CN113073343B - Synthetic efficient electrocatalysis CO 2 Method for reducing copper-zinc bimetallic catalyst - Google Patents

Synthetic efficient electrocatalysis CO 2 Method for reducing copper-zinc bimetallic catalyst Download PDF

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CN113073343B
CN113073343B CN202110273928.7A CN202110273928A CN113073343B CN 113073343 B CN113073343 B CN 113073343B CN 202110273928 A CN202110273928 A CN 202110273928A CN 113073343 B CN113073343 B CN 113073343B
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CN113073343A (en
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罗景山
万丽丽
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Abstract

Synthetic efficient electrocatalysis CO 2 The method for reducing the copper-zinc bimetallic catalyst comprises the steps of utilizing an atomic layer deposition technology, a hydrothermal method and a high-temperature annealing simple three-step method, taking a copper net with copper oxide nanowires grown in situ as a substrate, utilizing the atomic layer deposition technology to obtain copper oxide with a shell-core structure and zinc oxide nanowires, wrapping a layer of ZIF-8 on the surface of the copper oxide with the hydrothermal method, and finally calcining at high temperature under the protection of inert atmosphere to obtain the copper-zinc bimetallic nanowire material with a phase separation structure. The phase-separated copper-zinc bimetallic nanowire reported by the method has the advantages of simple synthesis method, easy operation and electrocatalysis of CO 2 High efficiency and stability of reduction.

Description

Synthetic efficient electrocatalysis CO 2 Method for reducing copper-zinc bimetallic catalyst
Technical Field
The invention belongs to the technical field of preparation and application of nano materials, and relates to a preparation technology and application of a phase separation copper-zinc bimetallic nanowire material, in particular to a method for preparing a phase separation copper-zinc bimetallic nanowire based on three steps of an atomic layer deposition technology, a hydrothermal method, external layer coating of ZIF-8 and high-temperature calcination, and application of the phase separation copper-zinc bimetallic nanowire in electrocatalysis of CO 2 A method applied in the reduction.
Background
Electrocatalytic reduction of carbon dioxide (CO) 2 ) Is a power system using electric energy as driving force, CO 2 An artificial process for converting electrical energy into chemical energy for the raw material to obtain carbonaceous fuel while achieving carbon neutralization 1 . In this process, CO 2 Can be reduced into carbon compounds such as carbon monoxide, methane, formic acid, acetic acid and ethanol, but CO still exists in the technology 2 The selectivity of the reduction product is poor, the stability of the catalyst material is poor and the like. Zinc metal has high CO selectivity, but zinc metal electrodes and copper-zinc alloy electrodes electrocatalysis CO 2 The Faraday Efficiency (FE) of reducing and preparing CO is always limited to about 80 percent and has poor stability 2-4 . To promote electrocatalysis of CO by zinc-based catalysts 2 In the application process of the industrial field of CO reduction preparation, the catalytic efficiency and stability of the zinc-based catalyst material need to be further improved.
Reference documents
1.Nitopi S,Bertheussen E,Scott S B,et al.Progress and perspectives of electrochemical CO 2 reduction on copper in aqueous electrolyte[J]. Chemical reviews,2019,119(12):7610-7672.
2.Hori Y,Wakebe H,Tsukamoto T,et al.Electrocatalytic process of CO selectivity in electrochemical reduction of CO 2 at metal electrodes in aqueous media[J].Electrochimica Acta,1994,39(11-12):1833-1839.
3.Hori Y.Electrochemical CO 2 reduction on metal electrodes[M]//Modern aspects of electrochemistry.Springer,New York,NY,2008:89-189.
4.Katoh A,Uchida H,Shibata M,et al.Design of Electrocatalyst for CO 2 Reduction:V.Effect of the Microcrystalline Structures of Cu-Sn and Cu-Zn Alloys on the Electrocatalysis of Reduction[J].Journal of the Electrochemical Society,1994,141(8):2054.
Disclosure of Invention
The invention aims to further improve the electrocatalytic reduction of CO by the copper-zinc bimetallic nanowire catalyst 2 The efficiency and stability of the preparation of CO are improved, and the method for preparing the copper-zinc bimetallic nanowire with the phase separation structure through three steps of atomic layer deposition technology, outer layer coating of ZIF-8 by a hydrothermal method and high-temperature calcination is provided, wherein the nanowire with the structure has high efficiency and stable electrocatalysis of CO 2 Performance of reduction to produce CO.
The technical scheme provided by the invention is as follows:
synthetic high-efficiency electrocatalysis CO 2 The method for reducing the Cu-Zn bimetallic catalyst comprises the step of synthesizing high-efficiency electrocatalytic CO by an atomic layer deposition technology 2 The method for preparing the CO phase-separated copper-zinc bimetallic nanowire through reduction comprises the steps of firstly depositing a layer of 30-80nm zinc oxide on the surface of a copper oxide nanowire obtained through anodic oxidation and high-temperature annealing through an atomic layer deposition technology, then coating a layer of ZIF-8 on the surface of the copper oxide @ zinc oxide nanowire with a core-shell structure through a hydrothermal method, and finally performing high-temperature annealing under the protection of inert gas to obtain the phase-separated copper-zinc bimetallic nanowire. The method is characterized by comprising the following specific processes:
step S1: preparing a layer of compact copper hydroxide nanowire on the surface of the copper substrate in an alkaline solution by using an anodic oxidation method, and annealing at high temperature in an air atmosphere to obtain the copper oxide nanowire.
Step S2: depositing a layer of zinc oxide with the thickness of 30-80nm on the surface of the obtained copper oxide nanowire by utilizing an atomic layer deposition technology and taking diethyl zinc as a zinc source and water as an oxygen source to obtain the copper oxide @ zinc oxide nanowire with the shell-core structure.
And step S3: and (3) taking dimethyl imidazole as a precursor, taking zinc oxide on the surface of the copper oxide @ zinc oxide nanowire obtained in the step (S2) as a zinc source, and preparing ZIF-8 by a hydrothermal method to obtain the copper oxide @ zinc oxide nanowire with the surface wrapped by the ZIF-8.
And step S4: and (4) calcining the copper oxide @ zinc oxide nanowire of the ZIF-8 obtained in the step (S3) at a high temperature in an inert atmosphere, carbonizing the ZIF-8, reducing zinc oxide and copper oxide on the surface of the nanowire by using the carbonized ZIF-8 as a reducing agent, and volatilizing the zinc obtained by reduction at a high temperature to obtain the phase-separated copper-zinc bimetallic nanowire consisting of the copper obtained by reducing the zinc oxide and the copper oxide.
Further limiting, the thickness of the copper oxide @ zinc oxide nanowire zinc oxide of the shell-core structure in the step S2 of preparing the phase-separated copper-zinc bimetallic nanowire precursor is 50nm.
Further limiting, the preparation method of the copper oxide @ zinc oxide nanowire coated with ZIF-8 in the step S3 of preparing the phase-separated copper-zinc bimetal nanowire precursor is that the copper oxide @ zinc oxide nanowire in the previous limitation is placed in 1.2mM dimethyl imidazole solution (V) DMF ：V H2O =3: 1) Standing at 70 deg.C for 6h.
And further limiting, and calcining the copper oxide @ zinc oxide nanowire wrapped with ZIF-8 obtained in the last step at 850 ℃ for 1h in an inert atmosphere to obtain the phase-separated copper-zinc bimetallic nanowire.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is based on the atomic layer deposition technology, and obtains the copper-zinc bimetallic nanowire material with the phase separation structure by utilizing a hydrothermal method and a high-temperature annealing mode.
2. The method has simple operation and high controllability, and can obtain the copper-zinc bimetal nanowire with the phase separation structure by a simple three-step method.
3. The phase-separated copper-zinc bimetallic nanowire synthesized by the method has a unique phase-separated nanowire structure, and is different from the shell-core structure and the alloy structure reported in the past.
4. The phase-separated copper-zinc bimetallic nanowire synthesized by the invention can be used for electrocatalysis of CO 2 In the reduction performance test, excellent catalytic CO is shown 2 The performance of CO is prepared by reduction, the Faraday efficiency is up to 93 percent, and the stable operation can be carried out for at least 15h.
5. The phase-separated copper-zinc bimetallic nanowire catalyst provided by the invention effectively improves the electrocatalysis of CO by the zinc metal catalyst 2 The Faraday efficiency and stability of the reduction preparation of CO have obvious technical effect and popularization value.
Drawings
Fig. 1 is a schematic view of a scanning electron microscope of a shell-core structured copper oxide @ zinc oxide nanowire and a phase-separated copper-zinc bi-metal nanowire, wherein: (A) The copper oxide @ zinc oxide nanowire with the shell-core structure is adopted as the (B), and the copper zinc bimetallic nanowire with the phase separation is adopted as the (C) and the (D).
Fig. 2 is a schematic view of a shell-core structured copper oxide @ zinc oxide nanowire and a phase-separated copper-zinc bimetallic nanowire projection electron microscope and EDX mapping, wherein: the preparation method comprises the following steps of (A) a shell-core structure copper oxide @ zinc oxide nanowire TEM schematic diagram, (B) a shell-core structure copper oxide @ zinc oxide nanowire EDX mapping schematic diagram, (C) a phase separation copper-zinc bimetallic nanowire TEM schematic diagram, and (D) a phase separation copper-zinc bimetallic nanowire EDX mapping schematic diagram.
Fig. 3 is a shell-core structured copper oxide @ zinc oxide nanowire and phase separated copper-zinc bimetallic nanowire XRD schematic diagram, wherein: the grey line is a shell-core structure copper oxide @ zinc oxide nanowire, and the black line is a phase separation copper-zinc bimetal nanowire.
FIG. 4 shows electrocatalytic reduction of CO by copper oxide @ zinc oxide nanowires in shell-core structure and phase-separated copper-zinc bimetallic nanowires 2 Preparation of CO Faraday efficiency.
FIG. 5 shows electrocatalytic reduction of CO by copper oxide @ zinc oxide nanowires with shell-core structure and phase-separated copper-zinc bimetallic nanowires 2 A stability profile, wherein: (A) Phase separation of copper and zincA bimetallic nanowire, and (B) a shell-core structure copper oxide @ zinc oxide nanowire.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: preparation of core-shell structure copper oxide @ zinc oxide nanowire
Selecting a copper mesh as a copper substrate material, carrying out ultrasonic cleaning on the copper mesh with a certain area in ethanol and dilute hydrochloric acid solution for 5min, washing with deionized water, and quickly drying with nitrogen; the cleaned copper mesh is used as a working electrode, copper sheets with the same area are used as counter electrodes, 3M KOH is used as electrolyte in a two-electrode system, and the electrolyte concentration is 8mA/cm 2 Carrying out anodic oxidation under the current density of the copper net to obtain copper hydroxide nanowires growing on the surface of the copper net; and calcining for 1.5h at 150 ℃ in an air atmosphere to obtain the copper oxide nanowire growing on the surface of the copper mesh.
The method is characterized in that diethyl zinc is used as a zinc source, water is used as an oxygen source, and the atomic layer deposition instrument is provided with a gas mixing tank, a tail gas pipe and upper and lower heaters of a deposition cavity, wherein the temperatures of the heaters are respectively 90 ℃, 100 ℃ and 100 ℃. And depositing 30-80nm zinc oxide on the surface of the copper oxide nanowire to obtain the core-shell structure copper oxide @ zinc oxide nanowire.
Example 2: copper-zinc bimetal nanowire with phase separation structure
Selecting a copper mesh as a copper substrate material, carrying out ultrasonic cleaning on the copper mesh with a certain area in ethanol and dilute hydrochloric acid solution for 5min, washing with deionized water, and quickly drying with nitrogen; the cleaned copper mesh is used as a working electrode, copper sheets with the same area are used as counter electrodes, 3M KOH is used as electrolyte in a two-electrode system, and the concentration of the electrolyte is 8mA/cm 2 Carrying out anodic oxidation under the current density of the copper net to obtain copper hydroxide nanowires growing on the surface of the copper net; and calcining for 1.5h at 150 ℃ in an air atmosphere to obtain the copper oxide nanowire growing on the surface of the copper mesh.
The method is characterized in that diethyl zinc is used as a zinc source, water is used as an oxygen source, and the atomic layer deposition instrument is provided with a gas mixing tank, a tail gas pipe and upper and lower heaters of a deposition cavity, wherein the temperatures of the heaters are respectively 90 ℃, 100 ℃ and 100 ℃. And depositing zinc oxide with the thickness of 30-80nm on the surface of the copper oxide nanowire to obtain the core-shell structure copper oxide @ zinc oxide nanowire.
Putting the copper oxide @ zinc oxide nanowire with the core-shell structure into DMF/H of 1.2mM dimethyl imidazole 2 And (2) putting the O solution (volume ratio =3: 1) in an oven at 50-100 ℃ for 4-10h, cooling to room temperature, and repeatedly washing with ethanol to obtain the ZIF-8 coated copper oxide @ zinc oxide nanowire.
And (2) placing the ZIF-8 coated copper oxide @ zinc oxide nanowire in a nitrogen atmosphere tube furnace, heating to 600-1000 ℃ at a speed of 5 ℃/min, maintaining for 0.5-3h, and naturally cooling to room temperature to obtain the copper-zinc bimetal nanowire with the phase separation structure.
Example 3: examples 1 and 2 give physicochemical characterization of nanowires
(1) Scanning Electron Microscope (SEM) topography detection
As shown in fig. 1, (a) (B) is copper oxide @ zinc oxide nanowire with a shell-core structure, and the shell-core structure is shown in fig. 2 (a) (B); (C) And (D) is a phase-separated copper-zinc bimetallic nanowire, and the nanowire structure consisting of copper and zinc two-phase separated metals is shown in figures 2 (C) (D).
(2) Transmission Electron Microscope (TEM) and elemental distribution spectroscopy (EDX) detection
FIG. 2 (A) shows the nanowire as a core-shell structure, and as can be seen from FIG. 2 (B), the inner layer is copper oxide and the outer layer is zinc oxide; fig. 2 (C) is a TEM schematic diagram of a phase-separated copper-zinc bimetallic nanowire, and fig. 2 (D) demonstrates that it is a bimetallic nanowire composed of phase-separated copper and zinc.
(3) XRD crystal and component composition detection
And (3) ultrasonically treating the two samples in ethanol for 30min to obtain corresponding nanowire ethanol dispersion, dripping the nanowire ethanol dispersion on the surface of the glass, and performing XRD detection after drying. Because the zinc oxide deposited by the atomic layer deposition technology is in an amorphous state, the copper oxide @ zinc oxide nanowire with the shell-core structure only belongs to the diffraction peak of the copper oxide, as shown in figure 3. And the phase separation copper-zinc bimetal nanowire shows diffraction peaks of zinc oxide, cuprous oxide and copper, and confirms the existence of two components of copper and zinc.
Example 4: electrocatalytic CO 2 Reduction Performance test
Electrocatalytic CO 2 The reduction performance detection is carried out in a double-chamber sealed H-cell, a corresponding nanowire sample is taken as a working electrode, iridium oxide is taken as a counter electrode, silver/silver chloride is taken as a reference electrode, and CO 2 Saturated 0.1M KHCO 3 As electrolyte, CO in the test procedure 2 The flow was continued at 10 sccm. The samples obtained in example 1 and example 2 were tested separately for electrocatalytic CO at different potentials 2 The reduction performance, each potential test was 40min, gas chromatography injection started after 100s of electrolysis, gas samples were collected every 8 min, and fig. 4 shows the average value of the 40min tests.
Electrocatalytic CO of two samples, as shown in FIG. 4 2 The main products of reduction are CO, but the copper oxide with a shell-core structure @ zinc oxide nanowire still has a large amount of byproduct hydrogen, and the Faraday efficiency of CO is obviously reduced in a stability test of 9 h (FIG. 5 (B)). And the phase-separated Cu-Zn bimetal nano wire electrocatalysis CO 2 The faradaic efficiency for CO production by reduction reached 93% at-1.2v vs. rhe (figure 4). Meanwhile, the phase-separated copper-zinc bimetallic nanowires exhibited excellent stability, and the faraday efficiency of CO did not significantly decrease in the stability test of 15h (fig. 5 (a)).
In summary, the invention provides a method for obtaining a copper-zinc bimetal nanowire material with a phase separation structure by using a hydrothermal method and a high-temperature annealing simple three-step method based on an atomic layer deposition technology. At the same time, electrocatalysis of CO 2 Reduction performance test proves that the phase separation copper-zinc bimetal nano wire electrocatalysis CO 2 High-efficiency and stable electrocatalytic CO with Faraday efficiency of 93 percent and stable operation for at least 15h for preparing CO by reduction 2 Reducing the copper-zinc bimetallic catalyst.

Claims (2)

1. Synthetic efficient electrocatalysis CO 2 The method for reducing the copper-zinc bimetallic catalyst is characterized by comprising the following steps: the method utilizes an atomic layer deposition technology, a hydrothermal method and a high-temperature annealing simple three-step method, takes a conductive matrix with copper oxide nanowires grown in situ as a substrate, utilizes the atomic layer deposition technology to deposit zinc oxide with controllable thickness on the surface of the conductive matrix to obtain the copper oxide @ zinc oxide nanowires with shell-core structures,coating a layer of ZIF-8 on the surface of the copper oxide coated zinc oxide nanowire by a hydrothermal method to obtain a ZIF-8 coated copper oxide coated zinc oxide nanowire, and finally calcining the copper oxide coated zinc oxide nanowire at high temperature under the protection of inert atmosphere to obtain a copper-zinc bimetallic nanowire material with a phase separation structure;
preparing a layer of compact copper hydroxide nanowire on the surface of a copper substrate in an alkaline solution by using an anodic oxidation method, and annealing at high temperature in an air atmosphere to obtain the copper oxide nanowire; in a two-electrode system, 3M KOH is used as electrolyte and 8mA/cm 2 Anodizing at the current density of (1);
wherein the deposition thickness of the zinc oxide of the copper oxide with the shell-core structure @ zinc oxide nanowire is 30-80nm;
wherein the hydrothermal method is carried out by using 0.8-1.6mM dimethyl imidazole in DMF/H 2 The method comprises the following steps of (1) taking an O solution (volume ratio = 3);
when the copper-zinc bimetallic nanowire with the phase separation structure is obtained by calcining the ZIF-8-coated copper oxide @ zinc oxide nanowire at high temperature under the protection of inert atmosphere, the ZIF-8 is carbonized and used as a reducing agent to reduce zinc oxide and copper oxide on the surface of the nanowire, and zinc obtained by reduction volatilizes at high temperature to obtain the phase separation copper-zinc bimetallic nanowire consisting of the zinc oxide and copper obtained by reduction of the copper oxide, wherein the calcining temperature is 850 ℃ and the calcining time is 1h.
2. The method of claim 1, wherein the phase-separated bimetallic Cu-Zn nanowires are obtained in the presence of CO 2 Saturated 0.1M KHCO 3 In the electrolyte, CO is electrocatalyzed in the reduction potential range of-1.0 to-1.6V vs. RHE 2 The reduction performance is efficient and stable.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437278A (en) * 2018-12-04 2019-03-08 复旦大学 It is a kind of based on copper oxide-tin oxide core-shell nano cable architecture air-sensitive nano material, preparation process and its application
CN109569695A (en) * 2019-01-18 2019-04-05 南开大学 A kind of preparation method and its application method of the catalyst with core-casing structure for hydrogenation of carbon dioxide
CN109746022A (en) * 2019-01-18 2019-05-14 南开大学 A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction
CN110342563A (en) * 2019-07-17 2019-10-18 湖北大学 A kind of cupric oxide nano line and its preparation method and application

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* Cited by examiner, † Cited by third party
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WO2014021530A1 (en) * 2012-08-02 2014-02-06 인하대학교산학협력단 Sensor including core-shell nanostructure, and method for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437278A (en) * 2018-12-04 2019-03-08 复旦大学 It is a kind of based on copper oxide-tin oxide core-shell nano cable architecture air-sensitive nano material, preparation process and its application
CN109569695A (en) * 2019-01-18 2019-04-05 南开大学 A kind of preparation method and its application method of the catalyst with core-casing structure for hydrogenation of carbon dioxide
CN109746022A (en) * 2019-01-18 2019-05-14 南开大学 A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction
CN110342563A (en) * 2019-07-17 2019-10-18 湖北大学 A kind of cupric oxide nano line and its preparation method and application

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