CN114931948A - Potassium intercalation molybdenum oxide nano array material and preparation method and application thereof - Google Patents

Potassium intercalation molybdenum oxide nano array material and preparation method and application thereof Download PDF

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CN114931948A
CN114931948A CN202210302455.3A CN202210302455A CN114931948A CN 114931948 A CN114931948 A CN 114931948A CN 202210302455 A CN202210302455 A CN 202210302455A CN 114931948 A CN114931948 A CN 114931948A
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molybdenum oxide
potassium
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magnetron sputtering
oxide nano
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CN114931948B (en
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程合锋
姜为易
黄柏标
王泽岩
刘媛媛
王朋
郑昭科
张倩倩
张晓阳
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Shandong University
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • 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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The invention discloses a potassium intercalation molybdenum oxide nano array material and a preparation method and application thereof. Modifying a trace amount of Au nano particles on the surface of the potassium-doped molybdenum oxide array to be used as an active site for photocatalytic nitrogen reduction, so that the use amount of noble metals is saved, the cost is reduced, and the photocatalytic nitrogen reduction performance which is much higher than that of other photocatalysts of the same type is obtained.

Description

Potassium intercalation molybdenum oxide nano array material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a potassium intercalation molybdenum oxide nano array material and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
To date, the synthesis of ammonia has relied on the Haber-Bosch process with a hundred years history, using iron-based or ruthenium-based catalysts at high temperatures and ultra-high pressures to synthesize N 2 Reduction to NH 3 . However, industrial ammonia production consumes more than 2% of the world's energy, and the production process produces over 3 million tons of CO per year 2 And (4) discharging. In order to avoid huge energy consumption and carbon dioxide emissions, it is imperative to explore alternatives for the production of ammonia at room temperature and pressure. Research on the synthesis of ammonia gas by nitrogen reduction under mild conditions has been carried out with many efforts, including molecular enzyme catalysis, electrocatalysis, and photocatalysis. However, the existing photocatalytic ammonia production by nitrogen reduction still has the problems of low reaction rate, poor stability and the like.
Disclosure of Invention
Compared with the traditional semiconductor photocatalyst, the photocatalyst with the local surface plasma resonance effect has greater advantages in the aspect of solar energy conversion efficiency, so that the photocatalyst is widely researched. However, the common material with the local surface plasmon resonance effect is precious metal nanoparticles such as Au, Ag, Cu, and the like, and the high price of the precious metal nanoparticles limits further application. Also, the ammonia gas yield of conventional surface plasmon materials is low due to the lack of photogenerated carrier separation means. The defects limit the application of the local surface plasma resonance effect in the photocatalytic nitrogen reduction to generate ammonia.
Aiming at the defects in the prior art, the invention aims to provide a potassium intercalation molybdenum oxide nano array material and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a potassium intercalation molybdenum oxide nano array material, which comprises a substrate, a potassium-doped molybdenum oxide nano thin layer attached to the surface of the substrate, and gold nanoparticles modified on the potassium-doped molybdenum oxide nano thin layer.
In a second aspect, the invention provides a preparation method of the potassium intercalation molybdenum oxide nano array material, which comprises the following steps:
putting the molybdenum substrate into a sylvite solution, carrying out anodic oxidation for a set time, then carrying out cathodic reduction, and inserting a potassium atom into a molybdenum oxide crystal structure;
calcining the obtained material in an inert atmosphere, and modifying gold nanoparticles on the surface of a matrix by utilizing magnetron sputtering to obtain the potassium intercalation molybdenum oxide material.
In a third aspect, the invention provides an application of the potassium intercalated molybdenum oxide nano array material in ammonia gas production through photocatalytic nitrogen reduction.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the molybdenum oxide material with potassium intercalation is obtained through experiments, the K atom intercalation enters the molybdenum oxide crystal structure, and Mo 5+ And Mo 6 + The electron transition between the two can cause the molybdenum oxide array of the K intercalation to generate a wide local plasma resonance within a visible light range, thereby greatly improving the utilization efficiency of solar energy.
Micro Au nano particles are modified on the molybdenum oxide array substrate with the potassium intercalation, namely the Au nano particles can be used as reaction active sites for photocatalytic nitrogen reduction and can promote photon-generated electrons generated by the resonance absorption of visible light by local and other organisms. Thereby greatly improving the photocatalytic nitrogen reduction performance of the material.
The potassium-doped molybdenum oxide nano array has a wide-range visible light absorption local surface plasma resonance effect, and can efficiently utilize solar energy. Modifying a trace amount of Au nano particles on the surface of the potassium-doped molybdenum oxide array to be used as an active site for photocatalytic nitrogen reduction, so that the use amount of noble metals is saved, the cost is reduced, and the photocatalytic nitrogen reduction performance which is much higher than that of other photocatalysts of the same type is obtained. Through the design of the energy band structure, hot electrons generated by the local surface plasma resonance effect hardly have energy loss during transfer, and the photocatalytic nitrogen reduction performance of the material is improved.
The synthesis method is convenient and fast, and the molybdenum oxide nano array material with the potassium intercalation can be obtained by simple methods such as anodic oxidation, tubular furnace calcination, magnetron sputtering modification and the like. The Au nano particles are modified by inserting K atoms into molybdenum oxide, so that better photon-generated carrier separation capability and nitrogen reduction capability can be obtained. Has better photocatalytic nitrogen reduction performance than similar photocatalysts. In the presence of visible light (wavelength)>420nm) of NH 3 The yield exceeds 9 mu gcm -2 h -1 。
The catalyst obtained by the invention has simple preparation method, has great guiding significance in practical application, provides a new thought and approach for driving other photocatalytic reactions (such as carbon dioxide reduction, hydrogen production by water decomposition and oxygen production) by utilizing surface plasma, and has great commercial value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an XRD of a pure phase molybdenum oxide prepared in comparative example 1 and a K-atom intercalated molybdenum oxide photocatalyst prepared in examples under different experimental conditions;
FIG. 2 is an SEM of a pure phase molybdenum oxide prepared in comparative example 1 and a K atom intercalated molybdenum oxide photocatalyst prepared in examples under different experimental conditions;
FIG. 3 is X-ray photoelectron spectroscopy (XPS) analysis spectra of the pure-phase molybdenum oxide prepared in comparative example 1 and the K-atom intercalated molybdenum oxide photocatalyst prepared in examples under different experimental conditions, wherein K2 p XPS spectra, Mo 3d XPS spectra and Au 4f XPS spectra are taken as the spectra.
FIG. 4 is a graph of the light absorption spectrum of K-atom intercalated molybdenum oxide obtained by the test of example 1 and the efficiency of the K-atom intercalated molybdenum oxide in the reduction of nitrogen by monochromatic light photocatalysis at different wavelengths;
FIG. 5 is a graph of the efficiency of visible photocatalytic nitrogen reduction to ammonia for pure phase molybdenum oxide prepared in comparative example 1 and for K-atom intercalated molybdenum oxide photocatalyst prepared in example under different experimental conditions;
FIG. 6 is a diagram of the mechanism of the visible light photocatalytic nitrogen reduction ammonia production reaction of the K atom intercalated molybdenum oxide photocatalyst prepared in the example.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the present invention provides a potassium intercalation molybdenum oxide nano array material, which comprises a substrate, a potassium-doped molybdenum oxide nano thin layer attached to the surface of the substrate, and gold nanoparticles modified on the potassium-doped molybdenum oxide nano thin layer.
In some embodiments, the mass ratio of molybdenum oxide, potassium atoms, and gold nanoparticles is 0.8-1.2: 0.05-0.15: 0.01, preferably 1: 0.11: 0.01.
in a second aspect, the invention provides a preparation method of the potassium intercalated molybdenum oxide nano array material, which comprises the following steps:
putting the molybdenum substrate into a sylvite solution, carrying out anodic oxidation for a set time, then carrying out cathodic reduction, and inserting a potassium atom into a molybdenum oxide crystal structure;
calcining the obtained material in an inert atmosphere to improve the crystallinity of the material to obtain better stability, and modifying the gold nanoparticles on the surface of the matrix by utilizing magnetron sputtering to obtain the gold nanoparticle.
In some embodiments, the potassium salt solution is a potassium fluoride solution. Tests show that other potassium salts cannot obtain similar products.
Preferably, the concentration of the potassium salt solution is 0.05-0.5mol/L, and the solvent is water, glycerol or a mixture of water and glycerol. By adjusting the proportion of water and glycerol, the reaction rate of anodic oxidation reaction is controlled, and the microscopic morphology of the material is further controlled, so that the materials with different morphologies and different photocatalytic nitrogen reduction performances can be obtained. The content of K ions in the anodic oxidation solution influences the number of K atoms inserted into molybdenum oxide by intercalation, and further influences the photocatalytic nitrogen reduction performance of the material.
In some embodiments, the temperature of calcination is 200-800 ℃; preferably, the calcining temperature is 300-600 ℃; further preferably 400 ℃. Specifically, the temperature may be 200 ℃, 300 ℃, 400 ℃, 600 ℃, 800 ℃ or the like.
In some embodiments, the voltage of the anodization is 5-50V and the time is 5-120 min; preferably, the voltage of anodic oxidation is 30-50V, and the time is 50-120 min; further preferably, the voltage of anodic oxidation is 35-45V, and the time is 50-70 min; more preferably, the anodic oxidation voltage is 40V and the time is 60 min.
In some embodiments, the voltage of the cathodic reduction is-0.1 to-5V, and the time is 10 to 6000 s; preferably, the voltage of cathode reduction is-0.1 to-1V, and the time is 10 to 600 s; further preferably, the voltage of cathode reduction is-0.1 to-0.7V, and the time is 50 to 200 s; more preferably, the voltage of cathode reduction is-0.3 to-0.7V, and the time is 70 to 150 s; still more preferably, the voltage for cathodic reduction is-0.5V and the time is 100 s.
In some embodiments, the magnetron sputtering current is 5-100mA, and the magnetron sputtering time is 1-100 s; preferably, the current of magnetron sputtering is 10-70mA, and the magnetron sputtering time is 10-70 s; further preferably, the current of magnetron sputtering is 10-50mA, and the magnetron sputtering time is 10-50 s; still further preferably, the magnetron sputtering current is 10-40mA, and the magnetron sputtering time is 10-40 s; more preferably, the magnetron sputtering current is 15mA, and the magnetron sputtering time is 20 s.
In a third aspect, the invention provides an application of the potassium intercalated molybdenum oxide nano array material in ammonia gas production through photocatalytic nitrogen reduction.
The potassium atoms intercalated into the molybdenum oxide can enable the molybdenum oxide to generate obvious local surface plasmon resonance effect of visible light range response. Meanwhile, the gold nanoparticles modified on the nano array can be used as catalytic active sites for nitrogen reduction and improve the separation efficiency of photon-generated carriers, so that the photocatalytic nitrogen reduction performance of the material is greatly improved.
The present invention will be further described with reference to the following examples.
Example 1
A K atom intercalated molybdenum oxide photocatalyst and a preparation method thereof comprise the following steps:
(1) dissolving 1.6g of potassium fluoride in 60 ml of glycerol, anodizing a molybdenum sheet in the solution for 60 minutes at 40V, and then reducing the molybdenum sheet for 100s at-0.5V;
(2) calcining the molybdenum sheet after electrochemical treatment for 2 hours at 600 ℃ in a tubular furnace in Ar atmosphere;
(3) and carrying out magnetron sputtering on the molybdenum sheet after the treatment in a magnetron sputtering device for 20s at a current of 15mA to obtain AKMO-1.
Example 2
Different from example 1, the voltage of anodic oxidation in step (1) was 60V, and AKMO-2 was obtained.
Example 3
Different from example 1, the calcination temperature in step (2) was 400 ℃ to obtain AKMO-3.
Comparative example 1
Pure MoO 3 Except that step (2) was calcination in air without step (3) in the preparation of (1).
For examples 1-3, the experiments of the wavelength-dependent photocatalytic nitrogen reduction of the samples prepared in comparative example 1 were carried out under the following experimental conditions:
samples prepared at saturation of KClO 4 In the solution, and continuously introducing high-purity N 2 Under the condition of (1), the xenon lamp with filters with different wavelengths is used for irradiation, so that the optical power density is always 10mW/cm 2 。
Photocatalytic nitrogen reduction test:
1. the test method comprises the following steps:
photochemical nitrogen reduction experiments were performed in a single chamber glass cell with a quartz window. The size of the test is 1 multiplied by 1cm 2 The material of (1). At room temperature and normal pressure, pure N is added 2 Continuously introducing saturated KClO 4 And (3) solution. The ammonia synthesis measurement was performed under visible light illumination, supplied from a 300W xenon lamp equipped with a cut-off filter, and ethanol was added to the electrolyte as a sacrificial agent. Spectrophotometric determination of NH produced by indophenol blue method 3 The concentration of (c). 2mL of the electrolyte was removed from the electrochemical reaction vessel, and 2mL of 1M NaOH solutions containing 5 wt% salicylic acid and 5 wt% sodium citrate were added to the solutions, respectively. Then, 1mL of 0.05M sodium hypochlorite and 0.2mL of 1 wt% sodium nitrosoferricyanide were added to the above solution. Standing at room temperature in dark place for 2h, measuring the ultraviolet-visible absorption spectrum, and calculating the actual ammonia yield.
2. And (3) test results:
XRD of K-intercalated molybdenum oxide photocatalyst under different experimental conditions as prepared in comparative example 1 and example is shown in fig. 1. It can be seen that the products obtained in the different examples and comparative examples all maintain the basic crystal structure.
Scanning Electron Microscopy (SEM) of K-intercalated molybdenum oxide photocatalysts prepared in comparative example 1 and example under different experimental conditions is shown in figure 2. It can be seen that the products obtained in the different examples and comparative examples all show similar nanotube array morphologies.
X-ray photoelectron spectroscopy (XPS) analysis of the K-intercalated molybdenum oxide photocatalyst under different experimental conditions prepared in comparative example 1 and example is shown in fig. 3. XPS characterization was performed to further study elemental valence states and K doping sites. From the XPS spectrum results, it can be concluded that potassium atoms have been intercalated into MoO 3 And the Au nanoparticles were successfully supported on the surface thereof.
The results of the experimental tests are shown in figure 4. The wavelength-dependent photocatalytic nitrogen reduction rate is nearly identical to the plasma absorption of K-intercalated molybdenum oxide nanoarrays. The highest photocatalytic nitrogen reduction rate occurs at a monochromatic light wavelength of 808nm, approximately at the absorption peak of the plasmonic nanoarray (805nm), confirming the photocatalytic nitrogen reduction driven by the local plasmon resonance effect of the K-intercalated molybdenum oxide nanoarray. Notably, an exceptionally low photocatalytic nitrogen reduction rate was obtained at a monochromatic light wavelength of 600nm, approaching the plasmon absorption peak (570nm) of Au nanoparticles. This indicates that unfavorable kinetics of high-energy electron transfer exist in the surface plasmon overlap region of Au nanoparticles and K-intercalated molybdenum oxide nanoarrays, which are not favorable for photocatalytic nitrogen reduction.
The photocatalytic nitrogen reduction performance of the K-intercalated molybdenum oxide photocatalyst under different experimental conditions prepared in comparative example 1 and example is shown in fig. 5. Under the irradiation of visible light, the pure molybdenum oxide nano array shows 0.37 mu g cm -2 h -1 NH of (2) 3 Yield. However, the photocatalytic nitrogen reduction performance of the K-intercalated molybdenum oxide nanoarrays under different preparation conditions in the examples is greatly enhanced. The photocatalytic nitrogen reduction rate of the catalyst prepared in example 1 was 2.0. mu.g cm -2 h -1 (ii) a The photocatalytic nitrogen reduction rate of the catalyst prepared in example 2 was 4.38. mu.g cm -2 h -1 (ii) a The photocatalytic nitrogen reduction rate of the catalyst prepared in example 3 was 9.6. mu.g cm -2 h -1 (ii) a 5.4 times, 11.8 times and 28 times the photocatalytic nitrogen reduction rate of the pure molybdenum oxide nanoarrays prepared in the comparative example.
Fig. 6 shows a reaction mechanism of visible light catalysis nitrogen reduction ammonia generation of the K-atom intercalated molybdenum oxide photocatalyst, and under irradiation of visible light, plasma-induced high-energy thermal electrons in the K-intercalated molybdenum oxide nano array will be transferred to the opposite Au nanoparticles through Mo. Au is used as an active site for nitrogen reduction, has high-energy thermal electrons and is also combined with N 2 And water, so that efficient photocatalytic nitrogen reduction occurs.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A potassium intercalation molybdenum oxide nano array material is characterized in that: comprises a substrate, a potassium-doped molybdenum oxide nano thin layer attached to the surface of the substrate and gold nanoparticles modified on the potassium-doped molybdenum oxide nano thin layer.
2. The potassium intercalated molybdenum oxide nanoarray material of claim 1, wherein: the mass ratio of molybdenum oxide to potassium atoms to gold nanoparticles is 0.8-1.2: 0.05-0.15: 0.01, preferably 1: 0.11: 0.01.
3. the method for preparing the potassium intercalated molybdenum oxide nano array material of claim 1 or 2, which is characterized by comprising the following steps: the method comprises the following steps:
putting the molybdenum substrate into a sylvite solution, carrying out anodic oxidation for a set time, then carrying out cathodic reduction, and inserting potassium atoms into a molybdenum oxide crystal structure;
calcining the obtained material in an inert atmosphere, and modifying gold nanoparticles on the surface of a matrix by utilizing magnetron sputtering to obtain the potassium intercalation molybdenum oxide material.
4. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the potassium salt solution is a potassium fluoride solution.
5. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the concentration of the potassium salt solution is 0.05-0.5mol/L, and the solvent is water, glycerol or a mixture of water and glycerol.
6. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the calcining temperature is 200-800 ℃; preferably, the calcination temperature is 300-600 ℃; further preferably 400 ℃.
7. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the anodic oxidation voltage is 5-50V, and the time is 5-120 min; preferably, the voltage of anodic oxidation is 30-50V, and the time is 50-120 min; further preferably, the voltage of anodic oxidation is 35-45V, and the time is 50-70 min; more preferably, the anodic oxidation voltage is 40V and the time is 60 min.
8. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the voltage of cathode reduction is-0.1 to-5V, and the time is 10 to 6000 s; preferably, the voltage of cathode reduction is-0.1 to-1V, and the time is 10 to 600 s; further preferably, the voltage of cathode reduction is-0.1 to-0.7V, and the time is 50 to 200 s; more preferably, the voltage of cathode reduction is-0.3 to-0.7V, and the time is 70 to 150 s; still more preferably, the voltage for cathodic reduction is-0.5V and the time is 100 s.
9. The method for preparing the potassium intercalated molybdenum oxide nano array material according to claim 3, wherein the method comprises the following steps: the current of magnetron sputtering is 5-100mA, and the magnetron sputtering time is 1-100 s; preferably, the current of magnetron sputtering is 10-70mA, and the magnetron sputtering time is 10-70 s; further preferably, the current of magnetron sputtering is 10-50mA, and the magnetron sputtering time is 10-50 s; still further preferably, the magnetron sputtering current is 10-40mA, and the magnetron sputtering time is 10-40 s; more preferably, the magnetron sputtering current is 15mA, and the magnetron sputtering time is 20 s.
10. The use of the potassium intercalated molybdenum oxide nanoarray material of claim 1 or 2 in the photocatalytic reduction of nitrogen to produce ammonia gas.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670360A (en) * 1984-08-18 1987-06-02 Basf Aktiengesellschaft Fuel cell
WO2013133770A1 (en) * 2012-03-08 2013-09-12 Nanyang Technological University A molybdenum oxide phototransistor and method of synthesis thereof
CN105148910A (en) * 2015-07-17 2015-12-16 济南大学 Preparation method for hexagonal flaky molybdenum oxide loaded with gold nanometer particles
CN109132999A (en) * 2018-09-05 2019-01-04 天津瑞晟晖能科技有限公司 Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670360A (en) * 1984-08-18 1987-06-02 Basf Aktiengesellschaft Fuel cell
WO2013133770A1 (en) * 2012-03-08 2013-09-12 Nanyang Technological University A molybdenum oxide phototransistor and method of synthesis thereof
CN105148910A (en) * 2015-07-17 2015-12-16 济南大学 Preparation method for hexagonal flaky molybdenum oxide loaded with gold nanometer particles
CN109132999A (en) * 2018-09-05 2019-01-04 天津瑞晟晖能科技有限公司 Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery

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