CN110124722A - A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application - Google Patents
A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application Download PDFInfo
- Publication number
- CN110124722A CN110124722A CN201910501816.5A CN201910501816A CN110124722A CN 110124722 A CN110124722 A CN 110124722A CN 201910501816 A CN201910501816 A CN 201910501816A CN 110124722 A CN110124722 A CN 110124722A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- catalyst
- preparation
- metal
- doped carbon
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010953 base metal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000005416 organic matter Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 claims description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 239000013522 chelant Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 15
- 229940107698 malachite green Drugs 0.000 description 15
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 6
- 241000907663 Siproeta stelenes Species 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The present invention provides a kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application.The present invention selects hard template method to prepare the monatomic catalyst of metal, using amino-contained organism and organism containing chlorine as polymerized monomer, using transition metal salt as source metal, pass through the proportionate relationship and reaction condition between control accurate template, organic monomer, metallic salt, organic monomer can be achieved in the in-situ polymerization of template surface and synchronous chelate transitional metal ion, prepare the monoatomic metal catalyst of high exposure.This method for preparing catalyst can guarantee the load capacity of monoatomic metal to the full extent, and can avoid the appearance that nitrogen-doped carbon material wraps up metal oxide situation by Reasonable Regulation And Control preparation condition.Furthermore the also active advantage high, metal loss rate is low and power of regeneration is strong of the fenton catalyst of this method preparation.
Description
Technical field
The present invention relates to material preparation technical field more particularly to a kind of monatomic catalyst of nitrogen-doped carbon Base Metal and
Preparation method and application.
Background technique
Fenton oxidation technology is with ferrous ion (Fe2+) it is catalyst, with hydrogen peroxide (H2O2) carry out chemical oxidation
Wastewater treatment method.Fenton reagent is also referred to as by the system that ferrous ion and hydrogen peroxide form, it can generate the hydroxyl of strong oxidizing property
Base free radical generates organic free radical with hardly degraded organic substance in aqueous solution and is allowed to structure destruction, final oxygenolysis.Fenton
Oxidation technology is due to easy to operate, and the advantages that oxidability is strong is widely used, however there are iron ions to be easy to run off for Fenton's reaction,
The problems such as scum yield is big, and regeneration efficiency is low, and catalyst service life is short limits its further scale application.
Porous carbon materials are due to excellent with conductivity height, resistance to acid and alkali, large specific surface area and adjustable pore structure etc.
Point has been obtained in catalysis oxidation field and is quite widely applied, and iron ion, which is supported on porous carbon materials, to be passed through
The strong suction-operated of carbon material avoids the loss of iron ion to a certain extent, solves what iron ion in Fenton reagent was easy to run off
Problem.But when the carbon-supported catalysts being commonly used are used for catalytic oxidation treatment polluted water body, still remain reaction rate
Slowly, catalyst activity is poor, and required throwing amount is larger and catalyst stability is poor, the problem of can not reusing.In order into
One step improves the activity and stability of catalyst, researches and develops a kind of novel carbon-supported catalysts, to solve the problems, such as that Fenton reagent is intrinsic,
It has a very important significance.
Summary of the invention
For the carbon-supported catalysts being commonly used in the prior art for when handling polluted water body, there is reaction speed
Rate is slow, and catalyst activity is poor, and required throwing amount is larger and catalyst stability is poor, the problem of can not reusing, this hair
It is bright that a kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application is provided.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal, the preparation method include the following steps:
Step 1: soluble transition metal salt and template are added to the water, impregnate, it is dry, obtain presoma；
Step 2: the presoma, the amine-containing organic matter of liquid and liquid chlorinated organics are mixed, it is uniformly dispersed, flows back
Reaction, it is dry, obtain preliminary catalytic agent；
Step 3: the preliminary catalytic agent is carried out high temperature cabonization under inert atmosphere protection, secondary catalysts are obtained；
The secondary catalysts are immersed in acid solution or aqueous slkali and remove template agent removing by step 4, are washed, dry, obtain institute
State the monatomic catalyst of nitrogen-doped carbon Base Metal.
Compared with the existing technology, the preparation of the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal provided by the invention
Method has the advantages that
In the preparation method of existing polymer chelated mineral salt catalyst, due to metal salt and containing existing between carbon polymer
Stronger physisorption causes carbon containing polymer surfaces to be adsorbed with a large amount of metal salt, so that being carbonized subsequent
Metal salt is oxidized so that the catalyst surface finally prepared limits catalyst activity there are a large amount of metal oxide in journey
Further increase.The present invention uses template dispersed metal ion, is conducive to metal ion and is dispersed on carrier；Pass through
Organic monomer synchronous chelated metal ions during template in situ Polymerization generates carbon nitrogen carriers, avoid metal from
Physical absorption between son and carbon nitrogen carriers, not only increases the load capacity of metal salt, it is ensured that without metal oxygen in catalyst
Compound occurs, and significantly improves the activity of catalyst.
Meanwhile using amine-containing Orqanics Monomer and chlorinated organics monomer as the polymerization for preparing carbon nitrogen carriers in the present invention
The HCl that monomer can be such that polymerization process occurs rapidly, and remove in polymerization process can also build the acyclic acidic of polymer surfaces
Border, to guarantee at a certain temperature, metal ion during the synchronous chelated metal ions reaction of organic monomer in-situ polymerization
Will not oxidation by air generate metal oxide, for metal ion during participating in catalysis reaction, catalytic efficiency is obvious high
In metal oxide, therefore, the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal provided by the invention is remarkably improved
The catalytic activity of catalyst.In addition to this, the amino in amine-containing organic matter has reduction, so as to directly utilize property more
The catalyst containing bivalent metal ion is prepared in stable trivalent metal salt, avoids in preparation process metal to be oxidized as far as possible and asks
The appearance of topic.
The present invention generates the synchronous chelated metal ions of carbon nitrogen carriers in template in situ Polymerization by organic monomer
Metal ion activity component and carbon nitrogen catalysis material are organically combined, significantly improve rate of catalysis reaction, greatly reinforce by method
To the degradation effect of organic pollutant；Meanwhile catalyst prepared by the present invention can by the chelation between metal-N
The reunion of metal ion in preparation process is avoided, the loss of metal ion in catalytic reaction process can be also significantly reduced, improve
The power of regeneration of catalyst；And preparation method is simple, has broad application prospects.
Heretofore described inert gas is the inert gas of this field routine, such as nitrogen, helium.
Preferably, the soluble transition metal salt is iron chloride, frerrous chloride, cobalt chloride, nickel chloride, ferric nitrate, nitre
At least one of sour cobalt, ferrous nitrate or nickel nitrate.
It is furthermore preferred that the soluble transition metal salt is iron chloride.
Preferred transition metal salt is conducive to metal element chelate on carbon nitrogen carriers, improve metal ion and carrier it
Between binding force, reduce catalyst in active component loss, improve the activity and service life of catalyst.
Preferably, the template is SBA-16, calcium carbonate, γ-Al2O3, silica, MCM-41 or MCM-48.
It is furthermore preferred that the template is calcium carbonate.
Material structure and pattern directly affect catalytic performance, and the preparation method in the present invention has universality, using not
The monatomic catalyst of metal of various structure and pattern is prepared in isostructural template.
Currently preferred template can make the cellular structure of catalyst more excellent, and pore distribution is more uniform, make
Catalyst obtained has high-specific surface area and hierarchical porous structure, to provide more active sites for catalysis reaction, improves
The reactivity of catalyst, and preferred template is removed more easily by pickling or alkali cleaning in the follow-up process.
Preferably, the amine-containing organic matter of the liquid is amino-containing C3Aliphatic hydrocarbon.
Preferably, the amine-containing organic matter of the liquid is 1,2- propane diamine or 1,3- propane diamine.
It is furthermore preferred that the amine-containing organic matter is 1,2- propane diamine.
Preferably, the liquid chlorinated organics are the 1- chlorinated aliphatic hydrocarbon containing 1-4 carbon atom.
Preferably, the chlorinated organics be carbon trichloride, carbon tetrachloride, dichloroethanes, n-propyl chloride, dichloropropane or
1,4- dichloroetane.
It is furthermore preferred that the chlorinated organics are carbon tetrachloride.
By dehydrogenation and dechlorination polymerization occurs for preferred amine-containing organic matter and chlorinated organics, and polymerization reaction is rapid,
Carbon nitrogen skeleton can be quickly formed, good coordination environment is built, chelates metal ion and carbon nitrogen skeleton, and utilize nitrogen
Supplied for electronic acts on the power of regeneration that catalyst can be improved.
Preferably, in step 1, the molar ratio of the template, soluble metallic salt and water is 1:0.01-0.05:15-
35。
It is furthermore preferred that the molar ratio of the template, soluble metallic salt and water is 1:0.0179:16.7 in step 1.
Preferably, in step 2, the mass ratio of the amine-containing organic matter of the presoma, liquid and liquid chlorinated organics is 1:
1-5:5-10。
It is furthermore preferred that in step 2, the mass ratio of the amine-containing organic matter of the presoma, liquid and liquid chlorinated organics is
1:2.7:6.0。
The ratio of preferred each substance, is conducive to metal ion and is equably doped in carbon nitrogen skeleton, and in carbon nitrogen skeleton
N chelate, avoid metal ion more, cause metal ion mixing uneven, form more metal oxide, in turn
Cause digestion of metallic ion more in Fenton oxidation reaction；Or metal ion is less, the appearance of the bad problem of activity.
Optionally, in step 1, dip time 15-30min.
Preferably, in step 1, drying temperature is 100-120 DEG C, drying time 8-10h.
Preferably, in step 2, reflux temperature is 40-120 DEG C, reflux time 6-8h.
It is furthermore preferred that reflux temperature is 70 DEG C, reflux time 8h in step 2.
Optionally, in step 2, drying temperature is 110-130 DEG C, drying time 8-10h.
Preferably, in step 3, the heating rate of high temperature cabonization is 3-10 DEG C/min, and stopping temperature is 400-800 DEG C, is stopped
Staying the time is 4-6h.
It is furthermore preferred that in step 3, the heating rate of high temperature cabonization is 5 DEG C/min, and stopping temperature is 600 DEG C, when stop
Between be 5h.
Preferred reaction temperature, reaction time, drying temperature, drying time and high temperature cabonization mode, are conducive to construct
Specific surface area is high, structure and inoxidizability is stable, active site the is highly exposed monatomic catalyst of metal.
Preferably, the acid solution is hydrochloric acid solution or hydrofluoric acid solution, and the aqueous slkali is sodium hydroxide solution；It is described
The concentration of acid solution/or the aqueous slkali is 1-3mol/L.
The present invention also provides a kind of monatomic catalyst of nitrogen-doped carbon Base Metal, and the material is by above-mentioned preparation method system
It is standby.
The present invention also provides the above-mentioned monatomic catalyst of nitrogen-doped carbon Base Metal in catalyzing oxidizing degrading organic pollutant
In application.
The monatomic catalyst of the metal that the present invention is prepared has excellent catalytic activity, and metal ion is (such as ferrous iron
Ion) exist with the N in carbon nitrogen skeleton in the form chelated, metal ion is equably entrained in carbon nitrogen skeleton, realizes gold
The immobilization for belonging to ion, compared with traditional Fenton reagent, catalytic activity and degradation of the catalyst provided by the invention to organic matter
Efficiency significantly improves, moreover, avoiding metal ion readily soluble appearance gone wrong during Fenton oxidation, significantly improves and urges
The service life of agent can effectively solve the intrinsic of current fenton catalyst as the fenton catalyst of degradation of organic substances
Problem.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo for the monatomic catalyst of nitrogen-doped carbon Base Metal that embodiment 1 is prepared；
Fig. 2 is the X-ray diffraction (XRD) that Fig. 1 is the monatomic catalyst of nitrogen-doped carbon Base Metal that embodiment 1 is prepared
Map；
Fig. 3 is transmission electron microscope (TEM) photo for the monatomic catalyst of nitrogen-doped carbon Base Metal that embodiment 2 is prepared；
Fig. 4 is transmission electron microscope (TEM) photo for the monatomic catalyst of nitrogen-doped carbon Base Metal that embodiment 3 is prepared；
Fig. 5 is transmission electron microscope (TEM) photo for the monatomic catalyst of nitrogen-doped carbon Base Metal that embodiment 4 is prepared.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
In order to better illustrate the present invention, it is illustrated below by embodiment is further.
Embodiment 1
Step 1: the Iron trichloride hexahydrate of 1.0g (0.01mol) calcium carbonate and 0.0483g (0.000179mol) is dissolved in
In the deionized water of 3ml, 25min is stood, 110 DEG C of dry 9h obtain FeCl3@CaCO3Presoma；
Step 2: taking 1.0g FeCl3@CaCO3Presoma, 2.7g 1,2- propane diamine and 6.0g carbon tetrachloride in flask,
Ultrasonic disperse 5~10 minutes, in 70 DEG C of reflux 8h, 120 DEG C of dry 10h；
Step 3: solid after drying is placed in tube furnace, vacuumize, lead to nitrogen, be carbonized 5h at 600 DEG C, heating speed
Degree is 5 DEG C/min, obtains carbonized product；
Step 4: washing carbonized product with the HCl solution of 1mol/L, repeatedly washed with deionized water, it is dry at 110 DEG C
8h obtains to obtain the monatomic catalyst of nitrogen-doped carbon Base Metal (Fe-N-C catalyst).
The catalytic performance of catalyst is evaluated using the method for Fenton oxidation degrading malachite green, prepares 50mg/L malachite
Clear water solution, takes 100mL in conical flask, weighs M-N-C catalyst 0.03g, is added in conical flask, adds the dioxygen of 15 μ L
Conical flask is put into shaking table by water, and shaking table temperature is 25 DEG C, revolving speed 120rpm, is reacted 5 hours, and malachite green removal rate is
96.8%.After repeating five times according to above-mentioned experiment condition, the removal rate of malachite green is 89.5%.
Transmission electron microscope (TEM) photo for the Fe-N-C catalyst being prepared is as shown in Figure 1.
The XRD spectrum for the Fe-N-C catalyst being prepared is as shown in Fig. 2, it can be seen from the figure that inside in catalyst
There is no a presence of metallic crystal, it was demonstrated that metal is existing in the form of an ion.
The BET test result of calcium carbonate template in catalyst and embodiment 1 prepared by embodiment 1 is as shown in table 1.
Table 1
| Material | Specific surface area (m2/g) | Kong Rong (cm3/g) | Aperture (nm) |
| Calcium carbonate | 35.691 | 30.512 | 0.208 |
| Fe-N-C catalyst | 306.871 | 0.073 | 3.811 |
Embodiment 2
A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal:
Step 1: the Iron trichloride hexahydrate of 0.5g (0.005mol) calcium carbonate and 0.049g (0.00018mol) is dissolved in
In the deionized water of 3ml, 20min is stood, 110 DEG C of dry 9h obtain FeCl3@CaCO3Presoma；
Step 2: taking 0.5g FeCl3@CaCO3Presoma, 2.5g 1,2- propane diamine and 5.0g carbon tetrachloride in flask,
Ultrasonic disperse 5~10 minutes, in 70 DEG C of reflux 8h, 120 DEG C of dry 9h；
Step 3: the solid after drying is placed in tube furnace, vacuumize, lead to nitrogen, be carbonized 6h at 400 DEG C, heating
Speed is 3 DEG C/min, obtains carbonized product；
Step 4: washing carbonized product with the HCl solution of 2mol/L, repeatedly washed with deionized water, it is dry at 110 DEG C
9h obtains the monatomic catalyst of nitrogen-doped carbon Base Metal (Fe-N-C catalyst).
Transmission electron microscope (TEM) photo of the monatomic catalyst of nitrogen-doped carbon Base Metal is as shown in Figure 3.
The catalytic performance of catalyst is evaluated using the method for Fenton oxidation degrading malachite green, prepares 50mg/L malachite
Clear water solution, takes 100mL in conical flask, weighs Fe-N-C catalyst 0.03g, is added in conical flask, adds the dioxygen of 15 μ L
Conical flask is put into shaking table by water, and shaking table temperature is 25 DEG C, revolving speed 120rpm, is reacted 5 hours, and malachite green removal rate is
90.5%.After repeating five times according to above-mentioned experiment condition, the removal rate of malachite green is 80.3%.
Embodiment 3
A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal:
Step 1: the Iron trichloride hexahydrate of 1.0g (0.01mol) calcium carbonate and 0.049g (0.000103mol) is dissolved in
In the deionized water of 3ml, 30min is stood, 100 DEG C of dry 10h obtain FeCl3@CaCO3Presoma；
Step 2: taking 1.0g FeCl3@CaCO3Presoma, 1.7g 1,2- propane diamine and 5.2g carbon tetrachloride in flask,
Ultrasonic disperse 5~10 minutes, in 70 DEG C of reflux 8h, 120 DEG C of dry 8h；
Step 3: the solid after drying is placed in tube furnace, vacuumize, lead to nitrogen, be carbonized 4h at 800 DEG C, heating
Speed is 10 DEG C/min, obtains carbonized product；
Step 4: washing carbonized product with the HCl solution of 3mol/L, repeatedly washed with deionized water, it is dry at 110 DEG C
8h obtains the monatomic catalyst of nitrogen-doped carbon Base Metal (Fe-N-C catalyst).
Transmission electron microscope (TEM) photo of the monatomic catalyst of nitrogen-doped carbon Base Metal is as shown in Figure 4.
The catalytic performance of catalyst is evaluated using the method for Fenton oxidation degrading malachite green, prepares 50mg/L malachite
Clear water solution, takes 100mL in conical flask, weighs Fe-N-C catalyst 0.03g, is added in conical flask, adds the dioxygen of 15 μ L
Conical flask is put into shaking table by water, and shaking table temperature is 25 DEG C, revolving speed 120rpm, is reacted 5 hours, and malachite green removal rate is
85.7%.After repeating five times according to above-mentioned experiment condition, the removal rate of malachite green is 73.6%.
Embodiment 4
A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal:
Step 1: the Iron trichloride hexahydrate of 1.0g (0.01mol) calcium carbonate and 1.28g (0.00049mol) is dissolved in 6ml
Deionized water in, stand 150min, 120 DEG C of dry 8h obtain FeCl3@CaCO3Presoma；
Step 2: taking 1.0g FeCl3@CaCO3Presoma, 3.5g 1,2- propane diamine and 7.6g carbon tetrachloride in flask,
Ultrasonic disperse 5~10 minutes, in 70 DEG C of reflux 8h, 120 DEG C of dry 9h；
Step 3: the solid after drying is placed in tube furnace, vacuumize, lead to nitrogen, be carbonized 5h at 600 DEG C, heating
Speed is 5 DEG C/min, obtains carbonized product；
Step 4: washing carbonized product with the HCl solution of 1mol/L, repeatedly washed with deionized water, it is dry at 110 DEG C
8h obtains the monatomic catalyst of nitrogen-doped carbon Base Metal (Fe-N-C catalyst).
Transmission electron microscope (TEM) photo of the monatomic catalyst of nitrogen-doped carbon Base Metal is as shown in Figure 5.
The catalytic performance of catalyst is evaluated using the method for Fenton oxidation degrading malachite green, prepares 50mg/L malachite
Clear water solution, takes 100mL in conical flask, weighs Fe-N-C catalyst 0.03g, is added in conical flask, adds the dioxygen of 15 μ L
Conical flask is put into shaking table by water, and shaking table temperature is 25 DEG C, revolving speed 120rpm, is reacted 5 hours, and malachite green removal rate is
88.3%.After repeating five times according to above-mentioned experiment condition, the removal rate of malachite green is 80.3%.
Embodiment 5-9
The preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal of embodiment 5-9 is same as Example 1, specific anti-
Answer condition referring to table 1.
1 embodiment 5-9 reaction condition of table
In embodiment 5-9, when template is silica, washed in step 4 using the sodium hydroxide solution of 1-3mol/L
Carbide is washed, template is removed；When template is SBA-16, MCM-41, MCM-48, the hydrogen of 1-3mol/L is used in step 4
Fluorspar acid solution washs carbide, removes template；Template is γ-Al2O3When, carbon is washed using the hydrochloric acid solution of 1-3mol/L
Compound removes template.
Comparative example 1
This comparative example provides a kind of preparation method of monatomic catalyst of metal:
Step 1: 2.7g melamine is dissolved in methanol, 0.0483g (0.000179mol) ferric chloride (FeCl36H2O) is molten
Yu Shuizhong after mixing above two solution, 1.0g (0.01mol) calcium carbonate is added under agitation, is uniformly dispersed, stands
30min obtains presoma in 110 DEG C of dry 8h；
Step 2: the presoma in step 1 is warming up to 600 DEG C under nitrogen atmosphere protection, heating rate is 5 DEG C/
Min, be carbonized 5h, obtains catalyst intermediate；
Step 3: the catalyst intermediate prepared in step 2 is cleaned with the hydrochloric acid solution of 1-3mol/L, it is dry, it obtains
Catalyst.
The catalytic performance of catalyst is evaluated using the method for Fenton oxidation degrading malachite green, prepares 50mg/L malachite
Clear water solution, takes 100mL in conical flask, weighs catalyst 0.03g, is added in conical flask, adds the hydrogen peroxide of 15 μ L, will bore
Shape bottle is put into shaking table, and shaking table temperature is 25 DEG C, revolving speed 120rpm, and after reaction 5 hours, malachite green removal rate is
75.3%.After repeating five times according to above-mentioned experiment condition, the removal rate of malachite green is 59.7%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal, which comprises the steps of:
Step 1: soluble transition metal salt and template are added to the water, impregnate, it is dry, obtain presoma；
Step 2: the presoma, the amine-containing organic matter of liquid and liquid chlorinated organics are mixed, it is uniformly dispersed, back flow reaction,
It is dry, obtain preliminary catalytic agent；
Step 3: the preliminary catalytic agent is carried out high temperature cabonization under inert atmosphere protection, secondary catalysts are obtained；
The secondary catalysts are immersed in acid solution or aqueous slkali and remove template agent removing by step 4, are washed, dry, obtain the nitrogen
Adulterate the monatomic catalyst of carbon based metal.
2. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as described in claim 1, which is characterized in that it is described can
Dissolubility transition metal salt is iron chloride, frerrous chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate, ferrous nitrate or nickel nitrate
At least one of；And/or
The template is SBA-16, calcium carbonate, γ-Al2O3, silica, MCM-41 or MCM-48.
3. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as claimed in claim 1 or 2, which is characterized in that institute
Stating the amine-containing organic matter of liquid is amino-containing C3Aliphatic hydrocarbon；And/or
The liquid chlorinated organics are the 1- chlorinated aliphatic hydrocarbon containing 1-4 carbon atom.
4. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as claimed in claim 3, which is characterized in that the liquid
The amine-containing organic matter of state is 1,2- propane diamine or 1,3- propane diamine；And/or
The liquid chlorinated organics are carbon trichloride, carbon tetrachloride, dichloroethanes, n-propyl chloride, dichloropropane or 1,4- bis-
Chlorobutane.
5. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as described in claim 1, which is characterized in that step 1
In, the molar ratio of the template, soluble metallic salt and water is 1:0.01-0.05:15-35；And/or
In step 2, the mass ratio of the amine-containing organic matter of the presoma, liquid and liquid chlorinated organics is 1:1-5:5-10.
6. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as described in claim 1, which is characterized in that step 1
In, drying temperature is 100-120 DEG C, drying time 8-10h；And/or
In step 2, reflux temperature is 40-120 DEG C, reflux time 6-8h.
7. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as described in claim 1, which is characterized in that step 3
In, the heating rate of high temperature cabonization is 3-10 DEG C/min, and stopping temperature is 400-800 DEG C, residence time 4-6h.
8. the preparation method of the monatomic catalyst of nitrogen-doped carbon Base Metal as described in claim 1, which is characterized in that the acid
Solution is hydrochloric acid solution or hydrofluoric acid solution, and the aqueous slkali is sodium hydroxide solution；The acid solution and/or the aqueous slkali
Concentration be 1-3mol/L.
9. a kind of monatomic catalyst of nitrogen-doped carbon Base Metal, which is characterized in that mixed by the described in any item nitrogen of claim 1-8
The preparation method of the miscellaneous monatomic catalyst of carbon based metal is prepared.
10. the monatomic catalyst of nitrogen-doped carbon Base Metal as claimed in claim 9 is in catalysis Fenton oxidation degradable organic pollutant
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910501816.5A CN110124722A (en) | 2019-06-11 | 2019-06-11 | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910501816.5A CN110124722A (en) | 2019-06-11 | 2019-06-11 | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110124722A true CN110124722A (en) | 2019-08-16 |
Family
ID=67581068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910501816.5A Pending CN110124722A (en) | 2019-06-11 | 2019-06-11 | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110124722A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110743602A (en) * | 2019-11-21 | 2020-02-04 | 河北科技大学 | Composite photocatalyst and preparation method and application thereof |
| CN111054417A (en) * | 2019-12-17 | 2020-04-24 | 国网山东综合能源服务有限公司 | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof |
| CN112569963A (en) * | 2019-09-27 | 2021-03-30 | 财团法人工业技术研究院 | Catalyst, method for forming the same and method for removing volatile organic compounds |
| CN112675856A (en) * | 2021-01-25 | 2021-04-20 | 郑州大学 | Hyaluronic acid modified FeCo bimetallic synergistic monatomic catalyst and preparation method and application thereof |
| CN112768712A (en) * | 2019-10-21 | 2021-05-07 | 中国科学院福建物质结构研究所 | Composite, preparation method thereof, catalyst containing composite and electrochemical neutralization energy battery |
| CN113318767A (en) * | 2021-06-22 | 2021-08-31 | 邯郸市赵都精细化工有限公司 | Catalyst for preparing amino acid by ammoniating carbonyl acid and preparation method and application thereof |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
| CN114367295A (en) * | 2020-10-15 | 2022-04-19 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013116754A1 (en) * | 2012-02-01 | 2013-08-08 | Stc.Unm | Cathode catalysts for fuel cells |
| CN104971760A (en) * | 2015-06-25 | 2015-10-14 | 浙江大学 | Preparation method of macroporous carbon oxygen reduction catalyst containing sulfur, nitrogen and transition metal element |
| CN106622244A (en) * | 2016-12-31 | 2017-05-10 | 中南民族大学 | Nitrogen-doped carbon material encapsulated cobalt catalyst and method of using the catalyst to prepare secondary amine compounds |
| CN106784871A (en) * | 2016-11-23 | 2017-05-31 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of nitrogen-doped carbon area load mononuclear catalyst |
| CN107308976A (en) * | 2017-07-08 | 2017-11-03 | 陕西理工大学 | A kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application |
| CN108187717A (en) * | 2017-12-27 | 2018-06-22 | 浙江大学 | A kind of Fe-N compounds doping carried catalyst, preparation method and application |
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
| CN109225306A (en) * | 2018-10-26 | 2019-01-18 | 清华大学 | Monatomic catalyst and catalysis process for low-carbon dehydrogenation of hydrocarbons producing light olefins |
-
2019
- 2019-06-11 CN CN201910501816.5A patent/CN110124722A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013116754A1 (en) * | 2012-02-01 | 2013-08-08 | Stc.Unm | Cathode catalysts for fuel cells |
| CN104971760A (en) * | 2015-06-25 | 2015-10-14 | 浙江大学 | Preparation method of macroporous carbon oxygen reduction catalyst containing sulfur, nitrogen and transition metal element |
| CN106784871A (en) * | 2016-11-23 | 2017-05-31 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of nitrogen-doped carbon area load mononuclear catalyst |
| CN106622244A (en) * | 2016-12-31 | 2017-05-10 | 中南民族大学 | Nitrogen-doped carbon material encapsulated cobalt catalyst and method of using the catalyst to prepare secondary amine compounds |
| CN107308976A (en) * | 2017-07-08 | 2017-11-03 | 陕西理工大学 | A kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application |
| CN108187717A (en) * | 2017-12-27 | 2018-06-22 | 浙江大学 | A kind of Fe-N compounds doping carried catalyst, preparation method and application |
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
| CN109225306A (en) * | 2018-10-26 | 2019-01-18 | 清华大学 | Monatomic catalyst and catalysis process for low-carbon dehydrogenation of hydrocarbons producing light olefins |
Non-Patent Citations (2)
| Title |
|---|
| XUNING LI ET AL.: "Single Cobalt Atoms Anchored on Porous N-Doped Graphene with Dual Reaction Sites for Efficient Fenton-like Catalysis", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 陈昆柏等: "《农业固体废物处理与处置》", 30 November 2016, 河南科学技术出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112569963A (en) * | 2019-09-27 | 2021-03-30 | 财团法人工业技术研究院 | Catalyst, method for forming the same and method for removing volatile organic compounds |
| CN112569963B (en) * | 2019-09-27 | 2023-08-08 | 财团法人工业技术研究院 | Catalyst, method for forming the same and method for removing volatile organic compounds |
| CN112768712A (en) * | 2019-10-21 | 2021-05-07 | 中国科学院福建物质结构研究所 | Composite, preparation method thereof, catalyst containing composite and electrochemical neutralization energy battery |
| CN112768712B (en) * | 2019-10-21 | 2022-04-19 | 中国科学院福建物质结构研究所 | Composite, preparation method thereof, catalyst containing composite and electrochemical neutralization energy battery |
| CN110743602A (en) * | 2019-11-21 | 2020-02-04 | 河北科技大学 | Composite photocatalyst and preparation method and application thereof |
| CN111054417A (en) * | 2019-12-17 | 2020-04-24 | 国网山东综合能源服务有限公司 | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof |
| CN111054417B (en) * | 2019-12-17 | 2023-01-31 | 国网山东综合能源服务有限公司 | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof |
| CN114367295A (en) * | 2020-10-15 | 2022-04-19 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
| CN114367295B (en) * | 2020-10-15 | 2023-04-18 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
| CN112675856A (en) * | 2021-01-25 | 2021-04-20 | 郑州大学 | Hyaluronic acid modified FeCo bimetallic synergistic monatomic catalyst and preparation method and application thereof |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
| CN113318767A (en) * | 2021-06-22 | 2021-08-31 | 邯郸市赵都精细化工有限公司 | Catalyst for preparing amino acid by ammoniating carbonyl acid and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110124722A (en) | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application | |
| CN109626670B (en) | Porous Fe/C/N composite material and preparation method thereof | |
| CN109382092A (en) | Ozone oxidation catalyst and preparation method thereof based on the balloon borne body of active gama-alumina | |
| CN109894115A (en) | A kind of preparation method of the modified active carbon catalyst for the processing of class Fenton | |
| CN106040239A (en) | Controllable high-dispersion nano simple-substance metal/carbon composite material preparation method and electrical catalytic application thereof | |
| CN107020144B (en) | Magnetic N doping redox graphene composite catalyst and its preparation method and application | |
| CN110694691A (en) | photo-Fenton catalyst, preparation method and application method | |
| CN105771968A (en) | Method for preparing loaded catalyst for heterogeneous phase ozone oxidizing | |
| CN109569729B (en) | Supported bimetal advanced oxidation catalyst, preparation method and analysis method of each enhanced function contribution of supported bimetal advanced oxidation catalyst | |
| CN106881111A (en) | Composite bismuth vanadium photocatalyst of cuprous oxide and silver-colored mutual load and its preparation method and application | |
| CN109382107A (en) | Ozone oxidation catalyst and preparation method thereof based on absorbent charcoal carrier | |
| CN103990452A (en) | Catalyst and catalyst carrier for deep treatment of waste water and preparation methods of catalyst and catalyst carrier | |
| CN106955728A (en) | A kind of preparation method of high efficiency load type ozone oxidation catalyst and application | |
| CN106881090A (en) | A kind of ozone catalytic oxidation catalyst method of modifying | |
| CN110152639A (en) | The preparation method of modified aluminium oxide supports and the preparation method and application of supported bi-metallic oxide catalyst | |
| CN114797917B (en) | High-activity cobalt-based catalyst with pH self-buffering capacity and preparation method and application thereof | |
| CN109529814A (en) | A kind of counter opal catalysis material of visible optical drive, preparation method and its degradation of organic pollutants in water body is removed | |
| CN113198517B (en) | High-dispersion cobalt-iron bimetallic catalyst and preparation method and application thereof | |
| CN106964333B (en) | Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone | |
| CN113244945B (en) | Preparation method of heterogeneous Fenton catalyst for wastewater treatment | |
| CN110302819A (en) | Bimetallic magnetic Nano porous carbon ozone catalyst and application derived from a kind of MOFs | |
| CN115591587A (en) | MoS 2 Hydrophilic sponge, preparation method thereof and application thereof in assisted fenton | |
| CN109433224A (en) | A kind of Fenton's reaction catalyst and preparation method thereof | |
| CN114768809A (en) | Defect-state catalytic membrane derived from metal organic framework and preparation method and application thereof | |
| CN109663589B (en) | Cerium-titanium oxide mesoporous millimeter ball ozone catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190816 |
|
| RJ01 | Rejection of invention patent application after publication |