CN105945298A - Preparation method for hollow palladium nanospheres - Google Patents

Preparation method for hollow palladium nanospheres Download PDF

Info

Publication number
CN105945298A
CN105945298A CN201610261081.XA CN201610261081A CN105945298A CN 105945298 A CN105945298 A CN 105945298A CN 201610261081 A CN201610261081 A CN 201610261081A CN 105945298 A CN105945298 A CN 105945298A
Authority
CN
China
Prior art keywords
preparation
palladium
hollow
hollow palladium
nanospheres
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.)
Granted
Application number
CN201610261081.XA
Other languages
Chinese (zh)
Other versions
CN105945298B (en
Inventor
陈煜�
汉术和
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.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal 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 Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN201610261081.XA priority Critical patent/CN105945298B/en
Publication of CN105945298A publication Critical patent/CN105945298A/en
Application granted granted Critical
Publication of CN105945298B publication Critical patent/CN105945298B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0549—Hollow particles, including tubes and shells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B22F1/0655—Hollow particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method for hollow palladium nanospheres. The preparation method comprises the steps that polyethyleneimine serves as a stabilizer, and ascorbic acid serves as a reducing agent; cuprous oxide nanospheres are synthesized at first; and then, the cuprous oxide nanospheres are used as a mold plate, hydrazine hydrate is used as a reducing agent, and potassium tetrachloropalladate or palladium chloride is reduced into the hollow palladium nanospheres which are regular in shape, uniform in size and good in dispersibility and stability through a hydrothermal reduction method. The preparation method for the hollow palladium nanospheres is simple and economical, and the prepared hollow palladium nanospheres show excellent electro-catalysis activity and stability to a formic acid catalytic reaction, have potential application prospects in the direct formic acid fuel cell field and are suitable for industrial large-scale production.

Description

A kind of preparation method of hollow palladium nanosphere
Technical field
The present invention relates to the preparation method of a kind of Pd nano particle, particularly relate to the preparation of a kind of hollow palladium nanosphere Method, this Pd nano particle shows higher catalysis activity and stability as catalyst to formic acid.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) with hydrogen as fuel owing to price is high, without suitable hydrogen source and The problems such as less than 0 DEG C Nafion membrane icing, also fail to commercialization so far.DMFC (DMFC) Have fuel handling and easy to use, volume is little and specific energy advantages of higher, but methanol is poisonous, volatile, high Inflammable, and easily cause battery performance to decline through Nafion membrane.Research in recent years finds, formic acid is a kind of Preferably methanol alternative fuel, direct methanoic acid fuel cell (DFAFC) has lot of advantages, as nontoxic in formic acid, Nonflammable etc..Owing to Nafion membrane having between sulfonic acid group and formate anion repulsive interaction, therefore, formic acid Much lower to the permeability ratio methanol of Nafion membrane, DFAFC receives more and more attention.
In DFAFC, formic acid oxidation on palladium catalyst is mainly carried out by direct way, and therefore palladium is urged Agent is more much better than platinum catalyst to the electro catalytic activity of formic acid oxidation.Therefore palladium catalyst increasingly comes into one's own. But, owing to palladium reserves are rare, how under the activity and selectivity premise improving palladium-based catalyst, to reduce palladium Consumption is still the study hotspot in this field.
Show according to previously research: owing to the performance of palladium catalyst is had relatively by particle diameter, pattern and the crystal face of palladium particle Big impact, therefore, the palladium nanostructured of design pattern and size tunable seems most important.Such as: by { 100} The small size Pd nano particle that crystal face is constituted to the catalytic performance of formic acid ratio by { 110} and { 111} crystal face is constituted Pd nano particle is much better.At present, the palladium nanostructured of different-shape, as octahedra in nanometer tetrahedron, nanometer, Nanosphere, nano wire, nano-hollow ball and nanocube, (include template by different synthetic methods Method, crystal seed method, chemical reduction method, sol-gel process and thermal decomposition method etc.) prepare.
Summary of the invention
The technical problem to be solved is to provide the preparation of a kind of simple and effective hydrothermal reduction method to have Uniformly and the method for the controlled hollow palladium nanosphere of pattern, size and composition.
Solve the technical scheme that above-mentioned technical problem used to be made up of following step:
1, Nano balls of cuprous oxide is prepared
It is that 1:1～3:1～1.5 adds steaming in molar ratio by copper chloride or copper sulfate, polymine, ascorbic acid In distilled water, mix homogeneously, with the pH value of sodium hydrate aqueous solution regulation gained mixed liquor to 10～13, room temperature Stir 20～30 minutes, obtain Nano balls of cuprous oxide solution.
2, hollow palladium nanosphere is prepared
By the aqueous solution of potassium chloropalladite or Palladous chloride. with 0.5mol/L sodium hydrate aqueous solution regulation pH value extremely After 10～13, join in Nano balls of cuprous oxide solution, and add hydrazine hydrate, wherein potassium chloropalladite or chlorine Change palladium, hydrazine hydrate, the mol ratio of Red copper oxide are 1:7～20:1.5～2, at 50～80 DEG C reduction reaction 20～ 40 minutes, then it is stirred at room temperature 16～24 hours, is centrifuged, washs, is dried, obtain hollow palladium nanosphere.
In above-mentioned steps 1, preferably copper chloride or copper sulfate, polymine, the mol ratio of ascorbic acid is 1:2:1.2, the number-average molecular weight of wherein said polymine is 300～1200.
In above-mentioned steps 2, preferably potassium chloropalladite or Palladous chloride., hydrazine hydrate, the mol ratio of Red copper oxide is 1:10:1.85。
In above-mentioned steps 2, further preferably reduction reaction 30 minutes at 60 DEG C.
Beneficial effects of the present invention is as follows:
1, the present invention uses a small amount of polymine (PEI) to be stabilizer and guiding agent, in preparation oxidation Asia During copper nanosphere, PEI is as the stabilizer of copper chloride, the N therein and Cu in copper chloride2+Complexation, Make copper chloride gentleer with the speed of ascorbic acid generation reduction reaction, thus obtain size and morphology controllable Nano balls of cuprous oxide, the PEI Molecular Adsorption of excess is on the surface of Nano balls of cuprous oxide；Preparing hollow palladium During nanosphere, adsorb the PEI on Nano balls of cuprous oxide surface as palladium in Red copper oxide superficial growth Guiding agent, make palladium be easier to be grown in Nano balls of cuprous oxide surface, adsorb at Nano balls of cuprous oxide simultaneously The PEI on surface is again as Cu2+Stabilizer, make Red copper oxide be easy to by the dioxygen oxidation in air.
2, the present invention is with Nano balls of cuprous oxide as template, with sodium chloropalladite for palladium presoma, Pd2+In absorption Under the guiding of the PEI on Nano balls of cuprous oxide surface, oriented growth is on Nano balls of cuprous oxide surface, then exists The lower Red copper oxide of the effect of PEI is become Cu by the dioxygen oxidation in air2+Ion, Cu2+Ion is by washing i.e. Can remove, finally give the hollow palladium nanosphere of pattern, size uniformity.
3, the present invention need not high temperature, it is not necessary to the longer response time, it is not necessary to complicated pH regulation process, Simple to operate, product yield is high and homogeneity is good, is suitable for large-scale production.
4, hollow palladium nanosphere prepared by the present invention is compared with commercialization palladium black, shows excellent to Catalyzed by Formic Acid reaction Different electro catalytic activity and stability, have potential application prospect in direct methanoic acid fuel cell field.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the hollow palladium nanosphere of embodiment 1 preparation.
Fig. 2 is the TEM figure of the hollow palladium nanosphere of embodiment 1 preparation.
Fig. 3 is the TEM figure of the hollow palladium nanosphere of embodiment 2 preparation.
Fig. 4 is the TEM figure of the hollow palladium nanosphere of embodiment 3 preparation.
Fig. 5 is the TEM figure of the hollow palladium nanosphere of embodiment 4 preparation.
Fig. 6 is the TEM figure of the hollow palladium nanosphere of embodiment 5 preparation.
Fig. 7 is the TEM figure of the hollow palladium nanosphere of embodiment 6 preparation.
Fig. 8 is the TEM figure of the hollow palladium nanosphere of embodiment 7 preparation.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not only It is limited to these embodiments.
Embodiment 1
1, Nano balls of cuprous oxide is prepared
Take the CuCl of 1mL 0.05mol/L2Aqueous solution, 0.2mL 0.5mol/L number-average molecular weight are the poly-second of 600 Alkene imines aqueous solution, the aqueous ascorbic acid of 0.6mL 0.1mol/L add 10mL distilled water, stir mixing 3 After minute, with the pH value of the sodium hydrate aqueous solution regulation gained mixed liquor of 0.5mol/L to 11.5, room temperature is stirred Mix 20 minutes, obtain Nano balls of cuprous oxide solution.
2, hollow palladium nanosphere is prepared
The potassium chloropalladite aqueous solution of 0.45mL 0.06mol/L 0.5mol/L sodium hydrate aqueous solution is regulated PH value, to after 11.5, joins in the Nano balls of cuprous oxide solution that step 1 obtains, and adds 15.5 μ L matter Amount mark is the hydrazine hydrate aqueous solution of 80%, heating in water bath to 60 DEG C, constant temperature reduction reaction 30 minutes, then Be stirred at room temperature 24 hours, washing centrifugal with distilled water, 60 DEG C be dried, obtain hollow palladium nanosphere (see Fig. 1 With 2).
Embodiment 2
In embodiment 1, copper chloride used is replaced with equimolar copper sulfate, potassium chloropalladite equimolar Palladous chloride. replace, other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 3).
Embodiment 3
In embodiment 1,0.2mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine use of 600 0.1mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine replacement of 600, other steps and embodiment 1 Identical, obtain hollow palladium nanosphere (see Fig. 4).
Embodiment 4
In embodiment 1,0.2mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine use of 600 0.3mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine replacement of 600, other steps and embodiment 1 Identical, obtain hollow palladium nanosphere (see Fig. 5).
Embodiment 5
In embodiment 1,15.5 μ L mass fractions are that the hydrazine hydrate aqueous solution of 80% is with 30 μ L mass fractions The hydrazine hydrate aqueous solution of 80% is replaced, and other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 6).
Embodiment 6
In the step 1 and 2 of embodiment 1, with 0.5mol/L sodium hydrate aqueous solution regulation pH value to 13, Other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 7).
Embodiment 7
In the step 2 of embodiment 1, heating in water bath to 80 DEG C, constant temperature reduction reaction 20 minutes, other steps The most same as in Example 1, obtain hollow palladium nanosphere (see Fig. 8).

Claims (5)

1. the preparation method of a hollow palladium nanosphere, it is characterised in that it is made up of following step:
(1) Nano balls of cuprous oxide is prepared
It is that 1:1～3:1～1.5 adds steaming in molar ratio by copper chloride or copper sulfate, polymine, ascorbic acid In distilled water, mix homogeneously, with the pH value of sodium hydrate aqueous solution regulation gained mixed liquor to 10～13, room temperature Stir 20～30 minutes, obtain Nano balls of cuprous oxide solution；
(2) hollow palladium nanosphere is prepared
By the aqueous solution of potassium chloropalladite or Palladous chloride. with 0.5mol/L sodium hydrate aqueous solution regulation pH value extremely After 10～13, join in Nano balls of cuprous oxide solution, and add hydrazine hydrate, wherein potassium chloropalladite or chlorine Change palladium, hydrazine hydrate, the mol ratio of Red copper oxide are 1:7～20:1.5～2, at 50～80 DEG C reduction reaction 20～ 40 minutes, then it is stirred at room temperature 16～24 hours, is centrifuged, washs, is dried, obtain hollow palladium nanosphere.
The preparation method of hollow palladium nanosphere the most according to claim 1, it is characterised in that: in step (1) In, described copper chloride or copper sulfate, polymine, the mol ratio of ascorbic acid are 1:2:1.2.
The preparation method of hollow palladium nanosphere the most according to claim 1 and 2, it is characterised in that: described The number-average molecular weight of polymine be 300～1200.
The preparation method of hollow palladium nanosphere the most according to claim 1, it is characterised in that: in step (2) In, described potassium chloropalladite or Palladous chloride., hydrazine hydrate, the mol ratio of Red copper oxide are 1:10:1.85.
5. according to the preparation method of the hollow palladium nanosphere described in claim 1 or 4, it is characterised in that: described In step (2), reduction reaction 30 minutes at 60 DEG C.
CN201610261081.XA 2016-04-25 2016-04-25 A kind of preparation method of hollow palladium nanosphere Expired - Fee Related CN105945298B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610261081.XA CN105945298B (en) 2016-04-25 2016-04-25 A kind of preparation method of hollow palladium nanosphere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610261081.XA CN105945298B (en) 2016-04-25 2016-04-25 A kind of preparation method of hollow palladium nanosphere

Publications (2)

Publication Number Publication Date
CN105945298A true CN105945298A (en) 2016-09-21
CN105945298B CN105945298B (en) 2018-01-12

Family

ID=56915678

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610261081.XA Expired - Fee Related CN105945298B (en) 2016-04-25 2016-04-25 A kind of preparation method of hollow palladium nanosphere

Country Status (1)

Country Link
CN (1) CN105945298B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824084A (en) * 2017-03-15 2017-06-13 天津大学 The preparation method of the carbon-supported catalyst of a kind of nano cuprous oxide/copper modification and except iodine application
CN107470649A (en) * 2017-08-01 2017-12-15 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Pt alloys
CN107520462A (en) * 2017-08-01 2017-12-29 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Au alloys
CN110676473A (en) * 2019-10-10 2020-01-10 陕西师范大学 Preparation method of multi-stage porous Rh nanosheet
CN110976906A (en) * 2019-12-04 2020-04-10 山西大学 Fluorescent palladium nanocluster and synthesis method and application thereof
CN111687427A (en) * 2019-03-15 2020-09-22 华中农业大学 Hollow palladium nanotube with two open ends, preparation method and application thereof
CN115960367A (en) * 2022-12-26 2023-04-14 浙江科曼奇生物科技股份有限公司 Preparation method and application of quaternized polyethyleneimine zinc oxide or cuprous oxide particles
CN115960367B (en) * 2022-12-26 2024-11-19 浙江科曼奇生物科技股份有限公司 Preparation method and application of quaternized polyethylene imidized zinc oxide or cuprous oxide particles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
CN102036773A (en) * 2008-03-19 2011-04-27 巴斯夫欧洲公司 Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines
CN104722775A (en) * 2015-03-11 2015-06-24 浙江大学 Two-dimensional hollow palladium nanocrystal and preparation method thereof
CN105013476A (en) * 2015-06-26 2015-11-04 陕西师范大学 Preparation method of chemically functionalized Pd nano-wires

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
CN102036773A (en) * 2008-03-19 2011-04-27 巴斯夫欧洲公司 Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines
CN104722775A (en) * 2015-03-11 2015-06-24 浙江大学 Two-dimensional hollow palladium nanocrystal and preparation method thereof
CN105013476A (en) * 2015-06-26 2015-11-04 陕西师范大学 Preparation method of chemically functionalized Pd nano-wires

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824084A (en) * 2017-03-15 2017-06-13 天津大学 The preparation method of the carbon-supported catalyst of a kind of nano cuprous oxide/copper modification and except iodine application
CN107470649A (en) * 2017-08-01 2017-12-15 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Pt alloys
CN107520462A (en) * 2017-08-01 2017-12-29 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Au alloys
CN111687427A (en) * 2019-03-15 2020-09-22 华中农业大学 Hollow palladium nanotube with two open ends, preparation method and application thereof
CN110676473A (en) * 2019-10-10 2020-01-10 陕西师范大学 Preparation method of multi-stage porous Rh nanosheet
CN110676473B (en) * 2019-10-10 2022-04-15 陕西师范大学 Preparation method of multi-stage porous Rh nanosheet
CN110976906A (en) * 2019-12-04 2020-04-10 山西大学 Fluorescent palladium nanocluster and synthesis method and application thereof
CN115960367A (en) * 2022-12-26 2023-04-14 浙江科曼奇生物科技股份有限公司 Preparation method and application of quaternized polyethyleneimine zinc oxide or cuprous oxide particles
CN115960367B (en) * 2022-12-26 2024-11-19 浙江科曼奇生物科技股份有限公司 Preparation method and application of quaternized polyethylene imidized zinc oxide or cuprous oxide particles

Also Published As

Publication number Publication date
CN105945298B (en) 2018-01-12

Similar Documents

Publication Publication Date Title
CN105945298A (en) Preparation method for hollow palladium nanospheres
CN107175125B (en) Activation method of MOFs base oxygen reduction electrocatalyst
CN104028269B (en) Graphene-loaded metal nanocomposite, preparation method and application
CN102078811B (en) Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method
CN106179415B (en) A kind of preparation method of nano-titanium dioxide/molybdenum disulfide composite material film
CN106784881B (en) A kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst and preparation method thereof
CN108355717A (en) A kind of preparation method of cellulose/BiOBr composite photocatalyst materials
CN106669763A (en) Nitrogen-doped carbon-coated nanoflower-shaped MoSe2 composite material and preparation and application
CN105789644A (en) Preparation method for Fe-N/C oxygen reduction reaction composite electrocatalyst
CN102873337A (en) Poly-allylamine oriented platinum nano cube preparation method
CN108520965A (en) A kind of preparation method of platinum-noble metal-copper ternary alloy nano hollow cube
CN108579818A (en) The preparation method of solid polymer electrolyte water electrolysis membrane electrode catalyst pulp
CN106180751B (en) A kind of nanometer platinum-nickel alloy and its preparation and application
CN103611575B (en) Containing the preparation method of the catalyst of imidazole and its derivants
CN104525189A (en) Polyhedral Pd-Pt alloy nano catalyst and preparation method and application of nano catalyst
CN101279262A (en) Preparation of highly selective epoxidized nano composite oxides for catalyzing olefin hydrocarbon and air
CN105810960A (en) Composite material taking foam nickel as matrix and preparation method of composite material
CN109364906A (en) A kind of boron doping gold/mesoporous carbon catalyst and its preparation method and application of ball-milling method preparation
CN111326753B (en) Supported nano electro-catalyst and preparation method and application thereof
CN104888769A (en) Preparation method of charcoal-supported palladium-silver nanometer composite catalyst for direct methanol fuel cells
CN104815682A (en) High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof
CN110540196A (en) boron-nitrogen co-doped porous graphene and preparation method and application thereof
CN106381716A (en) Preparation method of fabric photochromic finishing liquid
Duan et al. Monovacancy Coupled Pyridinic N Site Enables Surging Oxygen Reduction Activity of Metal-Free CN x Catalyst
CN105561999A (en) Preparation method of Al2O3 fiber-loaded nickel-based catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180112

Termination date: 20200425