CN106563463B - A kind of preparation method of Cu oxide surface recombination manganese oxide layer materials - Google Patents
A kind of preparation method of Cu oxide surface recombination manganese oxide layer materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000006798 recombination Effects 0.000 title claims abstract description 30
- 238000005215 recombination Methods 0.000 title claims abstract description 30
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 32
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 4
- 235000019441 ethanol Nutrition 0.000 claims description 10
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 8
- 229910017566 Cu-Mn Inorganic materials 0.000 abstract description 4
- 229910017871 Cu—Mn Inorganic materials 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000012761 high-performance material Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 CuO compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910016553 CuOx Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
-
- B01J35/30—
-
- B01J35/40—
Abstract
A kind of preparation method of Cu oxide surface recombination manganese oxide layer materials is in water, alcohol or water-alcohol mixed solution, by containing+7 valence oxidation state Mn element (Mn (VII)) soluble M n source compound such as KMnO4With Cu2O matrix surface carries out redox displacement reaction and obtains Cu2(multivalent state manganese oxide coexists is denoted as MnO to O surface recombination manganese oxide layerx) material new method, then be heat-treated, can further obtain CuO surface recombination MnOxMaterial.This method feature is MnOxCan with molecular scale thin layer high dispersive, uniformly, be closely compound in Cu2O or CuO material surface；Its properity is mainly by Mn element and Cu2O chemistry molar ratio determines, easily realizes sample series regulation, scope of the invention 0.02-1.0.Research and application field to concern Cu-Mn composite construction or interfacial interaction, this method can provide reference for high performance material development.
Description
Technical field
The present invention relates to a kind of preparation methods of Cu oxide surface recombination Mn oxide material, belong to oxide solid-state table
The controlledly synthesis and associated materials application field of the microcosmic composite construction in interface.
Background technique
Relative to pure component material, solid-oxide multicomponent composite materials have superior physical and chemical performance, because
And many important applied fields for example photoelectric conversion, sensor, in terms of receive much attention.For these applications, material
Its surface and interface structure can be depended on, the scale of usual this surface and interface structure between 1-3 layers of solid-state material surface molecule or
In atomic layer level thickness scope, therefore one of the basic point effectively optimized to this kind of material property is to realize it microcosmic ruler
Spend the surface and interface structure regulating synthesis in scope.However, preparing two class main methods of oxide composite at present in this side
Face all has apparent defect: one kind is to be divided into matrix with a kind of group to support other components deposition thereon, and defect is to deposit
The uncontrollability of process causes the scale for supporting component and their distribution situations on matrix to be difficult to control, and is especially difficult
They are difficult to form effective table on a microscopic scale with less than the 3 layers uniform high dispersive of molecular layers thick in matrix surface
Interfacial oxide composite construction；It is another kind of be by various ingredients carry out simultaneously solidification i.e. body it is mutually compound, such methods are asked at all
Topic is and is not concerned with for the recombination process between component to be controlled in the micro-scale scope of solid surface and interface, therefore is also difficult to reality
The fining regulation of existing material surface and interface structure and performance.In view of the above-mentioned problems, the present invention is pair with Cu-Mn composite oxides
As proposing and having practiced one kind in Cu oxide (Cu2O or CuO) (multivalent state manganese oxide is total for surface direct construction manganese thin oxide layer
It deposits, is denoted as MnOx) composite material new method, Cu specially not oxidized with surface2O material is matrix, is introduced directly into appropriate
Compound such as KMnO containing+7 valence oxidation state Mn elements4, in water, alcohol or water-alcohol mixed solution, pass through Cu2The surface O with
MnO4 -Redox replace reaction, i.e. Cu2O surface molecular is oxidized to Cu2+While abjection, MnO4 -It is reduced to MnOxIt is heavy
Product is in Cu2On O matrix, thus to obtain Cu2O surface recombination MnOxLayer material, on this basis, carrying out heat treatment to sample will
Cu2O matrix converted in-situ is CuO, can further obtain the surface the CuO compound MnO of high dispersivexMaterial.This method feature is:
Preparation process is substantially one and occurs in Cu2The heterogeneous oxidation reduction displacement reaction of O matrix surface, only Cu2O matrix surface
Molecular layer can be used as MnO4 -Reduction is deposited as MnOxReaction and cover interface, thus ensure that MnO from principlexIt can be to divide
Sub- scale thin layer dispersion degree, uniformly, be closely compound in Cu2CuO derived from O(or subsequent heat treatment) material surface；MnOxDispersion
The overall performance of form and sample is mainly by the Mn element and Cu in preparation system2The decision of O chemistry molar ratio, this application involves
Proportional region is 0.02-1.0, the performance regulation of thus easily achieving sample, such as prepared sample Mn:Cu2O control is 0.1-
When 0.7 range, it can express good low temperature (410K) catalytic performance for nitrous oxides selectivity reduction elimination reaction.To poly-
Coke in the research and application field of solid-state Mn compound disperse properties and Cu-Mn oxide composite structure or interfacial interaction,
This method is expected to provide easy effective new reference for the development of related high performance material, hereby patent protection.
Summary of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, providing a kind of Cu oxide surface recombination Mn oxide material
Preparation method proposes and has practiced the Cu with brand-new2O particle (pattern, size are unlimited) is matrix, can be with by its surface molecular
Compound such as KMnO containing+7 valence oxidation state Mn elements4Between carry out redox displacement reaction, pass through Mn in adjustment and control system
Element and Cu2O chemistry molar ratio realizes the MnO after making displacementxWith molecular scale thin layer high dispersive, uniformly, be closely compound in
Cu2O material surface obtains Cu2O surface recombination MnOxThe new method of layer material, carrying out further heat treatment to sample will
Cu2O matrix converted in-situ is CuO, can be obtained CuO surface recombination MnOxMaterial.This method is for focusing on solid-state Mn chemical combination
Object disperse properties and Cu-Mn oxide interface are a kind of important material controls mutually or the research and application field of compound action
Synthesized reference processed.
Preparation method of the present invention includes:
(1) composition of synthetic system are as follows:
Freshly prepared Cu2O material (guarantee material surface not oxidized be CuO): pattern is unlimited, cube, octahedron,
Sphere, porous sphere, random body all may be used；Size is unlimited, from nanometer to centimetre all may be used；Dosage is weighed according to needed for.Contain
There is the soluble compound such as KMnO of+7 valence oxidation states such as Mn element4, dispersion is pure deionized water, water-soluble alcohol (second
Alcohol, isopropanol or 2- butanol) or water and above-mentioned alcohol arbitrary proportion mixed solution, Mn element and Cu in system2The chemistry of O rubs
You are than being 0.02-1.0.
(2) preparation step:
Weigh the not oxidized Cu for CuO of material surface2O 200-400 mg, be scattered under normal temperature and pressure 300 mL go from
In sub- water, water-soluble alcohol or water-alcohol mixed liquor, the water-soluble alcohol is ethyl alcohol, isopropanol, 2- butanol, is based on material structure, property
It can be mainly by Mn element and Cu2O chemistry molar ratio determines that the present invention controls Mn element and Cu2The chemical molar ratio of O is 0.02-
1.0, that is, weigh 32-263 mg KMnO4Be added in above-mentioned dispersion, stirring 2 hours after, stand system 30 minutes, then from
The heart isolates sediment, is repeatedly washed with the solvent of above-mentioned dispersion, obtains sample after vacuum 333K is 6 hours dry.By upper
Experiment condition control is stated, it can be achieved that MnOxWith molecular scale thin layer high dispersive, uniformly, be closely compound in Cu2O material surface, i.e.,
Obtain Cu2O surface recombination MnOxLayer material, to resulting materials in air atmosphere, temperature is higher than 623K processing 3 hours or more,
By matrix Cu2O is converted into CuO, and CuO surface recombination MnO can be obtainedxLayer material.
By prepared CuO surface recombination MnOxLayer material restores elimination reaction for nitrogen oxides, selects Mn and CuO
Chemical molar ratio 0.05-0.35(is corresponding prepare when Mn and Cu2The chemical molar ratio of O is the sample in 0.1-0.7) range,
180 mg filling quartz tube reactor is weighed, is passed through volume group as NO:NH3:O2:N2The reaction of=0.1:0.1:5:94.8
Gas, air speed are 10000-50000 h-1, temperature-programmed reaction test is carried out, the sample for measuring best performance can be in 410-513 K
Between realize nitrogen oxides convert removing completely, the treatment temperature window relative under the conditions of same test industrial catalyst drop
Low about 200K.
Beneficial effects of the present invention:
(1) MnOxIt can be with molecular scale thin layer high dispersive, uniformly, be closely compound in a nanometer Cu2O or CuO material surface.
(2) MnOxDispersing morphology and sample overall performance mainly by the Mn element and Cu in preparation system2O chemistry rubs
You than determine, this application involves proportional region be 0.02-1.0, thus easily achieving sample batch preparation and performance regulation.
(3) control of sample Mn:CuO molar ratio prepared by is Mn and Cu when 0.05-0.35(corresponds to preparation2The chemistry mole of O
When than for 0.1-0.7) range, it can express good low temperature for nitrous oxides selectivity reduction elimination reaction and convert completely
(minimum 410K) catalytic performance.
Detailed description of the invention
Fig. 1 a is scanning electron microscope (SEM) the matrix Cu of typical sample2O spherical nanoparticle photo；
Fig. 1 b is scanning electron microscope (SEM) Cu of typical sample2O surface recombination MnOxParticle photo；
Fig. 1 c is scanning electron microscope (SEM) the CuO surface recombination MnO of typical samplexParticle photo；
Fig. 2 a is (XPS) Cu species spectral peak spectrogram of typical sample；Fig. 2 b is (XPS) Mn species spectral peak of typical sample；
In figure: a is matrix Cu2O spherical nanoparticle；B is Cu2O surface recombination MnOxParticle；C is CuO surface recombination
MnOxParticle；
Fig. 3 is the XRD spectra of typical sample；
In figure: a is matrix Cu2O spherical nanoparticle；B is Cu2O surface recombination MnOxParticle；C is CuO surface recombination
MnOxParticle；
Fig. 4 is the nitrous oxides selectivity reduction removal performance test curve of typical sample；
In figure: a is matrix Cu2O spherical nanoparticle；B is Cu2O surface recombination MnOxParticle；C is CuO surface recombination
MnOxParticle.
Specific embodiment
Implement example
Ball shaped nano CuO surface recombination MnOxThe synthetic method of material, analysis and use example
Synthetic method: under normal temperature and pressure, the Cu for being 200 nm by the size of brand-new2O spheric granules weighs in right amount such as
360mg is scattered in 300 mL water, by Mn element and Cu2The chemical molar ratio modification scope of O is 0.1-0.7, that is, weighs 32-
263 mg KMnO4It is added in above-mentioned aqueous dispersion and carries out reaction preparation, after high degree of agitation 2 hours, stand system 30 minutes,
It is then centrifugated out sediment, after repeatedly being washed with deionized water, obtains a nanometer Cu after vacuum 333K is 6 hours dry2The surface O
The compound MnO of high dispersivexLayer material handles 3 hours for matrix Cu in 623K to resulting materials in air atmosphere2O is converted into
The nanometer CuO surface compound MnO of high dispersive can be obtained in CuOxLayer material.
Analysis: basis material Cu is chosen2O spherical nanoparticle (a), ball shaped nano Cu2O surface recombination MnOxParticle (b) with
And ball shaped nano CuO surface recombination MnOxThree kinds of typical samples of particle (c), by scanning electron microscope (SEM), X-ray electronics energy
Spectrum (XPS) and X-ray diffraction spectrogram (XRD) have carried out pattern, surface condition and structural analysis.Fig. 1 a- Fig. 1 c is three kinds of samples
SEM photograph, it is seen that three kinds of samples are all similar nanometer spherical state, it is meant that compound MnOxMaterial and basis material afterwards
Cu2O, which compares whole pattern, does not have significant changes.It is shown by XPS result figure 2a and Fig. 2 b, relative to basis material Cu2O (a) contains
The sample (b) and (c) of Mn is other than having corresponding Cu oxide species spectral peak, and there are also+2(II) ,+3 (III) ,+4 (IV) valence Mn elements
Feature spectral peak；And show that sample (b) containing Mn and (c) only have the diffraction maximum of corresponding Cu oxide matrix by XRD spectra Fig. 3, it is comprehensive
It closes the result shows that these material bodies are mutually that main body is still maintained Cu oxide, and forms and be evenly distributed on its surface, dispersion degree
Higher multivalent state MnOxCompound thin layer, i.e. two kinds of samples containing Mn are the compound manganese oxide layer materials of CuO surface.
It uses example: nitrous oxides selectivity reduction removing has been carried out by ammonia reduction NO reaction to above-mentioned three kinds of typical samples
Performance test weighs 180 mg samples filling quartz tube reactor respectively, is passed through volume group as NO:NH3:O2:N2=0.1:
The reaction gas of 0.1:5:94.8, air speed are 10000-50000 h-1, carry out temperature-programmed reaction test, test result such as Fig. 4 institute
Show, CuO surface recombination MnOxSample can realize that nitrogen oxides converts removing completely between 410-513 K, urge relative to industry
Agent reduces about 200K.
Claims (2)
1. a kind of preparation method of Cu oxide surface recombination manganese oxide layer materials, it is characterised in that: weigh material surface not by
It is oxidized to the Cu of CuO2O 200-400mg is scattered in 300mL deionized water, alcohol or water-alcohol mixed liquor under normal temperature and pressure；Base
In material structure, performance mainly by Mn element and Cu2O chemistry molar ratio determines, controls Mn element and Cu2The chemical molar ratio of O is
0.02-1.0 weighs 32-263mg KMnO4It is added in above-mentioned dispersion and is reacted, after stirring 2 hours, stand system
30 minutes；It is then centrifugated out sediment, after repeatedly being washed with the solvent of above-mentioned dispersion, vacuum 333K is 6 hours dry；
By the above experiment condition can realize manganese oxide layer can with molecular scale thin layer high dispersive, uniformly, be closely compound in Cu2O material table
Face to get arrive Cu2O surface recombination MnOxLayer material；To resulting materials in air atmosphere, temperature is higher than 623K and handles 3 hours
More than, by matrix Cu2O is converted into CuO, and CuO surface recombination MnO can be obtainedxLayer material.
2. a kind of preparation method of Cu oxide surface recombination manganese oxide layer materials according to claim 1, feature exist
In the alcohol is ethyl alcohol, isopropanol or 2- butanol.
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| CN109569582A (en) * | 2018-11-23 | 2019-04-05 | 南昌大学 | It is a kind of based on electrostatic anchoring-redox curing technology composite oxides preparation method and application |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342516A (en) * | 2000-06-26 | 2002-04-03 | 王琪玮 | Deoxidizing agent using MnO or CuO as its active component |
| CN103394322A (en) * | 2013-07-17 | 2013-11-20 | 常州大学盱眙凹土研发中心 | Gasoline desulfurization adsorbent and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342516A (en) * | 2000-06-26 | 2002-04-03 | 王琪玮 | Deoxidizing agent using MnO or CuO as its active component |
| CN103394322A (en) * | 2013-07-17 | 2013-11-20 | 常州大学盱眙凹土研发中心 | Gasoline desulfurization adsorbent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Account of Nitroarene Reduction with Size- and Facet-Controlled CuO-MnO2 Nanocomposites;Jaya Pal et al.;《ACS Applied Materials & Interfaces》;20140530;第6卷;说明书第9173-9184页 |
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