CN106629871B - A kind of spherical NiMnO3The synthetic method of bimetallic oxide and its application - Google Patents

A kind of spherical NiMnO3The synthetic method of bimetallic oxide and its application Download PDF

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CN106629871B
CN106629871B CN201610915959.7A CN201610915959A CN106629871B CN 106629871 B CN106629871 B CN 106629871B CN 201610915959 A CN201610915959 A CN 201610915959A CN 106629871 B CN106629871 B CN 106629871B
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nimno
libh
spherical
bimetallic oxide
solution
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CN106629871A (en
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焦丽芳
王菁
王一菁
徐晓红
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of 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
    • B01J23/002—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
    • B01J23/70—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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A kind of spherical NiMnO3The synthetic method of bimetallic oxide, comprises the following steps：1) by NiCl2·6H2O and MnCl2·4H2O adds the NaHCO that concentration is 1M3In solution, stirred after well mixed, obtain the precursor solution of white；2) above-mentioned precursor solution is centrifuged under 3000r/min revolutions, by gained solid, with distilled water, ethanol, respectively washing three times, dries 5h at 60 DEG C respectively, then calcines 1h, the spherical NiMnO of finished product at 500 DEG C of high temperature3Bimetallic oxide.It is an advantage of the invention that：The synthesising method reacting condition is gentle, favorable reproducibility, technique is simple, cost is low；Load LiBH simultaneously4NiMnO3For meso-hole structure, there is nanometer confinement and catalyzing cooperation effect, to LiBH4Hydrogen discharging performance be significantly improved.

Description

A kind of spherical NiMnO3The synthetic method of bimetallic oxide and its application
Technical field
The present invention relates to hydrogen storage material field, particularly a kind of spherical NiMnO3The synthetic method of bimetallic oxide and its Using.
Background technology
As the increasingly consumption of traditional fossil energy, environmental pollution are increasingly severe.It is a kind of new that people have been working on exploitation The energy.Hydrogen Energy is a kind of preferable secondary energy sources, is one of following promising novel energy, by the wide of researchers General concern.However, the bottleneck that the storage of hydrogen is Hydrogen Energy to be developed and utilized at this stage.In recent years, with LiBH4For the light of Typical Representative Metal-complexing metal hydride turns into the study hotspot of emerging hydrogen storage material.
Nanometer confinement is that material is filled into nano pore, promotes reaction using the interaction of material and nano pore Progress, for chemical reaction one unique microenvironment is provided.LiBH4With higher hydrogen content (18.5 wt%) and volume Hydrogen density (121kg/m3), however, heat endurance is good, it is slow to put hydrogen and the factor such as poorly reversible hinders LiBH4Practical application. NiMnO3LiBH can be catalyzed4Hydrogen is put, improves its thermodynamics and kineticses performance, the NiMnO of sheet3It is equal by what is be connected with each other One nano particle composition, the pore passage structure between particle is LiBH4Confinement provide may so that NiMnO3It is possibly realized Confinement skeleton.In addition, NiMnO3Can also be to LiBH4Hydrogen of putting play catalytic action, the synergy of confinement and catalysis causes LiBH4Hydrogen discharging performance greatly improved.
The content of the invention
The purpose of the present invention is to be directed to above-mentioned problem, there is provided a kind of NiMnO3The synthetic method of bimetallic oxide And its application, and in this, as LiBH4The catalyst and confinement skeleton of hydrogen are put, so as to effectively reduce LiBH4Hydrogen discharging temperature, together Its hydrogen desorption capacity of Shi Tigao.
Technical scheme：
A kind of spherical NiMnO3The synthetic method of bimetallic oxide, comprises the following steps：
1) by NiCl2·6H2O and MnCl2·4H2O adds the NaHCO that concentration is 1M3In solution, NiCl2·6H2O、 MnCl2·4H2O and NaHCO3The amount ratio of solution is 2.5mmol：3.5mmol：50mL, 0.5h is stirred after well mixed, is obtained The precursor solution of white；
2) above-mentioned precursor solution is centrifuged under 3000r/min revolutions, by gained solid respectively with distilled water, second Respectively washing three times, dries 5h to alcohol at 60 DEG C, then calcines 1h, the spherical NiMnO of finished product at 500 DEG C of high temperature3Bimetallic Oxide.
A kind of synthesized spherical NiMnO3The application of bimetallic oxide, prepare NiMnO3-LiBH4As LiBH4Put The catalyst and confinement skeleton of hydrogen, NiMnO3-LiBH4Preparation comprise the following steps：
1) by the spherical NiMnO of preparation3Bimetallic oxide is put into three neck round bottom containers of connection Xi Laike devices, 1min is vacuumized under vacuum -0.1MPa, then passes to argon gas；
2) in the glove box under argon atmosphere protection, by LiBH4It is dissolved in anhydrous tetrahydro furan (THF) solvent and obtains LiBH4/ THF solution, LiBH4Amount ratio with anhydrous tetrahydro furan is 0.1g：2mL；
3) by above-mentioned LiBH4/ THF solution, which adds, contains spherical NiMnO3In three neck round bottom containers of bimetallic oxide, NiMnO3With LiBH4Mass ratio be 1：0.5-2,3h is stirred, 48h is then heated at 60 DEG C to remove tetrahydrofuran solvent, NiMnO is made3-LiBH4, and be transferred in glove box and preserved.
It is an advantage of the invention that：The synthesising method reacting condition is gentle, favorable reproducibility, technique is simple, cost is low；Bear simultaneously Carry LiBH4NiMnO3For meso-hole structure, there is nanometer confinement and catalyzing cooperation effect, to LiBH4Hydrogen discharging performance have significantly Improve.
Brief description of the drawings
Fig. 1 is the NiMnO of synthesis3XRD, wherein：(a) be synthesis NiMnO3XRD, (b) is NiMnO3's Standard card figure.
Fig. 2 is the NiMnO of synthesis3SEM figure.
Fig. 3 is NiMnO3-LiBH4The IR figures before and after hydrogen are put, wherein：(a) it is before putting hydrogen, (b) is after putting hydrogen.
Fig. 4 is pure LiBH4With NiMnO3-LiBH4(1:2) the TPD figures of hydrogen are put, wherein：.(a) it is pure LiBH4, (b) is NiMnO3-LiBH4Compound.
Fig. 5 is pure LiBH4With NiMnO3-LiBH4(1:2) hydrogen desorption capacity curve, wherein：(a) it is pure LiBH4, (b) is NiMnO3-LiBH4Compound.
Embodiment
The present invention is described in further detail with reference to specific embodiment
Embodiment：
A kind of spherical NiMnO3The synthetic method of bimetallic oxide, comprises the following steps：
1) by 2.5mmol NiCl in 100mL beakers2·6H2O and 3.5mmol MnCl2·4H2O adds 50mL concentration For 1M NaHCO3In solution, 0.5h is stirred after well mixed, obtains the precursor solution of white；
2) above-mentioned precursor solution is centrifuged under 3000r/min revolutions, by gained solid respectively with distilled water, second Respectively washing three times, dries 5h to alcohol at 60 DEG C, then calcines 1h, the spherical NiMnO of finished product at 500 DEG C of high temperature3Bimetallic Oxide.
Gained finished product matches with standard card JCPDS 75-2089, and its XRD and SEM figures are respectively as schemed
Shown in 1 and 2.
A kind of synthesized spherical NiMnO3The application of bimetallic oxide, prepare NiMnO3-LiBH4As LiBH4Put The catalyst and confinement skeleton of hydrogen, NiMnO3-LiBH4Preparation comprise the following steps：
1) the spherical NiMnO for preparing 0.2g3Bimetallic oxide is put into three neck round bottom containers of connection Xi Laike devices In, 1min is vacuumized under vacuum -0.1MPa, then passes to argon gas；
2) in the glove box under argon atmosphere protection, by 0.2g LiBH4It is dissolved in 4mL anhydrous tetrahydro furan solvents and obtains To LiBH4/ THF solution；
3) by above-mentioned LiBH4/ THF solution, which adds, contains spherical NiMnO3In three neck round bottom containers of bimetallic oxide, stir 3h is mixed, 48h is then heated at 60 DEG C to remove tetrahydrofuran solvent, NiMnO is made3-LiBH4, and be transferred in glove box Preserved.
Detect sample NiMnO3-LiBH4The method of hydrogen discharging performance：
70mg NiMnO is weighed in glove box3-LiBH4Sample, put it into temperature programmed desorption and put hydrogen (TPD) survey In test tube, first lead to half an hour argon gas, then from 30 DEG C with 2 DEG C of min-1It is heated to 500 DEG C；Flow velocity 35.3mLmin-1, use high-purity Ar Make carrier gas stream；Put after hydrogen terminates, continue logical argon gas one hour, finally close instrument.
Fig. 3 is NiMnO3-LiBH4The IR figures before and after hydrogen are put, wherein：(a) it is before putting hydrogen, (b) is after putting hydrogen.From Fig. 3 In (a) it can be seen that B-H keys characteristic flexural vibration peak and stretching vibration peak, show LiBH4It has been immersed in NiMnO3In, And the characteristic absorption peak of B-H keys disappears in (b) in Fig. 3, show LiBH4Decompose completely.
Fig. 4 is pure LiBH4With NiMnO3-LiBH4(1:2) the TPD figures of hydrogen are put, wherein：.(a) it is pure LiBH4, (b) is NiMnO3-LiBH4Compound.Show in figure, NiMnO3-LiBH4The hydrogen discharging temperature of compound is substantially reduced, and hydrogen temperature is put in starting Degree is at 135 DEG C, and maximum hydrogen discharging temperature is at about 300 DEG C, and 290 DEG C of the starting hydrogen discharging temperature compared to pure LiBH4, maximum puts hydrogen temperature 440 DEG C of degree is compared, hence it is evident that is reduced.
Fig. 5 is pure LiBH4With NiMnO3-LiBH4(1:2) hydrogen desorption capacity curve, wherein：(a) it is pure LiBH4(b) it is NiMnO3-LiBH4Compound.Show in figure：At 500 DEG C, calculated by integral area, NiMnO3-LiBH4Compound put Hydrogen amount is higher than pure LiBH4。

Claims (1)

  1. A kind of 1. spherical NiMnO3The application of bimetallic oxide, the spherical NiMnO3The synthetic method bag of bimetallic oxide Include following steps：
    A) by NiCl2·6H2O and MnCl2·4H2O adds the NaHCO that concentration is 1M3In solution, NiCl2·6H2O、MnCl2· 4H2O and NaHCO3The amount ratio of solution is 2.5mmol：3.5mmol：50mL, 0.5h is stirred after well mixed, before obtaining white Body solution；
    B) above-mentioned precursor solution is centrifuged under 3000r/min revolutions, gained solid is each with distilled water, ethanol respectively Washing three times, dries 5h at 60 DEG C, then calcines 1h, the spherical NiMnO of finished product at 500 DEG C of high temperature3Bimetallic aoxidizes Thing；
    Characterized in that, the spherical NiMnO3The application of bimetallic oxide is to prepare NiMnO3-LiBH4As LiBH4Put hydrogen Catalyst and confinement skeleton, NiMnO3-LiBH4Preparation comprise the following steps：
    1) by the spherical NiMnO of preparation3Bimetallic oxide is put into three neck round bottom containers of connection Xi Laike devices, in vacuum 1min is vacuumized under degree -0.1MPa, then passes to argon gas；
    2) in the glove box under argon atmosphere protection, by LiBH4It is dissolved in anhydrous tetrahydro furan (THF) solvent and obtains LiBH4/ THF solution, LiBH4Amount ratio with anhydrous tetrahydro furan is 0.1g：2mL；
    3) by above-mentioned LiBH4/ THF solution, which adds, contains spherical NiMnO3In three neck round bottom containers of bimetallic oxide, NiMnO3 With LiBH4Mass ratio be 1：0.5-2,3h is stirred, 48h is then heated at 60 DEG C to remove tetrahydrofuran solvent, is made NiMnO3-LiBH4, and be transferred in glove box and preserved.
CN201610915959.7A 2016-10-21 2016-10-21 A kind of spherical NiMnO3The synthetic method of bimetallic oxide and its application Expired - Fee Related CN106629871B (en)

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CN109273274B (en) * 2018-09-21 2020-07-21 大连海事大学 NiMnO3 electrode material with high specific surface area and preparation method and application thereof
CN110797541B (en) * 2019-11-19 2022-05-06 广东石油化工学院 Cathode dual-function electrocatalyst for molten salt iron air battery and application of cathode dual-function electrocatalyst
CN110776020B (en) * 2019-11-20 2022-01-21 江苏师范大学 NiMnO of stick equipment3Method for synthesizing nanoflower

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3380919A (en) * 1964-02-06 1968-04-30 Ampex Preparation of ferromagnetic nimno
CN102583586A (en) * 2011-01-15 2012-07-18 北京化工大学 Preparation method and application of ilmenite-type nickel manganese multiple oxide (NiMnO3)
CN103274355A (en) * 2013-06-07 2013-09-04 南开大学 LiBH4 high-capacity hydrogen storage composite material preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380919A (en) * 1964-02-06 1968-04-30 Ampex Preparation of ferromagnetic nimno
CN102583586A (en) * 2011-01-15 2012-07-18 北京化工大学 Preparation method and application of ilmenite-type nickel manganese multiple oxide (NiMnO3)
CN103274355A (en) * 2013-06-07 2013-09-04 南开大学 LiBH4 high-capacity hydrogen storage composite material preparation method

Non-Patent Citations (1)

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Title
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