CN103143361B - Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof - Google Patents
Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103143361B CN103143361B CN201310106570.4A CN201310106570A CN103143361B CN 103143361 B CN103143361 B CN 103143361B CN 201310106570 A CN201310106570 A CN 201310106570A CN 103143361 B CN103143361 B CN 103143361B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dense
- minutes
- graphite
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a graphene-promoted hydrotalcite-based denitration catalyst and a preparation method thereof, belonging to the technical field of environmental protection catalysts. The chemical formula of the catalyst is M<2>2Mg<2>Al<3>(O), wherein M<2> is one or a combination of more of Cu<2>, Co<2>, Ni<2> and Mn<2>, and the mole ratio of M<2> to Mg<2> to Al<3> is 2: 1: 1; and the catalyst has the specific surface area of 80-110 m<2>/g and the pore volume of 0.3-0.4 cc/g, and the pore size distribution is of mesoporous distribution. According to the catalyst, hydrotalcite (LDHs) nanosheets are loaded to the surface of graphene through a co-precipitation method, and M<2>2Mg<2>Al<3>(O) is obtained after calcinations. The catalyst and the preparation method of the catalyst have the advantages that the catalyst has high catalytic activity and better stability to the storage capacity of NOx, is much better than a graphene-promoted-free hydrotalcite-based catalyst and has enhanced direct NO decomposition capability.
Description
Technical field
The invention belongs to catalysts for environmental protection technical field, a kind of Graphene promoted type hydrotalcite denitrating catalyst and preparation method thereof is particularly provided.
Technical background
Since entering 21st century, along with the development of national economy and transportation, directly drive motor vehicle industry constantly to push ahead, output and the recoverable amount of motor vehicle are increased sharply, this is when the life of giving us offers convenience, and the environment of also depending on for existence to us has caused serious pollution.Wherein, NO in motor-vehicle tail-gas
xdischarge (being mainly NO) become one of main source of atmospheric pollution, thus form photochemical fog and acid rain urban environment and public health have been caused to serious threat.Consider the efficient utilization to fossil fuel, lean-burn automotive is the development trend that is following motor vehicle, therefore, under lean-burn condition to NO
xremove and become of field of Environment Protection study hotspot and difficult point.In numerous denitration technologies, nitrogen oxide storage and reduction technology (NO
xstorage-Reduction, NSR) be that moving source removes NO
xthe Development Technology of tool prospect.Storge quality is the very important feature that NSR catalyst has, and it directly affects NO
xremoving completely under proper condition, therefore its NOx storage amount (NO
xstorage Capacity, NSC) be an importance investigating catalyst activity height.
Hydrotalcite (LDHs) is by positively charged laminate and interlayer anion ordered fabrication and the lamellar compound forming, and its chemical composition can be expressed as with general formula: [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M
2+and M
3+be respectively divalence and trivalent metal cation on main body laminate, A
n-for interlayer anion, x (=M
3+/ (M
2++ M
3+)) be molar ratio.The composite metal oxide obtaining as presoma roasting taking LDHs has distributions of metallic elements homogeneous and intrinsic alkalescence concurrently, has direct decomposition, storage and reduction multifunctionality in denitration reaction, thereby has been subject to extensive concern in NSR technical research.But the LDHs particle diameter of being prepared by traditional co-precipitation method is conventionally larger, and easy sintering in high-temperature roasting.Therefore the composite metal oxide being obtained by the roasting of LDHs precursor exists that specific area is little, the shortcoming of particle bad dispersibility conventionally, thereby makes catalyst activity decreased.There are some researches show again that higher this shortcoming performance of sintering temperature is more obvious simultaneously.As 2009, Li etc. reported in Applied Catalysis B:Environmental the 91st volume 406-415 page, the LDHs base Co being prepared by coprecipitation
2.5mg
0.5alO O composite metallic oxide catalyst improves the NOx storage amount of catalyst with sintering temperature and reduces rapidly, and this is mainly to reduce and due to Active sites quantity reduces due to the specific area that sintering of catalyst causes.
At present, by selecting some suitable carriers, the research of the decentralization of raising nanocatalyst particles and then raising catalytic activity has evoked broad interest.For example, have much as the report of carbon fiber (CF), active carbon (AC) and CNT (CNT) even load metal simple-substance/metal oxide about New Type of Carbon carrier in recent years.2011, the people such as Li reported CNT (CNT) supported V at Journal of Hazardous Materials the 192nd volume 915-921 page
2o
5/ TiO
2catalyst, the facilitation of CNT shows the specific area and the pore volume that have improved catalyst, thereby provides more active sites for catalytic reaction.2012, Graphene (Graphene) load Au, Pt, Pd nano-particle catalyst that the people such as Xu report in The Journal of Physical Chemistry C the 112nd volume 19841-19845 page demonstrate huge application potential at catalytic field, and wherein very important reason is exactly the peptizaiton of Graphene carrier to active component.Above example explanation selects suitable carbon carrier can improve the decentralization of metal simple-substance or metal oxide, thereby improves catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of Graphene promoted type hydrotalcite denitrating catalyst and preparation method thereof.Easy and the mild condition of preparation process, without any need for organic reagent, hydrotalcite nano chip size homogeneous and high dispersive in the graphene-supported hydrotalcite composite material of gained.The Graphene promoted type hydrotalcite catalyst obtaining after roasting demonstrates excellent NO in denitration reaction
xstorage capacity and decomposability, the high dispersive facilitation owing to Graphene to active component.
Graphene oxide is metal cation in first initial preparation adsorbs salting liquid with electrostatic force, growth and the reunion of hydrotalcite nucleus in nucleation process, are suppressed, thereby obtain the hydrotalcite catalyst of high dispersive, size homogeneous, and then overcome the not high shortcoming of the general NOx storage amount of hydrotalcite catalyst in prior art.This catalyst under lean-burn condition to NO
xremove and presented very high storage capacity and good directly decomposability, be greatly better than without Graphene promoted type hydrotalcite catalyst, simultaneously easy, the mild condition of preparation process.Catalyst recycling 4 times, storage capacity, resolution ratio remain unchanged substantially, show that catalyst has higher stability.
The chemical formula of Graphene promoted type hydrotalcite denitrating catalyst of the present invention is M
2+ 2mg
2+al
3+(O); Wherein, M
2+for Cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination, M
2+: Mg
2+: Al
3+mol ratio be 2:1:1; Specific surface area of catalyst is 80～110 m
2/ g, pore volume is 0.3～0.4 cc/g, pore-size distribution is mesoporous distribution.
This catalyst is carried on Graphene (Graphene) surface by coprecipitation by hydrotalcite (LDHs) nanometer sheet, obtains M after roasting
2+ 2mg
2+al
3+(O).
Graphene of the present invention promotes that the preparation method of hydrotalcite catalyst is first by a certain proportion of M
2+(Cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination), Mg
2+, Al
3+salting liquid mix with graphene oxide colloidal solution, metal cation Electrostatic Absorption is in graphene oxide surface, then under alkaline environment, original position generates the hydrotalcite nano piece of small particle diameter, high dispersive, obtains corresponding catalyst after roasting.Specifically comprise the steps:
(1) pre-oxidation of graphite: successively by dense H
2sO
4, K
2s
2o
4and P
2o
5join in flask, under stirring, add graphite powder, finally 60～80
oin C water-bath, react 6～8 hours, washing is to neutral, dry, for subsequent use; Wherein graphite: dense H
2sO
4: K
2s
2o
4: P
2o
5mass ratio be 1:4～8:0.5:0.5.
(2) preparation of graphene oxide: measure dense H in four-hole boiling flask
2sO
4, 0～10
ounder C stirring condition successively by pre-oxidation graphite powder and NaNO
3join dense H
2sO
4in, and slowly add KMnO
4, stirring reaction 60～90 minutes; Then flask is transferred to 35
oin the water bath with thermostatic control of C, continue to stir 30～60 minutes; Finally in stirring, add deionized water, control reaction temperature in 95～98
obetween C, continue to stir 30～60 minutes; Use 3% H
2o
230～50 ml processing reaction liquid are to presenting golden yellow, then filter while hot, then with 5% HCl and deionized water fully wash in filtrate without SO4
2-; Wherein graphite: dense H
2sO
4: NaNO
3: KMnO
4mass ratio be 1:42:0.5:3, dense H
2sO
4: H
2the volume ratio of O is 1:2.
(3) M
2+ 2mg
2+al
3+(O) preparation of catalyst: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, under stirring condition, within ultrasonic 0.5～2 hour, obtain finely dispersed graphene oxide colloidal solution with 100W～1000W frequency, its mass concentration is 2mg/ml; Take 0.007～0.021 mol M
2+(NO
3)
2xH
2o, M
2+cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination, 0.0035～0.0105 mol Mg (NO
3)
26H
2o, 0.0035～0.0105 mol Al (NO
3)
39H
2o is dissolved in 100 ml deionized waters and pours in 500 ml graphene oxide colloidal solution, stirs 30～60 minutes and assisting ultrasonic; Again by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, keeps 30～50 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10 ± 0.5; Last 65
oc crystallization 4 hours, centrifugal, washing, 60～80
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtains catalyst after 4 hours and is expressed as M
2+ 2mg
2+al
3+(O).
The present invention compared with prior art has the following advantages and feature:
(1) prepared hydrotalcite/Graphene (LDH/Graphene) composite with the simple synthetic route of one, gained carrier stability is high, be easy to that hydrotalcite nano piece disperses, size homogeneous.
(2) the prepared hydrotalcite denitrating catalyst of the present invention spinelle particle high degree of dispersion, particle diameter are little, and recycled for multiple times still has very high NO
xstorage capacity (NSC), has good commercial application prospect, and hydrotalcite denitrating catalyst of a kind of high storage capacity and preparation method thereof is provided.
Brief description of the drawings
Fig. 1 is the SEM spectrogram of embodiment 1 precursor.
Fig. 2 is the TEM spectrogram of embodiment 1 precursor.
Fig. 3 is gained CATALYST Co after embodiment 1 precursor roasting
2+ 2mg
2+al
3+(O) SEM spectrogram.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:
(1) pre-oxidation of graphite: successively by the dense H of 24 ml
2sO
4, 5 g K
2s
2o
4with 5 g P
2o
5join in flask, under stirring, add 10 g graphite powders, finally 80
oin C water-bath, react 6 hours, washing is to neutral, dry, for subsequent use.
(2) preparation of graphene oxide: measure the dense H of 115 ml in 500 ml flasks
2sO
4, in ice-water bath under stirring condition successively by 5 g pre-oxidation graphite powders and 2.5 g NaNO
3join dense H
2sO
4in, and slowly add 15 g KMnO
4, stirring reaction 90 minutes; Then flask is transferred to 35 ± 3
oin the water bath with thermostatic control of C, continue to stir 30 minutes; Finally in stirring, add 230 ml deionized waters, control reaction temperature lower than 98
oc, continues to stir 30 minutes; Use 3% H
2o
230ml processing reaction liquid is to presenting golden yellow, then filter while hot, with 5% HCl and deionized water fully wash in filtrate without SO4
2-.
(3) Co
2+ 2mg
2+al
3+(O) preparation of catalyst: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, obtain finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.007 mol Co (NO
3)
26H
2o, 0.0035mol Mg (NO
3)
26H
2o, 0.0035mol Al (NO
3)
39H
2o is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2mg
2+al
3+(O).
Embodiment 2:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, within under agitation ultrasonic 1 hour, obtain finely dispersed graphene oxide colloidal solution, its mass concentration is 2mg/ml; Take 0.014 mol Co (NO
3)
26H
2o, 0.007mol Mg (NO
3)
26H
2o, 0.007mol Al (NO
3)
39H
2o is dissolved in 100ml deionized water and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2mg
2+al
3+(O).
Embodiment 3:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, within under agitation ultrasonic 1 hour, obtain finely dispersed graphene oxide colloidal solution, its mass concentration is 2mg/ml; Take 0.021 mol Co (NO
3)
26H
2o, 0.0105 mol Mg (NO
3)
26H
2o, 0.0105 mol Al (NO
3)
39H
2o is dissolved in 100ml deionized water and pours in 500 ml graphene oxide solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2mg
2+al
3+(O).
Embodiment 4:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, within under agitation ultrasonic 1 hour, obtain finely dispersed graphene oxide colloidal solution, its mass concentration is 2mg/ml; Take 0.007 mol Cu (NO
3)
23H
2o, 0.0035 mol Mg (NO
3)
26H
2o, 0.0035 mol Al (NO
3)
39H
2o is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtained Catalysts Cu after 4 hours
2+ 2mg
2+al
3+(O).
Embodiment 5:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, within under agitation ultrasonic 1 hour, obtain finely dispersed graphene oxide colloidal solution, its mass concentration is 2mg/ml; Take 0.007 mol Ni (NO
3)
26H
2o, 0.0035 mol Mg (NO
3)
26H
2o, 0.0035 mol Al (NO
3)
39H
2o is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtains catalyst n i after 4 hours
2+ 2mg
2+al
3+(O).
Embodiment 6:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500 ml by deionized water, within under agitation ultrasonic 1 hour, obtain finely dispersed graphene oxide colloidal solution, its mass concentration is 2mg/ml; Take 0.007 mol Mn (NO
3)
2, 0.0035mol Mg (NO
3)
26H
2o, 0.0035 mol Al (NO
3)
39H
2o is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; Finally by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, keeps about 40 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10; Last 65
oc crystallization 4 hours, centrifugal, washing, 60
oc is dried, by product in Muffle furnace 500
oin C air atmosphere, roasting obtains catalyst Mn after 4 hours
2+ 2mg
2+al
3+(O).
Claims (2)
1. a Graphene promoted type hydrotalcite denitrating catalyst, is characterized in that, the chemical formula of this catalyst is M
2+ 2mg
2+al
3+(O); Wherein, M
2+for Cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination, M
2+: Mg
2+: Al
3+mol ratio be 2:1:1; Specific surface area of catalyst is 80～110m
2/ g, pore volume is 0.3～0.4cc/g, pore-size distribution is mesoporous distribution;
This catalyst is carried on Graphene surface by coprecipitation by hydrotalcite nano piece, after roasting, obtains; Concrete preparation process is as follows:
(1) pre-oxidation of graphite: successively by dense H
2sO
4, K
2s
2o
4and P
2o
5join in flask, under stirring, add graphite powder, finally in 60～80 DEG C of water-baths, react 6～8 hours, washing is to neutral, dry, for subsequent use; Wherein graphite: dense H
2sO
4: K
2s
2o
4: P
2o
5mass ratio be 1:4～8:0.5:0.5;
(2) preparation of graphene oxide: measure dense H in four-hole boiling flask
2sO
4, under 0～10 DEG C of stirring condition successively by pre-oxidation graphite powder and NaNO
3join dense H
2sO
4in, and add KMnO
4, stirring reaction 60～90 minutes; Then flask is transferred in the water bath with thermostatic control of 35 DEG C, continues to stir 30～60 minutes; Finally in stirring, add deionized water, control reaction temperature between 95～98 DEG C, continue to stir 30～60 minutes; Use 3%H
2o
230～50ml processing reaction liquid is to presenting golden yellow, then filter while hot, then with 5%HCl and deionized water fully wash in filtrate without SO4
2-; Wherein graphite: dense H
2sO
4: N
anO
3: KMnO
4mass ratio be 1:42:0.5:3, dense H
2sO
4: H
2the volume ratio of O is 1:2;
(3) M
2+ 2mg
2+al
3+(O) preparation of catalyst: 1g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500ml by deionized water, under stirring condition, within ultrasonic 0.5～2 hour, obtain finely dispersed graphene oxide colloidal solution with 100W～1000W frequency, its mass concentration is 2mg/ml; Take 0.007～0.021mol M (NO
3)
2xH
2o, M
2+cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination, 0.0035～0.0105mol Mg (NO
3)
26H
2o, 0.0035～0.0105mol Al (NO
3)
39H
2o is dissolved in 100ml deionized water and pours in 500ml graphene oxide colloidal solution, stirs 30～60 minutes and assisting ultrasonic; Again by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, keeps 30～50 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10 ± 0.5; Last 65 DEG C of crystallization 4 hours, centrifugal, washing, 60～80 DEG C of oven dry; By product in Muffle furnace in 500 DEG C of air atmospheres roasting after 4 hours, obtain catalyst and be expressed as M
2+ 2mg
2+al
3+(O).
2. a preparation method for Graphene promoted type hydrotalcite denitrating catalyst claimed in claim 1, is characterized in that, comprises the following steps:
(1) pre-oxidation of graphite: successively by dense H
2sO
4, K
2s
2o
4and P
2o
5join in flask, under stirring, add graphite powder, finally in 60～80 DEG C of water-baths, react 6～8 hours, washing is to neutral, dry, for subsequent use; Wherein graphite: dense H
2sO
4: K
2s
2o
4: P
2o
5mass ratio be 1:4～8:0.5:0.5;
(2) preparation of graphene oxide: measure dense H in four-hole boiling flask
2sO
4, under 0～10 DEG C of stirring condition successively by pre-oxidation graphite powder and NaNO
3join dense H
2sO
4in, and add KMnO
4, stirring reaction 60～90 minutes; Then flask is transferred in the water bath with thermostatic control of 35 DEG C, continues to stir 30～60 minutes; Finally in stirring, add deionized water, control reaction temperature between 95～98 DEG C, continue to stir 30～60 minutes; Use 3%H
2o
230～50ml processing reaction liquid is to presenting golden yellow, then filter while hot, then with 5%HCl and deionized water fully wash in filtrate without SO4
2-; Wherein graphite: dense H
2sO
4: NaNO
3: KMnO
4mass ratio be 1:42:0.5:3, dense H
2sO
4: H
2the volume ratio of O is 1:2;
(3) M
2+ 2mg
2+al
3+(O) preparation of catalyst: 1g graphite oxide is transferred in 1L four-hole boiling flask, diluted 500ml by deionized water, under stirring condition, within ultrasonic 0.5～2 hour, obtain finely dispersed graphene oxide colloidal solution with 100W～1000W frequency, its mass concentration is 2mg/ml; Take 0.007～0.021mol M (NO
3)
2xH
2o, M
2+cu
2+, Co
2+, Ni
2+, Mn
2+in one or more combination, 0.0035～0.0105mol Mg (NO
3)
26H
2o, 0.0035～0.0105mol Al (NO
3)
39H
2o is dissolved in 100ml deionized water and pours in 500ml graphene oxide colloidal solution, stirs 30～60 minutes and assisting ultrasonic; Again by mol ratio [Na
2cO
3]/[Al (NO
3)
39H
2o]=2, [NaOH]/[Na
2cO
3the mixed alkali liquor of]=3.2 drips in flask, keeps 30～50 minutes, and alkali lye drips pH value of solution while end and is stabilized in 10 ± 0.5; Last 65 DEG C of crystallization 4 hours, centrifugal, washing, 60～80 DEG C of oven dry; By product in Muffle furnace in 500 DEG C of air atmospheres roasting after 4 hours, obtain catalyst and be expressed as M
2+ 2mg
2+al
3+(O).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310106570.4A CN103143361B (en) | 2013-03-29 | 2013-03-29 | Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310106570.4A CN103143361B (en) | 2013-03-29 | 2013-03-29 | Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103143361A CN103143361A (en) | 2013-06-12 |
| CN103143361B true CN103143361B (en) | 2014-12-03 |
Family
ID=48541837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310106570.4A Expired - Fee Related CN103143361B (en) | 2013-03-29 | 2013-03-29 | Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103143361B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769048B (en) * | 2014-01-22 | 2015-11-25 | 中国科学院合肥物质科学研究院 | A kind of preparation method of three-dimensional porous graphene-supported nano magnalium hydrotalcite defluorinating agent |
| CN103920497B (en) * | 2014-04-02 | 2016-03-30 | 北京化工大学 | A kind of preparation method of graphene-supported atomic-level thickness super thin metal sheet |
| CN104056629B (en) * | 2014-06-17 | 2016-08-17 | 中国天辰工程有限公司 | A kind of catalyst for low carbon alcohol by synthetic gas, its preparation method and application |
| CN104190409B (en) * | 2014-08-19 | 2016-08-17 | 南京师范大学 | The low-temperature SCR sulfur resistant catalyst of graphene-supported titanium-based core shell structure and preparation method |
| CN104857960B (en) * | 2015-04-22 | 2017-10-10 | 北京化工大学 | Graphene is oriented to multilevel hierarchy composite oxide catalysts and preparation method thereof |
| CN105289537A (en) * | 2015-10-30 | 2016-02-03 | 广东电网有限责任公司电力科学研究院 | Middle-temperature carbon dioxide solid absorbent and preparation method thereof |
| CN105776261B (en) * | 2016-01-07 | 2017-06-23 | 北京化工大学 | A kind of fast preparation method of Multilevel-structure hydrotalcite and graphene oxide composite material |
| CN108927170B (en) * | 2018-08-17 | 2021-02-05 | 太原理工大学 | Preparation method and application of low-temperature flue gas denitration catalyst based on CoMnAl hydrotalcite-like compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102824907A (en) * | 2012-07-21 | 2012-12-19 | 大连理工大学 | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst |
| CN102921443A (en) * | 2012-11-06 | 2013-02-13 | 北京化工大学 | Nickel titanium hydrotalcite and graphene composite photocatalyst responsive to visible lights and method for preparing same |
-
2013
- 2013-03-29 CN CN201310106570.4A patent/CN103143361B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102824907A (en) * | 2012-07-21 | 2012-12-19 | 大连理工大学 | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst |
| CN102921443A (en) * | 2012-11-06 | 2013-02-13 | 北京化工大学 | Nickel titanium hydrotalcite and graphene composite photocatalyst responsive to visible lights and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 水滑石的改性及其在碱催化反应中的应用研究;高媛;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20121215;55-56页第5.1实验部分 * |
| 高媛.水滑石的改性及其在碱催化反应中的应用研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2012, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103143361A (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103143361B (en) | Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof | |
| Yang et al. | Syntheses and applications of noble-metal-free CeO2-based mixed-oxide nanocatalysts | |
| Tang et al. | One-step electrospinning synthesis of TiO2/g-C3N4 nanofibers with enhanced photocatalytic properties | |
| Zhang et al. | Heterostructures construction on TiO2 nanobelts: a powerful tool for building high-performance photocatalysts | |
| Wang et al. | Preparation and characterization of a novel and recyclable InVO4/ZnFe2O4 composite for methylene blue removal by adsorption and visible-light photocatalytic degradation | |
| Li et al. | Facile synthesis of 3D flowerlike CeO2 microspheres under mild condition with high catalytic performance for CO oxidation | |
| Feng et al. | Facile fabrication of trepang-like CeO2@ MnO2 nanocomposite with high catalytic activity for soot removal | |
| Tan et al. | Co3O4 nanoparticles-loaded BiOCl nanoplates with the dominant {001} facets: efficient photodegradation of organic dyes under visible light | |
| Seeharaj et al. | Ultrasonically-assisted surface modified TiO2/rGO/CeO2 heterojunction photocatalysts for conversion of CO2 to methanol and ethanol | |
| CN104190409B (en) | The low-temperature SCR sulfur resistant catalyst of graphene-supported titanium-based core shell structure and preparation method | |
| Zhang et al. | Spatially separated catalytic sites supplied with the CdS–MoS 2–In 2 O 3 ternary dumbbell S-scheme heterojunction for enhanced photocatalytic hydrogen production | |
| CN103991903B (en) | A kind of preparation method of mixed phase titanium dioxide nanosheet photocatalyst | |
| Li et al. | Halloysite–CeO2–AgBr nanocomposite for solar light photodegradation of methyl orange | |
| CN108517537A (en) | Double scale transition metal phosphides of a kind of nitrogen-doped carbon load and its preparation method and application | |
| CN104857960A (en) | Graphene-oriented multi-level structure composite oxide catalyst and preparation method thereof | |
| Abbas et al. | Inexpensive synthesis of a high-performance Fe 3 O 4-SiO 2-TiO 2 photocatalyst: Magnetic recovery and reuse | |
| CN105344350A (en) | Preparation method for molybdenum-doped TiO2 nanowire/graphene compound with high catalytic degradation activity under visible light | |
| CN114768841B (en) | Oxygen doped ZnIn modified by transition metal phosphide 2 S 4 Polarized photocatalytic material and preparation method and application thereof | |
| Zhang et al. | Enhanced visible-light photocatalytic H2 production of hierarchical g-C3N4 hexagon by one-step self-assembly strategy | |
| Chen et al. | In situ deposition of 0D CeO2 quantum dots on Fe2O3-containing solid waste NH3-SCR catalyst: Enhancing redox and NH3 adsorption ability | |
| Fang et al. | Effect of crystalline/amorphous structure on light absorption and carrier separationof CeO2-TiO2 heterojunctions | |
| Yu et al. | Facile preparation of amorphous CenMnOx catalysts and their good catalytic performance for soot combustion | |
| Chen et al. | Review on advances in structure–activity relationship, reaction & deactivation mechanism and rational improving design of selective catalytic reduction deNOx catalysts: Challenges and opportunities | |
| Wu et al. | Solvothermal synthesis of Bi2O3/BiVO4 heterojunction with enhanced visible-light photocatalytic performances | |
| CN104525181A (en) | Catalyst for catalytic combustion of soot particulates and preparation method and application of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141203 Termination date: 20160329 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |