CN115433957A - Transition metal composite copper-based catalyst, and preparation method and application thereof - Google Patents

Transition metal composite copper-based catalyst, and preparation method and application thereof Download PDF

Info

Publication number
CN115433957A
CN115433957A CN202211251789.9A CN202211251789A CN115433957A CN 115433957 A CN115433957 A CN 115433957A CN 202211251789 A CN202211251789 A CN 202211251789A CN 115433957 A CN115433957 A CN 115433957A
Authority
CN
China
Prior art keywords
transition metal
based catalyst
metal composite
solution
composite copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211251789.9A
Other languages
Chinese (zh)
Inventor
夏霖
张小明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Zhongkeling Carbon Biotechnology Co ltd
Shenzhen Institute of Advanced Technology of CAS
Original Assignee
Shenzhen Zhongkeling Carbon Biotechnology Co ltd
Shenzhen Institute of Advanced Technology of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Zhongkeling Carbon Biotechnology Co ltd, Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Zhongkeling Carbon Biotechnology Co ltd
Priority to CN202211251789.9A priority Critical patent/CN115433957A/en
Publication of CN115433957A publication Critical patent/CN115433957A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a transition metal composite copper-based catalyst, the chemical formula of which is Cu x M 2‑x Te 2 Wherein the subscript indicates an atomic ratio between elements, x =0-2 (excluding 0), and M is at least one element selected from the group consisting of transition metals Ni, co, mn, fe, and Zn. The composite catalyst is used for preparing carbon dioxide by electrocatalysis and reductionThe acetic acid product has good selectivity, high catalytic activity, strong stability and low overpotential of catalytic reaction. Meanwhile, the preparation method has mild conditions and simple reaction, and is easy for industrial production.

Description

Transition metal composite copper-based catalyst, preparation method and application thereof
Technical Field
The invention relates to a carbon dioxide energy regeneration system, belongs to the technical field of carbon neutralization, and particularly relates to a transition metal composite copper-based catalyst for synthesizing ethylene by electrocatalysis of carbon dioxide, a preparation method and application.
Background
The continuous increase in the consumption of fossil fuels has led to a dramatic increase in the level of carbon dioxide in the atmosphere, causing deterioration in the human living environment, limiting sustainable health development.
More and more research is being conducted to provide a clean and environmentally friendly solution to replace non-renewable petrochemical fuels and to reduce the emission of carbon dioxide to solve the current energy crisis. By adopting the electrocatalysis technology, renewable green electric energy is utilized to simulate the photosynthesis of green plants, so that the reduction treatment of carbon dioxide is realized, the emission level of carbon dioxide can be reduced, the carbon dioxide can be recycled, and the method is an effective and promising alternative scheme.
On the other hand, carbon dioxide is a large and cheap waste resource, and the electrocatalytic technology can convert the waste gas resource into various high-value chemicals. The core of the electrocatalytic technology lies in the catalyst, and researches prove that a large number of catalysts can efficiently reduce carbon dioxide into one-carbon compounds such as carbon monoxide and formate, but the C-C coupling reaction generated by other catalysts except Cu is rarely observed on the other catalysts to generate high-value C 2+ And (3) obtaining the product.
Studies have shown that CO is the most critical intermediate in the reduction of carbon dioxide to two-carbon and multi-carbon products. The close proximity of the two CO molecules (or their derived one-carbon intermediates) to the catalyst surface is sufficient to allow further carbon-carbon coupling reactions to occur, which places very stringent requirements on the affinity between the catalyst and the CO, since there is a conflicting factor on this parameter: on one hand, the surface of the catalyst needs to have strong enough adsorption capacity to CO so as to ensure that the CO has high enough coverage on the surface and further coupling occurs; on the other hand, however, the activation energy barrier of the coupling reaction also increases with the surface enhancement of the CO adsorption capacity. In many metals, the affinity of the Cu surface and CO is moderate, and the requirements of CO surface concentration and coupling reaction activation energy can be met, so that the method has the advantages of low cost, high yield and high yieldShows unique performance of catalyzing and generating two-carbon and multi-carbon products. Moreover, among the numerous catalysts, copper-based catalysts are low cost, are the most effective catalysts for reducing carbon dioxide to hydrocarbons, have advantages in increasing the selectivity of the carbon dioxide conversion product, and are most typically capable of converting carbon dioxide to a high value C 2+ An effective catalyst for the product.
However, while the high conversion rate of the divalent carbon is realized by the traditional copper-based catalyst, a mixed product of a plurality of carbon sources is generated, such as ethanol, acetic acid, ethylene and the like, especially ethanol and acetic acid generally have the same potential window and are generated simultaneously, and the problem of low product selectivity is easily caused.
On the other hand, the current traditional copper-based catalyst also has the defects of high overpotential and poor stability, which causes over-high reaction energy consumption and short service life.
We found that part of the valence electrons of transition metal (non-copper metal) are in d orbital, and d orbital is adjacent to fermi level, and the change of d orbital electron filling changes the relative position of d orbital center and fermi level, thereby showing multiple catalytic activities. The electrocatalytic carbon dioxide reduction is a multi-electron and proton coupling process, and the intrinsic activity of the catalyst is determined by the surface electronic structure of the catalyst. Therefore, by adding additional transition metals to the copper-based compound, the variability of the valence shell electron orbitals of the transition metals makes them ideal catalysts for increasing the selectivity of copper-based catalysts for electrocatalysis of carbon dioxide.
On the other hand, transition metals are used as CO 2 The catalytic center of RR reacts through an intermediate step of absorbing oxygen-containing intermediate, and the electron density near the center of transition metal influences the absorption and charge transfer rate of the reaction intermediate, thereby reducing the electrocatalytic CO 2 The overpotential of RR. The transition metal selenide or telluride has lower overpotential as a catalyst due to lower anion electronegativity, if research shows that Cu 2 Se exhibits lower CO than Cu or CuO 2 RR overpotential.
In addition, the traditional preparation method of the copper-based catalyst usually adopts an electrodeposition and hydrothermal preparation method or a preparation method needing adding a strong reducing agent, the reaction conditions are severe, the steps are complicated, and the amplification production is difficult.
The invention prepares a transition metal composite Cu-based telluride catalyst (Cu) at room temperature x M 2-x Te 2 ) By adjusting the electron density near the center of the transition metal and changing the binding energy or binding energy configuration of the intermediate on the surface of the catalyst, the catalyst has the synergistic effect of the element Te with higher electronegativity and the element M with the transition metal introduced, and has extremely high catalytic activity, low over-potential of catalytic reaction, stability and high selectivity to acetic acid.
Disclosure of Invention
The invention aims to solve the problems of large overpotential, low selectivity, poor stability and severe preparation conditions of an electrocatalytic carbon dioxide reduction catalyst in the prior art, and provides a room-temperature synthesis method for preparing a transition metal composite metal copper-based telluride catalyst. Meanwhile, the preparation method has mild conditions and simple reaction, and is easy for industrial production.
In order to solve the technical problems, the invention provides a transition metal composite Cu-based telluride catalyst, wherein the chemical formula of the catalyst is Cu x M 2-x Te 2 Wherein the subscript indicates an atomic ratio between elements, x =0-2 (excluding 0), and M is at least one element selected from the group consisting of transition metals Ni, co, mn, fe, and Zn.
The invention also provides a preparation method of the transition element composite copper-based metal telluride catalyst, which comprises the following steps:
the first step, preparing solution A, dissolving x mol Cu metal salt and (2-x) mol M metal salt in deionized water, mixing with tartaric acid, controlling pH with ammonia water to form M 2+ Complexes with ammonium tartrate;
secondly, preparing solution B, dissolving 1mol of tellurium oxide powder in tartaric acid, heating in water bath for a certain time, and controlling dissolution by ammonia waterpH of the solution to form Te 4+ Complexes with ammonium tartrate;
thirdly, slowly pouring the solution B prepared in the second step into the solution A prepared in the first step, and slowly adding the sodium borohydride solution at the same time, and stirring at a certain rotating speed to finally see that the suspended Cu exists x M 2-x Te 2 Nanoparticle generation;
fourthly, after the reaction is finished, performing centrifugal treatment on the product, washing the product by deionized water and ethanol in sequence, and drying the product under inert atmosphere or vacuum condition to obtain the final Cu x M 2-x Te 2 Catalyst nanoparticles.
Wherein, in the first step, M = at least one element selected from the group consisting of Ni, co, mn, fe, zn, preferably Ni and Co, which has high selectivity to acetic acid.
Wherein the first step to the fourth step are all performed at room temperature.
The copper metal salt and the M metal salt are preferably acetates, and other soluble nitrates, sulfates and the like can be selected.
Wherein, the concentration ranges of the M metal salt and the copper metal salt are preferably 0.01mol/L-0.1mol/L, more preferably 0.02mol/L-0.06mol/L respectively, if the concentration is too large, a catalyst with the size of nano particles cannot be formed, the specific surface area is too small, the active sites are few, and further the catalytic activity is low.
Wherein, the concentration of the tartaric acid is 2-3 times of the sum of the concentrations of the M metal salt and the copper metal salt, and more preferably 2-2.2 times.
Wherein the pH in the first and second steps is 9-10, more preferably 9.5-10.
Wherein, the water bath heating time in the second step is 30min-90min, and more preferably 60min.
Wherein the water bath heating temperature in the second step is 50-100 ℃, and more preferably 60-80 ℃.
Wherein, the concentration range of the solution of sodium borohydride in the third step is preferably 0.1mmol/L-0.2mol/L, and the addition amount is 0.5-2 times of the mole number of tellurium oxide.
Wherein, the washing conditions in the fourth step are specifically as follows: washing with deionized water for 1-3 times, and then washing with ethanol for 1-3 times.
Wherein, the inert gas in the fourth step is nitrogen or argon and other inert gases.
Wherein the drying temperature in the fourth step is 50 to 90 ℃, more preferably 70 to 80 ℃.
Wherein the drying time in the fourth step is 2-6h, more preferably 4h.
The invention also provides a method for preparing acetic acid by using carbon dioxide, which comprises the following steps:
firstly, preparing an electrolytic cell, wherein an anode is an electrode with iridium oxide loaded on carbon paper, a cathode is an electrode with the prepared transition element composite copper-based metal telluride catalyst loaded on the carbon paper, the loading capacity is 1mg/cm & lt 2 & gt, a reference electrode is a saturated Ag/AgCl electrode, a catholyte adopts potassium bicarbonate, the concentration range is 0.2-1mol/L, and an anolyte adopts potassium hydroxide, the concentration range is 0.5-10mol/L;
secondly, introducing carbon dioxide gas into the electrolytic cell, wherein the reduction potential is-0.25 VvsRHE, the reaction time is 20-50min, and the concentration of carbon dioxide is more than 70%.
The invention has the advantages of
(1) The products generated in the reduction process of the carbon dioxide are various, and the subsequent fussy separation and purification steps increase the industrialization difficulty of the carbon dioxide. For this reason, the higher the single selectivity of the product, the better. Moreover, the catalyst for reducing carbon dioxide into a dicarbonic product is single in selection and slightly deficient in stability. Therefore, improving the selectivity and stability of the reduction of carbon dioxide to a dicarbonic product is an important indicator of the reduction effect of the catalyst material. The invention provides a transition metal composite copper-based telluride catalyst, which has high selectivity of a reduction product, low overpotential and large catalytic current, and when the reduction potential is-0.25 VvsRHE, the main product is acetic acid which is far higher than the level of most of the existing reported catalysts.
(2) The catalyst has good stability, and the LSV curve change before and after the cycle is extremely small and is 50mA/cm after 30000 cycles of cyclic voltammetry 2 At current density of (D), Δ V<50mV。
Drawings
FIG. 1 Scanning Electron Microscope (SEM) image of a composite metal telluride catalyst prepared in example 1;
figure 2 graph comparing faradaic efficiency of acetic acid at different constant potentials for example 1, example 4 and comparative examples 2, 3;
FIG. 3 comparative plot of linear voltammograms of examples 1, 2, 3, 4 and comparative example 1;
fig. 4 comparative plot of LSV before and after 30000 cycles of CV cycle for example 1.
Detailed Description
The following embodiments of the present invention will be described in detail with reference to the accompanying drawings and examples, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Faradaic efficiency is the ratio of the number of transferred charges corresponding to the product to the total number of consumed charges; the yield is the ratio of the corresponding mass of the product to the total product mass.
EXAMPLE 1 catalyst CuCoTe 2
(1) Preparing a solution A, dissolving 1mmol of cobalt acetate and 1mmol of copper acetate in 25ml of deionized water, then adding 4mmol of tartaric acid, and dropwise adding ammonia water to keep the pH value of the solution at about 10;
(2) Preparation of solution B, 2mmol of TeO 2 Dissolving the powder in 4mmol tartaric acid solution, adding dropwise ammonia water to maintain pH at about 10, heating in 80 deg.C water bath for 1 hr to obtain TeO 2 Completely dissolving the powder;
(3) Slowly pouring the solution B into the solution A, and slowly adding a sodium borohydride solution with the concentration of 0.5mol/L at the same time, wherein the addition amount of the sodium borohydride is 1mol, and finally obtaining CuCoTe 2 A mixed nanoparticle;
(4) The obtained CuCoTe is used 2 The nano particles are centrifugally washed three times by deionized water, washed once by ethanol and then dried for 4 hours at 80 ℃ under the vacuum condition to obtain the final CuCoTe 2 And (3) compounding a catalyst.
FIG. 1 shows CuCoTe 2 Scanning Electron Microscope (SEM) image of the catalyst, it can be seen that the nanoparticlesThe size distribution of the particles is relatively uniform, the nano particles are relatively round, and relatively, the specific surface area is larger and more active sites are exposed, so that the reaction activity of the catalyst is facilitated.
EXAMPLE 2 catalyst Cu 1.5 Co 0.5 Te 2
(1) Preparing a solution A, dissolving 0.5mmol of cobalt acetate and 1.5mmol of copper acetate in 25ml of deionized water, then adding 4mmol of tartaric acid, and dropwise adding ammonia water to keep the pH value of the solution at about 10;
(2) Preparation of solution B, 2mmol of TeO 2 Dissolving the powder in 4mmol tartaric acid solution, adding dropwise ammonia water to maintain pH at about 10, heating in 80 deg.C water bath for 1 hr to obtain TeO 2 Completely dissolving the powder;
(3) Slowly pouring the solution B into the solution A, and simultaneously slowly adding a sodium borohydride solution with the concentration of 0.5mol/L, wherein the addition amount of the sodium borohydride is 1mol, and finally obtaining the mixed Cu 1.5 Co 0.5 Te 2 The nanoparticles of (1);
(4) Centrifugally washing the obtained nano particles with deionized water for three times, washing with ethanol for one time, and drying at 80 ℃ for 4 hours under a vacuum condition to obtain the final Cu 1.5 Co 0.5 Te 2 And (3) compounding a catalyst.
EXAMPLE 3 catalyst Cu 0.5 Co 1.5 Te 2
(1) Preparing a solution A, dissolving 1.5mmol of cobalt acetate and 0.5mmol of copper acetate in 25ml of deionized water, then adding 4mmol of tartaric acid, and dropwise adding ammonia water to keep the pH value of the solution at about 10;
(2) Preparation of solution B, 2mmol of TeO 2 Dissolving the powder in 4mmol tartaric acid solution, adding dropwise ammonia water to maintain pH at about 10, heating in 80 deg.C water bath for 1 hr to obtain TeO 2 Completely dissolving the powder;
(3) Slowly pouring the solution B into the solution A, and simultaneously slowly adding a sodium borohydride solution with the concentration of 0.5mol/L, wherein the addition amount of sodium borohydride is 1mol;
(4) Centrifugally washing the obtained nano particles with deionized water for three times, and then washing with ethanol for one time, thenThen drying for 4h at 80 ℃ under the vacuum condition to obtain the final Cu 0.5 Co 1.5 Te 2 And (4) synthesizing a catalyst.
EXAMPLE 4 preparation of catalyst CuNiTe 2
The same production method as in example 1 was used except that in the first step, cobalt acetate in the solution for production a was replaced with nickel acetate.
Comparative example 1 catalyst CuCoSe 2
Prepared by the same preparation method as in example 1, except that in the second step, seO is used for preparing the solution B 2 Replacement TeO 2 。
Comparative example 2 catalyst CuTe
(1) Preparing a solution A, dissolving 1mmol of copper acetate in 25ml of deionized water, then adding 2mmol of tartaric acid, and dropwise adding ammonia water to keep the pH value of the solution at about 10;
(2) Preparation of solution B, 1mmol of TeO 2 Dissolving the powder in 1mmol tartaric acid solution, adding dropwise ammonia water to maintain pH at about 10, heating in 80 deg.C water bath for 1 hr to obtain TeO 2 Completely dissolving the powder;
(3) Slowly pouring the solution B into the solution A, and simultaneously slowly adding a sodium borohydride solution with the concentration of 0.5mol/L, wherein the addition amount of sodium borohydride is 1mol, so as to finally obtain CuTe mixed nano particles;
(4) And centrifugally washing CoTe nano particles with deionized water for three times, washing with ethanol for one time, and drying at 80 ℃ for 4 hours under a vacuum condition to obtain the final CuTe nano catalyst.
Comparative example 3 catalyst ZnCuTe 2
The same preparation method as in example 1 was employed except that cobalt acetate in the preparation a solution was replaced with zinc acetate.
Respectively taking 2.25mg of catalyst powder prepared in the examples or the comparative examples, 1.1mg of carbon black, 30uL 5wt% nafion solution, 285uL of ethanol and 285uL of deionized water, mixing, performing ultrasonic treatment for 30min to obtain uniformly dispersed catalyst ink, dropwise adding the catalyst ink onto hydrophobic carbon paper with the area of 1.5cmX 1.5cm, uniformly dispersing, and drying to obtain a cathode;
the obtained cathode was tested by Flow-Cell, and the electrolyte was 0.2M KHCO 3 The solution is firstly activated by CV, and is tested at constant potential, wherein the test potential is-0.25, -0.4, -0.6V vs RHE. The gas phase product was analyzed by Gas Chromatography (GC), the liquid phase product was dissolved in the electrolyte, and quantitative analysis was performed by nuclear magnetism after collecting the electrolyte.
Verification 1
The faradaic efficiencies of acetic acid under different constant potential conditions were tested for example 1, example 4, comparative examples 2 and 3 and the results are shown in table 1 and fig. 2.
TABLE 1 comparison of faradaic efficiencies of acetic acids in examples and comparative examples under different potential conditions
Figure BDA0003887416580000071
Table 1 and fig. 2 compare the faradaic efficiencies and relative concentrations of acetic acid under different potential conditions for example 1, example 4, comparative example 2, and comparative example 3. It can be seen that the CuTe catalyst of comparative example 2 has poor selectivity of acetic acid product under low/high potential conditions; and CuCoTe prepared in example 1 and example 4 2 Composite nanocatalyst and CuNiTe 2 The composite nano catalyst has high-content electronegativity anions, so that the adsorption capacity of metal ions on a CO intermediate can be improved, the leaching of Te and the degradation of the catalyst are prevented by a Cu/Co-Te bond and a Cu/Ni-Te bond, and the stability of the Cu-based catalyst is improved to a certain extent by introducing Co and Ni. The experiment proves that CuCoTe 2 h and CuNiTe 2 The two catalysts show synergistic effect, not only improves the selectivity of acetic acid/formic acid, but also greatly improves the defect of insufficient stability of a pure Cu catalyst. And ZnCuTe prepared in comparative example 3 2 The faradaic efficiency of (a) is low relative to examples 1 and 4, and selectivity to acetic acid is relatively worse, but selectivity is better relative to comparative example 2.
Authentication 2
The linear voltammetry performance curves of examples 1, 2, 3, 4 and comparative example 1 were tested and the results are shown in table 2 and fig. 3.
TABLE 2 examples and comparative examples at a current density of 50mA cm -2 Potential comparison of time
sample Potential @50mA cm -2 (V vs RHE)
Example 1 -0.218
Example 2 -0.319
Example 3 -0.367-
Example 4 -0.252
Comparative example 1 0.284
The LSV curves of the catalysts were compared and the comparison is shown in table 2 and fig. 3; this demonstrates that the effect of the atomic ratio content of Cu and Co on the catalyst performance is large, with Cu/Co =1, the composite catalyst has a lower initial potential, a smaller overpotential and a smaller tafel slope. This shows that in the interval of Cu/Co =0.3-3, the synergistic effect of the Cu/Co ratio is more obvious near 1, and the effect of 1+1 > 2 is reflected. Next, coCuTe was compared 2 And CoCuSe 2 The comparison of the two performances is moreThe catalyst has low overpotential and smaller Tafel slope, and has more excellent catalytic performance. This indicates that the element Te with stronger electronegativity is more favorable for improving the electron energy density of the transition metal, thereby increasing the catalytic activity thereof.
Authentication 3
The stability test was evaluated using the LSV performance curves before and after cyclic voltammetry, compared to the LSV curves before and after 30000 cycles of the catalyst of example 1, and the results are shown in fig. 4.
As shown in FIG. 4, after 30000 cycles of cyclic voltammetry, the LSV curve before and after the cycle has very little change at 50mA/cm 2 At current density of (D), Δ V<50mV, which fully illustrates the excellent stability of the catalyst.
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (10)

1. A transition metal composite copper-based catalyst is characterized in that: the chemical formula of the catalyst is Cu x M 2-x Te 2 Wherein subscripts denote atomic ratios between elements, x =0-2 (0 is not included), and M is at least one element selected from the group consisting of transition metals Ni, co, mn, fe, zn.
2. The transition metal composite copper-based catalyst according to claim 1, wherein: and M is at least one of Ni or Co elements.
3. A method for producing a transition metal composite copper-based catalyst according to claim 1 or 2, characterized by comprising:
first, a solution A is prepared by dissolving a Cu metal salt and a M metal salt in deionized water, then mixing with tartaric acid, controlling the pH with ammonia to form M 2+ Complexes with ammonium tartrate;
secondly, preparing solution B, dissolving tellurium oxide powder in tartaric acid, heating in water bath for a certain time, controlling the pH value of the solution by ammonia water to form Te 4+ Complexes with ammonium tartrate;
thirdly, slowly pouring the solution B prepared in the second step into the solution A prepared in the first step, and slowly adding the sodium borohydride solution at the same time, and stirring at a certain rotating speed to finally see that the suspended Cu exists x M 2-x Te 2 Nanoparticle generation;
fourthly, after the reaction is finished, performing centrifugal treatment on the product, washing the product by deionized water and ethanol in sequence, and drying the product under inert atmosphere or vacuum condition to obtain the final Cu x M 2-x Te 2 Catalyst nanoparticles.
4. The method for producing a transition metal composite copper-based catalyst according to claim 3, characterized in that: in the first step, M = at least one element selected from the group consisting of Ni, co, mn, fe, zn.
5. The method for producing a transition metal composite copper-based catalyst according to claim 3, characterized in that: and in the first step, M = Ni and Co.
6. The process for producing a transition metal composite copper-based catalyst according to claim 4 or 5, characterized in that: the copper metal salt and the M metal salt are acetate, nitrate or sulfate.
7. The process for producing a transition metal composite copper-based catalyst according to claim 4 or 5, characterized in that: the concentration ranges of the M metal salt and the copper metal salt are respectively 0.01mol/L-0.1mol/L.
8. The process for producing a transition metal composite copper-based catalyst according to claim 4 or 5, wherein: the pH in the first and second steps is 9-10.
9. Use of the transition metal composite copper-based catalyst according to claim 1 or 2 in the process of preparing acetic acid by electrocatalytic reduction of carbon dioxide.
10. A method for preparing acetic acid by electrocatalysis of carbon dioxide, which is characterized by comprising the following steps:
preparing an electrolytic cell by adopting a three-electrode system, wherein a cathode adopts an electrode which is formed by loading the transition metal composite copper-based catalyst in the claim 1 or 2 on carbon paper;
secondly, introducing carbon dioxide gas into the electrolytic cell, wherein the reduction potential is-0.25 VvsRHE, and the reaction time is 20-50min.
CN202211251789.9A 2022-10-12 2022-10-12 Transition metal composite copper-based catalyst, and preparation method and application thereof Pending CN115433957A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211251789.9A CN115433957A (en) 2022-10-12 2022-10-12 Transition metal composite copper-based catalyst, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211251789.9A CN115433957A (en) 2022-10-12 2022-10-12 Transition metal composite copper-based catalyst, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115433957A true CN115433957A (en) 2022-12-06

Family

ID=84250361

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211251789.9A Pending CN115433957A (en) 2022-10-12 2022-10-12 Transition metal composite copper-based catalyst, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115433957A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116676615A (en) * 2023-07-21 2023-09-01 深圳先进技术研究院 For electrocatalytic CO 2 Gas-phase diffusion electrode for reducing formic acid, preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116676615A (en) * 2023-07-21 2023-09-01 深圳先进技术研究院 For electrocatalytic CO 2 Gas-phase diffusion electrode for reducing formic acid, preparation method and application
CN116676615B (en) * 2023-07-21 2024-05-17 深圳先进技术研究院 For electrocatalytic CO2Gas-phase diffusion electrode for reducing formic acid, preparation method and application

Similar Documents

Publication Publication Date Title
Chen et al. Amination strategy to boost the CO 2 electroreduction current density of M–N/C single-atom catalysts to the industrial application level
Zhou et al. Atomic regulation of metal–organic framework derived carbon-based single-atom catalysts for the electrochemical CO 2 reduction reaction
CN108745340A (en) A kind of preparation method and application of carbon load bismuth nanoparticle catalyst
CN113437314B (en) Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof
JP7434372B2 (en) Method for producing nickel-iron catalyst material, use in oxygen evolution reaction, method for producing hydrogen and/or oxygen by water electrolysis, and method for producing liquid solar fuel
CN113026047B (en) Method for synthesizing methanol by electrochemically catalyzing and converting carbon dioxide
CN110560075B (en) Nano Cu-Eu alloy catalyst with core-shell structure and preparation method and application thereof
CN116139867B (en) MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof
CN111841616A (en) Preparation method of bifunctional atom dispersed iron-nitrogen coordination material catalyst
CN115433957A (en) Transition metal composite copper-based catalyst, and preparation method and application thereof
CN114243030A (en) Preparation method and application of doping type tubular cobalt-based material based on template-free method
CN109012673B (en) Preparation method and application of oxygen evolution catalyst
CN114808026B (en) Two-dimensional metal organic framework nano-sheet supported noble metal monoatomic catalyst and preparation method and application thereof
CN113649054B (en) NiFe@NC/Al-SrTiO 3 Composite photocatalyst and application thereof
CN113774425B (en) Preparation method and application of Ru-modified FeCo @ NF electrocatalyst
CN115404499A (en) Copper-silver composite catalyst and preparation method and application thereof
CN111244481B (en) Preparation method of fulvic acid lamella-based MOFs-derived electrocatalyst material
CN114774983A (en) Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof
CN113881955A (en) Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof
CN115491699A (en) Nano copper-based catalyst, preparation method thereof and application of nano copper-based catalyst in electrocatalytic reduction of carbon dioxide and carbon monoxide
Al-Rowaili et al. Electrochemical reduction of carbon dioxide to methanol using metal-organic frameworks and non-metal-organic frameworks catalyst
CN112376079A (en) Preparation method of bimetallic phosphide material for electrocatalytic hydrogen evolution
CN115650317B (en) Amorphous polymetallic boride catalysts and their use
CN115475936B (en) BiAg nano alloy catalyst and preparation method and application thereof
CN114318408B (en) Self-supporting Cu 3 P-based heterojunction electrocatalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination