CN111268723B - Method for controlling morphology of tin dioxide, tin-tin dioxide composite material and application - Google Patents
Method for controlling morphology of tin dioxide, tin-tin dioxide composite material and application Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- SOQBSQLGTKQSGQ-UHFFFAOYSA-N oxo(oxostannanylidene)tin Chemical compound O=[Sn]=[Sn]=O SOQBSQLGTKQSGQ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 230000001276 controlling effect Effects 0.000 claims abstract description 21
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000002135 nanosheet Substances 0.000 claims description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 239000002077 nanosphere Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XBVGWPOYILXGKI-UHFFFAOYSA-N [Sn](=O)=O.[Sn](=O)=O Chemical compound [Sn](=O)=O.[Sn](=O)=O XBVGWPOYILXGKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a method for controlling the morphology of tin dioxide, a tin-tin dioxide composite material and application, wherein the control method comprises the following steps: the tin dioxide is prepared by a hydrothermal method, and the morphology of the tin dioxide is regulated and controlled by controlling the volume ratio of a solvent to the volume of a reaction kettle in the hydrothermal method. The invention can control the appearance of the tin dioxide, so that the tin-tin dioxide composite material has adjustable special appearance, and the tin-tin dioxide composite material has higher dynamic reaction speed, higher current density and higher stability.
Description
Technical Field
The present invention belongs to the field of electrocatalytic reduction (CO) of carbon dioxide2RR) technical field, and relates to a method for controlling the morphology of tin dioxide, a tin-tin dioxide composite material and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, CO has been introduced2By electrocatalytic reduction (CO)2RR) technology into organic raw materials having high added values, such as formic acid, carbon monoxide, methanol, ethanol, and the like, has attracted much attention from scientists because it can not only alleviate environmental problems caused by global warming, but also produce fuels having high energy density. Naturally enriched metals (e.g. tin, copper) are considered to be the most potent CO compared to noble metal electrocatalysts2An RR electrocatalyst. Meanwhile, tin and its oxides (e.g., SnO2) The semiconductor material has good selectivity for formate and carbon monoxide synthesis, is rich in global resources, is eco-friendly, and is chemically stable, so that the semiconductor material attracts people's attention. However, the inventors of the present invention have found through studies that pure SnO2The electrocatalyst has the problems of poor catalytic activity, slow reaction kinetics, poor stability and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing dioxygen with different morphologiesA tin melting method, and preparation and application of a tin-tin dioxide composite material. The invention can control the appearance and the composition of the tin dioxide, so that the tin-tin dioxide composite material has adjustable special appearance, and the tin-tin dioxide composite material is in CO2RR shows better catalytic activity, faster dynamic reaction speed, higher current density and stronger stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in the first aspect, the tin dioxide is prepared by a hydrothermal method, and the morphology of the tin dioxide is regulated and controlled by controlling the volume ratio of a solvent to a reaction kettle in the hydrothermal method.
Experiments prove that SnO with different shapes can be generated by controlling the volume of the added solvent2. When the volume ratio of the solvent to the reaction kettle is 8-12: 50, the obtained stannic oxide is nanospheres; when the volume ratio of the solvent to the reaction kettle is 18-22: 50, the obtained stannic oxide is a nanosheet assembly with a cubic structure; when the volume ratio of the solvent to the volume of the reaction kettle is 28-32: 50, the obtained stannic oxide is a nanosheet assembly with a large cubic block structure. Wherein, SnO has a nano-spherical structure2Compared with small cubic blocks assembled by nano sheets, the nano sheet assembled large cubic blocks with the same morphology expose fewer active sites than small cubic blocks, so that the generated SnO with the small cubic block morphology2The nanosheet assembly can be CO2RR provides more reactive sites.
In a second aspect, tin dioxide is obtained by the method for controlling the morphology of tin dioxide.
In a third aspect, the tin dioxide is used for preparing a tin-tin dioxide composite material.
In a fourth aspect, a preparation method of a tin-tin dioxide composite material, the tin dioxide is calcined for not more than 4 hours in a mixed atmosphere; the calcining temperature is not higher than 450 ℃, and the mixed atmosphere refers to inert atmosphere and reducing atmosphere.
The invention can obtain different Sn/SnO by controlling the calcination time2The composite material in proportion.
In a fifth aspect, a tin-tin dioxide composite material is obtained by the above preparation method.
In a sixth aspect, use of the above tin dioxide or the above tin-tin dioxide composite material in electrocatalytic reduction of carbon dioxide.
In a seventh aspect, a working electrode for electrocatalytic reduction of carbon dioxide, comprising the above tin dioxide or the above tin-tin dioxide composite.
The invention has the beneficial effects that:
the invention generates SnO with specific morphology by controlling solvents with different volumes2Assembling the body; by further compacting the small cubic block structure of SnO2Nanosheet assembly in Ar/H2Calcining for different time under mixed atmosphere to obtain three Sn/SnO with different proportions2A composite assembly material. On one hand, the composite material improves the conductivity of the material by converting part of tin dioxide into metallic tin, and on the other hand, the mixed surface electronic state of the metallic tin and the tin dioxide improves SnO2Stability at negative potentials, therefore, the synergistic effect of the two increases CO2RR catalytic Performance. Thereby enabling the Sn/SnO prepared by the present disclosure2The composite material has excellent CO2RR catalytic Performance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photograph of samples prepared in examples 1 to 6 of the present invention, wherein a and d are SnO2(p) -10, b, e are SnO2(p) -20, c, f are SnO2(p) -30, g, j are SnO2-10, h and k are SnO2-20, i, l are SnO2-30；
FIG. 2 is a TEM image of transmission electron microscopy of samples prepared in examples 1 to 6 of the present invention, wherein a is SnO2(p) -10, b is SnO2(p) -20, c is SnO2(p) -30, d is SnO2-10, e is SnO2-20, f is SnO2-30；
FIG. 3 is a comparison of XRD results for samples prepared according to examples 1-6 of the present invention;
FIG. 4 is a scanning electron microscope photograph of samples prepared in examples 5, 7, 8 and 9 of the present invention, wherein a is SnO2(p) -20, b is Sn/SnO2-1h, c is Sn/SnO2-2h, d is Sn/SnO2-3h；
FIG. 5 is a comparison of XRD results of samples prepared according to examples 5, 7, 8 and 9 of the present invention;
FIG. 6 shows the formation of CO, formate and H at different voltages for samples prepared in examples 4-6 of the present invention2A is SnO2(p) -10, b is SnO2(p) -20, c is SnO2(p)-30；
FIG. 7 is a graph showing the electrocatalytic performance characteristics of samples prepared in examples 5, 7, 8 and 9 of the present invention, wherein a is the samples prepared in examples 5, 7, 8 and 9 of the present invention in CO2Saturation with N2Saturated 0.5M KHCO3Comparing LSV test curves in the electrolyte, and sweeping the LSV test curves at a speed of 20mV s-1And b is the voltage and j of the samples prepared in examples 5, 7, 8 and 9 of the present inventionC1The relationship curve of (1);
FIG. 8 shows the formation of CO, formate and H at different voltages for the samples prepared in examples 5, 7, 8 and 9 of the present invention2A is SnO2(p) -20, b is Sn/SnO2-1h, c is Sn/SnO2-2h, d is Sn/SnO2-3h。
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of pure SnO2The invention provides a method for controlling the morphology of tin dioxide, a tin-tin dioxide composite material and application thereof.
The invention provides a typical embodiment of a method for controlling the morphology of tin dioxide, wherein a hydrothermal method is adopted to prepare tin dioxide, and the morphology of tin dioxide is regulated and controlled by controlling the volume ratio of a solvent to a reaction kettle in the hydrothermal method.
Experiments prove that SnO with different shapes can be generated by controlling the volume of the added solvent2。
The hydrothermal method is a method for carrying out hydrothermal reaction, and the hydrothermal reaction is a reaction that a reaction system using water as a solvent is heated under a closed condition and is carried out at a high temperature (not less than 100 ℃) and a high pressure (higher than 0.1 MPa).
When the volume ratio of the solvent to the reaction kettle is 8-12: 50, the obtained stannic oxide is nanospheres; when the volume ratio of the solvent to the reaction kettle is 18-22: 50, the obtained stannic oxide is in the shape of small cubic blocks assembled by nano sheets; when the volume ratio of the solvent to the reaction kettle is 28-32: 50, the obtained stannic oxide is in a large cubic block assembled by nano sheets. Wherein, SnO has a nano-spherical structure2Compared with small cubic blocks assembled by nano sheets, the nano sheet assembled large cubic blocks with the same morphology expose fewer active sites than small cubic blocks, so that the generated SnO with the morphology of the nano sheet assembled small cubic blocks2Can be CO2RR provides more reactive sites. Thus, in one or more embodiments of this embodiment, the ratio of the volume of solvent to the volume of the reaction vessel is 18 to 22: 50.
Experiments show that although the morphology of tin dioxide can be controlled by controlling the volume ratio of the solvent to the volume of the reaction kettle, the uniformity of the morphology of the prepared tin dioxide is poor, and in one or more examples of the embodiment, terephthalic acid is added into the hydrothermal reaction system. Experiments show that when terephthalic acid is added into a hydrothermal reaction system, the tin dioxide is more uniform in appearance.
In the series of examples, the molar ratio of the tin source to the terephthalic acid is 1: 0.9-1.1.
The tin source in the invention is a tin-containing compound which can prepare tin dioxide through hydrothermal reaction, such as stannous chloride, stannic chloride, sodium stannate and the like. The embodiment of the invention adopts stannous chloride as a tin source, and has better effect.
In one or more embodiments of this embodiment, the solvent in the hydrothermal process is a mixture of tetramethylammonium hydroxide and water. When the volume ratio of the tetramethylammonium hydroxide to the water is 1: 0.9-1.1, the reaction effect is better.
In one or more embodiments of this embodiment, the reaction conditions for the hydrothermal process are: reacting for 20-28 h at 175-185 ℃.
In one or more embodiments of the present disclosure, the concentration of the tin source in the hydrothermal reaction system is 0.8 to 1.2 mol/L.
In one or more embodiments of this embodiment, the tin source is added to a mixture of tetramethylammonium hydroxide and water and mixed prior to hydrothermal reaction.
In another embodiment of the invention, the tin dioxide is obtained by the method for controlling the morphology of the tin dioxide.
In a third embodiment of the invention, there is provided a use of the above tin dioxide in the preparation of a tin-tin dioxide composite material.
In a fourth embodiment of the invention, a preparation method of a tin-tin dioxide composite material is provided, wherein the tin dioxide is calcined for not more than 4 hours in a mixed atmosphere; the calcining temperature is not higher than 450 ℃, and the mixed atmosphere refers to inert atmosphere and reducing atmosphere.
The invention can obtain different Sn/SnO by controlling the calcination time2The composite material in proportion.
The inert atmosphere in the present invention is a gas atmosphere formed by a gas such as nitrogen, helium, argon, or the like.
The reducing atmosphere in the present invention is a gas atmosphere containing a reducing gas such as hydrogen or carbon monoxide.
Experiments show that the reducing atmosphere is 4-6% of the total volume of the mixed atmosphere, and the effect is better.
In one or more embodiments of this embodiment, the calcination time is 1.8 to 2.2 hours. Experiments show that the catalytic effect is better under the calcination condition.
In one or more embodiments of this embodiment, the calcination temperature is 395-405 ℃.
In a fifth embodiment of the invention, a tin-tin dioxide composite material is provided, which is obtained by the preparation method.
In a sixth embodiment of the present invention, there is provided a use of the above tin dioxide or the above tin dioxide-tin dioxide composite material in electrocatalytic reduction of carbon dioxide.
In a seventh embodiment of the present invention, there is provided a working electrode for electrocatalytic reduction of carbon dioxide, comprising the above tin dioxide or the above tin-tin dioxide composite.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
The reagents used in the following examples were: stannous chloride dihydrate (SnCl)2·2H2O, 98%), terephthalic acid (H)2BDC：C8H6O4) Tetramethylammonium hydroxide (TMAH: c4H13NO, 25% aqueous AR) from alatin. Argon-hydrogen (V)Ar：VH295%: 5%), ultra pure nitrogen, air, and carbon dioxide were purchased from denyang gas, inc.
Example 1
1.0mmol of SnCl2·2H2O is dissolved in 10mL of water-TMAH (volume ratio is 1:1) solution, and the solution is stirred magnetically at room temperature, and becomes clear gradually from milky white with stirring. After 30min, the solution was poured into a 50mL reaction vessel and reacted at 180 ℃ for 24 h. Naturally cooling to room temperature, centrifugally washing with deionized water for three times, and freeze-drying to obtain yellow-white SnO2Powder, marking the resulting sample material as SnO2-10。
Example 2
This example is the same as example 1, except that: adding 2.0mmol of SnCl2·2H2O is dissolved in 20mL of water-TMAH (volume ratio of 1:1) solution, and the obtained sample material is marked as SnO2-20。
Example 3
This example is the same as example 1, except that: adding 3.0mmol of SnCl2·2H2O is dissolved in 30mL of water-TMAH (volume ratio of 1:1) solution, and the obtained sample material is marked as SnO2-30。
Example 4
This example is the same as example 1, except that: 1.0mmol of SnCl2·2H2O and 1.0mmol H2BDC was dissolved in 10mL of water-TMAH (volume ratio 1:1) solution and the resulting sample material was labeled SnO2(p)-10。
Example 5
This example is the same as example 1, except that: adding 2.0mmol of SnCl2·2H2O and 2.0mmol H2BDC was dissolved in 20mL of water-TMAH (volume ratio 1:1) solution and the resulting sample material was labeled SnO2(p)-20。
Example 6
This example is the same as example 1, except that: adding 3.0mmol of SnCl2·2H2O and 3.0mmol H2BDC was dissolved in 30mL of water-TMAH (volume ratio 1:1) solution and the resulting sample material was labeled SnO2(p)-30。
Example 7
The sample obtained in example 5 was placed in Ar-H2(VAr：VH295%: 5%) at the rate of 5 deg.C/min to 400 deg.C, heat-treating at constant temperature for 1h, naturally cooling to room temperature, and marking the obtained sample material as Sn/SnO2-1h。
Example 8
This example is the same as example 7, except that: the sample is subjected to constant temperature heat treatment for 2h at 400 ℃, and the obtained sample material is marked as Sn/SnO2-2h。
Example 9
This example is the same as example 7, except that: the sample is subjected to constant temperature heat treatment at 400 ℃ for 3h, and the obtained sample material is marked as Sn/SnO2-3h。
The sample materials prepared in the above examples were characterized as follows:
composition and structural characterization: x-ray diffraction (XRD) was measured by a Rigaku Dmax-rc X-ray diffractometer. Scanning Electron Microscopy (SEM) was performed on a Gemini-SEM-300, Carl Zeiss Microcopy GmbH, and Transmission Electron Microscopy (TEM) was performed on a JEOL 2100 PLUS. X-ray photoelectron spectroscopy (XPS) was performed with an electron spectrometer (ESCALAB 250).
And (3) electrochemical performance characterization: electrochemical testing was performed by using a CHI 760E electrochemical workstation (CH Instrument, Shanghai) with a three-electrode system. Hydrophobic carbon paper (1X 1 cm) coated with the prepared catalyst-2) Used as the working electrode, while the Ag/AgCl electrode and the Pt plate were used as the reference electrode and the counter electrode, respectively. All potentials were measured relative to the Ag/AgCl electrode and calibrated to the reversible hydrogen electrode according to the following equation: eRHE＝EAg/AgCl+0.198+0.0591 × pH. To prepare a catalyst sample liquid, 1mg of each sample prepared in example, 0.5mg of acetylene black, and 40. mu.L of Nafion (5 wt%) were blended in 360. mu.L of an ethanol solution (240. mu.L of water + 120. mu.L of anhydrous ethanol) under ultrasonic treatment to obtain a uniform catalyst sample liquid. Then, 200. mu.L of a catalyst sample was dropped onto the surface of the carbon paper and dried at room temperature to obtain a working electrode (0.5mg cm)-2). The electrolytic cell is a two-chamber H-type electrolytic cell, and the cathode chamber of the working electrode and the anode chamber of the auxiliary electrode are separated by Nafion 117 proton exchange membrane for preventing cathodeThe products of the reduction of the polar chamber are further oxidized. 25mL of electrolyte (0.5M KHCO) was added to each of the positive and negative chambers3). 18mL min before testing-1Introducing CO into the electrolyte by the gas flow2Or N2It was saturated for 30min and was always 18mL min during the test-1Is aerated.
And (3) product detection: the gas product is detected by gas chromatograph (GC7290), equipped with hydrogen flame detector (FID) and Thermal Conductivity Detector (TCD), using N2As a carrier gas. Electrolyzing for 0.5H and 1H at different voltages with an on-line detection system, detecting gas product, and detecting H with TCD2CO was detected with FID. The peak area of the gas is converted to gas volume using a calibration curve. Detecting the liquid product with High Performance Liquid Chromatograph (HPLC) ultraviolet detector HPX-87H chromatographic column, collecting the liquid product after electrolysis for 1 hr, introducing 30 μ L each time, and adding 1mM H2SO4The aqueous solution is mobile phase at a flow rate of 0.6mL min-1The detection is carried out at a temperature of 60 ℃. During the test, magnetons are used for stirring in the cathode chamber, so that the transmission and diffusion of substances are facilitated.
And (3) characterization results:
the morphology and structure of all samples were observed by SEM and TEM. SnO as shown in FIGS. 1a and d2(p) -10 is a nanosphere structure with smooth surface and uniform size, and when no H exists2SnO produced in the presence of BDC2The-10 (FIG. 1g, j) is a nano-sphere structure with surface ravines and non-uniform size. And when the total volume of the solvent is 20mL, the prepared SnO2(p) -20 (FIGS. 1b, e) is a cubic structure with uniform size and self-assembled nanosheets, and likewise, H is absent2At BDC, SnO2The-20 (FIG. 1h, k) cubes feature non-uniform topographic dimensions. SnO self-assembled by nanosheets when the total volume of solvent is further increased to 30mL2(p) -30 (FIG. 1c, f) cube structures increased in size without the addition of H2At BDC, SnO2-30 (FIG. 1i, l) surface roughness reduction of the cube.
FIGS. 2a and d are SnO2(p) -10 and SnO2-10 of nanospheresTEM image, from which SnO can be seen2(p) -10 nanospheres have a diameter of about 700nm, while SnO2The-10 nanospheres have non-uniform particle size. From FIG. 2b, it can be seen that the nanosheets self-assembled SnO with uniform size2(p) -20 cubic structures with sides of about 400nm, and SnO2The sides of the (p) -30 (FIG. 2c) cubic structures were approximately 600 nm. Thus, with SnO2(p) -10 and SnO2(p) -30 comparison, SnO2(p) -20 has a smaller size structure and a larger specific surface area, which in turn exposes more active sites. In addition, in the absence of H2At BDC, the nanosheet assembled cubic structures (fig. 2e, f) exhibited morphology non-uniformity and roughness reduction, consistent with SEM results.
SnO2(p)-10，SnO2-10，SnO2(p)-20，SnO2-20，SnO2(p) -30 and SnO2The XRD test results of-30 are shown in FIG. 3, from which it can be seen that although SnO is generated at different solvent volumes2The morphologies are different, but they have the same lattice structure, and H2Whether BDC is added or not does not change the lattice structure of the product, and the BDC and SnO are mixed2(PDF # 41-1445).
FIG. 4 is SnO2(p) -20 (FIG. 4a), Sn/SnO2-1h (FIG. 4b), Sn/SnO 22h (FIG. 4c) and Sn/SnO2SEM image of-3H (FIG. 4d), as seen in Ar-H2Sn/SnO obtained by calcining for different times in atmosphere2-1h、Sn/SnO2The composite material still maintains a cubic structure assembled by the nano-sheets after 2h, only part of the tin dioxide is reduced to metallic tin, and the volume is shrunk. Sn/SnO assembled by nanosheets after calcination21h of cube structure edge length of about 380nm, and Sn/SnO2The side length of the cubic block of-2 h becomes about 270nm, and the nano sheet is more fluffy, and the surface of the cubic block is rougher. And in Ar-H2After calcining for three hours in the atmosphere, the obtained Sn/SnO2Collapse of the-3 h composite cube structure, probably due to excessive oxygen loss from the surface. FIG. 5 is SnO2(p)-20、Sn/SnO2-1h、Sn/SnO 22h and Sn/SnO2XRD test result of-3H sample, from which Ar-H at 400 deg.C2Under the condition of pure SnO2(PDF #41-1445) the peak intensity of metallic Sn (PDF #04-0675) is gradually increased with the time of calcination, which shows that more and more SnO is generated with the time of calcination2Quilt H2Reduction to metallic Sn, i.e. Sn/SnO2In the composite material, the percentage of Sn is gradually increased.
CO2The constant voltage electrolysis adopts an online H-shaped electrolytic cell, the online detection of gas products is carried out by gas chromatography, and the detection of liquid products is carried out by high performance liquid chromatography. SnO treated under different voltages (-0.8V-1.3V vs. RHE)2(p)-10、SnO2(p) -20 and SnO2(p) -30 samples were subjected to potentiostatic electrolysis. Through detection, the electrocatalytic products of the three catalysts are CO, formate and H2The faradaic efficiencies of the three products are calculated as shown in figure 6. Overall, formate was present as CO in all three samples2Main products of reduction, and CO and H2The Faradaic Efficiency (FE) at different voltages is relatively small. As the voltage becomes negative, the FE of the formate shows a tendency to increase and then decrease, with the highest faradaic efficiency at-1.1V. Notably, three samples did not differ much in formate Faraday efficiency at-1.1V (FE)SnO2(p)-10～54％、FESnO2(p)-20～55％、FESnO2(p)-3053%), which may be attributed to their same material composition. In addition, H is present over a wide voltage range (-0.8V-1.3V vs. RHE), H2All the Faraday efficiencies are higher (>20％)。
Furthermore, a three-electrode system is adopted, respectively with SnO2(p)-20、Sn/SnO2-1h、Sn/SnO 22h and Sn/SnO2-3h as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt sheet as a counter electrode, in N2And CO2Saturated 0.5MKHCO3The measurement of linear sweep cyclic voltammetry (LSV) was performed in solution, and the resulting current values were compared. As shown in fig. 7a, four electrodes (SnO)2(p)-20、Sn/SnO2-1h、Sn/SnO 22h and Sn/SnO2Current density at saturated CO of-3 h)2The values obtained in the electrolyte are much higher than in saturated N2The value obtained in the electrolyte. Furthermore, the starting potentials of the four electrodes are at saturated CO2N to be saturated in the electrolyte2In the electrolyte. These results indicate that the catalyst is on CO2The reduction has good catalytic activity. The comparison result of four electrodes shows that Sn/SnO2The-2 h electrode showed the largest current density and the smallest starting point. When the voltage value is-1.22V, the current value reaches 60mA cm under the condition of no iR correction-2And the other three electrodes SnO2(p)-20、Sn/SnO2-1h and Sn/SnO2Voltages of-1.23V, -1.27V and-1.28V are required to reach the same current density for-3 h. The above Sn/SnO2The current density of the-2 h electrode is improved mainly because the introduction of the metal Sn improves the conductivity of the composite material, which is beneficial to the transfer of electrons, so that the adsorbed CO is in an adsorbed state2To obtain an electron (e)-) Rapid conversion to CO2 ·-An intermediate. And Sn/SnO with further extension of calcination time2The current density of the-3 h electrode instead decreased, which could be attributed to the disruption of the nanosheet assembled cubic structure morphology under long-term calcination.
FIG. 7b shows C at different potentials for four electrodes1The current density of the product, Sn/SnO, can be seen from the figure22h showed the maximum current density at each potential in the graph, indicating that it has higher electrocatalytic activity at each potential. And at-1.1V, Sn/SnO2J of-2 hC1Reach 33.02mA cm-2And more particularly its precursor SnO2(p)-20jC1(16.42mA cm-2) 2.01 times of the total weight of the powder. And Sn/SnO2-1h and Sn/SnO2-3h j at this potentialC1Are also respectively SnO2(p)-20jC11.90 times and 1.47 times of that of the metallic Sn doped Sn/SnO2Composite material has a specific SnO2Excellent electrocatalytic activity.
The same as the above method, Sn/SnO is reacted under different voltages (-0.8V-1.3V vs. RHE)2-1h、Sn/SnO 22h and Sn/SnO2Three samples were subjected to potentiostatic electrolysis for-3 h, and the faradaic efficiency of each product was calculated (FIG. 8). Through detection, the electrocatalytic products of the three catalysts are CO, formate and H2. With SnO2Compared with the (p) -20 precursor (FIG. 8a), the formate FE of the three catalysts is greatly improved. FIG. 8b is Sn/SnO2CO of-1 h2The faradaic efficiency profile of the reduction product, as can be seen from the figure, the faradaic efficiency of formic acid increases gradually with the potential becoming negative, reaching a maximum of 78.88% at-1.3V. Sn/SnO2The Faraday efficiency profile for-2 h is shown in FIG. 8c, where the FE of formate shows a tendency to increase and decrease with increasing voltage, and the highest Faraday efficiency is 79.82% at-1.1V. And Sn/SnO under wide voltage range (-0.8V-1.3V vs. RHE)2-2h of FEHCOOH-(FIG. 8c) is greater than 60% and FE is found in this broad intervalC1All are more than 85 percent, effectively inhibit the hydrogen evolution competition reaction and show the maximum FE at the position of-1.0VC1The content was 92.53%. As can be seen in FIG. 8c, Sn/SnO2The hydrogen evolution competition reaction of the-3 h sample is intensified under a more negative potential, so that the optimal FE is shown under the potential of-1.0VHCOOH-The content was 67.89%. Notably, three Sn/SnO groups2FE of composite materialsCOThe voltage shows a decreasing trend with decreasing voltage, indicating that a more positive potential favors CO production.
In summary, the present disclosure allows for efficient control of SnO by controlling the solvent volume of the hydrothermal reaction2The shape of the nano material is controlled to synthesize the cubic shapes assembled by nanospheres and nano sheets, and H is added into a solvent2BDC can generate SnO with uniform size2A self-assembled body. In SnO2(p) -20 is a precursor, by reaction at Ar-H2The electrocatalytic material with excellent performance is obtained by calcining under the atmosphere. Wherein Sn/SnO2The highest formate Faraday efficiency of 79.82% at-1.1V for-2 h, and FE at-0.8V-1.3V vs. RHEHCOOH-both greater than 60%, and FE in this broad intervalC1Are all greater than 85%, effectiveInhibit the hydrogen evolution competition reaction, and has the maximum FE at-1.0VC1The content was 92.53%. In addition, at-1.1V, Sn/SnO2J of-2 hC1Reach 33.02mA cm-2Is its precursor SnO2(p) -20 jC1(16.42mA cm-2) 2.01 times of that of the Sn/SnO2The composite material has excellent electrocatalytic activity. This may be attributed to the metals Sn and SnO2On the one hand, the existence of metal Sn improves SnO2Conductivity of the precursor, favouring e-Transport over the surface of the material; metallic Sn and SnO on the other hand2The mixed surface electronic state can effectively relieve SnO2Reduction of (2) to increase SnO2Stability at negative potentials.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A method for controlling the morphology of tin dioxide is characterized in that a hydrothermal method is adopted to prepare tin dioxide, and the morphology of tin dioxide is regulated and controlled by controlling the volume ratio of a solvent to the volume of a reaction kettle in the hydrothermal method; when the volume ratio of the solvent to the reaction kettle is 8-12: 50, the obtained stannic oxide is nanospheres; when the volume ratio of the solvent to the reaction kettle is 18-22: 50, the obtained stannic oxide is a nanosheet assembly with a cubic structure; when the volume ratio of the solvent to the volume of the reaction kettle is 28-32: 50, the obtained stannic oxide is a nanosheet assembly with a large cubic block structure; the solvent in the hydrothermal method is a mixture of tetramethylammonium hydroxide and water; the reaction conditions of the hydrothermal method are: reacting for 20-28 h at 175-185 ℃; in the hydrothermal reaction system, the concentration of the tin source is 0.08-0.12 mol/L.
2. The method for controlling the morphology of tin dioxide as claimed in claim 1, wherein terephthalic acid is added to the hydrothermal reaction system.
3. The method of claim 2, wherein the molar ratio of the tin source to the terephthalic acid is 1:0.9 to 1.1.
4. The method of claim 1 wherein the tin source is added to a mixture of tetramethylammonium hydroxide and water and mixed prior to hydrothermal reaction.
5. Tin dioxide, characterized in that it is obtained by the method for controlling the morphology of tin dioxide according to any one of claims 1 to 4.
6. Use of the tin dioxide according to claim 5 for the preparation of a tin-tin dioxide composite.
7. A method for preparing a tin-tin dioxide composite material is characterized in that the tin dioxide of claim 5 is calcined in a mixed atmosphere for not more than 4 hours; the calcining temperature is not higher than 450 ℃, and the mixed atmosphere refers to inert atmosphere and reducing atmosphere.
8. The method according to claim 7, wherein the calcination time is 1.8 to 2.2 hours.
9. The method according to claim 8, wherein the calcination temperature is 395-405 ℃.
10. A tin-tin dioxide composite material, characterized by being obtained by the production method according to claim 7.
11. Use of the tin dioxide of claim 5 in the electrocatalytic reduction of carbon dioxide.
12. A working electrode for electrocatalytic reduction of carbon dioxide comprising the tin dioxide of claim 5.
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