CN111333104B - Preparation method and application of nanoscale tin dioxide - Google Patents
Preparation method and application of nanoscale tin dioxide Download PDFInfo
- Publication number
- CN111333104B CN111333104B CN202010130964.3A CN202010130964A CN111333104B CN 111333104 B CN111333104 B CN 111333104B CN 202010130964 A CN202010130964 A CN 202010130964A CN 111333104 B CN111333104 B CN 111333104B
- Authority
- CN
- China
- Prior art keywords
- tin dioxide
- tin
- copper
- carbon dioxide
- formic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 26
- 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 abstract description 23
- 235000019253 formic acid Nutrition 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000013384 organic framework Substances 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims abstract description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 2
- 239000010411 electrocatalyst Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000001000 micrograph Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a preparation method and application of nano-grade tin dioxide. The method comprises the steps of mixing and reacting a copper-organic framework material with a tin salt aqueous solution, carrying out centrifugal drying to obtain a precursor mixture, calcining the precursor mixture to obtain tin dioxide, and controlling the particle size and the dispersibility of tin dioxide particles by regulating and controlling the calcination temperature. The tin dioxide powder has good catalytic selectivity and catalytic activity for electrocatalytic carbon dioxide reduction reaction, and when the constant potential electrolysis is carried out on a potassium bicarbonate electrolyte aqueous solution of saturated carbon dioxide gas in a potential range of-1.2V to-1.8V relative to an Ag/AgCl electrode, an electrolysis product is mainly formic acid.
Description
Technical Field
The invention belongs to the technical field of metal oxide nano material preparation, and particularly relates to a preparation method and application of nano-grade tin dioxide.
Background
At present, with the continuous development of the human industrialization process, the concentration of carbon dioxide in the atmosphere is continuously generated, the global temperature is increased due to the greenhouse effect, and the environmental problems of sea level rise, land desertification, species extinction and the like are caused.
Electrocatalytic carbon dioxide reduction (CO) 2 RR) is a green technology that can convert greenhouse gases into fuels, and can solve not only environmental problems caused by greenhouse gases, but also energy crisis faced by humans. However, CO 2 Has a highly stable chemical structure and is not easy to react. Wherein, CO 2 The first step in the RR electrocatalytic reaction isTo CO 2 Transfer an electron to convert it to CO 2 The reaction is difficult to proceed kinetically because of the need to climb a very large energy barrier, and a large overpotential is required to consume a large amount of electric energy. The use of an electrocatalyst can reduce the energy barrier of the reaction and accelerate the reaction. In addition, CO 2 The RR electrocatalytic reaction is a reaction of a multiple electron transfer process, and generates numerous reaction products, which are mixed together and difficult to separate.
Therefore, the development of low overpotential, high efficiency, high selectivity and stable CO 2 RR electrocatalyst is widely concerned by researchers, and is a research hotspot in the field at present.
In CO 2 Although many studies have been reported on the electrochemical reduction of (1) metal materials, the stability of the metal materials is an important issue, and the metal electrodes are liable to electrolytically reduce CO for a long period of time 2 In the process of (1) activity decay occurs. In contrast, metal oxides are relatively stable in electrolytic processes, and in this regard, there have been attempts to develop metal oxides as catalysts which are highly stable and have high current efficiency. However, due to conductivity, a few metal oxide catalysts are available.
Disclosure of Invention
The invention provides a novel method for preparing nano-scale tin dioxide, which can prepare the nano-scale tin dioxide and find that the prepared tin dioxide has good catalytic selectivity and catalytic activity for electrocatalytic carbon dioxide reduction reaction.
The technical scheme provided by the invention is as follows: a preparation method of nano-scale tin dioxide comprises the following steps:
(1) dissolving copper salt in methanol to obtain a solution A; uniformly mixing the solution A with a methanol solution of a ligand to obtain a mixed solution, centrifuging and drying to obtain a copper-organic framework material;
(2) stirring and mixing the copper-organic framework material obtained in the step (1), tin salt and water solution, centrifuging and drying to obtain a precursor mixture;
(3) and (3) calcining the precursor mixture obtained in the step (2), namely, heating to over 300 ℃ in an air atmosphere, preserving the heat for a certain time, and then naturally cooling to room temperature.
Preferably, the calcination temperature is from 400 ℃ to 600 ℃, more preferably from 450 ℃ to 550 ℃, and most preferably 500 ℃.
Preferably, the particle size of the tin dioxide is less than 100 nm, and more preferably less than 50 nm.
Preferably, the heating rate is 5 to 10 ℃/min.
The copper salt is not limited, and can be selected from one or more of copper chloride dihydrate, copper nitrate trihydrate, copper sulfate pentahydrate, copper nitrate hexahydrate and the like.
The ligand is not limited and may be selected from trimesic acid, biphenyldicarboxylic acid and terephthalic acid, preferably trimesic acid.
Preferably, in the step (1), the mixed solution includes a surfactant, and the surfactant is not limited and may be one or more selected from polyvinylpyrrolidone, hexamethylenetetramine, cetyltrimethylammonium bromide, and the like.
The tin salt is not limited, and comprises one or more of stannous chloride dihydrate, stannous oxalate, stannous sulfate and the like.
The holding time is preferably 1 to 5 hours, more preferably 2 to 4 hours.
In the step (2), the ratio of the molar weight of copper in the copper-organic framework material to the molar weight of tin in the tin salt is greater than or equal to 1: 1.
Compared with the prior art, the invention has the following beneficial effects that the copper-organic framework material, the tin salt and the aqueous solution are mixed and reacted, and the product is calcined to obtain the nano-grade tin dioxide:
(1) the preparation method is simple and easy to implement, can prepare the nano-grade tin dioxide, has no cluster and larger particles, has particle size even less than 50 nanometers, and has good dispersibility;
(2) in the preparation method, the particle size of the tin dioxide particles is related to the calcination temperature under the same other conditions, and experiments prove that the tin dioxide particles are fine and uniform and have good dispersibility when the calcination temperature is over 400 ℃, and particularly, the particle size is less than 50 nanometers and has good dispersibility when the calcination temperature is 450-550 ℃, so that the particle size and the dispersibility of the tin dioxide particles can be regulated and controlled by regulating the calcination temperature;
(3) the tin dioxide powder prepared by the method has good catalysis effect on electrocatalytic carbon dioxide reduction reaction, and when the constant potential electrolysis is carried out on the potassium bicarbonate electrolyte aqueous solution saturated with carbon dioxide gas in the potential range of-1.2V to-1.8V relative to an Ag/AgCl electrode, the main products are formic acid, CO and H 2 When the calcination temperature is selected to be higher than 400 ℃, the product is mainly formic acid, and has good catalytic selectivity, and when the calcination temperature is 450-600 ℃, the faradaic efficiency of formic acid is higher than 80% when the potential is-1.7V, and when the calcination temperature is 500 ℃, the faradaic efficiency of formic acid is even higher than 84% when the potential is-1.7V, and has good catalytic activity.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a tin dioxide electrocatalyst prepared according to examples 1-4 of the present invention.
Figure 2A is a scanning electron microscope image of a tin dioxide electrocatalyst prepared according to example 1 of the present invention.
FIG. 2B is a scanning electron microscope image of a tin dioxide electrocatalyst made in example 2 of the present invention.
Figure 2C is a scanning electron microscope image of a tin dioxide electrocatalyst made in example 3 of the present invention.
Figure 2D is a scanning electron microscope photograph of a tin dioxide electrocatalyst prepared according to example 4 of the present invention.
FIG. 3 is a graph showing the potentiostatic electrolysis product distribution of the tin dioxide electrocatalyst prepared in example 1 of the present invention.
FIG. 4 is a graph showing the potentiostatic electrolysis product distribution of the tin dioxide electrocatalyst prepared in example 2 of the present invention.
FIG. 5 is a graph showing the potentiostatic electrolysis product distribution of the tin dioxide electrocatalyst prepared in example 3 of the present invention.
FIG. 6 is a graph showing the potentiostatic electrolysis product distribution of the tin dioxide electrocatalyst prepared in example 4 of the present invention.
Figure 7 is a graph of the formic acid faradaic efficiency of tin dioxide electrocatalysts prepared in examples 1-4 of the present invention.
FIG. 8 is a graph of KHCO at 0.1M saturated with carbon dioxide at constant voltage of-1.8V (vs. Ag/AgCl electrode) for example 3 of the invention 3 Time-current density curve in electrolyte.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1:
in this embodiment, the preparation method of tin dioxide is as follows:
(1) preparation of copper-organic framework materials
Dissolving 36g of copper nitrate hexahydrate and 16g of polyvinylpyrrolidone K-30(PVP-K30) in 2L of methanol to obtain a solution A, dissolving 17.2g of trimesic acid in 2L of methanol to obtain a solution B, pouring the solution A into the solution B, stirring uniformly, and standing at room temperature for 24 h; then, the product was centrifuged and dried at 80 ℃ for 12 hours to obtain a copper-organic framework material (Cu-BTC).
(2) Preparation of tin dioxide precursor
And (2) dissolving 50mg of the copper-organic framework material (Cu-BTC) prepared in the step (1) in 250mL of deionized water, dissolving 25mg of stannous chloride dihydrate in 250mL of deionized water, mixing the two solutions, stirring for 6 hours at room temperature, then carrying out centrifugal treatment, and drying the centrifugal product for 12 hours at 80 ℃ to obtain a stannic oxide precursor.
(3) Calcination treatment
And (3) putting the tin dioxide precursor obtained in the step (2) into a tube furnace, heating to 300 ℃ at the heating rate of 5 ℃/min, keeping for 4 hours, and then naturally cooling to room temperature.
The material obtained above was subjected to X-ray diffraction analysis, and its powder X-ray diffraction pattern is shown in FIG. 1. The characteristic peak of the tin dioxide can be observed as a steamed bread peak from the graph, and the fact that the tin dioxide obtained by calcining at the temperature is poor in crystal form and is amorphous is proved.
The morphology of the tin dioxide powder is analyzed, and a scanning electron microscope image of the tin dioxide powder is shown in fig. 2A, so that the tin dioxide particle morphology is not very clear and the agglomeration phenomenon exists.
The prepared tin dioxide powder is used as an electrocatalyst to be applied to electrocatalytic reduction of carbon dioxide, and the specific method is as follows:
(1) preparation of catalyst slurry:
12.5 mg of this tin dioxide powder was weighed, ultrasonically dispersed for half an hour with 652. mu.L deionized water and 326. mu.L absolute ethanol, and 22. mu.L of 5% naphthol surfactant was added to obtain a catalyst slurry.
(2) The three-electrode system is used for carrying out electrocatalysis performance characterization on the catalyst, and specifically comprises the following steps:
in an H-shaped sealed glass electrolytic cell, a 0.1M potassium bicarbonate aqueous solution containing saturated carbon dioxide gas is used as an electrolyte, a platinum wire electrode is used as a counter electrode, and the area of the electrode coated with 40 mu L of catalyst slurry is 1cm 2 The carbon cloth is used as a working electrode, and electrolytic analysis is carried out in a potential range of-1.2V to-1.8V relative to an Ag/AgCl electrode. The electrolysis time was fixed at 1800s and the electrolysis interval was 100 mV. 3mL of the gas product obtained after 1800s was subjected to gas chromatography detection, and 10. mu.L of the electrolyzed electrolyte was subjected to nuclear magnetic resonance detection.
The detection results are shown in FIG. 3, from which it is clear that: the main products are formic acid, CO and H in the potential range of-1.2V to-1.8V 2 Wherein formic acid and H 2 The yield of (A) is more and equivalent; the faradaic efficiency of formic acid is more than 45% and less than 60% at a potential of-1.7V.
Example 2:
in this embodiment, the preparation method of tin dioxide is as follows:
(1) preparation of copper-organic framework materials
Same as in example 1.
(2) Preparation of tin dioxide precursor
Same as in example 1.
(3) Calcination treatment
And (3) putting the tin dioxide precursor obtained in the step (2) into a tube furnace, heating to 400 ℃ at the heating rate of 5 ℃/min, keeping for 4 hours, and then naturally cooling to room temperature.
When the material obtained above was subjected to X-ray diffraction analysis, the characteristic peaks of tin dioxide could be observed as shown in fig. 1, which confirmed that tin dioxide was successfully obtained.
The morphology of the tin dioxide powder is analyzed, and a scanning electron microscope image of the tin dioxide powder is shown in fig. 2B, so that the tin dioxide nanoparticles are relatively uniform, but a part of the tin dioxide nanoparticles are agglomerated.
The tin dioxide powder prepared above was used as an electrocatalyst in the electrocatalytic reduction of carbon dioxide, and the specific method was the same as in example 1.
The detection results are shown in FIG. 4, from which it is clear that: the main products are formic acid, CO and H in the potential range of-1.2V to-1.8V 2 Products are mainly formic acid within the potential range of-1.4V to-1.8V, and the faradaic efficiency of the formic acid is more than 45 percent and less than 80 percent.
Example 3:
in this embodiment, the preparation method of tin dioxide is as follows:
(1) preparation of copper-organic framework materials
Same as in example 1.
(2) Preparation of tin dioxide precursor
Same as in example 1.
(3) Calcination treatment
And (3) putting the tin dioxide precursor obtained in the step (2) into a tube furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, keeping for 4 hours, and then naturally cooling to room temperature.
When the material obtained above was subjected to X-ray diffraction analysis, the characteristic peaks of tin dioxide could be observed as shown in fig. 1, which confirmed that tin dioxide was successfully obtained.
The tin dioxide powder prepared by the method is subjected to morphology analysis, and a scanning electron microscope image of the tin dioxide powder is shown in fig. 2C, so that the tin dioxide nanoparticles are uniform, and the particle size of the tin dioxide particles is 12-22 nanometers.
The tin dioxide powder prepared above was used as an electrocatalyst in the electrocatalytic reduction of carbon dioxide, and the specific method was the same as in example 1.
The detection results are shown in FIG. 5, from which it is clear that: the main products are formic acid, CO and H in the potential range of-1.2V to-1.8V 2 Products are mainly formic acid in the potential range of-1.2V to-1.8V, and the faradaic efficiency of formic acid reaches 84.9% when the potential is-1.7V.
FIG. 8 is 0.1M KHCO saturated with carbon dioxide at constant voltage-1.8V 3 From the time-current density curve in the electrolyte, it can be known that the current density of the catalyst in the electrochemical reaction process gradually increases along with the reaction time, reflecting the high carbon dioxide electrocatalytic activity and stability.
Example 4:
in this embodiment, the preparation method of tin dioxide is as follows:
(1) preparation of copper-organic framework materials
Same as in example 1.
(2) Preparation of tin dioxide precursor
Same as in example 1.
(3) Calcination treatment
And (3) putting the tin dioxide precursor obtained in the step (2) into a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping for 4 hours, and then naturally cooling to room temperature.
When the material obtained above was subjected to X-ray diffraction analysis, the characteristic peaks of tin dioxide could be observed as shown in fig. 1, which confirmed that tin dioxide was successfully obtained.
The tin dioxide powder prepared by the method is subjected to morphology analysis, and a scanning electron microscope image of the tin dioxide powder is shown in fig. 2B, so that the tin dioxide nanoparticles are uniform, and the particle size of the tin dioxide particles is between 20 and 40 nanometers.
The tin dioxide powder prepared above was used as an electrocatalyst in the electrocatalytic reduction of carbon dioxide, and the specific method was the same as in example 1.
The detection results are shown in FIG. 6, from which it is clear that: the main products are formic acid, CO and H in the potential range of-1.2V to-1.8V 2 Products are mainly formic acid in the potential range of-1.3V to-1.8V, and the faradaic efficiency of formic acid reaches 80.1% when the potential is-17. V.
The faradaic efficiencies of the electrocatalysts in the above examples 1 to 4 for the electrocatalysts for the electrocatalysis of carbon dioxide reduction to formic acid are shown in the following table:
comparing examples 1 to 4, it can be seen that the tin dioxide in examples 1 to 4 all have catalytic action on the electrocatalytic reduction reaction of carbon dioxide, wherein examples 2, 3 and 4 have good catalytic selectivity, especially the best catalytic selectivity in example 3, and examples 2, 3 and 4 have higher catalytic activity, especially the best catalytic activity in example 3.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. A preparation method of nano-scale tin dioxide is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving copper salt in methanol to obtain a solution A; uniformly mixing the solution A with a methanol solution of a ligand to obtain a mixed solution, centrifuging and drying to obtain a copper-organic framework material; the ligand is selected from one or more of trimesic acid, biphenyldicarboxylic acid and terephthalic acid;
(2) stirring, mixing and reacting the copper-organic framework material obtained in the step (1), tin salt and aqueous solution, and then centrifuging and drying to obtain a precursor mixture;
(3) and (3) calcining the precursor mixture obtained in the step (2), namely, heating to 400-600 ℃ in air atmosphere, preserving heat for a certain time, and then naturally cooling to room temperature.
2. The method of claim 1, wherein: in the step (3), the temperature is raised to 450-550 ℃.
3. The method of claim 1, wherein: the grain diameter of the tin dioxide is less than 100 nanometers.
4. The method of claim 3, wherein: the grain diameter of the tin dioxide is less than 50 nanometers.
5. The method of claim 1, wherein: in the step (1), the copper salt is selected from one or more of copper chloride dihydrate, copper nitrate trihydrate, copper sulfate pentahydrate and copper nitrate hexahydrate.
6. The method of claim 1, wherein: in the step (1), the mixed solution contains a surfactant.
7. The method of claim 6, wherein: the surfactant is selected from one or more of polyvinylpyrrolidone, hexamethylenetetramine and hexadecyl trimethyl ammonium bromide.
8. The method of claim 1, wherein: in the step (2), the tin salt comprises one or more of stannous chloride dihydrate, stannous oxalate and stannous sulfate.
9. The method of claim 1, wherein: in the step (2), the ratio of the molar weight of copper in the copper-organic framework material to the molar weight of tin in the tin salt is greater than or equal to 1: 1.
10. The method of claim 1, wherein: in the step (3), the heating rate is 5-20 ℃/min.
11. The method of claim 1, wherein: in the step (3), the heat preservation time is 1-5 h.
12. The method of claim 11, wherein: in the step (3), the heat preservation time is 2-4 h.
13. The tin dioxide powder obtained by the production method according to claim 1 is used as a catalyst for electrocatalytic carbon dioxide reduction.
14. The tin dioxide powder of claim 13 as a catalyst for electrocatalytic carbon dioxide reduction, wherein: when the constant potential electrolysis is carried out on the potassium bicarbonate electrolyte aqueous solution saturated with carbon dioxide gas in the potential range of-1.2V to-1.8V relative to the Ag/AgCl electrode, the main products are formic acid, CO and H 2 。
15. The tin dioxide powder of claim 13 as a catalyst for electrocatalytic carbon dioxide reduction, wherein: in the step (3), when the temperature is raised to be higher than 400 ℃, the electrolysis product is mainly formic acid.
16. The tin dioxide powder of claim 15 as a catalyst for electrocatalytic carbon dioxide reduction, wherein: in the step (3), when the temperature is raised to 450-600 ℃, the formic acid Faraday efficiency is more than 80% when the potential is minus 1.7V.
17. The tin dioxide powder of claim 16 as a catalyst for electrocatalytic carbon dioxide reduction, wherein: in the step (3), when the temperature is raised to 500 ℃, the formic acid Faraday efficiency is more than 84% when the potential is minus 1.7V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010130964.3A CN111333104B (en) | 2020-02-28 | 2020-02-28 | Preparation method and application of nanoscale tin dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010130964.3A CN111333104B (en) | 2020-02-28 | 2020-02-28 | Preparation method and application of nanoscale tin dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111333104A CN111333104A (en) | 2020-06-26 |
| CN111333104B true CN111333104B (en) | 2022-09-20 |
Family
ID=71177888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010130964.3A Active CN111333104B (en) | 2020-02-28 | 2020-02-28 | Preparation method and application of nanoscale tin dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111333104B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114855192B (en) * | 2022-03-31 | 2023-12-08 | 浙江大学杭州国际科创中心 | Method for preparing benzyl ketone/aldehyde compound by electrochemical oxidation of transition metal oxide catalyst |
| CN115259210B (en) * | 2022-08-29 | 2024-02-02 | 北京化工大学 | MOF-derived SnO 2 Preparation method and application of (C) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267718A (en) * | 2011-06-30 | 2011-12-07 | 上海大学 | Synthesis method of tin dioxide nanometer material |
| CN104556209A (en) * | 2015-01-09 | 2015-04-29 | 太原理工大学 | Preparation method for spherical tin dioxide self-assembled from nano-fragments |
| CN105948106A (en) * | 2016-06-29 | 2016-09-21 | 渤海大学 | Preparation method of narrow-bandgap stannic oxide semiconductor nanomaterial |
| CN106000384A (en) * | 2016-05-13 | 2016-10-12 | 淮北师范大学 | Preparation method of tin-based oxide with controllable components and photocatalytic application of tin-based oxide |
| CN108441878A (en) * | 2018-03-01 | 2018-08-24 | 浙江大学 | A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst and the preparation method and application thereof |
| CN109675545A (en) * | 2018-12-20 | 2019-04-26 | 华中科技大学 | A kind of SnO with multi-layer structurexCatalyst, preparation method and application |
-
2020
- 2020-02-28 CN CN202010130964.3A patent/CN111333104B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267718A (en) * | 2011-06-30 | 2011-12-07 | 上海大学 | Synthesis method of tin dioxide nanometer material |
| CN104556209A (en) * | 2015-01-09 | 2015-04-29 | 太原理工大学 | Preparation method for spherical tin dioxide self-assembled from nano-fragments |
| CN106000384A (en) * | 2016-05-13 | 2016-10-12 | 淮北师范大学 | Preparation method of tin-based oxide with controllable components and photocatalytic application of tin-based oxide |
| CN105948106A (en) * | 2016-06-29 | 2016-09-21 | 渤海大学 | Preparation method of narrow-bandgap stannic oxide semiconductor nanomaterial |
| CN108441878A (en) * | 2018-03-01 | 2018-08-24 | 浙江大学 | A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst and the preparation method and application thereof |
| CN109675545A (en) * | 2018-12-20 | 2019-04-26 | 华中科技大学 | A kind of SnO with multi-layer structurexCatalyst, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 纳米氧化铜与氧化锡复合物(SnO2-CuO)催化剂的制备及CO2电催化还原性能研究;马承愚等;《功能材料》;20171231;第48卷(第4期);第04090-04095页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111333104A (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Enhanced photocatalytic CO2 reduction over 2D/1D BiOBr0. 5Cl0. 5/WO3 S-scheme heterostructure | |
| CN110479379B (en) | Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof | |
| Chen et al. | Non-noble metal Cu as a cocatalyst on TiO2 nanorod for highly efficient photocatalytic hydrogen production | |
| CN111333104B (en) | Preparation method and application of nanoscale tin dioxide | |
| CN110625135B (en) | Method for efficiently, simply and easily synthesizing Ru nanocrystals with different morphologies | |
| CN108855173B (en) | Method for producing hydrogen by photoelectrocatalysis water decomposition, plasma catalyst used in method and preparation method | |
| CN111215104A (en) | Phosphorus-doped carbon-loaded molybdenum-tungsten carbide catalyst, and preparation and application thereof | |
| CN112993278A (en) | Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof | |
| CN115369422A (en) | Low-iridium electrolyzed water catalyst, and preparation method and application thereof | |
| CN104815682B (en) | High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof | |
| CN114525542A (en) | For electrocatalytic reduction of CO2Nano palladium alloy catalyst, and preparation method and application thereof | |
| CN113549937A (en) | For CO2Electrocatalytic material Cu of RR2Preparation method of O @ h-BN | |
| CN110961101B (en) | Platinum-based catalyst, preparation method and application thereof | |
| CN109569285B (en) | Nitrogen-doping-based graphene-based electrocatalyst and preparation and application thereof | |
| CN115505951B (en) | Porous iridium oxide nano material, preparation method and application thereof | |
| CN116377505A (en) | MnO (MnO) 2 /RuO 2 Heterogeneous oxygen evolution reaction electrocatalyst, preparation method and application | |
| CN113774403A (en) | Water decomposition electrocatalyst Ag8W4O16/CoWO4Preparation method of (1) | |
| CN111437831B (en) | Pt @ Ni-SNT/graphene hydrogen evolution catalyst and preparation method and application thereof | |
| CN114824319A (en) | N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst | |
| KR20120014704A (en) | Pt-pd alloy catalyst for fuel cell and method of preparing the same | |
| CN111268723A (en) | Method for controlling morphology of tin dioxide, tin-tin dioxide composite material and application | |
| CN111346649A (en) | Pd @ Ni-SNT/graphene hydrogen evolution catalyst and preparation method and application thereof | |
| CN115074774B (en) | Rhodium-based hollow porous microsphere/nickel foam electrode and preparation method and application thereof | |
| CN116037953B (en) | PtIr alloy nano material and preparation method and application thereof | |
| CN115094466B (en) | Hollow carbon dodecahedron packaging WC, W 2 C or diphase WC/W 2 Preparation method of C nanoparticle electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lin Yichao Inventor after: Hao Fei Inventor after: Chen Liang Inventor before: Lin Yichao Inventor before: Hepei Inventor before: Chen Liang |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |