CN115094473B - For CO 2 Electrocatalytic material Ti-Cu of RR 2 O preparation method - Google Patents

For CO 2 Electrocatalytic material Ti-Cu of RR 2 O preparation method Download PDF

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CN115094473B
CN115094473B CN202210714532.6A CN202210714532A CN115094473B CN 115094473 B CN115094473 B CN 115094473B CN 202210714532 A CN202210714532 A CN 202210714532A CN 115094473 B CN115094473 B CN 115094473B
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preparation
precursor
solution
electrocatalytic
mixing
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CN115094473A (en
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严乙铭
姚烨波
张惠颖
孙彦飞
杨志宇
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

For CO 2 Electrocatalytic material Ti-Cu of RR 2 A preparation method of O belongs to the field of electrocatalytic materials. Comprising the preparation of a precursor solution, followed by the addition of TiCl 3 Solution preparation of dark yellow solid Ti-Cu 2 O. The invention is mainly used for preparing Ti-Cu 2 O electrocatalytic CO 2 Reducing material, solving the problem of pure Cu in the direction 2 O is used for CO 2 And the RR performance and stability are poor. In addition, with commercial Cu 2 Compared with O, the invention takes the copper chloride solution as the copper source and the titanium chloride precursor as the titanium source to obtain the Ti-Cu through complex precipitation 2 O, and shows more excellent C 2 Product C 2 H 5 OH selectivity and stability.

Description

For CO 2 Electrocatalytic material Ti-Cu of RR 2 O preparation method
Technical Field
The invention belongs to electrocatalytic reduction of CO 2 Preparation C 2 H 5 OH field, specifically disclose a method for CO 2 Electrocatalytic material Ti-Cu of RR 2 O is prepared by a method.
Background
With the development of technology, there is an increasing demand for fossil fuels, however, excessive use of fossil fuels generates a large amount of carbon dioxide (CO) 2 ) The gas causes a sharp rise in the carbon dioxide content of the air. In solving CO 2 On the problem of pollution, the most promising method at present is to electrically catalyze CO 2 The product is reduced into a product with high added value, which can simultaneously solve the problem of too high carbon dioxide concentration in the atmosphere and relieve the current situation of energy shortage. In CO 2 Conversion of numerous products, C 2 The product has higher utilization value and economic value compared with carbon monoxide methane. Numerous studies have found that copper-based materials are the only electrochemical reduction of carbon dioxide to C 2 Compounds and methods for their preparationTransition metal catalysts for high value and high energy density products such as alcohols. However, cu-based catalysts have small differences in starting potentials when they produce different products, resulting in selectivity and stability that remain limited.
Electrocatalytic CO 2 RR the current research direction is to modify the existing catalyst or understand the relationship between the catalyst performance and structure, so that the catalyst can electrochemically reduce CO by designing the specific size, structure, morphology and composition of the catalyst 2 The medium performance reaches the industrialization level. The commercial cuprous oxide catalyst has the problems of poor selectivity to products, low conversion rate and poor stability. The catalyst we prepared was prepared by incorporating Ti into Cu 2 In O, ti is hybridized with Cu and O, so that the electronic structure of the material is regulated, meanwhile, due to different valence states of Ti, ti in Cu-O-Ti hybridization receives electrons given from Cu, an active site Cu (I) is stabilized, and meanwhile, the ethanol corresponding to the active site Cu (I) is high in selectivity and activity, and meanwhile, the stability of the ethanol is obviously improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for conveniently and quickly preparing electrocatalytic CO 2 Reduction catalyst Ti-Cu 2 O method can obviously improve CO in the electrochemical process 2 Conversion selectivity, while greatly improving catalyst stability.
In order to solve the technical problems, the invention provides a catalyst for electrocatalytic reduction of CO 2 Ti-Cu of (C) 2 O material and its preparation method, including the following steps:
(1) Preparing a precursor A mixed solution; mixing ultrapure water, sodium citrate and copper chloride for complex precipitation to obtain a precursor A mixed solution;
(2)Ti-Cu 2 preparing O; mixing the precursor A with TiCl 3 Mixing the solution, precipitating, centrifugally washing and drying to obtain solid Ti-Cu 2 And (3) an O catalyst.
The molar ratio of the sodium citrate to the copper chloride corresponding to the step (1) is 1:1, a step of; the physical mixing is realized by magnetic stirring, the specific stirring time is 1h, and blue sediment is completely formed;
step (2) precursor A mixed solution and TiCl 3 The relation of the dosage of the solution is that the molar ratio of Cu to Ti is 3:1-1:1; the solvent used in the centrifugal washing is ultrapure water and absolute ethyl alcohol, the washing times are 3 times, and the centrifugal washing is carried out for 10 minutes at the rotating speed of 10000 rpm. The obtained product is put into a baking oven for vacuum drying, and the solid dark yellow Ti-Cu is obtained 2 O, the specific conditions of the vacuum drying are as follows: -30MPa, 60℃and 3h.
The catalyst Ti-Cu obtained by the invention 2 O for electrocatalytic reduction of CO 2 Preparation C 2 H 5 OH. Electrochemical synthesis of ethanol was performed in a typical gas-tight H-cell using a three-electrode system comprising a working electrode, a reference electrode and an auxiliary electrode, the anode and cathode compartments being separated by a cation exchange membrane (Nafion 115 DuPont) to prevent ionic contamination between the anode and cathode compartments. The working electrode is loaded with Ti-Cu 2 O hydrophobic carbon paper, ag/AgCl electrode as reference electrode and platinum sheet electrode as auxiliary electrode; after electrode preparation was completed, 40mL of 0.5mol/L KHCO was added to each of the two chambers of the H-cell 3 The solution was subjected to electrochemical electrolysis at a potential set at-1.0V to-1.4V vs. rhe, and the gas and liquid phase products of the process were collected.
The invention shortens the time required for synthesizing the material and has better C while ensuring that the prepared material has certain catalytic activity 2 Product selectivity and stability. The above features contribute to CO 2 The mechanism of the RR process catalyst is studied intensively.
Drawings
FIG. 1 shows the invention applied to CO 2 Electrocatalytic material Ti-Cu of RR 2 Schematic of the microscopic morphology of O;
FIG. 2 shows the invention applied to CO 2 Electrocatalytic material Ti-Cu of RR 2 Schematic of X-ray photoelectron spectroscopy of O;
FIG. 3 shows the invention applied to CO 2 Electrocatalytic material Ti-Cu of RR 2 O and Cu 2 C of O 2 A product selectivity comparison schematic;
Detailed Description
The following is a further detailed description of the embodiments: the present invention is not limited to the following examples.
Example 1
Referring to FIG. 1, a process for CO 2 Electrocatalytic material Ti-Cu of RR 2 O, the material mainly consists of nano-sheets.
The preparation method comprises the following steps: the dosage of the ultrapure water, the sodium citrate and the cupric chloride is respectively 70ml of ultrapure water, 20mmol of sodium citrate and 20mmol of cupric chloride; thoroughly mixing the materials by stirring to form blue precipitate; then mixing the precursor A with TiCl 3 Of solutions (TiCl) 3 Content 20%) was thoroughly mixed, wherein the molar ratio of Cu to Ti was 1:1, and the mixture was dried by centrifugal washing to give dark yellow Ti-Cu 2 And (3) an O catalyst.
In this embodiment, the microscopic morphology of the electrode is characterized and analyzed by using a scanning electron microscope, and it can be seen in fig. 1 that the material mainly consists of nanosheets, and the particle distribution is obviously seen on the surface, which is caused by the introduction of Ti substances.
FIG. 2 is a diagram of the material Ti-Cu of the present invention 2 Schematic of X-ray photoelectron spectroscopy of O; as can be seen from the XPS spectrum of the Cu2p orbit in fig. 2 (a), the prepared material contains a large amount of low-valence copper, and the valence state of the catalyst cannot be accurately judged because the Cu (0) and Cu (I) peaks appear at the same positions. To determine whether the low valence copper is Cu (0) or Cu (I), copper Auger spectroscopy is used to distinguish the valence states of copper. It can be seen from fig. 2 (b) that the low-priced copper exists mainly in the form of Cu (I), so that it can be confirmed that the material contains only Cu (I). Furthermore, it can be seen from the Ti 2p orbitals of FIG. 2 (c) that the catalyst contains significantly Ti element and that O1s of FIG. 2 (d) contains predominantly Cu-O bonds.
FIG. 3 is a schematic representation of product selectivity at different potentials of the material of the present invention; the specific experimental parameters are as follows: the potential is set to be-1.0V to-1.4V vs. RHE, and the point taking interval is 0.05s; run time 3600s; sensitivity is 0.1A/V; the ambient atmosphere of the battery is CO at 30mL/min 2 The gas flow rate was continuously vented to the cell for 30 min. As can be seen from FIG. 3, the material of the present invention Ti-Cu 2 O pairCH 3 CH 2 The FE value of OH reaches 18.28% at the highest, and the selectivity to HCOOH is only 1.29%, indicating Ti-Cu 2 O for CH 3 CH 2 OH has very high selectivity. Whereas commercial Cu 2 O for CH 3 CH 2 The FE value of OH is almost zero, and C 2 The products being mainly C 2 H 4 C thereof 2 H 4 The highest FE value was 11.72% and the selectivity to HCOOH was 10.35%, indicating commercial Cu 2 O selectivity is poor. The material of the invention has higher selectivity through comparison. Preliminary demonstration of Ti-Cu 2 The O material has higher selectivity to ethanol products, thereby proving better performance.
The foregoing is merely exemplary embodiments of the present invention, and specific structures and features that are well known in the art are not described in detail herein. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.

Claims (6)

1. Ti-Cu 2 The preparation method of the O material is characterized by comprising the following steps:
(1) Preparing a precursor A mixed solution; mixing ultrapure water, sodium citrate and copper chloride for complex precipitation to obtain a precursor A mixed solution;
(2)Ti-Cu 2 preparing O; mixing the precursor A with TiCl 3 Mixing the solution, precipitating, centrifugally washing and drying to obtain solid Ti-Cu 2 An O catalyst;
the molar ratio of the sodium citrate to the copper chloride corresponding to the step (1) is 1:1, a step of;
step (2) precursor A mixed solution and TiCl 3 The relation of the dosage of the solution is as follows: the molar ratio of Cu to Ti is 3:1 to 1: 1.
2. A Ti-Cu alloy according to claim 1 2 The preparation method of the O material is characterized by comprising the following steps ofStep (1) is carried out by magnetic stirring for a specific period of 1h, which results in complete formation of a blue precipitate.
3. A Ti-Cu alloy according to claim 1 2 The preparation method of the O material is characterized in that,
and (3) the solvents used in the centrifugal washing in the step (2) are ultrapure water and absolute ethyl alcohol.
4. A Ti-Cu alloy according to claim 1 2 The preparation method of the O material is characterized in that,
placing the product obtained in the step (2) into an oven for vacuum drying to obtain solid dark yellow Ti-Cu 2 O, the specific conditions of the vacuum drying are as follows: -30MPa, 60℃and 3h.
5. A Ti-Cu alloy prepared by the method of any one of claims 1 to 4 2 And O material.
6. A Ti-Cu alloy prepared by the method of any one of claims 1 to 4 2 Application of O material for electrocatalytic reduction of CO 2 Preparation C 2 H 5 OH。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109536991A (en) * 2018-12-14 2019-03-29 天津大学 A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide
CN113549937A (en) * 2021-08-28 2021-10-26 北京化工大学 For CO2Electrocatalytic material Cu of RR2Preparation method of O @ h-BN

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017156330A1 (en) * 2016-03-09 2017-09-14 Qatar University Method of making a copper oxide-titanium dioxide nanocatalyst
DE102017208518A1 (en) * 2017-05-19 2018-11-22 Siemens Aktiengesellschaft Production of dendritic electrocatalysts for the reduction of CO2 and / or CO

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109536991A (en) * 2018-12-14 2019-03-29 天津大学 A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide
CN113549937A (en) * 2021-08-28 2021-10-26 北京化工大学 For CO2Electrocatalytic material Cu of RR2Preparation method of O @ h-BN

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Electrochemical CO2 Reduction to Ethanol with Copper-Based Catalysts;Dilan Karapinar et al.;ACS Energy Letters;第6卷(第2期);第694-706页 *

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