CN113578305A - Modified indium oxide catalyst, application thereof and method for preparing carbon monoxide by catalytic reduction of carbon dioxide - Google Patents
Modified indium oxide catalyst, application thereof and method for preparing carbon monoxide by catalytic reduction of carbon dioxide Download PDFInfo
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- CN113578305A CN113578305A CN202110467760.3A CN202110467760A CN113578305A CN 113578305 A CN113578305 A CN 113578305A CN 202110467760 A CN202110467760 A CN 202110467760A CN 113578305 A CN113578305 A CN 113578305A
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Abstract
The invention provides a modified indium oxide catalyst, application thereof and a method for preparing carbon monoxide by catalytic reduction of carbon dioxide, belonging to the field of CO2The technical field of recovery and utilization. The modified indium oxide catalyst provided by the invention is prepared by annealing indium oxide; the atmosphere of the annealing treatment is hydrogen. In the present invention, H is an annealing treatment process2Reaction with lattice oxygen at the indium oxide surface to produce H2O, the oxygen vacancy concentration of the indium oxide surface is improved, and the electronic structure, charge transport and surface property can be adjusted to promote CO2And the increase of the oxygen vacancy concentration enables the modified indium oxide catalyst to have more electron aggregation at the Fermi energy level, and is more favorable for CO2To CO2Has high catalytic activity of CO2The conversion energy efficiency is high; also, the obtained improvementThe sexual catalyst has simple components.
Description
Technical Field
The invention relates to CO2In particular to a modified indium oxide catalyst and application thereof, and a method for preparing carbon monoxide by catalytic reduction of carbon dioxide.
Background
With the continuous development and utilization of fossil resources, CO in the atmosphere is caused2Is increased, and CO2Is a main component of greenhouse gases and seriously threatens human health and social development. Therefore, how to remove CO from the atmosphere2Efficient conversion to high value added fuels (such as CO) and chemicals has become a hotspot of current research. CO 22Has high thermodynamic stability and needs a large amount of energy input to break the C ═ O bond. And, CO2The reduction reaction is a transfer process of multiple electrons, and the reaction kinetics is slow. The research at home and abroad finds that the CO can be effectively reduced by adding the catalyst in the reaction process2Activation barrier for the reaction. For example, chinese patent CN110215916A discloses In grown on rGO (reduced graphene oxide)2O3A nano-catalyst; chinese patent CN109821526A discloses a method for constructing a metal-doped indium oxide photocatalyst based on heteronuclear MOFs (metal-organic framework material) templates; chinese patent CN111632612A discloses an indium phosphide-indium oxide p-n junction porous microsphere composite material; chinese patent CN110841622A discloses a controllable preparation of In based on MOF template2O3@ ZnO nanometer heterojunction photocatalytic material. However, the above catalyst is complicated in composition and low in energy efficiency, and the catalyst is not high enough in reactivity.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified indium oxide catalyst, an application thereof, and a method for preparing carbon monoxide by catalytic reduction of carbon dioxide, wherein the modified indium oxide catalyst provided by the present invention has the advantages of simple components, high energy efficiency, and excellent catalytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified indium oxide catalyst, which is prepared by annealing indium oxide; the atmosphere of the annealing treatment is hydrogen.
Preferably, the temperature of the annealing treatment is 200-600 ℃, and the time is 1-10 h.
The invention provides application of the indium oxide catalyst in the technical scheme in preparation of carbon monoxide through catalytic reduction of carbon dioxide.
The invention provides a method for preparing carbon monoxide by catalytic reduction of carbon dioxide, which comprises the following steps:
the adopted reaction device comprises a friction nanometer generator, a rectifier bridge and a plasma component; the plasma assembly comprises a discharge probe and a working electrode plate; the single surface of the working electrode plate is loaded with the modified indium oxide catalyst in the technical scheme; the alternating current input end of the rectifier bridge is electrically connected with the output end of the friction nano generator, the negative direct current output end of the rectifier bridge is connected with the discharge probe, and the positive direct current output end of the rectifier bridge is connected with the working electrode plate;
and electrifying the reaction device to generate triboelectric plasma, mixing the triboelectric plasma with carbon dioxide, and then carrying out catalytic reduction reaction to obtain carbon monoxide.
Preferably, the loading capacity of the modified indium oxide catalyst on the surface of the working electrode plate is 0.01-10 mg/cm 2.
Preferably, the temperature of the catalytic reduction reaction is 5-40 ℃, and the pressure is 0.1-10 MPa.
Preferably, the friction nano-generator is an independent layer rotary friction nano-generator;
the rotating speed of the friction nano generator is 10-1000 rpm;
the discharging mode of the friction nanometer generator is spark direct current discharging.
Preferably, the discharge voltage of the friction nano generator is 1-10 kV, and the discharge current is 10-100 muA.
Preferably, the distance between the discharge probe and the working electrode plate is less than or equal to 1 mm.
Preferably, the curvature of the discharge probe is 1 to 10 μm.
The invention provides a modified indium oxide catalyst, which is prepared by annealing indium oxide; the atmosphere of the annealing treatment is hydrogen. In the present invention, H is an annealing treatment process2Reaction with lattice oxygen at the indium oxide surface to produce H2O, increasing the oxygen vacancy concentration of the indium oxide surface, increasing the oxygen vacancy concentration to allow In2O3The electrons in the catalyst are localized near the Fermi level and are used for catalyzing CO2In the process of preparing CO by reduction, the friction nano generator is combined with the plasma component, has the characteristic of high voltage, generates a large amount of high-energy free electrons under the action of the voltage and induces CO2Gas discharge to generate triboelectric plasma CO2 -Active species, CO2 -Easily transferring its electrons to In containing oxygen vacancies2O3Catalyst empty rail, effective avoidance of CO2 -Ionic recombination reaction to increase CO2 -The speed of reaction, thereby effectively stabilizing the CO with high activity2 -Species, effective reduction of CO2Potential barrier of decomposition, realizing adjustment of electronic structure, charge transport and surface property to promote CO2And the increase of the oxygen vacancy concentration enables the modified indium oxide catalyst to have more electron aggregation at the Fermi energy level, and is more favorable for CO2To CO2Has high catalytic activity of CO2The conversion energy efficiency is high; moreover, the obtained modified catalyst component is simple.
The invention provides a method for preparing carbon monoxide by catalytic reduction of carbon dioxide. The method provided by the invention utilizes the high-energy electrons generated by the friction nano generator and the plasma component to be directly injected into CO2LUMO energy level of (C) to form CO2 —Active species, effectively overcomes working electrode and CO2The electron transfer barrier between molecules accelerates electrons to CO2Effectively improve CO2A phenomenon of low reduction activity; the modified indium oxide catalyst has high oxygen vacancy concentration, and can be used for promoting CO by adjusting electronic structure, charge transport and surface property2And the increase of the oxygen vacancy concentration enables the modified indium oxide catalyst to have more electron aggregation at the Fermi energy level, and is more favorable for CO2The catalytic reduction reaction of (2) and the energy efficiency of the modified indium oxide catalyst are high.
Drawings
FIG. 1 is a CO of the present invention2Schematic diagram of a reaction apparatus for producing CO by catalytic reduction of (1);
FIG. 2 is a schematic diagram of modified indium oxide catalysts prepared in example 1 and comparative example 1;
FIG. 3 is a representation of EPR of the catalysts prepared in example 1 and comparative examples 1-2;
FIG. 4 is a PL characterization plot of catalysts prepared in example 1 and comparative examples 1-2;
FIG. 5 is a UV characterization chart of the catalysts prepared in example 1 and comparative examples 1-2;
FIG. 6 is a graph of discharge current and discharge voltage for example 2;
FIG. 7 is a graph showing the catalytic activity (CO formation rate) of the catalysts of examples 2 to 4 and comparative examples 3 to 11;
FIG. 8 is a graph showing energy efficiency of examples 2 to 4 and comparative examples 3 to 11.
Detailed Description
The invention provides a modified indium oxide catalyst, which is prepared by annealing indium oxide; the atmosphere of the annealing treatment is hydrogen.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the annealing treatment temperature is preferably 200-600 ℃, more preferably 300-500 ℃, and most preferably 400 ℃; the time of the annealing treatment is preferably 1-10 h, more preferably 2-8 h, and most preferably 4-6 h; the annealing treatment is preferably carried out in a tube furnace.
In the present invention, in the annealing treatment, H2Reaction with lattice oxygen at the indium oxide surface to produce H2O, resulting in an increase in the oxygen vacancy concentration at the indium oxide surface.
The invention provides application of the indium oxide catalyst in the technical scheme in preparation of carbon monoxide through catalytic reduction of carbon dioxide.
The invention provides a method for preparing carbon monoxide by catalytic reduction of carbon dioxide, which comprises the following steps:
the adopted reaction device comprises a friction nanometer generator, a rectifier bridge and a plasma component; the plasma assembly comprises a discharge probe and a working electrode plate; the single surface of the working electrode plate is loaded with the modified indium oxide catalyst in the technical scheme; the alternating current input end of the rectifier bridge is electrically connected with the output end of the friction nano generator, the negative direct current output end of the rectifier bridge is connected with the discharge probe, and the positive direct current output end of the rectifier bridge is connected with the working electrode plate;
and electrifying the reaction device, and introducing carbon dioxide to perform catalytic reduction reaction to obtain carbon monoxide.
In the invention, the schematic diagram of the reaction device is shown in fig. 1, the reaction device is composed of a friction nanometer generator (TENG), a rectifier bridge and a plasma assembly, the plasma assembly is formed by a discharge probe and a working electrode plate which are oppositely arranged, and the surface of the working electrode plate is loaded with the modified indium oxide catalyst; the discharge probe is fixed by the three-dimensional moving platform, and the discharge distance between the discharge probe and the working electrode plate is accurately regulated and controlled by moving the three-dimensional moving platform. In the invention, the friction nano generator converts mechanical energy into electric energy and drives the plasma component to generate plasma, and the plasma and the modified indium oxide catalyst on the surface of the working electrode react with CO2Carrying out catalytic reduction.
In the present invention, the triboelectric nanogenerator is preferably a self-contained layer rotary triboelectric nanogenerator; the rotation speed of the friction nano generator is preferably 10-1000 rpm, more preferably 100-800 rpm, and most preferably 200-500 rpm; the discharging mode of the friction nano generator is preferably power generation spark direct current discharging; the discharging voltage of the friction nano generator is preferably 1-10 kV, more preferably 1.5-8 kV, and most preferably 5-6 kV; the discharge current of the friction nano generator is preferably 10-100 muA, more preferably 30-80 muA, and most preferably 50-60 muA.
In the present invention, the discharge probe is preferably a tungsten needle electrode; the curvature of the discharge probe is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 5-6 μm. The type of the working electrode plate is not particularly limited, and a conductive electrode known to those skilled in the art can be used, specifically, a Pt electrode, a Fe electrode, a Cu electrode, an Au electrode, an ITO electrode, or a zinc oxide doped Aluminum (AZO) electrode. In the invention, the preferable load capacity of the modified indium oxide catalyst on the surface of the working electrode plate is 0.01-10 mg/cm2More preferably 1 to 8mg/cm2Most preferably 3 to 5mg/cm2. In the invention, the distance between the discharge probe and the working electrode plate is preferably less than or equal to 1mm, namely the discharge distance is preferably less than or equal to 1mm, more preferably 0.1-0.8 mm, and most preferably 0.4-0.6 mm.
In the present invention, the catalytic reduction reaction is preferably performed at normal temperature and pressure; the catalytic reduction reaction is preferably carried out in a quartz glass reaction vessel; the plasma component is positioned in the quartz glass reaction vessel, and the friction nano generator is positioned outside the quartz glass reaction vessel and is used as a driving energy device. In the present invention, the purity of the carbon dioxide is preferably not less than 99.99%.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Putting indium oxide into a tube furnace, and annealing for 1H under the conditions of hydrogen atmosphere and 300 ℃ to obtain the modified indium oxide catalyst (abbreviated as H)2-In2O3)。
Comparative example 1
Annealing indium oxide at 300 deg.C for 1h In Air atmosphere to obtain modified indium oxide catalyst (abbreviated as Air-In)2O3)。
Comparative example 2
Indium oxide (abbreviated as Bulk In) without annealing treatment2O3)。
A schematic diagram of the modified indium oxide catalysts prepared in example 1 and comparative example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that in H2Annealing under an atmosphere can increase the oxygen vacancy concentration of indium oxide, while annealing under an air atmosphere can decrease the oxygen vacancy concentration due to H2Will react with lattice oxygen on the surface of the indium oxide to generate H2O, resulting in an increase in the concentration of oxygen vacancies at the catalyst surface; o in air2Will react with oxygen vacancies at the indium oxide surface resulting in a reduction in the oxygen vacancy concentration at the catalyst surface.
EPR, PL and UV characterizations of the catalysts prepared in example 1 and comparative examples 1-2 are shown in FIG. 3, 4 and 5, respectively. As can be seen from FIGS. 3 to 5, H2Atmosphere treated In2O3In having the highest oxygen vacancy concentration and treated with air atmosphere2O3The oxygen vacancy concentration of (a) shows a tendency to decrease.
Example 2
The reaction device shown in FIG. 1 is adopted, and the adopted reaction device comprises an independent layer rotary friction nano generator, a rectifier bridge and a plasma component; the plasma assembly comprises a tungsten needle electrode with the curvature of 5 mu m and a Pt electrode; the alternating current input end of the rectifier bridge is electrically connected with the output end of the friction nano generator, the negative direct current output end of the rectifier bridge is connected with the tungsten needle electrode, and the positive direct current output end of the rectifier bridge is connected with the Pt electrode; wherein the catalyst prepared in example 1 is loaded on the surface of the Pt electrode, and the loading amount of the catalyst is 3 x 10-3g/cm2(ii) a The tungsten needle electrode is fixed by a three-dimensional displacement platform, and the discharge distance between the tungsten needle electrode and the Pt electrode is accurately controlled to be 0.6mm by moving the three-dimensional displacement platform; the discharge voltage of the independent layer rotary friction nano generator is-1.4 kV, and the discharge current is 60 muA; the Pt electrode is placed in a 500mL quartz glass reaction vessel with good sealing performance;
electrifying the reaction device to generate friction plasma; and mixing the friction plasma with carbon dioxide, and carrying out catalytic reduction reaction at normal temperature and normal pressure to obtain carbon monoxide.
The discharge current and discharge voltage curves of example 2 are shown in fig. 6. As can be seen from FIG. 6, the independent layer rotary type friction nano-generator generates the output characteristic of negative electricity through rectification, when the discharge distance is 0.6mm, 2 pulse voltage peaks are generated in a half period, the potential difference between the tungsten needle electrode and the Pt electrode is reduced to-1.4 kV, and simultaneously, the pulse current output of about-60 muA is accompanied.
Examples 3 to 4
The carbon monoxide is prepared by catalytic reduction of carbon dioxide according to the method of example 2, and the preparation conditions for preparing carbon monoxide by catalytic reduction of carbon dioxide in examples 3 to 4 are shown in table 1.
Comparative examples 3 to 11
The preparation conditions for preparing carbon monoxide by catalytic reduction of carbon dioxide according to the method of example 2 and the preparation conditions for preparing carbon monoxide by catalytic reduction of carbon dioxide in comparative examples 3 to 11 are shown in table 1.
TABLE 1 preparation conditions of examples 2 to 4 and comparative examples 3 to 11
The catalytic activity (CO formation rate) of the catalysts of examples 2 to 4 and comparative examples 3 to 11 is shown in FIG. 7 and Table 2, and the energy efficiency is shown in FIG. 8 and Table 3.
TABLE 2 results of CO production rates (mmol. g) of examples 2 to 4 and comparative examples 3 to 11-1·h-1)
As can be seen from FIG. 7 and Table 2, the CO production rate of the modified indium oxide catalyst prepared by the present invention can reach 0.21 mmol/g under the same discharge distance-1·h-1The catalytic activity of the indium oxide catalyst is far higher than that of indium oxide subjected to annealing treatment and non-annealing treatment in an air atmosphere, which shows that the catalytic activity of the modified indium oxide catalyst provided by the invention is high.
TABLE 3 energy efficiency (%)
As can be seen from fig. 8 and table 3, the energy efficiency of the modified indium oxide catalyst prepared by the present invention is as high as 10.8% at the same discharge distance, which is much higher than the energy efficiency of the annealing treatment, the non-annealing treatment and the non-adding catalyst under the air atmosphere, indicating that the energy efficiency of the modified indium oxide catalyst provided by the present invention is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A modified indium oxide catalyst is characterized by being prepared by indium oxide annealing treatment; the atmosphere of the annealing treatment is hydrogen.
2. The modified indium oxide catalyst according to claim 1, wherein the annealing temperature is 200 to 600 ℃ and the annealing time is 1 to 10 hours.
3. Use of an indium oxide catalyst according to claim 1 or 2 in the preparation of carbon monoxide by catalytic reduction of carbon dioxide.
4. A method for preparing carbon monoxide by catalytic reduction of carbon dioxide is characterized by comprising the following steps:
the adopted reaction device comprises a friction nanometer generator, a rectifier bridge and a plasma component; the plasma assembly comprises a discharge probe and a working electrode plate; the modified indium oxide catalyst according to claim 1 or 2 is supported on one surface of the working electrode plate; the alternating current input end of the rectifier bridge is electrically connected with the output end of the friction nano generator, the negative direct current output end of the rectifier bridge is connected with the discharge probe, and the positive direct current output end of the rectifier bridge is connected with the working electrode plate;
and electrifying the reaction device to generate triboelectric plasma, mixing the triboelectric plasma with carbon dioxide, and then carrying out catalytic reduction reaction to obtain carbon monoxide.
5. The method according to claim 4, wherein the modified indium oxide catalyst is loaded on the surface of the working electrode plate at a load of 0.01-10 mg/cm2。
6. The method according to claim 4, wherein the temperature of the catalytic reduction reaction is 5 to 40 ℃ and the pressure is 0.1 to 10 MPa.
7. The method of claim 4, wherein the triboelectric nanogenerator is a standalone layer rotary triboelectric nanogenerator;
the rotating speed of the friction nano generator is 10-1000 rpm;
the discharging mode of the friction nanometer generator is power generation spark direct current discharging.
8. The method according to claim 4 or 7, wherein the discharge voltage of the triboelectric nanogenerator is 1 to 10kV, and the discharge current is 10 to 100 μ A.
9. The method of claim 4, wherein the distance between the discharge probe and the working electrode plate is less than or equal to 1 mm.
10. The method according to claim 4 or 9, wherein the curvature of the discharge probe is 1 to 10 μm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2890789A1 (en) * | 2014-05-07 | 2015-11-07 | Geoffrey A. Ozin | Nanostructured metal oxide compositions for applied photocatalysis |
| CN109647373A (en) * | 2018-11-28 | 2019-04-19 | 天津大学 | Black oxidation indium ultrathin nanometer piece and preparation method thereof and photo-thermal catalytic applications |
| CN112221344A (en) * | 2020-09-03 | 2021-01-15 | 河南大学 | CO (carbon monoxide)2Catalytic reduction apparatus and method |
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- 2021-04-28 CN CN202110467760.3A patent/CN113578305A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2890789A1 (en) * | 2014-05-07 | 2015-11-07 | Geoffrey A. Ozin | Nanostructured metal oxide compositions for applied photocatalysis |
| CN109647373A (en) * | 2018-11-28 | 2019-04-19 | 天津大学 | Black oxidation indium ultrathin nanometer piece and preparation method thereof and photo-thermal catalytic applications |
| CN112221344A (en) * | 2020-09-03 | 2021-01-15 | 河南大学 | CO (carbon monoxide)2Catalytic reduction apparatus and method |
Non-Patent Citations (2)
| Title |
|---|
| LU WANG ET AL.: "Black indium oxide a photothermal CO2 hydrogenation catalyst", 《NATURE COMMUNICATIONS》 * |
| PINKI DEVI ET AL.: "Selective Electrochemical Reduction of CO2 to CO on CuO/In2O3 Nanocomposite: Role of Oxygen Vacancies", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
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Application publication date: 20211102 |