Method for preparing multi-metal co2 reduction electrocatalyst and application thereof

Abstract

The present application relates to the technical field of electrocatalytic CO2 reduction, and aims at the structure and performance of zero-dimensional perovskite material of organic metal halide and the problem that the material is unstable in humid environment or water, and provides a preparation method and application of multi-metal CO2 reduction electrocatalyst, wherein zero-dimensional perovskite crystal material containing at least two metal halides or a combination of zero-dimensional perovskite crystal materials containing different metal halides is calcined at 300-1200 DEG C, so that the target crystal material is decomposed into oxides of the contained metals and / or halogen in the metal halide is removed to form a single atom, thereby obtaining a zero-dimensional perovskite-derived multi-metal CO2 reduction electrocatalyst. The multi-metal CO2 reduction electrocatalyst provided by the present application has the characteristics of high catalytic activity, easy preparation and good stability, can be applied in water phase, and expands the application range of zero-dimensional perovskite material of organic metal halide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalytic CO2 reduction, in particular to a preparation method of a multi-metal CO2 reduction electrocatalyst and application thereof. BACKGROUND

[0002] The organic metal halide zero-dimensional perovskite material has special structural characteristics, and the metal halide octahedron, pentahedron and tetrahedron can be used as a basic unit to realize assembly. In these zero-dimensional structures, the metal halide unit is completely isolated and is isolated by high-energy organic cations, and cannot form a band structure and does not have a quantum size effect, so that the properties of the metal halide basic unit can be presented in a single crystal material, so that the organic metal halide zero-dimensional perovskite material exhibits excellent luminescent properties. However, such materials are extremely sensitive to H2O and cannot maintain their structure and performance stability for a long time in a humid environment. For this reason, when such materials are applied in photocatalytic CO2 reduction, the reaction can usually only be carried out in organic solvents such as ethyl acetate and acetonitrile, or a gas-solid reaction, and efficient electrocatalytic CO2 reduction in an aqueous environment faces great challenges. At present, there is no effective solution that can both utilize the photoelectric properties of the organic metal halide zero-dimensional perovskite material and overcome the defects of unstable structure and performance in a humid environment or water. SUMMARY

[0003] The purpose of the present application is to solve the problem of unstable structure and performance of the organic metal halide zero-dimensional perovskite material in a humid environment or water, based on the structural characteristics of the metal halide polyhedron that can be assembled in the zero-dimensional perovskite structure of the organic metal halide, a preparation method of a multi-metal CO2 reduction electrocatalyst and application thereof are provided. Based on the special structure of the zero-dimensional perovskite crystal material, a plurality of metal polyhedrons can be assembled into the crystal structure, and a plurality of target electrocatalysts such as multi-metal oxide electrocatalysts and multi-metal anchored single-atom catalysts can be obtained by adjusting the calcination atmosphere and calcination temperature. The multi-metal CO2 reduction electrocatalyst provided by the present application has the characteristics of high catalytic activity, easy preparation and good stability, and expands the application range of the organic metal halide zero-dimensional perovskite material.

[0004] In order to achieve the above purpose, the present application provides a preparation method of a multi-metal CO2 reduction catalyst, comprising the following steps:

[0005] The zero-dimensional perovskite crystal material containing at least two metal halides or the combination of zero-dimensional perovskite crystal materials containing different metal halides is calcined at 300-1200 DEG C, so that the target crystal material is decomposed into the oxides of the contained metals and / or the halogens in the metal halides are removed to form single atoms, thereby obtaining a zero-dimensional perovskite-derived multi-metal CO2 reduction electrocatalyst.

[0006] Further, the zero-dimensional perovskite crystal material containing at least two metal halides or the combination of zero-dimensional perovskite crystal materials containing different metal halides is calcined in an air atmosphere at 300-700℃ for 4-6 hours, so that the target crystal material is decomposed into oxides of the contained metals;

[0007] Further, the zero-dimensional perovskite crystal material containing at least two metal halides or the combination of zero-dimensional perovskite crystal materials containing different metal halides is calcined in an air atmosphere at 300-700℃ for 4-6 hours, so that the target crystal material is decomposed into oxides of the contained metals;

[0008] Further, any one or a combination of two or more of the following is preferred: a bimetallic halide zero-dimensional perovskite crystal material, a trimetallic halide zero-dimensional perovskite crystal material, a tetrametallic halide zero-dimensional perovskite crystal material, and a pentametallic halide zero-dimensional perovskite crystal material.

[0009] Further, the metal halide is selected from BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, NiX2, FeX2, CoX2, PbX2, InX3, AgX, GeX2, ZrX4 or TeX4, wherein X = Cl, Br or I.

[0010] Further, the zero-dimensional perovskite crystal material containing different metal species is synthesized by a solution method.

[0011] Further, two or more metal halides are selected and mixed with an organic halide of the same halogen, wherein the molar ratio of the metal halide to the organic halide is 1:2, dissolved in a DMF solution at a high temperature of 100-120℃ to form a transparent solution, and cooled to room temperature to obtain a zero-dimensional perovskite crystal material of metal halide.

[0012] Further, the organic halide is tetramethyl halide, tetraethyl halide, tetrapropyl halide or tetrabutyl halide.

[0013] Further, the first calcination is performed in a tube furnace.

[0014] The application also provides the use of the multi-metal CO2 reduction electrocatalyst prepared by the above method. In particular, the electrocatalytic reduction of CO2 in an aqueous environment.

[0015] The beneficial effects of the application are:

[0016] A multi-metal CO2 reduction electrocatalyst was obtained by calcination, which combines multiple metals to provide multiple catalytic active sites, resulting in high catalytic activity; it is easy to prepare and has good stability; it can be used in aqueous phase, thus expanding the application range of organometal halide zero-dimensional perovskite materials. Attached Figure Description

[0017] Figure 1 Image of TTA4CuBiCl5 raw material prepared in Example 1 of this invention;

[0018] Figure 2 The bimetallic TTA4CuBi prepared in Example 1 of this invention 1-x Photo of Cl9 catalyst;

[0019] Figure 3 Bimetallic TTA4CuBi with different Bi contents prepared in Example 1 of this invention 1-x Electrocatalytic performance of Cl9 catalyst for CO2 reduction;

[0020] Figure 4 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x Cl9 raw material image

[0021] Figure 5 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x Cl9 single crystal structure diagram

[0022] Figure 6 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x Image of Cl9 after calcination at 400℃

[0023] Figure 7 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x LSV curve measured after Cl9 was calcined at 400℃

[0024] Figure 8 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x Electrocatalytic performance of CO2 reduction measured after Cl9 calcination at 400℃.

[0025] Figure 9 The trimetallic TTA4MnSb prepared in Example 2 of this invention x Bi 1-x Electrocatalytic performance of Cl9 material for CO2 reduction measured after calcination at different temperatures. Detailed Implementation

[0026] The present invention will now be described in detail with reference to specific embodiments.

[0027] The detailed steps for preparing the zero-dimensional perovskite-derived multimetallic CO2 reduction electrocatalyst material described in this invention and for preparing the electrode are as follows:

[0028] (I) Preparation of Organometal Halogen Zero-Dimensional Calcium-Titanium Materials

[0029] S1: Preparation of bimetallic zero-dimensional perovskites:

[0030] Two metal halides, such as BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, NiX2, FeX2, CoX2, PbX2, InX3, AgX, GeX2, ZrX4, and TeX4 (X = Cl, Br, I), were selected and mixed with organohalides of the same halogen (including tetramethylamine halides, tetraethylamine halides, tetrapropylamine halides, and tetrabutylamine halides, etc.) and dissolved in DMF solution at 100℃-120℃ to form a transparent solution. The molar ratio of metal halide to organohalide was 1:2. After cooling to room temperature and standing for 12 hours, a bimetallic zero-dimensional perovskite crystal material was obtained.

[0031] S2: Preparation of trimetallic zero-dimensional perovskite:

[0032] Three metal halides, such as BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, NiX2, FeX2, CoX2, PbX2, InX3, AgX, GeX2, ZrX4, and TeX4 (X = Cl, Br, I), were selected and mixed with organohalides of the same halogen (including tetramethylamine halide, tetraethylamine halide, tetrapropylamine halide, and tetrabutylamine halide, etc.) and dissolved in DMF solution at 100℃-120℃ to form a transparent solution. The molar ratio of metal halide to organohalide was 1:2. After cooling to room temperature and standing for 12 hours, a trimetallic zero-dimensional perovskite crystal material was obtained.

[0033] S3: Preparation of tetrametallic zero-dimensional perovskites:

[0034] Select four kinds of metal halides, such as BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, NiX2, FeX2, CoX2, PbX2, InX3, AgX, GeX2, ZrX4, TeX4(X=Cl, Br, I) and the like, mix them with organic halides of the same halogen (including tetramethyl halide, tetraethyl halide, tetrapropyl halide, and tetrabutyl halide, etc.) at a high temperature of 100-120°C to dissolve in DMF solution to form a transparent solution, and the molar ratio of metal halide to organic halide is 1:2. After cooling to room temperature, stand for 12 hours to obtain four-metal zero-dimensional perovskite crystal materials.

[0035] S4: Preparation of five-metal zero-dimensional perovskite:

[0036] Select five kinds of metal halides, such as BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, NiX2, FeX2, CoX2, PbX2, InX3, AgX, GeX2, ZrX4, TeX4(X=Cl, Br, I) and the like, mix them with organic halides of the same halogen (including tetramethyl halide, tetraethyl halide, tetrapropyl halide, and tetrabutyl halide, etc.) at a high temperature of 100-120°C to dissolve in DMF solution to form a transparent solution, and the molar ratio of metal halide to organic halide is 1:2. After cooling to room temperature, stand for 12 hours to obtain five-metal zero-dimensional perovskite crystal materials.

[0037] (II) Preparation of multi-metal CO2 reduction electrocatalyst material derived from organic metal halide zero-dimensional perovskite

[0038] Different atmospheres and calcination temperatures will obtain different catalyst materials.

[0039] 1. Preparation of multi-metal CO2 reduction electrocatalyst:

[0040] Take at least one of the samples prepared in S1-S4, place it in a tube furnace, and calcine it in an air atmosphere at 300-700°C for 4-6 hours, so that the target crystal is decomposed into oxides and / or oxyhalides of the contained metals, the semiconductor performance of the material is increased, and the active sites are increased.

[0041] 2. Preparation of multi-metal single-atom CO2 reduction electrocatalyst:

[0042] Take at least one of the samples prepared in S1-S4, place it in a tube furnace, and calcine it in an inert gas atmosphere at 600-1200°C for 4-6 hours, so that the organic part is carbonized, the halogen in the metal halide is removed to form a single atom, and the metal single atom is uniformly distributed on the carbon substrate, and the active site is increased.

[0043] (III) Electrocatalytic CO2 reduction performance test of organometal halide zero-dimensional perovskite-derived multimetal electrocatalysts:

[0044] A measured amount of the target catalyst was weighed, added to Nafion solution, and then a measured amount of anhydrous ethanol was added. After ultrasonic dispersion for 30 min, the catalyst was uniformly drop-coated onto carbon paper to prepare an electrode. After drying, an electrocatalytic CO2 reduction test was performed.

[0045] Example 1: Preparation of a bimetallic CO2 reduction electrocatalyst

[0046] Weigh out 1 mmol BiCl3, 1 mmol CuCl2 and 4 mmol C8H respectively. 20 NCl, weigh out the salts, mix them, add an appropriate amount of DMF solution, heat at 120℃ to dissolve, and after complete dissolution, cool to room temperature, wash, and obtain as shown. Figure 1 The deep yellow TTA4CuBiCl5 particles shown are obtained. After grinding the above material evenly, it is placed in a tube furnace and calcined at 500°C in air atmosphere to obtain... Figure 2 The catalyst sample is shown. A quantitative amount of the target catalyst was weighed, ground evenly, and then Nafion solution was added. A quantitative amount of anhydrous ethanol was then added, and the mixture was ultrasonically dispersed for 30 min. The dispersion was then uniformly drop-coated onto carbon paper to prepare an electrode. After drying, electrocatalytic CO2 reduction tests were performed. The HCOOH ion yield was the highest among the electrocatalytic reduction products, with a Faradaic efficiency as high as 95.8%. The Faradaic efficiency of the HCOOH ion can be controlled by adjusting the Bi content, such as... Figure 3 As shown.

[0047] Example 2: Preparation of a trimetallic CO2 reduction electrocatalyst

[0048] Weigh out 2 mmol MnCl2, 1 mmol BiCl3, 1 mmol SbCl3 and 8 mmol C8H respectively. 20 NCl, weigh out the salts, mix them, add an appropriate amount of DMF solution, heat at 120℃ to dissolve, and after complete dissolution, cool to room temperature, wash, and obtain as shown. Figure 4 The light yellow TTA4MnSb shown x Bi 1-x Cl9 particles. For example, ... Figure 5 The image shows its corresponding single-crystal structure. After grinding the above material evenly, it was placed in a tube furnace and calcined at 400°C in air atmosphere to obtain... Figure 6 The catalyst sample is shown. A measured amount of the target catalyst was weighed, ground evenly, and then Nafion solution was added. A measured amount of anhydrous ethanol was then added, and the mixture was ultrasonically dispersed for 30 min. The dispersion was then uniformly drop-coated onto carbon paper to prepare the electrode. After drying, the electrocatalytic CO2 reduction was tested. Its LSV curve is shown below. Figure 7As shown. The products of electrocatalytic reduction include H2, CO, and HCOOH, such as... Figure 8 As shown, the HCOOH ion yield was the highest, with a Faradaic efficiency as high as 86%. The electrocatalytic CO2 reduction performance of the target catalyst obtained after calcination at different temperatures is as follows: Figure 9 As shown.

[0049] Example 3: Preparation of a trimetallic single-atom CO2 reduction electrocatalyst

[0050] Weigh out 2 mmol MnCl2, 1 mmol BiCl3, 1 mmol SbCl3 and 8 mmol C8H respectively. 20 NCl, weigh out the salts, mix them, add an appropriate amount of DMF solution, heat at 120℃ to dissolve, and after complete dissolution, cool to room temperature, wash, and obtain as shown. Figure 4 The TTA4MnSb shown x Bi 1-x Cl9 particles. For example, ... Figure 5 The image shows its corresponding single-crystal structure. After grinding the above material evenly, it was placed in a tube furnace and calcined at 600-1200℃ under inert gas protection. This process allowed organic groups, such as tetraethylammonium chloride, to form a trimetallic single-atom catalyst based on carbonization. The metal single atoms were uniformly distributed on the carbon substrate, increasing the number of active sites. The catalyst reduction performance testing method in this embodiment is the same as in Example 1.

[0051] The embodiments described above are merely some embodiments of the present invention, and not all embodiments. The embodiments described are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method of preparing a multimetallic CO2reduction electrocatalyst, characterized in that, Comprising the following steps: Zero-dimensional perovskite crystal materials containing at least two metal halides are calcined in an air atmosphere at 300-700℃ for 4-6 hours, so that the target crystal material is decomposed into oxides of the contained metals, obtaining a zero-dimensional perovskite-derived multi-metal CO2 reduction electrocatalyst.

2. The production method according to claim 1, characterized by, The metal halide is selected from BiX3, SbX3, SnX2, MnX2, CuX2, ZnX2, PbX2, InX3, wherein X = Cl, Br or I.

3. The production method according to claim 1, characterized by, Two or more metal halides are selected in equimolar ratio, mixed with organic halides of the same halogen, and dissolved in a DMF solution at a high temperature of 100-120℃ to form a transparent solution, and a metal halide zero-dimensional perovskite crystal material is obtained after cooling to room temperature.

4. The production method according to claim 3, characterized by, The organic halide is tetramethylammonium halide, tetraethylammonium halide, tetrapropylammonium halide or tetrabutylammonium halide.

5. The preparation method according to claim 1, characterized in that, The calcination is carried out in a tube furnace.

6. Use of the multi-metallic CO2-reduction electrocatalyst produced by the method of claim 1, characterized in that, The electrocatalytic reduction of CO2 is carried out in an aqueous phase environment.

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