CN104014344A - Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride - Google Patents

Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride Download PDF

Info

Publication number
CN104014344A
CN104014344A CN201410254394.3A CN201410254394A CN104014344A CN 104014344 A CN104014344 A CN 104014344A CN 201410254394 A CN201410254394 A CN 201410254394A CN 104014344 A CN104014344 A CN 104014344A
Authority
CN
China
Prior art keywords
catalyst
solution
ternary alloy
hydrolysis
amorphous ternary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410254394.3A
Other languages
Chinese (zh)
Other versions
CN104014344B (en
Inventor
邹勇进
程军
向翠丽
孙立贤
徐芬
褚海亮
邱树君
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.)
Guilin University of Electronic Technology
Original Assignee
Guilin University of Electronic Technology
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 Guilin University of Electronic Technology filed Critical Guilin University of Electronic Technology
Priority to CN201410254394.3A priority Critical patent/CN104014344B/en
Publication of CN104014344A publication Critical patent/CN104014344A/en
Application granted granted Critical
Publication of CN104014344B publication Critical patent/CN104014344B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Catalysts (AREA)

Abstract

The invention relates to an amorphous ternary alloy/graphene composite catalyst as well as application of the catalyst to hydrolysis of boron hydride. The novel boron hydride hydrolysis catalyst is produced by compounding amorphous alloy Co-Zn-B nano particles in a flaky structure of graphene, and the prepared material is after-treated to improve the catalytic activity of the composite material. The novel catalyst is high in catalytic efficiency, capable of achieving a good catalyzing effect at normal temperature, reusable and simple in preparation process. By virtue of the novel amorphous ternary alloy/graphene composite catalyst prepared through the method, the contact area between the catalyst and a reaction material is increased, and the reaction speed is increased, namely the hydrogen production speed is high; moreover, the novel catalyst preparation process has the advantages of being simple and low in manufacturing cost and the catalyst has great advantages when being applied to the hydrolysis of boron hydride.

Description

Amorphous ternary alloy/graphite alkene composite catalyst and the application in hydroboron hydrolysis thereof
Technical field
The present invention relates to the application of amorphous ternary alloy/graphite alkene composite catalyst, specifically a kind of amorphous ternary alloy/graphite alkene composite catalyst and the application in hydroboron hydrolysis thereof.
Background technology
The energy is the lifeblood of national economy, along with the exhaustion day by day of global conventional energy resource resource and the series of environmental problems that utilizes in a large number fossil energy to bring, the mankind must find the alternative energy source of sustainable development, and exploitation are clean, green novel energy source is undoubtedly final outlet.Hydrogen Energy, as clean, desirable secondary energy sources, is the most important thing of the research of educational circles of current Energy Section, yet the storage of hydrogen and technology of preparing remain the key technology of restriction Hydrogen Energy commercial applications.Borohydride hydrolytic hydrogen production is subject to extensive concern in recent years, and it realizes the release of high-purity hydrogen under temperate condition again, and can be to environment.But the hydrolysis of boron hydride is subject to the restriction of catalyst, develop the key that cheap non-precious metal catalyst becomes borohydride hydrolytic.Therefore the invention of novel amorphous ternary alloy/graphite alkene composite catalyst is to efficiently utilizing Hydrogen Energy to have very important significance.
Summary of the invention
The object of the invention is to provide a kind of amorphous ternary alloy/graphite alkene composite catalyst and the application in hydroboron hydrolysis thereof.
The technical scheme that realizes the object of the invention is:
A preparation method for amorphous ternary alloy/graphite alkene composite catalyst, comprises the steps:
(1) get a certain amount of CoSO 4or NiSO 4with a certain amount of ZnSO 4, join in deionized water;
(2) get a certain amount of Graphene and join in above-mentioned solution, ultrasonic 0.5-3h, pH value is 5-7;
(3) the NaOH solution of configuration 0.05-2 mol/L, gets a certain amount of NaBH 4add in NaOH solution:
(4) solution of step (3) is dripped lentamente with base buret in step (2) solution, and with magnetic stirring apparatus, the solution of step (2) is stirred;
(5) after being added dropwise to complete, filter, wash, be dried,
(6) in 20-30%NaOH solution, flood 1h;
(7) filter, wash, be dried, grind and obtain amorphous ternary alloy/graphite alkene powder.
The application of above-mentioned amorphous ternary alloy/graphite alkene composite catalyst in hydroboron hydrolysis, is:
A) prepared catalyst is distributed to 0.1M NaBH 45% NaOH solution in, sealing, controls the temperature of solution by water bath with thermostatic control;
B) hydrogen of generation is collected to the volume of the hydrogen producing in record unit time, the speed that obtains putting hydrogen by drainage.
The present invention is by the hydrolysis of composite catalyst catalysis boron hydride; It can realize catalyzing hydrolysis at normal temperatures and pressures, and the speed that hydrogen is put in hydrolysis can reach 300 ml/min.
Operation principle of the present invention is:
Metal ion, under the effect of boron hydride, is reduced out, controls reaction condition, can obtain nano metal ion, its concrete reaction principle is as follows: the present invention adopts sodium borohydride as reducing agent, Co, Zn, B is restored from solution, and load on Graphene matrix.
BH 4 + 2H 2O→BO 2 + 4H 2↑
BH 4 + 2Co 2+ + 2H 2O→2Co + BO 2 - + 4H + + 2H 2↑
BH 4 - + H 2O→B + OH + 2.5H 2↑
Prepared nano composite material can be used as again the catalyst of the hydrolysis of boron hydride simultaneously.Under the effect of high alkali liquid, Zn is corroded out from alloy, thereby forms activity site at alloy surface, has further improved the catalytic activity of composite.
Advantage of the present invention is:
1. can catalysis borohydride hydrolytic: the graphene composite material of amorphous ternary alloy of the present invention load, as catalyst, has improved catalytic efficiency, has reduced cost;
2. effect is good: the catalyst dispersive property adopting is good, can in the process of hydrolysis, be suspended in solution, has improved the contact area of catalyst and solution, has improved catalytic efficiency;
3. preparation technology is simple, and properties of product are stable: prepared catalyst preparation is simple, be applicable to large batch of preparation, and aftertreatment technology is simple;
4. easy to use: catalyst is directly mixed with reactant liquor, and also easy and simple to handle, favorable reproducibility.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of Co-Zn-B/ graphen catalyst;
Fig. 2 be Co-Zn-B/ graphen catalyst to NaBH 4hydrolyzation catalysis;
Fig. 3 is the curve that recycles of catalyst of the present invention.
The specific embodiment
Embodiment 1:
1) get 5g CoSO 4, the ZnSO of 0.1g 4, join in 100ml deionized water;
2) get the Graphene of 0.2g, join in above-mentioned solution, ultrasonic 1h, is designated as M solution, and pH is 6;
3) the NaOH solution 20-100 ml of configuration 0.1 mol/L, gets 2 g NaBH 4add in NaOH solution, be designated as N solution;
4) N solution is dripped lentamente with base buret in M solution, and with magnetic stirring apparatus, M solution is stirred;
5) after being added dropwise to complete, filter, wash, be dried,
6) in 30%NaOH solution, flood 1h;
7) then filter, wash, be dried, grind and obtain amorphous ternary alloy/graphite alkene powder, i.e. amorphous ternary alloy/graphite alkene composite catalyst;
8) prepared catalyst is distributed to 0.1M NaBH 45% NaOH solution in, sealing, controls the temperature of solution by water bath with thermostatic control.The hydrogen of generation is collected to the volume of the hydrogen producing in record unit time, the speed that obtains putting hydrogen by drainage.
Embodiment 2:
1) get 5g NiSO 4, the ZnSO of 0.1g 4, join in 100ml deionized water;
2) get the Graphene of 0.2g, join in above-mentioned solution, ultrasonic 1h, is designated as M solution, and pH is 6;
3) the NaOH solution 20-100 ml of configuration 0.1 mol/L, gets 2 g NaBH 4add in NaOH solution, be designated as N solution;
4) N solution is dripped lentamente with base buret in M solution, and with magnetic stirring apparatus, M solution is stirred;
5) after being added dropwise to complete, filter, wash, be dried;
6) in 30%NaOH solution, flood 1h;
7) then filter, wash, be dried, grind and obtain amorphous ternary alloy/graphite alkene powder, i.e. amorphous ternary alloy/graphite alkene composite catalyst;
8) prepared catalyst is distributed to 0.1 M NaBH 45% NaOH solution in, sealing, controls the temperature of solution by water bath with thermostatic control.The hydrogen of generation is collected to the volume of the hydrogen producing in record unit time, the speed that obtains putting hydrogen by drainage.

Claims (2)

1. a preparation method for amorphous ternary alloy/graphite alkene composite catalyst, is characterized in that: comprise the steps:
(1) get a certain amount of CoSO 4or NiSO 4with a certain amount of ZnSO 4, join in deionized water;
(2) get a certain amount of Graphene and join in above-mentioned solution, ultrasonic 0.5-3h, pH value is 5-7;
(3) the NaOH solution of configuration 0.05-2 mol/L, gets a certain amount of NaBH 4add in NaOH solution:
(4) solution of step (3) is dripped lentamente with base buret in step (2) solution, and with magnetic stirring apparatus, the solution of step (2) is stirred;
(5) after being added dropwise to complete, filter, wash, be dried,
(6) in 20-30%NaOH solution, flood 1h;
(7) filter, wash, be dried, grind and obtain amorphous ternary alloy/graphite alkene powder.
2. the application of amorphous ternary alloy/graphite alkene composite catalyst claimed in claim 1 in hydroboron hydrolysis, is characterized in that:
A) prepared catalyst is distributed to 0.1M NaBH 45% NaOH solution in, sealing, controls the temperature of solution by water bath with thermostatic control;
B) hydrogen of generation is collected to the volume of the hydrogen producing in record unit time, the speed that obtains putting hydrogen by drainage.
CN201410254394.3A 2014-06-10 2014-06-10 Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride Active CN104014344B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410254394.3A CN104014344B (en) 2014-06-10 2014-06-10 Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410254394.3A CN104014344B (en) 2014-06-10 2014-06-10 Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride

Publications (2)

Publication Number Publication Date
CN104014344A true CN104014344A (en) 2014-09-03
CN104014344B CN104014344B (en) 2017-04-19

Family

ID=51431508

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410254394.3A Active CN104014344B (en) 2014-06-10 2014-06-10 Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride

Country Status (1)

Country Link
CN (1) CN104014344B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111604072A (en) * 2020-05-15 2020-09-01 桂林电子科技大学 Nano particle-graphene-foam nickel composite material with bionic structure and preparation method thereof
CN112844427A (en) * 2021-03-04 2021-05-28 桂林电子科技大学 Co-B-P-O nanoparticle loaded reduced graphene oxide composite material and preparation method and application thereof
CN114225955A (en) * 2021-12-24 2022-03-25 沈阳师范大学 Double-carrier modified ternary alloy nanocavity catalyst and preparation method and application thereof
CN114433165A (en) * 2022-02-18 2022-05-06 沈阳师范大学 Fluffy-structure bimetal-based composite catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
CN102784652A (en) * 2012-08-28 2012-11-21 青岛农业大学 Co-Ce-B/attapulgite catalyst and preparation method thereof and application in hydrogen generation by hydrolysis of hydroboron
CN103691480A (en) * 2014-01-15 2014-04-02 辽宁石油化工大学 Preparation technology of catalyst used for preparing hydrogen by hydrolyzing sodium borohydride

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
CN102784652A (en) * 2012-08-28 2012-11-21 青岛农业大学 Co-Ce-B/attapulgite catalyst and preparation method thereof and application in hydrogen generation by hydrolysis of hydroboron
CN103691480A (en) * 2014-01-15 2014-04-02 辽宁石油化工大学 Preparation technology of catalyst used for preparing hydrogen by hydrolyzing sodium borohydride

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FERHAT BAYDAROGLU ET AL.: "An effective synthesis route for improving the catalytic activity of carbon-supported Co-B catalyst for hydrogen generation through hydrolysis of NaBH4", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
OGUZ KAAN OZDEMIR ETAL.: "Synthesis of graphene-based Co-B catalyst via simultaneous chemical reduction for hydrolysis of sodium borohydride", 《JOURNAL OF RENEWABLE AND SUSTAINABLE ENERGY》 *
刘自力等: "锌对非晶态Co-B合金的改性及催化肉桂醛加氢为肉桂醇的研究", 《分子催化》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111604072A (en) * 2020-05-15 2020-09-01 桂林电子科技大学 Nano particle-graphene-foam nickel composite material with bionic structure and preparation method thereof
CN112844427A (en) * 2021-03-04 2021-05-28 桂林电子科技大学 Co-B-P-O nanoparticle loaded reduced graphene oxide composite material and preparation method and application thereof
CN114225955A (en) * 2021-12-24 2022-03-25 沈阳师范大学 Double-carrier modified ternary alloy nanocavity catalyst and preparation method and application thereof
CN114433165A (en) * 2022-02-18 2022-05-06 沈阳师范大学 Fluffy-structure bimetal-based composite catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN104014344B (en) 2017-04-19

Similar Documents

Publication Publication Date Title
Liu et al. Robust NiCoP/CoP heterostructures for highly efficient hydrogen evolution electrocatalysis in alkaline solution
Hu et al. Novel cobalt–iron–vanadium layered double hydroxide nanosheet arrays for superior water oxidation performance
CN109518219B (en) Preparation method and application of graphene-based nickel-cobalt bimetallic oxygen evolution catalyst
Pan et al. Self-assembly synthesis of LaPO 4 hierarchical hollow spheres with enhanced photocatalytic CO 2-reduction performance
CN111229232A (en) Foam nickel-based porous NiFe hydrotalcite nanosheet and preparation and application thereof
CN109499576A (en) A kind of Co-B/NGO composite nano materials and its preparation method and application
CN106180747B (en) A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application
CN102407147A (en) Preparation method and application of ZnIn2S4-graphene composited photochemical catalyst
CN102125853B (en) Nano zinc ferrite-graphene composite photocatalyst of visible light response and preparation method thereof
CN103949272A (en) NiPt@RGO composite nano catalyst for producing hydrogen by using hydrazine borane and preparation method thereof
CN104882298A (en) Method for preparing NiCo2O4/graphene supercapacitor material with microwave method
Wei et al. Co− O− P composite nanocatalysts for hydrogen generation from the hydrolysis of alkaline sodium borohydride solution
CN104014344A (en) Amorphous ternary alloy/graphene composite catalyst as well as application thereof to hydrolysis of boron hydride
CN105140475A (en) Preparation method of anode material Fe3O4/MoS2 for lithium ion battery
CN104148084B (en) The preparation of a kind of nanoporous quad alloy catalyzer and the application in ammonia borane hydrolysis hydrogen manufacturing thereof
Bekirogullari Catalytic activities of non-noble metal catalysts (CuB, FeB, and NiB) with C. Vulgaris microalgal strain support modified by using phosphoric acid for hydrogen generation from sodium borohydride methanolysis
CN107188122A (en) Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic
CN103991888B (en) A kind of method of preparing high activity aluminium hydroxide suspension and producing hydrogen with pure aluminium powder precursor reactant
CN109023416A (en) The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel
CN104310376A (en) Postprocessing crosslinking method of hydrothermally carbonized spherical particles of biomass carbon source material
Zhang et al. Facile synthesis of Co–Fe layered double hydroxide nanosheets wrapped on Ni-doped nanoporous carbon nanorods for oxygen evolution reaction
CN102145282A (en) Preparation method of graphene-supported nano MnOOH composite material
CN105148918B (en) Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst
CN110013855B (en) High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof
CN104538648A (en) Graphene loaded platinum-cobalt alloy nanoparticle composite catalyst and preparation method thereof

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