CN112589090B - 一种单质态和氧化态共混的金属纳米粉末的制备方法 - Google Patents

一种单质态和氧化态共混的金属纳米粉末的制备方法 Download PDF

Info

Publication number
CN112589090B
CN112589090B CN202011226968.8A CN202011226968A CN112589090B CN 112589090 B CN112589090 B CN 112589090B CN 202011226968 A CN202011226968 A CN 202011226968A CN 112589090 B CN112589090 B CN 112589090B
Authority
CN
China
Prior art keywords
equal
metal
powder
amorphous alloy
less
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
CN202011226968.8A
Other languages
English (en)
Other versions
CN112589090A (zh
Inventor
朱正旺
赵博文
张海峰
张宏伟
李宏
付华萌
王爱民
李正坤
张龙
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.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
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 Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Priority to CN202011226968.8A priority Critical patent/CN112589090B/zh
Publication of CN112589090A publication Critical patent/CN112589090A/zh
Application granted granted Critical
Publication of CN112589090B publication Critical patent/CN112589090B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0081—Preparation by melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0848—Melting process before atomisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

本发明提供了一种利用非晶合金为前驱体制备成分可控的金属单质态和氧化态共混纳米粉末的方法，具体为：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；按原子百分比计，Zr基非晶合金化学成分为：二元Zr基非晶合金：ZrxM100‑x，50≤x≤80，M代表Ni或Pd；三元Zr基非晶合金：ZrxCuyM’100‑x‑y，40≤x≤75，15≤y≤35，M’代表Ag或Al；四元Zr基非晶合金：ZrxCuyAlzM”100‑x‑y‑z，40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种。本发明采用空气气氛燃烧和机械球磨相结合的方法，制备出金属单质态和金属氧化态共混的纳米粉末，合成路线简单可靠，可得到纯度高、尺寸小、分散度好、形貌优良、成分可控、活性高、选择性好的纳米粉末。

Description

一种单质态和氧化态共混的金属纳米粉末的制备方法
技术领域
本发明属于金属氧化物的制备技术领域，具体涉及一种单质态和氧化态共混的金属纳米粉末的制备方法。该纳米粉末可应用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解等多种化学反应过程。
背景技术
金属氧化物在物理、化学和材料科学等众多领域中起着至关重要的作用。金属氧化物一直是功能材料研究领域的热点，由于具有氧化物特有的物理化学性质，被广泛应用于光学、催化、电子及生物医学等行业。同时，金属氧化物拥有较好的热稳定性和化学稳定性，易于制备和进一步功能化，通常被用作氧化催化剂或者还原催化剂，在化学催化反应中有着重要作用。由于纳米材料具有表面与界面效应、小尺寸效应、量子尺寸效应和宏观隧道效应等独特性能，将金属氧化物催化剂纳米化处理或者合成金属氧化物纳米材料，可以明显减小催化剂的尺寸，进而增大其比表面积，提高催化剂的催化活性和选择性。此外，催化剂中形成的金属氧化物的种类和形态在催化反应中尤为重要，因此，迫切需要开发一种成分可控的金属氧化物纳米材料的制备方法。本发明所述的燃烧法为金属氧化物纳米粉末的制备提供了一条简单、绿色、有效的合成路线，能够实现金属单质态和金属氧化态混合的纳米粉末催化剂的高效制备。
发明内容
为了克服金属纳米粉末制备过程中存在的问题，本发明提供了一种利用非晶合金为前驱体制备成分可控且分布均匀、颗粒尺寸均一、稳定性高以及比表面积大的金属单质态和氧化态共混纳米粉末的有效方法。
为了实现上述目的，本发明可以通过以下措施完成：
一种单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；
按原子百分比计，Zr基非晶合金化学成分为：
二元Zr基非晶合金：ZrxM100-x
其中：50≤x≤80，M代表Ni或Pd；
三元Zr基非晶合金：ZrxCuyM’100-x-y
其中：40≤x≤75，15≤y≤50，M’代表Ag或Al；
四元Zr基非晶合金：ZrxCuyAlzM”100-x-y-z
其中：40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种。
本发明所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：将不同成分的合金通过气雾化法制备成非晶粉末，并使其在空气气氛下发生燃烧反应，然后将燃烧所得氧化产物研磨至200目以下置于行星式球磨机中进行高能球磨得到混合粉体；
气雾化制粉参数：喷粉气体流量：0.4～0.8m3/h；球磨参数：球料比：10:1～30:1，转速：100～400rpm/min，球磨时间：0.5～12h。
进一步优选为：气雾化制粉参数：喷粉气体流量：0.45～0.65m3/h；球磨参数：球料比：15:1～30:1，转速：250～350rpm/min，球磨时间：2～4h。
本发明选用纯度≥99.5wt％的纯金属单质原材料锆、铜、镍、钯、铝、银、钛、钆或钇制备Zr基非晶合金粉末。
采用本发明所述方法制备的单质态和氧化态共混的金属纳米粉末，其特征在于，所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物；该粉末具有良好催化反应活性和高选择性等优势。
本发明的有益效果为：
本发明采用空气气氛燃烧和机械球磨相结合的方法，制备出金属单质态和金属氧化态共混的纳米粉末，合成路线简单可靠，可得到纯度高、尺寸小、分散度好、形貌优良、成分可控、活性高、选择性好的纳米粉末。可广泛应用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解等多种化学反应过程。
附图说明
图1是分别由实施例1-2实验过程中得到的OP和NP实物图。
图2是由实施例1所制金属单质态和氧化态共混的纳米粉末NP的TEM照片。
图3是由实施例1中研磨工艺后所制氧化物粉末OP的XRD曲线。
图4是由实施例2中研磨工艺后所制氧化物粉末OP的XRD曲线。
图5是由实施例3中研磨工艺后所制氧化物粉末OP的XRD曲线。
具体实施方式
为使本发明的目的、技术方案和优势更加清楚，下面将结合各实施方式进行详细的阐述，可以实现本发明各权利要求所要求保护的技术方案。
实施例1-7
由非晶合金粉末制备金属单质和金属氧化态共混纳米粉末的方法包括如下步骤：
1、非晶粉末及氧化产物的制备
(1)将按照化学成分原子百分比配制好的合金成分(纯度大于99.5％)放入到非自耗真空电弧熔炼炉内，预抽真空至3.0×10-3Pa后，充入高纯氩气作为保护气，利用电弧加热熔炼金属原料，多次反复熔炼以致完全均匀得到母合金锭。
(2)将步骤(1)熔炼均匀的母合金切割成大小适中的小块合金锭放入气雾化坩埚内，控制气体流量为0.1m3/h，保护母合金融化过程中不被氧化，同时通过气压阀控制体系的气压达到气雾化压力值0.15MPa，然后利用感应加热将合金锭融化，迅速加大进入气雾化坩埚气体流量至0.45～0.65m3/h进而得到非晶粉末，所得非晶粉末通过连续加热反应器使非晶粉末发生类燃烧反应得到金属氧化复合物粉末并研磨至200目以下，记为OP。
2、金属单质和氧化态共混纳米粉末的制备
将上述所得的金属氧化物复合粉末置于行星式球磨机中进行高能球磨处理进而得到纳米粉末，记为NP。球磨参数：球料比：15:1～25:1，转速：250～350rpm/min，球磨时间：2～4h。
实施例1-7的Zr基非晶合金的化学成分元素比例详见表1。
实施例1-7的由Zr基非晶合金制备的纳米粉末中氧化物的种类详见表2。
表1Zr基非晶合金的化学成分元素比例
Figure BDA0002763884590000051
表2纳米粉末中氧化物的种类
Figure BDA0002763884590000052
Figure BDA0002763884590000061
本发明未尽事宜为公知技术。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (6)

1.一种单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；
按原子百分比计，Zr基非晶合金化学成分为：
二元Zr基非晶合金：ZrxM100-x
其中：50≤x≤80，M代表Ni或Pd；
三元Zr基非晶合金：ZrxCuyM’100-x-y
其中：40≤x≤75，15≤y≤50，M’代表Ag或Al；
四元Zr基非晶合金：ZrxCuyAlzM”100-x-y-z
其中：40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种；
所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物。
2.按照权利要求1所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：将不同成分的合金通过气雾化法制备成非晶粉末，并使其在空气气氛下发生燃烧反应，然后将燃烧所得氧化产物研磨至200目以下置于行星式球磨机中进行高能球磨得到混合粉体；
气雾化制粉参数：喷粉气体流量：0.4～0.8m3/h；球磨参数：球料比：10：1～30：1，转速：100～400rpm/min，球磨时间：0.5～12h。
3.按照权利要求1或2所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：喷粉气体流量：0.45～0.65m3/h；球磨参数：球料比：15：1～30：1，转速：250～350rpm/min，球磨时间：2～4h。
4.按照权利要求1所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：选用纯度≥99.5wt％的纯金属单质原材料锆、铜、镍、钯、铝、银、钛、钆或钇制备Zr基非晶合金粉末。
5.一种采用权利要求1所述方法制备的单质态和氧化态共混的金属纳米粉末，其特征在于，所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物。
6.一种权利要求5所述单质态和氧化态共混的金属纳米粉末的应用，其特征在于：所述单质态和氧化态共混的金属纳米粉末用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解化学反应过程。
CN202011226968.8A 2020-11-06 2020-11-06 一种单质态和氧化态共混的金属纳米粉末的制备方法 Active CN112589090B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011226968.8A CN112589090B (zh) 2020-11-06 2020-11-06 一种单质态和氧化态共混的金属纳米粉末的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011226968.8A CN112589090B (zh) 2020-11-06 2020-11-06 一种单质态和氧化态共混的金属纳米粉末的制备方法

Publications (2)

Publication Number Publication Date
CN112589090A CN112589090A (zh) 2021-04-02
CN112589090B true CN112589090B (zh) 2022-05-10

Family

ID=75182829

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011226968.8A Active CN112589090B (zh) 2020-11-06 2020-11-06 一种单质态和氧化态共混的金属纳米粉末的制备方法

Country Status (1)

Country Link
CN (1) CN112589090B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115475618B (zh) * 2022-10-17 2023-09-22 南京工程学院 一种基于可燃非晶条带的多棱柱形四元光催化剂制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2016514C (en) * 1989-05-11 1998-05-12 Ykk Corporation Alloy catalyst for oxidation of hydrogen
CN104445356A (zh) * 2014-10-30 2015-03-25 东南大学 含铜金属复合氧化物光催化材料的制备方法
CN106892496A (zh) * 2017-03-31 2017-06-27 中国科学院金属研究所 铜基非晶态合金作为催化功能材料在废水处理中的应用
CN111304558A (zh) * 2020-04-08 2020-06-19 辽宁大学 一种纳米多孔包覆的Fe基非晶合金及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2823494B2 (ja) * 1993-09-29 1998-11-11 健 増本 非晶質金属超微粒子及びその製造方法
CN103170340A (zh) * 2013-04-15 2013-06-26 厦门大学 一种用于制备合成天然气的催化剂及其制备方法
JP6358246B2 (ja) * 2015-01-08 2018-07-18 セイコーエプソン株式会社 粉末冶金用金属粉末、コンパウンド、造粒粉末、焼結体および装飾品
JP7087557B2 (ja) * 2018-03-29 2022-06-21 マツダ株式会社 パティキュレート浄化用触媒材及びその製造方法
CN108671925B (zh) * 2018-05-28 2021-03-19 国网山东省电力公司电力科学研究院 纳米TiO2-非晶铜基合金复合光催化材料及其制备方法与用途
CN109589980B (zh) * 2018-10-29 2020-12-18 华中科技大学 一种复合材料催化剂的制备方法、及其产品和应用
CN111360272B (zh) * 2020-04-21 2021-10-15 华中科技大学 一种氧化物界面增韧非晶基复合材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2016514C (en) * 1989-05-11 1998-05-12 Ykk Corporation Alloy catalyst for oxidation of hydrogen
CN104445356A (zh) * 2014-10-30 2015-03-25 东南大学 含铜金属复合氧化物光催化材料的制备方法
CN106892496A (zh) * 2017-03-31 2017-06-27 中国科学院金属研究所 铜基非晶态合金作为催化功能材料在废水处理中的应用
CN111304558A (zh) * 2020-04-08 2020-06-19 辽宁大学 一种纳米多孔包覆的Fe基非晶合金及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Cu基非晶合金的电催化氧化性能研究;张威;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170315;全文 *
Preparation of nanostructured Cu/Zr metal mixed oxides via self-sustained oxidation of a CuZr binary amorphous alloy;xingzhou li et.al;<Journal of Materials Science & Technology>;20190831;第1602页第2.1节，第3节第1段 *

Also Published As

Publication number Publication date
CN112589090A (zh) 2021-04-02

Similar Documents

Publication Publication Date Title
WO2021020377A1 (ja) 合金ナノ粒子、合金ナノ粒子の集合体、触媒および合金ナノ粒子の製造方法
CN101250639B (zh) 纳米相弥散强化铜及其制备方法和产品生产工艺
EP1926681B1 (en) Methods and devices for flame spray pyrolysis
US20230321720A1 (en) Method of preparing nano-porous powder material
CN104593651B (zh) 一种Mg-Ti-RE-Ni基贮氢合金及其制备方法
CN113579246B (zh) 一种纳米高熵合金粉末的制备方法
CN111545767A (zh) 一种纳米尺度多元合金的制备方法
CN111940750A (zh) 一种合金粉体材料的制备方法
CN105063457A (zh) 一种纳米石墨复合的高容量RE-Mg-Ni基贮氢材料及其制备方法
CN112387976B (zh) 一种燃料电池用易活化RE-Ti-Fe合金及其制备方法
CN112589090B (zh) 一种单质态和氧化态共混的金属纳米粉末的制备方法
CN111041318A (zh) 一种钨铜合金及其制备方法
CN107099724B (zh) 纳米三氟化钛催化Mg-RE-Ni-Al-Ti-Co基贮氢合金的制备方法
CN103633339B (zh) 一种纳米CeO2催化的高容量RE-Mg-Ni基贮氢合金及其制备方法
CN101439871B (zh) 一种复合纳米SnO2粉末材料及其制备方法
Hesse et al. High-energy ball milling of intermetallic Ti-Cu alloys for the preparation of oxide nanoparticles
WO2015140328A1 (en) Novel process and product
Ardestani et al. Synthesis of WC–20 wt.% Cu composite powders by co-precipitation and carburization processes
JP3720250B2 (ja) 高水素吸蔵合金とその製造方法
Yang et al. Synergistic effects of carbon-encapsulated cobalt/tricobalt tetroxide nanocapsules on hydrogenation of 4-nitrophenol
JP3872465B2 (ja) 高水素吸蔵材料とその製法
CN112264006A (zh) 一种多金属氧化态共存的纳米粉末的制备方法
CN111151762A (zh) 一种低成本细粒度低氧钛及钛合金粉末的制备方法
CN115611242B (zh) 一种难熔金属高熵氮化物粉体及其制备方法
JPH0892672A (ja) 分散強化型合金の製造方法

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