CN105537614B - A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template - Google Patents

A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template Download PDF

Info

Publication number
CN105537614B
CN105537614B CN201510994851.7A CN201510994851A CN105537614B CN 105537614 B CN105537614 B CN 105537614B CN 201510994851 A CN201510994851 A CN 201510994851A CN 105537614 B CN105537614 B CN 105537614B
Authority
CN
China
Prior art keywords
cuprous oxide
noble metal
nanometer material
prepared
metal nanometer
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
CN201510994851.7A
Other languages
Chinese (zh)
Other versions
CN105537614A (en
Inventor
田亮亮
杨聪
陈艳玲
伍沈平
夏楷东
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.)
Jiangsu jinyufeng New Material Co.,Ltd.
Original Assignee
Chongqing University of Arts and Sciences
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 Chongqing University of Arts and Sciences filed Critical Chongqing University of Arts and Sciences
Priority to CN201510994851.7A priority Critical patent/CN105537614B/en
Priority to CN201711108148.7A priority patent/CN107900374B/en
Publication of CN105537614A publication Critical patent/CN105537614A/en
Application granted granted Critical
Publication of CN105537614B publication Critical patent/CN105537614B/en
Active 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
    • 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

Abstract

The invention discloses a kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template, comprise the following steps：（1）Cuprous oxide is dispersed in low mass molecule alcohol, adds the low mass molecule alcohol solution of precious metal salt, ultrasonic agitation mixing under agitation；（2）By step（1）Obtained mixed liquor, which is added dropwise in water, to react；（3）Cuprous oxide core is removed after the completion of reaction, obtains hollow noble metal nanometer material.The present invention uses and cuprous oxide and precious metal salt is first stirred by ultrasonic to mixing in low mass molecule alcohol, the method reacted in water is added dropwise to again, overcome conventional method reaction it is uneven the shortcomings that, the uniform accurate hollow noble metal nanometer material for replicating cuprous oxide template pattern is prepared.

Description

A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template
Technical field
The present invention relates to hollow nano-material technical field, and in particular to one kind prepares hollow expensive using cuprous oxide as template The method of metal nano material.
Background technology
It is hollow nanostructured that there is big specific surface area and abundant pore structure, small component units such as nanometer Grain, nanocube, nanometer sheet etc. constitute the porous wall of hollow-core construction, it is had unique performance in actual applications, Substantial amounts of guest molecule or larger-size molecule can be accommodated.And the noble metal nanometer material with hollow-core construction combines sky The advantages of core structure and noble metal nano particles, there is the property such as density is low, specific surface area is big, high stability and Surface Permeability Matter, there is more active site, electro catalytic activity increases substantially, in necks such as biochemistry, catalysis, material science Domain has special application prospect.And, hollow-core construction can both increase substantially electro catalytic activity, again due to noble metal costly Save cost.
Cu2O is a kind of P-type semiconductor, has more application in energy storage, catalysis and sensor field.Cu2O/Cu redox Electricity is to value（‒0.36V）Than precious metals pt Cl6 2‒/Pt（0.735V）、PdCl4 2‒/Pd（0.987V）It is much lower Deng noble metal, because This Cu2O can be with PtCl6 2‒、PdCl4 2‒Deng spontaneous oxidation reduction reaction occurs so as to reaching in its Surface coating precious metal element Purpose, finally remove Cu2O templates obtain being based on Cu2The noble metal hollow structure of O patterns.With Cu2O is to sacrifice template to prepare Noble metal hollow material has advantages below：(1) use of reducing agent is avoided so as to reduce the negative effect to environment； (2) Cu2O production costs are low, and technical maturity is easy to control, suitable for mass production；(3) Cu2The diversity of O patterns and size Support is provided to design and synthesizing Bu Tong polynary noble metal hollow structure.
It is that the method that template prepares hollow noble metal nanometer material is currently with cuprous oxide：First by Cu2O ultrasonic disperses In water, precious metal salt solution is then added to Cu under agitation2In O suspension, noble metal bag is obtained by reaction The Cu covered2O cores, finally remove Cu2O templates, obtain being based on Cu2The noble metal hollow structure of O patterns.Such method is in noble metal Salting liquid is added to Cu2When in O suspension, due to the uneven Cu that can cause first to contact precious metal salt of reactant in system2O Excessively coated, cause the uneven of reaction, so as to cause the inhomogeneities of final hollow noble metal nanometer material, shown as not Can accurate backed stamper plate shape looks, substantial amounts of local broken and surface roughness increase.
The content of the invention
In view of this, hollow noble metal nano material is prepared by template of cuprous oxide it is an object of the invention to provide one kind The method of material, the uniform accurate hollow noble metal nanometer material for replicating cuprous oxide template pattern can be obtained.
To reach above-mentioned purpose, the present invention provides following technical scheme：
A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template, comprises the following steps：
（1）Cuprous oxide is dispersed in low mass molecule alcohol, adds the low mass molecule alcohol of precious metal salt under agitation Solution, ultrasonic agitation mixing；
（2）By step（1）Obtained mixed liquor, which is added dropwise in water, to react；
（3）Cuprous oxide core is removed after the completion of reaction, obtains hollow noble metal nanometer material.
Further, the cuprous oxide is the cuprous oxide of cubic structure.
Further, the cuprous oxide of the cubic structure is prepared by following methods：It is past under 50-60 DEG C of stirring condition CuCl2Excessive NaOH solution reaction 0.5-1h is added in solution, ascorbic acid solution is then slowly added dropwise again, after reacting 3-4h Centrifugation, then cleaned respectively with water and ethanol, finally it is dried in vacuo, obtains the cuprous oxide of cubic structure.
Further, the step（1）In, the anion of precious metal salt is PtCl6 2‒Or/and PdCl4 2‒。
Further, the step（1）In, precious metal salt H2PtCl6Or/and Na2PdCl4。
Further, the step（1）In, low mass molecule alcohol is the one or more in methanol, ethanol and ethylene glycol.
Further, the step（1）In, the precious metal salt of addition and the mol ratio of cuprous oxide are 1.4-2.3:1.
Further, the step（1）In, the ultrasonic agitation mixing 60-90min at 20-25 DEG C.
Further, the step（2）In, mixed liquor is added dropwise to 10-15 times of volume with 12-20ml/min rate of addition 30-60min is reacted in water.
Further, the step（3）In, product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, The ammoniacal liquor complexing for adding 18%-25% removes cuprous oxide core, and the nitric acid for then adding 0.1-0.5mol/L reacts at 10-25 DEG C Copper caused by removing disproportionated reaction, obtains hollow noble metal nanometer material.
The beneficial effects of the present invention are：
The present invention uses and cuprous oxide and precious metal salt is first stirred by ultrasonic to mixing in low mass molecule alcohol, then is added dropwise in water The method of reaction, overcome conventional method reaction it is uneven the shortcomings that, be prepared and uniform accurate replicate cuprous oxide mould The hollow noble metal nanometer material of plate shape looks.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out Explanation：
Fig. 1 is the stereoscan photograph of cube hollow Pt nano materials prepared by embodiment 1；
Fig. 2 is the stereoscan photograph of cube hollow Pt nano materials prepared by comparative example 1.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
According to cuprous oxide pattern and the diversity of size, the hollow noble metal nano of different structure can be designed and synthesized Material, following examples and comparative example are by taking the cuprous oxide of cubic structure as an example.
The cuprous oxide for the cubic structure that following examples and comparative example are used is prepared by following methods：
Under 55 DEG C of stirring conditions, to the CuCl that 100 ml concentration are 0.01mol/L210mL concentration is added in solution is 2mol/L NaOH solution, after reacting 0.5h, then the ascorbic acid solution that 10ml concentration is 0.6mol/L is slowly added dropwise, instead After answering 3h, centrifugation, cleaned respectively with water and ethanol, 12 h of last 40 DEG C of vacuum drying, obtain the cuprous oxide of cubic structure.
Embodiment 1
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 1, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml ethanol, adds 20mM under agitation H2PtCl6Ethanol solution, make H2PtCl6Mol ratio with cuprous oxide is 1.4:1, mixing is stirred by ultrasonic at 25 DEG C 60min；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 15 times of volumes with 20ml/min rate of addition to react 30min；
（3）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammoniacal liquor complexing for adding 20% removes oxidation Asia Copper core, then add 0.1mol/L nitric acid react at 25 DEG C removal disproportionated reaction caused by copper, obtain a cube hollow Pt and receive Rice material.
Embodiment 2
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 2, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml methanol, adds 30mM under agitation Na2PdCl4Methanol solution, make Na2PdCl4Mol ratio with cuprous oxide is 2.0:1, mixing is stirred by ultrasonic at 25 DEG C 70min；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 12 times of volumes with 15ml/min rate of addition to react 50min；
（3）Product is centrifuged into 5min under the conditions of 8000 turns after the completion of reaction, the ammoniacal liquor complexing for adding 20% removes oxidation Asia Copper core, then add 0.2mol/L nitric acid react at 20 DEG C removal disproportionated reaction caused by copper, obtain a cube hollow Pd and receive Rice material.
Embodiment 3
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 3, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml ethylene glycol, added under agitation 20mM H2PtCl6The Na of ethylene glycol solution and 30mM2PdCl4Ethylene glycol solution, make H2PtCl6And Na2PdCl4Sum and oxidation Cuprous mol ratio is 2.3:1, the ultrasonic agitation mixing 90min at 20 DEG C；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 10 times of volumes with 12ml/min rate of addition to react 60min；
（3）Product is centrifuged into 2min under the conditions of 10000 turns after the completion of reaction, the ammoniacal liquor complexing for adding 18% removes oxidation Cuprous core, then add 0.5mol/L nitric acid react removal disproportionated reaction at 10 DEG C caused by copper, obtain cube hollow PtPd nano materials.
Comparative example 1
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of comparative example 1, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml water, adds 20mM's under agitation H2PtCl6The aqueous solution, make H2PtCl6Mol ratio with cuprous oxide is 1.4:1, the stirring reaction 60min at 25 DEG C；
（2）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammoniacal liquor complexing for adding 20% removes oxidation Asia Copper core, then add 0.1mol/L nitric acid react at 25 DEG C removal disproportionated reaction caused by copper, obtain a cube hollow Pt and receive Rice material.
The stereoscan photograph of cube hollow Pt nano materials prepared by embodiment 1 and comparative example 1 as depicted in figs. 1 and 2, The roughness of cube hollow Pt nano materials prepared by embodiment 1 be 10-20nm, cube hollow Pt nanometers of the preparation of comparative example 1 The roughness of material is 20-50nm.
As can be seen from the above results, comparative example 1 reacts uneven, and cube hollow Pt nano materials for causing to obtain are uneven It is even, it is impossible to accurate backed stamper plate shape looks, substantial amounts of local broken and surface roughness increase occur；And embodiment 1 overcomes instead The shortcomings that uneven is answered, obtained cube hollow Pt nano materials are uniform and accurate backed stamper plate shape looks.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (3)

  1. A kind of 1. method that hollow noble metal nanometer material is prepared using cuprous oxide as template, it is characterised in that：Including following step Suddenly：
    （1）Cuprous oxide is dispersed in low mass molecule alcohol, adds the low mass molecule alcohol solution of precious metal salt under agitation, Ultrasonic agitation mixing；The cuprous oxide is the cuprous oxide of cubic structure, and the precious metal salt is H2PtCl6Or/and Na2PdCl4, the low mass molecule alcohol is the one or more in methanol, ethanol and ethylene glycol, and the precious metal salt of addition and oxidation are sub- The mol ratio of copper is 1.4-2.3:1；
    The cuprous oxide of the cubic structure is prepared by following methods：Under 50-60 DEG C of stirring condition, toward CuCl2Added in solution Excessive NaOH solution reaction 0.5-1h, is then slowly added dropwise ascorbic acid solution, is centrifuged after reacting 3-4h, then use water respectively again Cleaned with ethanol, finally vacuum drying is made；
    （2）By step（1）Obtained mixed liquor is added dropwise in the water of 10-15 times of volume instead with 12-20ml/min rate of addition Answer 30-60min；
    （3）Cuprous oxide core is removed after the completion of reaction, obtains hollow noble metal nanometer material.
  2. 2. the method according to claim 1 that hollow noble metal nanometer material is prepared using cuprous oxide as template, its feature It is：The step（1）In, the ultrasonic agitation mixing 60-90min at 20-25 DEG C.
  3. 3. the method according to claim 1 that hollow noble metal nanometer material is prepared using cuprous oxide as template, its feature It is：The step（3）In, product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, adds 18%-25% Ammoniacal liquor complexing remove cuprous oxide core, then add 0.1-0.5mol/L nitric acid react at 10-25 DEG C removal disproportionation instead Copper caused by answering, obtains hollow noble metal nanometer material.
CN201510994851.7A 2015-12-28 2015-12-28 A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template Active CN105537614B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510994851.7A CN105537614B (en) 2015-12-28 2015-12-28 A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template
CN201711108148.7A CN107900374B (en) 2015-12-28 2015-12-28 Preparation method of cubic platinum nano material with good uniformity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510994851.7A CN105537614B (en) 2015-12-28 2015-12-28 A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201711108148.7A Division CN107900374B (en) 2015-12-28 2015-12-28 Preparation method of cubic platinum nano material with good uniformity

Publications (2)

Publication Number Publication Date
CN105537614A CN105537614A (en) 2016-05-04
CN105537614B true CN105537614B (en) 2017-11-28

Family

ID=55817427

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510994851.7A Active CN105537614B (en) 2015-12-28 2015-12-28 A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template
CN201711108148.7A Active CN107900374B (en) 2015-12-28 2015-12-28 Preparation method of cubic platinum nano material with good uniformity

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201711108148.7A Active CN107900374B (en) 2015-12-28 2015-12-28 Preparation method of cubic platinum nano material with good uniformity

Country Status (1)

Country Link
CN (2) CN105537614B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109055961B (en) * 2018-08-29 2020-08-28 深圳先进技术研究院 Noble metal supported nano-frame catalyst and preparation method and application thereof
CN109759135B (en) * 2019-02-02 2020-02-21 哈尔滨工业大学 Preparation method of composite material for removing heavy metal/hydrophobic ppcps in reclaimed water
CN112028109B (en) * 2020-08-24 2022-11-08 广东省医疗器械研究所 Composite nano material and preparation method and application thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0251666B2 (en) * 1980-03-24 1990-11-08 Iyutokemisuka Inst
JPS56136904A (en) * 1980-03-31 1981-10-26 Toshiba Corp Production of platinum group particle
JP2837910B2 (en) * 1990-03-01 1998-12-16 チタン工業株式会社 Method for producing noble metal fine particles using emulsion type liquid film method
JPH0657314A (en) * 1992-08-06 1994-03-01 Sumitomo Metal Mining Co Ltd Production of fine palladium powder
CN1304107C (en) * 2004-10-22 2007-03-14 马贞亮 Preparation process of photocatalyzing active nano TiO2 collosol
CN101690977B (en) * 2009-09-14 2011-06-01 西安交通大学 Preparation method of hollow noble metal nanoparticles
CN103043703B (en) * 2013-01-05 2014-06-11 河北工业大学 Preparation method of hollow Cu2O cubic box
CN103042231B (en) * 2013-01-11 2014-09-03 哈尔滨工业大学 Preparation method of precious metal nano-particles
CN103447549B (en) * 2013-09-13 2015-02-25 重庆文理学院 Preparation method of cobalt nanosphere
CN104259473B (en) * 2014-09-23 2017-01-11 中国科学院化学研究所 Hollow spherical precious metal nanometer material preparation method

Also Published As

Publication number Publication date
CN105537614A (en) 2016-05-04
CN107900374B (en) 2020-06-23
CN107900374A (en) 2018-04-13

Similar Documents

Publication Publication Date Title
CN104084240B (en) Magnetic core/shell/shell triple structure material with noble metal nano particles being at double-shell interlayer and preparation method of material
CN102989450B (en) Preparation method, structural feature and application of carrying type nanometer electrocatalyst
CN103977794B (en) A kind of support type three-dimensional structure noble metal catalyst and its preparation method and application
CN106378194B (en) A kind of UiO-66-NH of carrying transition metal copper2Composite catalyst and the preparation method and application thereof
CN105537614B (en) A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template
CN105431230B (en) Method for forming noble metal nanoparticles on a support
CN104646025B (en) A kind of preparation method of hollow Pt/Ni alloys and graphene aerogel composite
CN105879887B (en) A kind of Cu2O@Cu/AgBr composite photo-catalyst and preparation method thereof
CN103111307B (en) Preparation method of graphene supported nickel/platinum core-shell nano compound
CN105879881A (en) Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction
CN106957068A (en) A kind of α-MnO2The preparation method of nano wire
CN102355952A (en) Catalyst with supported platinum-group metal, process for producing water in which hydrogen peroxide has been decomposed, process for producing water from which dissolved oxygen has been removed, and method of cleaning electronic part
CN110756225A (en) Metal/MOFs nano catalyst and preparation method and application thereof
CN103657643B (en) A kind of method preparing nano palladium metal catalyst
CN104096578A (en) Preparation method for an Ag/AgBr/GO nano-composite photocatalyst
CN104474984A (en) Mesoporous organic-inorganic hybrid hollow sphere having multilayer structure and preparation method of mesoporous organic-inorganic hybrid hollow sphere
CN102717090A (en) Method for preparing ultrafine platinum powder by adopting liquid-phase reduction
CN103638988B (en) Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material
CN109732100A (en) A kind of preparation method of the dendritic Pt nanoparticle of small size
CN110560103B (en) Preparation method and application of porous nano hydroxyapatite-loaded nano gold catalyst
Yu et al. Porous wood decorated with gold nanoparticles as flow-through membrane reactor for catalytic hydrogenation of methylene blue and 4-nitrophenol
CN109453762A (en) A kind of preparation method and application of modified clay mine loaded palladium catalyst
CN104959136B (en) A kind of preparation method for adding hydrogen into resin egg-shell catalyst
CN103638974A (en) Catalyst taking graphene nano-sheet as framework as well as preparation method and application of catalyst
CN101966455B (en) Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process

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
CB03 Change of inventor or designer information

Inventor after: Tian Liangliang

Inventor after: Wu Shenping

Inventor before: Tian Liangliang

Inventor before: Yang Cong

Inventor before: Chen Yanling

Inventor before: Wu Shenping

Inventor before: Xia Kaidong

CB03 Change of inventor or designer information
TR01 Transfer of patent right

Effective date of registration: 20200918

Address after: No. 2-2-1-61, No. 319, Haier Road, Jiangbei District, Chongqing

Patentee after: Chongqing Steady Technology Co.,Ltd.

Address before: No. 319 Chongqing District of Yongchuan City, Honghe Avenue 402160

Patentee before: CHONGQING University OF ARTS AND SCIENCES

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201211

Address after: 221000 Shengqiang Road, Xinhe Town, Pizhou City, Xuzhou City, Jiangsu Province

Patentee after: Jiangsu jinyufeng New Material Co.,Ltd.

Address before: 2-2-1-61, No. 319, Haier Road, Jiangbei District, Chongqing

Patentee before: Chongqing Steady Technology Co.,Ltd.

TR01 Transfer of patent right