CN106861738A - The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application - Google Patents

The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application Download PDF

Info

Publication number
CN106861738A
CN106861738A CN201510920930.3A CN201510920930A CN106861738A CN 106861738 A CN106861738 A CN 106861738A CN 201510920930 A CN201510920930 A CN 201510920930A CN 106861738 A CN106861738 A CN 106861738A
Authority
CN
China
Prior art keywords
preparation
catalyst
iron
phen
solvent
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
Application number
CN201510920930.3A
Other languages
Chinese (zh)
Inventor
杨启华
姚毅
郑圆圆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201510920930.3A priority Critical patent/CN106861738A/en
Publication of CN106861738A publication Critical patent/CN106861738A/en
Pending legal-status Critical Current

Links

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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
    • C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of preparation of the catalyst using CNT as supported carrier iron-nitrogen-carbon ternary active component.Comprise the following steps that：Appropriate soluble ferric iron salt and 1,10- Phen are dissolved in the middle of solvent under room temperature condition, by stirring until the two coordination is complete.To adding appropriate carbon nanotube carrier in the solution, and it is homogeneous to cause that the suspension reaches by ultrasound for a long time.The presoma of catalyst is obtained after the method such as natural drying or rotary evaporation removes alcohol solvent, the presoma is obtained into product after the time of specifying is processed in atmosphere of inert gases under 600-1000 degrees Celsius.

Description

The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application
Technical field
It is used for nitrobenzene derivative hydrogen as supported carrier iron-nitrogen-carbon activity component the present invention relates to CNT Change the method for preparing catalyst of reaction, it is specifically a kind of using CNT as carrier, containing nitrogen, carbon, Iron active component, the non-precious metal catalyst of the nitryl group being capable of on the reduction phenyl ring of chemo-selective high Preparation method.
Background technology
Carbon nano-tube material has just caused the wide of academic and industrial quarters since the eighties are found from last century General attention.This new carbon can regard the cylinder of several layers of limited graphite-structure curlings as, and it is unique One-dimentional structure, the electronic conductivity of hollow pattern and uniqueness can make it in functional material, catalyst carrier, The field such as analysis detection and electrochemistry is widely applied.Some research discoveries, CNT in recent years Tube chamber is inside and outside to have significant difference in nature in space structure, electronics atmosphere etc., and this species diversity can be to tube chamber The inside and outside catalytic active center for supporting causes tremendous influence.By using this species diversity, existing various high activities CNT supported catalyst be able to successfully develop (Angewandte Chemie International Edition,2011,50,4913-4917).On the other hand, the noble metal based on iron-nitrogen-carbon ternary component is substituted The correlative study of catalyst also high speed development in recent years.By the species of modulation presoma, proportioning and system Preparation Method, the catalyst of acquisition is in electrochemical oxygen reduction reaction, nitrobenzene derivative hydrogenation, double bond epoxy Excellent activity (Science, 2013,342,1073) has all been embodied during change etc..At the same time, with Noble metal catalyst also possesses chemo-selective such as high, high stability and antitoxin compared to this class catalyst The advantages such as change ability.Even so, too low activity causes that iron-nitrogen-carbon three-way catalyst is difficult to real realization Using.Based on background above, we are by combining CNT and iron-nitrogen-carbon ternary active in the middle of this patent Component, obtains the nitrobenzene derivative with chemo-selective high and hydrogenates instead using presoma cheap and easy to get Answer catalyst.It not only has good stability and chemo-selective, while there is high activity, can Effective for the hydro-reduction reaction containing sensitive group nitrobenzene derivative.
The content of the invention
It is an object of the invention to provide a kind of simple method to prepare CNT as carrier, iron-nitrogen-carbon As the catalyst of active component.The inventive method obtain material can be used for high activity, high selectivity it is non- Noble metal nitrobenzene derivative hydro-reduction reacts.
To achieve the above object, commodity in use carbon nano tube of the present invention is used as carrier, while using adjacent phenanthrene Sieve quinoline and containing molysite as nitrogen source and iron presoma, by the mixing for being pyrolyzed above component under an inert atmosphere Thing obtains product.Regulation iron content can control the activated centre ratio of material, and the product for obtaining has high living Property and high selectivity.
Can specifically operate as follows：
(1) prepared by iron, nitrogen precursor：The Phen solid of required quality is weighed, according to the amount ratio of material It is 1:2 to 1:4 ratio measures corresponding molysite, Phen and molysite is mixed and added into a certain amount of Solvent, keeps Phen+molysite:The scope of solvent is in 0.1g:50ml-0.5g:50ml or so.Stirring Or ultrasound causes that molysite and Phen are completely dissolved, and obtains clear claret solution.The solution is existed 40-60 degrees Celsius of stirring condition realizes the coordination completely of Phen and molysite；
(2) prepared by catalyst precursor：Weigh the CNT of required quality and be scattered in above-mentioned solution and work as In, realize being completely dispersed for CNT within continual ultrasonic 2-10 hours.By spontaneously dry, heating or The modes such as rotary evaporation remove solvent, obtain catalyst precursor；
(3) prepared by final products：By foregoing presoma under 600-1000 degrees Celsius in atmosphere of inert gases Lower pyrolysis 30-120 minutes.Black powder as final products are obtained after furnace temperature is reduced to room temperature.
Preparation method of the invention has the following advantages that：
1. material synthesis method is simple, mild condition；Reaction unit is simple, and course of reaction is not It is related to the use of inflammable small molecule, it is easy to control, it is safe；
2., using cheap organic ligand as nitrogen source, ammonia is not used, it is small to equipment damage, it is right Environment is without significantly pollution；
3. the high-temperature process time is shorter, and energy consumption is low；
4. catalyst chemical is selectively good, and activity is high.
Brief description of the drawings
Fig. 1 is that active component is wrapped in the transmission electron microscope of the catalyst inside CNT in embodiment 1 Photo；
Fig. 2 be embodiment 1 in active component be supported on carbon nanotube outer catalyst transmission electron microscope Photo；
Fig. 3 is the XRD diffraction patterns of different iron-holder catalyst in embodiment 1-3.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated, but it is not intended to limit each appended claims and wants Seek defined invention scope.
Embodiment 1
The mass fraction for preparing iron is 1.5% catalyst.0.043 gram of ferric trichloride solid is weighed, is added 0.1593 gram of Phen, adds 50 milliliters of ethanol afterwards, and stirring causes that molysite and Phen are complete Dissolving, obtains clear claret solution.The solution is flowed back 12 hours at 60 c makes molysite It is coordinated completely with Phen.Weigh in 0.7973 gram of material above-mentioned solution of addition, continual ultrasonic 4 is small When be completely dispersed CNT, then revolving remove solvent, obtain catalyst precursor.By presoma in It is pyrolyzed under nitrogen atmosphere under 800 degrees Celsius 120 minutes, furnace temperature is down to after room temperature and obtains black powder and be Catalyst.
Embodiment 2
The mass fraction for preparing iron is 3.0% catalyst.Preparation method consolidates ferric trichloride with reference to example 1 Weight is changed into 0.0871 gram, and Phen quality is changed to 0.3186 gram.
Embodiment 3
The mass fraction for preparing iron is 6.0% catalyst.Preparation method consolidates ferric trichloride with reference to example 1 Weight is changed into 0.1783 gram, and Phen quality is changed to 0.637 gram.
Table 1 is the reaction result of different substrates
Reaction condition：0.5mmol substrates, the catalyst of embodiment 1 relative to substrate 4.5mol%Fe, 4 milliliters of solvent (2ml H2O + 2ml THF), 130 DEG C, 5Mpa H2,a110 DEG C, 5Mpa H2。
Spread out for nitrobenzene as supported carrier iron-nitrogen-carbon activity component using CNT the present invention relates to one kind The method for preparing catalyst of biohydrogenation reaction.Particularly, iron is obtained using Phen and molysite coordination Nitrogen presoma；Part presoma is introduced inside CNT by ultrasound；Finally by heat under noble gas atmosphere Iron nitrogen presoma is converted into iron-nitrogen-carbon activity component by solution, and the active component is supported on carbon nanotube carrier Tube chamber in and tube chamber outside.The catalyst for obtaining is capable of the hydrogenation of efficient catalytic nitrobenzene derivative, With excellent chemo-selective, it is expected to substitute what is be widely used now in fields such as fine chemistry industry, pharmacy Noble metal catalyst.

Claims (9)

1. the preparation method of nitrobenzene derivative hydrogenation catalyst, it is characterised in that including following preparation Step：
(1) Phen solid is weighed, according to Phen:The amount proportion of iron substance is 2:1-4:1 Interval in add and soluble ferric iron salt and mix both；
(2) above-mentioned solid mixture is dissolved using solvent, the use of solvent during 0.1g-0.5g mixtures It is 50ml to measure；Further stir to realize Phen and iron ion in the range of 40-60 degree after dissolving Coordination completely；
(3) to CNT is added in above-mentioned solution, the quality of addition is according to mass ratio iron:Carbon nanometer Pipe=0.005-0.10；
(4) it is in sonic oscillation instrument that above-mentioned suspension is ultrasonic more than 2 hours；
(5) the above-mentioned homogeneous suspension for obtaining through the presoma for being dried to obtain catalyst preparation；
(6) by the presoma in being pyrolyzed 30-180 under atmosphere of inert gases under 600-1000 degrees Celsius Minute obtains final products.
2. preparation method according to claim 1, it is characterised in that：The soluble ferric iron salt bag Containing but be not limited to iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, second One or two or more kinds in acyl acetone iron.
3. preparation method according to claim 1, it is characterised in that：The solvent for being used includes But the one kind being not limited in water, ethanol or two kinds of mixtures of arbitrary proportion.
4. preparation method according to claim 1, it is characterised in that：Will be above-mentioned solid using solvent Can be aided in by methods such as stirring or ultrasounds in the course of dissolution of body mixture dissolving.
5. preparation method according to claim 1, it is characterised in that：Stirred in the range of 40-60 degree More than 12 hours time.
6. preparation method according to claim 1, it is characterised in that：The CNT for being used In 5-100nm, pipe thickness is 2-50nm to its internal diameter.
7. preparation method according to claim 1, it is characterised in that：The inert atmosphere is nitrogen One kind in gas or argon gas atmosphere or two kinds.
8. the catalyst that a kind of any preparation methods of claim 1-7 are obtained.
9. application of the solid catalyst in nitrobenzene derivative hydrogenation described in a kind of claim 8.
CN201510920930.3A 2015-12-11 2015-12-11 The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application Pending CN106861738A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510920930.3A CN106861738A (en) 2015-12-11 2015-12-11 The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510920930.3A CN106861738A (en) 2015-12-11 2015-12-11 The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application

Publications (1)

Publication Number Publication Date
CN106861738A true CN106861738A (en) 2017-06-20

Family

ID=59177359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510920930.3A Pending CN106861738A (en) 2015-12-11 2015-12-11 The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application

Country Status (1)

Country Link
CN (1) CN106861738A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108232209A (en) * 2017-12-18 2018-06-29 北京航空航天大学 Medium temperature metal-carbide framework compound counter-boring techniques are prepared for highly active Fe nitrogen C catalyst
CN113314719A (en) * 2021-04-09 2021-08-27 国联汽车动力电池研究院有限责任公司 Integrated cathode with high catalytic performance, preparation method thereof and battery
CN115608398A (en) * 2022-09-28 2023-01-17 天津大学 M-N-C catalyst and application thereof in synthesis of benzotriazole compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020136A (en) * 2007-03-03 2007-08-22 大连理工大学 Prepn of nanometer carbon material supported metal catalyst for hydrogenating chloronitrobenzene to synthesize chloroaniline
CN102806108A (en) * 2011-05-31 2012-12-05 中国科学院大连化学物理研究所 Method for dispersing metal and/or metal oxide in lumens of carbon nanotubes
CN103962139A (en) * 2013-02-05 2014-08-06 中国科学院大连化学物理研究所 Preparation method and application of graphene-supported non-noble metal electrocatalyst
CN104174421A (en) * 2014-08-08 2014-12-03 浙江大学 Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020136A (en) * 2007-03-03 2007-08-22 大连理工大学 Prepn of nanometer carbon material supported metal catalyst for hydrogenating chloronitrobenzene to synthesize chloroaniline
CN102806108A (en) * 2011-05-31 2012-12-05 中国科学院大连化学物理研究所 Method for dispersing metal and/or metal oxide in lumens of carbon nanotubes
CN103962139A (en) * 2013-02-05 2014-08-06 中国科学院大连化学物理研究所 Preparation method and application of graphene-supported non-noble metal electrocatalyst
CN104174421A (en) * 2014-08-08 2014-12-03 浙江大学 Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
RAJENAHALLY V. JAGADEESH ET AL.: ""Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines"", 《SCIENCE》 *
WEI CHEN ET AL.: ""Tuning of Redox Properties of Iron and Iron Oxides via Encapsulation within Carbon Nanotubes"", 《J. AM. CHEM. SOC》 *
XIULIAN PAN ET AL.: ""Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles"", 《NATURE MATERIALS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108232209A (en) * 2017-12-18 2018-06-29 北京航空航天大学 Medium temperature metal-carbide framework compound counter-boring techniques are prepared for highly active Fe nitrogen C catalyst
CN108232209B (en) * 2017-12-18 2021-06-08 北京航空航天大学 Medium-temperature carbonized metal skeleton compound hole expanding technology for preparing high-activity iron-nitrogen-carbon catalyst
CN113314719A (en) * 2021-04-09 2021-08-27 国联汽车动力电池研究院有限责任公司 Integrated cathode with high catalytic performance, preparation method thereof and battery
CN115608398A (en) * 2022-09-28 2023-01-17 天津大学 M-N-C catalyst and application thereof in synthesis of benzotriazole compounds
CN115608398B (en) * 2022-09-28 2024-04-30 天津大学 M-N-C catalyst and application thereof in synthesis of benzotriazole compounds

Similar Documents

Publication Publication Date Title
Wang et al. Facile synthesis of metal-organic frameworks/ordered mesoporous carbon composites with enhanced electrocatalytic ability for hydrazine
Lopa et al. A Ni-based redox-active metal-organic framework for sensitive and non-enzymatic detection of glucose
Yang et al. Highly dispersed AuPd alloy nanoparticles immobilized on UiO-66-NH2 metal-organic framework for the detection of nitrite
Haldorai et al. An enzyme-free electrochemical sensor based on reduced graphene oxide/Co3O4 nanospindle composite for sensitive detection of nitrite
Dong et al. Metal–organic framework MIL-53 (Fe): facile microwave-assisted synthesis and use as a highly active peroxidase mimetic for glucose biosensing
Meng et al. Facile synthesis of platinum-embedded zirconia/porous carbons tri-component nanohybrids from metal-organic framework and their application for ultra-sensitively detection of methyl parathion
Kokulnathan et al. A cerium vanadate interconnected with a carbon nanofiber heterostructure for electrochemical determination of the prostate cancer drug nilutamide
Zhai et al. MoS2 microflowers based electrochemical sensing platform for non-enzymatic glucose detection
CN106268631A (en) Graphene-noble metal nano particles Compound Water, aeroge and preparation method thereof, application
Shi et al. A new bifunctional electrochemical sensor for hydrogen peroxide and nitrite based on a bimetallic metalloporphyrinic framework
Fan et al. ZIF-90 with biomimetic Zn–N coordination structures as an effective nanozyme to mimic natural hydrolase
Lu et al. Hydrothermal synthesized urchin-like nickel-cobalt carbonate hollow spheres for sensitive amperometric detection of nitrite
Mo et al. Nitrogen-doped carbon dodecahedron embedded with cobalt nanoparticles for the direct electro-oxidation of glucose and efficient nonenzymatic glucose sensing
CN108927185A (en) A kind of oxygen reduction catalyst and preparation method thereof of the carbon nanotube loaded phosphatization Fe nanometer particles of Heteroatom doping
CN106861738A (en) The preparation of nitrobenzene derivative hydrogenation catalyst and catalyst and application
Jia et al. Electrocatalytically active cuprous oxide nanocubes anchored onto macroporous carbon composite for hydrazine detection
Chen et al. Solvent-free synthesis of N-doped carbon-based catalyst for high-efficient reduction of 4-nitrophenol
Zhang et al. Magnetically recyclable nanocomposites via lanthanide-based MOFs grown on natural sea sponge: Screening hydrogenation of nitrophenol to aminophenol
Sudha et al. NiCo2O4 nanorod: Synthesis and electrochemical sensing of carcinogenic hydrazine
CN109557138A (en) A kind of graphene-based gas sensing materials of Metal Palladium load and preparation and application
An et al. Fabrication of electrocatalytically active, cobalt-embedded nitrogen-doped ordered macroporous carbon for sensitive detection of nitrobenzene
CN111330565A (en) Carbon-loaded nano bismuth composite material and preparation method and application thereof
Song et al. Facile preparation of Prussian blue/polypyrrole hybrid nanofibers as robust peroxidase mimics for colorimetric detection of L-cysteine
CN107159287A (en) Pt/α‑MoC1‑xApplication of the loaded catalyst in catalytic hydrogenation reaction
Jia et al. Preparation of Ni, Co doped hollow carbon nanocage from core-shell structure ZIF-8@ ZIF-67 for nitrobenzene monitoring

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170620

WD01 Invention patent application deemed withdrawn after publication