CN117026287A - Electrocatalytic material and preparation method and application thereof - Google Patents
Electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN117026287A CN117026287A CN202310850403.4A CN202310850403A CN117026287A CN 117026287 A CN117026287 A CN 117026287A CN 202310850403 A CN202310850403 A CN 202310850403A CN 117026287 A CN117026287 A CN 117026287A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 238000003487 electrochemical reaction Methods 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 abstract description 16
- 229910006404 SnO 2 Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007970 homogeneous dispersion Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229940079864 sodium stannate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses an electrocatalytic material, a preparation method and application thereof, wherein the electrocatalytic material is boron-doped nano tin dioxide; the mass percentage of the boron element is 0.5-5% based on the total mass of the electrocatalytic material. The electrocatalytic material provided by the invention is nonmetal boron doped weak crystalline state SnO 2 The nanospheres can effectively increase the number of Sn active sites and reduce SnO due to the introduction of boron 2 Surface. Formation energy barrier of OCHO intermediate can effectively raise electrocatalytic activity, stability and wide potential window.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to an electrocatalysis material, a preparation method and application thereof.
Background
With the rapid development of human society and the excessive use of fossil fuels, energy crisis and global warming are increasingly serious. The realization of carbon neutralization and zero carbon emission has become a major task in the current stage of countries worldwide. Electrocatalytic CO 2 Reduction reaction (CO) 2 RR) can convert CO 2 Conversion to value-added chemicals, materials, fuels, etc., is considered an effective strategy to address global warming and energy crisis. However, CO 2 Is a nonpolar molecule which is very stable in thermodynamics, so that CO 2 RR processes are extremely challenging, currently electrocatalytic CO 2 The reduction conversion also has the bottleneck problems of low selectivity, high overpotential, poor stability and the like. Therefore, it is extremely important to design and construct a novel electrocatalyst that catalyzes efficiently.
Currently, many metal-based catalysts (Sn, bi, in, pd, etc.) are CO due to their high hydrogen evolution overpotential 2 The reduction to formic acid shows good selectivity. Wherein, the non-noble metal Sn-based catalyst has the advantages of low cost, low toxicity, environmental protection and the like, and is used in CO 2 The most widespread interest is obtained in RR. But Sn-based electrode at CO 2 Further application is hindered during RR due to the narrow window of their selection potential and poor stability.
Therefore, there is a need to develop a new electrocatalytic material with high catalytic activity, wide potential window and high stability.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the first aspect of the present invention proposes an electrocatalytic material capable of effectively improving electrocatalytic activity, stability and a wide potential window.
The second aspect of the invention also provides a preparation method of the electrocatalytic material.
The third aspect of the invention also provides the use of an electrocatalytic material.
Fourth aspect of the inventionThe face also provides an electrocatalytic CO 2 A method for preparing formic acid by reduction.
According to the electrocatalytic material provided by the embodiment of the first aspect of the invention, the electrocatalytic material is boron-doped nano tin dioxide; the mass percentage of the boron element is 0.5-5% based on the total mass of the electrocatalytic material.
The electrocatalytic material provided by the embodiment of the invention has at least the following beneficial effects:
the electrocatalytic material provided by the invention is nonmetal boron doped weak crystalline state SnO 2 The nanospheres can effectively increase the number of Sn active sites and reduce SnO due to the introduction of boron 2 Surface. Formation energy barrier of OCHO intermediate can effectively raise electrocatalytic activity, stability and wide potential window.
According to some embodiments of the invention, the boron element is 1-3% by mass based on the total mass of the electrocatalytic material.
According to some embodiments of the invention, the electrocatalytic material has an average particle size of 40-60 nm.
According to a second aspect of the present invention, there is provided a method for preparing the electrocatalytic material, comprising the steps of:
mixing the boron-containing compound, tin salt and water, and carrying out reflux reaction to obtain the electrocatalytic material.
According to some embodiments of the invention, the concentration of the tin salt is 0.1 to 1.0mol L -1 。
According to some embodiments of the invention, the tin salt comprises at least one of tin tetrachloride, tin nitrate, sodium stannate.
According to some embodiments of the invention, the boron-containing compound has a concentration of 200 to 1000mg L -1 。
According to some embodiments of the invention, the boron-containing compound comprises at least one of boric acid or diboron trioxide.
According to some embodiments of the invention, the reflux reaction is at a temperature of 80 to 95 ℃.
According to some embodiments of the invention, the reflux reaction time is 2 to 5 hours.
The third aspect of the invention provides the use of the electrocatalytic material described above in the electrocatalytic reduction of carbon dioxide to formic acid.
In a fourth aspect the invention provides an electrocatalytic CO 2 The method for preparing the formic acid by reduction comprises the following steps:
and constructing an electrochemical reaction system, wherein the electrochemical reaction system comprises a working electrode, the electrocatalytic material is loaded on a substrate of the working electrode, and the electrocatalytic reaction is carried out by electrifying.
According to some embodiments of the invention, the electrochemical reaction system further comprises an electrolytic reaction device, a working electrode, a reference electrode, a counter electrode, a membrane, and an electrolyte.
According to some embodiments of the invention, the electrolytic reaction device comprises an H-type electrolytic cell and a gas diffusion electrode.
According to some embodiments of the invention, the substrate of the working electrode comprises at least one of carbon cloth, carbon paper or carbon fiber.
According to some embodiments of the invention, the reference electrode comprises a saturated calomel electrode (Hg/Hg) 2 Cl 2 ) Or a silver/silver chloride (Ag/AgCl) reference electrode.
According to some embodiments of the invention, the counter electrode comprises an electrode made of carbon and/or platinum.
According to some embodiments of the invention, the membrane comprises a proton exchange membrane.
According to some embodiments of the invention, the electrolyte comprises KHCO 3 At least one of a solution, a KOH solution, or an ionic liquid.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows boron doped SnO in example 1 of the present invention 2 TEM image of nanosphere material;
FIG. 2 is a boron doped SnO of example 1 of the present invention 2 XRD spectrum of nanosphere material;
FIG. 3 is a boron doped SnO of example 2 of the present invention 2 TEM image of nanospheres;
FIG. 4 shows boron doped SnO in example 2 of the present invention 2 Electrochemical reduction of CO by electrodes 2 A Faraday efficiency map of formic acid production;
FIG. 5 shows boron doped SnO in example 2 of the present invention 2 Electrochemical reduction of CO at-1.0V vs. RHE 2 A stability map;
FIG. 6 shows boron doped SnO in example 3 of the present invention 2 TEM image of nanospheres;
FIG. 7 shows boron doped SnO in example 3 of the present invention 2 Electrode electrocatalytic CO 2 A Faraday efficiency map of reduction to formate;
FIG. 8 shows SnO in comparative example 1 of the present invention 2 TEM image of nanospheres;
FIG. 9 is SnO in comparative example 1 of the present invention 2 Electrode electrocatalytic CO 2 A Faraday efficiency map of reduction to formate;
FIG. 10 is a schematic diagram of a commercial SnO in comparative example 2 of the present invention 2 XRD pattern of nanospheres;
FIG. 11 is a schematic diagram of a commercial SnO in comparative example 2 of the present invention 2 Electrode electrocatalytic CO 2 Faraday efficiency plot of formate reduction.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Example 1 provides an electrocatalytic material, which is 0.65wt% boron element doped nano tin dioxide, and the preparation method thereof is as follows:
first, 0.2mol L was prepared -1 100mL of tin tetrachloride solution; to the above solution, 20mg of boron oxide solid powder was added, and stirring was continued for 30 minutes. The resulting dispersion was transferred to a 250mL round bottom flask and heated to reflux at 95 ℃ for 2 hours; after naturally cooling to room temperature, obtaining white precipitate after centrifugal separation; washing with ethanol for several times, and vacuum drying at 60deg.C overnight to obtain boron doped SnO 2 。
The electrocatalytic material prepared in example 1 of the present invention was characterized.
Referring to fig. 1 and 2, fig. 1 is a TEM image provided in example 1 of the present invention, showing the microscopic morphology of nanospheres with an average particle size of 50nm. Fig. 2 is an XRD pattern provided in example 1 of the present invention, where the X-ray diffraction peak spectrum of the material shows a broad peak and low intensity weak crystalline state, which can enhance adsorption of carbon dioxide molecules on the surface of the material.
Example 2
Example 2 provides an electrocatalytic material, which is 3.32wt% boron doped nano tin dioxide, and the preparation steps are as follows:
preparation of 0.4mol L -1 100mL of sodium stannate solution; to the above solution, 60mg of boron oxide solid powder was added, and stirring was continued for 30 minutes. The resulting homogeneous dispersion was transferred to a 250mL round bottom flask and heated to reflux at 90 ℃ for 4 hours. After naturally cooling to room temperature, obtaining white precipitate after centrifugal separation; washing with ethanol for several times, and vacuum drying at 60deg.C overnight to obtain boron doped SnO 2 。
The electrocatalytic material prepared in example 2 of the present invention was characterized.
Referring to FIG. 3, FIG. 3 is a TEM image provided in example 2 of the present invention, showing boron doped SnO 2 Is a highly dispersed nanosphere with an average diameter of about 50nm and the sphere is solid and has serrated edges.
CO treatment of the electrocatalytic Material prepared in example 2 of the present invention 2 The electroreduction test comprises the following steps: constructing a three-electrode H-type electrolytic cell system, wherein a diaphragm adopts Nafion117 proton exchange membrane, electrochemical workstation adopts Chenhua CHI 660E. Saturated calomel electrode is used as reference electrode, platinum net is used as counter electrode, carbon cloth loaded with catalytic material is used as working electrode, and the concentration of the catalyst is 0.5mol L -1 CO in potassium bicarbonate electrolyte 2 And (5) electric reduction testing. Before testing, at least CO is introduced into the electrolyte 2 The gas is discharged for more than 30 minutes to remove all air, and CO is continuously introduced into the electrolyte in the electrocatalytic reaction process 2 Gas, CO 2 The flow rate of the gas was 20mL min -1 。
The results are as follows:
referring to fig. 4 and 5, fig. 4 is a diagram of CO according to embodiment 2 of the present invention 2 Electroreduction to formate performance diagram, boron doped SnO 2 The faraday efficiency of formic acid generation increases sharply with increasing operating potential, a maximum of 95.1% is achievable at-1.0 v vs. rhe, and the faraday efficiency of formic acid is maintained above 90% over a wide potential window of-0.7 to-1.3 v vs. rhe. FIG. 5 is a graph of CO provided in example 2 of the present invention 2 Stability graph of reduction test, boron doped SnO after 60 hours of stability test 2 The electrode can still maintain high formic acid current density and Faraday efficiency, and the excellent catalytic stability of the electrode is proved.
Example 3
Example 3 provides an electrocatalytic material, which is 4.36wt% boron doped nano tin dioxide, and the preparation steps are as follows:
preparation of 0.6mol L -1 100mL of tin tetrachloride solution; 80mg of boric acid solid powder was added to the above solution, and stirring was continued for 30 minutes; the resulting homogeneous dispersion was transferred to a 250mL round bottom flask and heated to reflux at 85 ℃ for 5 hours. After naturally cooling to room temperature, obtaining white precipitate after centrifugal separation; washing with ethanol for several times, and vacuum drying at 60deg.C overnight to obtain boron doped SnO 2 。
Referring to FIG. 6, FIG. 6 is a TEM image of the nanosphere according to example 3 of the present invention, showing a microscopic morphology of the nanospheres, but with a slight decrease in the size of the sample, about 40nm, illustrating the excessive boron incorporation into SnO 2 The morphology has a weak influence.
CO performed on the electrocatalytic Material provided in example 3 of the present invention 2 The electroreduction test, test method was the same as that of example 2.
The results are shown in FIG. 7, FIG. 7 is a graph of CO provided in example 3 of the present invention 2 The electroreduction yields a formate performance map with a Faraday efficiency of 86.7% for formate at-1.1 Vvs. RHE.
Comparative example 1
Comparative example 1 provides an electrocatalytic material which is a tin dioxide nanosphere, and the preparation method is as follows:
under the condition of continuous stirring at room temperature, firstly, 0.4mol L is prepared -1 100mL of tin tetrachloride solution; the resulting homogeneous dispersion was transferred to a 250mL round bottom flask and heated to reflux at 90 ℃ for 3 hours. And after naturally cooling to room temperature, obtaining white precipitate after centrifugal separation. Washing with ethanol for several times, and vacuum drying at 60deg.C overnight to obtain boron-free doped SnO 2 。
The electrocatalytic material prepared in comparative example 1 was characterized.
Referring to fig. 8, fig. 8 is a TEM image provided in comparative example 1 of the present invention, which shows a microscopic morphology of nanospheres, with a size of about 50nm.
CO performed on the electrocatalytic Material provided in comparative example 1 of the present invention 2 Electroreduction test, test method was the same as in example 2.
The results are shown in FIG. 9, FIG. 9 is the CO provided in comparative example 1 2 The electroreduction gives a formate performance map with a Faraday efficiency of 82.5% for formate at-1.1V vs. RHE.
Comparative example 2
Comparative example 2 provides a commercial SnO 2 Nanospheres, available from alaa Ding Shiji (Shanghai) limited.
Commercial SnO provided in comparative example 2 2 Nanospheres were characterized.
Referring to FIG. 10, FIG. 10 is an XRD pattern provided in comparative example 2, and an X-ray diffraction peak pattern of the material shows characteristic peaks with good crystallinity and crystalline SnO 2 Matching with each other。
Comparative example 2 electrocatalytic Material CO 2 Electroreduction test, test method was the same as in example 2.
The results are shown in FIG. 11, FIG. 11 is the CO provided in comparative example 2 2 The electroreduction gives a formate performance map with a Faraday efficiency of 65.8% for formate at-1.1V vs. RHE.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. An electrocatalytic material is characterized in that the electrocatalytic material is boron element doped nano tin dioxide; the mass percentage of the boron element is 0.5-5% based on the total mass of the electrocatalytic material.
2. Electrocatalytic material according to claim 1, wherein the mass percentage of boron element is 2-4% based on the total mass of the electrocatalytic material.
3. Electrocatalytic material according to claim 1, wherein the average particle size of the electrocatalytic material is 40-60 nm.
4. A method for preparing an electrocatalytic material according to any one of claims 1 to 3, comprising the steps of:
mixing the boron-containing compound, tin salt and water, and carrying out reflux reaction to obtain the electrocatalytic material.
5. The process according to claim 4, wherein the concentration of the tin salt is 0.1 to 1.0mol L -1 。
6. The method according to claim 4, wherein the concentration of the boron-containing compound is 200 to 1000mg L -1 。
7. The method of claim 4, wherein the boron-containing compound comprises at least one of boric acid or diboron trioxide.
8. The process according to claim 4, wherein the temperature of the reflux reaction is 80 to 95 ℃.
9. Use of an electrocatalytic material according to any one of claims 1-3 for electrocatalytic carbon dioxide reduction to formic acid.
10. Electrocatalytic CO 2 The method for preparing the formic acid by reduction is characterized by comprising the following steps:
an electrochemical reaction system is constructed, the electrochemical reaction system comprises a working electrode, the electrocatalytic material of any one of claims 1-3 is loaded on a substrate of the working electrode, and the electrocatalytic reaction is carried out by electrifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310850403.4A CN117026287A (en) | 2023-07-11 | 2023-07-11 | Electrocatalytic material and preparation method and application thereof |
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