CN103058151A - Hiberarchy bismuth telluride nanocrystal and preparation method thereof - Google Patents

Hiberarchy bismuth telluride nanocrystal and preparation method thereof Download PDF

Info

Publication number
CN103058151A
CN103058151A CN2013100163485A CN201310016348A CN103058151A CN 103058151 A CN103058151 A CN 103058151A CN 2013100163485 A CN2013100163485 A CN 2013100163485A CN 201310016348 A CN201310016348 A CN 201310016348A CN 103058151 A CN103058151 A CN 103058151A
Authority
CN
China
Prior art keywords
tellurium
hierarchy
room temperature
nanocrystalline
bismuth acetate
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
CN2013100163485A
Other languages
Chinese (zh)
Other versions
CN103058151B (en
Inventor
邹勃
肖冠军
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.)
Jilin University
Original Assignee
Jilin 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 Jilin University filed Critical Jilin University
Priority to CN201310016348.5A priority Critical patent/CN103058151B/en
Publication of CN103058151A publication Critical patent/CN103058151A/en
Application granted granted Critical
Publication of CN103058151B publication Critical patent/CN103058151B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

The invention relates to a hiberarchy bismuth telluride nanocrystal and a preparation method thereof, belonging to the technical field of nanometer materials and synthesis methods thereof. The preparation method comprises the following steps of putting bismuth acetate, oleic acid and octadecene into a container and stirring with magnetic force, heating up under the protection of nitrogen till completely dissolving bismuth acetate, then cooling down to room temperature, adding trioctylphosphine solution of tellurium prepared in advance into the container at room temperature, reacting at 140-240 DEG C, and keeping the temperature for 0.5-6 hours. The hiberarchy bismuth telluride nanocrystal is prepared by a sol-gel method, and the grain size and appearance of the bismuth telluride nanocrystal can be controlled by changing the reaction time and temperature.

Description

A kind of Tellurobismuthite of hierarchy is nanocrystalline and preparation method thereof
Technical field
The invention belongs to the technical field of nano material and synthetic method thereof, particularly nanocrystalline the and method of a kind of (hierarchical) for preparing hierarchy.
Background technology
Because the burning of coal and the discharging of vehicle exhaust cause gradually global warming and produce a lot of used heat.The overdevelopment electric material then is the effective way that addresses this problem, and converts the electric energy useful to the mankind to because thermoelectric material can utilize extraneous used heat.Tellurobismuthite (Bi 2Te 3) owing to having high quality factor (ZT) under the room temperature, therefore in traditional technology, usually be widely studied as thermoelectric material potential under the room temperature.And nano material can effectively reduce lattice thermal conductivity for the body material, thereby improves the thermoelectricity capability of nano material.Recently, Bi 2Te 3One of be suggested as the simplest three-dimensional topology isolator, the body electronic state of this polymorphic material is that its surface of isolator of energy gap is arranged then is metallic state without energy gap.With respect to macroscopical block materials, topological isolator nano material has large specific surface area, the contribution of energy establishment figure current carrier, thus highlight topological surperficial state property matter.Therefore, people are seeking a kind of more effective means always and are realizing Bi 2Te 3Preparation.
Existing Bi 2Te 3All be to form by the solid state powder sintering under the comparatively high temps, or utilize ball mill grinding to make corresponding pressed powder.And great majority are based on the Bi of body material 2Te 3Preparation.So far, utilize the colloid chemistry method to prepare the Bi of hierarchy 2Te 3The nanocrystalline report that yet there are no.
Summary of the invention
The technical problem to be solved in the present invention is, provides a kind of Tellurobismuthite that utilizes sol-gel method to prepare hierarchy nanocrystalline method, the simple easy handling of the method, and realize that size, pattern are controlled.
The technical characterictic of product of the present invention is as described below:
A kind of Tellurobismuthite of hierarchy is nanocrystalline, and molecular formula is Bi 2Te 3The similar nanometer sheet of pattern be crossed as flower-shaped after, link to each other to consist of the caterpillar shape; Mean diameter is 230 ~ 565nm.
Preparation hierarchy Bi 2Te 3Nanocrystalline technical scheme is:
The preparation method that a kind of Tellurobismuthite of hierarchy is nanocrystalline has following process,
(1) the tri octyl phosphine solution of preparation tellurium: tellurium powder and tri octyl phosphine are mixed, naturally be down to room temperature after keeping 2 ~ 4 hours being warming up to 200 ~ 250 ℃ under the protection of nitrogen, the tri octyl phosphine solution storage of tellurium that obtains concentration and be 0.2mol/L is for subsequent use;
(2) hierarchy Bi 2Te 3Nanocrystalline preparation: with bismuth acetate, oleic acid and octadecylene are packed into and are carried out magnetic agitation in the container, be warming up to bismuth acetate and dissolve fully under the protection of nitrogen; Be down to gradually afterwards room temperature, the tri octyl phosphine solution of tellurium is joined in the container, under 140 ~ 240 ℃, react and be incubated 0.5 ~ 6 hour; Obtain the Tellurobismuthite powder through the centrifugal sample of washing; Bismuth acetate in molar ratio wherein: tellurium=2: 3, by volume oleic acid: octadecylene=1: 6, the consumption of oleic acid add 5mL oleic acid by every mmol bismuth acetate and calculate.
The described centrifugal sample of washing carries out according to a conventional method.
The invention has the beneficial effects as follows and prepare Bi 2Te 3Nanocrystalline; And can by changing temperature of reaction and soaking time, realize size, the controlled nanocrystalline preparation of Tellurobismuthite of pattern.
Description of drawings
Fig. 1 is the Bi of embodiment 2 preparations 2Te 3The X-ray diffraction spectrum of sample.
Fig. 2 is that embodiment 2 is at 140 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 3 is that embodiment 3 is at 160 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 4 is that embodiment 4 is at 180 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 5 is that embodiment 5 is at 200 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 6 is that embodiment 6 is at 220 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 7 is that embodiment 7 is at 240 ℃ of Bi that prepare after keeping 2 hours 2Te 3The stereoscan photograph of sample.
Fig. 8 is that embodiment 8 is at 200 ℃ of Bi that prepare after keeping 30 minutes 2Te 3The stereoscan photograph of sample.
Fig. 9 is that embodiment 9 is at 200 ℃ of Bi that prepare after keeping 1 hour 2Te 3The stereoscan photograph of sample.
Figure 10 is that embodiment 9 is at 200 ℃ of Bi that prepare after keeping 1 hour 2Te 3The high-resolution-ration transmission electric-lens photo of sample.
Figure 11 is that embodiment 10 is at 200 ℃ of Bi that prepare after keeping 4 hours 2Te 3The stereoscan photograph of sample.
Figure 12 is that embodiment 11 is at 200 ℃ of Bi that prepare after keeping 6 hours 2Te 3The stereoscan photograph of sample.
Embodiment
Now more specifically describe the present invention in conjunction with the following example, if no special instructions, agents useful for same is commercially available obtainable product, does not add further purification and uses.
The preparation of the tri octyl phosphine solution of embodiment 1 tellurium
Compound concentration is the tri octyl phosphine solution of the tellurium of 0.2mol/L, and concrete operations technique is as follows: tellurium powder and tri octyl phosphine are mixed in the 50mL round bottom three-necked bottle, be warming up under the protection of nitrogen 200 ℃ keep 4 hours after naturally near room temperature, and storage is with for subsequent use.
Also can be warming up under the protection of nitrogen 250 ℃ keep 2 hours after naturally near room temperature, prepare and obtain the tri octyl phosphine solution that concentration is the tellurium of 0.2mol/L.
Embodiment 2 is 140 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 140 ℃ and kept 2 hours.Fig. 1 is the X-ray diffractogram of the sample that makes, is rhombohedral Bi 2Te 3As shown in Figure 2, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 230nm.
Embodiment 3 is 160 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 160 ℃ and kept 2 hours.As shown in Figure 3, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 345nm.
Embodiment 4 is 180 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 180 ℃ and kept 2 hours.As shown in Figure 4, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 450nm.
Embodiment 5 is 200 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 200 ℃ and kept 2 hours.As shown in Figure 5, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 470nm.
Embodiment 6 is 220 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 220 ℃ and kept 2 hours.As shown in Figure 6, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 520nm.
Embodiment 7 is 240 ℃ of hierarchy Bi that prepare after keeping 2 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 240 ℃ and kept 2 hours.As shown in Figure 7, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 565nm.
Embodiment 8 is 200 ℃ of hierarchy Bi that prepare after keeping 30 minutes in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 200 ℃ and kept 30 minutes.As shown in Figure 8, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 320nm.
Embodiment 9 is 200 ℃ of hierarchy Bi that prepare after keeping 1 hour in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 200 ℃ and kept 1 hour.As shown in Figure 9, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 430nm.The high resolution transmission electron microscopy of the sample from Figure 10 can see, fringe spacing is
Figure BDA00002744280700051
Corresponding to rhombohedral (015) spacing.
Embodiment 10 is 200 ℃ of hierarchy Bi that prepare after keeping 4 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 200 ℃ and kept 4 hours.As shown in figure 11, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is 535nm.
Embodiment 11 is 200 ℃ of hierarchy Bi that prepare after keeping 6 hours in temperature of reaction 2Te 3Nanocrystalline
At first with the 0.2mmol bismuth acetate, 1mL oleic acid and 6mL octadecylene are packed in the 50mL round bottom three-necked bottle and are accompanied by strong magnetic agitation, progressively be warming up to bismuth acetate and dissolve fully under the protection of nitrogen.Be down to gradually subsequently room temperature.The tri octyl phosphine solution 1.5mL of the 0.2mol/L tellurium that at room temperature will prepare in advance joins in the three-necked bottle, then rises to 200 ℃ and kept 6 hours.As shown in figure 12, can see hierarchy Bi from the stereoscan photograph of prepared sample 2Te 3Nanocrystalline diameter is about 550nm.

Claims (2)

1. the Tellurobismuthite of a hierarchy is nanocrystalline, and molecular formula is Bi 2Te 3Pattern be nanometer sheet be crossed as flower-shaped after, link to each other to consist of the caterpillar shape; Mean diameter is 230 ~ 565nm.
2. the nanocrystalline preparation method of the Tellurobismuthite of the hierarchy of a claim 1 has following process,
(1) the tri octyl phosphine solution of preparation tellurium: tellurium powder and tri octyl phosphine are mixed, naturally be down to room temperature after keeping 2 ~ 4 hours being warming up to 200 ~ 250 ℃ under the protection of nitrogen, the tri octyl phosphine solution storage of tellurium that obtains concentration and be 0.2mol/L is for subsequent use;
(2) hierarchy Bi 2Te 3Nanocrystalline preparation: with bismuth acetate, oleic acid and octadecylene are packed into and are carried out magnetic agitation in the container, be warming up to bismuth acetate and dissolve fully under the protection of nitrogen; Be down to afterwards room temperature, the tri octyl phosphine solution of tellurium is joined in the container, under 140 ~ 240 ℃, react and be incubated 0.5 ~ 6 hour; Obtain the Tellurobismuthite powder through the centrifugal sample of washing; Bismuth acetate in molar ratio wherein: tellurium=2: 3, by volume oleic acid: octadecylene=1: 6, the consumption of oleic acid add 5mL oleic acid by every mmol bismuth acetate and calculate.
CN201310016348.5A 2013-01-16 2013-01-16 Hiberarchy bismuth telluride nanocrystal and preparation method thereof Expired - Fee Related CN103058151B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310016348.5A CN103058151B (en) 2013-01-16 2013-01-16 Hiberarchy bismuth telluride nanocrystal and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310016348.5A CN103058151B (en) 2013-01-16 2013-01-16 Hiberarchy bismuth telluride nanocrystal and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103058151A true CN103058151A (en) 2013-04-24
CN103058151B CN103058151B (en) 2015-02-04

Family

ID=48101095

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310016348.5A Expired - Fee Related CN103058151B (en) 2013-01-16 2013-01-16 Hiberarchy bismuth telluride nanocrystal and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103058151B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108584887A (en) * 2018-03-07 2018-09-28 南京航空航天大学 A kind of Bi with 3-D nano, structure2Te3Material and its preparation method and application
CN113149076A (en) * 2021-05-27 2021-07-23 吉林大学 Preparation method of phosphorus-selenium co-doped niobium disulfide nano material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1384048A (en) * 2002-06-21 2002-12-11 清华大学 Nano level metal telluride preparing process
US6872330B2 (en) * 2002-05-30 2005-03-29 The Regents Of The University Of California Chemical manufacture of nanostructured materials
CN101513994A (en) * 2009-03-10 2009-08-26 中国科学院上海硅酸盐研究所 Bismuth base hydrogen storage material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872330B2 (en) * 2002-05-30 2005-03-29 The Regents Of The University Of California Chemical manufacture of nanostructured materials
CN1384048A (en) * 2002-06-21 2002-12-11 清华大学 Nano level metal telluride preparing process
CN101513994A (en) * 2009-03-10 2009-08-26 中国科学院上海硅酸盐研究所 Bismuth base hydrogen storage material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JAE SUNG SON等: "n-Type Nanostructured Thermoelectric Materials Prepared from Chemically Synthesized Ultrathin Bi2Te3 Nanoplates", 《NANO LETTERS》 *
JIPENG FU等: "Bi2Te3 nanoplates and nanoflowers: Synthesized by hydrothermal process and their enhanced thermoelectric properties", 《CRYSTENGCOMM》 *
LIANGLIANG CHEN等: "Facile synthesis of ultra-small Bi2Te3 nanoparticles, nanorods and nanoplates and their morphology-dependent Raman spectroscopy", 《MATERIALS LETTERS》 *
RAHUL P. GUPTA等: "Inorganic Colloidal Solution-Based Approach to Nanocrystal Synthesis of (Bi,Sb)2Te3", 《JOURNAL OF ELECTRONIC MATERIALS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108584887A (en) * 2018-03-07 2018-09-28 南京航空航天大学 A kind of Bi with 3-D nano, structure2Te3Material and its preparation method and application
CN113149076A (en) * 2021-05-27 2021-07-23 吉林大学 Preparation method of phosphorus-selenium co-doped niobium disulfide nano material
CN113149076B (en) * 2021-05-27 2022-07-01 吉林大学 Preparation method of phosphorus-selenium co-doped niobium disulfide nano material

Also Published As

Publication number Publication date
CN103058151B (en) 2015-02-04

Similar Documents

Publication Publication Date Title
US10177295B2 (en) P-type high-performance thermoelectric material with reversible phase change, and preparation method therefor
Wang et al. Improved Thermoelectric Properties of La1− x Sr x CoO3 Nanowires
KR20110052225A (en) Nanocomposite thermoelectric material, and thermoelectric device and thermoelectric module comprising same
CN102443848B (en) Method for improving thermoelectric properties of bismuth sulfide polycrystal
Zhao et al. First-principles study on the doping effects of nitrogen on the electronic structure and optical properties of Cu 2 O
CN100503444C (en) 1CdS, CdSe or CdTe hollow Nano ring, and preparation method
CN103236493B (en) TmCuTe2Compound and its preparation and use
CN101435029A (en) Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material
Peng et al. Highly efficient broadband green emission of (TPA) CuCl2 single crystals: Understanding the formation of self-trapped states
CN106145062B (en) A kind of quick method for preparing antimony telluride thermoelectric material
CN101759162B (en) Low-temperature liquid phase synthesizing method of monodisperse square crystalline phase ferrous selenide square nanometer sheet
CN103058151B (en) Hiberarchy bismuth telluride nanocrystal and preparation method thereof
CN105036175B (en) Method of preparing copper sulfide-zinc sulfide heterojunction three-dimensional nanostructure by using solid phase method
Yao et al. All-inorganic zero-dimensional Sn-doped Rb4CdCl6 with near-unity quantum efficiency
CN101728477B (en) Method for preparing CeyFe4Sb12/Ca3Co4O9(y=0.8-1.2) based block gradient thermoelectric material
CN104362248A (en) Method for preparing high-seebeck-coefficient tellurium/tellurium oxide nanocomposite with solvothermal
CN102849786A (en) Method for preparing cluster indium sulfide material
CN107689414A (en) A kind of preparation method of the compound calcium manganate base oxide pyroelectric material of the equally distributed multiphase of conductive gold symbolic animal of the birth year
US20130284989A1 (en) Method for preparing and use of Sb2Te3 nanocrystals in thermoelectric materials
CN102807195A (en) Method for preparing semi-arc Bi2Se3ultrathin nanosheets
CN104047059B (en) Prepare the Cu of thermoelectric material3sbSe4nanocrystal and synthetic method thereof
KR20150027560A (en) Preparation of copper selenide compound controlling particle size and composition
CN109384202A (en) One kind having room temperature inorganic electronic materials flexible and preparation method thereof
CN101973583B (en) Preparation method of lead tungstate powder with high scintillation property
Zhang et al. Synthesis and characterization of multipod frameworks of Cu 2 O microcrystals and Cu 7 S 4 hollow microcages

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150204

Termination date: 20160116

EXPY Termination of patent right or utility model