CN111111691B - Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof - Google Patents

Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof Download PDF

Info

Publication number
CN111111691B
CN111111691B CN202010045006.6A CN202010045006A CN111111691B CN 111111691 B CN111111691 B CN 111111691B CN 202010045006 A CN202010045006 A CN 202010045006A CN 111111691 B CN111111691 B CN 111111691B
Authority
CN
China
Prior art keywords
metal
graphene
composite material
iron oxyhydroxide
ternary composite
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
CN202010045006.6A
Other languages
Chinese (zh)
Other versions
CN111111691A (en
Inventor
孙华明
林德智
高子伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN202010045006.6A priority Critical patent/CN111111691B/en
Publication of CN111111691A publication Critical patent/CN111111691A/en
Application granted granted Critical
Publication of CN111111691B publication Critical patent/CN111111691B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts 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
    • B01J23/8906Iron and noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a nano iron oxyhydroxide/metal/graphene ternary composite material and a preparation method thereof. The preparation method disclosed by the invention is simple in preparation process, no extra reducing agent or stabilizer is required to be added, the nano iron oxyhydroxide loaded on the graphene is in a strip shape and is uniformly distributed on the surface of the graphene, the wettability of the surface of the graphene is controllable, the operation process is simple, the production cost is low, the industrial production is easy to realize, and the obtained nano iron oxyhydroxide/metal/graphene ternary composite material has good amphipathy, is acid-base-resistant and high-temperature-resistant relative to graphene oxide, has high catalytic activity of metal species, and has potential application in two-phase organic reaction catalyzed by emulsion.

Description

Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of nano composite materials, and particularly relates to a nano iron oxyhydroxide/metal/graphene ternary composite material and a preparation method thereof.
Background
The graphene material has the characteristics of large specific surface area, excellent physical properties, adjustable surface chemical properties and the like, and is concerned in recent years. Graphene oxide, which is an important member of a graphene family, shows good hydrophilicity due to the rich oxygen-containing functional groups, while the carbon of the main sheet layer makes the graphene oxide have certain hydrophobicity, and the performance of the graphene oxide is close to that of a two-dimensional surfactant, so that the graphene oxide already shows certain interfacial activity. However, the acid-base stability and the thermal stability of the graphene oxide are poor, so that the application of the graphene oxide in the aspect of interfacial catalysis organic chemical reaction is limited. The hydrophilic and hydrophobic solid particle hybridization synergistic effect can play a role in surface activity regulation, and the solid nanoparticles have more excellent thermal stability and acid and alkali stability compared with organic functional groups, so that a new idea is provided for graphene oxide interface regulation.
However, in the prior art, graphene is mainly used as a carrier material of a catalyst, and a metal nanoparticle is mainly supported by an immersion reduction method, a precipitation deposition method, or the like. In the reduction process of these methods, a liquid phase chemical reduction method using highly toxic hydrazine, hydrazine hydrate or the like as a reducing agent or a high temperature reduction method using a gas such as hydrogen, carbon monoxide or the like is generally used. The methods cannot effectively control the size, the dispersity and the loading amount of the loaded metal nanoparticles, and the loaded metal nanoparticles have poor binding force with a matrix, so that the interfacial activity of the surface of graphene is weakened, and the metal nanoparticles are easy to fall off from the matrix or agglomerate in the catalysis process, thereby reducing the catalytic activity. In fact, in these conventional methods, the biggest problem faced is that graphene is irreversibly agglomerated during the preparation process, and monodisperse graphene is not easily obtained; the interaction between the catalyst nanoparticles and the carrier is weak, graphene is difficult to be agglomerated together, and most of reported graphene sheets modified by the metal nanoparticles are in an aggregation state. Thus, the huge specific surface area of the graphene cannot be fully utilized, and the synergistic catalytic action of the compound cannot be fully exerted.
Disclosure of Invention
The invention aims to provide an acid-base-resistant and high-temperature-resistant nano iron oxyhydroxide/metal/graphene ternary composite material with good amphipathy and catalytic activity, and a simple preparation method for the ternary composite material, so that strip-shaped iron oxyhydroxide particles and metal are not coated by a surfactant and distributed on the surface of graphene in a monodisperse state, and the interfacial activity of the surface of the graphene is maintained.
Aiming at the purposes, the nano iron oxyhydroxide/metal/graphene ternary composite material adopted by the invention is prepared by the following method: ultrasonically dispersing graphite oxide in deionized water to obtain graphite oxide dispersion liquid; adding metal chloride into the graphite oxide dispersion liquid under the stirring condition, adding an organic solution containing iron pentacarbonyl, reacting for 1-3 hours under the closed condition at 50-80 ℃, filtering, washing and drying after the reaction is finished, thus obtaining the nano iron oxyhydroxide/metal/graphene ternary composite material.
In the above production method, the mass volume concentration of graphite oxide in the graphite oxide dispersion liquid is preferably 1 to 15mg/mL.
The metal chloride is any one of palladium chloride, nickel chloride and ruthenium chloride, the mass ratio of graphite oxide to metal chloride is preferably 5 to 1300, and the mass ratio of graphite oxide to metal chloride is more preferably 5 to 150.
In the above production method, the mass-to-volume ratio of graphite oxide to iron pentacarbonyl is preferably 0.01 to 5g, more preferably 0.03 to 1g.
In the organic solution containing iron pentacarbonyl, the volume concentration of the iron pentacarbonyl is preferably 1.5-135 mL/L.
The organic solution is any one of acetonitrile, acetone and benzaldehyde.
The invention has the following beneficial effects:
according to the invention, water and an organic solvent are simultaneously used as solvents, iron pentacarbonyl is used for reducing graphite oxide and metal chloride, no other reducing agent is added, and the nano-hydroxyl iron oxide/metal/graphene ternary composite material is prepared through a one-step reaction. The iron oxyhydroxide and the metal particles are loaded on the surface of the graphene in a nano-scale manner, the particle size is small, the iron oxyhydroxide and the metal particles are uniformly distributed on the surface of the graphene, and the stability and the dispersibility are good. The shape of the nano iron oxyhydroxide is a nano belt, and the nano belt is distributed on the surface of the graphene oxide in a monodisperse state. The method has the advantages of few synthesis steps, low production cost and easy realization of industrial production.
The nano iron oxyhydroxide/metal/graphene ternary composite material prepared by the invention has good amphipathy, and is acid-base-resistant and high-temperature-resistant compared with graphene oxide. And the surface wettability of the composite material can be regulated and controlled by regulating the proportion of the iron oxyhydroxide. Meanwhile, the composite material has metal species with high catalytic activity and has potential application in two-phase organic reaction catalyzed by emulsion.
Drawings
Fig. 1 is an XRD pattern of graphite oxide, nano-iron oxyhydroxide/palladium/graphene ternary composite material prepared in example 1, and an XRD standard card of iron oxyhydroxide.
Fig. 2 is a transmission electron microscope image of the nano iron oxyhydroxide/palladium/graphene ternary composite material prepared in example 1.
Fig. 3 is a contact angle of the nano iron oxyhydroxide/palladium/graphene ternary composite prepared in example 2 (a), example 3 (B), and example 4 (C).
FIG. 4 is a scanning electron microscope image of the ternary composite material of nano-iron oxyhydroxide/nickel/graphene prepared in example 5.
FIG. 5 is a transmission electron microscope image of the nano iron oxide hydroxide/nickel/graphene ternary composite material prepared in example 5.
Fig. 6 is a scanning electron microscope image of the nano iron oxyhydroxide/ruthenium/graphene ternary composite material prepared in example 6.
FIG. 7 is a transmission electron microscope image of the ternary composite material of nano-iron oxyhydroxide/ruthenium/graphene prepared in example 6.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Adding 150mg of Graphite Oxide (GO) into 15mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid. Under the condition of stirring, adding 1mg of palladium chloride into the graphite oxide dispersion liquid, then transferring the graphite oxide dispersion liquid into a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 16.7mL/L of iron pentacarbonyl, reacting for 2 hours at 60 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/palladium/graphene ternary composite material (Pd/FeOOH @ RGO).
The XRD spectrum in figure 1 shows that the obtained product is a nano iron oxyhydroxide/palladium/graphene ternary composite material, figure 2 shows that the nano iron oxyhydroxide is in a strip shape, the width is about 15nm, the nano iron oxyhydroxide is dispersed on the surface of graphene, and the size of the nano palladium particle is about 5 nm.
Example 2
And adding 25mg of graphite oxide into 5mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid. Under the stirring condition, adding 5mg of palladium chloride into the graphite oxide dispersion liquid, then transferring the graphite oxide dispersion liquid into a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 5mL/L iron pentacarbonyl, reacting for 2 hours at 50 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/palladium/graphene ternary composite material.
Example 3
And adding 25mg of graphite oxide into 5mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid. Under the condition of stirring, adding 5mg of palladium chloride into the graphite oxide dispersion liquid, then transferring to a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 20mL/L iron pentacarbonyl, reacting for 2 hours at 50 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/palladium/graphene ternary composite material.
Example 4
And adding 25mg of graphite oxide into 5mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid. Under the stirring condition, adding 5mg of palladium chloride into the graphite oxide dispersion liquid, then transferring the graphite oxide dispersion liquid into a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 50mL/L iron pentacarbonyl, reacting for 2 hours at 50 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/palladium/graphene ternary composite material.
As can be seen from fig. 3, in examples 2, 3 and 4, the contact angle of the nano iron oxyhydroxide/palladium/graphene ternary composite material can be changed by controlling the concentration of the added iron pentacarbonyl, so as to change the wettability and surface activity of the composite material. With the increase of the concentration of the iron pentacarbonyl, the hydrophilicity of the composite material is reduced, and the lipophilicity is increased.
Example 5
Adding 125mg of graphite oxide into 15mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid; under the condition of stirring, adding 1mg of nickel chloride into the graphite oxide dispersion liquid, then transferring the graphite oxide dispersion liquid into a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 16.7mL/L of iron pentacarbonyl, reacting for 2 hours at 60 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/nickel/graphene ternary composite material. As can be seen from fig. 4 and 5, the composite material maintains the sheet structure of graphene, and the nano iron oxyhydroxide is in the form of a band and is dispersed on the surface of graphene.
Example 6
Adding 125mg of graphite oxide into 15mL of deionized water, and performing ultrasonic dispersion to obtain a graphite oxide dispersion liquid; under the condition of stirring, adding 1mg of ruthenium chloride into the graphite oxide dispersion liquid, then transferring the graphite oxide dispersion liquid into a 150mL round-bottom flask, adding 15mL of acetonitrile solution with the volume concentration of 16.7mL/L of iron pentacarbonyl, reacting for 2 hours at 60 ℃ under the closed condition, filtering after the reaction is finished, washing with deionized water, and freeze-drying to obtain the nano iron oxyhydroxide/ruthenium/graphene ternary composite material. As can be seen from fig. 6 and 7, the composite material maintains the sheet structure of graphene, and the nano iron oxyhydroxide is in the form of a band and is dispersed on the surface of graphene.

Claims (9)

1. A preparation method of a nano iron oxyhydroxide/metal/graphene ternary composite material is characterized by comprising the following steps: ultrasonically dispersing graphite oxide in deionized water to obtain graphite oxide dispersion liquid; adding metal chloride into the graphite oxide dispersion liquid under the stirring condition, adding an organic solution containing iron pentacarbonyl, reacting for 1-3 hours at 50-80 ℃ under a closed condition, filtering, washing and drying after the reaction is finished to obtain a nano iron oxyhydroxide/metal/graphene ternary composite material; the metal chloride is any one of palladium chloride, nickel chloride and ruthenium chloride.
2. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 1, characterized in that: the mass volume concentration of the graphite oxide in the graphite oxide dispersion liquid is 1-15 mg/mL.
3. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 1, characterized in that: the mass ratio of the graphite oxide to the metal chloride is 5-1300.
4. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 3, characterized in that: the mass ratio of the graphite oxide to the metal chloride is 5-150.
5. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 1, characterized in that: the mass volume ratio of the graphite oxide to the iron pentacarbonyl is 0.01-5 g.
6. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 5, characterized in that: the mass volume ratio of the graphite oxide to the iron pentacarbonyl is 0.03-1 g.
7. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 1, characterized in that: in the organic solution containing iron pentacarbonyl, the volume concentration of the iron pentacarbonyl is 1.5-135 mL/L.
8. The preparation method of the nano iron oxyhydroxide/metal/graphene ternary composite material according to claim 1, characterized in that: the organic solution is any one of acetonitrile, acetone and benzaldehyde.
9. The nano iron oxyhydroxide/metal/graphene ternary composite material prepared by the method of any one of claims 1 to 8.
CN202010045006.6A 2020-01-16 2020-01-16 Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof Active CN111111691B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010045006.6A CN111111691B (en) 2020-01-16 2020-01-16 Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010045006.6A CN111111691B (en) 2020-01-16 2020-01-16 Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111111691A CN111111691A (en) 2020-05-08
CN111111691B true CN111111691B (en) 2022-10-21

Family

ID=70490302

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010045006.6A Active CN111111691B (en) 2020-01-16 2020-01-16 Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111111691B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5652192A (en) * 1992-07-10 1997-07-29 Battelle Memorial Institute Catalyst material and method of making
US7829140B1 (en) * 2006-03-29 2010-11-09 The Research Foundation Of The State University Of New York Method of forming iron oxide core metal shell nanoparticles
KR20150116489A (en) * 2014-04-07 2015-10-16 인하대학교 산학협력단 METHOD OF PREPARING IRON OXIDE-GRAPHENE COMPOSITES AND THE IRON OXIDE(β-FEOOH)-GRAPHENE COMPOSITES PREPARED BY THE SAME METHOD
CN106082351A (en) * 2016-06-01 2016-11-09 浙江大学 The preparation method of a kind of FeOOH nanometer sheet and product thereof
CN110152569A (en) * 2018-04-28 2019-08-23 浙江大学 A kind of nanometer Fe O (OH) composite aerogel, preparation method and use

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130099153A1 (en) * 2011-10-23 2013-04-25 Postech Academy-Industry Foundation Hybrid material comprising graphene and iron oxide, method for manufacturing the same, and apparatus for treating waste water using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5652192A (en) * 1992-07-10 1997-07-29 Battelle Memorial Institute Catalyst material and method of making
US7829140B1 (en) * 2006-03-29 2010-11-09 The Research Foundation Of The State University Of New York Method of forming iron oxide core metal shell nanoparticles
KR20150116489A (en) * 2014-04-07 2015-10-16 인하대학교 산학협력단 METHOD OF PREPARING IRON OXIDE-GRAPHENE COMPOSITES AND THE IRON OXIDE(β-FEOOH)-GRAPHENE COMPOSITES PREPARED BY THE SAME METHOD
CN106082351A (en) * 2016-06-01 2016-11-09 浙江大学 The preparation method of a kind of FeOOH nanometer sheet and product thereof
CN110152569A (en) * 2018-04-28 2019-08-23 浙江大学 A kind of nanometer Fe O (OH) composite aerogel, preparation method and use

Also Published As

Publication number Publication date
CN111111691A (en) 2020-05-08

Similar Documents

Publication Publication Date Title
Jia et al. Colloidal metal nanoparticles as a component of designed catalyst
CN106914255B (en) Non-alloy metal compound and preparation method and application thereof
CN108525669B (en) Highly-dispersed silicon dioxide nanotube supported nickel catalyst and preparation method thereof
Izgi et al. Hydrogen production by using Ru nanoparticle decorated with Fe3O4@ SiO2–NH2 core-shell microspheres
CN103007963A (en) Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier
CN102883809A (en) Supported precious metal catalysts via hydrothermal deposition
Guo et al. Novel honeycomb nanosphere Au@ Pt bimetallic nanostructure as a high performance electrocatalyst for methanol and formic acid oxidation
JP2020023745A (en) High-yield production of two-dimensional copper nano-sheet
CN1970143A (en) Method for preparing high-activity hydrogenation catalyst nano Ru/C
Long et al. Construction of trace silver modified core@ shell structured Pt-Ni nanoframe@ CeO 2 for semihydrogenation of phenylacetylene
CN115770603B (en) Nitrogen-doped carbon-coated copper catalyst and preparation method and application thereof
CN111617785B (en) Supported ruthenium-based phosphide catalyst and preparation method thereof
Liu et al. Ultrafine AuPd nanoparticles supported on amine functionalized monochlorotriazinyl β-cyclodextrin as highly active catalysts for hydrogen evolution from formic acid dehydrogenation
CN106881089B (en) A kind of preparation method of controllable graphene-supported cheap IB-VIIIB race duplex metal nano granule composite material
CN111111691B (en) Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof
CN106984314A (en) A kind of preparation method of high-dispersion loading type copper-based nano-catalyst
Du et al. Microwave irradiation assisted rapid synthesis of Fe–Ru bimetallic nanoparticles and their catalytic properties in water-gas shift reaction
CN110339844A (en) Fe nanometer rods and Pt@Fe Nanorods Catalyst and synthesis and application
Hua et al. Ultrafine Ru and γ-Fe2O3 particles supported on MgAl2O4 spinel for water-gas shift reaction
CN113877614B (en) Modified graphene roll and preparation method and application thereof
CN109465018B (en) Preparation method of nano-scale supported molybdenum sulfide catalyst
JP4919699B2 (en) Method for producing metal fine particle-carbon composite
CN116779887A (en) Synthesis of bimetallic structures for use as catalysts
Wu et al. Supportless oxygen reduction electrocatalysts of CoCuPt hollow nanoparticles
CN114425333B (en) Catalyst for methane catalytic combustion and preparation method thereof

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