CN116288417A - Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction - Google Patents
Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction Download PDFInfo
- Publication number
- CN116288417A CN116288417A CN202211500606.2A CN202211500606A CN116288417A CN 116288417 A CN116288417 A CN 116288417A CN 202211500606 A CN202211500606 A CN 202211500606A CN 116288417 A CN116288417 A CN 116288417A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon dioxide
- composite nano
- cuprous oxide
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of electrocatalytic application, relates to a composite catalytic electrode, and in particular relates to an application method of a tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction, which comprises the following steps: to load BiVO 4 Is used as a working electrode to load Cu 2 O‑SnO 2 The carbon paper of the composite nano particles is used as a counter electrode, and the prepared CO is added to two sides of an H-type electrolytic cell 2 Saturated electrolyte solution, continuously introducing CO 2 To remove oxygen and then to remove 20 to 100The catalytic reduction of carbon dioxide is carried out under the condition of no illumination or illumination at the gas flow rate of 20-30 ℃ in mL/min. The invention is realized by adopting the pellet-shaped SnO 2 Cu compounded in concave octahedron 2 The O surface effectively reduces the electrochemical impedance of the catalyst and accelerates CO 2 The formation of RR intermediate enhances the electrochemical active area of the catalyst, and the anode shows stronger catalytic activity after being excited by light, thus having good application prospect in the fields of environment, energy sources and the like.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic application, relates to a composite catalytic electrode, and particularly relates to an application method of a tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction.
Background
In recent decades, the concentration of carbon dioxide has increased, CO 2 Reduction (CO) 2 RR) becomes an imperative solution. Although the electrocatalytic and photocatalytic reduction modes are relatively mature, both methods face their limitations, such as electrocatalytic methods which rely heavily on the input of electrical energy, and the CO of photocatalytic methods 2 Conversion efficiency and product selectivity are still not ideal. The photoelectrocatalysis reduction method combines the advantages of electrocatalysis and photocatalysis to improve CO 2 Conversion efficiency and reduced energy input offer a promising approach. To date, the application of photoelectrocatalysis carbon dioxide reduction using a photoanode as a working electrode has been recently disclosed. Kim et al prepared BiVO in a photoanode (working electrode) -photocathode system 4 040 crystal face of (2) enables the cathode copper sheet to resist CO under different bias voltages 2 Reduction gives higher selectivity. Liu et al efficiently photoelectrocatalyze the reduction of carbon dioxide to liquid fuel by preparing a flower-sphere-shaped BiOBr photocatalyst and a platy CuO catalyst in a photoanode-photocathode (working electrode) system.
BiVO 4 Is a typical n-type semiconductor, its O2 p and Bi 6s orbitals can promote the transmission of electrons from the Valence Band (VB) to the Conduction Band (CB), reduce the band gap energy and maintain excellent stability in aqueous solutions, and is an excellent photoanode material. In aqueous electrolytes, many high performance electrocatalysts often rely on the use of precious metals, and the high cost has prevented their industrial use. Copper-based electrodes have been widely studied for their non-toxicity, low cost, simple synthesis, and abundant resources. Sn doping and modification with low price can obviously improve copper-based electrocatalystThe Faraday efficiency of CO is calculated according to the Density Functional Theory (DFT) of the related literature, and the existence of Sn greatly influences the adsorption capacity of Cu, so that the adsorption capacity of H is greatly reduced, and the selectivity of CO is improved.
In a photoanode (working electrode) -electric cathode system, the invention synthesizes BiVO by electrodeposition 4 The photo anode is used as a working electrode, and the CSx nano catalyst prepared by the carbon paper substrate is regulated and controlled to perform photoelectrocatalytic reduction on carbon dioxide in different electrolytes. In addition, a platinum sheet-CS 4 system and BiVO are respectively designed 4 -Cu 2 The O system was subjected to a control experiment.
Disclosure of Invention
The invention aims to disclose a tin dioxide doped cuprous oxide composite nano catalyst (Cu 2 O-SnO 2 Abbreviated as CSx, x=1, 2,3,4, 5) in the photoelectrocatalytic reduction of carbon dioxide.
The technical scheme is as follows:
bismuth nitrate, potassium iodide, p-benzoquinone, ethanol and FTO conductive glass are used as raw materials, and an electrodeposition method and calcination treatment are used for growing BiVO on the surface of the FTO 4 . Copper sulfate, oleic acid, sodium hydroxide and sodium ascorbate are used as raw materials, and are stirred at constant temperature to prepare concave octahedral Cu 2 And O, using sodium chloride, stannic chloride, ethanol and conductive carbon paper as raw materials, and stirring and precipitating to obtain the CSx.
Tin dioxide doped cuprous oxide (Cu 2 O-SnO 2 ) The application method of the composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide comprises the following steps: to load BiVO 4 Is used as a working electrode to load Cu 2 O-SnO 2 The carbon paper of the composite nano particles is used as a counter electrode, and the prepared CO is added to two sides of an H-type electrolytic cell 2 Saturated electrolyte solution, continuously introducing CO 2 To remove oxygen, and then carrying out catalytic reduction of carbon dioxide under the condition of no illumination or illumination at the temperature of 20-30 ℃ at the gas flow rate of 20-100 mL/min.
In a preferred embodiment of the present invention, the CO-based catalyst is 2 The saturated electrolyte solution is prepared with concentration of 0.1-0.5mol.L -1 Preferably, youSelecting 0.1 mol.L -1 KHCO of (C) 3 Placing KOH or NaCl solution in dark place, introducing CO 2 So as to saturate the same.
In a preferred embodiment of the present invention, the load Cu 2 O-SnO 2 The preparation method of the carbon paper of the composite nanoparticle catalyst comprises the following steps: preparation of concave octahedral Cu 2 50mL of O ethanol solution is added with 5mL of 0.1-0.3 MNaCl solution, and SnCl is prepared 4 50mL of ethanol solution, and the molar ratio of Cu to Sn is 10-50:1; the SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) in an ethanol solution of O, reacting for 5-10 min, centrifuging, cleaning, drying at the vacuum temperature of 50 ℃ to obtain catalyst particles, taking carbon paper as a load substrate, uniformly ultrasonically and then dripping the catalyst particles on the surface of the substrate, and drying to obtain the catalyst.
In the preferred embodiment of the invention, the working voltage of the electrolytic cell is 1.2-1.6V.
BiVO according to the invention 4 The preparation method of the FTO tablet is shown in CN110408951A; the concave octahedral Cu 2 O, its preparation is described in CN107720803A.
The invention is characterized in that:
(1) Tin element is introduced to form concave octahedral Cu 2 O-supported small spherical SnO 2 The nano-particle catalyst of the (2) effectively improves the electrochemical active area of the catalyst, thereby increasing active sites, and in addition, the reduction of impedance also enables the electron transfer to be faster;
(2) The system of photo anode (working electrode) -electric cathode is used, and CO selectivity is improved and hydrogen evolution effect is effectively inhibited through the addition of the photo anode.
The CSx composite nanoparticle catalyst prepared by the invention utilizes instruments such as X-ray diffraction (XRD), scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), X-ray photoelectron spectroscopy (XPS) and the like to analyze the morphology structure and the composition of the product, and a standard three-electrode electrochemical workstation is used for measuring a photocurrent density curve (J-V) and the like so as to evaluate the photoelectrocatalysis carbon dioxide reduction performance.
The reagent reagents used in the present invention are all commercially available.
Advantageous effects
The method synthesizes BiVO through an electrodeposition method and calcination post-treatment 4 The photoelectric anode material synthesizes Cu through simple constant temperature stirring and deposition 2 O-SnO 2 Cathode material, pellet type SnO prepared by the method 2 Cu compounded in concave octahedron 2 The O surface effectively reduces the electrochemical impedance of the catalyst and accelerates CO 2 Formation of RR intermediate, enhanced electrochemical active area of catalyst, and strong catalytic activity of the whole system after light excitation of anode, and photoanode (working electrode) -photocathode system and prepared Cu 2 O-SnO 2 The catalyst has good application prospect in the fields of environment, energy sources and the like.
Drawings
FIG. 1 XRD patterns of CS4 nanoparticle catalysts prepared in example 4;
FIG. 2 XPS spectrum of CS4 nanoparticle catalyst prepared in example 4;
FIG. 3 is an SEM image of a CS4 nanoparticle catalyst prepared according to example 4;
FIG. 4 is a TEM image of the CS4 nanoparticle catalyst prepared in example 4;
FIG. 5A counter electrode, biVO, of the CS4 nanoparticle catalyst prepared in example 4 4 The photoelectric anode is a Faraday efficiency graph of the working electrode;
FIG. 6A BiVO with the CSx nanoparticle catalyst prepared in examples 1-5 as the counter electrode 4 The photoelectric anode is a Faraday efficiency graph of the working electrode;
FIG. 7 BiVO prepared in examples 4, 6 and 7 4 When the photo-anode and the platinum sheet are respectively working electrodes, the CS4 nanoparticle catalyst is a counter electrode and BiVO 4 When the photoelectric anode is a working electrode, cu 2 Faraday efficiency plot of O nanoparticle catalyst.
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
Example 1
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C1) composite nano-particles as a working electrode, taking carbon paper loaded with CS1 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS1 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.06mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 10:1 (abbreviated as CS 1). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS1 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 32%, 38%, and 19.6%, respectively.
Example 2
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C1) composite nano-particles as a working electrode, taking carbon paper loaded with CS1 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS2 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.03mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 20:1 (abbreviated as CS 2). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS2 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 19%, 50%, and 14%, respectively.
Example 3
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C/S) as a working electrode, taking carbon paper loaded with CS3 composite nano particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS3 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.02mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 30:1 (abbreviated as CS 3). The SnCl 4 Is added dropwise into the ethanol solution of the (2) concave octahedral acidBulk Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS3 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 16.8%, 40%, 37%, respectively.
Example 4
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C4) composite nano-particles as a working electrode, taking carbon paper loaded with CS4 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS4 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.015mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 40:1 (abbreviated as CS 4). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS4 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 14%, 55%, 25%, respectively.
The presence of cuprous oxide is clearly observed from the XRD results of FIG. 1, but the characteristics of Sn element cannot be observedThe peak, probably due to the excessively low content of Sn element. The presence of Sn was confirmed by the XPS results in fig. 2, and it was further confirmed by combining the scanning electron microscope of fig. 3 with the transmission electron microscope of fig. 4 that Sn was successfully loaded with the cuprous oxide surface. Subsequently, the photoelectrocatalytic carbon dioxide reduction test using CS4 catalyst as the photocathode clearly observed that the Faraday efficiency of CO reached a maximum of 55% at 1.4V, at which time H 2 The Faraday efficiencies with HCOOH were 14% and 25%, respectively.
Example 5
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C5) composite nano-particles as a working electrode, taking carbon paper loaded with CS5 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS5 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.012mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 50:1 (abbreviated as CS 5). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS5 nano catalyst is in the range of 1.2-1.6V, and H when the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 16.9%, 44%, 30%, respectively.
Example 6
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. platinum sheet is used as working electrode, CS4 composite nano particle loaded carbon paper is used as counter electrode, and prepared CO is added into two sides of H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide at 25℃with a gas flow rate of 50mL/min was carried out without illumination.
The preparation method of the CS4 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.015mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 40:1 (abbreviated as CS 4). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS4 nano catalyst is in the range of 1.2V-1.6V, and H is generated when the optimal voltage is 1.4V 2 The Faraday efficiencies of CO and HCOOH were 60%, 4% and 14%, respectively.
Example 7
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 KHCO of (C) 3 The solution is placed in the dark and CO is introduced 2 Saturating the solution for 30 min;
B. to load BiVO 4 FTO of (a) as working electrode with load concave octahedral Cu 2 The carbon paper of O is a counter electrode, and the prepared CO is added to two sides of an H-type electrolytic cell 2 Saturated KHCO 3 The solution is prepared into a liquid preparation,continuous CO feeding 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The concave octahedral Cu 2 O takes carbon paper as a load substrate, and catalyst particles are dripped on the surface of the carbon paper after ultrasonic homogenization.
Cu 2 H when O nano catalyst is in the range of 1.2-1.6V and optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 77%, 5.3%, and 13.7%, respectively.
Example 8
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 Is placed in the dark and is filled with CO 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C4) composite nano-particles as a working electrode, taking carbon paper loaded with CS4 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS4 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.015mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 40:1 (abbreviated as CS 4). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS4 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 35%, 30%, 28%, respectively.
Example 9
An application method of a tin dioxide doped cuprous oxide composite nanoparticle catalyst in photoelectrocatalysis of carbon dioxide reduction comprises the following steps:
A. preparing 60mL of the solution with the concentration of 0.1 mol.L -1 Is placed in the dark and is filled with CO 2 Saturating the solution for 30 min;
B. to load BiVO 4 Taking FTO of (C4) composite nano-particles as a working electrode, taking carbon paper loaded with CS4 composite nano-particles as a counter electrode, and adding prepared CO at two sides of an H-type electrolytic cell 2 Saturated KHCO 3 Continuously introducing CO into the solution 2 To remove oxygen and then catalytic reduction of carbon dioxide under light conditions was carried out at 25℃again at a gas flow rate of 50 mL/min.
The preparation method of the CS4 composite nanoparticle catalyst-loaded carbon paper comprises the following steps: preparation of 0.3mM concave octahedral Cu 2 50mL of O ethanol solution was followed by 5mL of 0.2M NaCl solution and 0.015mM SnCl 4 50ml of ethanol solution, the molar ratio of cu to Sn is 40:1 (abbreviated as CS 4). The SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) reacting in ethanol solution of O for 5-10 min, centrifuging the obtained solution, cleaning, drying at the temperature of 50 ℃ in vacuum, then taking carbon paper as a load substrate, and dripping catalyst particles on the surface of the uniform ultrasonic treatment.
CS4 nano catalyst is in the range of 1.2-1.6V, and H is the optimal voltage is 1.4V 2 The Faraday efficiencies of CO, HCOOH were 32%, 35%, 25%, respectively.
As shown in fig. 6, when the anode in the system becomes a platinum sheet, the carbon dioxide conversion ability is extremely low, and the faraday efficiencies of CO and HCOOH are 4% and 14%, respectively. When the system takes the unloaded cuprous oxide as the electric cathode, the Faraday efficiencies of CO and HCOOH are respectively 5.3 percent and 13.7 percent, and compared with the prior art, the total Faraday efficiency of the gas is obviously higher than that of the gas participating in the condition without illumination. Meanwhile, as can be seen from fig. 7, the CS4 catalyst at 1.4V has the strongest hydrogen evolution inhibiting ability and has higher selectivity to CO.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (8)
1. An application method of a tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide is characterized in that: to load BiVO 4 Is used as a working electrode to load Cu 2 O-SnO 2 The carbon paper of the composite nano particles is used as a counter electrode, and the prepared CO is added to two sides of an H-type electrolytic cell 2 Saturated electrolyte solution, continuously introducing CO 2 To remove oxygen and then to perform catalytic reduction of carbon dioxide at 20-30 ℃ at a gas flow rate of 20-100 mL/min.
2. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the warp CO 2 The saturated electrolyte solution is prepared with concentration of 0.1-0.5mol.L -1 KHCO of (C) 3 Placing KOH or NaCl solution in dark place, introducing CO 2 So as to saturate the same.
3. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the warp CO 2 The saturated electrolyte solution is prepared with concentration of 0.1 mol.L -1 KHCO of (C) 3 Placing KOH or NaCl solution in dark place, introducing CO 2 So as to saturate the same.
4. The method for applying the tin dioxide doped cuprous oxide composite nano catalyst to photoelectrocatalytic reduction of carbon dioxide according to claim 1, wherein the supported Cu is as follows 2 O-SnO 2 The preparation method of the carbon paper of the composite nanoparticle catalyst comprises the following steps: preparing concave octahedralBulk Cu 2 50mL of O ethanol solution is added with 5mL of 0.1-0.3M NaCl solution, and SnCl is prepared 4 50mL of ethanol solution, and the molar ratio of Cu to Sn is 10-50:1; the SnCl 4 Is added dropwise with concave octahedral Cu 2 And (3) in an ethanol solution of O, reacting for 5-10 min, centrifuging, cleaning, drying at the vacuum temperature of 50 ℃ to obtain catalyst particles, taking carbon paper as a load substrate, uniformly ultrasonically and then dripping the catalyst particles on the surface of the substrate, and drying to obtain the catalyst.
5. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the working voltage of the electrolytic cell is 1.2-1.6V.
6. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the catalytic reduction of carbon dioxide is carried out in the absence of light or under light conditions.
7. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the BiVO 4 The preparation method of the FTO tablet is shown in CN110408951A.
8. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that: the concave octahedral Cu 2 O, its preparation is described in CN107720803A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211500606.2A CN116288417A (en) | 2022-11-28 | 2022-11-28 | Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211500606.2A CN116288417A (en) | 2022-11-28 | 2022-11-28 | Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116288417A true CN116288417A (en) | 2023-06-23 |
Family
ID=86819144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211500606.2A Pending CN116288417A (en) | 2022-11-28 | 2022-11-28 | Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116288417A (en) |
-
2022
- 2022-11-28 CN CN202211500606.2A patent/CN116288417A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guan et al. | CdS@ Ni 3 S 2 core–shell nanorod arrays on nickel foam: a multifunctional catalyst for efficient electrochemical catalytic, photoelectrochemical and photocatalytic H 2 production reaction | |
| Chen et al. | Enhanced photoelectrochemical water splitting performance of α-Fe2O3 nanostructures modified with Sb2S3 and cobalt phosphate | |
| Yang et al. | Molybdenum doped CuWO4 nanoflake array films as an efficient photoanode for solar water splitting | |
| Zhang et al. | Nanoparticle metal Ni cocatalyst on NiTe2 microsphere for improved photocatalytic hydrogen evolution | |
| CN107252705B (en) | Catalyst for electrochemical reduction of carbon dioxide and preparation method thereof | |
| Hu et al. | Enhanced electrocatalytic ethanol oxidation reaction in alkaline media over Pt on a 2D BiVO 4-modified electrode under visible light irradiation | |
| CN111118539B (en) | Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method | |
| CN114525540B (en) | Nano material with noble metal particles dispersed on surface of non-noble metal substrate, and preparation method and application thereof | |
| CN112103520A (en) | Anode catalyst of alcohol fuel cell | |
| Mohanta et al. | Encapsulating band gap engineered CoSnO3 mixed metal oxide nanocomposite in rGO matrix: a novel catalyst towards LED light induced photoelectrocatalytic water oxidation at neutral pH | |
| Yang et al. | Three-phase interface of SnO2 nanoparticles loaded on hydrophobic MoS2 enhance photoelectrochemical N2 reduction | |
| CN111068717B (en) | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof | |
| CN114525542A (en) | For electrocatalytic reduction of CO2Nano palladium alloy catalyst, and preparation method and application thereof | |
| Yang et al. | Efficient CO2 reduction to formate in a photoanode-driven photoelectrocatalysis system using a Bi2Se3/Bi2O3 nanocomposite cathode | |
| CN109569285B (en) | Nitrogen-doping-based graphene-based electrocatalyst and preparation and application thereof | |
| Dai et al. | Controllable synthesis of Co nanoparticles with the assistance of cucurbit [6] uril and its efficient photoelectrochemical catalysis in water splitting on a gC 3 N 4 photoanode | |
| CN108360017B (en) | Catalyst for electrochemically reducing carbon dioxide into formic acid and preparation method thereof | |
| CN111333104A (en) | Preparation method and application of nanoscale tin dioxide | |
| CN116288417A (en) | Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction | |
| CN114774983B (en) | Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof | |
| CN114561655B (en) | Preparation method and application of rare earth cerium doped nickel sulfide/iron sulfide heterojunction material | |
| CN114959792A (en) | Preparation method of monatomic Pt catalyst and hydrogen evolution application thereof | |
| CN111155138A (en) | Containing g-C3N4And metal-doped BiVO4And its application in photoelectrocatalysis | |
| Morgante et al. | Microbial bioelectrochemical cells for hydrogen generation based on irradiated semiconductor photoelectrodes | |
| CN112850860A (en) | Preparation method and application of nitrogen-doped ordered mesoporous carbon electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |