CN115672397A - Organic coated composite semiconductor material and preparation method and application thereof - Google Patents
Organic coated composite semiconductor material and preparation method and application thereof Download PDFInfo
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Images
Classifications
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- 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
Abstract
The application discloses an organic coating type composite semiconductor material and a preparation method and application thereof, belonging to the field of semiconductor materials. An organic cladding type composite semiconductor material comprises small organic molecules and a semiconductor; the organic small molecules are coated on the surface of the semiconductor. Compared to the initial semiconductor, the encapsulated semiconductor introduces small organic molecules to the initial semiconductor surface. The photoresponse range of the semiconductor is widened and the charge separation efficiency is improved through charge transfer interaction; the coated semiconductor material has the performances of wide photoresponse range and high charge separation: the hydrogen production efficiency of ZnS wrapped by double-end phenyl viologen under the irradiation of an AM1.5 sunlight simulated xenon lamp of 300W is basically maintained unchanged within 48 hours; the photoelectric detection can be realized for the xenon lamp light with the 300W output wavelength being more than 420 nanometers.
Description
Technical Field
The application relates to an organic coating type composite semiconductor material and a preparation method and application thereof, belonging to the field of semiconductor materials.
Background
The semiconductor refers to a material with electric conductivity between a conductor and an insulator at normal temperature. From the viewpoint of the electronic band structure, the semiconductor has a band gap that allows free carriers to rise to the conduction band. At present, semiconductors are in the aspects of people's lives. Therefore, the importance of semiconductors is enormous from the viewpoint of technological or economic development. The photoelectric effect of semiconductors is always the key research point in the semiconductor field, and photocatalysis and photoelectric detection are two important research directions for utilizing the photoelectric effect of semiconductors. Widening the photoresponse range of semiconductors and improving the charge separation efficiency of semiconductors are difficult problems in the field of semiconductors.
With the increase of population and the development of human socioeconomic performance, more and more energy sources need to be used. At present, fossil energy still occupies most of global energy consumption, and the fossil energy cannot be regenerated after being developed and utilized, and can be consumed in the near future if being exploited in large scale for a long time. The use of fossil energy is bound to discharge a large amount of carbon dioxide, along with the emission of carbon dioxide of various countries, greenhouse gases are increased greatly, a series of environmental problems such as glacier dissolution, sea level rising, ocean acidification and the like are caused, a life system is threatened, and climate change is a global problem faced by human beings. Therefore, it is extremely important to pursue green utilization of greenhouse gases such as carbon dioxide, development of carbon-neutral green energy, and chemical production processes. Sunlight is one of recyclable clean energy sources and is widely concerned by the international society and scientific community. Sunlight can be irradiated on most regions of the earth, and the energy of the sun is extremely large, scientists calculate a time limit of at least six million years, which is unlimited for human beings. The most fossil energy sources are used nowadays, the breeding problem is not only the discharge of wastes, but the more the energy sources are exhausted, the pollution is relatively increased. Although nuclear energy is a high-efficiency energy production mode, nuclear energy generation has the danger of nuclear leakage, once the nuclear leakage occurs, a great ecological crisis is caused, and solar energy has no danger and pollution. Under the principle that human beings are in peace with nature, the most green and safe solar energy is used, and if equipmentWhen used properly, the device needs very little cost after being finished, and at least 10 products can be produced each year 17 Kilowatt of electricity. The hydrogen is prepared by photocatalysis by sunlight, so that green production of green high-calorific-value fuel can be realized; the sunlight is utilized to carry out photocatalytic carbon dioxide reduction, so that the greenhouse gas can be converted into industrial raw materials or industrial primary products; the sunlight is utilized to carry out chemical reactions such as photocatalysis carbon-hydrogen bond activation and the like, so that the chemical reactions and conversion under mild conditions can be realized, and the emission of carbon pollution can be controlled from a reaction source by utilizing the photocatalysis reaction. The use of solar photocatalytic reactions is therefore one of the promising chemical approaches that is currently of the greatest interest.
In order to improve the catalytic efficiency of semiconductor photocatalysts, the current common strategies include designing a new single-component semiconductor photocatalyst and improving the existing semiconductor photocatalyst. Methods in which semiconductor-semiconductor heterojunctions, doping or co-doping are incorporated are often used to improve the performance of existing semiconductor photocatalysts. However, the semiconductor performance optimization methods have poor universality, small range of broadened semiconductor photoresponse and low efficiency of improving charge separation. Therefore, the development of the universal optimization method of the semiconductor photocatalyst, which can widen the photoresponse range of the semiconductor photocatalyst in a large range and greatly improve the charge separation, has important practical significance in promoting the industrialization of the semiconductor photocatalyst.
With the rapid development of the information age, semiconductors serve as the high-technology core of the age, and the photoelectric response range of the semiconductors is an important measurement parameter in the fields of photoelectric detection, solar energy conversion and the like. At present, the light response range of commercial materials is narrow, for example, the light response range of Si-based and Ge-based semiconductors is in a visible light region, the light response range of InGaAs-based semiconductors is in a short-wave infrared region, and the full solar spectrum cannot be covered, so that at least two semiconductor devices are required to be combined to meet the detection requirement to realize the full solar spectrum photoelectric response, and the equipment is complex, difficult to maintain and high in cost. Therefore, the development of the wide-spectrum response semiconductor material has very important practical significance in the field of photoelectric detection.
Disclosure of Invention
According to a first aspect of the present application, there is provided an organic clad type composite semiconductor material. The composite semiconductor material adopts organic micromolecules as coating materials, and solves the problems of narrow semiconductor light absorption range and low photo-generated charge separation efficiency by utilizing charge transfer interaction. Compared with the traditional method for improving the light absorption range or charge separation efficiency of the semiconductor, the cladding material is introduced into the surface interface of the semiconductor through post-treatment. In addition to preserving the photoresponse properties of the initial semiconductor, post-processing methods that incorporate small organic molecules can improve the photoresponse range or charge separation efficiency of the semiconductor.
The composite semiconductor material can be used as a photoelectric detection material, and the photocurrent/dark current response of ultraviolet-visible-infrared light is more than 10. Can also be used as a photocatalyst for the stable catalyst of reactions such as photolysis of water to produce hydrogen, carbon dioxide reduction, carbon-hydrogen bond activation and the like, and can realize green photochemical synthesis. For example, under the condition of a xenon lamp with sunlight simulating AM1.5, the hydrogen production efficiency of the zinc sulfide semiconductor material coated by the double-end phenyl viologen is not obviously reduced within 48 hours.
An organic cladding type composite semiconductor material comprises small organic molecules and a semiconductor;
the organic small molecules are coated on the surface of the semiconductor.
Optionally, the mass of the small organic molecules accounts for 0.1-10% of the total mass of the composite semiconductor material.
Optionally, the mass of the small organic molecules accounts for 0.5% -5% of the total mass of the composite semiconductor material.
Optionally, the mass fraction of the small organic molecules is independently selected from any value of 0.1%, 0.5%, 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or a range between any two.
Optionally, the semiconductor is micro-scale and/or nano-scale.
Optionally, the semiconductor has a size of 50nm to 10 μm.
Optionally, the semiconductor has a size of 50nm to 200nm.
Optionally, the size of the semiconductor is independently selected from any of 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or a range between any two.
Optionally, the organic small molecule is selected from at least one of viologens, tetrathiafulvalenes, naphthalimides and aromatic diphenols.
Optionally, the small organic molecule is selected from at least one of bis-methyl viologen, bis-ethyl viologen, mono-terminal phenyl viologen, bis-terminal phenyl viologen, tetrathiafulvalene, catechol.
Optionally, the semiconductor is selected from ZnS, tiO 2 At least one of CdS, UIO and MIL.
The UIO series material is a rigid metal organic framework material which takes Zr or other metals as the center and consists of terephthalic acid series organic ligands. The MIL series material refers to Laval Hill skeleton series material, and is a rigid metal organic framework synthesized by using different transition metal elements and dicarboxylic acid ligands such as succinic acid, glutaric acid and the like.
According to a second aspect of the present application, a method of preparing a composite semiconductor material is provided. The method adopts an ultrasonic-stirring-soaking synthesis method to prepare the coated semiconductor material. Conventional methods for increasing the photoelectric response range or the photo-generated charge separation efficiency of semiconductors require a great deal of effort to improve the compatibility of "guest" and "host" semiconductors, such as doping or co-doping, heterojunctions, etc. Compared with other traditional methods, the synthesis method of post-treatment has higher universality.
The preparation method of the composite semiconductor material comprises the following steps:
s1, mixing materials containing organic micromolecules and a solvent to obtain a coating solution;
and S2, dispersing a mixture containing the coating solution and the semiconductor to obtain the composite semiconductor material.
The mixing in step S1 is the simplest way to obtain a mixture containing small organic molecules and solvent, for example, stirring.
Optionally, in step S1, the solvent is at least one selected from water, ethanol, methanol, acetone, ethylene glycol, N-dimethylformamide, and N, N-dimethylacetamide.
Optionally, in step S1, the concentration of the small organic molecules is 0.001mg/mL to 100mg/mL.
Alternatively, the concentration of the small organic molecule is independently selected from any of 0.001mg/mL, 0.005mg/mL, 0.010mg/mL, 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1mg/mL, 5mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, or a range between any two.
Optionally, in step S2, dispersing includes ultrasonic, stirring, and soaking.
Alternatively, the conditions of the ultrasound are as follows:
the time is 1-5 h.
Optionally, the time is independently selected from any of 1h, 2h, 3h, 4h, 5h, or a range of values between any two.
Alternatively, the conditions of stirring are as follows:
the time is 12 to 24 hours;
the rotating speed is 800 rpm-1000 rpm.
Optionally, the time is independently selected from any of 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, or a range of values between any two.
Alternatively, the soaking conditions are as follows:
the time is 12-72 h.
Optionally, time is independently selected from any of 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, 50h, 52h, 54h, 56h, 58h, 60h, 62h, 64h, 66h, 68h, 70h, 72h, or a range of values between any two.
Optionally, the method comprises the following steps:
and adding a semiconductor into a mixed solution containing organic micromolecules and a solvent, and carrying out ultrasonic treatment, stirring and soaking to obtain the composite semiconductor material.
According to a third aspect of the present application, there is provided a use of a composite semiconductor material.
The composite semiconductor material and/or the composite semiconductor material obtained by the preparation method are applied to photocatalysis and wide-spectrum photoelectric detection.
Optionally, the hydrogen production efficiency of the composite semiconductor material under the irradiation of 300W and AM1.5 sunlight simulated xenon lamps is kept unchanged within 48 h.
Optionally, the photocurrent/dark current response of the composite semiconductor material to uv-visible-ir light is greater than 10.
Optionally, the composite semiconductor material realizes photoelectric detection on xenon lamp light with 300W output wavelength being more than 420 nanometers.
According to one embodiment of the present application, it is prepared by an ultrasonic-stirring-soaking synthesis method. The preparation steps are as follows:
(1) Dissolving the organic small molecules in a solvent.
(2) Dispersing an initial semiconductor in a solution of organic micromolecules, carrying out ultrasonic treatment, stirring at a high speed, and finally standing and soaking.
(3) And centrifuging at high speed and washing to obtain the coated semiconductor material.
The organic micromolecule in the step (1) can be any one or more of double-end methyl viologen, double-end ethyl viologen, single-end phenyl viologen, double-end phenyl viologen, tetrathiafulvalene and catechol, and preferably double-end phenyl viologen.
The dispersing solvent in the step (1) can be water, ethanol, methanol, acetone, ethylene glycol, N-dimethylformamide, N-dimethylacetamide and the like as a solvent according to the solubility of the organic small molecules, and water or ethanol is preferred. The concentration of the small organic molecules is designed according to the coating amount, and the concentration can range from 0.001mg/mL to 100mg/mL.
The ultrasonic time in the step (2) is accumulated for 1-5 hours, the high-speed stirring time is accumulated for 12-24 hours, and the soaking time is accumulated for 12-72 hours. Preferably, the ultrasonic treatment is carried out for 2 hours, the stirring is carried out at a high speed for 12 hours, and the soaking is carried out for 72 hours.
The invention aims to provide application of a coated semiconductor material, which can be used for photocatalysis and can realize green photochemical synthesis. A photocatalytic reactor is adopted, a coated semiconductor material is used as a photocatalyst to be dispersed in a reactant environment, and a target product is obtained under the irradiation of a xenon lamp.
The invention aims to provide application of a coated semiconductor material, which can be used for broadband spectrum photoelectric detection and can realize broadband spectrum photoelectric detection of a single semiconductor material. A semiconductor tester is adopted to prepare the cladding semiconductor material into a photoelectric detection device, and under the voltage of-20V-20V, light with the wavelength larger than 300 nanometers is converted into an electric signal by utilizing photoelectric response, so that photoelectric detection is realized.
The beneficial effects that this application can produce include:
1) Compared with an initial semiconductor, the coated semiconductor introduces small organic molecules to the surface of the initial semiconductor. The photoresponse range of the semiconductor is widened and the charge separation efficiency is improved through charge transfer interaction; the coated semiconductor material has the performances of wide photoresponse range and high charge separation: the hydrogen production efficiency of ZnS wrapped by double-end phenyl viologen under the irradiation of an AM1.5 sunlight simulated xenon lamp of 300W is basically maintained unchanged within 48 hours; the photoelectric detection can be realized for the xenon lamp light with the 300W output wavelength being more than 420 nanometers.
2) Compared with the traditional semiconductor optimization method, the preparation method of the composite semiconductor material provided by the application reserves the basic properties of the initial semiconductor by introducing the organic small molecules at the later stage, and the optimization method has universality for the semiconductor.
Drawings
Fig. 1 is a uv-vis diffuse reflectance graph of the cladding semiconductor material and the initial semiconductor of example 1. The figure shows that the clad semiconductor material has a wider light absorption range relative to the original semiconductor.
FIG. 2 is a graph of the photoelectric response of the encapsulated semiconductor material and the initial semiconductor in examples 4 and EE to 300W xenon lamp light with an output wavelength of greater than 420 nm. The figure shows that the cladding semiconductor can realize photoelectric detection on visible light-infrared light.
FIG. 3 is a plot of the space-time yield of hydrogen evolution reaction from simulated photolysis of sunlight between the encapsulated semiconductor material and the initial semiconductor in examples 8 and B, and the catalyst evaluation conditions are shown in example A. The figure shows that the coated semiconductor has good hydrogen production performance and stability.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.
Coated semiconductor material prepared by ultrasonic-stirring-soaking synthesis method
A certain amount of organic micromolecules are dissolved in 10mL of solvent to prepare solution. 200mg of the initial semiconductor was dispersed in the organic small molecule solution. And (3) carrying out ultrasonic treatment on the dispersion liquid to fully mix and contact the semiconductor and the organic small molecules. Stirring at high speed after the ultrasonic treatment is finished, and then standing and soaking to ensure that the semiconductor and the organic micromolecules are completely mixed and contacted. And finally, centrifuging at a high speed and washing to obtain the coated semiconductor. Specific experimental parameters for the 8 catalyst preparation examples are detailed in table 1.
TABLE 1 Experimental parameters for the preparation of clad semiconductors
Evaluation of hydrogen production by simulated decomposition of sunlight
A certain amount of coated semiconductor photocatalyst is put into a photocatalytic reactor, 100mL of sacrificial agent solution is added, and argon is bubbled for 0.5-2 hours to remove oxygen in the reactor. The reactor is irradiated by sunlight simulation xenon lamps, and argon gas with the flow rate of 1-5mL/min is used as carrier gas to detect the hydrogen evolution efficiency on line. The specific test conditions of the 7 catalyst evaluation examples are shown in table 2.
TABLE 2 Experimental parameters for catalyst evaluation
| Example No. 1 | Type and concentration of sacrificial agent | Flow rate of carrier gas |
| A | 0.35M Na 2 S and 0.25M Na 2 SO 3 | 1mL/min |
| B | 0.35M Na 2 S and 0.25M Na 2 SO 3 | 5mL/min |
| C | Lactic acid; 10% volume fraction | 5mL/min |
| D | Triethylamine; 10% volume fraction | 1mL/min |
| E | Triethanolamine; 10% volume fraction | 3mL/min |
| F | 0.35M ascorbic acid | 3mL/min |
| G | 0.35M sodium ascorbate | 5mL/min |
The photocatalyst hydrogen production efficiency is calculated by using the following formula:
space Time Yield (Space Time Yield, STY) = (p.alpha.A.v) Flow )/(R·T·m)
p-pressure (N.m) -2 ) Alpha-chromatogram calibration factor (1.73X 10) -8 ) A-integrated peak area of chromatogram, v Flow The gas flow rate (m) at the end of the reactor 3 ·h -1 ) R-general gas constant (8.3145 N.m.mol) -1 ·K -1 ) T-Room temperature (298K), m-catalyst mass (g)
Evaluation of broadband spectrum photoelectric detection performance
A certain amount of coated semiconductors are prepared into photoelectric detection devices, and photoelectric properties are tested by using a semiconductor tester or an electrochemical workstation. The photo-detection was tested at-20V-20V bias. The specific test conditions for the 8 photodetector devices evaluated the examples are shown in table 3.
TABLE 3 Experimental parameters for semiconductor photoelectric detection evaluation
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. An organic cladding type composite semiconductor material is characterized in that the composite semiconductor material comprises small organic molecules and a semiconductor;
the organic small molecules are coated on the surface of the semiconductor.
2. The composite semiconductor material according to claim 1, wherein the mass of the small organic molecules is 0.1-10% of the total mass of the composite semiconductor material;
preferably, the mass of the organic micromolecules accounts for 0.5-5% of the total mass of the composite semiconductor material.
3. The composite semiconductor material of claim 1, wherein the semiconductor is microscale and/or nanoscale;
preferably, the size of the semiconductor is 50nm to 10 μm;
preferably, the size of the semiconductor is 50nm to 200nm.
4. The composite semiconductor material according to claim 1, wherein the small organic molecules are selected from at least one of viologens, tetrathiafulvalenes, naphthalimides, and aromatic diphenols;
preferably, the organic small molecule is selected from at least one of methyl viologen, ethyl viologen, phenyl viologen, tetrathiafulvalene and catechol;
preferably, the semiconductor is selected from ZnS, tiO 2 At least one of CdS, UIO and MIL.
5. A method for producing the composite semiconductor material according to any one of claims 1 to 4, characterized by comprising the steps of:
s1, mixing materials containing organic micromolecules and a solvent to obtain a coating solution;
and S2, dispersing a mixture containing the coating solution and the semiconductor to obtain the composite semiconductor material.
6. The method according to claim 5, wherein in step S1, the solvent is at least one selected from the group consisting of water, ethanol, methanol, acetone, ethylene glycol, N-dimethylformamide, and N, N-dimethylacetamide;
preferably, in step S1, the concentration of the small organic molecules is 0.001 mg/mL-100 mg/mL.
7. The method according to claim 5, wherein in step S2, the dispersing comprises ultrasonic treatment, stirring, and soaking;
preferably, the conditions of sonication are as follows:
the time is 1-5 h;
preferably, the conditions of stirring are as follows:
the time is 12 to 24 hours;
the rotating speed is 800 rpm-1000 rpm;
preferably, the soaking conditions are as follows:
the time is 12-72 h.
8. The method of claim 5, comprising the steps of:
and adding a semiconductor into a mixed solution containing organic micromolecules and a solvent, and carrying out ultrasonic treatment, stirring and soaking to obtain the composite semiconductor material.
9. Use of the composite semiconductor material according to any one of claims 1 to 4 and/or the composite semiconductor material obtained by the preparation method according to any one of claims 5 to 8 in photocatalysis and wide-spectrum photodetection.
10. The application of the composite semiconductor material as claimed in claim 9, wherein the hydrogen production efficiency of the composite semiconductor material under the irradiation of 300W and AM1.5 sunlight simulated xenon lamps is kept unchanged within 48 h;
preferably, the photocurrent/dark current response of the composite semiconductor material to uv-visible-ir light is greater than 10;
preferably, the composite semiconductor material realizes photoelectric detection on xenon lamp light with 300W output wavelength being more than 420 nanometers.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
| CN108389732A (en) * | 2018-02-02 | 2018-08-10 | 陕西科技大学 | A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN108654669A (en) * | 2018-04-28 | 2018-10-16 | 成都新柯力化工科技有限公司 | A kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making |
| CN108735902A (en) * | 2017-04-20 | 2018-11-02 | 丛聪 | Flexible all band photoelectric material, photoelectric device and its manufacturing method |
| CN109817808A (en) * | 2019-01-11 | 2019-05-28 | 电子科技大学 | A kind of Van der Waals heterojunction type photoelectric detector and preparation method |
| CN110227492A (en) * | 2019-04-29 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of Nano semiconductor photochemical catalyst and preparation method thereof |
| CN114256364A (en) * | 2021-03-04 | 2022-03-29 | 中国科学院宁波材料技术与工程研究所 | Application of self-PN junction semiconductor nano material as infrared photoelectric detector |
| CN115121287A (en) * | 2021-03-24 | 2022-09-30 | 曾繁根 | Composite material for photocatalytic hydrogen production and photocatalytic hydrogen production catalyst |
-
2022
- 2022-11-14 CN CN202211426162.2A patent/CN115672397A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
| CN108735902A (en) * | 2017-04-20 | 2018-11-02 | 丛聪 | Flexible all band photoelectric material, photoelectric device and its manufacturing method |
| CN108389732A (en) * | 2018-02-02 | 2018-08-10 | 陕西科技大学 | A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material |
| CN108654669A (en) * | 2018-04-28 | 2018-10-16 | 成都新柯力化工科技有限公司 | A kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN109817808A (en) * | 2019-01-11 | 2019-05-28 | 电子科技大学 | A kind of Van der Waals heterojunction type photoelectric detector and preparation method |
| CN110227492A (en) * | 2019-04-29 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of Nano semiconductor photochemical catalyst and preparation method thereof |
| CN114256364A (en) * | 2021-03-04 | 2022-03-29 | 中国科学院宁波材料技术与工程研究所 | Application of self-PN junction semiconductor nano material as infrared photoelectric detector |
| CN115121287A (en) * | 2021-03-24 | 2022-09-30 | 曾繁根 | Composite material for photocatalytic hydrogen production and photocatalytic hydrogen production catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 张明伦著: "信息科学技术专著丛书 可见光通信技术", vol. 2022, 31 August 2022, 北京邮电大学出版社, pages: 11 * |
| 檀苗苗;丁娅莉;山鹏禹;李紫晗;卢金荣;: "Cu_2O/PTCDI复合材料的制备及其光催化活性", 化工环保, no. 03, 15 June 2020 (2020-06-15), pages 322 - 328 * |
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