CN106853365A - A kind of porous carbon materials SO2Electrochemical oxidation catalyst and its preparation method and application - Google Patents
A kind of porous carbon materials SO2Electrochemical oxidation catalyst and its preparation method and application Download PDFInfo
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- CN106853365A CN106853365A CN201510894999.3A CN201510894999A CN106853365A CN 106853365 A CN106853365 A CN 106853365A CN 201510894999 A CN201510894999 A CN 201510894999A CN 106853365 A CN106853365 A CN 106853365A
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Abstract
The present invention relates to a kind of porous carbon materials SO2Electrochemical oxidation catalyst and its preparation method and application, the process for being pre-processed particular by amorphous carbon material, adulterating and being heat-treated twice obtains the loose porous carbon material catalyst without metal.By constant potential, electrokinetic potential process, test prepares the SO of catalyst2Catalyst is to SO when electrochemical oxidation ability and externally-applied potential2Response in situ；Test shows that this catalyst has obvious desulfurized effect.The porous carbon materials catalyst prepared by amorphous carbon material, micropore area increases 33%-40%, Micropore volume increase 28%-30%；Outer hole area increases 55%-60%, and total specific surface area increases 48%-50%, and is doped with some elements in porous carbon materials catalyst surface, has modified some functional groups.SO under the constant catalyst current potential2Electrochemical oxidation effect is good, in gas phase, liquid phase SO2There is huge application potential in electrochemical oxidation field, to solving increasingly serious SO2Pollution problem has positive effect.
Description
Technical field
The present invention relates to electrochemical oxidation desulfuration field, specifically there is SO on one kind2The conduction of electrochemical oxidation ability
Porous carbon materials of adsoption catalysis and its preparation method and application.
Background technology
SO2It is one of current Air Pollutants, is mostly derived from the burning of fossil fuel, such as power plant and boiler emission
Flue gas etc..Traditional flue gas desulfurization technique mainly uses alkaline absorbent to catch and removes the SO in flue gas with chemical method2；This
Sulfur content is still higher in tail gas after a little sulfur removal technology treatment, and further deep removal SO2It is difficult and uneconomical, so grinding
Study carefully electrochemical oxidation deep desulfuration significant.
The current research about electrochemical oxidation desulfurization focuses mostly in liquid desulfuration system；And Junxiang Zhai etc. grind
Study carefully and devise a kind of gas phase desulfurizing purifier device, for gas phase high-efficiency desulfurization provides new approaches (Junxiang Zhai, Ming
Hou,Dong Liang,et al.Investigation on the electrochemical removal of SO2in
ambient air for proton exchange membrane fuel cells[J].Electrochemical
communications,2012,18,131-134.)；Current relevant SO2The exploration and catalysis of electrochemical catalytic oxidation mechanism
The research of agent is concentrated mainly on noble metal desulphurization catalyst, and wherein Pt classes catalyst is considered as desulfurization performance preferably SO2Electricity
Chemical oxidation catalyst, such as document (David E Ramaker, Daniel Gatewood, Anna Korovina, Yannick
Garsany,Karen E.Swider-Lyons.Resolving Sulfur Oxidation and removal from Pt
and Pt3Co electrocatalysts using in suit X-ray Absorption Spectroscopy[J]
.J.Phys.Chem.C,2010,114,11886-11887.Olga A.Baturina,Benjamin D.Gould,Anna
Korovina,Yannick Garsany,Richard Stroman,Paul A.Northrup.Production of
SO2Adsorption on Fuel Cell Electrocatalysts by Combination of Sulfur K-Edge
XANES and Electrochemistry.) it is described.However, using the SO in noble metal catalyst removing waste gas2Or purification
Air, lacks certain economic feasibility, therefore study non-noble metal desulphurization catalyst for electrochemical oxidation desulfurization technology
Application have important practical significance, to solving increasingly serious SO2Pollution problem has important influence.
The carbon black materials of carbon material especially high conductivity, due to larger specific surface area, being conducive to catalyst point
Dissipate and with good electric conductivity, be common catalyst material and carrier material.Carbon material is directly used as activity during catalyst
Smaller, carbon black is directly used in SO2Activity is relatively low during electrochemical oxidation.Therefore, the catalytic performance gesture for further improving carbon material exists
Must go.This mainly includes：1) dispersed metal catalyst is loaded；2) pore structure is adjusted, changes transitivity of the material in three phase boundary
Can, increase reaction surface area；3) element doping changes distribution of charges, and catalytic performance is changed using electronic effect；The present invention passes through
A series of heat treatment steps, the pore structure of modulation carbon material increased catalytic action area, change surface charge distribution, prepare
Porous carbon materials SO2Electrochemical oxidation catalyst, and its SO is tested by electrochemical system2Electrochemical oxidation ability, it was demonstrated that
The catalyst has SO2Oxidation susceptibility.
The content of the invention
In order to develop a kind of cost-effective catalyst suitable for electrochemical method oxidation sweetening application, mesh of the invention
Be that a kind of nonmetallic SO is provided2Electrochemical oxidation catalyst preparation method, is gas phase, liquid-phase system SO2Electrochemical oxidation
Application provide technical support.Catalyst has obvious SO2The advantages of electrochemical oxidation ability.
Porous carbon materials SO2The preparation method of electrochemical oxidation catalyst, it is characterised in that：By the relatively low nothing of desulfurization performance
Amorphous carbon material, ultrasound, stirring, oil bath doping；By the simple procedure such as higher temperature heat treatment and higher temperature heat treatment, change
Become pore structure, distribution, surface functional group and the catalysis activity of material, the catalyst desulfurizing performance for preparing in this way is substantially carried
It is high.
To achieve the above object, the technical scheme is that：
The present invention provides a kind of SO2The preparation method of the porous carbon materials catalyst of electrochemical oxidation, to unformed carbon materials
Material is pre-processed, adulterated and is heat-treated twice, obtains porous carbon materials catalyst, and concrete operations are：
(1) amorphous carbon material is pre-processed：Amorphous carbon material is scatter in deionized water, sonic oscillation
Detergent surface, to adding aqueous slkali to adjust pH value to 8-13 in scattered slurries, is sufficiently stirred for；
(2) adulterate：Pretreated mixture is put into oil bath, under conditions of 110-160 DEG C, oil bath treatment 5-
8h so that amorphous carbon material surface carries out the modification of element doping and functional group；Material after treatment is washed with deionized,
It is placed in vacuum drying chamber after centrifugation, 60 DEG C -80 DEG C, dries 4-6h；
(3) it is heat-treated for the first time：Dried sample, is put into Muffle furnace, under air or oxygen atmosphere, 300-500 DEG C, preferably
450 DEG C of temperature, processes 3-7h；
(4) it is heat-treated for second：Tube furnace will be put into by the powder of heat treatment for the first time, 650 DEG C under an inert atmosphere-
850 DEG C, preferable temperature is 700 DEG C, is heat-treated 0.5-2h；Room temperature is naturally cooled to, grinding obtains loose structure carbon material SO2Electricity
Chemical oxidation catalyst.
The amorphous carbon material is selected from XC-72, EC-300J, and BP2000, EC600 apply to electro-catalysis field common
Conductive black material, wherein preferred carbon material is XC-72.
Aqueous slkali described in pretreatment is the NH of 0.05~0.15M3·H2O、Na2CO3, sodium citrate, sodium phosphate, phosphorus
A sour hydrogen is received, sodium dihydrogen phosphate, sodium perborate.
Described in step (2) adulterate element be nitrogen, oxygen, phosphorus, boron, it is therein one or more.Step (2) is described
Functional group be carbonyl O, lactone group carbon oxide structure, graphite nitrogen.
Inert atmosphere is Ar, N described in second heat treatment2、He。
The porous carbon materials catalyst prepared by amorphous carbon material, micropore area increases 33%-40%, micropore hole
Hold increase 28%-30%；Outer hole area increases 55%-60%, and total specific surface area increases 48%-50%, and in porous carbon
Material catalyst surface is doped with some elements and has modified some functional groups.
The present invention also provides the porous carbon materials catalyst in SO2Application in electrochemical oxidation removing.
Mechanism of the invention is：The element doping and modified with functional group of carbon material surface receive each step treatment conditions in the present invention
Influence is larger, specifically the element doping and surface function in its processing procedure of the patterns affect of alkali of pretreatment stage selection
The modification of group, such as ammoniacal liquor, sodium phosphate is doped with N, P element etc. on a catalyst respectively；The property of alkali, concentration significantly affect place
To the property of removal ability and modification containing O functional groups of the unstable agraphitic carbon of material surface during reason.The doping treatment stage
Temperature, time effects its doping effect.Higher temperature heat treatment process greatly changes the pore property of material, increased ratio
Surface area, changes pore size distribution, hole size, have impact on surface O functional groups.The inert atmosphere heat treatment process of higher temperature is main
Carbon material surface N, O constituent content is have impact on, the conversion such as nucleophilic of carbon material degree of graphitization and influence functional group is changed
The ratio of active carbonyl group functional group, because the treatment of high temperature changes the connected mode of C, O.
The features of the present invention and beneficial effect：
(1) heat treatment process that the present invention passes through multistep, SO has been prepared into by the weaker amorphous carbon material of catalytic action2
The porous carbon materials catalyst of electrochemical oxidation effect.
(2) present invention easy can prepare cheap porous carbon materials catalyst.
(3) it is heat-treated by oil bath during adulterating, carbon material surface is changed in the presence of hydrothermal system alkaline environment
Doped chemical and functional group, increased irregular graphitized carbon structure, have impact on catalytic performance.
(4) changed by the hole size of BET test processes rear catalysts, pore size distribution, specific surface area increase；Pass through
The change of XPS test catalyst surfaces element species, content and combination energy, a small amount of N element of surface doping, O content is significantly reduced,
Combination can change between element；Carbon material degree of graphitization in proving processing procedure is characterized by Raman certain change occurs.It is above-mentioned because
Element is probably the main cause for causing in processing procedure catalyst desulfurizing performance to improve.
(5) SO prepared by the present invention2Electrochemical oxidation catalyst is loose structure carbon material, by a series of heat treatment
Increased micro content and specific surface area；Exit orifice increase is conducive to mass transfer；Surface functional group changes, SO2Electrochemical oxidation energy
Power increases, and has significant application value and prospect of the application in flue gas desulfurization and field of gas purification.
Brief description of the drawings
Fig. 1 is the SO that the galvanostatic pulse method test of embodiment 1 prepares catalyst and 20%Pt/C2Electrochemistry oxidation performance is contrasted
Figure；
Fig. 2 is the SO2 electrochemistry oxidation performances pair that the linear voltage sweep test of embodiment 2 prepares catalyst and 20%Pt/C
Than figure；
Fig. 3 is that the cyclic voltammetry test of embodiment 3 prepares catalyst SO2Electrochemistry oxidation performance comparison diagram；
Fig. 4 is the TEM comparison diagrams for preparing catalyst；A () original carbon material TEM figures, it is two kinds of carbon balls of size of size；
B () prepares the TEM figures of catalyst, have the irregular graphitized carbon of small size to generate；
Fig. 5 is the Raman comparison diagrams for preparing catalyst；
Fig. 6 is property comparison diagram of the hole test result with XC-72 holes for preparing catalyst；
Fig. 7 is comparison diagram of the XPS analysis with XC-72 for preparing catalyst.
Specific embodiment
Below in conjunction with the accompanying drawings to porous carbon materials SO2Electrochemical oxidation catalyst desulfurization performance and structural property do further
Explanation.
Take 100mg XC-72 and add 66mL deionized waters, sonic oscillation treatment 1h, fully dispersed and detergent；To point
0.1M dilute ammonia solutions are added in the slurries for having dissipated, pH value 11 is adjusted, stirring is abundant；110 DEG C of oil bath 8h；After washing doping
Carbon material is washed with deionized, is centrifuged several times；It is subsequently placed in vacuum drying chamber 60 DEG C and dries 6h；In placing into Muffle furnace,
450 DEG C process 5h in air atmosphere；Treated powder is put into tube furnace, in N2Under atmosphere, 700 DEG C for the treatment of 2h；It is natural
Room temperature is cooled to, grinding obtains loose structure carbon material desulphurization catalyst.Said process changes the pore structure of XC-72, expands
Pore size distribution, increased reaction surface area, have impact on functional group and the element species such as O on surface etc., its SO2Electrochemical oxidation
Such as Fig. 1 respectively can be tested, shown in 2,3.
The desulfurization performance of catalyst is tested with three-electrode system, architecture is：There-necked flask, electrolyte solution is
The H of 100mL 0.5M2SO4, working electrode is the rotating disk electrode (r.d.e) for coating catalyst film layer, is Pt plate electrodes, reference to electrode
Electrode is saturated calomel electrode, and electrolyte solution is by N2Saturation, test system is CHI730D.Rotating disk electrode (r.d.e) Membrane catalysis layer
Preparation：5mg catalyst, 1mL isopropanols, ultrasonic 30min are added in the sample bottle of 10mL；Plus the μ L of 5%Nafion solution 50, surpass
Sound 30min, takes the above-mentioned scattered slurries of 10 μ L, rotating disk electrode (r.d.e) surface is coated in four times, as working electrode.
Embodiment 1
The desulfurization performance of catalyst is tested in three-electrode system.H of the coated disk electrode in 0.5M2SO4In carry out
Cyclic voltammetric (CV) is activated：CV-100mV/s-15 is enclosed, 3 times；Test initial activity：CV-50mV/s-3 is enclosed；Constant potential (CA)
0.8V tests desulfurization performance：CA-0.8V- high speed rotation -1600r/min, quickly stop the disconnection beginning and remove charging current after 10min,
Continuation constant potential test, uses what the syringe with soft conduit was prepared to addition 10mL 0.5M sulfuric acid in system after 10min
1g/L Na2SO3Solution, in N2In double stirring systems of disturbance and 1600r/min rotations, catalyst is under 0.8V to a certain amount of
SO2Produce immediate current step response.Change constant potential value, catalytic desulfurization performance of the test catalyst under 1.2V.20%
Pt/C contrasts as shown in Figure 1 with desulfurization performance of the catalyst under two current potentials is prepared, it is seen that preparing catalyst has obvious SO2
Electrochemistry oxidation performance, although its desulfurization performance is lower than Pt under 0.8V, but still have obvious desulphurizing ability；And under 1.2V
SO2Oxidability it is suitable with Pt even slightly higher, illustrate that catalyst has obvious desulfurization performance.It is de- by modulation electrochemical oxidation
The operating potential of sulphur, the catalyst can be used for SO2Electrochemistry removing, and its prepare it is simple, it is cheap.
Embodiment 2
The desulfurization performance of catalyst, H of the electrode in 0.5M are tested in three-electrode system2SO4In activated：CV-100mV/
S-15 is enclosed, and 3；Test initial activity CV-50mV/s-3 circles；Change the Na that electrolyte solution is the 1g/L that 0.5M sulfuric acid is prepared2SO3
Solution, electrode rotating speed 1600r/min, linear voltage sweep speed 5mV/s, compares 20%Pt/C and prepares catalyst in different electricity
Desulfurization performance under position is as shown in Figure 2, it is seen that although preparing catalyst desulfurizing performance relatively compared with Pt under compared with low potential
Low, it has had been provided with obvious catalysis oxidation SO2Performance, desulphurizing ability is stronger under high potential.
Embodiment 3
The desulfurization performance of catalyst, H of the electrode in 0.5M are tested in three-electrode system2SO4Middle activation：CV-100mV/s-15
Circle, 3 times；Test initial activity CV-50mV/s-3 circles；Change the Na that electrolyte solution is the 1g/L that 0.5M sulfuric acid is prepared2SO3It is molten
Liquid, carries out CV tests；Rotation electrode 1600r/min, test catalyst desulfurization performance, its test result contrast as shown in figure 3,
It can be seen that preparing catalyst to SO2There is obvious electrochemical oxidation ability, when electrode rotates at a high speed, its desulphurizing ability is greatly enhanced.
On the one hand it is, because in rotary course, the adsorbed product of electrode surface can depart from rapidly, to be conducive to subsequent reactions to carry out；It is another
Aspect is that, due to high-speed rotation, the reactant concentration for reducing or even eliminating electrode surface is poor, and surface reactant concentration is big,
Oxidation current is high.It has also been found that electrode after desulfurization when being transferred in clean sulfuric acid solution in experiment, catalyst surface does not almost have
SO2Remnants, its oxidation sweetening characteristic is significantly different with Pt, is more beneficial for continuous firing removing SO2。
Claims (8)
1. a kind of porous carbon materials SO2The preparation method of electrochemical oxidation catalyst, it is characterised in that：
Amorphous carbon material is pre-processed, adulterated and is heat-treated twice, obtained porous carbon materials catalyst, concrete operations
For：
(1) amorphous carbon material is pre-processed：Amorphous carbon material is scatter in deionized water, sonic oscillation washing
Material surface, to adding aqueous slkali to adjust pH value to 8-13 in scattered slurries, is sufficiently stirred for；
(2) adulterate：Pretreated mixture is put into oil bath, under the conditions of 110-160 DEG C, oil bath treatment 5-8h；After treatment
Material be washed with deionized, be placed in after centrifugation 60 DEG C -80 DEG C in vacuum drying chamber, dry 4-6h；
(3) it is heat-treated for the first time：Dried sample, is put into Muffle furnace, under air or oxygen atmosphere, 300-500 DEG C, processes 3-
7h；
(4) it is heat-treated for second：Tube furnace will be put into by the powder of heat treatment for the first time, 650 DEG C -850 under an inert atmosphere
DEG C, it is heat-treated 0.5-2h；Room temperature is naturally cooled to, grinding obtains loose structure carbon material SO2Electrochemical oxidation catalyst.
2. preparation method according to claim 1, it is characterised in that：The amorphous carbon material is selected from XC-72, EC-
300J, BP2000, EC600, acetylene black, titanium nitride, the conductive black material of activated carbon class electro-chemical activity.
3. preparation method according to claim 1, it is characterised in that：Aqueous slkali described in step (1) for 0.05~
The NH of 0.15M3·H2O、Na2CO3, sodium citrate, sodium phosphate, the hydrogen of phosphoric acid one receive, the one kind in sodium dihydrogen phosphate, sodium perborate
Or it is two or more.
4. preparation method according to claim 1, it is characterised in that：Mixing in the alkali and step (2) that are added in step (1)
Miscellaneous process, makes amorphous carbon material surface carry out the modification of element doping and functional group, the element of the doping is nitrogen, oxygen, phosphorus,
One or more in boron；Described functional group be carbonyl O, lactone group carbon oxide structure, graphite nitrogen in one or two
More than.
5. preparation method according to claim 1, it is characterised in that：Inert atmosphere described in second heat treatment be Ar,
N2, He classes the atmosphere yet not reduced is not aoxidized to carbon material system.
6. the porous carbon materials SO that the preparation method according to claim 1-5 is prepared2Electrochemical oxidation catalyst.
7. porous carbon materials SO according to claim 62Electrochemical oxidation catalyst, it is characterised in that：By unformed carbon materials
The porous carbon materials catalyst that material is prepared, micropore area increases 33%-40%, Micropore volume increase 28%-30%；Exit orifice
Area increases 55%-60%, and total specific surface area increases 48%-50%.
8. porous carbon materials catalyst described in claim 6 is in SO2Application in electrochemical oxidation removing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114735672A (en) * | 2022-04-24 | 2022-07-12 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
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| CN104518226A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Lithium.air or lithium-oxygen battery positive electrode porous carbon material |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
| CN104826581A (en) * | 2015-03-17 | 2015-08-12 | 北京大学 | Porous carbon material treated by ammonia gas and application thereof in formaldehyde adsorption |
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2015
- 2015-12-08 CN CN201510894999.3A patent/CN106853365B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104518226A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Lithium.air or lithium-oxygen battery positive electrode porous carbon material |
| CN104826581A (en) * | 2015-03-17 | 2015-08-12 | 北京大学 | Porous carbon material treated by ammonia gas and application thereof in formaldehyde adsorption |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114735672A (en) * | 2022-04-24 | 2022-07-12 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
| CN114735672B (en) * | 2022-04-24 | 2023-08-25 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
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