CN103657629A - Method for preparing high-dispersibility nano Pt-SnO2/C catalyst - Google Patents

Method for preparing high-dispersibility nano Pt-SnO2/C catalyst Download PDF

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CN103657629A
CN103657629A CN201310742630.1A CN201310742630A CN103657629A CN 103657629 A CN103657629 A CN 103657629A CN 201310742630 A CN201310742630 A CN 201310742630A CN 103657629 A CN103657629 A CN 103657629A
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CN103657629B (en
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王峰
郭壮
刘景军
宋夜
李志林
吉静
贾怡
覃事永
张良虎
康建忠
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Beijing University of Chemical Technology
Bluestar Beijing Chemical Machinery Co Ltd
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Abstract

The invention discloses a method for preparing a high-dispersibility nano Pt-SnO2/C catalyst. Carbon black loaded nano tin dioxide and loaded platinum-based tin dioxide binary composite catalyst is prepared by an ultrasonic-assisted method, and the prepared catalyst has high electrocatalytic activity and durability on oxygen reduction reaction under the acidic condition. Compared with a platinum/carbon black catalyst, the high-dispersibility nano Pt-SnO2/C catalyst has the characteristics of low price, stable performance and the like.

Description

High dispersancy nano Pt-SnO 2the preparation method of/C catalyst
Technical field
The invention belongs to chemical field, in particular to a kind of high dispersancy nano Pt-SnO 2the preparation method of/C catalyst, particularly a kind of method of utilizing ultrasonic auxiliary law to prepare Supported Pt Nanoparticles base tin ash composite catalyst.
Background technology
The energy, as the important substance basis of social and economic development, is the prerequisite that improves people's living standard.In recent years, due to the extravagance and waste of energy development, cause a large amount of losses of national economy, therefore, energy-saving and emission-reduction, efficiently utilize the energy to become the pursuit emphasis of entire society.At present, at low-temperature fuel cell, the fields such as metal-air battery, the application of oxygen reduction reaction be one must be through step, but due to oxygen reduction reaction self dynamic process and hand over high reaction overpotential slowly, caused a large amount of losses of electric energy, the oxygen reduction reaction eelctro-catalyst of therefore seeking a kind of excellence has profound significance.
At present, generally acknowledge that in the world best oxygen reduction reaction eelctro-catalyst is platinum (Pt) catalyst, but due to Pt self fancy price, serious obstruction its process of industrialization.In recent years, research emphasis has turned to the research and development of Pt based composite catalyst, and object is by adding one or more other compositions, makes catalyst have identical with Pt catalyst or better catalytic performance.At present the catalyst of research is main mainly with Pt base binary or multicomponent catalyst, PtRu for example, and PtRuW, PtRuOsIr etc., but Pt base oxide catalyst is also more and more concerned, as TiO 2, SnO 2and CeO 2deng.
Research is found, SnO 2can improve largely the specific activity surface area of eelctro-catalyst, there is the advantages such as higher electrode mobility and electrical conductivity.Platinum base SnO 2composite catalyst, by platinum and SnO 2between difunctional mechanism effect, make catalyst compared with Pt/C catalyst, there is more excellent electro catalytic activity to oxygen reduction reaction, greatly reduce catalyst cost simultaneously.At present, for nano SnO 2preparation method mainly contain infusion process, sol-gal process etc., these method preparation process are complicated, the poor and particle diameter of load pattern, more than 50nm, is therefore found a kind of preparation technology simple, dispersed high, the carbon black loadings nano SnO that particle diameter is little 2and be applied in and on Pt/C catalyst, there is pioneering meaning.Therefore an urgent demand based on clean energy resource commercial applications such as fuel cell, metal-air batterys, developing highly active platinum base tin ash oxygen reduction eelctro-catalyst will have huge prospects for commercial application.
Summary of the invention
Object of the present invention is to provide a kind of carbon black loadings nano SnO of polymolecularity on the one hand 2the method of catalyst; In another aspect of this invention, relate to a kind of high dispersancy nano Pt-SnO 2the preparation method of/C catalyst.
In the present invention, unless otherwise indicated, generally speaking, the ratio of weight portion and parts by volume is g/ml.
One aspect of the present invention relates to carbon black loadings nano SnO 2the preparation method of catalyst, described catalyst is pressed powder, average grain diameter is at the SnO of 5 ~ 15nm 2nano particle is dispersed in carbon blacksurface, and the load factor scope of tin dioxide nano-particle is 10% ~ 100%, it is characterized in that described preparation method comprises the steps:
(1) 1 weight portion carbon black of nitric acid acidifying is placed in to aqueous isopropanol, the volume of isopropyl alcohol is 10 ~ 100 weight portions, and ultrasonic dispersion 5min ~ 30min makes carbon black Solution Dispersion even;
(2) by unit mass carbon black loadings 10% ~ 100%(, be preferably 20% ~ 60%) SnO 2amount, can solution pink salt toward adding in carbon black solution, regulator solution pH value is 1 ~ 3 simultaneously, puts into the ultrasonic 10 ~ 100min of supersonic cleaning machine, obtains containing pink salt, the suspension of acidifying carbon black;
(3) solution is put in baking oven and be dried; temperature is 60 ° of C～100 ° C; after evaporate to dryness, collect sample; pressed powder is heat-treated under the condition of protective gas at inert gas (argon gas and/or nitrogen): first the heating rate with 5～10 ° of C/min is warming up to 200 ° of C～500 ° C; after insulation roasting 0.5h～5h; cooling with stove, obtain carbon black loadings nano-stannic oxide composite catalyst.
In a preferred embodiment of the present invention, the ultrasonic power of described supersonic cleaning machine is set within the scope of 20Hz ~ 100Hz.
In a preferred embodiment of the present invention, described solubility pink salt is two hydrated stannous chlorides, and described carbon black is Vulcan XC-72 and/or GCB.
In a preferred embodiment of the present invention, acetic acid is as pH adjusting agent.
The invention still further relates to a kind of Pt-SnO of blend state 2the preparation method of/C catalyst, described preparation method comprises the step of above-mentioned preparation carbon black loadings nano-stannic oxide composite catalyst, characterized by further comprising following steps: take a certain amount of carbon black loadings nano-stannic oxide composite catalyst, under ultrasonic state, be scattered in ethylene glycol solution, with respect to above-mentioned catalyst, Pt theoretical negative carrying capacity by 20%, under stirring, adding concentration is the ethylene glycol solution of the chloroplatinic acid of 0.01M, after mixing, add certain density sodium hydroxide solution to regulate between pH to 9-10, be heated to 130 ℃, condensing reflux reaction certain hour, then be down to after room temperature centrifugal, ethylene glycol and chlorion are removed in washing, the 70-90 ℃ of dry Pt-SnO that obtains above for 10 hours under vacuum 2/ C catalyst.
The present invention also relates to prepared blend state Pt-SnO on the other hand 2the application of/C eelctro-catalyst, the electrochemical catalysis oxygen reduction reaction under acid condition, under acid condition, to oxygen reduction, reaction has more excellent electro catalytic activity compared with Pt/C catalyst.
The present invention adopts a kind of new method to prepare the carbon black loadings stannic oxide nanometer composite catalyst of polymolecularity, and method is simple to operate, and without adding of excess oxygen agent, particle diameter is little, is evenly distributed.The blend state Pt-SnO that utilizes above-mentioned catalyst to prepare 2under acid condition, to oxygen reduction, reaction has excellent electro catalytic activity to/C eelctro-catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of embodiment 1 gained catalyst;
Fig. 2 is embodiment 1 gained SnO 2the scanning electron microscope diagram sheet of/C catalyst;
Fig. 3 is embodiment 1 gained Pt-SnO 2the transmission electron micrograph of/C catalyst;
Fig. 4 is the oxygen reduction reaction rotating circular disk test curve of embodiment 1 gained catalyst;
Fig. 5 is the oxygen reduction reaction polarization curve test curve of embodiment 1 gained catalyst.
The specific embodiment
Embodiment 1
Carbon black loadings nano-stannic oxide composite catalyst and high dispersancy nano Pt-SnO that preparation load capacity is 20% 2/ C catalyst
(1) adopt ultrasonic method to prepare 20% carbon black loadings nanometer titanium dioxide tin catalyst
Figure 171642DEST_PATH_IMAGE001
by in the 1g carbon black aqueous isopropanol of nitric acid acidifying, the volume of isopropyl alcohol is 30 ~ 70ml, and ultrasonic dispersion 5min ~ 30min makes carbon black Solution Dispersion even;
Figure 151100DEST_PATH_IMAGE002
by the SnO of unit mass carbon black loadings 20% 2amount, can solution pink salt toward adding in carbon black solution, regulator solution pH value is 1 ~ 3 simultaneously, puts into the ultrasonic 10 ~ 100min of ultrasonic washer, ultrasonic power is 30Hz ~ 100Hz, obtains containing pink salt, the suspension of acidifying carbon black;
Figure 743886DEST_PATH_IMAGE003
solution is put in baking oven dry; temperature is 60 ° of C～100 ° C; after evaporate to dryness, collect sample; pressed powder is heat-treated under the condition of protective gas at inert gas (argon gas and/or nitrogen): first the heating rate with 5～10 ° of C/min is warming up to 200 ° of C～500 ° C; after insulation roasting 0.5h～5h; cooling with stove, obtain carbon black loadings nano-stannic oxide composite catalyst.
(2) the carbon black loadings nano-stannic oxide composite catalyst of preparing in step (1) completes and carries Pt as carrier, the Pt-SnO of preparation blend state 2/ C catalyst.
Take a certain amount of carbon black loadings nano-stannic oxide composite catalyst, under ultrasonic state, be scattered in ethylene glycol solution, with respect to above-mentioned catalyst, Pt theoretical negative carrying capacity by 20%, under stirring, adding concentration is the ethylene glycol solution of the chloroplatinic acid of 0.01M, after mixing, add certain density sodium hydroxide solution to regulate between pH to 9-10, be heated to 130 ℃, condensing reflux reaction certain hour, then be down to after room temperature centrifugally, ethylene glycol and chlorion are removed in washing, 70 ~ 90 ℃ of dry Pt-SnO that obtain above for 10 hours under vacuum 2/ C catalyst.The catalyst obtaining is carried out to electrochemical property test.
Carbon black loadings nano SnO 2and blend state Pt-SnO 2the XRD spectra of/C catalyst is shown in Fig. 1, known SnO 2successfully load on carbon blacksurface, for blend state Pt-SnO 2there is equally Pt and SnO in/C catalyst 2characteristic peak.Fig. 2 is carbon black loadings nano SnO 2scanning electron microscope (SEM) photograph, can find out nano SnO 2be dispersed in very uniformly carbon blacksurface, and particle diameter is in 10nm left and right.Fig. 3 is blend state Pt-SnO 2the transmission electron microscope picture of/C catalyst, known carbon blacksurface distribution of particles is even, and agglomeration does not occur, and particle diameter is all in 10nm left and right.Blend state Pt-SnO 2the oxygen reduction reaction rotating circular disk test curve of/C catalyst is shown in Fig. 4, and under known this catalyst action, approximate 4 electronic processes occur in oxygen reduction reaction.Blend state Pt-SnO 2the polarization curve test curve of the oxygen reduction reaction of/C catalyst is shown in Fig. 5, and to oxygen reduction, reaction has more excellent catalytic performance compared with Pt/C catalyst to this catalyst.
Embodiment 2
Carbon black loadings nano-stannic oxide composite catalyst and high dispersancy nano Pt-SnO that preparation load capacity is 40% 2/ C catalyst
(1) adopt ultrasonic method to prepare 40% carbon black loadings nanometer titanium dioxide tin catalyst
by in the 1g carbon black aqueous isopropanol of nitric acid acidifying, the volume of isopropyl alcohol is 30 ~ 70 weight portions, and ultrasonic dispersion 5min ~ 30min makes carbon black Solution Dispersion even;
Figure 828834DEST_PATH_IMAGE002
by the SnO of unit mass carbon black loadings 40% 2amount, can solution pink salt toward adding in carbon black solution, regulator solution pH value is 1 ~ 3 simultaneously, puts into the ultrasonic 10 ~ 100min of ultrasonic washer, ultrasonic power is 10Hz ~ 50Hz, obtains containing pink salt, the suspension of acidifying carbon black;
Figure 713613DEST_PATH_IMAGE003
solution is put in baking oven dry; temperature is 60 ° of C～100 ° C; after evaporate to dryness, collect sample; pressed powder is heat-treated under the condition of protective gas at inert gas (argon gas and/or nitrogen): first the heating rate with 5～10 ° of C/min is warming up to 200 ° of C～500 ° C; after insulation roasting 0.5h～5h; cooling with stove, obtain carbon black loadings nano-stannic oxide composite catalyst.
(2) the carbon black loadings nano-stannic oxide composite catalyst of preparing in step (1) completes and carries Pt as carrier, the Pt-SnO of preparation blend state 2/ C catalyst.
Take a certain amount of carbon black loadings nano-stannic oxide composite catalyst, under ultrasonic state, be scattered in ethylene glycol solution, with respect to above-mentioned catalyst, Pt theoretical negative carrying capacity by 20%, under stirring, adding concentration is the ethylene glycol solution of 0.01M chloroplatinic acid, after mixing, add certain density sodium hydroxide solution to regulate between pH to 9-10, be heated to 130 ℃, condensing reflux reaction certain hour, then be down to after room temperature centrifugally, ethylene glycol and chlorion are removed in washing, 70 ~ 90 ℃ of dry Pt-SnO that obtain above for 10 hours under vacuum 2/ C catalyst.
The XRD collection of illustrative plates of the carrier nanometer catalyst of preparing by ultrasonic method determines that composite catalyst is Pt and SnO 2, each particle is all dispersed in carbon black carrier surface uniformly, and particle diameter is all in 10nm left and right.By oxygen reduction, react electrocatalysis characteristic and test, find SnO 2add the humidification of the catalytic performance of Pt/C catalyst obvious, excellent performance.
Embodiment 3
Carbon black loadings nano-stannic oxide composite catalyst and high dispersancy nano Pt-SnO that preparation load capacity is 60% 2/ C catalyst
(1) adopt ultrasonic method to prepare 60% carbon black loadings nanometer titanium dioxide tin catalyst
Figure 793696DEST_PATH_IMAGE001
by in the 1g carbon black aqueous isopropanol of nitric acid acidifying, the volume of isopropyl alcohol is 10 ~ 100 weight portions, and ultrasonic dispersion 5min ~ 30min makes carbon black Solution Dispersion even;
Figure 992596DEST_PATH_IMAGE002
by the SnO of unit mass carbon black loadings 60% 2amount, can solution pink salt toward adding in carbon black solution, regulator solution pH value is 1 ~ 3 simultaneously, puts into the ultrasonic 10 ~ 100min of ultrasonic washer, ultrasonic power is 10Hz ~ 50Hz, obtains containing pink salt, the suspension of acidifying carbon black;
Figure 536841DEST_PATH_IMAGE003
solution is put in baking oven dry; temperature is 60 ° of C～100 ° C; after evaporate to dryness, collect sample; pressed powder is heat-treated under the condition of protective gas at inert gas (argon gas and/or nitrogen): first the heating rate with 5～10 ° of C/min is warming up to 200 ° of C～500 ° C; after insulation roasting 0.5h～5h; cooling with stove, obtain carbon black loadings nano-stannic oxide composite catalyst.
(2) the carbon black loadings nano-stannic oxide composite catalyst of preparing in step (1) completes and carries Pt as carrier, the Pt-SnO of preparation blend state 2/ C catalyst.
Take a certain amount of carbon black loadings nano-stannic oxide composite catalyst, under ultrasonic state, be scattered in ethylene glycol solution, with respect to above-mentioned catalyst, Pt theoretical negative carrying capacity by 20%, under stirring, adding concentration is the ethylene glycol solution of 0.01M chloroplatinic acid, after mixing, add certain density sodium hydroxide solution to regulate between pH to 9-10, be heated to 130 ℃, condensing reflux reaction certain hour, then be down to after room temperature centrifugally, ethylene glycol and chlorion are removed in washing, 70 ~ 90 ℃ of dry Pt-SnO that obtain above for 10 hours under vacuum 2/ C catalyst.
The XRD collection of illustrative plates of the carrier nanometer catalyst of preparing by ultrasonic method determines that composite catalyst is Pt and SnO 2, each particle is all dispersed in carbon black carrier surface uniformly, and particle diameter is all in 10nm left and right.By oxygen reduction, react electrocatalysis characteristic and test, find SnO 2add the humidification of the catalytic performance of Pt/C catalyst obvious, excellent performance.
Above embodiment shows and has described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; rather than limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.

Claims (6)

1. carbon black loadings nano SnO 2the preparation method of catalyst, described catalyst is pressed powder, average grain diameter is at the SnO of 5 ~ 15nm 2nano particle is dispersed in carbon blacksurface, and the load factor scope of tin dioxide nano-particle is 10% ~ 100%, it is characterized in that described preparation method comprises the steps:
(1) 1 weight portion carbon black of nitric acid acidifying is placed in to aqueous isopropanol, the volume of isopropyl alcohol is 10 ~ 100 weight portions, and ultrasonic dispersion 5min ~ 30min makes carbon black Solution Dispersion even;
(2) by unit mass carbon black loadings 10% ~ 100%(, be preferably 20% ~ 60%) SnO 2amount, can solution pink salt toward adding in carbon black solution, regulator solution pH value is 1 ~ 3 simultaneously, puts into the ultrasonic 10 ~ 100min of supersonic cleaning machine, obtains containing pink salt, the suspension of acidifying carbon black;
(3) solution is put in baking oven and be dried; temperature is 60 ° of C～100 ° C; after evaporate to dryness, collect sample; pressed powder is heat-treated under the condition of protective gas at inert gas (argon gas and/or nitrogen): first the heating rate with 5～10 ° of C/min is warming up to 200 ° of C～500 ° C; after insulation roasting 0.5h～5h; cooling with stove, obtain carbon black loadings nano-stannic oxide composite catalyst.
2. preparation method according to claim 1, the ultrasonic power of described supersonic cleaning machine is set within the scope of 20Hz ~ 100Hz.
3. preparation method according to claim 1, described solubility pink salt is two hydrated stannous chlorides, described carbon black is Vulcan XC-72 and/or GCB.
4. preparation method according to claim 1,, acetic acid is as pH adjusting agent.
5. the Pt-SnO of a blend state 2the preparation method of/C catalyst, described preparation method comprises the step of above-mentioned preparation carbon black loadings nano-stannic oxide composite catalyst, characterized by further comprising following steps: take a certain amount of carbon black loadings nano-stannic oxide composite catalyst, under ultrasonic state, be scattered in ethylene glycol solution, with respect to above-mentioned catalyst, Pt theoretical negative carrying capacity by 20%, under stirring, adding concentration is the ethylene glycol solution of the chloroplatinic acid of 0.01M, after mixing, add certain density sodium hydroxide solution to regulate between pH to 9-10, be heated to 130 ℃, condensing reflux reaction certain hour, then be down to after room temperature centrifugal, ethylene glycol and chlorion are removed in washing, the 70-90 ℃ of dry Pt-SnO that obtains above for 10 hours under vacuum 2/ C catalyst.
6. the prepared blend state Pt-SnO of preparation method claimed in claim 5 2/ C is as the application of eelctro-catalyst, preferred, for the electrochemical catalysis oxygen reduction reaction under acid condition.
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CN110198781A (en) * 2016-08-26 2019-09-03 阿里尔科技创新公司 Catalyst, its preparation based on tin and the fuel cell using it
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CN112921344A (en) * 2021-01-19 2021-06-08 华南理工大学 Tin oxide-bismuth oxychloride composite particle and preparation method and application thereof
CN114507338A (en) * 2022-03-02 2022-05-17 万华化学集团股份有限公司 Preparation method of poly (butylene succinate) with low cyclic by-product
CN114507338B (en) * 2022-03-02 2024-04-09 万华化学集团股份有限公司 Preparation method of polybutylene succinate with low cyclic byproducts
CN114622244A (en) * 2022-03-15 2022-06-14 南京师范大学 Ru-SnO2Hydrogen evolution reaction catalyst and preparation method thereof

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