the thin layer (see upper right corner of b in fig. 3, steps are indicated by dots, dislocations are indicated by boxes).
Example 2
The present embodiment provides a method for preparing a defect-rich copper-based nano catalyst (DeCu-4W), comprising the steps of:
(1) Preparing a hydrochloric acid solution with the mass fraction of 20%, and dissolving benzotriazole in the hydrochloric acid solution to obtain a hydrochloric acid solution containing benzotriazole, wherein the mass fraction of benzotriazole in the hydrochloric acid solution containing benzotriazole is 1%;
(2) Weighing 0.25g of 200-300 mesh Wide alloy particles (P-AlCuZn), pouring the Wide alloy particles into the hydrochloric acid solution containing benzotriazole obtained in the step (1), and standing at 80 ℃ for reaction for 1 hour;
(3) After the reaction was stopped, the remaining solution was poured off, washed six times with deionized water and absolute ethyl alcohol, suction filtered, and the collected particles were dried in a vacuum oven at 80 ℃ for 6 hours.
Example 3
The present embodiment provides a method for preparing a defect-rich copper-based nano catalyst (DeCu-6W), comprising the steps of:
(1) Preparing a sulfuric acid solution with the mass fraction of 5%, and dissolving the methylbenzotriazole in the sulfuric acid solution to obtain a sulfuric acid solution containing the methylbenzotriazole, wherein the mass percentage of the methylbenzotriazole in the sulfuric acid solution containing the methylbenzotriazole is 0.1%;
(2) Weighing 0.25g of 200-300 mesh Wide alloy particles (P-AlCuZn), pouring the Wide alloy particles into the sulfuric acid solution containing the methylbenzotriazole obtained in the step (1), and standing at 30 ℃ for reaction for 12 hours;
(3) Pouring out the residual solution after the reaction is stopped, washing three times by deionized water and absolute ethyl alcohol respectively, carrying out suction filtration, and placing the collected particles in a vacuum drying oven at 20 ℃ for drying for 12 hours to obtain the copper-based nano catalyst (DeCu-6W) rich in defects.
Comparative example 1
The present embodiment provides a method for preparing a less defective copper-based nanocatalyst (DeCu-3 WO), the method comprising the steps of:
(1) Preparing hydrochloric acid solution with the mass fraction of 10%;
(2) Weighing 0.25g of 200-300 mesh Wide alloy particles (P-AlCuZn), pouring the Wide alloy particles into hydrochloric acid solution, and standing at 80 ℃ for reaction for 3 hours;
(3) Pouring out the residual solution after the reaction is stopped, washing three times by deionized water and absolute ethyl alcohol respectively, carrying out suction filtration, and placing the collected particles in a vacuum drying oven at 60 ℃ for drying for 10 hours to obtain the copper-based nano catalyst (DeCu-3 WO) with fewer defects.
FIG. 4 is an SEM image of the less defective copper-based nanocatalyst (DeCu-3 WO) obtained in comparative example 1, and it can be observed from FIG. 4 that the less defective copper-based nanocatalyst (DeCu-3 WO) obtained exhibits a large particle shape (about 300 nm) with small particles attached thereto, which has a rough surface. FIG. 5 is a TEM image of the less defective copper-based nanocatalyst (DeCu-3 WO) obtained in comparative example 1, from which it can be seen that the surface of the catalyst has an amorphous thin layer containing a small number of crystal domains whose Fourier transform diffraction pattern shows that it contains 211 crystal planes (see upper left corner of b in FIG. 5) with lattice defects such as vacancies and dislocations (see upper right corner of b in FIG. 5, vacancies are circled and dislocations are framed by square frames).
The X-ray diffraction (XRD) characterization results of the 200-300 mesh Wildalloy particles (P-AlCuZn) obtained above, the defect-rich copper-based nanocatalyst (DeCu-3W) obtained in example 1, and the less defect copper-based nanocatalyst (DeCu-3 WO) obtained in comparative example 1 are shown in FIG. 6. The main phase structure of the P-AlCuZn is Al 2 Cu, minor of Al 4.2 Cu 3.2 Zn 0.7 . The etched DeCu-3W and DeCu-3WO basically lose the original phase structure, which shows that the composition and structure of the Wilde alloy are completely changed.
The defect-rich copper-based nanocatalyst (DeCu-3W) prepared in example 1 was used to electrocatalytic carbon dioxide reduction.
The electrocatalytic carbon dioxide reduction reaction is carried out in an H-type electrolytic cell of a three-electrode system, the electrolytic cell having a cathode and an anode separated by a proton exchange membrane. Mixing catalyst, isopropanol and Nafion solution, ultrasonic treating to form homogeneous slurry, and dropping the slurry onto glassy carbon electrode to form working electrode and referenceThe electrode is a silver-silver chloride electrode, the counter electrode is a platinum sheet, and the electrolyte is CO 2 Saturated 0.1M potassium bicarbonate solution. Carbon dioxide is subjected to electrolytic reduction reaction under constant voltage, and CO is continuously introduced in the electrolytic reaction process 2 And (3) gas.
The product distribution of the defect-rich copper-based nanocatalyst (DeCu-3W) prepared in example 1, at different voltages (respectively, -1.0V vs RHE, -1.1V vs RHE, -1.2V vs RHE, -1.3V vs RHE, -1.4V vs RHE) for electrocatalytic carbon dioxide reduction is shown in FIG. 7. From fig. 7, it can be seen that the faraday efficiencies of the hydrogen are all about 20% in the voltage range of-1.0V to-1.3V, which indicates that the defect-rich copper-based nano-catalyst has good hydrogen inhibition performance and stronger tendency to the reduction path of carbon dioxide. The faradaic efficiency of CO was 30% at-1.0V, the CO yield was significantly reduced with increasing voltage, the formation of C2 products (ethylene and ethanol) was continuously increased, and the best at-1.3V, i.e., the excellent selectivity with faradaic efficiency higher than 60%, indicated that the defect-rich copper-based nanocatalyst could strongly adsorb CO intermediates and effectively reduce the activation energy of C-C coupling reactions at appropriate voltage, promote C-C coupling reactions, and thus generate a large amount of high carbon compounds.
Finally, it should be noted that: the foregoing detailed description of the embodiments and the related drawings is merely illustrative of the technical solution of the present invention and not limiting, and the present invention is not limited to the above-described specific embodiments, and any modifications or equivalent substitutions by one having ordinary skill in the art without departing from the spirit and scope of the present invention should be covered in the scope of the claims of the present invention.
Claims (7)
1. A method for preparing a copper-based nano catalyst rich in defects, which is characterized by comprising the following steps:
(1) Crushing the purchased Wildd alloy by a crusher, and screening the Wildd alloy particles with uniform granularity; the mesh number of the Wide alloy particles is 200-300 meshes;
(2) Placing the screened Wide alloy particles with uniform granularity into an acid solution containing a corrosion inhibitor, and heating for reaction; the mass fraction of the acid solution is 5% -20%; the corrosion inhibitor is more than one of benzotriazole and methylbenzotriazole; the mass percentage of the corrosion inhibitor in the acid solution containing the corrosion inhibitor is 0.1% -1%; the temperature of the heating reaction is 30-80 ℃, and the time of the heating reaction is 1-12 hours;
(3) Washing the reacted particles, filtering, and drying in a vacuum environment to obtain the copper-based nano catalyst rich in defects.
2. The method of claim 1, wherein the first wid alloy in step (1) is an aluminum-copper-zinc alloy.
3. The method for preparing the defect-rich copper-based nano catalyst according to claim 1, wherein the acid solution in the step (2) is one or more of hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution and perchloric acid solution.
4. The method for preparing a defect-rich copper-based nanocatalyst according to claim 1, wherein the washing of the reacted particles in step (3) is performed 3 to 6 times with water and ethanol, respectively; and (3) drying in the step (3) in a vacuum drying oven at 20-80 ℃ to dry 6-12h.
5. A defect-rich copper-based nanocatalyst prepared by the method of any of claims 1-4.
6. Use of a defect-rich copper-based nanocatalyst according to claim 5 for electrocatalytic reduction of carbon dioxide to higher carbon compounds.
7. The use of a defect-rich copper-based nano-catalyst according to claim 6 for electrocatalytic reduction of carbon dioxide to high carbon compounds, wherein the defect-rich copper-based nano-catalyst is dripped on a glassy carbon electrode as a working electrode, silver-silver chloride as a reference electrode, a platinum sheet as a counter electrode, and a potassium bicarbonate solution as an electrolyte, and electrocatalytic reaction is performed in an H-cell.
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