CN109161922A - One kind realizing C1 fueled electrochemical reducing catalyst and its preparation and application by carbon dioxide - Google Patents

One kind realizing C1 fueled electrochemical reducing catalyst and its preparation and application by carbon dioxide Download PDF

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CN109161922A
CN109161922A CN201811179165.4A CN201811179165A CN109161922A CN 109161922 A CN109161922 A CN 109161922A CN 201811179165 A CN201811179165 A CN 201811179165A CN 109161922 A CN109161922 A CN 109161922A
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catalyst
carbon
sno
preparation
tube
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CN109161922B (en
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乔锦丽
张琦
刘佳闻
彭芦苇
刘俊宇
周玥
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Donghua University
Shanghai Jinyuan Senior High School
National Dong Hwa University
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Shanghai Jinyuan Senior High School
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to one kind to realize C1 fueled electrochemical reducing catalyst and its preparation and application by carbon dioxide, and catalyst loads SnO using carbon nanotube as carrierxNanometer sheet.Preparation: stannous chloride and sodium citrate is soluble in water, and stirring and dissolving obtains precursor solution；Disperse solvent for carbon nanotube, ultrasound, obtain carbon nano-tube solution, after mixing carry out hydro-thermal reaction to get.Electrochemical reduction catalyst produced by the present invention has distinct (101) and (002) crystal face, to CO2Electrochemical reduction is that C1 product has both high catalytic activity and selectivity, efficiently hydrogen gas byproduct is inhibited to generate, and show long-term stability in electrolytic process.In addition, method for preparing catalyst of the invention is easy to operate, green, C1 selectivity of product is high, have a extensive future.

Description

One kind by carbon dioxide realize C1 fueled electrochemical reducing catalyst and its preparation and Using
Technical field
The invention belongs to carbon dioxide electrochemical reduction catalyst and its preparation and application fields, in particular to one kind is by two Carbonoxide realizes C1 fueled electrochemical reducing catalyst and its preparation and application.
Background technique
As the mankind are to the excessive use of fossil fuel, energy crisis and thus bring carbon dioxide excessive emissions are drawn The global warming issue risen also increasingly aggravates, and is thus captured and efficiently used the extensive pass that (CCU) causes the whole world to carbon Note.Carbon dioxide electrochemical reduction technology (CO2RR) prepares the raw material of industry and low-carbon fuel is the great plan for alleviating this problem Slightly, simultaneously because CO2RR can be driven by clean energy resource, therefore the mankind can be transferred to the dependence of fossil fuel by the technology In Carbon balance energy circulation [Catalysis Today, 270,19-30 (2016)].During Carbon dioxide electrochemical reduction, Due to lower electron transmission quantity and relatively quick dynamic characteristic, C1 product (HCOOH/HCOO-And CO) generation more It is feasible.On the other hand, formic acid is one of very potential liquid hydrogen storage compound, can be widely applied to hydrogen carrier and combustion Expect battery；And CO is the important source material in chemical industry, such as can be used for Fischer-Tropsch synthesis.However, due to CO2High degree of symmetry molecular structure, CO2It restores and not only needs to overcome the competition between evolving hydrogen reaction (HER), while complicated High-energy potential barrier in multielectron transfer dynamics and reaction process, generally produces the mixture of voluminous object.Therefore, exploitation tool The effective catalyst of high catalytic activity, selectivity and stability is to solve CO2The key point of effective use.
The selectivity of product of Carbon dioxide electrochemical reduction is heavily dependent on the property of metal electrode.Noble metal is such as Au, Ag and Pd have universal higher catalytic activity and selectivity, but the low abundance and height of these noble metals to CO or formates Cost limits its sizable application.Non-noble metallic materials such as transition metal and its compound (such as Cu, Sn, Bi, Pb, In, CO3O4、SnO2、MoS2、SnS2) can be effectively by CO2It is reduced into CO or HCOOH.In these catalyst, Sn sill is due to it High abundance, low cost, hypotoxicity and highly selective to formic acid and be widely used.However, the low activity of polycrystalline Sn limits Its practical application is made.Studies have shown that tin oxide (the SnO of metal Sn electrode surfacex) layer can effectively inhibit the precipitation of hydrogen, and Stablize * CO2 ·-, to improve CO2Reduction efficiency [Journal of Materials Chemistry A, 2,1647-1651 (2014)].Recent studies have shown that Sn base catalyst can provide biggish specific surface area in conjunction with carbon support materials to increase The number of active site, and pass through the aggregation in Anchoring Effect inhibitory activity site, to promote electronics transfer, wherein nano-sized carbon For material because of its high mechanical strength, thermal stability, electric conductivity and thermal conductivity are good and are concerned.Currently, carbon material supported tinbase Carbon dioxide electro-catalysis reducing catalyst is widely studied in the whole world, is produced however, the type catalyst is still remained to target Object poor selectivity [Angewandte Chemie International Edition, 57 (11), 2943-2947 (2018)], electricity Current density is smaller [Material Letters, 141,63-66 (2015)], energy efficiency it is low [Nature Communication, 7,12697 (2016)] the disadvantages of.Therefore the type catalyst is to CO2The selectivity and energy efficiency of electrochemical reduction product are also Far from meeting industrial requirement.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind to realize C1 fueled electrochemical reduction catalysts by carbon dioxide Agent and its preparation and application overcome the defects of prior art is low to C1 selectivity of product, current density is small, energy consumption is larger, the hair It is bright to propose a kind of leaf shape SnOxNanometer sheet and different functional groups functionalization MWCNT are compound as CO2Electrochemical reduction catalysis Agent utilizes SnOx(SnO or SnO2) to CO2Catalytic selectivity, meanwhile, MWCNTs is conducive to electron-transport to SnOxAnd it provides CO2The channel of gas diffusion.The catalyst not only has very high electro catalytic activity, but also it is anti-to effectively inhibit liberation of hydrogen It answers, so that the faradic efficiency of C1 product be made to reach nearly 100%.
Of the invention is a kind of by carbon dioxide realization C1 fueled electrochemical reducing catalyst, and the catalyst is with carbon nanotube For carrier, SnO is loadedxNanometer sheet, wherein (1,2) x=.
The carbon nanotube is functionalized carbon nano-tube；SnOxNanometer sheet is the nanometer sheet of leaf shape structure.
The functionalized carbon nano-tube are as follows: carboxylic carbon nano-tube, aminated carbon nano tube, in hydroxyl carbon nano tube It is one or more of.
Preferably, best carbon nanotube is-COOH carbon nano tube and-NH2Carbon nano tube.
One kind of the invention preparation method that C1 fueled electrochemical reducing catalyst is realized by carbon dioxide, comprising:
Stannous chloride and sodium citrate is soluble in water, and stirring and dissolving obtains precursor solution；It disperses carbon nanotube in Solvent, ultrasonic 1-1.5h, obtains carbon nano-tube solution；
By above two solution mix and ultrasound 1.5-2.5h, addition alkali, be sufficiently stirred, be then transferred into reaction kettle into Row hydro-thermal reaction, centrifuge washing after cooling is dry, grinds and realizes C1 fueled electrochemical reducing catalyst up to by carbon dioxide SnOx/ MWCNTs catalyst composite.
The preferred embodiment of above-mentioned preparation method is as follows:
The mass ratio of the stannous chloride and sodium citrate is 1:3~1:4；Tin carbon mass ratio is 15:1~5:1；Alkali It is 8:1~10:1 with stannous chloride molar ratio.
It is further preferred that tin carbon mass ratio is 8:1~7:1 in reactant.
The precursor solution, carbon nano-tube solution volume ratio be 10~20:20~40.
The diameter of the carbon nanotube is 10~20nm, and length is 20~30 μm；Solvent be the ethyl alcohol that mixes in equal volume and The mixed solution of deionized water；Alkali is potassium hydroxide.
The hydrothermal temperature is 100~120 DEG C, and the time is 6~10h.
The hydro-thermal reaction is to be placed in reactant in reaction kettle to carry out, and reaction kettle is with polytetrafluoroethylliner liner, no 50~100mL hydrothermal reaction kettle of rust steel sleeve.
The washing is respectively washed for several times using deionized water and dehydrated alcohol to neutral；Dry is to stay overnight for 60 DEG C in baking oven.
A kind of application for realizing C1 fueled electrochemical reducing catalyst by carbon dioxide of the invention.
Carbon described in claim 1 is loaded the present invention also provides a kind of gas-diffusion electrode, on gas-diffusion electrode ontology to receive Mitron/nano SnOxComposite material.
The present invention provides a kind of preparation method of gas-diffusion electrode, specifically: C1 fuel electricity will be realized by carbon dioxide Electronation catalyst carbon nanotube/nano SnOxComposite material is distributed in aqueous isopropanol, and AS-4 alkali anion is added Binder (Japanese Tokuyama Products) solution and ultrasound, obtain catalyst dispersion, by this dispersion to gas On diffusion electrode ontology, it is put into baking oven and dries.
Preferably, the size of the gas-diffusion electrode ontology is 1 × 1cm2~3 × 3cm2, load by carbon dioxide Realize C1 fueled electrochemical reducing catalyst (carbon nanotube/nano SnOxComposite material) load capacity be 1~4mg/cm2。
The gas-diffusion electrode is as CO2The application of cathode gas diffusion electrode in electrochemical reduction device.
Preferably, the gas-diffusion electrode ontology is carbon paper, carbon cloth.
Preferably, described that C1 fueled electrochemical reducing catalyst (carbon nanotube/nano SnO is realized by carbon dioxidexIt is compound Material) it with the dry matter weight ratio of AS-4 alkali anion binder solution is 1:1~5:1.
Further preferably, described that C1 fueled electrochemical reducing catalyst (carbon nanotube/nano SnO is realized by carbon dioxidex Composite material) it with the dry matter weight ratio of AS-4 alkali anion binder solution is 3:1.
Preferably, the concentration of the AS-4 alkali anion binder solution is 0.5~5wt%.
Beneficial effect
(1) CO of the invention2Electrochemical reduction catalyst shows excellent electro-chemical activity and selectivity, especially- NH2Change catalyst (SnOx/MWCNT-NH2) in -1.45V vs.SHE show highest current density -25.6mA cm-2, solve (current density is -10.4mA cm for non-loaded functionalized carbon nano-tube reduction current density too low problem-2)；In -1.25V 99.6% has been reached to the faradic efficiency of C1 product when vs.SHE, has greatly inhibited CO2It is adjoint in electro-reduction process Evolving hydrogen reaction；
(2) present invention is used for H slot CO with the catalyst preparation gas-diffusion electrode2Electrochemical reduction device, in 0.5M KHCO3Excellent electrochemical stability is obtained in solution, at -1.25V vs.SHE can continuous electrolysis 20h or more, and keep steady Fixed current density and C1 product faradic efficiency, wherein SnOx/MWCNT-NH2Catalyst electric current in the continuous electrolysis of 20h is close Degree is maintained at -10.5mA cm-2, decaying of the C1 product faradic efficiency after 20h only less than 19%；
(3) SnO of the inventionx/ MWCNTs catalyst is that different functional groups functionalized carbon nano-tube loads ultra-thin leaf shape SnOxCrystal has distinct SnO (101) and (110) crystal face, to CO2Restore electro catalytic activity with higher；Efficiently inhibit Hydrogen gas byproduct generates, and long-term stability is shown in electrolytic process, in addition, method for preparing catalyst of the invention Easy to operate, green, high (nearly 100%) of faradic efficiency of C1 selectivity of product；
(4) catalyst of the present invention utilizes different function (- NH2,-COOH ,-OH) carbon nanotube make carrier, had There is the SnO of special appearance (ultra-thin leaf shape) structurexNanometer sheet couples carbon nanotube (SnOx/ MWCNTs) it is used as CO2Electrochemistry is also Raw catalyst；
(5) present invention is not only environmentally protective, raw material is easy to get, at low cost, and has simple process, practical, and controllability is strong The advantages that, it is easy to large-scale production, is that can operate with CO2The electrode for secondary battery such as electrochemical reduction, lithium ion battery field Good electrode catalyst, has a good application prospect.
Detailed description of the invention
Fig. 1 is that gained-COOH carbon nano tube loads leaf shape nano SnO in embodiment 2xThe transmission electron microscope of catalyst Figure；
Fig. 2 is that different function carbon nano tube loads leaf shape nano SnO in embodiment 2 and embodiment 5~7xCatalyst X-ray powder diffraction curve graph；
Fig. 3 is that the gas-diffusion electrode load-COOH carbon nano tube in Examples 1 to 4 loads leaf shape nano SnOx Catalyst is in CO2The 0.5M KHCO of saturation3Linear scan curve in solution；
Fig. 4 is that the gas-diffusion electrode in embodiment 2 and embodiment 5~7 loads different function carbon nano tube load tree Lobate nano SnOxCatalyst is in CO2The 0.5M KHCO of saturation3Linear scan curve in solution；
Fig. 5 is the gas-diffusion electrode load different function carbon nano tube load leaf implemented in 2 and embodiment 5~7 Shape nano SnOxCatalyst is in CO2The 0.5M KHCO of saturation3C1 obtained by 1h is electrolysed in solution under -1.25V vs.SHE voltage to produce The faradic efficiency histogram of object；
Fig. 6 is that-COOH the carbon nano tube in embodiment 2 loads leaf shape nano SnOxCatalyst is in CO2Saturation 0.5MKHCO3Current density-time graph obtained by 20h and C1 product farad are electrolysed in solution under -1.25V vs.SHE voltage Efficiency chart；
Fig. 7 is the-NH in embodiment 52Carbon nano tube loads leaf shape nano SnOxCatalyst is in CO2The 0.5M of saturation KHCO3Current density-time graph obtained by 20h and C1 product faraday effect are electrolysed in solution under -1.25V vs.SHE voltage Rate figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.(SnO in embodimentxMiddle x=1,2)
Embodiment 1
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；30mg carboxylated The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder, grinds to get SnO is arrived after 60 DEG C big vast case is 12 hours dryx/ MWCNT-COOH(15:1)Catalyst (15:1 refers to reactant tin carbon mass ratio in synthesis process).
Embodiment 2
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg carboxylated The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT-COOH(8:1)Catalyst (8:1 refers to reactant tin carbon mass ratio in synthesis process).
Test results are shown in figure 1 for scanning electron microscope (SEM), SnOx/MWCNT-COOH(8:1)SnO in catalystxNanometer sheet is in Now apparent multilayer leaf shape structure and it is anchored on carbon nano tube surface, carbon nanotube is interspersed and around SnOxNanometer sheet week It encloses.SnOxNanometer sheet is having a size of 100-200nm.Test results are shown in figure 2 for X-ray powder diffraction (XRD), SnOx/MWCNT- COOH(8:1)The main crystal face of catalyst is (101), (110) and (112) crystal face of SnO, the high intensity of signal peak in XRD curve The high-crystallinity of SnO is reflected with acutance.
Embodiment 3
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg carboxylated The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 120 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT-COOH(120-10)Catalyst (120-10 indicates that hydrothermal temperature is 120 DEG C, time 10h).
Embodiment 4
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg carboxylated The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 6h.To neutrality, gained is consolidated in centrifuge separation for obtained solid deionized water and ethyl alcohol centrifuge washing after reaction Body obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT-COOH(100-6)Catalyst (100-6 indicates that hydrothermal temperature is 100 DEG C, time 6h).
Embodiment 5
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg amination The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT-NH2(100-10)Catalyst (100-10 indicates that hydrothermal temperature is 100 DEG C, time 10h).
Test results are shown in figure 2 for X-ray powder diffraction (XRD), SnOx/MWCNT-NH2(100-10)The main crystalline substance of catalyst Face is (101), (110) and (112) crystal face of SnO, and the high intensity and acutance of signal peak reflect the high knot of SnO in XRD curve Brilliant degree.
Embodiment 6
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg hydroxylating The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in carbon nanotube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT-OH(100-10)Catalyst (100-10 indicates that hydrothermal temperature is 100 DEG C, time 10h).
Test results are shown in figure 2 for X-ray powder diffraction (XRD), SnOx/MWCNT-OH(100-10)The main crystalline substance of catalyst Face is (101) and (110) crystal face of SnO, and the high intensity and acutance of signal peak reflect the high-crystallinity of SnO in XRD curve.
Embodiment 7
By 0.9026g SnCl2·2H2O and 2.9410g sodium citrate is dissolved in 20mL deionized water；60mg is without function The mixed solution of 20mL ethyl alcohol and 20mL deionized water, ultrasonic 1h is added in group's functionalized carbon nano-tube.
Above-mentioned two groups of mixtures are mixed and 1.1222g KOH is added after ultrasound 2h, 10min is sufficiently stirred, then shifts Into the 100mL hydrothermal reaction kettle with polytetrafluoroethylliner liner, stainless steel outer sleeve, reaction kettle is put into baking oven at 100 DEG C Carry out hydro-thermal reaction 10h.Obtained solid deionized water and ethyl alcohol centrifuge washing are centrifugated, to neutrality by gained after reaction Solid obtains black with argentine gloss solid powder in 60 DEG C after oven drying 12 hours, and grinding is to get arriving SnOx/ MWCNT(100-10)Catalyst (100-10 indicates that hydrothermal temperature is 100 DEG C, time 10h).
Test results are shown in figure 2 for X-ray powder diffraction (XRD), SnOx/MWCNT(100-10)The main crystal face of catalyst is (101) and (110) crystal face of SnO.As shown in Figure 2 XRD curve it can be concluded that, SnO in embodiment 2 and embodiment 5x/MWCNT- COOH(8:1)And SnOx/MWCNT-NH2(100-10)The SnO crystallinity of catalyst is higher.
Embodiment 8
Respectively by the CO in embodiment 1-72Electrochemical reduction catalyst 15mg is distributed to the isopropyl that 1mL concentration is 100% In alcoholic solution, and 100mg 5wt%AS-4 alkali anion binder solution is added, then ultrasound 0.5h is obtained uniformly mixed This mixed solution is coated to having a size of 2 × 2cm by catalyst dispersion2Gas-diffusion electrode ontology (carbon paper) on, be put into baking 60 DEG C of drying 3h in case, obtaining load has CO2The gas-diffusion electrode of electrochemical reduction catalyst, load capacity 3mg/cm2。
Embodiment 9
With the chemical property of electrochemical workstation measurement catalyst.Reaction unit is H-type electrolytic cell, is loaded with catalyst It is working electrode at gas-diffusion electrode (GDE), saturated calomel electrode is reference electrode, and platinum electrode is that auxiliary electrode constitutes three Electrode system, Nafion membrane are amberplex, and electrolyte is 0.5M KHCO3Solution.It is passed through carbon dioxide in the electrolytic solution 30min, measuring the electrolytic experiment of linear scan (LSV) curve of catalyst and lasting 20h in embodiment 1-7 respectively, (i-t is bent Line), and electrochemical reduction product is analyzed.
Experimental result is as shown in fig. 3 to 7.Fig. 3-4 is the LSV curve of catalyst in embodiment 1-7, it can be seen that works as catalysis Tin carbon mass ratio is 8:1 in agent synthesis process, when hydrothermal temperature and time are respectively 100 DEG C and 10h, catalyst table Reveal highest electro-chemical activity, SnOx/MWCNT-COOH(8:1)Under -1.45V vs.SHE current potential current density reach - 17.5mA cm-2, take-off potential is only -0.88V vs.SHE；When carbon nanotube is-NH2When functionalization, SnOx/MWCNT- NH2(100-10)Reach maximum current density -25.6mA cm at -1.45V vs.SHE-2；As shown in figure 5, SnOx/MWCNT- NH2(100-10)It is electrolysed the faradic efficiency of C1 product obtained by 1h at -1.25V vs.SHE up to nearly 100%, shows optimal Electrocatalysis characteristic.Continue the electrolytic experiment result of 20h as shown in fig. 6-7 to embodiment 2 and embodiment 5, up to 20h's In continued electrolysis, SnOx/MWCNT-COOH(8:1)With SnOx/MWCNT-NH2(100-10)The current density of catalyst does not occur obviously The faradic efficiency attenuation rate of decaying, C1 product is no more than 19%, illustrates that catalyst is with good stability.
Electrochemical operation instrument (CHI760E) is purchased from Shanghai Chen Hua company, and AS-4 alkali anion binder is Japan The production of Tokuyama company, solvent is methanol.

Claims (10)

1. a kind of realize C1 fueled electrochemical reducing catalyst by carbon dioxide, which is characterized in that the catalyst is with carbon nanometer Pipe is carrier, loads SnOxNanometer sheet forms carbon nanotube/nano SnOxComposite material, wherein (1,2) x=.
2. catalyst according to claim 1, which is characterized in that the carbon nanotube is functionalized carbon nano-tube；SnOxNanometer Piece is the nanometer sheet of leaf shape structure.
3. catalyst according to claim 2, which is characterized in that the functionalized carbon nano-tube are as follows: carboxylic carbon nano-tube, One or more of aminated carbon nano tube, hydroxyl carbon nano tube.
4. the preparation method of C1 fueled electrochemical reducing catalyst is realized described in a kind of claim 1 by carbon dioxide, comprising:
Stannous chloride and sodium citrate is soluble in water, and stirring and dissolving obtains precursor solution；It disperses carbon nanotube in molten Agent, ultrasound, obtains carbon nano-tube solution；
By the mixing of above two solution and ultrasound, alkali is added, then stirring carries out hydro-thermal reaction, centrifuge washing after cooling is done It is dry to get catalyst.
5. preparation method according to claim 4, which is characterized in that the mass ratio of the stannous chloride and sodium citrate is 1: 3~1:4；Tin carbon mass ratio is 15:1~5:1；Alkali and stannous chloride molar ratio are 8:1~10:1.
6. preparation method according to claim 4, which is characterized in that the diameter of the carbon nanotube is 10~20nm, length It is 20~30 μm；Solvent is the mixed solution of the ethyl alcohol mixed in equal volume and deionized water；Alkali is potassium hydroxide.
7. preparation method according to claim 4, which is characterized in that the hydrothermal temperature is 100~120 DEG C, the time For 6~10h.
8. the application of C1 fueled electrochemical reducing catalyst is realized described in a kind of claim 1 by carbon dioxide.
9. a kind of gas-diffusion electrode, which is characterized in that load described in claim 1 on gas-diffusion electrode ontology by titanium dioxide Carbon realizes C1 fueled electrochemical reducing catalyst.
10. a kind of preparation method of gas-diffusion electrode, comprising: will realize C1 fueled electrochemical reducing catalyst by carbon dioxide It is distributed in aqueous isopropanol, AS-4 alkali anion binder solution and ultrasound is added, catalyst dispersion is obtained, by this point Dispersion liquid is coated on gas-diffusion electrode ontology, drying.
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CN110052281A (en) * 2019-03-10 2019-07-26 天津大学 A kind of Lacking oxygen enriched in nitrogen doped stannum oxide and its preparation method and application
CN110510663A (en) * 2019-08-07 2019-11-29 山东大学深圳研究院 The tin oxide nano sheet material and preparation method of the covering of nitrogen-doped carbon part and application
CN113564624A (en) * 2021-07-16 2021-10-29 华中科技大学 Method for preparing formate by recovering lead material through carbon dioxide reduction

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052281A (en) * 2019-03-10 2019-07-26 天津大学 A kind of Lacking oxygen enriched in nitrogen doped stannum oxide and its preparation method and application
CN110052281B (en) * 2019-03-10 2021-11-05 天津大学 Oxygen vacancy enriched nitrogen doped tin oxide and preparation method and application thereof
CN110510663A (en) * 2019-08-07 2019-11-29 山东大学深圳研究院 The tin oxide nano sheet material and preparation method of the covering of nitrogen-doped carbon part and application
CN110510663B (en) * 2019-08-07 2022-04-12 山东大学深圳研究院 Nitrogen-doped carbon partially-covered tin oxide nanosheet material, and preparation method and application thereof
CN113564624A (en) * 2021-07-16 2021-10-29 华中科技大学 Method for preparing formate by recovering lead material through carbon dioxide reduction

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