CN109647355A - A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide - Google Patents

A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide Download PDF

Info

Publication number
CN109647355A
CN109647355A CN201811529517.4A CN201811529517A CN109647355A CN 109647355 A CN109647355 A CN 109647355A CN 201811529517 A CN201811529517 A CN 201811529517A CN 109647355 A CN109647355 A CN 109647355A
Authority
CN
China
Prior art keywords
spinning
growth
manganese dioxide
situ
solution
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
CN201811529517.4A
Other languages
Chinese (zh)
Inventor
厉宗洁
康卫民
刘雍
程博闻
赵义侠
李晓捷
庄旭品
鞠敬鸽
李磊
王利媛
邓南平
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.)
Tianjin Polytechnic University
Original Assignee
Tianjin Polytechnic University
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 Tianjin Polytechnic University filed Critical Tianjin Polytechnic University
Priority to CN201811529517.4A priority Critical patent/CN109647355A/en
Publication of CN109647355A publication Critical patent/CN109647355A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds

Abstract

The present invention relates to a kind of preparation methods of efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide, it is after preparing redox graphene doping ultra-fine polymer nano fibrous membrane by electrostatic spinning, it is grown obtained by one layer of manganese dioxide in its surface in situ, its feature includes the configuration of 1) spinning solution, 2) electrostatic spinning, 3) Situ Hydrothermal growth three steps of manganese dioxide.Nano-fibre supported type adsorbent produced by the present invention has compared with high adsorption lead ion, has broad application prospects in heavy metal ion field.

Description

A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide
Technical field
The present invention relates to a kind of preparation methods of efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide, and in particular in conjunction with Electrostatic spinning technique and hydrothermal growth prepare a kind of fine polymer nano fibrous membrane load manganese dioxide (MnO2) efficient lead The preparation method of ion adsorbent belongs to functional high molecular fibre technical field.
Technical background
Nano-metal-oxide has a wide range of applications in removal of heavy metal ions field, mainly includes Fe2O3、Fe3O4、 ZnO、Al2O3、CeO2、MnO2、Mn3O4Equal nano-oxides.Wherein, nanometer MnO2Due to biggish specific surface area, surface There is stronger adsorptivity to heavy metal ion with microcellular structure and containing great amount of hydroxy group, and then obtained the wide of researcher General concern.However, in practical adsorption process, nanometer MnO2Due to surface energy with higher, easily reunite;Meanwhile how By the nanometer MnO after absorption2It is still a problem to be solved that adsorbent is separated from water body.
In order to solve this problem,Etc. first reported a kind of cellulose acetate load MnO2Adsorbent, this It can be easy to separate (BRAND O M S B.GALEMBECK F.Copper, lead from solution after kind adsorbent absorption and zinc adsorption on MnO2-impregnated cellulose acetate[J].Colloids& Surfaces, 1990,48 (4): 351-362.).Luo et al. develops a kind of by MnO2Nanoparticle spontaneously deposits to poly- third Then the method on alkene nitrile nanofibre surface passes through poly- pyrrole that is, first in one strata pyrroles of polyacrylonitrile nanofiber surface aggregate The redox reaction between potassium permanganate is coughed up by the MnO of generation2Nanoparticle deposit to nanofiber surface (LUO C, WANG J Q, JIA P, et al.Hierarchically structured polyacrylonitrile nanofiber mat as highly efficient lead adsorbent for water treatment[J].Chemical Engineering Journal, 2015,262:775-784.).
The present invention inquires into out a kind of fine polymer nano fibrous membrane growth in situ MnO2The preparation method of adsorbent.Pass through The adsorbent of this method preparation is because it is with biggish specific surface area and MnO2The homoepitaxial of nanometer sheet makes it have excellent Lead ion absorption property.Here is specific summary of the invention.
Summary of the invention
The present invention relates to a kind of fine polymer nano fibrous membrane growth in situ MnO2The preparation method of adsorbent, using this The technical solution of invention can prepare a kind of efficient adsorbents for lead ion pyrolytic, ultra-fine to be capable of providing biggish specific surface area, reduction The introducing of graphene oxide (RGO) can make MnO2Nanometer sheet is uniformly grown in fiber surface, and then provides more for adsorbent More active sites.Superfine nano tunica fibrosa growth in situ MnO prepared by the present invention2Adsorbent is in heavy metal ion adsorbed neck Domain has broad application prospects.
A kind of preparation method of efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide of the present invention, feature exist In, comprising:
(1) configuration of spinning solution: a certain amount of redox graphene powder is added to containing a certain amount of four hexyls bromination In the high polymeric solution of ammonium, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;The high polymer is cellulose acetate, nylon 6; The high polymeric solution concentration is 8~20%;The redox graphene accounts for the polymer dope quality percentage Than being 0.1~0.3%;The four hexyl bromination ammonium concentrations are 0.05~0.15mol L-1
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, at room temperature, relative humidity 20 using method of electrostatic spinning ± 10%, spinning voltage is 15~35kV, and receiving distance is 10~20cm, and feed flow rate is 0.5~1.5mL/h, and reduction is made Graphene oxide doped ultra-fine polymer nano fibrous membrane;
(3) growth in situ manganese dioxide: a certain amount of potassium permanganate is dissolved into deionized water, fibre prepared by previous step It ties up film to take out, be added in liquor potassic permanganate;It is added dropwise into above-mentioned solution after 1h is stirred at room temperature in a certain amount of concentrated sulfuric acid, it will be above-mentioned Mixture is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, and reaction terminates, and tunica fibrosa taking-up deionized water repeated flushing is dried It is dry, growth in situ manganese dioxide adsorbents for lead ion pyrolytic is made;The mass fraction 0.01~0.1% of the liquor potassic permanganate; The mass percent that the concentrated sulfuric acid accounts for the liquor potassic permanganate is 1~3%.
It states technical solution and can be seen that the present invention and ultra-fine polymer nano fibrous membrane is prepared using electrospinning process, By the way that RGO is added in spinning solution, redox reaction, the MnO of generation then occur between RGO and potassium permanganate2Nanometer sheet It is uniformly grown in its surface, so that superfine nano tunica fibrosa growth in situ MnO be made2Adsorbent.The adsorbent is to lead ion Adsorptivity with higher and reusability.
Advantages of the present invention is as follows compared with prior art:
(1) present invention uses a step electrostatic spinning technique, by the way that a certain amount of four hexyls bromination is added into polymer solution Ammonium prepares fine polymer nano fibrous membrane, and wherein minimum fiber diameter can reach 5nm, and it is with higher to assign the tunica fibrosa Specific surface area.
(2) present invention is by being added a certain amount of RGO into spinning solution, and in hydrothermal reaction process, RGO and potassium permanganate occur Redox reaction, to make MnO2Nanometer sheet is uniformly grown in fiber surface.
(3) superfine nano tunica fibrosa growth in situ MnO provided by the present invention2Adsorbent is to lead ion suction with higher Attached property, and there is good recycling.
Picture and text are briefly described
Fig. 1 is the ultra-fine nylon 6/nanometer fiber growth in situ MnO prepared using the embodiment of the present invention 12Adsorbent is swept Retouch Electronic Speculum schematic diagram.
Fig. 2 is the ultra-fine cellulose acetate nanofiber growth in situ MnO prepared using the embodiment of the present invention 52Absorption The scanning electron microscope schematic diagram of agent.
Specific embodiment
Embodiment 1
(1) configuration of spinning solution: 50mg redox graphene powder is taken to be added to containing tetra- hexyl ammonium bromide of 1.0g In 6 solution of nylon that mass fraction is 18%, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, spinning technology parameter are as follows: room temperature using method of electrostatic spinning Under, relative humidity is 20 ± 5%, spinning voltage 30kV, and receiving distance is 15cm, and feed flow rate is 1.0mL/h, and reduction is made The ultra-fine nylon 6/nanometer tunica fibrosa of graphene oxide doped;
(3) growth in situ manganese dioxide: 0.13g potassium permanganate is dissolved into 30mL deionized water, is prepared by previous step Tunica fibrosa take out, be added in liquor potassic permanganate;It, will be upper after into above-mentioned solution, 1h is stirred at room temperature in the dropwise addition 0.7g concentrated sulfuric acid It states mixture and is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, reaction terminates, by tunica fibrosa taking-up deionized water repeated flushing, Growth in situ MnO is made in drying2Adsorbents for lead ion pyrolytic.Fig. 1 is the ultra-fine nylon 6/nanometer prepared using the embodiment of the present invention 1 Fiber growth in situ MnO2The scanning electron microscope schematic diagram of adsorbent.10mg adsorbent obtained above is taken, 30mL concentration is added to For the Pb of 100mg/L2+Adsorption liquid;Adsorption temp is 25 DEG C;Adsorption time is for 24 hours;Adsorption liquid pH value is 6.After the completion of absorption, adopt With residue Pb in icp ms (ICP, Varian 715-ES, Varian company, the U.S.) test solution2+'s Concentration obtains the adsorbent to Pb2+Adsorbance be 308.6mg/g.
Embodiment 2
(1) configuration of spinning solution: 100mg redox graphene powder is taken to be added to containing tetra- hexyl ammonium bromide of 1.5g In 6 solution of nylon that mass fraction is 14%, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, spinning technology parameter are as follows: room temperature using method of electrostatic spinning Under, relative humidity is 20 ± 5%, spinning voltage 35kV, and receiving distance is 15cm, and feed flow rate is 0.6mL/h, and reduction is made The ultra-fine nylon 6/nanometer tunica fibrosa of graphene oxide doped;
(3) growth in situ manganese dioxide: 0.25g potassium permanganate is dissolved into 30mL deionized water, is prepared by previous step Tunica fibrosa take out, be added in liquor potassic permanganate;It, will be upper after into above-mentioned solution, 1h is stirred at room temperature in the dropwise addition 1.3g concentrated sulfuric acid It states mixture and is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, reaction terminates, by tunica fibrosa taking-up deionized water repeated flushing, Growth in situ MnO is made in drying2Adsorbents for lead ion pyrolytic.10mg adsorbent obtained above is taken, being added to 30mL concentration is The Pb of 100mg/L2+Adsorption liquid;Adsorption temp is 25 DEG C;Adsorption time is for 24 hours;Adsorption liquid pH value is 6.After the completion of absorption, use Icp ms (ICP, Varian 715-ES, Varian company, the U.S.) test residue Pb in solution2+It is dense Degree, obtains the adsorbent to Pb2+Adsorbance be 328.7mg/g.
Embodiment 3
(1) configuration of spinning solution: 60mg redox graphene powder is taken to be added to containing tetra- hexyl ammonium bromide of 0.8g In the cellulose acetate solution that mass fraction is 9%, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, spinning technology parameter are as follows: room temperature using method of electrostatic spinning Under, relative humidity is 40 ± 10%, spinning voltage 40kV, and receiving distance is 15cm, and feed flow rate is 0.8mL/h, is made also The former ultra-fine cellulose acetate nano fibrous membrane of graphene oxide doped;
(3) growth in situ manganese dioxide: with embodiment 1.10mg adsorbent obtained above is taken, being added to 30mL concentration is The Pb of 100mg/L2+Adsorption liquid;Adsorption temp is 25 DEG C;Adsorption time is for 24 hours;Adsorption liquid pH value is 6.After the completion of absorption, use Icp ms (ICP, Varian 715-ES, Varian company, the U.S.) test residue Pb in solution2+It is dense Degree, obtains the adsorbent to Pb2+Adsorbance be 343.6mg/g.
Embodiment 4
(1) configuration of spinning solution: 80mg redox graphene powder is taken to be added to containing tetra- hexyl ammonium bromide of 0.8g In 6 solution of nylon that mass fraction is 16%, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, spinning technology parameter are as follows: room temperature using method of electrostatic spinning Under, relative humidity is 20 ± 5%, spinning voltage 30kV, and receiving distance is 15cm, and feed flow rate is 0.5mL/h, and reduction is made The ultra-fine nylon 6/nanometer tunica fibrosa of graphene oxide doped;
(3) growth in situ manganese dioxide: 0.05g potassium permanganate is dissolved into 30mL deionized water, is prepared by previous step Tunica fibrosa take out, be added in liquor potassic permanganate;It, will after into above-mentioned solution, 1h is stirred at room temperature in the dropwise addition 0.27g concentrated sulfuric acid Said mixture is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, and reaction terminates, tunica fibrosa taking-up is rushed repeatedly with deionized water It washes, dries, growth in situ MnO is made2Adsorbents for lead ion pyrolytic.10mg adsorbent obtained above is taken, being added to 30mL concentration is The Pb of 100mg/L2+Adsorption liquid;Adsorption temp is 25 DEG C;Adsorption time is for 24 hours;Adsorption liquid pH value is 6.After the completion of absorption, use Icp ms (ICP, Varian 715-ES, Varian company, the U.S.) test residue Pb in solution2+It is dense Degree, obtains the adsorbent to Pb2+Adsorbance be 258.7mg/g.
Embodiment 5
(1) configuration of spinning solution: 150mg redox graphene powder is taken to be added to containing tetra- hexyl ammonium bromide of 0.5g In the cellulose acetate solution that mass fraction is 11%, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
(2) previous step spinning solution electrostatic spinning: is subjected to spinning, spinning technology parameter are as follows: room temperature using method of electrostatic spinning Under, relative humidity is 20 ± 5%, spinning voltage 40kV, and receiving distance is 15cm, and feed flow rate is 0.6mL/h, and reduction is made The ultra-fine cellulose acetate nano fibrous membrane of graphene oxide doped;
(3) growth in situ manganese dioxide: 0.10g potassium permanganate is dissolved into 30mL deionized water, is prepared by previous step Tunica fibrosa take out, be added in liquor potassic permanganate;It, will be upper after into above-mentioned solution, 1h is stirred at room temperature in the dropwise addition 0.3g concentrated sulfuric acid It states mixture and is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, reaction terminates, by tunica fibrosa taking-up deionized water repeated flushing, Growth in situ MnO is made in drying2Adsorbents for lead ion pyrolytic.Fig. 2 is the ultra-fine acetate fiber prepared using the embodiment of the present invention 5 Plain nanofiber growth in situ MnO2The scanning electron microscope schematic diagram of adsorbent.10mg adsorbent obtained above is taken, is added to 30mL concentration is the Pb of 100mg/L2+Adsorption liquid;Adsorption temp is 25 DEG C;Adsorption time is for 24 hours;Adsorption liquid pH value is 6.Absorption After the completion, using in icp ms (ICP, Varian 715-ES, Varian company, the U.S.) test solution Remaining Pb2+Concentration, obtain the adsorbent to Pb2+Adsorbance be 234.3mg/g.

Claims (1)

1. a kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide characterized by comprising
(1) configuration of spinning solution: a certain amount of redox graphene powder is added to containing a certain amount of four hexyls ammonium bromide In high polymeric solution, ultrasonic disperse 0.5h obtains electrostatic spinning liquid;
The high polymer is cellulose acetate, nylon 6;
The high polymeric solution concentration is 8~20%;
It is 0.1~0.3% that the redox graphene, which accounts for the polymer dope mass percent,;
The four hexyl bromination ammonium concentrations are 0.05~0.15mol L-1
(2) electrostatic spinning: by previous step spinning solution using method of electrostatic spinning carry out spinning, at room temperature, relative humidity be 20 ± 10%, spinning voltage is 15~35kV, and receiving distance is 10~20cm, and feed flow rate is 0.5~1.5mL/h, and oxygen reduction is made Graphite alkene adulterates ultra-fine polymer nano fibrous membrane;
(3) growth in situ manganese dioxide: a certain amount of potassium permanganate is dissolved into deionized water, tunica fibrosa prepared by previous step It takes out, is added in liquor potassic permanganate;It is added dropwise into above-mentioned solution after 1h is stirred at room temperature in a certain amount of concentrated sulfuric acid, by above-mentioned mixing Object is transferred to hydrothermal reaction kettle, 60 DEG C of reaction 6h, and reaction terminates, and tunica fibrosa taking-up deionized water repeated flushing is dried, system Obtain growth in situ manganese dioxide adsorbents for lead ion pyrolytic;
The mass fraction 0.01~0.1% of the liquor potassic permanganate;
The mass percent that the concentrated sulfuric acid accounts for the liquor potassic permanganate is 1~3%.
CN201811529517.4A 2018-12-11 2018-12-11 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide Pending CN109647355A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811529517.4A CN109647355A (en) 2018-12-11 2018-12-11 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811529517.4A CN109647355A (en) 2018-12-11 2018-12-11 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide

Publications (1)

Publication Number Publication Date
CN109647355A true CN109647355A (en) 2019-04-19

Family

ID=66114165

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811529517.4A Pending CN109647355A (en) 2018-12-11 2018-12-11 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide

Country Status (1)

Country Link
CN (1) CN109647355A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111135802A (en) * 2020-01-19 2020-05-12 浙江大学 Preparation method for constructing water treatment biomembrane by modifying manganese dioxide particles with silk fibroin planar wires
CN111422977A (en) * 2020-01-19 2020-07-17 浙江大学 Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102275903A (en) * 2011-05-24 2011-12-14 东华大学 Preparation method of graphene and manganese dioxide composite material
CN102709061A (en) * 2012-07-03 2012-10-03 电子科技大学 Graphene-cladding manganese dioxide combination electrode material and method for producing same
CN106129356A (en) * 2016-07-14 2016-11-16 扬州大学 A kind of preparation method of hollow meso-porous titanium dioxide manganese pipe/sulfur composite
CN106925220A (en) * 2017-04-22 2017-07-07 杨彦成 A kind of preparation method of manganese dioxide/carbon composite nano tube
CN107557894A (en) * 2017-08-01 2018-01-09 东华大学 A kind of efficiently two-dimension netted superfine nanofiber water-oil separating material of high flux and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102275903A (en) * 2011-05-24 2011-12-14 东华大学 Preparation method of graphene and manganese dioxide composite material
CN102709061A (en) * 2012-07-03 2012-10-03 电子科技大学 Graphene-cladding manganese dioxide combination electrode material and method for producing same
CN106129356A (en) * 2016-07-14 2016-11-16 扬州大学 A kind of preparation method of hollow meso-porous titanium dioxide manganese pipe/sulfur composite
CN106925220A (en) * 2017-04-22 2017-07-07 杨彦成 A kind of preparation method of manganese dioxide/carbon composite nano tube
CN107557894A (en) * 2017-08-01 2018-01-09 东华大学 A kind of efficiently two-dimension netted superfine nanofiber water-oil separating material of high flux and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHIMIN LI ET AL.: "Preparation of a two-dimensional flexible MnO2/graphene thin film and its application in a supercapacitor", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111135802A (en) * 2020-01-19 2020-05-12 浙江大学 Preparation method for constructing water treatment biomembrane by modifying manganese dioxide particles with silk fibroin planar wires
CN111422977A (en) * 2020-01-19 2020-07-17 浙江大学 Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate

Similar Documents

Publication Publication Date Title
Ye et al. Facile assembled biochar-based nanocomposite with improved graphitization for efficient photocatalytic activity driven by visible light
Cai et al. High-performance supercapacitor electrode materials from cellulose-derived carbon nanofibers
Peng et al. Electrospun carbon nanofibers and their hybrid composites as advanced materials for energy conversion and storage
Zhou et al. Preparation of CuWO4@ Cu2O film on copper mesh by anodization for oil/water separation and aqueous pollutant degradation
Wei et al. 2020 roadmap on pore materials for energy and environmental applications
CN103225135B (en) Porous carbon fiber and preparation method thereof and application
CN106192201B (en) A kind of graphene fiber non-woven fabrics and preparation method thereof
CN102971900B (en) The manufacture method of proton-conductive films
CN105057003B (en) A kind of nano titania preparation method of composite film
US7070753B2 (en) Modification of nanotubes oxidation with peroxygen compounds
Thavasi et al. Electrospun nanofibers in energy and environmental applications
CN105161312B (en) A kind of carbon nano-fiber graphene composite aerogel and its collaboration process for assembly preparing
CN102120619B (en) Preparation method of brain-coral-shaped birnessite type manganese dioxide
Yuan et al. Synthesis and utilization of RuO 2· xH 2 O nanodots well dispersed on poly (sodium 4-styrene sulfonate) functionalized multi-walled carbon nanotubes for supercapacitors
KR101127307B1 (en) Composite materials comprising carbon nanotubes and metal carbonates
CN103480399B (en) Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof
Wang et al. Poly (ethyleneimine) nanofibrous affinity membrane fabricated via one step wet-electrospinning from poly (vinyl alcohol)-doped poly (ethyleneimine) solution system and its application
Wang et al. Selected-control hydrothermal synthesis of α-and β-MnO2 single crystal nanowires
CN101770869B (en) Method for preparing titanium dioxide films for dye-sensitized solar battery
US7413723B2 (en) Methods of oxidizing multiwalled carbon nanotubes
Zhang et al. Controlled growth of BiOCl with large {010} facets for dye self-photosensitization photocatalytic fuel cells application
Hao et al. Controllable electrostatic self-assembly of sub-3 nm graphene quantum dots incorporated into mesoporous Bi 2 MoO 6 frameworks: efficient physical and chemical simultaneous co-catalysis for photocatalytic oxidation
Wang et al. Hierarchical structured MnO2@ SiO2 nanofibrous membranes with superb flexibility and enhanced catalytic performance
TWI326723B (en)
WO2009098812A1 (en) Carbon catalyst, slurry containing the carbon catalyst, process for producing carbon catalyst, and fuel cell, storage device, and environmental catalyst each employing carbon catalyst

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190419