CN106492866A - Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application - Google Patents
Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application Download PDFInfo
- Publication number
- CN106492866A CN106492866A CN201610845700.XA CN201610845700A CN106492866A CN 106492866 A CN106492866 A CN 106492866A CN 201610845700 A CN201610845700 A CN 201610845700A CN 106492866 A CN106492866 A CN 106492866A
- Authority
- CN
- China
- Prior art keywords
- aza
- palladium
- magnetic
- mesoporous carbon
- gold
- 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.)
- Pending
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 141
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 67
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010931 gold Substances 0.000 title claims abstract description 56
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002940 palladium Chemical class 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 235000019253 formic acid Nutrition 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000004044 response Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 17
- 235000019254 sodium formate Nutrition 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000004280 Sodium formate Substances 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 description 67
- 238000006722 reduction reaction Methods 0.000 description 23
- 229910052804 chromium Inorganic materials 0.000 description 16
- 229910021065 Pd—Fe Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000010531 catalytic reduction reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000258920 Chilopoda Species 0.000 description 1
- 230000009946 DNA mutation Effects 0.000 description 1
- 241000270322 Lepidosauria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000002759 chromosomal effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003226 mitogen Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application, the carrier that wherein magnetic carries the aza catalyst of target is aza mesoporous carbon, and Pd nano particle and Fe nanometer particles are supported in the surface and micropore of aza mesoporous carbon.Its preparation method is：Palladium salt dissolving is obtained palladium salt solution, aza for magnetic mesoporous carbon is added in palladium salt solution and is obtained mixed liquor；Formic acid solution is added to heating response in mixed liquor, magnetic is obtained and is carried the aza gold/mesoporous carbon catalyst of palladium.The magnetic of the present invention carries the aza gold/mesoporous carbon catalyst Stability Analysis of Structures of palladium, catalytic performance is high, be prevented from the reunion of palladium Fe nanometer particles, can be applicable to remove the hexavalent chromium in water body.
Description
Technical field
The invention belongs to gold/mesoporous carbon catalyst field, and in particular to a kind of magnetic carry the aza gold/mesoporous carbon catalyst of palladium and its
Preparation method and application.
Background technology
Chromium mainly has two kinds of particle shapes, trivalent chromium and Cr VI in water body, and wherein Cr VI is that the generally acknowledged mankind kill
Hand.Because Cr VI Cr (VI) toxicity extremely strong, therefore be considered as one of three big severe pollutants in the world.Cr VI can pass through food
Thing chain, drinking-water multiple channel enter human body, and health is caused to have a strong impact on.Cr VI Cr (VI) is an a kind of conventional huge sum of money
Category, during industrial production, such as steel industry, apparel industry etc. have a wide range of applications.Due to chromic in life
Leakage and improper use, can often occur serious pollution of chromium, and this is the main source of Heavy-Metal-Contaminated Environments.Cr VI is a kind of
Strong carcinogen, and the source of the well-known disease of the mankind.Used as the industrial five poisonous creatures: scorpion, viper, centipede, house lizard, toad, Cr VI affects seed germination, suppresses biological
Cell mitogen, causes chromosomal structural variation.The World Health Organization issues a statement, and the risk that Cr VI has been found to includes
Increase DNA mutation and carcinogenicity and acute toxicity.And trivalent chromium comparatively toxicity is relatively low, with chemical inertness and difficult
To take in transfer, by as the nutriment played an important role by the mankind, the lipid-metabolism of animal and sugar.By Cr VI in water body
Being changed into chromic technology becomes needed for life, and the Cr (VI) in reduction minimizing waste water and underground water has caused very big
Concern, how efficient catalytic is reduced, and making the Cr VI in water body be changed into trivalent chromium also becomes the research emphasis of each subject.
At present, for the water remediation method of heavy metal pollution can be divided into method of chemical treatment, materialization treatment process, biology
Facture, redox facture, absorption method etc..Wherein in redox facture, bimetallic catalyst be apply the widest
General catalyst, but generally existing metallic is easy to reunite, water-soluble low problem.
Content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of Stability Analysis of Structures, catalytic performance
Magnetic that is high, being prevented from the reunion of palladium Fe nanometer particles carries the aza gold/mesoporous carbon catalyst of palladium, and accordingly provides one kind with chaff amine
Magnetic for carbon nitrogen source carries the preparation method of the aza gold/mesoporous carbon catalyst of palladium and answering in the process of water body containing hexavalent chromium
With.
For solving above-mentioned technical problem, the present invention is employed the following technical solutions：
A kind of magnetic carries the aza gold/mesoporous carbon catalyst of palladium, it is characterised in that catalyst carrier is aza mesoporous carbon, palladium
Nano-particle and Fe nanometer particles are supported in the surface and micropore of the aza mesoporous carbon.
Above-mentioned magnetic carries the aza gold/mesoporous carbon catalyst of palladium, it is preferred that the club shaped structure of the aza mesoporous carbon it
Between distance be 0.4 μm～0.5 μm, the particle diameter of the Pd nano particle is 40nm～50nm, the particle diameter of the Fe nanometer particles
For 40nm～50nm.
As a total technology design, present invention also offers a kind of above-mentioned magnetic carries the aza mesoporous carbon catalysis of palladium
The preparation method of agent, comprises the following steps：
S1, by palladium salt dissolving obtain palladium salt solution, aza for magnetic mesoporous carbon is added in the palladium salt solution and is obtained
Mixed liquor,
S2, formic acid is added to heating response in the mixed liquor, obtains magnetic and carry the aza gold/mesoporous carbon catalyst of palladium.
Further, in S1 steps, after palladium salt solution is adjusted pH for neutrality, then aza for magnetic mesoporous carbon is added to
In the palladium salt solution.
Above-mentioned preparation method, it is preferred that in the S1 steps, the aza mesoporous carbon of the magnetic adopt following preparation side
Method is prepared：
S1-1, by iron salt dissolved, be mixed to get complex solution with mesoporous silicon template and chaff amine；
S1-2, in the atmosphere of protective gas, the complex solution of the S1-1 steps is calcined at 600 DEG C～1000 DEG C
1h～4h obtains calcined product；
S1-3, the silicon template in the calcined product of the S1-2 steps is removed with sodium hydroxide solution, obtain magnetic azepine
Change mesoporous carbon.
Above-mentioned preparation method, it is preferred that in the S1-1 steps, the molysite are Fe (NO3)3·9H2O.Further
, the solvent for dissolving the molysite is absolute ethyl alcohol, and the molysite is 1g～1.1g: 10mL with the mass volume ratio of absolute ethyl alcohol
～15mL.Further, the mesoporous silicon template is SBA-15.Further, the Fe (NO3)3·9H2O, chaff amine and mesoporous
The mass volume ratio of silicon template SBA-15 is 1g～2g: 2mL～4mL: 1g～2g.
Above-mentioned preparation method, it is preferred that the temperature for removing silicon template in the S1-3 steps is 40 DEG C～100 DEG C, institute
The concentration for stating sodium hydroxide solution is 1M～4M.
Above-mentioned preparation method, it is preferred that the preparation method of mesoporous silicon template SBA-15 is as follows：
Tetraethyl orthosilicate is added in the hydrochloric acid solution of block copolymer containing P123, the laggard water-filling thermal response of heating water bath,
Hydrothermal product is obtained, by above-mentioned hydrothermal product roasting, mesoporous silicon template SBA-15 is obtained；The block copolymer P123 and positive silicon
The mass ratio of acetoacetic ester is 8: 17～23；The temperature of heating water bath is 30 DEG C～35 DEG C；The temperature of hydro-thermal reaction be 140 DEG C～
150 DEG C, the time of hydro-thermal reaction is 23h～25h；Sintering temperature is 530 DEG C～550 DEG C, and roasting time is 4h～5h.
Above-mentioned preparation method, it is preferred that palladium salt described in the S1 steps is PdCl2.Further, the palladium salt is molten
Liquid is dissolved in for palladium salt and obtains in HCl solution, and the palladium salt is 0.05g～0.1g: 5mL with the mass volume ratio of HCl solution
～10mL.Further, the palladium salt is 0.05g～0.1g with the mass ratio of the aza gold/mesoporous carbon catalyst of the magnetic:
0.5g～1g.
Above-mentioned preparation method, it is preferred that the concentration of formic acid described in the S2 steps is 3M.
Above-mentioned preparation method, it is preferred that the volume ratio of the formic acid and the mixed liquor is 10mL～15mL: 10mL～
15mL.
As a total technology design, present invention also offers a kind of above-mentioned magnetic carries the aza mesoporous carbon catalysis of palladium
The magnetic that agent or above-mentioned preparation method are prepared carries the aza gold/mesoporous carbon catalyst of palladium in the process of water body containing hexavalent chromium
In application.
Above-mentioned application, it is preferred that the application process is：The magnetic is carried the aza gold/mesoporous carbon catalyst of palladium to add
Oscillation treatment is carried out in the water body containing hexavalent chromium and sodium formate, the catalysis to hexavalent chromium is completed and is reduced.
Above-mentioned application, it is preferred that it is 150mg/L～1000mg/L that the concentration of the sodium formate solution is concentration.Enter one
Step, the concentration of the sodium formate is 600mg/L.
Above-mentioned application, it is preferred that the concentration of the hexavalent chromium is 50mg/L～200mg/L.Further, described
The pH value of water body solution is 2～7.Further, the addition that the magnetic carries the aza gold/mesoporous carbon catalyst of palladium is 4mg/
50mL～10mg/50mL.Further, the rotating speed of the vibration is 150rpm～200rpm, time of vibration be 2min～
120min, the temperature of oscillation treatment is 15 DEG C～40 DEG C.Further, the temperature of oscillation treatment is 30 DEG C.
Compared with prior art, it is an advantage of the current invention that：
(1) magnetic of the invention carries the aza gold/mesoporous carbon catalyst of palladium, with aza mesoporous carbon as carrier, nitrogen atom doping
In mesoporous carbon, compared with other mesoporous carbons, not only the meso-hole structure of mesoporous carbon is more stable, and can make Pd nano particle,
Fe nanometer particles distribution is more uniform, prevents the better of its reunion.Pd nano particle and Fe nanometer particles are supported on azepine
Change in the surface and micropore of mesoporous carbon, both ensure that magnetic and the catalytic of palladium Fe nanometer particles, and because palladium Fe nanometer particles
Synergy so that the aza gold/mesoporous carbon catalyst of supported palladium Fe nanometer particles to Cr VI in water body have preferably urges
Change reduction effect.
(2) magnetic of the invention carries the preparation method of the aza gold/mesoporous carbon catalyst of palladium, first aza Jie of synthesizing magnetic
Hole C catalyst, then palladium nano-particles be carried in the aza mesoporous carbon of magnetic well, not only there is high catalysis to reduce
Effect, and catalysis reduction can be realized in acidity, neutral environment.
(3) magnetic of the invention carries the preparation method of the aza gold/mesoporous carbon catalyst of palladium, using chaff amine as carbon source and nitrogen
Source, prepared magnetic carry the aza mesoporous carbon of palladium compared to the mesoporous carbon for adopting phenol to prepare for carbon source, and meso-hole structure is more
Stable, and Fe nanometer particles and Pd nano particle can be made to be more evenly distributed in its surface and micropore.
(4) magnetic of the invention carries the aza gold/mesoporous carbon catalyst of palladium Cr VI Cr (VI) in catalysis reduction treatment water body
In application, with sodium formate as reducing agent, can carry out in the neutrality, sour environment that pH is 2～7, suitable environment is loose, and
And catalysis degradation modulus reach more than 99%.
Magnetic is carried shown in the principle following equation of the aza gold/mesoporous carbon catalyst catalysis reduction of hexavalent chromium of palladium：
HCOO-+H2O→CO2+H3O++2e-；
Cr2O7 2-+14H3O++6e-→Cr3++21H2O；E0 (V)=+ 1.33.
Description of the drawings
Fig. 1 is the electron microscope that the magnetic of the embodiment of the present invention 1 carries the aza gold/mesoporous carbon catalyst of palladium, and wherein a figures are magnetic
The scanning electron microscope (SEM) photograph of the aza mesoporous carbon of palladium is carried, b figures are the transmission electron microscope picture that magnetic carries the aza mesoporous carbon of palladium.
Fig. 2 is the Fourier transform infrared spectroscopy figure that the magnetic of the embodiment of the present invention 1 carries the aza gold/mesoporous carbon catalyst of palladium.
Fig. 3 is the N that the magnetic of the embodiment of the present invention 1 carries the aza gold/mesoporous carbon catalyst of palladium2Adsorption-desorption figure and aperture point
Cloth curve map.
Fig. 4 is catalyzed also respectively for HCOONa, Pd-Fe/NMC, Fe/NMC, Fe/NMC+HCOONa, Pd-Fe/NMC+HCOONa
During raw water body hexavalent chromium Cr (VI), percent reduction and time changing curve figure is catalyzed.
Fig. 5 carries the aza gold/mesoporous carbon catalyst catalysis reduction water body hexavalent chromium of palladium for the magnetic of the embodiment of the present invention 1
During Cr (VI), the pH change curves of percent reduction and solution are catalyzed.
Fig. 6 carries the aza gold/mesoporous carbon catalyst catalysis reduction water body hexavalent chromium of palladium for the magnetic of the embodiment of the present invention 1
During Cr (VI), percent reduction and reaction temperature change curve is catalyzed.
Fig. 7 carries the aza gold/mesoporous carbon catalyst catalysis reduction water body hexavalent chromium of palladium for the magnetic of the embodiment of the present invention 1
During Cr (VI), percent reduction and different Cr (VI) initial concentration change curve is catalyzed.
Specific embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Raw material and instrument employed in following examples is commercially available.
Embodiment 1
A kind of magnetic of the present invention carries the aza gold/mesoporous carbon catalyst of palladium, and catalyst carrier is aza mesoporous carbon, and palladium is received
Rice corpuscles and Fe nanometer particles are supported in the surface and micropore of aza mesoporous carbon.
Wherein, the distance between club shaped structure of aza mesoporous carbon is 0.4 μm～0.5 μm, the particle diameter of Pd nano particle
For 40nm～50nm；The particle diameter of Fe nanometer particles is 40nm～50nm.
Above-mentioned magnetic carries the preparation method of the aza gold/mesoporous carbon catalyst of palladium, comprises the following steps：
(1) synthesising mesoporous silicon template SBA-15
8g block copolymer P123 are placed in hydrochloric acid solution and are dissolved, add 17g tetraethyl orthosilicates, heating water bath, temperature
Control is at 35 DEG C；Above-mentioned gained mixture is carried out hydro-thermal reaction in 140 DEG C of heating 24h, rear suction filtration is washed to neutrality, is air-dried；
Again hydrothermal product is put in resistance furnace, in atmosphere 550 DEG C of roasting 4h, obtains mesoporous silicon template SBA-15.
(2) the aza gold/mesoporous carbon catalyst of synthesizing magnetic
By 1.082g Fe (NO3)3·9H2O is dissolved in 10mL absolute ethyl alcohols, obtains iron salt solutions, in iron salt solutions
Mesoporous silicon template SBA-15 for adding 1000mg steps (1) to obtain and the chaff amine (chaff amine is used as carbon nitrogen source) of 2mL obtain polynary molten
Liquid.The complex solution of above-mentioned gained is heated 10h to be dried at 80 DEG C, then desciccate is placed in nitrogen in 900 DEG C
Lower calcining 2h obtains calcined product.The NaOH solution that the calcined product concentration of gained is 2M is removed silicon template at 90 DEG C,
Filter, washing dries at 40 DEG C, obtains the aza mesoporous carbon of magnetic, and be stored in the glove box full of nitrogen.
(3) prepare magnetic and carry the aza gold/mesoporous carbon catalyst of palladium
By 0.05g PdCl2It is dissolved in the HCl solution of 5mL, 1M, ultrasonic dissolution half an hour, temperature control are obtained at 60 DEG C
Palladium salt solution.Above-mentioned palladium salt solution is adjusted to neutral (in order to not allow the follow-up magnetic nitrogen for adding with the NaOH solution of 5mL, 1M
Hybrid mesoporous carbon and H therein+Reaction, it is ensured that the presence of source of iron), add aza Jie of magnetic obtained in 0.5g steps (2)
Hole carbon, obtains mixed liquor.Above-mentioned mixed liquor is placed on magnetic stirring apparatus after stirring 30min, by the formic acid of 10mL, 3M at 70 DEG C
Under the conditions of mix with above-mentioned mixed liquor, after stirring 4h (whipping process will also control temperature for 70 DEG C), carry out suction filtration, wash into
Property, then Magnetic Isolation and vacuum drying is carried out, and obtaining magnetic and carry the aza gold/mesoporous carbon catalyst of palladium, oxygen barrier is preserved.
The magnetic of embodiment 1 is carried the aza gold/mesoporous carbon catalyst of palladium carries out Electronic Speculum sign, and Fig. 1 is manufactured in the present embodiment
Magnetic carries the Electronic Speculum phenogram of the aza gold/mesoporous carbon catalyst of palladium, and wherein, a figures are the scanning electricity that magnetic carries the aza mesoporous carbon of palladium
Mirror figure, b figures are the transmission electron microscope picture that magnetic carries the aza mesoporous carbon of palladium.As shown in Figure 1, iron Pd nano particle uniform load is in nitrogen
In the surface and micropore of hybrid mesoporous carbon, the distance between aza mesoporous carbon club shaped structure is 0.4 μm～0.5 μm, and magnetic is received
The particle diameter of rice grain (Fe and Pd) is 40nm～50nm.It is Pd- that obtained magnetic carries the aza gold/mesoporous carbon catalyst numbering of palladium
Fe/NMC.
The magnetic of embodiment 1 is carried the aza gold/mesoporous carbon catalyst of palladium has carried out Fourier transform infrared experiment, referring to figure
2：Magnetic carries the aza mesoporous carbon wideband frequency band of palladium and concentrates on 3000cm-1There is absworption peak in place, this respectively with material in C-H
Key is corresponding with the stretching vibration characteristic peak of N-H keys；Two other concentrates on 1120cm-1The peak at place, corresponding to two kinds of nanoparticles
The stretching vibration characteristic peak of sub- C-O keys, represents mesoporous carbon and there is skeleton structure.The introducing of nitrogen causes the characteristic peak of C-N keys simultaneously
Stretch mode is in 1630cm-1Place.
The magnetic of embodiment 1 carries the aza gold/mesoporous carbon catalyst of palladium and has carried out N2Absorption-desorption is tested, in the Mike of 77K
Specific surface area analysis are carried out on 2020 analyzers, analysis result is referring to Fig. 3.As can be known from Fig. 3, magnetic carries the aza mesoporous carbon of palladium
Catalyst has IV type Standerd isotherms, and P/Po values are near 0.6～0.7；Specific surface area is about in 523.5m2·g-1Left
Right；Pore-size distribution peak value is mainly appeared as near 4.313nm and near 5.0nm；Pore volume is about in 0.68nm cm3·g-1.
Comparative example 1
A kind of aza gold/mesoporous carbon catalyst of magnetic, with mesoporous silicon as template, aza mesoporous carbon is carrier, iron nanoparticle
Son is supported in the surface and micropore of aza mesoporous carbon.
The preparation method of the aza gold/mesoporous carbon catalyst of above-mentioned magnetic, essentially identical with the preparation method of embodiment 1, which is not
It is only that with putting, this preparation method does not include step (3).The aza mesoporous carbon numbering of obtained magnetic is Fe/NMC.
Embodiment 2：Investigate the catalysed reductive that magnetic carries the aza gold/mesoporous carbon catalyst of palladium
Prepare solution of 3 batches of identicals per batches of 5 groups 50mL concentration for the Cr containing hexavalent chromium (VI) of 50mg/L, to each
5 groups for criticizing are separately added into 8mg HCOONa, 8mg Pd-Fe/NMC, 8mg Fe/NMC, 8mg Fe/NMC+8mgHCOONa, 8mg
Pd-Fe/NMC+8mg HCOONa.It is 2 to adjust pH value, in 30 DEG C, carries out catalytic reduction reaction under 150rpm speed conditions, vibrates
Time is 1h, takes 80 μ L of supernatant after taking solution 1.5mL Magnetic Isolations, determines supernatant heavy metal concentration, meter after being diluted to 8ml
Calculate chromic removal amount.Remaining part, after being diluted to 100ml, measures with atomic absorption instrument and ultraviolet spectrophotometry
After Pd-Fe/NMC process in solution total Cr and Cr (VI) concentration, calculate catalysis also commercial weight.3 batches of experimental results are averaged.
Experimental result as shown in figure 4, as shown in Figure 4, when Cr (VI) concentration is 50mg/L, only Pd-Fe/NMC+
HCOONa experimental groups catalysis reduction effect is substantially better than other groups, it is possible to achieve Cr (VI) to Cr (III) catalytic reduction efficiency is
99.97% high rate of rotation；And the experiment was quickly completed within 20 minutes；It is in first 10 points for reacting that Cr (VI) reduces 88%
Clock.HCOONa- lures the catalysis reduction rate of Cr (VI) in the presence of without Pd-Fe/NMC catalyst, and this reacted
The reduction rate of journey removes reaction speed to chromic much more slowly than when Pd-Fe/NMC catalyst is added under experimental conditions
Degree；As a result show the removal efficiency of Cr (VI) within the time of 20 minutes just to 35%.
Embodiment 3：Investigate different acid-base conditions to carry magnetic six in the aza gold/mesoporous carbon catalyst catalysis reduction water body of palladium
The impact of valency chromium ion Cr (VI).
Prepare 3 batches of identical water body solution, wherein per batch including that 4 groups of 50mL, concentration are 50mg/L containing hexavalent chromium
The solution of Cr (VI) and the HCOONa that concentration is 600mg/L, and 4 groups of solution are adjusted pH value respectively for 2,3,5,7.To per batch
In 4 groups of Cr containing hexavalent chromium (VI) solution, the magnetic for adding 8mg embodiments 1 to prepare carries the aza gold/mesoporous carbon catalyst of palladium, in
30 DEG C, carry out catalytic reduction reaction under 150rpm speed conditions, duration of oscillation is 1h.Take the solution after catalytic reduction reaction
1.5mL, takes 80 μ L of supernatant after Magnetic Isolation, determine the heavy metal concentration of supernatant, calculate chromic going after being diluted to 8mL
Except amount.Take after supernatant 1mL is diluted to 100mL, with atomic absorption instrument and ultraviolet spectrophotometry measurement through Pd-Fe/NMC at
After reason in solution total Cr and Cr (VI) concentration, calculate catalysis also commercial weight.The experimental result of above-mentioned 3 batches of solution is averaged.
Experimental result is as shown in figure 5, when pH value is 2.0,3.0,5.0 and 7.0 respectively, the clearance of corresponding chromium reaches respectively
To 99.97%, 99.89%, 99.68% and 99.33%, while the reaction was quickly completed in 20 minutes.Can also send out from Fig. 4
Existing, the removal efficiency of Cr VI Cr (VI) constantly diminishes and increases, the removal wherein when pH is 2 to chromium from 7 to 2 with pH
Efficiency highest, it could even be possible to reach more than 97%.
The formates (sodium formate) for only using, removes to chromic reduction, after pH is less than 2, with pH value of solution
Reduction catalyst does not increase to chromic removal efficiency, and change less substantially, or even has the trend of removal efficiency reduction.
And in the application, the aza gold/mesoporous carbon catalyst of palladium being carried using magnetic prepared by embodiment 1, under acid condition, treatment effect improves
The reason for：On the one hand, chromic reduction is carried out under HCOOH/HCOONa systems, adds H2SO4Both solution can ensure that
Acidity, contribute to H atom and Cr again6+Between electro transfer；On the other hand, low ph value be conducive to negatively charged formic acid and
Dichromic acid reaction is adsorbed onto catalyst composite surface, promotes the carrying out of catalytic reaction.
Embodiment 4：Investigating different catalytic reduction reaction temperature, the aza gold/mesoporous carbon catalyst catalysis of palladium is carried to magnetic also
The impact of hexavalent chromium Cr (VI) in raw water body.
Prepare 3 batches of identical water body solution, wherein per batch including that 4 groups of 50mL, concentration are 50mg/L containing hexavalent chromium
The solution of Cr (VI), wherein HCOONa concentration are 600mg/L, and 4 groups of solution are adjusted solution ph respectively for 2.To per 4 for criticizing
The aza gold/mesoporous carbon catalyst of the magnetic load palladium that adds 8mg embodiments 1 to prepare in group Cr containing hexavalent chromium (VI) solution, will be per
The reaction temperature of the 4 groups of water body solution that criticizes is respectively set to 15 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, carries out under 150rpm speed conditions
Catalytic reduction reaction, duration of oscillation are 80min.Above-mentioned solution 1.5mL is taken, and 80 μ L of supernatant are taken after Magnetic Isolation, 8mL is diluted to
Determine the heavy metal concentration of supernatant afterwards, calculate chromic removal amount.Taken after above-mentioned supernatant 1mL is diluted to 100mL again, fortune
The concentration of total Cr and Cr (VI) in solution after Pd-Fe/NMC process, meter with atomic absorption instrument and ultraviolet spectrophotometry measurement
Calculate catalysis also commercial weight.The experimental result of above-mentioned 3 batches of solution is averaged.
Experimental result as shown in fig. 6, when temperature is 30 DEG C, initial Cr (VI) clearance reaches 99.97%, and instead
Should complete in 20 minutes.In the presence of Pd-Fe/NMC, temperature has bigger influence power to catalysis reduction chromium, with temperature
Increase, Pd-Fe/NMC catalyst increases to 96.6% and 99.9% to chromic removal efficiency from 85.9%, reaches in temperature
No longer rise when 40 DEG C.
Embodiment 5：Investigating difference Cr (VI) initial concentration, the aza gold/mesoporous carbon catalyst catalysis reductive water of palladium is carried to magnetic
The impact of hexavalent chromium Cr (VI) in body.
Prepare 3 batches of identical water body solution, wherein per batch including that the hexavalent chromium Cr (VI) that 4 groups of 50mL, pH are 2.0 is molten
Liquid, wherein HCOONa concentration are 600mg/L, and are 50mg/L, 80mg/ by the initial concentration that 4 groups of solution adjust Cr (VI) respectively
L, 120mg/L, 200mg/L, to above-mentioned per batch 4 groups of solution in be separately added into the Pd-Fe/NMC catalyst of 8mg embodiments 1, in
30 DEG C, carry out catalytic reduction reaction under 150rpm speed conditions, the concussion time is 120min.Take above-mentioned solution 1.5mL, magnetic point
80 μ L of supernatant are taken after, determine the heavy metal concentration of supernatant, calculate chromic removal amount after being diluted to 8mL.Take again
State after supernatant 1mL is diluted to 100mL, with atomic absorption instrument and ultraviolet spectrophotometry measurement through Pd-Fe/NMC process after
The concentration of total Cr and Cr (VI) in solution, calculates catalysis also commercial weight.The experimental result of above-mentioned 3 batches of solution is averaged.
As shown with 7, the optimum initial concentration of Cr VI Cr (VI) is 80mg/L, wherein Cr VI Cr (VI) 30 to experimental result
Reduced by catalysis in minute completely.Additionally, with the rising of Cr VI Cr (VI) initial concentration, being catalyzed the significant decline of percent reduction.
When the initial concentration of Cr VI Cr (VI) is respectively 50mg/L, 80mg/L, 120mg/L, 200mg/L, corresponding catalysis reduction
Rate is respectively and reaches 100%, 97%, 73%, 54%.
Above example is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for this technology neck
For the those of ordinary skill in domain, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications
Should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of magnetic carries the aza gold/mesoporous carbon catalyst of palladium, it is characterised in that with aza mesoporous carbon as carrier, palladium nanoparticle
Son and Fe nanometer particles are supported in the surface and micropore of the aza mesoporous carbon.
2. magnetic according to claim 1 carries the aza gold/mesoporous carbon catalyst of palladium, it is characterised in that described aza mesoporous
The distance between club shaped structure of carbon is 0.4 μm～0.5 μm, and the particle diameter of the Pd nano particle is 40nm～50nm, the iron
The particle diameter of nano-particle is 40nm～50nm.
3. the magnetic described in a kind of claim 1 or 2 carries the preparation method of the aza gold/mesoporous carbon catalyst of palladium, it is characterised in that
Comprise the following steps：
S1, by palladium salt dissolving obtain palladium salt solution, aza for magnetic mesoporous carbon is added in the palladium salt solution and is mixed
Liquid；
S2, formic acid is added to heating response in the mixed liquor, obtains magnetic and carry the aza gold/mesoporous carbon catalyst of palladium.
4. preparation method according to claim 3, it is characterised in that in the S1 steps, the magnetic is aza mesoporous
Carbon is prepared using following preparation method：
S1-1, by iron salt dissolved, be mixed to get complex solution with mesoporous silicon template and chaff amine；
S1-2, in the atmosphere of protective gas, the complex solution of S1-1 steps is calcined at 600 DEG C～1000 DEG C 1h～
4h obtains calcined product；
S1-3, with sodium hydroxide solution remove S1-2 steps the calcined product in silicon template, obtain aza Jie of magnetic
Hole carbon.
5. preparation method according to claim 4, it is characterised in that in the S1-1 steps, the molysite are Fe
(NO3)3·9H2O；The solvent for dissolving the molysite is absolute ethyl alcohol, the mass volume ratio of the molysite and absolute ethyl alcohol be 1g～
1.1g: 10mL～15mL；The mesoporous silicon template is SBA-15；Fe (the NO3)3·9H2O, chaff amine and mesoporous silicon template SBA-
15 mass volume ratio is 1g～2g: 2mL～4mL: 1g～2g；
And/or, the temperature for removing silicon template in the S1-3 steps is 40 DEG C～100 DEG C, the concentration of the sodium hydroxide solution
For 1M～4M.
6. the preparation method according to any one of claim 3 to 5, it is characterised in that palladium salt described in the S1 steps
For PdCl2；The palladium salt solution is dissolved in for palladium salt and obtains in HCl solution, the mass volume ratio of the palladium salt and HCl solution
For 0.05g～0.1g: 5mL～10mL；The mass ratio of the palladium salt and the aza gold/mesoporous carbon catalyst of the magnetic be 0.05g～
0.1g: 0.5g～1g.
7. the preparation method according to any one of claim 3 to 5, it is characterised in that formic acid described in the S2 steps
Concentration be 3M；The formic acid is 10mL～15mL: 10mL～15mL with the volume ratio of the mixed liquor.
8. a kind of magnetic as claimed in claim 1 or 2 carries the aza gold/mesoporous carbon catalyst of palladium or as appointed in claim 3～7
The magnetic that preparation method described in one is prepared carries the aza gold/mesoporous carbon catalyst of palladium in the process of water body containing hexavalent chromium
In application.
9. application according to claim 8, it is characterised in that the application process is：The magnetic is carried palladium aza
Gold/mesoporous carbon catalyst is added in the water body containing hexavalent chromium and sodium formate and carries out oscillation treatment, completes to hexavalent chromium
Catalysis reduction.
10. application according to claim 9, it is characterised in that it is 150mg/L that the concentration of the sodium formate solution is concentration
～1000mg/L；The concentration of the hexavalent chromium is 50mg/L～200mg/L；The pH value of the water body solution is 2～7；Institute
The addition for stating the aza gold/mesoporous carbon catalyst of magnetic load palladium is 4mg/50mL～10mg/50mL；The rotating speed of the vibration is
150rpm～200rpm, the time of vibration is 2min～120min, and the temperature of oscillation treatment is 15 DEG C～40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610845700.XA CN106492866A (en) | 2016-09-23 | 2016-09-23 | Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610845700.XA CN106492866A (en) | 2016-09-23 | 2016-09-23 | Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106492866A true CN106492866A (en) | 2017-03-15 |
Family
ID=58290811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610845700.XA Pending CN106492866A (en) | 2016-09-23 | 2016-09-23 | Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106492866A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109622004A (en) * | 2018-09-26 | 2019-04-16 | 同济大学 | A kind of Ferrious material for electro-catalysis/nitrogen/carbon composite preparation method and applications |
| CN111621027A (en) * | 2020-04-29 | 2020-09-04 | 华南师范大学 | Preparation method and application of cationic porous material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007962A (en) * | 2012-12-14 | 2013-04-03 | 北京格林凯默科技有限公司 | Metal oxide assisted palladium carbon catalyst and preparation method thereof |
| CN104307512A (en) * | 2014-10-14 | 2015-01-28 | 武汉大学苏州研究院 | Supported palladium catalyst and preparation method and application thereof |
| CN104324690A (en) * | 2014-10-31 | 2015-02-04 | 湖南大学 | Magnetic two-peak mesoporous carbon containing iron-nickel double metals, preparation method and application thereof |
| CN105536867A (en) * | 2015-12-18 | 2016-05-04 | 浙江省冶金研究院有限公司 | Method for preparing coated-type palladium carbon catalyst |
-
2016
- 2016-09-23 CN CN201610845700.XA patent/CN106492866A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007962A (en) * | 2012-12-14 | 2013-04-03 | 北京格林凯默科技有限公司 | Metal oxide assisted palladium carbon catalyst and preparation method thereof |
| CN103007962B (en) * | 2012-12-14 | 2014-12-31 | 北京格林凯默科技有限公司 | Metal oxide assisted palladium carbon catalyst and preparation method thereof |
| CN104307512A (en) * | 2014-10-14 | 2015-01-28 | 武汉大学苏州研究院 | Supported palladium catalyst and preparation method and application thereof |
| CN104324690A (en) * | 2014-10-31 | 2015-02-04 | 湖南大学 | Magnetic two-peak mesoporous carbon containing iron-nickel double metals, preparation method and application thereof |
| CN105536867A (en) * | 2015-12-18 | 2016-05-04 | 浙江省冶金研究院有限公司 | Method for preparing coated-type palladium carbon catalyst |
Non-Patent Citations (1)
| Title |
|---|
| SISI LI ET AL: ""Catalytic reduction of hexavalent chromium by a novel nitrogen-functionalized magnetic ordered mesoporous carbon doped with Pd nanoparticles"", 《ENVIRON SCI POLLUT RES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109622004A (en) * | 2018-09-26 | 2019-04-16 | 同济大学 | A kind of Ferrious material for electro-catalysis/nitrogen/carbon composite preparation method and applications |
| CN109622004B (en) * | 2018-09-26 | 2020-05-29 | 同济大学 | Preparation method and application of iron-based metal/nitrogen/carbon composite material for electrocatalysis |
| CN111621027A (en) * | 2020-04-29 | 2020-09-04 | 华南师范大学 | Preparation method and application of cationic porous material |
| CN111621027B (en) * | 2020-04-29 | 2022-04-19 | 华南师范大学 | Preparation method and application of cationic porous material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | One-step synthesis of nitrogen and sulfur co-doped mesoporous graphite-like carbon nanosheets as a bifunctional material for tetracycline removal via adsorption and catalytic degradation processes: Performance and mechanism | |
| Zhao et al. | Ultrafast degradation of emerging organic pollutants via activation of peroxymonosulfate over Fe3C/Fe@ NCx: Singlet oxygen evolution and electron-transfer mechanisms | |
| Zhu et al. | Preparing copper doped carbon nitride from melamine templated crystalline copper chloride for Fenton-like catalysis | |
| Li et al. | Enhancement of Cr (VI) removal efficiency via adsorption/photocatalysis synergy using electrospun chitosan/g-C3N4/TiO2 nanofibers | |
| Xie et al. | Degradation of tetracycline hydrochloride through efficient peroxymonosulfate activation by B, N co-doped porous carbon materials derived from metal-organic frameworks: Nonradical pathway mechanism | |
| Chang et al. | Synthesis of magnetic graphene oxide–TiO2 and their antibacterial properties under solar irradiation | |
| CN106076393B (en) | Fe2O3 doping carbonitride/mesoporous graphitic carbon composite catalyst preparation method, product and application | |
| Gu et al. | Highly U (VI) immobilization on polyvinyl pyrrolidine intercalated molybdenum disulfide: Experimental and computational studies | |
| Li et al. | Flower-like direct Z-scheme WS2/Bi2O2CO3 photocatalyst with enhanced photocatalytic activity | |
| CN107983300A (en) | Biological carbon composite of manganese dioxide modification and its preparation method and application | |
| Liu et al. | Highly dispersed copper single-atom catalysts activated peroxymonosulfate for oxytetracycline removal from water: Mechanism and degradation pathway | |
| Huang et al. | Novel Au@ C modified g-C3N4 (Au@ C/g-C3N4) as efficient visible-light photocatalyst for toxic organic pollutant degradation: Synthesis, performance and mechanism insight | |
| Cheng et al. | Facile synthesis of reduced graphene oxide/silver nanoparticles composites and their application for detecting heavy metal ions | |
| CN107126971A (en) | A kind of preparation and application of compound CoP/g C3N4 photochemical catalysts | |
| Liang et al. | Facile synthesis of NiAl2O4/g-C3N4 composite for efficient photocatalytic degradation of tetracycline | |
| CN103480333A (en) | Compound grapheme absorption agent, method for preparing compound grapheme absorption agent and application of compound grapheme absorption agent | |
| CN107983295B (en) | Core-shell structure iron-copper bi-metal material and its preparation method and application | |
| CN110217850A (en) | A kind of method of antibiotic in photocatalytic degradation water body | |
| Yu et al. | Visible-light photocatalytic tetracycline degradation over nanodots-assembled N-ZrO2− x nanostructures: Performance, degradation pathways and mechanistic insight | |
| CN106492866A (en) | Magnetic carries aza gold/mesoporous carbon catalyst of palladium and its preparation method and application | |
| Jiang et al. | Characterization and application of expanded graphite modified with phosphoric acid and glucose for the removal of Ni (II) from aqueous solution | |
| Chen et al. | A novel pomegranate peel-derived biochar for highly efficient removal of sulfamethoxazole by activation of peroxymonosulfate through a non-radical pathway | |
| Liu et al. | 3D variable Co species carbon foam enhanced reactive oxygen species generation and ensured long-term stability for water purification | |
| CN104874349A (en) | Preparation method of three-dimensional mesoporous Fe3O4-C nano adsorption material | |
| He et al. | Microwave-assisted synthesis of amorphous cobalt nanoparticle decorated N-doped biochar for highly efficient degradation of sulfamethazine via peroxymonosulfate activation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170315 |
|
| WD01 | Invention patent application deemed withdrawn after publication |