CN115044929B - Hydrogen-containing metal zinc catalyst, preparation method and CO 2 Reduction application - Google Patents

Hydrogen-containing metal zinc catalyst, preparation method and CO 2 Reduction application Download PDF

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CN115044929B
CN115044929B CN202210705947.7A CN202210705947A CN115044929B CN 115044929 B CN115044929 B CN 115044929B CN 202210705947 A CN202210705947 A CN 202210705947A CN 115044929 B CN115044929 B CN 115044929B
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zinc catalyst
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CN115044929A (en
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夏川
罗赖昊
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University of Electronic Science and Technology of China
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Abstract

The invention disclosesA hydrogen-containing metal zinc catalyst, its preparation method and CO are disclosed 2 Reduction application, which belongs to the technical field of metal catalysts, wherein hydrogen atoms are contained in zinc metal lattice gaps of a hydrogen-containing metal zinc catalyst, and the size of the zinc metal lattice is increased by 0.1-2.0 percent compared with that of a standard zinc metal lattice; the preparation method comprises the following steps: and (2) placing the metal zinc sheet on a cathode of a high-pressure electrolytic cell, electrolyzing at a constant current density of-1 to-200 milliamperes per square centimeter under a high-pressure atmosphere of 0.1 to 8.0 megapascals, and cleaning and drying the treated zinc sheet to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet. The hydrogen-containing metal zinc catalyst can be applied to carbon dioxide electroreduction reaction to realize high-efficiency electrocatalytic reduction from carbon dioxide to formic acid.

Description

Hydrogen-containing metal zinc catalyst, preparation method and CO 2 Reduction application
Technical Field
The invention belongs to the technical field of metal catalysts, and particularly relates to a hydrogen-containing metal zinc catalyst, a preparation method and CO 2 And (4) reduction application.
Background
The carbon dioxide electric reduction reaction can convert carbon dioxide into high-value chemicals such as formic acid, carbon monoxide, ethylene, ethanol and the like, not only provides an effective means for realizing the aims of carbon neutralization and carbon peak reaching, but also can be used as an energy storage mode to help solve the problem of difficulty in grid connection of renewable energy power generation. Studies have shown that of the many products of the carbon dioxide reduction reaction, only carbon monoxide and formic acid are expected to achieve positive benefits in the commercial process in recent years. Therefore, the development of a catalyst for producing carbon monoxide and formic acid by the electro-reduction of carbon dioxide with high efficiency has been a research hotspot in the field. The results of the current studies clearly show that different metals exhibit a clear selectivity for a particular product. For example, carbon dioxide on metals such as zinc, gold, silver, etc. forms COOH intermediates by carbon end adsorption after activation, exhibiting high selectivity to carbon monoxide; carbon dioxide on metals such as lead, bismuth, tin and the like is activated to form a HCOO intermediate through oxygen terminal adsorption, thereby exhibiting high selectivity for formic acid. On the basis, the electronic structure of the catalyst is adjusted by methods such as alloy formation, the adsorption energy of COOH or HCOO is regulated, and the hydrogen evolution side reaction is inhibited, so that the method becomes a main strategy for improving the Faraday efficiency and the catalytic activity of carbon monoxide or formic acid.
However, due to the existence of a linear scale relationship in the catalytic theory, it is often difficult for an alloy catalyst to simultaneously achieve high selectivity and high activity, and the regulation capability of the electronic structure of the catalyst is also limited in a certain range. If the precise hydrogenation process of the carbon end or the oxygen end can be realized by controlling the property of the hydrogen species on the surface of the catalyst, the problem that the electronic structure of the catalyst is controlled is hopefully avoided, the limitation of an inherent metal element system is broken through, and the catalyst which is cheaper, has easily obtained raw materials and is environment-friendly is developed.
Disclosure of Invention
Aiming at the problem of selectivity regulation in the prior art, the invention provides a hydrogen-containing metal zinc catalyst, a preparation method and CO 2 The reduction application breaks through the traditional cognition that the zinc-based catalyst mainly produces carbon monoxide, realizes the high-selectivity electrocatalytic reduction from carbon dioxide to formic acid of the zinc-based catalyst, has mild preparation conditions and simple procedures, and is more suitable for large-scale subsequent production and application.
In order to achieve the above purpose, the invention provides the following technical scheme:
the hydrogen-containing metal zinc catalyst is characterized in that the size of a zinc metal lattice of the hydrogen-containing metal zinc is increased by 0.1-2.0% compared with that of a standard zinc metal lattice, and hydrogen atoms are contained in gaps of the zinc metal lattice.
Further, the hydrogen-containing metallic zinc catalyst has an isotropic crystal lattice stretching direction.
Further, the hydrogen atom content (mass fraction) in the hydrogen-containing metal zinc catalyst is 0.0001 to 0.002%.
The preparation method of the hydrogen-containing metal zinc catalyst is characterized by comprising the following steps:
step 1: placing a metal zinc sheet at the cathode end of a high-pressure electrolytic cell, and electrolyzing at a constant current with a current density of-1 to-200 milliamperes per square centimeter under a high-pressure atmosphere of 0.1 to 8.0 megapascals to obtain a treated zinc sheet;
step 2: and (3) cleaning the treated zinc sheet obtained in the step (1), and drying the zinc sheet by blowing in an inert atmosphere to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Further, the constant current electrolysis time in the step 1 is 0.5-10 hours, and the electrolysis temperature is room temperature.
Further, the cutting size of the metal zinc sheet in the step 1 is 1 cm multiplied by 1 cm to 3 cm multiplied by 3 cm.
Further, the atmosphere used in step 1 is not limited to argon, carbon dioxide, nitrogen, or the like.
Further, in the step 1, before constant current electrolysis, the high-voltage electrolytic cell is inflated and deflated for 3 to 5 times to exhaust the internal air.
Further, the cathode electrolyte adopted by the high-pressure electrolytic cell in the step 1 is one or more of potassium chloride, sodium chloride and sodium bicarbonate.
Further, the anode electrolyte adopted by the high-pressure electrolytic cell in the step 1 is one or more of potassium sulfate, sodium sulfate and sodium bicarbonate.
The invention also provides an application of the hydrogen-containing metal zinc catalyst in any one of the technical schemes or the hydrogen-containing metal zinc catalyst obtained by the preparation method in any one of the technical schemes in carbon dioxide electroreduction reaction.
Further, the carbon dioxide electroreduction reaction is carried out in a sealed H-type electrolytic cell.
Further, the cathode electrolyte adopted by the H-shaped electrolytic cell is one or more of potassium chloride, sodium bicarbonate and the like.
Further, the anode electrolyte adopted by the H-shaped electrolytic cell is one or more of potassium sulfate, sodium sulfate and sodium bicarbonate.
Further, the carbon dioxide electroreduction reaction is carried out in a constant current mode under normal pressure, and the current interval is-1 to-20 milliamperes per square centimeter.
Further, the hydrogen-containing metal zinc catalyst can be used for carbon dioxide electroreduction reaction without other treatment.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a hydrogen-containing metal zinc catalyst, which is applied to carbon dioxide electroreduction reaction, and the introduction of hydrogen atoms is combined with the tensile stress of crystal lattices, so that surface hydrogen atoms formed in the electroreduction process can be directly added to the carbon end of carbon dioxide to form a HCOO intermediate, and the efficient electrocatalytic reduction of carbon dioxide to formic acid is realized;
2. the hydrogen-containing metal zinc catalyst is prepared by electrolyzing the zinc sheet in the high-pressure atmosphere, and the preparation method has the advantages of simple procedure and mild conditions;
3. the hydrogen-containing metal zinc catalyst provided by the invention shows more than 80% of Faraday efficiency on formic acid in a commercial H-shaped electrolytic cell, and the carbon monoxide Faraday efficiency is lower than 5%; in contrast, pure metallic zinc catalysts only exhibit a formic acid faradaic efficiency of less than 20% and a carbon monoxide faradaic efficiency of greater than 70% at the same potential interval; the method breaks through the traditional cognition that the zinc-based metal catalyst is mainly used for producing carbon monoxide through carbon dioxide electroreduction, expands the types of metals which can be selected by the catalyst for producing formic acid through carbon dioxide electroreduction, and has the advantages of low price, easily obtained raw materials and environmental friendliness compared with the traditional catalysts for producing formic acid such as lead, bismuth and the like.
Drawings
FIG. 1 is a schematic view of an apparatus for a high-pressure electrolytic cell used in example 1 of the present invention;
FIG. 2 is a high resolution TEM image of the hydrogen-containing zinc metal catalyst and the standard zinc metal catalyst obtained in example 1 of the present invention; wherein, (a) is a hydrogen-containing metal zinc catalyst, and (b) is a standard metal zinc catalyst;
FIG. 3 is the X-ray diffraction spectra of the hydrogen-containing metal zinc catalyst and the standard metal zinc catalyst obtained in example 1 of the present invention;
FIG. 4 is a time-of-flight secondary ion mass spectrum of the hydrogen-containing metal zinc catalyst and a standard metal zinc catalyst obtained in example 1 of the present invention;
FIG. 5 is a temperature programmed desorption-mass spectrometry spectrum of a hydrogen-containing metal zinc catalyst and a standard metal zinc catalyst obtained in example 1 of the present invention;
FIG. 6 is a graph of Faraday efficiency of a standard metallic zinc catalyst catalyzing carbon dioxide electroreduction reactions in an H-type electrolytic cell;
FIG. 7 shows the Faraday efficiency of hydrogen-containing metal zinc catalyst obtained in example 1 of the present invention in catalyzing carbon dioxide electroreduction reaction in an H-type electrolytic cell;
FIG. 8 is a graph of the potential-time curve and the Faraday efficiency-time curve of the constant current stability test of the hydrogen-containing metallic zinc catalyst obtained in example 1 of the present invention in catalyzing the carbon dioxide electroreduction reaction in an H-type electrolytic cell.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the art of analytical purity or atomic layer deposition.
All the raw materials and the process of the invention belong to the conventional trade marks or the abbreviation, each trade mark or the abbreviation is clear and definite in the field of related application, and the technical personnel in the field can purchase the raw materials or prepare the raw materials or the abbreviation from the market or prepare the raw materials or the abbreviation by a conventional method or adopt corresponding equipment to realize the raw materials or the abbreviation according to the trade marks, the abbreviation and the corresponding application.
The invention provides a hydrogen-containing metal zinc catalyst, which is characterized in that the size of a zinc metal crystal lattice of the hydrogen-containing metal zinc catalyst is increased by 0.1-2.0% compared with the crystal lattice of a standard zinc metal crystal, and hydrogen atoms are contained in gaps of the zinc metal crystal lattice.
Further, the lattice stretching direction is isotropic.
Further, the hydrogen atom content (mass fraction) in the hydrogen-containing metal zinc catalyst is 0.0001 to 0.002%.
Further, the hydrogen-containing metal zinc catalyst is preferably a catalyst for electrochemically catalyzing carbon dioxide reduction, and is more preferably a catalyst for electrochemically catalyzing carbon dioxide reduction to prepare formic acid.
The invention provides a preparation method of a hydrogen-containing metal zinc catalyst, which comprises the following steps:
step 1: placing a metal zinc sheet at the cathode end of a high-pressure electrolytic cell, and electrolyzing at a constant current with a current density of-1 to-200 milliamperes per square centimeter under a high-pressure atmosphere of 0.1 to 8.0 megapascals to obtain a treated zinc sheet;
step 2: and (4) washing the treated zinc sheet obtained in the step (1) with deionized water to remove surface electrolyte, and blow-drying with inert atmosphere to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Further, the cutting area of the metal zinc sheet in the step 1 is 1-9 square centimeters; preferably 1 to 5 square centimeters.
Further, the atmosphere used in step 1 is one or more of argon, carbon dioxide and nitrogen.
Further, in the step 1, before constant current electrolysis, the high-voltage electrolytic cell is inflated and deflated for 3-5 times to exhaust the internal air; preferably 4 to 5 times.
Further, the atmosphere pressure of the high-pressure atmosphere in step 1 is preferably 4 to 6 mpa.
Further, the cathode electrolyte adopted by the high-pressure electrolytic cell in the step 1 is one or more of potassium chloride, sodium chloride and sodium bicarbonate, and the concentration is 0.1-1.0 mol per liter; preferably potassium chloride, preferably in a concentration of 0.5 to 1.0 mole per liter.
Further, the anode electrolyte adopted by the high-voltage electrolytic cell in the step 1 is one or more of potassium sulfate, sodium sulfate and sodium bicarbonate, and the concentration is 0.1-1.0 mol/L; preferably potassium sulphate, preferably in a concentration of 0.2 to 0.5 mol per litre.
Further, the constant current in step 1 preferably has a current density of 100 to 200 milliamps per square centimeter.
Further, the constant current electrolysis in step 1 is carried out for a time period of 0.5 to 10 hours, preferably 1 to 6 hours, at room temperature.
The invention provides an application of the hydrogen-containing metal zinc catalyst in any one of the technical schemes or the hydrogen-containing metal zinc catalyst obtained by the preparation method in any one of the technical schemes in carbon dioxide electrocatalytic reduction reaction.
Further, the hydrogen-containing metal zinc catalyst can be used for carbon dioxide electroreduction reaction without other treatment.
Further, the carbon dioxide electroreduction reaction is carried out in a sealed H-type electrolytic cell.
Furthermore, the cathode electrolyte adopted by the H-type electrolytic cell is one or more of potassium chloride, sodium bicarbonate and the like, and the concentration is 0.1-1.0 mol/L; preferably potassium chloride, preferably in a concentration of 0.5 to 1.0 mole per liter.
Further, the anode electrolyte adopted by the H-shaped electrolytic cell is one or more of potassium sulfate, sodium sulfate and sodium bicarbonate, and the concentration is 0.1-1.0 mol per liter; preferably potassium sulphate, preferably in a concentration of 0.2 to 0.5 mole per litre.
Further, the carbon dioxide electroreduction reaction is carried out in a constant current mode under normal pressure, and the current interval is-1 to-20 milliamperes per square centimeter; preferably-4 to-16 milliamps per square centimeter.
In order to further illustrate the present invention, the following will describe in detail a hydrogen-containing metal zinc catalyst, a preparation method thereof, and an application thereof in preparing formic acid by carbon dioxide electro-reduction, with reference to examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and that detailed embodiments and specific procedures are given, only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into metal zinc sheets with the size of 1 cm multiplied by 1 cm;
step 2: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, assembling a high-pressure electrolytic cell shown in figure 1 by using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, separating a cathode chamber and an anode chamber by using a Nafion 117 ion exchange membrane, injecting 12 ml of a potassium chloride solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of a potassium sulfate solution with the concentration of 0.5 mol/L into the anode chamber;
and step 3: repeatedly charging argon with the pressure of 0.5 MPa for 5 times to remove air, and then charging argon to 6.0 MPa;
and 4, step 4: electrolytically treating for 1 hour in a constant current mode at a current density of-100 milliamps per square centimeter;
and 5: after the electrolysis treatment is finished, discharging argon to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and blowing the zinc sheet with argon to dry to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Example 2
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into metal zinc sheets with the size of 1 cm multiplied by 1 cm;
and 2, step: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, assembling a high-pressure electrolytic cell by using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, separating a cathode chamber and an anode chamber by using a Nafion 117 ion exchange membrane, injecting 12 ml of a potassium chloride solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of a potassium sulfate solution with the concentration of 0.5 mol/L into the anode chamber;
and step 3: repeatedly charging nitrogen gas with 0.5 MPa into the high-pressure electrolytic cell for 5 times to remove air, and then charging nitrogen gas to 6.0 MPa;
and 4, step 4: electrolytically treating for 2 hours in a constant current mode at a current density of-100 milliamps per square centimeter;
and 5: and after the electrolysis treatment is finished, discharging nitrogen to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and drying the zinc sheet with argon to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Example 3
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into metal zinc sheets with the size of 1 cm multiplied by 1 cm;
step 2: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode, using a platinum counter electrode as a counter electrode, assembling a high-pressure electrolytic cell, separating a cathode chamber and an anode chamber by using a Nafion 117 ion exchange membrane, injecting 12 ml of a potassium bicarbonate solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of a potassium bicarbonate solution with the concentration of 0.5 mol/L into the anode chamber;
and step 3: repeatedly charging and discharging carbon dioxide with 0.5 MPa for 5 times to remove air, and then charging carbon dioxide to 6.0 MPa;
and 4, step 4: electrolytically treating for 0.5 hour at a current density of-120 milliamps per square centimeter in a constant current mode;
and 5: and (3) after the electrolysis treatment is finished, discharging carbon dioxide to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and drying the zinc sheet with argon to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Example 4
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into metal zinc sheets with the size of 1 cm multiplied by 1 cm;
step 2: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, assembling a high-pressure electrolytic cell by using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, wherein the cathode chamber and the anode chamber are separated by using a Nafion 117 ion exchange membrane, injecting 12 ml of a potassium chloride solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of a potassium bicarbonate solution with the concentration of 0.5 mol/L into the anode chamber;
and step 3: repeatedly charging argon with the pressure of 0.5 MPa for 5 times to remove air, and then charging argon to 8.0 MPa;
and 4, step 4: electrolytically treating for 5 hours in galvanostatic mode at a current density of-200 milliamps per square centimeter;
and 5: after the electrolysis treatment is finished, discharging argon to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and blowing the zinc sheet with argon to dry to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Example 5
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into metal zinc sheets with the size of 1 cm multiplied by 1 cm;
step 2: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, assembling a high-pressure electrolytic cell by using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, separating a cathode chamber and an anode chamber by using a Nafion 117 ion exchange membrane, injecting 12 ml of sodium chloride solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of sodium sulfate solution with the concentration of 0.5 mol/L into the anode chamber;
and 3, step 3: repeatedly charging argon with the pressure of 0.5 MPa for 5 times to remove air, and then charging argon to 0.5 MPa;
and 4, step 4: electrolytically treating for 10 hours in a constant current mode at a current density of-50 milliamps per square centimeter;
and 5: and after the electrolysis treatment is finished, discharging argon to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and drying the zinc sheet with argon to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
Example 6
The embodiment prepares a hydrogen-containing metal zinc catalyst, and specifically comprises the following steps:
step 1: polishing a purchased commercial metal zinc sheet by using fine sand paper at normal temperature, removing a surface oxidation layer, and cutting into a metal zinc sheet with the size of 3 cm multiplied by 3 cm;
step 2: fixing the metal zinc sheet obtained in the step 1 by using a glassy carbon electrode clamp as a cathode, assembling a high-pressure electrolytic cell by using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, separating a cathode chamber and an anode chamber by using a Nafion 117 ion exchange membrane, injecting 12 ml of sodium chloride solution with the concentration of 1 mol/L into the cathode chamber, and injecting 12 ml of sodium sulfate solution with the concentration of 0.5 mol/L into the anode chamber;
and step 3: repeatedly charging argon with the pressure of 0.5 MPa for 3 times to remove air, and then charging argon to 6.0 MPa;
and 4, step 4: electrolytically treating for 10 hours in a constant current mode at a current density of-50 milliamps per square centimeter;
and 5: and after the electrolysis treatment is finished, discharging argon to normal pressure, taking out the treated zinc sheet, washing the zinc sheet with deionized water to remove residual electrolyte on the surface, and drying the zinc sheet with argon to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
The hydrogen-containing metal zinc catalyst obtained in this example was subjected to structural characterization.
The left image of fig. 2 is a high resolution tem of the hydrogen containing zinc metal catalyst obtained in example 1, and the right image is a high resolution tem of a standard zinc metal catalyst (i.e., zinc metal flakes), which shows that the lattice spacing of the hydrogen containing zinc metal catalyst is 2.49 a, and the lattice spacing of the standard zinc metal catalyst is 2.47 a. In contrast, the crystal lattice of the hydrogen-containing metallic zinc catalyst has a tensile stress of about 0.8%.
Fig. 3 is an X-ray diffraction pattern of the hydrogen-containing metallic zinc catalyst obtained in example 1 and a standard metallic zinc catalyst, wherein the peak position of the hydrogen-containing metallic zinc catalyst is shifted to a small angle direction relative to the standard metallic zinc catalyst, and it is proved that the crystal lattice is stretched by the incorporation of atomic hydrogen.
FIG. 4 shows the time-of-flight secondary ion mass spectrum of the hydrogen-containing metal zinc catalyst and the standard metal zinc catalyst obtained in example 1. The concentration of hydrogen species (namely metal hydrogen species) which are not related to hydroxide is judged by collecting the change of secondary ion signals scattered by the surface of the ion bombardment catalyst along with the depth and using the ratio of hydrogen ions to zinc oxide ions, and it can be seen that the signal intensity ratio of the hydrogen-containing metal zinc catalyst is gradually increased to about 5.0 along with the increase of bombardment time, while the signal intensity ratio of the standard metal zinc catalyst is maintained unchanged, which shows that compared with the standard metal zinc catalyst, the hydrogen-containing metal zinc has more metal hydrogen species in a deep layer, and further shows that atomic hydrogen is doped into a crystal lattice gap.
FIG. 5 shows the spectrum of temperature programmed desorption-mass spectrometry of the hydrogen-containing zinc metal catalyst and the standard zinc metal catalyst obtained in example 1. It can be seen that the hydrogen-containing metal zinc catalyst shows a desorption peak of hydrogen at about 325 ℃, and no hydrogen is released under the heating condition of the standard metal zinc catalyst, which indicates that atomic hydrogen is doped in the hydrogen-containing metal zinc catalyst.
The catalytic performance test of the carbon dioxide electroreduction reaction of the hydrogen-containing metal zinc catalyst obtained in example 1 specifically includes: directly taking the obtained hydrogen-containing metal zinc catalyst as a working electrode, a platinum wire as a counter electrode, a silver/silver chloride electrode containing saturated potassium chloride solution as a reference electrode, taking 1 mol per liter of potassium chloride solution as a cathode electrolyte and 0.5 mol per liter of potassium sulfate solution as an anode electrolyte, and carrying out carbon dioxide electroreduction performance test in an H-type electrolytic cell; the constant current method is adopted for testing, and the range of the added cathode current is-8 to-20 milliamperes. And carrying the reaction gas-phase product to gas chromatography detection through argon gas carrier, detecting the liquid-phase product by ion chromatography, calculating the coulomb amount corresponding to the product concentration, and obtaining data such as catalytic selectivity, catalytic activity and the like according to the total coulomb amount recorded by the electrochemical workstation.
Fig. 6 shows the faradaic efficiency of the electrochemical reduction reaction of carbon dioxide catalyzed by the standard metal zinc catalyst in the H-type electrolytic cell, and it can be seen that the main product of the carbon dioxide reduction reaction of the standard metal zinc catalyst is carbon monoxide under different cathode currents tested, and only a small amount of formic acid product can be obtained.
Fig. 7 shows faradaic efficiency of hydrogen-containing metallic zinc catalyst obtained in example 1 in catalyzing carbon dioxide electro-reduction reaction in H-type electrolytic cell, and it can be seen that under different cathode currents tested, the main product of carbon dioxide reduction reaction of hydrogen-containing metallic zinc catalyst is formic acid, and only a small amount of carbon monoxide is produced.
Fig. 8 is a potential-time curve and a faraday efficiency-time curve of a constant current stability test of the hydrogen-containing metallic zinc catalyst obtained in example 1 in an H-type electrolytic cell for catalyzing carbon dioxide electroreduction reaction, and the performance attenuation of the obtained hydrogen-containing metallic zinc catalyst is very small after a constant current test of a constant current density of-10 milliamperes per square centimeter for 200 hours, which indicates that the hydrogen-containing metallic zinc catalyst has good stability and is suitable for being applied to long-time catalytic reaction.
The invention provides a hydrogen-containing metal zinc catalyst, a preparation method and CO 2 The foregoing examples are presented to aid in the understanding of the principles and practice of the invention, including the best mode, and are intended to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (6)

1. The hydrogen-containing metal zinc catalyst is characterized in that the zinc metal lattice spacing of the hydrogen-containing metal zinc is increased by 0.1-2.0% compared with the standard zinc metal lattice, hydrogen atoms are contained in gaps of the zinc metal lattice, and the mass fraction of the hydrogen atoms is 0.0001-0.002%.
2. The preparation method of the hydrogen-containing metal zinc catalyst is characterized by comprising the following steps:
step 1: fixing a metal zinc sheet as a cathode by using a glassy carbon electrode clamp, using a silver/silver chloride electrode containing a saturated potassium chloride solution as a reference electrode and a platinum counter electrode as a counter electrode, assembling a high-pressure electrolytic cell, separating a cathode chamber and an anode chamber by using an ion exchange membrane, injecting a cathode electrolyte into the cathode chamber, injecting an anode electrolyte into the anode chamber, and then performing constant current electrolysis at a current density of-1 to-200 milliamperes per square centimeter under a high-pressure atmosphere of 0.1 to 8.0 megapascals to obtain a treated zinc sheet; wherein the cathode electrolyte is one or more of potassium chloride, sodium chloride and sodium bicarbonate; the anode electrolyte is one or more of potassium sulfate, sodium sulfate and sodium bicarbonate;
and 2, step: and (3) cleaning the treated zinc sheet obtained in the step (1), and drying the zinc sheet by blowing in an inert atmosphere to obtain the hydrogen-containing metal zinc catalyst on the surface of the zinc sheet.
3. The method for preparing a zinc catalyst containing hydrogen metal according to claim 2, wherein the constant current electrolysis is carried out for 0.5 to 10 hours at room temperature.
4. The method for preparing a zinc catalyst containing hydrogen metal according to claim 2, wherein the atmosphere used in step 1 is argon, carbon dioxide or nitrogen.
5. The use of the hydrogen-containing metallic zinc catalyst of claim 1 in an electroreduction reaction of carbon dioxide.
6. The use of the hydrogen-containing metallic zinc catalyst obtained by the preparation method according to any one of claims 2 to 4 in the carbon dioxide electroreduction reaction.
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