CN109772465A - A kind of preparation method of water solubility carbon dots modified perovskite type catalysis material - Google Patents
A kind of preparation method of water solubility carbon dots modified perovskite type catalysis material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of Ca-Ti ore type catalysis material that water-soluble carbon dots are modified comprising following steps, 1 proportionally mixes amino acid, alcohols and urea or citric acid, stirs evenly until forming transparent eutectic solvent；2, which weigh perovskite metal precursor, fuel and fuel additive, is mixed stirring, obtains predecessor mixed solution, in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite metal oxides catalyst；3 mix transparent eutectic solvent and perovskite metal oxides catalyst with deionized water；4 react 3-7h at 180-230 DEG C；5 is cooling, washing filtering；6 dry at 80 DEG C, then roast 1-3h at 600 DEG C.The present invention by addition containing carbon matrix precursor, that is, amino acid, alcohols and urea or citric acid come the physico-chemical property on optimization processing Ca-Ti ore type catalysis material surface, modified Ca-Ti ore type catalysis material obtained being capable of more efficiently catalytic degradation methane.
Description
Technical field
The invention belongs to chemical industry, environmental protection and catalysis material technical fields, specifically, it is related to a kind of modified perovskite type
The preparation method of catalysis material.
Background technique
Organic matter is that urban environment particulate matter mainly forms and PM and O3Important as precursors object.The volatilization of industrial discharge series
Property organic matter (VOCs) there is obvious " three cause " effect mostly, becoming influences residents ' health " malignant tumor ", is to restrict national economy hair
Open up environmentally friendly " bottleneck ".As country, place and industry VOCs discharge standard add sternly, VOCs depth is mineralized into certainty.
VOCs complicated component, gas velocity and fluctuation of concentration are big, the coupled catalysts purification techniques such as hot, ultraviolet and plasma
As first choice.Heat catalytic oxidation VOCs efficiency is higher, can depth mineralising VOCs be CO2And H2O is effectively avoided " secondary pollution ", but
Energy consumption is high, and operating cost is high；Such as about 200 DEG C of benzene homologues Open loop temperature, and permineralization then needs to reach 350 DEG C or more.Efficiently urge
Agent becomes VOCs depth mineralising key problem in technology.
Compared to high-cost noble metal, perovskite catalyst is due to its excellent redox property, hydrothermal stability
With extra long life etc. by more and more focus of attention.Such as external source cation is replaced into ABO3The site A or B for regulate and control urge
Agent surface Lacking oxygen becomes viable substitute of the platinum based noble metal material (PGMs) in many catalytic applications.But
The preparation of perovskite catalyst needs higher temperature and longer calcination time, causes surface area lower, surface-catalyzed reactions efficiency
It is lower.In order to increase the surface area of reactant and matrix interaction, people are dedicated to grinding for the porous perovskite of different-shape
Study carefully, forms orderly porosity material using template to increase the active contact area of reactant and material.Although ordered pore
The introducing of rate can significantly improve the catalytic activity of metal oxide, but this synthesis process is complicated and uneconomical；Other are various wet
There is also various disadvantages for perovskite material prepared by chemical reaction process, such as coprecipitated processing, collosol and gel, hydro-thermal process, such as
It is difficult to control the precipitation of anions in solution simultaneously in coprecipitation, frequently results in the separation of component；Sol-gel technique is logical
Expensive metal alkoxide is often used as raw material；Hydro-thermal method usually requires to react for a long time.Therefore, it is necessary to further explore out
Send out simpler, cheaper properties of perovskite mixed-oxide technology.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of water-soluble carbon dots modified perovskite type catalysis material, by adding
Add the materialization for coming optimization processing Ca-Ti ore type catalysis material surface containing carbon matrix precursor i.e. amino acid, alcohols and urea or citric acid
Matter, modified Ca-Ti ore type catalysis material obtained being capable of more efficiently catalytic degradation methane；Preparation side provided by the invention
Method is simple, efficient.
To achieve the above object, preparation method of the present invention includes the following steps,
(1) amino acid, alcohols and urea or citric acid are proportionally mixed, is stirred evenly molten up to forming transparent eutectic
Agent；The amino acid: alcohols: the molar ratio of urea or citric acid is 1:(4 ~ 6): (1 ~ 5)；
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth metal
Two or more in nitrate, transition metal nitrate and alkaline earth nitrate；The fuel is urea, sweet ammonia
It is a kind of in acid, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；
(3) by the transparent eutectic solvent that step (1) obtains and the calcium titanium that step (2) obtains
Mine metal oxide catalyst is mixed with deionized water, and the calcium that the amount of deionized water is obtained according to every gram of step (2) is added
Titanium ore metal oxide catalyst adds the ratio addition of 2-10mL deionized water；The transparent eutectic that step (1) obtains is molten
The mass ratio for the perovskite metal oxides catalyst that agent and step (2) obtain is 1:(1 ~ 6)；
(4) product that step (3) obtains is put into reaction kettle, reacts 3-7h at 180-230 DEG C after sealing；
(5) natural cooling alternately washs filter 23 ~ 6 time with ethyl alcohol and deionized water；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 1-3h at 600 DEG C.
Further, in step (1), the amino acid is selected from glycine, lysine, arginine, cysteine, ammonia of reviving
Acid, one of serine or histidine.
Further, in step (1), the alcohols is selected from ethylene glycol, glycerine, polyethylene glycol 200, polyethylene glycol 400
Or one of polyethylene glycol-800.
Further, in step (1), the amino acid: alcohols: the molar ratio of urea or citric acid is 1:6:3.
Further, in step (2), it is characterised in that: described to be by metal ion molality total in step (1)
1mol/L。
Further, in step (2), it is characterised in that: the molal quantity of the sum of fuel and fuel additive is added complete
1.5 times of the sum of portion's metal ion.
Further, in step (2), it is characterised in that: the molar ratio of the fuel and fuel additive is 4:1.
Further, in step (3), perovskite that the transparent eutectic solvent and step (2) that step (1) obtains obtain
The mass ratio of metal oxide catalyst is 1:2.
Further, in step (4), reaction temperature is 200 DEG C, reaction time 4h.
Further, in step (6), product roasts at 600 DEG C after being warming up to 600 DEG C with 3 DEG C/min after 80 DEG C of drying
Burn 1h.
Good effect of the present invention is as follows:
Preparation method of the present invention is simple, low in cost using non-noble metal oxide as the main synthetic material of catalyst.
The present invention carries out carbon dots modified perovskite catalysis material by the eutectic solvent of amino acids, increases perovskite
Surface water soluble group, i.e. carboxyl, hydroxyl and amide have modified the physico-chemical property on its surface；Hydro-thermal process makes catalyst simultaneously
By secondary crystallization, improve high-temperature roasting bring particle agglomeration phenomenon, and inhibits perovskite metal oxides catalyst granules
Increase, make the more active sites of material exposure, improve perovskite metal oxides catalyst and degrade methane performance.
The compound methanation catalyst of carbon dots/perovskite that the present invention obtains is compared with existing perovskite catalyst, methane T50%It reduces
100 DEG C or so.
Detailed description of the invention
Fig. 1 is the active testing map of 1 product of embodiment；
Fig. 2 is the active testing map of 2 product of embodiment；
Fig. 3 is the XRD spectrum of 1 product of embodiment；
Fig. 4 is the XRD spectrum of 2 product of embodiment；
Fig. 5 is the FT-IR map of 1 product of embodiment；
Fig. 6 is the FT-IR map of 2 product of embodiment.
Specific embodiment
Embodiment 1
Present embodiments provide a kind of preparation method of water-soluble carbon dots modified perovskite type catalysis material comprising following step
Suddenly,
(1) amino acid, alcohols and urea are proportionally mixed, wherein urea can be replaced with citric acid, be exactly by amino acid,
Alcohols and citric acid mixing, stir evenly until forming transparent eutectic solvent DES；The amino acid: alcohols: urea or lemon
The molar ratio of lemon acid is 1:(4 ~ 6): (1 ~ 5)；In step (1), the amino acid is selected from glycine, lysine, arginine, half Guang
Propylhomoserin, threonine, one of serine or histidine.In step (1), the alcohols is selected from ethylene glycol, glycerine, poly- second two
Alcohol 200, one of polyethylene glycol 400 or polyethylene glycol-800.
In the present embodiment, selection urea is raw material, and amino acid is arginine, specially L-arginine；Alcohols is glycerine,
Amino acid: alcohols: the molar ratio of urea or citric acid is 1:6:3.
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth
Two or more in metal nitrate, transition metal nitrate and alkaline earth nitrate；The fuel be urea,
It is a kind of in glycine, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；
Preferably, will obtain predecessor mixed solution be transferred in evaporating dish be placed in electric furnace pre-burning obtain after loose powder again into
Row roasting.
In the present embodiment, perovskite metal precursor is rare-earth metal nitrate and transition metal nitric acid, rare earth metal nitre
Hydrochlorate and transition metal nitric acid choose the nitrate of La and the nitrate of Co respectively；Fuel is urea；Fuel additive is acetic acid
Ammonium；Total metal ion molality is 1 mol/L in solution；The molal quantity of the sum of fuel and fuel additive is added complete
1.5 times of the sum of portion's metal ion；The molar ratio of fuel and fuel additive is 4:1；The predecessor is mixed molten
Liquid obtains perovskite metal oxides catalyst in 700 DEG C of roasting 3h；
(3) by the transparent eutectic solvent that step (1) obtains and the calcium titanium that step (2) obtains
Mine metal oxide catalyst is mixed with deionized water, and the calcium that the amount of deionized water is obtained according to every gram of step (2) is added
Titanium ore metal oxide catalyst adds the ratio addition of 2-10mL deionized water；The transparent eutectic that step (1) obtains is molten
The mass ratio for the perovskite metal oxides catalyst that agent and step (2) obtain is 1:(1 ~ 6)；
In the present embodiment, the amount that deionized water is added adds 2mL deionized water according to every gram of perovskite metal oxides catalyst
Ratio addition；The mass ratio of eutectic solvent and perovskite metal oxides catalyst is 1:2.
(4) product that step (3) obtains is put into reaction kettle, reacts 3-7h at 180-230 DEG C after sealing；This implementation
In example, in step (4), reaction temperature is 200 DEG C, reaction time 4h；
(5) natural cooling, with ethyl alcohol and deionized water alternately washing filtering 5 times；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 1-3h at 600 DEG C.
In the present embodiment, in step (6), product is after 80 DEG C of drying, after being warming up to 600 DEG C with 3 DEG C/min at 600 DEG C
Roast 1h.Obtain the water-soluble carbon dots modified perovskite type catalysis material LaCoO of embodiment 13。
Catalytic evaluation device is used to evaluate the carbon dots that the present embodiment 1 is formed using L-arginine and glycerine as carbon matrix precursor
The modified Ca-Ti ore type catalysis material LaCoO of aqueous solution3Performance, take the 1 catalyst 1mL of embodiment of preparation, carrier gas flux 100
ML/min, 10000 ppm of methane concentration.The active testing pictures of 1 final products of the present embodiment is as shown in Figure 1, by can be in figure
Find out, T50%=396 DEG C, illustrate the modified Ca-Ti ore type catalysis material LaCoO of 1 carbon dots of the embodiment of the present invention3Catalytic degradation first
Alkane has apparent advantage.The XRD spectrum of 1 final products of the present embodiment as shown in Figure 3, as can be seen from the figure the present embodiment carbon
The modified Ca-Ti ore type catalysis material LaCoO of point3Surface forms carbonizable substance.The FT-IR map of 1 final products of the present embodiment
As shown in Figure 5, as can be seen from the figure there are following for the modified Ca-Ti ore type catalysis material of 1 carbon dots of embodiment: C-OH's stretches
Contracting vibration (3209-3426cm-1), C-H(2921 cm-1), C=ONR(1664 cm-1) the water-soluble base such as surface hydroxyl and amide
Group, this suitable chemically reactive group are conducive to absorption and cracking methane molecule, thus more efficiently catalytic degradation methane.
Embodiment 2
Present embodiments provide a kind of preparation method of water-soluble carbon dots modified perovskite type catalysis material comprising following step
Suddenly,
(1) amino acid, alcohols and urea are proportionally mixed, wherein urea can be replaced with citric acid, be exactly by amino acid,
Alcohols and citric acid mixing, stir evenly until forming transparent eutectic solvent DES；The amino acid: alcohols: urea or lemon
The molar ratio of lemon acid is 1:(4 ~ 6): (1 ~ 5)；In step (1), the amino acid is selected from glycine, lysine, arginine, half Guang
Propylhomoserin, threonine, one of serine or histidine.In step (1), the alcohols is selected from ethylene glycol, glycerine, poly- second two
Alcohol 200, one of polyethylene glycol 400 or polyethylene glycol-800.
In the present embodiment, selection citric acid is raw material, and amino acid is lysine；Alcohols is ethylene glycol, amino acid: alcohols:
The molar ratio of urea or citric acid is 1:5:2.5.
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth
Two or more in metal nitrate, transition metal nitrate and alkaline earth nitrate；The fuel be urea,
It is a kind of in glycine, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；Preferably, it predecessor mixed solution will be obtained is transferred in evaporating dish to be placed in electric furnace pre-burning and obtain
It is roasted again after loose powder.
In the present embodiment, perovskite metal precursor is rare-earth metal nitrate, transition metal nitrate and alkaline-earth metal
Nitrate, rare-earth metal nitrate, transition metal nitrate and alkaline earth nitrate choose the nitre of the nitrate of La, Mn respectively
The nitrate of hydrochlorate and Mg；Fuel is glycine；Fuel additive is ammonium acetate；Total metal ion molality is in solution
1.2 mol/L；The molal quantity of the sum of fuel and fuel additive is 2 times of the sum of added whole metal ions；Combustion
The molar ratio of material and fuel additive is 5:1；By the predecessor mixed solution in 800 DEG C of roasting 5h, perovskite metal is obtained
Oxide catalyst；
(3) by the transparent eutectic solvent that step (1) obtains and the calcium titanium that step (2) obtains
Mine metal oxide catalyst is mixed with deionized water, and the calcium that the amount of deionized water is obtained according to every gram of step (2) is added
Titanium ore metal oxide catalyst adds the ratio addition of 2-10mL deionized water；The transparent eutectic that step (1) obtains is molten
The mass ratio for the perovskite metal oxides catalyst that agent and step (2) obtain is 1:(1 ~ 6)；
In the present embodiment, the amount that deionized water is added adds 7mL deionized water according to every gram of perovskite metal oxides catalyst
Ratio addition；The mass ratio of eutectic solvent and perovskite metal oxides catalyst is 1:3.
(4) product that step (3) obtains is put into reaction kettle, reacts 3-7h at 180-230 DEG C after sealing；This implementation
In example, in step (4), reaction temperature is 230 DEG C, reaction time 6h；
(5) natural cooling, with ethyl alcohol and deionized water alternately washing filtering 6 times；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 1-3h at 600 DEG C.
In the present embodiment, in step (6), product is after 80 DEG C of drying, after being warming up to 600 DEG C with 3 DEG C/min at 600 DEG C
Roast 3h.Obtain the water-soluble carbon dots modified perovskite type catalysis material LaMn of embodiment 20.9Mg0.1O3。
Catalytic evaluation device is used to evaluate the carbon dots water that the present embodiment 2 is formed using lysine and ethylene glycol as carbon matrix precursor
The Ca-Ti ore type catalysis material LaMn of solution modification0.9Mg0.1O3Performance, take the 2 catalyst 1mL of embodiment of preparation, carrier gas stream
Measure 100 mL/min, 10000 ppm of methane concentration.The active testing picture such as Fig. 2 institute for the final products that the present embodiment 2 obtains
Show, as can be seen from Figure, T50%=421 DEG C, illustrate the modified Ca-Ti ore type catalysis material of the water-soluble carbon dots of the embodiment of the present invention 2
Expect that catalytic degradation methane has apparent advantage.
The XRD spectrum of 2 final products of the present embodiment as shown in Figure 4, as can be seen from the figure the present embodiment water solubility carbon dots
Modified Ca-Ti ore type catalysis material surface forms carbonizable substance.The FT-IR map of 2 final products of the present embodiment is shown in Fig. 6 institute
Show, as can be seen from the figure there are following for the modified Ca-Ti ore type catalysis material of embodiment water solubility carbon dots: C-OH's is flexible
Vibrate (3209-3426cm-1), C-H(2921 cm-1), C=ONR(1664 cm-1) water soluble groups such as surface hydroxyl and amide,
This suitable chemically reactive group is conducive to absorption and cracking methane molecule, thus more efficiently catalytic degradation methane.
Embodiment 3
Present embodiments provide a kind of preparation method of water-soluble carbon dots modified perovskite type catalysis material comprising following step
Suddenly,
(1) amino acid, alcohols and urea are proportionally mixed, wherein urea can be replaced with citric acid, be exactly by amino acid,
Alcohols and citric acid mixing, stir evenly until forming transparent eutectic solvent DES；The amino acid: alcohols: urea or lemon
The molar ratio of lemon acid is 1:(4 ~ 6): (1 ~ 5)；In step (1), the amino acid is selected from glycine, lysine, arginine, half Guang
Propylhomoserin, threonine, one of serine or histidine.In step (1), the alcohols is selected from ethylene glycol, glycerine, poly- second two
Alcohol 200, one of polyethylene glycol 400 or polyethylene glycol-800.
In the present embodiment, selection urea is raw material, and amino acid is threonine；Alcohols is polyethylene glycol 200, amino acid: alcohol
Class: the molar ratio of urea or citric acid is 1:4:1.
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth
Two or more in metal nitrate, transition metal nitrate and alkaline earth nitrate；The fuel be urea,
It is a kind of in glycine, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；
Preferably, will obtain predecessor mixed solution be transferred in evaporating dish be placed in electric furnace pre-burning obtain after loose powder again into
Row roasting.
In the present embodiment, perovskite metal precursor is alkaline earth gold in alkaline earth nitrate and transition metal nitrate
Genus nitrobacter and transition metal nitrate choose the nitrate of Ca and the nitrate of Fe respectively；Fuel is sucrose；Fuel additive
For starch；Total metal ion molality is 0.5mol/L in solution；The molal quantity of the sum of fuel and fuel additive is
1 times of the sum of added whole metal ion；The molar ratio of fuel and fuel additive is 2:1；The predecessor is mixed
Solution is closed in 650 DEG C of roasting 4h, obtains perovskite metal oxides catalyst；
(3) by the transparent eutectic solvent that step (1) obtains and the calcium that step (2) obtains
Titanium ore metal oxide catalyst is mixed with deionized water, is added what the amount of deionized water was obtained according to every gram of step (2)
Perovskite metal oxides catalyst adds the ratio addition of 2-10mL deionized water；The transparent eutectic that step (1) obtains
The mass ratio for the perovskite metal oxides catalyst that solvent and step (2) obtain is 1:(1 ~ 6)；
In the present embodiment, the amount that deionized water is added adds 10mL deionized water according to every gram of perovskite metal oxides catalyst
Ratio addition；The mass ratio of eutectic solvent and perovskite metal oxides catalyst is 1:6.
(4) product that step (3) obtains is put into reaction kettle, at 180-230 DEG C after sealing
Lower reaction 3-7h；In the present embodiment, in step (4), reaction temperature is 210 DEG C, reaction time 7h；
(5) natural cooling, with ethyl alcohol and deionized water alternately washing filtering 4 times；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 2h at 600 DEG C.
In the present embodiment, in step (6), product is after 80 DEG C of drying, after being warming up to 600 DEG C with 3 DEG C/min at 600 DEG C
Roast 3h.Obtain the water-soluble carbon dots modified perovskite type catalysis material CaFeO of embodiment 33。
Catalytic evaluation device is used to evaluate what the present embodiment 3 was formed using threonine and polyethylene glycol 200 as carbon matrix precursor
The modified Ca-Ti ore type catalysis material CaFeO of carbon dots aqueous solution3Performance, take the 3 catalyst 1mL of embodiment of preparation, carrier gas stream
Measure 100 mL/min, 10000 ppm of methane concentration.By test, 3 T of the present embodiment50%=432 DEG C, illustrate the embodiment of the present invention 3
The modified Ca-Ti ore type catalysis material catalytic degradation methane of carbon dots has apparent advantage.
Embodiment 4
Present embodiments provide a kind of preparation method of water-soluble carbon dots modified perovskite type catalysis material comprising following step
Suddenly,
(1) amino acid, alcohols and urea are proportionally mixed, wherein urea can be replaced with citric acid, be exactly by amino acid,
Alcohols and citric acid mixing, stir evenly until forming transparent eutectic solvent DES；The amino acid: alcohols: urea or lemon
The molar ratio of lemon acid is 1:(4 ~ 6): (1 ~ 5)；In step (1), the amino acid is selected from glycine, lysine, arginine, half Guang
Propylhomoserin, threonine, one of serine or histidine.In step (1), the alcohols is selected from ethylene glycol, glycerine, poly- second two
Alcohol 200, one of polyethylene glycol 400 or polyethylene glycol-800.
In the present embodiment, selection citric acid is raw material, and amino acid is cysteine；Alcohols is polyethylene glycol 400, amino
Acid: alcohols: the molar ratio of urea or citric acid is 1:5:5.
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth
Two or more in metal nitrate, transition metal nitrate and alkaline earth nitrate；The fuel be urea,
It is a kind of in glycine, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；Preferably, it predecessor mixed solution will be obtained is transferred in evaporating dish to be placed in electric furnace pre-burning and obtain
It is roasted again after loose powder.
In the present embodiment, perovskite metal precursor is rare earth nitrades, transition metal nitrate and alkaline-earth metal nitric acid
Salt, rare earth nitrades, transition metal nitrate and alkaline earth nitrate choose the nitrate and Sr of the nitrate of La, Cr respectively
Nitrate；Fuel is citric acid；Fuel additive is polyethylene glycol；Total metal ion molality is 2mol/ in solution
L；The molal quantity of the sum of fuel and fuel additive is 1.6 times of the sum of added whole metal ions；Fuel and combustion
The molar ratio of feed additives is 3.8:1；By the predecessor mixed solution in 850 DEG C of roasting 65h, the oxidation of perovskite metal is obtained
Object catalyst；
(3) by the transparent eutectic solvent that step (1) obtains and the calcium titanium that step (2) obtains
Mine metal oxide catalyst is mixed with deionized water, and the calcium that the amount of deionized water is obtained according to every gram of step (2) is added
Titanium ore metal oxide catalyst adds the ratio addition of 2-10mL deionized water；The transparent eutectic that step (1) obtains is molten
The mass ratio for the perovskite metal oxides catalyst that agent and step (2) obtain is 1:(1 ~ 6)；
In the present embodiment, the amount that deionized water is added adds 3mL deionized water according to every gram of perovskite metal oxides catalyst
Ratio addition；The mass ratio of eutectic solvent and perovskite metal oxides catalyst is 1:1.
(4) product that step (3) obtains is put into reaction kettle, reacts 3-7h at 180-230 DEG C after sealing；This implementation
In example, in step (4), reaction temperature is 180 DEG C, reaction time 3h；
(5) natural cooling, with ethyl alcohol and deionized water, alternately washing filter 23 is secondary；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 1-3h at 600 DEG C.
In the present embodiment, in step (6), product is after 80 DEG C of drying, after being warming up to 600 DEG C with 3 DEG C/min at 600 DEG C
Roast 1.5h.Obtain the water-soluble carbon dots modified perovskite type catalysis material La of embodiment 40.9Sr0.1CrO3。
It uses catalytic evaluation device to evaluate the present embodiment 4 to be formed using cysteine and polyethylene glycol 400 as carbon matrix precursor
The modified Ca-Ti ore type catalysis material La of carbon dots aqueous solution0.9Sr0.1CrO3Performance, take 4 catalyst of embodiment of preparation
1mL, 100 mL/min of carrier gas flux, 10000 ppm of methane concentration.By test, the T of the present embodiment 450%=445 DEG C, explanation
The water-soluble modified Ca-Ti ore type catalysis material catalytic degradation methane of carbon dots of the embodiment of the present invention 4 has apparent advantage.
Embodiment 5
Present embodiment does not add eutectic solvent DES as carbon matrix precursor unlike the first embodiment；Remaining step and parameter
It is same as Example 1.Namely in the present embodiment, in step (3), eutectic solvent is not added, by " step (1) obtains
The perovskite metal oxides catalyst that transparent eutectic solvent and step (2) obtain is mixed with deionized water " it is changed to " step
(2) the perovskite metal oxides catalyst obtained is mixed with deionized water ".
Embodiment 6
Present embodiment does not add eutectic solvent DES as carbon matrix precursor as different from Example 2；Remaining step and parameter
It is same as Example 2.Namely in the present embodiment, in step (3), eutectic solvent is not added, by " step (1) obtains
The perovskite metal oxides catalyst that transparent eutectic solvent and step (2) obtain is mixed with deionized water " it is changed to " step
(2) the perovskite metal oxides catalyst obtained is mixed with deionized water ".
The final products and LaCoO that embodiment 1-2, embodiment 5-6 are obtained3Original sample and LaMn0.9Mg0.1O3It carries out as former state
Specific surface area and active testing, test result are shown in Table 1.
1 active testing result of table
(1) embodiment 1-2 is compared with embodiment 5-6 it can be seen from table 1 and Fig. 1-6, and embodiment 1-2 is corresponding better than respectively
Embodiment 5-6, be equally using hydro-thermal method, only embodiment 5-6 is not added with eutectic solvent DES, that is, is not added with
Amino acid and alcohols are as carbon matrix precursor；Fig. 3-4 XRD spectrum can be seen that embodiment 1-2 forms carbon on perovskite material surface
Substance；Surface functional group characterization is carried out by the FT-IR figure of Fig. 5-6 perovskite material modified to the carbon dots synthesized, with embodiment
5-6 is compared, and can obviously find that there are following by embodiment 1-2: the stretching vibration (3209-3426cm of C-OH-1), C-H(2921 cm-1), C=ONR(1664 cm-1) water soluble groups such as surface hydroxyl and amide, this suitable chemically reactive group is conducive to
Absorption and cracking methane molecule, thus more efficiently catalytic degradation methane, so embodiment 1-2 is better than embodiment 5-6.The present invention
Preparation method hydro-thermal method avoids the particle hard aggregation that high temperature is likely to form；Obtained powder dispersibility is good, soilless sticking, crystal form
Good, controlled shape, can be used for improving the deficiency (low specific surface area) that conventional sol gel method prepares material；
It can promote primitive solid particles dissolution recrystallization, when being greater than critical dimension, the particle meeting during secondary crystallization
Inhibiting effect is played as nucleus continued growth, and to subsequent growth；Carbonizable substance can cause perovskite metal to aoxidize simultaneously
Object crystal structure changes, and generates more Lacking oxygens, the more active sites of exposure, therefore degradation first that can be more efficient
Alkane.
(2) embodiment 5-6 is respectively and LaCoO3Original sample and LaMn0.9Mg0.1O3It compares as former state, embodiment 5-6 product difference is excellent
In respective original sample, the two is all without addition carbon matrix precursor, and only preparation method is different, so being made using hydro-thermal method of the invention
Catalyst granules agglomeration reduces, and specific surface area increases, and active site exposure significantly increases, thus more efficiently catalytic degradation
Methane.This illustrates that preparation method of the present invention avoids the particle hard aggregation that high temperature is likely to form；Obtained powder dispersibility is good,
Soilless sticking, crystal form be good, controlled shape, can be used for improving the deficiency (low specific surface area) that conventional sol gel method prepares material.
Reach 20-25m through the modified Ca-Ti ore type catalysis material specific surface area of carbon dots2/ g, surface increase a large amount of water-soluble
Property group, such as hydroxyl and amide, and surface forms carbonaceous material, and catalytic activity is obviously improved.Such as traditional colloidal sol
The perovskite metal oxides catalyst LaCoO of gel method preparation3 T50%=492 DEG C, activity is obvious after the modified hydro-thermal of carbon dots
It is promoted, T50%Value at most reduces by 100 DEG C or so.The optimized treatment method of the catalyst can be applied to Multimetal oxide material
The preparation of material, such as chlordene phosphate metal oxide catalyst, spinel metal oxide catalyst etc..Using metal ion and
Catalytic activity can be improved in perovskite metal oxides after hydro-thermal optimization processing, reduces energy consumption, reduces industrial waste gas, car tail
The discharge such as gas, brings huge economic benefit and social benefit.
We prepare Perovskite Catalytic material using solution combustion method in this research.This method can quickly form metastable
State phase, the mixing of initial reactant occurs in liquid in reaction process, convenient for controlling the uniformity and stoichiometry of reaction product
It learns；Technique is quick, is not necessarily to special installation.
By the method for hydro-thermal or microwave synthesis etc. " from bottom to top ", with citrate, carbohydrate and polymer-two
The molecules such as silica nanocomposite are usually torispherical nano particle as the CDs that carbon matrix precursor synthesizes, and are had uniform
Dispersion, does not reunite apparently, and particle diameter is 2 ~ 6 nm.The CDs oxygen content range of oxidation is 5 to 50%, and surface is contained largely
Carboxyl, the water soluble groups such as hydroxyl and amide, excellent water solubility and suitable chemically reactive group, for material into
The modification of one step physicochemical property.The amino acids DES of this method selection is a kind of green solvent of low toxicity and thermally and chemically stable
Property is good, and no biotoxicity.Contain amino and carboxyl Liang Zhong functional group in amino acid molecular, partial amino-acid has hydrophily.
The carbon dots that amino acids DES is formed as carbon matrix precursor are in a free form or key is integrated to the surface of perovskite catalyst, the carbon
The conjugated structure of point can promote the absorption of methane Yu perovskite surface, and then by hydroxyl and anaerobic group activation.At the same time,
Existing strong interaction with stable compound and promotes charge transfer process between perovskite metal oxides and CDs, thus
Lead to the catalytic performance of enhancing.In heterogeneous catalysis field, the present invention modifies perovskite catalyst table using CDs functionalization advantage
Face physico-chemical property, so that the Ca-Ti ore type catalysis material for the catalytic degradation organic exhaust gas that research and development can be more efficient, has important
Meaning.
To sum up, the present invention contains carbon matrix precursor, that is, amino acid, alcohols and urea or citric acid by addition come optimization processing calcium
The physico-chemical property on titanium ore type catalysis material surface, such as increase the surface carboxyl groups of Ca-Ti ore type catalysis material, hydroxyl and amide etc.
Water soluble group, this suitable chemically reactive group is conducive to absorption and cracking methane molecule, thus is more efficiently catalyzed
Degradation methane.Preparation method provided by the invention is simple, efficient, is of great significance to catalyst is prepared.
Claims (10)
1. a kind of preparation method for the Ca-Ti ore type catalysis material that water solubility carbon dots are modified, it is characterised in that: it includes following step
Suddenly,
(1) amino acid, alcohols and urea or citric acid are proportionally mixed, is stirred evenly molten up to forming transparent eutectic
Agent；The amino acid: alcohols: the molar ratio of urea or citric acid is 1:(4 ~ 6): (1 ~ 5)；
(2) perovskite metal precursor, fuel and fuel additive are weighed, the perovskite metal precursor is rare earth metal
Two or more in nitrate, transition metal nitrate and alkaline earth nitrate；The fuel is urea, sweet ammonia
It is a kind of in acid, sucrose or citric acid；The fuel additive is one of ammonium acetate, starch or polyethylene glycol；
Perovskite metal precursor is dissolved in deionized water, controlling metal ion molality total in solution is 0.5 ~ 2.0
Then fuel and fuel additive is added in mol/L；The molal quantity of the sum of the fuel and fuel additive is added before being
1 ~ 2 times of the sum of whole metal ions；The molar ratio of the fuel and fuel additive is (2 ~ 5): 1；It stirs at room temperature
0.5h is mixed, predecessor mixed solution is obtained, by the predecessor mixed solution in 650 ~ 850 DEG C of roasting 3-6h, obtains perovskite
Metal oxide catalyst；
(3) by the transparent eutectic solvent that step (1) obtains and the perovskite metal oxides catalyst that step (2) obtains with
Deionized water mixing, the amount that deionized water is added are added according to the perovskite metal oxides catalyst that every gram of step (2) obtains
The ratio of 2-10mL deionized water is added；The perovskite gold that the transparent eutectic solvent and step (2) that step (1) obtains obtain
The mass ratio for belonging to oxide catalyst is 1:(1 ~ 6)；
(4) product that step (3) obtains is put into reaction kettle, reacts 3-7h at 180-230 DEG C after sealing；
(5) natural cooling alternately washs filter 23 ~ 6 time with ethyl alcohol and deionized water；
(6) product for obtaining step (5) is dried at 80 DEG C, then roasts 1-3h at 600 DEG C.
2. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (1), the amino acid be selected from glycine, lysine, arginine, cysteine, threonine, serine or
One of histidine.
3. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (1), the alcohols is selected from ethylene glycol, glycerine, polyethylene glycol 200, polyethylene glycol 400 or polyethylene glycol
One of 800.
4. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (1), the amino acid: alcohols: the molar ratio of urea or citric acid is 1:6:3.
5. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (2), it is characterised in that: it is described by metal ion molality total in step (1) be 1mol/L.
6. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (2), it is characterised in that: the molal quantity of the sum of fuel and fuel additive is added whole metal ions
1.5 times of the sum of molal quantity.
7. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (2), it is characterised in that: the molar ratio of the fuel and fuel additive is 4:1.
8. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (3), perovskite metal oxides that the transparent eutectic solvent and step (2) that step (1) obtains obtain
The mass ratio of catalyst is 1:2.
9. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (4), reaction temperature is 200 DEG C, reaction time 4h.
10. a kind of preparation method of the modified Ca-Ti ore type catalysis material of water-soluble carbon dots according to claim 1, special
Sign is: in step (6), product roasts 1h at 600 DEG C after being warming up to 600 DEG C with 3 DEG C/min after 80 DEG C of drying.
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