CN106064098A - A kind of mesoporous class graphitic carbon nitride/palladium composite material, Its Preparation Method And Use - Google Patents
A kind of mesoporous class graphitic carbon nitride/palladium composite material, Its Preparation Method And Use Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229940005086 hydrogen peroxide 30 mg/ml Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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Abstract
The invention discloses a kind of mesoporous class graphitic carbon nitride/palladium composite material, Its Preparation Method And Use, the carrier of composite is mesoporous g C3N4, active component is Pd nanoparticle, and particle diameter is 10～20nm, load capacity is composite gross mass the 1.0～10% of described Pd nanoparticle.Preparation method is: first calcining obtains block g C3N4, then obtain mesoporous g C by oxidation and supersound process3N4, final load precious metals pd obtains target composite.Gained composite has bigger specific surface area and need not other any sacrifice templates, the load of more conducively Pd nanoparticle.By gained g C3N4/ Pd composite is applied to the reduction reaction of paranitrophenol as catalyst, demonstrates higher catalysis activity.
Description
Technical field
The present invention relates to a kind of composite, be specifically related to a kind of mesoporous g-C3N4/ Pd composite, belongs to material science
Field.
Background technology
Along with nano material synthetic technology is the most ripe, noble metal nano Pd catalyst is with its efficient catalytic performance, chi
Very little little, surface activity advantages of higher and the extensive concern of extremely researcher, range of application is also constantly expanding.But, traditional
There is drawbacks such as easily reuniting, be easy to run off and reclaim difficulty in homogeneous nano Pd catalyst in liquid phase reactor, thus seriously restricts
Its actual application and raising of catalytic performance.It is to solve the problems referred to above by there is the active nano Pd catalyst of catalysis immobilized
An important means.In recent years, the most eurypalynous carrier such as metal-oxide, inorganic silica gel and high molecular polymer etc. is all
Have application to load in homogeneous nano Pd catalyst.But, carried noble metal nano Pd catalyst is representing various superiority
While energy, it is faced with many equally and limits the practical problem of its application, as the strongest in the effect between active component and carrier, urge
The stability changed is the best, but activity can be affected；Otherwise, though the activity of catalyst is good, but noble metal in course of reaction
Nanoparticle is easily assembled and is even run off.As can be seen here, the support type that dispersion is high, catalysis activity is good, stability is strong is prepared
Noble metal nano Pd catalyst, the study hotspot that always catalytic science circle is paid close attention to for a long time.
Class graphitic carbon nitride (g-C3N4) because of its rich reserves, wide material sources, simple synthetic method, good economy performance and excellent
Elegant physicochemical property, has broad application prospects in fields such as photocatalysis, Solar use, environmental conservation.But, due to body phase
G-C3N4Material only has low-down specific surface area (< 10m2/ g), reduce somewhat it and carry as Pd nanoparticles
The probability of body, which greatly limits g-C3N4Material application in heterogeneous catalysis.Along with people are in carbon nitride material research side
Deepening continuously of face, various novel structures and the g-C of unique properties3N4Material is developed in succession.Wherein, most there is research
One of value is exactly mesoporous g-C3N4.Mesoporous g-C3N4Not only there is the excellent of the carbonitrides such as good stability, hardness is strong, density is low
Different characteristic, the biggest specific surface area and duct, the noble metal nano particles dispersibility on its surface can be improved, moreover it is possible to strengthen
Interaction between nano-particle and carrier, reduces the loss of noble metal catalyst.In recent years, with mesoporous g-C3N4Material is
Carrier loaded nano-noble metal (such as Au, Pd and Pt) has caused the extensive concern of researcher.But, mesoporous g-C3N4Material
Material the overwhelming majority be use template synthesis method, it is tediously long to there is synthesis step in the method, cost intensive, be unfavorable for industrialization generate and
The shortcomings such as popularization.Therefore, mesoporous g-C is prepared in the urgent need to a kind of inexpensive, safe method of exploitation3N4Material is to meet Pd nanometer
The requirement of particle carrier.Research currently, with respect to this respect rarely has report.
Summary of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide a kind of mesoporous class graphitic carbon nitride/palladium
Composite, the mesoporous g-C of gained3N4With general block g-C3N4Compare, there is bigger specific surface area and need not other
What sacrifices template, the load of more conducively Pd nanoparticle.
Further object is that the preparation method that mesoporous class graphitic carbon nitride/palladium composite material is provided.
One purpose of the load of the present invention is the use providing mesoporous class graphitic carbon nitride/palladium composite material to be used as catalyst
On the way, there is good stability and catalysis activity.
Mesoporous class graphitic carbon nitride/palladium composite material, its carrier is mesoporous g-C3N4, active component is Pd nanoparticle,
Pd nanoparticle is scattered in mesoporous g-C3N4Surface, described Pd nanoparticle load capacity is composite gross mass 1.0～
10%, Pd nano particle diameter is 10～20nm.
The preparation method of a kind of mesoporous class graphitic carbon nitride/palladium composite material, comprises the following steps:
(1) first melamine powder is calcined 2 hours at 600 DEG C, be down to room temperature, obtain the g-that yellow is block
C3N4；
(2) by yellow bulk g-C3N4After grinding to form powdery, join stirring 12～24 hours in concentrated sulphuric acid, the most slowly
Ground adds sodium nitrate and potassium permanganate, and is stirred at room temperature 5～10 hours.Then this mixed solution is diluted to deionized water
In and add hydrogen peroxide；Finally, it is dialyzed to neutrality, centrifugal collection；
Described block g-C3N4Ratio 20mg/mL with concentrated sulphuric acid；Described sodium nitrate and block g-C3N4Mass ratio be 1:
2～1:1；Described nanometer g-C3N4It is 1:5～1:2 with the mass ratio of potassium permanganate；Described block g-C3N and the ratio of hydrogen peroxide
30mg/mL；Hydrogen peroxide is 30% content specification；
(3) g-C that step (2) is obtained3N4Join in alcohol-water solution, supersound process 10～20 hours；Then will dispersion
System is at 3000min-1Under be centrifuged 10min, remove undispersed precipitate, at 40 DEG C be vacuum dried 12h, obtain off-white color solid
Powder is mesoporous g-C3N4；
The volume ratio of described alcohol-water solution is 1/1～3/1；Described block g-C3N4It is 2mg/mL with the ratio of alcohol-water solution；
Described alcohol is methanol, ethanol or isopropanol；
(4) by the mesoporous g-C of gained in step (3)3N4It is scattered in ethanol ultrasonic 30～60min, forms accurate homogeneous body
System, under stirring, the H of dropping 0.04mol/L2PdCl4Solution, continues stirring reaction 1h, and adding concentration is 0.5～1.0mol/L
Reducing agent, continues stirring 20min, centrifugation at 25～80 DEG C, washing, room temperature in vacuo is dried, and obtains mesoporous g-C3N4/ Pd is multiple
Condensation material；
Described H2PdCl4With mesoporous g-C3N4Mass ratio 1:15～1:40, described H2PdCl4Mol ratio with reducing agent
For 1:20～1:40.
Described reducing agent is sodium borohydride, hydrazine hydrate or ascorbic acid.
Mesoporous g-C3N4/ Pd composite may be used for catalytic degradation 4-NP, has good stability and catalysis activity.
Beneficial effect: mesoporous g-C prepared by (1) present invention3N4/ Pd composite not only specific surface is big, and preparation process
Template is sacrificed without any other；(2) preparation technology of the present invention is simple, and step is few, low cost, it is easy to accomplish industrialization, tool
There are important academic research meaning and potential application prospect.
Accompanying drawing explanation
Fig. 1 is the mesoporous g-C of embodiment 3 preparation3N4/ Pd composite x-ray diffractometer scanning figure, it is seen that have g-C3N4
(002) crystallographic plane diffraction peak and the crystallographic plane diffraction peak of Pd nanoparticle (111) (200), it was demonstrated that composite has above two component.
Fig. 2 is the mesoporous g-C of embodiment 3 preparation3N4/ Pd composite N2 adsorption and graph of pore diameter distribution, it is seen that g-C3N4/
The specific surface area of Pd composite reaches 83.547m2/ g, far above block g-C3N4(5m2/ g), and pore-size distribution has focused largely on
Within macropore range, g-C prepared by the present invention is described3N4/ Pd composite also can obtain preferable specific surface area without template.
Fig. 3 is the mesoporous g-C of embodiment 3 preparation3N4/ Pd composite transmission electron microscope picture, Pd nanoparticle is highly dispersed in
Mesoporous g-C3N4Surface, without significantly building up phenomenon.
Fig. 4 is the mesoporous g-C of embodiment 3 preparation3N4/ Pd composite property test figure (paranitrophenol ultraviolet absorptivity
Figure), a curve is the uv absorption before paranitrophenol reduction, and b curve is the uv absorption after paranitrophenol reduction, explanation
G-C prepared by the present invention3N4/ Pd composite has outstanding catalytic effect.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore protection scope of the present invention is confined to
Following embodiment, but limited by description and claims of this specification.
Supersound process involved in following example uses the ultrasonic processor that power is 300W, and hydrogen peroxide is
30% content specification.
Embodiment 1
A kind of mesoporous g-C3N4The preparation method of/Pd composite, step is as follows:
First 10g melamine powder is calcined 2 hours at 600 DEG C, after room temperature to be down to, obtain 2g yellow block
The g-C of shape3N4。
By 2g yellow bulk g-C3N4After grinding to form powdery, join stirring 12 hours in 100mL concentrated sulphuric acid, the most slowly
Ground adds 1g sodium nitrate and 4g potassium permanganate, and is stirred at room temperature 5 hours.Then this mixed solution is diluted to 300mL
In ionized water and add 67mL hydrogen peroxide.Finally, it is dialyzed to neutrality, centrifugal collection, obtain white g-C3N4。
The white g-C that will collect3N4Join in 1L methanol/water (V/V=1/1) solution, supersound process 10 hours；So
After by dispersion at 3000min-1Under be centrifuged 10min, remove undispersed precipitate, at 40 DEG C be vacuum dried 12h, obtain
1.5g off-white color pressed powder is mesoporous g-C3N4。
By mesoporous for 1.5g obtained above g-C3N4It is scattered in ultrasonic 30min in ethanol, forms dispersed system, stirring
Under, dropping 8mL concentration is the H of 0.04mol/L2PdCl4Solution, continues stirring reaction 1h, and adding 13mL concentration is 0.5mol/L's
Sodium borohydride, continues stirring 20min, centrifugation at 25 DEG C, washing, room temperature in vacuo is dried, and obtains mesoporous g-C3N4/ Pd is combined
Material.
Embodiment 2
A kind of mesoporous g-C3N4The preparation method of/Pd composite, step is as follows:
First 20g melamine powder is calcined 2 hours at 600 DEG C, after room temperature to be down to, obtain 4.5g yellow
Block g-C3N4。
By 4.5g yellow bulk g-C3N4After grinding to form powdery, join in 225mL concentrated sulphuric acid and stir 15 hours, then delay
Slowly add 3g sodium nitrate and 12g potassium permanganate, and be stirred at room temperature 8 hours.Then this mixed solution is diluted to 675mL
In deionized water and add 150mL hydrogen peroxide.Finally, it is dialyzed to neutrality, centrifugal collection, obtain white g-C3N4。
The white g-C that will collect3N4Join in 2.25L ethanol/water (V/V=2/1) solution, supersound process 15 hours；
Then by dispersion at 3000min-1Under be centrifuged 10min, remove undispersed precipitate, at 40 DEG C be vacuum dried 12h, obtain
4.0g off-white color pressed powder is mesoporous g-C3N4。
By mesoporous for 4.0g obtained above g-C3N4It is scattered in ultrasonic 40min in ethanol, forms dispersed system, stirring
Under, dropping 13mL concentration is the H of 0.04mol/L2PdCl4Solution, continues stirring reaction 1h, and adding 20mL concentration is 0.8mol/L
Hydrazine hydrate, at 50 DEG C continue stirring 20min, centrifugation, washing, room temperature in vacuo is dried, and obtains mesoporous g-C3N4/ Pd is combined
Material.
Embodiment 3
A kind of mesoporous g-C3N4The preparation method of/Pd composite, step is as follows:
First 30g melamine powder is calcined 2 hours at 600 DEG C, after room temperature to be down to, obtain 7g yellow block
The g-C of shape3N4。
By 7g yellow bulk g-C3N4After grinding to form powdery, join stirring 24 hours in 350mL concentrated sulphuric acid, the most slowly
Ground adds 7g sodium nitrate and 35g potassium permanganate, and is stirred at room temperature 10 hours.Then this mixed solution is diluted to 1050mL
In deionized water and add 233mL hydrogen peroxide.Finally, it is dialyzed to neutrality, centrifugal collection.
The white g-C that will collect3N4Joining in 3.5L isopropanol/water (V/V=3/1) solution, supersound process 20 is little
Time；Then by dispersion at 3000min-1Under be centrifuged 10min, remove undispersed precipitate, at 40 DEG C be vacuum dried 12h,
Obtain 6.5g off-white color pressed powder and be mesoporous g-C3N4。
By mesoporous for 6.5g obtained above g-C3N4It is scattered in ultrasonic 60min in ethanol, forms dispersed system, stirring
Under, dropping 13mL concentration is the H of 0.04mol/L2PdCl4Solution, continues stirring reaction 1h, and adding 21mL concentration is 1.0mol/L
Ascorbic acid, at 80 DEG C continue stirring 20min, centrifugation, washing, room temperature in vacuo is dried, and obtains mesoporous g-C3N4/ Pd is multiple
Condensation material.
Embodiment 4
Prepared by embodiment 3, the catalytic degradation performance test of mesoporous g-C3N4/Pd composite is as follows: preparation 3mL concentration
Being the paranitrophenol (4-nitrophenol is called for short 4-NP) of 1 × 10-4M, being subsequently adding 0.1mL concentration is 3 × 10-1M
Sodium borohydride (NaBH4) aqueous solution.G-C3N4/Pd composite 5mg embodiment 3 prepared again adds system, uses ultraviolet
The uv absorption change of spectral detection product.Test result is shown in Fig. 4, and g-C3N4/Pd composite wood prepared by the present invention is described
Material has outstanding catalytic effect.
Claims (6)
- The most mesoporous class graphitic carbon nitride/palladium composite material, it is characterised in that carrier is mesoporous g-C3N4, active component is that Pd receives Rice corpuscles, particle diameter is 10～20nm, load capacity is composite gross mass the 1.0～10% of described Pd nanoparticle.
- 2. the preparation method of the mesoporous class graphitic carbon nitride/palladium composite material described in claim 1, it is characterised in that include Following steps:Step (1), by melamine powder in calcining, be down to room temperature, obtain the g-C that yellow is block3N4；Step (2), by yellow bulk g-C3N4After grinding to form powdery, join stirring 12～24 hours in concentrated sulphuric acid, the most slowly Ground adds sodium nitrate and potassium permanganate, and is stirred at room temperature 5～10 hours；Then this mixed solution is diluted to deionized water In and add hydrogen peroxide；Finally, it is dialyzed to neutrality, centrifugal collection, obtain g-C3N4；Step (3), the g-C that step (2) is obtained3N4Join in alcohol-water solution, supersound process 10～20 hours；Then will divide A prose style free from parallelism ties up to 3000min-1Under be centrifuged 10min, remove undispersed precipitate, be vacuum dried 12h at 40 DEG C, obtain off-white color solid Body powder is mesoporous g-C3N4；Step (4), by the mesoporous g-C of gained in step (3)3N4It is scattered in ethanol ultrasonic 30～60min, forms accurate homogeneous body System, under stirring, the H of dropping 0.04mol/L2PdCl4Solution, continues stirring reaction 1h, and adding concentration is 0.5～1.0mol/L Reducing agent, continues stirring 20min, centrifugation at 25～80 DEG C, washing, room temperature in vacuo is dried, and obtains mesoporous g-C3N4/ Pd is multiple Condensation material.
- The preparation method of mesoporous class graphitic carbon nitride/palladium composite material the most according to claim 2, it is characterised in that In step (2), described block g-C3N4Ratio 20mg/mL with concentrated sulphuric acid；Described sodium nitrate and block g-C3N4Mass ratio be 1:2～1:1；Described nanometer g-C3N4It is 1:5～1:2 with the mass ratio of potassium permanganate；Described block g-C3N and the ratio of hydrogen peroxide Example 30mg/mL.
- The preparation method of mesoporous class graphitic carbon nitride/palladium composite material the most according to claim 2, it is characterised in that In step (3), the volume ratio of described alcohol-water solution is 1/1～3/1；Described block g-C3N4It is 2mg/ with the ratio of alcohol-water solution mL；Described alcohol is methanol, ethanol or isopropanol.
- The preparation method of mesoporous class graphitic carbon nitride/palladium composite material the most according to claim 2, it is characterised in that In step (4), described H2PdCl4With mesoporous g-C3N4Mass ratio 1:15～1:40, described H2PdCl4Mol ratio with reducing agent For 1:20～1:40；Described reducing agent is sodium borohydride, hydrazine hydrate or ascorbic acid.
- 6. the mesoporous class graphitic carbon nitride/palladium composite material described in claim 1 is for the purposes of catalytic degradation 4-NP.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984354A (en) * | 2017-04-26 | 2017-07-28 | 福州大学 | A kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104634386A (en) * | 2014-12-01 | 2015-05-20 | 邱家稳 | Intelligent aircraft system |
| CN104672159A (en) * | 2015-01-21 | 2015-06-03 | 扬州大学 | Graphite oxide phase carbon nitride as well as preparation method and application thereof |
| US20160145531A1 (en) * | 2011-09-30 | 2016-05-26 | Uchicago Argonne, Llc | Method to Produce Catalytically Active Nanocomposite Coatings |
-
2016
- 2016-06-02 CN CN201610388769.4A patent/CN106064098A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160145531A1 (en) * | 2011-09-30 | 2016-05-26 | Uchicago Argonne, Llc | Method to Produce Catalytically Active Nanocomposite Coatings |
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104634386A (en) * | 2014-12-01 | 2015-05-20 | 邱家稳 | Intelligent aircraft system |
| CN104672159A (en) * | 2015-01-21 | 2015-06-03 | 扬州大学 | Graphite oxide phase carbon nitride as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| ASALATHA A.S. NAIR ET AL.: ""Hydrogen storage performance of palladium nanoparticles decorated graphitic carbon nitride"", 《INTERNATIONAL JOURNAL O F HYDROGEN ENERGY》 * |
| YUKAI ZHAO ET AL.: ""Palladium Supported on Graphitic Carbon Nitride: An Efficient and Recyclable Heterogeneous Catalyst for Reduction of Nitroarenes and Suzuki Coupling Reaction"", 《CATAL LETT》 * |
| 李晨露 等: ""氮化碳纳米片层的制备及其应用研究进展"", 《广州化工》 * |
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