CN109592703B - CuO/Cu2O-La2O3Preparation method of multiphase composite sol - Google Patents

CuO/Cu2O-La2O3Preparation method of multiphase composite sol Download PDF

Info

Publication number
CN109592703B
CN109592703B CN201811566326.5A CN201811566326A CN109592703B CN 109592703 B CN109592703 B CN 109592703B CN 201811566326 A CN201811566326 A CN 201811566326A CN 109592703 B CN109592703 B CN 109592703B
Authority
CN
China
Prior art keywords
sol
nano
cuo
gas
solid content
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.)
Active
Application number
CN201811566326.5A
Other languages
Chinese (zh)
Other versions
CN109592703A (en
Inventor
沈涛
张玲洁
张继
杨辉
樊先平
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.)
Zigong Innovation Center of Zhejiang University
Original Assignee
Zigong Innovation Center of Zhejiang 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 Zigong Innovation Center of Zhejiang University filed Critical Zigong Innovation Center of Zhejiang University
Priority to CN201811566326.5A priority Critical patent/CN109592703B/en
Publication of CN109592703A publication Critical patent/CN109592703A/en
Application granted granted Critical
Publication of CN109592703B publication Critical patent/CN109592703B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—Specially adapted to detect a particular component
    • G01N33/0037—Specially adapted to detect a particular component for NOx

Abstract

The invention relates to the field of gas-sensitive materials, and aims to provide CuO/Cu2O‑La2O3A preparation method of multiphase composite sol. The method comprises the following steps: mixing nano CuO sol and nano Cu2Reacting the O sol at 60-120 ℃, and adding restricted space molecules; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 8-14 h at the temperature of 25-50 ℃ to finally obtain CuO/Cu2O‑La2O3And (3) multiphase composite sol. The invention adopts nano sol particles and rare earth oxide as modification components, utilizes nano activity effect and unique physicochemical properties of rare earth, prepares the high-dispersion type multiphase composite nano sol in a confined space molecular structure, and solves the problem of easy agglomeration of the traditional nano sol. If a centrifugal atomization method coating technology is further adopted, the controllable preparation of the high-quality and uniform multi-phase composite nano-film layer can be realized, and the NO of the material can be effectively improvedxSensitivity of gas, response-recovery characteristics.

Description

CuO/Cu2O-La2O3Preparation method of multiphase composite sol
Technical Field
The invention relates to the field of gas-sensitive materials, in particular to CuO/Cu2O-La2O3A preparation method of multiphase composite sol.
Background
The atmospheric pollution seriously threatens the health and survival of human beings, and the metal oxide gas sensor becomes an effective means for detecting harmful gases in the atmosphere due to the advantages of simple equipment, small volume, quick response, high sensitivity, low cost and the like. And as the core of the gas sensor, the gas sensitive material determines the detection and the use performance of the gas sensor. Conventional metal oxide gas sensing materials have earlier-discovered SnO2ZnO, alpha-iron oxide, gamma-iron oxide, and the like. However, the conventional gas sensitive material with a single component has certain limitations in detecting the type and sensitivity of gas, such as low sensitivity, low selectivity and the like, so some researchers improve the characteristics of the gas sensitive material, such as detection sensitivity and the like by doping trace elements, such as rare earth elements, adding different oxides and the like.
The nano material has certain advantages in the high-sensitivity application of the gas sensitive material due to the nano effects of high specific surface area, high chemical activity sites and the like. The smaller the particle size of the material particles, the larger the quantity and energy participating in the gas-sensitive reaction, and the more remarkable the gas-sensitive property is. Therefore, the gas sensitive element with excellent evaluation indexes such as sensitivity, selectivity, stability, response recovery characteristics and the like can be prepared by accurately controlling the chemical properties such as the component composition, the micro-morphology, the grain size, the crystallinity, the doping component and the like of the gas sensitive material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a CuO/Cu2O-La2O3A preparation method of multiphase composite sol.
In order to solve the technical problem, the solution of the invention is as follows:
provides a CuO/Cu2O-La2O3The preparation method of the multiphase composite sol comprises the following steps:
(1) according to the formula CuO and Cu2Taking nano CuO sol and nano Cu according to the molar ratio of O being 1: 12Adding the O sol into a reaction kettle, and reacting for 4-18 h at the temperature of 60-120 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 8-14 h at the temperature of 25-50 ℃ to finally obtain CuO/Cu2O-La2O3Multi-phase composite sol;
the restricted space molecule accounts for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 1-3%, and the nano La2O3La in the sol2O3Account for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 9-22%.
In the present invention, the solid content of the nano CuO sol is 0.5%.
In the invention, the nano Cu2The solids content of the O sol was 2%.
In the invention, the nano La is2O3The solids content of the sol was 1.5%.
In the present invention, the constrained space molecule is tannic acid, gallic acid, or polyethylene glycol (PEG 2000).
In the present invention, the stirring is magnetic stirring.
Description of the inventive principles:
the invention prepares the CuO/Cu2O-La2O3 multiphase composite nano sol with high dispersibility in a limited space molecular structure by utilizing a nano-dispersion combined rare earth doping modification composite technology. The nano sol can be further used as a precursor, the uniform coating of the nano sol is realized by adopting a centrifugal atomization method, and the nano sol has excellent sensitivity and response-recovery characteristics on the atmosphere pollution gas NOx.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts nano sol particles and rare earth oxide as modification components, and utilizes the nano activity effect and the unique physicochemical property of rare earth to prepare the high-dispersion CuO/Cu in the molecular structure of the restricted space2O-La2O3The multiphase composite nano sol solves the problem of easy agglomeration of the traditional nano sol.
(2) CuO/Cu obtained by the invention2O-La2O3The multiphase composite sol can further adopt a centrifugal atomization coating technology to realize high-quality and uniform CuO/Cu2O-La2O3Controllable preparation of multiphase composite nano coating, effectively improving NO of materialxSensitivity of gas, response-recovery characteristics.
Detailed Description
The nano CuO sol and the nano Cu are prepared by the method2O sol, nano La2O3The sol is prepared by the prior art and can be prepared by the conventional preparation method.
CuO/Cu prepared by the invention2O-La2O3A heterogeneous composite sol, which may furtherThe method is used for preparing the gas sensitive material coating. The coating is obtained by spraying a metal oxide gas-sensitive element by using a centrifugal atomization method, and specific examples are as follows:
CuO/Cu prepared by using the method2O-La2O3And (3) spraying the multiphase composite sol on the metal oxide gas-sensitive element by a centrifugal atomization method to obtain a gas-sensitive material coating on the surface of the element. The operating parameters of the centrifugal atomization spraying can be selected as follows: the centrifugal rate is 3000-5000 r/min; the atomization air pressure is 0.2-0.65 MPa; the spraying distance is 100-300 mm.
Example 1
(1) According to the formula CuO and Cu2Taking nano CuO sol and nano Cu according to the molar ratio of O being 1: 12Adding the O sol into a reaction kettle, and reacting for 18 hours at the temperature of 60 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 14h at the temperature of 25 ℃ to finally obtain CuO/Cu2O-La2O3Multi-phase composite sol;
the nano Cu2The solid content of the O sol is 2 percent, and the nano La2O3The solid content of the sol was 1.5%, and the solid content of the nano CuO sol was 0.5%. The restricted space molecule is tannic acid, and accounts for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 1 percent; nano La2O3La in the sol2O3Account for CuO and Cu2O and La2O3The molar percentage of the total solid content of the sol was 9%.
Preparation and performance evaluation of the coating:
(1) using the CuO/Cu obtained in this example2O-La2O3And (3) spraying the multiphase composite sol on the metal oxide gas-sensitive element by a centrifugal atomization method to obtain a gas-sensitive material coating on the surface of the element. The operating parameters of the centrifugal atomization spraying are as follows: the centrifugal rate is 3000 r/min; the atomization air pressure is 0.2 MPa; the spraying distance is 100 mm.
(2) To pairPrepared CuO/Cu2O-La2O3Heterogeneous composite nanocoating for NOxThe gas sensitivity characteristics (including sensitivity, response-recovery characteristics, etc.) of the gas are evaluated for detection.
Example 2
(1) According to the formula CuO and Cu2Taking nano CuO sol and nano Cu according to the molar ratio of O being 1: 12Adding the O sol into a reaction kettle, and reacting for 4 hours at 120 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 8h at the temperature of 50 ℃ to finally obtain CuO/Cu2O-La2O3Multi-phase composite sol;
the solid content of the nano CuO sol is 0.5 percent, and the nano Cu2The solid content of the O sol is 2 percent, and the nano La2O3The solids content of the sol was 1.5%. The confined space molecule is gallic acid, and accounts for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 3 percent; nano La2O3La in the sol2O3Account for CuO and Cu2O and La2O3The molar percentage of the total solid content of the sol was 22%.
Preparation and performance evaluation of the coating:
(1) using the CuO/Cu obtained in this example2O-La2O3And (3) spraying the multiphase composite sol on the metal oxide gas-sensitive element by a centrifugal atomization method to obtain a gas-sensitive material coating on the surface of the element. The operating parameters of the centrifugal atomization spraying are as follows: the centrifugal rate is 5000 r/min; the atomization air pressure is 0.65 MPa; the spraying distance is 300 mm.
(2) For the prepared CuO/Cu2O-La2O3Heterogeneous composite nanocoating for NOxThe gas sensitivity characteristics (including sensitivity, response-recovery characteristics, etc.) of the gas are evaluated for detection.
Example 3
(1) According to the formula CuO and Cu2Taking nano CuO sol and nano CuO sol with the molar ratio of O being 1: 1Cu2Adding the O sol into a reaction kettle, and reacting for 12 hours at 90 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 10h at the temperature of 40 ℃ to finally obtain CuO/Cu2O-La2O3Multi-phase composite sol;
the solid content of the nano CuO sol is 0.5 percent, and the nano Cu2The solid content of the O sol is 2 percent, and the nano La2O3The solids content of the sol was 1.5%. The restricted space molecule is polyethylene glycol (PEG2000) occupying CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 2 percent, and the nano La2O3La in the sol2O3Account for CuO and Cu2O and La2O3The molar percentage of the total solid content of the sol was 12%.
Preparation and performance evaluation of the coating:
(1) using the CuO/Cu obtained in this example2O-La2O3And (3) spraying the multiphase composite sol on the metal oxide gas-sensitive element by a centrifugal atomization method to obtain a gas-sensitive material coating on the surface of the element. The operating parameters of the centrifugal atomization spraying are as follows: the centrifugal rate is 4000 r/min; the atomization air pressure is 0.45 MPa; the spraying distance is 200 mm.
(2) For the prepared CuO/Cu2O-La2O3Heterogeneous composite nanocoating for NOxThe gas sensitivity characteristics (including sensitivity, response-recovery characteristics, etc.) of the gas are evaluated for detection.
Comparative example 4
(1) According to the formula CuO and Cu2Taking nano CuO sol and nano Cu according to the molar ratio of O being 1: 12Adding the O sol into a reaction kettle, and reacting for 12 hours at 90 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, carrying out sol reaction for 10h at the temperature of 40 ℃ to finally obtain CuO/Cu2O composite sol;
the solid content of the nano CuO sol is 0.5 percent, and the nano Cu2The solids content of the O sol was 2%. The restricted space molecule is tannic acid, and accounts for CuO and Cu2The mol percentage of the total solid content of the O sol is 1.5 percent, and the nano La2O3La in the sol2O3Is 0%.
Preparation and performance evaluation of the coating:
(1) using the CuO/Cu obtained in this example2And spraying the O composite sol on the metal oxide gas-sensitive element by a centrifugal atomization method to obtain a coating on the surface of the element. The operating parameters of the centrifugal atomization spraying are as follows: the centrifugal rate is 3500 r/min; the atomization air pressure is 0.25 MPa; the spraying distance is 150 mm.
(2) For the prepared CuO/Cu2O composite nanolayered coating with NOxThe gas sensitivity characteristics (including sensitivity, response-recovery characteristics, etc.) of the gas are evaluated for detection.
The invention utilizes the nanometer active effect and the unique physicochemical property of rare earth to successfully prepare the high-dispersion CuO/Cu in the molecular structure of the restricted space2O-La2O3The multiphase composite nano sol solves the problem of easy agglomeration of the traditional nano sol. Simultaneously, the centrifugal atomization coating technology can realize high-quality and uniform CuO/Cu2O-La2O3Controllable preparation of multiphase composite nano coating, effectively improving NO of materialxSensitivity of gas, response-recovery characteristics. Also, the results from the examples show that: gas sensitive materials prepared in examples 1 and 2 used in the present invention for NOxThe sensitivity and response-recovery characteristics of the gas are more excellent.
The results of the gas sensitive property test of each example are shown in the following table:
table 1 gas sensitive property test results of each example
Figure BDA0001911756850000051
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention.

Claims (5)

1. CuO/Cu2O-La2O3The preparation method of the multiphase composite sol is characterized by comprising the following steps:
(1) according to the formula CuO and Cu2Taking nano CuO sol and nano Cu according to the molar ratio of O being 1: 12Adding the O sol into a reaction kettle, and reacting for 4-18 h at the temperature of 60-120 ℃;
(2) introducing a reaction product into a round-bottom flask, and adding a restricted space molecule under the stirring condition; after fully and uniformly mixing, adding the nano La dropwise2O3Sol; then carrying out sol reaction for 8-14 h at the temperature of 25-50 ℃ to finally obtain CuO/Cu2O-La2O3Multi-phase composite sol;
the restricted space molecule is tannic acid, gallic acid or polyethylene glycol, and the restricted space molecule accounts for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 1-3%; nano La2O3La in the sol2O3Account for CuO and Cu2O and La2O3The mol percentage of the total solid content of the sol is 9-22%.
2. The method according to claim 1, wherein the nano CuO sol has a solid content of 0.5%.
3. The method of claim 1, wherein the nanocu2The solids content of the O sol was 2%.
4. The method of claim 1, wherein the nano-La is2O3The solids content of the sol was 1.5%.
5. The method of claim 1, wherein the stirring is magnetic stirring.
CN201811566326.5A 2018-12-18 2018-12-18 CuO/Cu2O-La2O3Preparation method of multiphase composite sol Active CN109592703B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811566326.5A CN109592703B (en) 2018-12-18 2018-12-18 CuO/Cu2O-La2O3Preparation method of multiphase composite sol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811566326.5A CN109592703B (en) 2018-12-18 2018-12-18 CuO/Cu2O-La2O3Preparation method of multiphase composite sol

Publications (2)

Publication Number Publication Date
CN109592703A CN109592703A (en) 2019-04-09
CN109592703B true CN109592703B (en) 2021-01-15

Family

ID=65963880

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811566326.5A Active CN109592703B (en) 2018-12-18 2018-12-18 CuO/Cu2O-La2O3Preparation method of multiphase composite sol

Country Status (1)

Country Link
CN (1) CN109592703B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114199953A (en) * 2021-12-15 2022-03-18 吉林大学 Based on Cu2Nitrogen dioxide sensor of O-CuO graded structure micron flower sensitive material and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63310720A (en) * 1987-06-12 1988-12-19 Fujikura Ltd Production of superconducting powder
CN1164526C (en) * 2002-11-20 2004-09-01 上海维来新材料科技有限公司 Complex super fine powder of copper-zinc compound as well as its preparing technique and usage
CN101927152B (en) * 2010-03-12 2012-10-03 大连海鑫化工有限公司 High-strength gas purifying and separating adsorbent as well as preparation and application thereof
CN102659166B (en) * 2012-05-21 2014-07-02 兰州大学 Method for preparing CuO/Cu2O block composite material with room-temperature ferromagnetism
WO2014164953A1 (en) * 2013-03-12 2014-10-09 Ut-Battelle, Llc Controllable reductive method for synthesizing metal-containing particles
CN106669716B (en) * 2016-12-07 2019-05-17 盐城工学院 A kind of Cu2O/CuO/WO3The preparation method of composite heterogenous junction film
CN106590728B (en) * 2016-12-15 2018-06-29 浙江工业大学 One kind is with Cu2O/SiO2-Al2O3The method that composite aerogel removes thiophene sulphur in fuel oil for adsorbent
CN107033946B (en) * 2017-03-14 2018-08-14 浙江工业大学 One kind is with Cu2O/SiO2-TiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil

Also Published As

Publication number Publication date
CN109592703A (en) 2019-04-09

Similar Documents

Publication Publication Date Title
CN110672670B (en) Planar flexible room temperature NO based on three-dimensional MXene folded ball/ZnO composite material2Sensor and preparation method thereof
Dong et al. A novel coral-shaped Dy2O3 gas sensor for high sensitivity NH3 detection at room temperature
CN100592082C (en) Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device
Rong et al. Highly selective and sensitive methanol gas sensor based on molecular imprinted silver-doped LaFeO3 core–shell and cage structures
CN106501449B (en) A kind of gas sensitive and element and preparation method for detecting formaldehyde gas
CN108732207A (en) A kind of sensitive material used in formaldehyde examination and preparation method and application
Nagornov et al. Zinc oxide obtained by the solvothermal method with high sensitivity and selectivity to nitrogen dioxide
CN113176305B (en) Composite gas-sensitive material and preparation method thereof, ethanol gas sensor and preparation method thereof
Shen et al. Highly sensitive ethanol gas sensor based on In 2 O 3 spheres
CN109592703B (en) CuO/Cu2O-La2O3Preparation method of multiphase composite sol
CN113834863A (en) Based on three-dimensional Ti3C2Room temperature high selectivity NO of Tx/rGO composite folded ball2Sensor and preparation method
CN101302121B (en) Modified ceramic oxygen permeable film with surface covered by nano-coating and making method thereof
Gong et al. Design of pn heterojunction on mesoporous ZnO/Co3O4 nanosheets for triethylamine sensor
CN102507662A (en) Preparation methods of lanthanum-doped cobalt nickel ferrite gas-sensitive powder and gas sensor
Liu et al. Ultrasensitive ammonia gas sensor based on Ti3C2Tx/Ti3AlC2 planar composite at room temperature
CN110514700A (en) A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method
KR20150085560A (en) Methyl benzene sensors using Pd-loaded SnO2 yolk shell spheres and fabrication method thereof
CN112403491A (en) Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof
CN109580885B (en) CuO/Cu2O-La2O3Preparation method of gas-sensitive material coating of multiphase composite sol
Qin et al. Preparation of P-LaFeO₃/n-Fe₂O₃ heterojunction composites by one-step hydrothermal method and gas sensing properties for acetone
CN109665556A (en) A kind of sea urchin shape copper oxide and its preparation method and application
CN112777586B (en) Preparation and application of sensing film for ammonia sensor
CN109557141B (en) Titanium dioxide/silver vanadate nano heterojunction and preparation method and application thereof
KR101293948B1 (en) A method of manufacturing hybrid material using gas sensor and hybrid material thereof
CN1219725C (en) Prepn. of high-performance composite oxide powder

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
GR01 Patent grant
GR01 Patent grant