CN110560075A - Nano Cu-Eu alloy catalyst with core-shell structure and preparation method and application thereof - Google Patents

Nano Cu-Eu alloy catalyst with core-shell structure and preparation method and application thereof Download PDF

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CN110560075A
CN110560075A CN201910909173.8A CN201910909173A CN110560075A CN 110560075 A CN110560075 A CN 110560075A CN 201910909173 A CN201910909173 A CN 201910909173A CN 110560075 A CN110560075 A CN 110560075A
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alloy catalyst
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surfactant
alcohol
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CN110560075B (en
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王志江
单晶晶
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Harbin Institute of Technology
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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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B01J35/33—
    • B01J35/396—
    • 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

Abstract

A nano Cu-Eu alloy catalyst with a core-shell structure and a preparation method and application thereof relate to a Cu-based alloy catalytic material and a preparation method and application thereof. The invention aims to solve the problem of CO catalytic reduction by using the existing Cu2Produce CH4Presence of CH4the problems of poor Faraday efficiency and low current density. The nanometer Cu-Eu alloy catalyst with a core-shell structure is compounded by taking Cu as a core and taking Cu-Eu alloy as a shell. The preparation method comprises the following steps: firstly, weighing; secondly, preparing a surfactant alcoholic solution; thirdly, preparing a precursor salt solution; fourthly, reduction; and fifthly, separating, cleaning and drying to obtain the core-shell structure nano Cu-Eu alloy catalyst. It is used as raw material for preparing working electrode for electrocatalytic reduction of CO2Manufacture of CH4. The advantages are that: for CO2Electrocatalytic reductionNative CH4Has high activity and selectivity and good stability.

Description

Nano Cu-Eu alloy catalyst with core-shell structure and preparation method and application thereof
Technical Field
The invention relates to a Cu-based alloy catalytic material and a preparation method and application thereof.
background
Since the industrial revolution, the human society has rapidly developed, and the demand for fossil energy such as coal, oil, natural gas, etc. has been increasing. Excessive mining and use of these fossil fuels not only leads to a stressful energy crisis, but also causes atmospheric CO2the concentration rises rapidlyhigh and thus bring about a range of global climate change. But CO as the most predominant greenhouse gas2CO, not at all, in the fields of green chemistry and organic synthesis2Is a chemical raw material with rich sources, low price, easy obtaining, no toxicity and no harm. To reduce greenhouse gas emissions while effectively relieving energy demand, it is desirable to utilize CO2As a hydrogen storage medium, converting it to CH3OH、CH4、C2H4the special fuel can be named as one arrow double carving, and has great development potential. Wherein carbon dioxide is converted to methane (CO)2+4H2→CH4+2H2O) converts a molecule that is difficult to store and transport (hydrogen) into a molecule that is relatively easy to store (methane), CH compared to hydrogen4easy liquefaction allows for safer storage and transport. CO 22the resource recycling has various ways, and methods such as catalytic hydrogenation, photocatalytic reduction, electrocatalytic reduction and the like are available. In which the CO is reduced electrocatalytically2Mild reaction conditions, no need of high temperature and high pressure, flexible equipment operation, high energy utilization efficiency, and can regulate and control product selectivity and reaction speed by simply changing electrolysis conditions, so the method is considered to be CO2the transformation technology with the most development prospect in resource utilization.
At present, electrocatalysis can not reach the standard of industrial production, and one of the main reasons is that the performance of the catalyst is poor. Therefore, the desire to achieve high performance electrocatalysis is dependent on the development of cathode materials. The common catalysts at present are: metal catalysts, non-metal catalysts, and molecular catalysts. Among them, the metal catalyst has been widely studied because of its mild reaction conditions, simple operation and many active sites. Compared with a single metal catalyst, the alloy catalyst is flexible in design, various in types and various in structure, often shows more excellent catalytic performance than the single metal forming the alloy catalyst, and is favored by researchers in the field of energy catalysis. In CO2In the electrocatalytic reduction reaction, the alloying process regulates and controls the binding energy of a reaction intermediate on the surface of the catalyst by changing the structure and the components of the catalyst, thereby achieving the purposes of reducing the reaction overpotential and improving the selectivity of a specific productthe purpose is. Thus, Cu-based binary and even multi-element alloy electrocatalysts are becoming CO2Hot spots in the RR domain.
Disclosure of Invention
The invention aims to solve the problem of CO catalytic reduction by using the existing Cu2Produce CH4Presence of CH4The problems of poor Faraday efficiency and low current density; and provides a nano Cu-Eu alloy catalyst with a core-shell structure and a preparation method and application thereof.
A nano Cu-Eu alloy catalyst with a core-shell structure is compounded by taking Cu as a core and taking Cu-Eu alloy as a shell.
A preparation method of a nano Cu-Eu alloy catalyst with a core-shell structure is specifically completed according to the following steps:
Firstly, weighing: weighing a surfactant, an alcohol-containing organic solvent, a copper salt and a europium salt; the method comprises the following steps of (1) equally dividing a surfactant into a surfactant I and a surfactant II, and sequentially dividing an alcohol-containing organic solvent into the alcohol-containing organic solvent I and the alcohol-containing organic solvent II according to a volume ratio of 18: 4; the volume ratio of the substance of the surfactant to the alcohol-containing organic solvent is (0.002-2) mmol:22 mL; the molar ratio of the copper element in the copper salt to the europium element in the europium salt is 1-9: 1; the volume ratio of the sum of the amounts of the copper element and the europium element in the copper salt to the alcohol-containing organic solvent II is (0.02-0.2) mmol:22 mL;
secondly, preparing a surfactant alcoholic solution: dissolving a surfactant I in an alcohol-containing organic solvent I to obtain a surfactant alcohol solution;
Thirdly, preparing a precursor salt solution: dissolving a surfactant II, a copper salt and a europium salt in an alcohol-containing organic solvent II to obtain a precursor salt solution;
Fourthly, reduction: stirring and heating the surfactant alcoholic solution obtained in the step two to 220-300 ℃; adding the precursor salt solution obtained in the third step into the surfactant alcoholic solution obtained in the second step at an addition rate of 0.05-0.3 mL/s, stirring and reacting at the temperature of 220-300 ℃ for 5-60 min, and cooling to room temperature at a cooling rate of 5-40 ℃/min after the reaction is finished to obtain a reaction product;
Fifthly, separation, cleaning and drying: and (3) carrying out centrifugal separation on the reaction product, sequentially washing the separated solid by using acetone, absolute ethyl alcohol and ultrapure water, washing for 1-3 times respectively to obtain a washed solid, and drying the washed solid in vacuum at room temperature for 12-24 hours to obtain the core-shell structure nano Cu-Eu alloy catalyst.
Application of nano Cu-Eu alloy catalyst with core-shell structure as raw material for preparing working electrode for electrocatalytic reduction of CO2Manufacture of CH4。
the invention has the advantages that:
Firstly, the rare earth resources in China are rich in reserves, have the advantages of complete mineral species and rare earth elements, reasonable rare earth grade and mineral site distribution and the like, but are used for Cu-based alloying and electrocatalytic reduction of CO2realization of CO2To CH4Has not been reported. The nano Cu-Eu alloy catalyst with the core-shell structure prepared by the invention is used for CO2Electrocatalytic reduction of CH4Has higher activity and selectivity.
Secondly, in the nano Cu-Eu alloy catalyst with the core-shell structure, Cu-Eu alloy is uniformly distributed outside Cu particles to form an amorphous shell layer, no agglomeration occurs among the alloy particles, and the stability is good;
Thirdly, the nano Cu-Eu alloy catalyst with the core-shell structure prepared by the invention shows obvious alloy effect, and the addition of Eu effectively improves CH4the product selectivity of (a) while inhibiting the formation of other products; when the molar ratio of the copper element to the europium element in the nano Cu-Eu alloy catalyst is 9:1, the catalyst has CH when the potential of the working electrode relative to the reference electrode is-2V4The highest Faraday efficiency can reach 74 percent, which is 3.5 times that of the Cu nano particles.
drawings
FIG. 1 is a TEM image of Cu nanoparticles prepared in example 4;
FIG. 2 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1;
FIG. 3 is an HR-TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1;
FIG. 4 is an EDS-Mapping chart of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1;
FIG. 5 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2;
FIG. 6 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3;
FIG. 7 is an XRD pattern, in which a represents a standard card pattern of XRD of metallic copper (pdf: 04-0836), b represents an XRD pattern of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, c represents an XRD pattern of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, d represents an XRD pattern of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3, and e represents an XRD pattern of the Cu nanoparticles prepared in example 4;
FIG. 8 is a XPS high resolution spectrum of Cu element, wherein a) shows the XPS high resolution spectrum of Cu element of Cu nanoparticle prepared in example 4, b) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, c) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, and d) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 3;
FIG. 9 is a high resolution XPS spectrum of Eu, wherein a) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, b) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, and c) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3;
FIG. 10 is CH4A in the current density chart, a represents CH of the Cu nanoparticles prepared in example 44B represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14C represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24D represents the product of example 3CH of prepared nano Cu-Eu alloy catalyst with core-shell structure4A current density map of (a);
FIG. 11 is CH4A represents CH of the Cu nanoparticles prepared in example 44Faraday efficiency graph, b represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14Faraday efficiency graph, c represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24Faraday efficiency graph, d represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 34Faraday efficiency plot;
FIG. 12 is CH4Wherein a represents CH of the Cu nanoparticles prepared in example 44B represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14C represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24D represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 34mass activity map of (1).
Detailed Description
The first embodiment is as follows: the embodiment is a core-shell structure nano Cu-Eu alloy catalyst, which is compounded by taking Cu as a core and Cu-Eu alloy as a shell.
the Cu-based alloy catalytic material is roughly divided into three types according to the electronegativity of the composite elements: the first type is that the electronegativity of the element exceeds 35% of that of copper, and the reaction easily transfers more than 12 electrons to obtain a C2 organic compound. The second type is an element with electronegativity equivalent to that of Cu, 2 electrons are easy to transfer in reaction, and the generated product is mainly CO. The third type is elements with electronegativity much lower than 35% of copper, as is typical for rare earth elements. Rare earth is alloyed with copper, such as Cu-La alloy and Cu-Eu alloy, and associated CO is made2Reduction test shows that the Cu-La alloy produces CH4The performance of the catalyst is not good, and the nano Cu-Eu alloy catalyst with the core-shell structure has better selectivity on methane.
The second embodiment is as follows: the embodiment is a preparation method of a nano Cu-Eu alloy catalyst with a core-shell structure, which is specifically completed by the following steps:
firstly, weighing: weighing a surfactant, an alcohol-containing organic solvent, a copper salt and a europium salt; the method comprises the following steps of (1) equally dividing a surfactant into a surfactant I and a surfactant II, and sequentially dividing an alcohol-containing organic solvent into the alcohol-containing organic solvent I and the alcohol-containing organic solvent II according to a volume ratio of 18: 4; the volume ratio of the substance of the surfactant to the alcohol-containing organic solvent is (0.002-2) mmol:22 mL; the molar ratio of the copper element in the copper salt to the europium element in the europium salt is 1-9: 1; the volume ratio of the sum of the amounts of the copper element and the europium element in the copper salt to the alcohol-containing organic solvent II is (0.02-0.2) mmol:22 mL;
Secondly, preparing a surfactant alcoholic solution: dissolving a surfactant I in an alcohol-containing organic solvent I to obtain a surfactant alcohol solution;
Thirdly, preparing a precursor salt solution: dissolving a surfactant II, a copper salt and a europium salt in an alcohol-containing organic solvent II to obtain a precursor salt solution;
Fourthly, reduction: stirring and heating the surfactant alcoholic solution obtained in the step two to 220-300 ℃; adding the precursor salt solution obtained in the third step into the surfactant alcoholic solution obtained in the second step at an addition rate of 0.05-0.3 mL/s, stirring and reacting at the temperature of 220-300 ℃ for 5-60 min, and cooling to room temperature at a cooling rate of 5-40 ℃/min after the reaction is finished to obtain a reaction product;
Fifthly, separation, cleaning and drying: and (3) carrying out centrifugal separation on the reaction product, sequentially washing the separated solid by using acetone, absolute ethyl alcohol and ultrapure water, washing for 1-3 times respectively to obtain a washed solid, and drying the washed solid in vacuum at room temperature for 12-24 hours to obtain the core-shell structure nano Cu-Eu alloy catalyst.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: in the first step, the surfactant is sodium dodecyl benzene sulfonate, PVP K30 or CTAB (cetyl trimethyl ammonium bromide). The rest is the same as the second embodiment.
PVP-K30 is one of the polyvinylpyrrolidone products, and has a K value of 30.
The fourth concrete implementation mode: the present embodiment differs from the second or third embodiment in that: in the step one, the copper salt is Cu (CH)3COO)2、CuCl2·2H2O or Cu (NO)3)2·3H2And O. The other embodiments are the same as the second or third embodiment.
the fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: in the first step, the europium salt is Eu (NO)3)3·5H2O、EuCl3·6H2O or Eu (CH)3COO)3·nH2and O. The other points are the same as those in the second to fourth embodiments.
the sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: in the first step, the alcohol-containing organic solvent is ethylene glycol, diethylene glycol or triethylene glycol. The rest is the same as the second to fifth embodiments.
The seventh embodiment: the embodiment is an application of a nano Cu-Eu alloy catalyst with a core-shell structure, wherein the nano Cu-Eu alloy catalyst with the core-shell structure is used as a raw material for preparing a working electrode for electrocatalytic reduction of CO2Manufacture of CH4。
the specific preparation method of the working electrode comprises the following steps:
Firstly, adding Nafion into absolute ethyl alcohol, uniformly mixing, adding a nano Cu-Eu alloy catalyst with a core-shell structure and carbon black, and performing ultrasonic oscillation for 30-60 min to obtain an ink-like mixed solution; polishing the glassy carbon electrode on chamois leather by using 500nm of aluminum oxide powder and 50nm of aluminum oxide powder in sequence until the mirror surface is smooth, ultrasonically cleaning the electrode for 1-3 times by using deionized water, then acoustically cleaning the electrode for 1-3 times by using ethanol, and drying the electrode to obtain a clean glassy carbon electrode; ③ according to the load of the nano Cu-Bi alloy catalyst is 0.04mg/cm2～0.08mg/cm2Transferring the ink-shaped mixed liquid drop on a clean glassy carbon electrode for a plurality of times by using a liquid transfer gun, wherein the single transfer amount of the liquid transfer gun is 2-3 mu L, and dripping the liquid drop from the second timeAnd (3) starting to wait for the natural drying of the ink-like mixed solution on the surface of the clean glassy carbon electrode, and then carrying out next transferring and dropwise adding to obtain the working electrode.
the electrocatalytic reduction of CO2Manufacture of CH4The specific process is as follows:
Firstly, assembling: an H-shaped three-electrode electrolytic cell is adopted, a cathode cell and an anode cell of the H-shaped three-electrode electrolytic cell are separated by a Nafion 117 proton ion exchange membrane, and KHCO with the concentration of 0.5mol/L is adopted3The aqueous solution is used as electrolyte and KHCO with the concentration of 0.5mol/L is adopted3Pouring an electrolyte into an H-shaped three-electrode electrolytic cell by taking an aqueous solution as the electrolyte, wherein the electrolyte in a cathode cell is 20mL, the electrolyte in an anode cell and the electrolyte in a cathode cell are kept horizontal, a platinum sheet is used as a counter electrode, the counter electrode is arranged in the anode cell of the H-shaped three-electrode electrolytic cell, a working electrode and a reference electrode are arranged in the cathode cell of the H-shaped three-electrode electrolytic cell, the reference electrode is a saturated KCl Ag/AgCl electrode, a cathode region air inlet and a cathode region air outlet are formed in the cathode cell, and CO is introduced into a CO region2The air inlet pipe extends to the position below the liquid level of the electrolyte through the air inlet of the cathode area, the air outlet of the cathode area is communicated with the gas collecting device, 1 magnetic stirring rotor is placed in the cathode pool, the cathode pool is sealed by adopting a sealing piece, and the contact positions of the working electrode and the reference electrode with the sealing piece are sealed to obtain the electro-catalytic reduction CO2Manufacture of CH4A device; ② electrocatalytic reduction: the gas flow rate is 10-30 mL/min for passing through CO2Introducing carbon dioxide gas into the electrolyte of the cathode pool through the gas inlet pipe, starting the power supply and the magnetic stirrer after the introduction time is 10-60 min, and carrying out CO stirring at the magnetic stirring rotating speed of 500-1200 r/min and under the potential of the working electrode relative to the reference electrode of-1.2V-2.2V2The gas collecting device collects the gas generated by the reaction in the cathode pool through the gas outlet of the cathode area, namely the electrocatalytic reduction of CO is completed2Manufacture of CH4。
The working electrode prepared by the embodiment is simple to operate, the nano Cu-Eu alloy catalyst with the core-shell structure does not need to be pretreated, carbon black serving as a carrier does not need to be treated by strong acid and strong base, and the consumption of raw materials is low.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests were carried out to confirm the effects of the present invention
Example 1: a preparation method of a nano Cu-Eu alloy catalyst with a core-shell structure is specifically completed according to the following steps:
Firstly, weighing: weighing a surfactant, an alcohol-containing organic solvent, a copper salt and a europium salt; the method comprises the following steps of (1) equally dividing a surfactant into a surfactant I and a surfactant II, and sequentially dividing an alcohol-containing organic solvent into the alcohol-containing organic solvent I and the alcohol-containing organic solvent II according to a volume ratio of 18: 4; the volume ratio of the substance of the surfactant to the alcohol-containing organic solvent is 0.02) mmol:22 mL; the molar ratio of the copper element in the copper salt to the europium element in the europium salt is 9: 1; the volume ratio of the sum of the contents of the copper element and the europium element in the copper salt to the alcohol-containing organic solvent II is 0.2mmol:22 mL; the surfactant is PVPK 30; the copper salt is Cu (CH)3COO)2(ii) a The europium salt is Eu (NO)3)3·5H2O; the alcohol-containing organic solvent is triethylene glycol;
Secondly, preparing a surfactant alcoholic solution: dissolving a surfactant I in an alcohol-containing organic solvent I to obtain a surfactant alcohol solution;
thirdly, preparing a precursor salt solution: dissolving a surfactant II, a copper salt and a europium salt in an alcohol-containing organic solvent II to obtain a precursor salt solution;
fourthly, reduction: stirring and heating the surfactant alcoholic solution obtained in the step two to 260 ℃; adding the precursor salt solution obtained in the third step into the surfactant alcoholic solution obtained in the second step at an addition rate of 0.25mL/s, stirring and reacting for 10min at the temperature of 260 ℃, and cooling to room temperature at a cooling rate of 40 ℃/min after the reaction is finished to obtain a reaction product;
Fifthly, separation, cleaning and drying: and (3) carrying out centrifugal separation on a reaction product, cleaning the separated solid for 1 time by using acetone, cleaning the separated solid for 3 times by using absolute ethyl alcohol, and finally cleaning the separated solid for 1 time by using ultrapure water to obtain a cleaned solid, and drying the cleaned solid in vacuum at room temperature for 24 hours to obtain the core-shell structured nano Cu-Eu alloy catalyst.
example 2: the present embodiment differs from embodiment 1 in that: the molar ratio of the copper element in the copper salt to the europium element in the europium salt in step one is 4:1, and the rest is the same as in example 1.
Example 3: the present embodiment differs from embodiment 1 in that: in the first step, the molar ratio of the copper element in the copper salt to the europium element in the europium salt is 1: 1. The rest is the same as in example 1.
example 4: the method for preparing the Cu nano particles is specifically completed according to the following steps:
Firstly, weighing: weighing a surfactant, an alcohol-containing organic solvent and copper salt; the method comprises the following steps of (1) equally dividing a surfactant into a surfactant I and a surfactant II, and sequentially dividing an alcohol-containing organic solvent into the alcohol-containing organic solvent I and the alcohol-containing organic solvent II according to a volume ratio of 18: 4; the volume ratio of the substance of the surfactant to the alcohol-containing organic solvent is 0.02) mmol:22 mL; the volume ratio of copper element in the copper salt to the alcohol-containing organic solvent II is 0.2mmol:22 mL; the surfactant is PVPK 30; the copper salt is Cu (CH)3COO)2(ii) a The alcohol-containing organic solvent is triethylene glycol;
secondly, preparing a surfactant alcoholic solution: dissolving a surfactant I in an alcohol-containing organic solvent I to obtain a surfactant alcohol solution;
Thirdly, preparing a precursor salt solution: dissolving a surfactant II and copper salt in an alcohol-containing organic solvent II to obtain a precursor salt solution;
Fourthly, reduction: stirring and heating the surfactant alcoholic solution obtained in the step two to 260 ℃; adding the precursor salt solution obtained in the third step into the surfactant alcoholic solution obtained in the second step at an addition rate of 0.25mL/s, stirring and reacting for 10min at the temperature of 260 ℃, and cooling to room temperature at a cooling rate of 40 ℃/min after the reaction is finished to obtain a reaction product;
Fifthly, separation, cleaning and drying: and (3) carrying out centrifugal separation on the reaction product, washing the separated solid for 1 time by using acetone, then washing for 3 times by using absolute ethyl alcohol, and finally washing for 1 time by using ultrapure water to obtain a washed solid, and drying the washed solid in vacuum at room temperature for 24 hours to obtain the Cu nano particles.
FIG. 1 is a TEM image of Cu nanoparticles prepared in example 4; it can be seen from fig. 1 that the Cu nanoparticles prepared in example 4 have significant agglomeration, the particles have no significant morphological features, and the average size is about 150 nm.
FIG. 2 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1; it can be seen from fig. 2 that after Eu is introduced by a one-step reduction method, the size of the nano Cu-Bi alloy catalyst prepared in example 2 is significantly reduced, the particles are relatively uniform, about 100nm, and the nano Cu-Bi alloy catalyst has better dispersibility; the sample exhibited a distinct core-shell structure.
FIG. 3 is an HR-TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1; as can be seen from fig. 3, the shell of the core-shell structured nano Cu — Eu alloy catalyst prepared in example 1 is an amorphous shell, the core inside has complete lattice stripes, and the lattice stripe distance is 0.209nm corresponding to the Cu (111) crystal plane.
FIG. 4 is an EDS-Mapping chart of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1; as can be seen from fig. 4, the distribution ranges of the Cu (yellow) element are almost completely overlapped, and the Eu (green) element is uniformly distributed in the shell layer.
FIG. 5 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2; it can be seen from fig. 5 that the morphology of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2 is consistent with that of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, except that the shell thickness is increased.
FIG. 6 is a TEM image of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3; it can be seen from fig. 6 that the morphology of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3 is consistent with that of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, except that the shell thickness is increased.
XRD tests were performed on the nano Cu-Eu alloy catalysts having the core-shell structure prepared in examples 1 to 3 and the Cu nanoparticles prepared in example 4, and the results are shown in FIG. 7 below, FIG. 7 is an XRD pattern, wherein a represents a standard card diagram of XRD of copper metal (pdf: 04-0836), in the figure, b represents the XRD pattern of the core-shell structure nano Cu-Eu alloy catalyst prepared in example 1, in the figure, c represents the XRD pattern of the core-shell structure nano Cu-Eu alloy catalyst prepared in example 2, in the figure, d represents the XRD pattern of the core-shell structure nano Cu-Eu alloy catalyst prepared in example 3, and e represents the XRD pattern of the Cu nanoparticles prepared in example 4, it can be seen from FIG. 7 that the diffraction peaks of all the prepared catalysts correspond to the (111), (200) and (220) crystal planes of Cu (PDF: 04-0836). In addition, the crystallinity of the sample becomes smaller as the shell thickness increases, which is consistent with the TEM results of fig. 2, 5 and 7; since Eu and Cu form an amorphous structure on the surface layer, no diffraction peak of Eu is observed in the spectrum.
FIG. 8 is a XPS high resolution spectrum of Cu element, wherein a) shows the XPS high resolution spectrum of Cu element of Cu nanoparticle prepared in example 4, b) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, c) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, and d) shows the XPS high resolution spectrum of Cu element of core-shell structured nano Cu-Eu alloy catalyst prepared in example 3; from FIG. 8, it can be seen that the core-shell structured nano Cu-Eu alloy catalysts prepared in examples 1, 2, and 3 have Cu particles in comparison with the Cu nanoparticles prepared in example 42+And Cu1+/0The peak moves to a higher binding energy of about 0.15eV, indicating that the copper transports electrons outward.
FIG. 9 is a high resolution XPS spectrum of Eu, wherein a) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, b) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 2, and c) represents the high resolution XPS spectrum of Eu in the core-shell structured nano Cu-Eu alloy catalyst prepared in example 3; as can be seen from fig. 9, Eu elements of the core-shell structured nano Cu-Eu alloy catalysts prepared in examples 2 and 3 are slightly red-shifted from the binding energy peak of Eu elements of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 1, probably because Eu obtains electrons.
Example 5: application of core-shell structure nano Cu-Eu alloy catalyst as raw material for preparing working electrode for electrocatalytic reduction of CO2；
The specific preparation method of the working electrode comprises the following steps:
Firstly, adding Nafion into absolute ethyl alcohol, uniformly mixing, adding a catalyst and carbon black, and performing ultrasonic oscillation for 45min to obtain an ink-like mixed solution; polishing the glassy carbon electrode on chamois leather by using 500nm of aluminum oxide powder and 50nm of aluminum oxide powder in sequence until the mirror surface is smooth, ultrasonically cleaning the electrode for 3 times by using deionized water, then acoustically cleaning the electrode for 3 times by using ethanol, and drying the electrode to obtain a clean glassy carbon electrode; thirdly, the load capacity of the nano Cu-Bi alloy catalyst is 0.06mg/cm2Transferring the ink-like mixed liquid on the clean glassy carbon electrode for a plurality of times by using a liquid transfer gun, wherein the single transfer amount of the liquid transfer gun is 2-3 mu L, and after the second dripping, performing the next transferring and dripping after naturally drying the ink-like mixed liquid on the surface of the clean glassy carbon electrode to obtain a working electrode; the catalyst was a nano Cu-Bi alloy catalyst prepared from example 1.
The electrocatalytic reduction of CO2Manufacture of CH4The specific process is as follows:
Firstly, assembling: an H-shaped three-electrode electrolytic cell is adopted, a cathode cell and an anode cell of the H-shaped three-electrode electrolytic cell are separated by a Nafion 117 proton ion exchange membrane, and KHCO with the concentration of 0.5mol/L is adopted3Pouring an electrolyte into an H-shaped three-electrode electrolytic cell by taking an aqueous solution as the electrolyte, wherein the electrolyte in a cathode cell is 20mL, the electrolyte in an anode cell and the electrolyte in a cathode cell are kept horizontal, a platinum sheet is used as a counter electrode, the counter electrode is arranged in the anode cell of the H-shaped three-electrode electrolytic cell, a working electrode and a reference electrode are arranged in the cathode cell of the H-shaped three-electrode electrolytic cell, the reference electrode is a saturated KCl Ag/AgCl electrode, a cathode region air inlet and a cathode region air outlet are formed in the cathode cell, and CO is introduced into a CO region2The air inlet pipe extends to the position below the liquid level of the electrolyte through the air inlet of the cathode region, and the air outlet of the cathode regionCommunicated with a gas collecting device, 1 magnetic stirring rotor is placed in a cathode pool, a sealing element is adopted to seal the cathode pool, and the contact positions of a working electrode and a reference electrode with the sealing element are sealed to obtain the electro-catalytic reduction CO2Manufacture of CH4A device; ② electrocatalytic reduction: passing CO at a gas flow rate of 20mL/min2carbon dioxide gas is introduced into the electrolyte of the cathode pool through the air inlet pipe, the rotating speed of magnetic stirring is 1200r/min, and CO is2Starting the electrochemical workstation after the introduction time is 30min, selecting the potential of the working electrode relative to the reference electrode to carry out CO treatment under the condition of-1.2V to-2.2V2The gas collecting device collects the gas generated by the reaction in the cathode pool through the gas outlet of the cathode area, namely the electrocatalytic reduction of CO is completed2Manufacture of CH4。
Example 6: the present embodiment is different from embodiment 5 in that: in the preparation process of the working electrode, the nano Cu-Eu alloy catalyst with the core-shell structure prepared in the embodiment 2 is adopted to replace the nano Cu-Eu alloy catalyst with the core-shell structure prepared in the embodiment 1. The rest is the same as in example 5.
Example 7 this example is different from example 5 in that: in the preparation process of the working electrode, the nano Cu-Eu alloy catalyst with the core-shell structure prepared in the embodiment 3 is adopted to replace the nano Cu-Eu alloy catalyst with the core-shell structure prepared in the embodiment 1. The rest is the same as in example 5.
Example 8 the example differs from example 5 in that: in the preparation process of the working electrode, the Cu nanoparticles prepared in the example 4 are adopted to replace the core-shell structure nano Cu-Eu alloy catalyst prepared in the example 1. The rest is the same as in example 5.
FIG. 10 is CH4A in the current density chart, a represents CH of the Cu nanoparticles prepared in example 44B represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14C represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24d represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 34FIG. 10 shows the current density of the sample in comparison with that of example 2,3 and 4, the core-shell structured nano Cu-Eu alloy catalyst pair CH prepared in example 14has the largest current density, which indicates it is for CH4The activity of (c) was highest.
FIG. 11 is CH4A represents CH of the Cu nanoparticles prepared in example 44Faraday efficiency graph, b represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14Faraday efficiency graph, c represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24Faraday efficiency graph, d represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 34Faraday efficiency graph, as seen from FIG. 11, the core-shell structure nano Cu-Eu alloy catalyst pair CH prepared in example 1 is referenced to the Cu nano catalyst prepared in example 44The highest selectivity, CH, at a potential of-2.0V of the working electrode relative to the reference electrode4The Faraday efficiency can reach 74%, which shows that it is to CH4The best selectivity is.
FIG. 12 is CH4Wherein a represents CH of the Cu nanoparticles prepared in example 44b represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 14C represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 24D represents CH of the core-shell structured nano Cu-Eu alloy catalyst prepared in example 34From FIG. 12, it can be seen that the nano Cu-Eu alloy catalyst having a core-shell structure prepared in example 1 is paired with CH, compared to the catalysts prepared in examples 2, 3, and 44Has the largest current density, which indicates it is for CH4The activity of (c) was highest.

Claims (7)

1. A nano Cu-Eu alloy catalyst with a core-shell structure is characterized in that the nano Cu-Eu alloy catalyst with the core-shell structure is compounded by taking Cu as a core and taking Cu-Eu alloy as a shell.
2. The preparation method of the core-shell structure nano Cu-Eu alloy catalyst according to claim 1, characterized in that the method is completed by the following steps:
Firstly, weighing: weighing a surfactant, an alcohol-containing organic solvent, a copper salt and a europium salt; the method comprises the following steps of (1) equally dividing a surfactant into a surfactant I and a surfactant II, and sequentially dividing an alcohol-containing organic solvent into the alcohol-containing organic solvent I and the alcohol-containing organic solvent II according to a volume ratio of 18: 4; the volume ratio of the substance of the surfactant to the alcohol-containing organic solvent is (0.002-2) mmol:22 mL; the molar ratio of the copper element in the copper salt to the europium element in the europium salt is 1-9: 1; the volume ratio of the sum of the amounts of the copper element and the europium element in the copper salt to the alcohol-containing organic solvent II is (0.02-0.2) mmol:22 mL;
secondly, preparing a surfactant alcoholic solution: dissolving a surfactant I in an alcohol-containing organic solvent I to obtain a surfactant alcohol solution;
Thirdly, preparing a precursor salt solution: dissolving a surfactant II, a copper salt and a europium salt in an alcohol-containing organic solvent II to obtain a precursor salt solution;
fourthly, reduction: stirring and heating the surfactant alcoholic solution obtained in the step two to 220-300 ℃; adding the precursor salt solution obtained in the third step into the surfactant alcoholic solution obtained in the second step at an addition rate of 0.05-0.3 mL/s, stirring and reacting at the temperature of 220-300 ℃ for 5-60 min, and cooling to room temperature at a cooling rate of 5-40 ℃/min after the reaction is finished to obtain a reaction product;
Fifthly, separation, cleaning and drying: and (3) carrying out centrifugal separation on the reaction product, sequentially washing the separated solid by using acetone, absolute ethyl alcohol and ultrapure water, washing for 1-3 times respectively to obtain a washed solid, and drying the washed solid in vacuum at room temperature for 12-24 hours to obtain the core-shell structure nano Cu-Eu alloy catalyst.
3. The method for preparing the core-shell structured nano Cu-Eu alloy catalyst according to claim 2, wherein the surfactant in the first step is sodium dodecyl benzene sulfonate, PVP K30 or CTAB.
4. the method for preparing the core-shell structured nano Cu-Eu alloy catalyst according to claim 2, wherein the copper salt in the first step is Cu (CH)3COO)2、CuCl2·2H2O or Cu (NO)3)2·3H2O。
5. The method for preparing nanometer Cu-Eu alloy catalyst with core-shell structure according to claim 2, wherein in step one, the europium salt is Eu (NO)3)3·5H2O、EuCl3·6H2O or Eu (CH)3COO)3·nH2O。
6. The method for preparing the core-shell structured nano Cu-Eu alloy catalyst according to claim 2, wherein the alcohol-containing organic solvent in the step one is ethylene glycol, diethylene glycol or triethylene glycol.
7. The application of the nano Cu-Eu alloy catalyst with the core-shell structure is characterized in that the nano Cu-Eu alloy catalyst with the core-shell structure is used as a raw material for preparing a working electrode for electrocatalytic reduction of CO2Manufacture of CH4。
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