CN113181936A - Heterojunction GeSe/TiO2Composite photocatalyst and preparation method thereof - Google Patents
Heterojunction GeSe/TiO2Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN113181936A CN113181936A CN202110464588.6A CN202110464588A CN113181936A CN 113181936 A CN113181936 A CN 113181936A CN 202110464588 A CN202110464588 A CN 202110464588A CN 113181936 A CN113181936 A CN 113181936A
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- 229910005866 GeSe Inorganic materials 0.000 title claims abstract description 86
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000007246 mechanism Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000002135 nanosheet Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005411 Van der Waals force Methods 0.000 claims description 4
- 239000013590 bulk material Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 206010034962 Photopsia Diseases 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000065 phosphene Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005867 GeSe2 Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus alkene Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/39—
-
- B01J35/61—
Abstract
The invention discloses a heterojunction GeSe/TiO2Composite photocatalyst and preparation method thereof, and GeSe and TiO are utilized2The contact forms a II-type heterojunction, and photoproduction holes and electrons can be effectively separated, so that the service life of the heterojunction is prolonged, and the catalytic efficiency is obviously improved. The photocatalyst introduces GeSe, and the material has a band gap relative to TiO2Smaller, wider acceptable effective light range and effectively improved light energy utilization efficiency. The photocatalyst GeSe/TiO2The reaction mechanism of (2) is Z-scheme, and the oxidation active sites and the reduction active sites are effectively separated, so that the overall photocatalytic activity is improved, and the hydrogen yield is greatly improved.
Description
Technical Field
The invention relates to a preparation method of a black phosphorus-like material and titanium dioxide composite photocatalyst, belonging to the technical field of semiconductor devices.
Background
The current society develops rapidly, human consumption on environmental resources and energy is more and more, traditional fossil fuels such as coal, petroleum, natural gas and the like still occupy a large proportion, and with the trend that the human society develops exponentially to increase the energy demand, when limited fossil fuels are determined to be exhausted, the development of the globally-explored fossil energy is estimated to be only dozens of years for human beings. And with the consumption of the traditional fossil fuel, a large amount of pollutant emission is inevitably generated, so that the ecological environment is seriously damaged, and the survival and development of human beings are also really influenced.
In order to solve the energy problem and the environmental problem caused by the conventional energy, there is an urgent need for a new energy source which can replace the conventional fossil fuel and is environmentally friendly. Hydrogen is just such a suitable new energy source, which does not imply extremely high energy density and the product water after combustion does not affect the environment. A photocatalytic technology developed in recent years is a technology for performing environmental purification and energy conversion by using solar energy. The energy conversion is to convert the energy in the sunlight into chemical energy which can be utilized by utilizing a photocatalysis technology, and decompose water into hydrogen with high-density energy.
The core of the photocatalytic technology is the preparation of a high-activity photocatalyst and the research of a reaction mechanism, and the currently applied photocatalyst is mainly a semiconductor catalyst. The core principle is that under the action of illumination, the interior of a semiconductor crystal can absorb photon energy to generate electron-hole separation, electrons are excited onto a conduction band, holes are left on a valence band, electrons in the conduction band have strong reducibility, and H in water can be separated+Reduced to hydrogen and the cavity can react with water molecules to produce oxygen and H+。
There are many types of semiconductors commonly used today, such as common TiO2,ZnO,SnO2And the like, conventional wide bandgap semiconductor catalysts. TiO2 is the most representative catalytic material, but TiO2 has wide band gap, relatively low utilization efficiency of absorbed sunlight and easy recombination of photo-generated electron-hole pairs, and greatly influences the catalytic efficiency of TiO 2.
In recent years, new semiconductor materials have been developed, and a series of new two-dimensional semiconductor materials have appearedMaterials, e.g. graphene, phospholene, MoS2And the like, which have many advantages over conventional three-dimensional materials. Recently, a black phosphorus-like material has been receiving a wide attention, and the material has similar characteristics with the phosphene and has better stability performance compared with the phosphene. The invention selects black phosphorus-like materials GeSe and TiO2 to combine into II type semiconductor photocatalyst, the photocatalyst effectively improves the light utilization rate and reduces the recombination efficiency of photo-generated electron hole pairs.
Invention container
The technical problem is as follows: the invention aims to provide a photocatalyst and a preparation method thereof,
the technical scheme is as follows: heterojunction GeSe/TiO2Composite photocatalyst, black phosphorus-like material GeSe and TiO2Forming type II heterojunction, with GeSe conduction band bottom higher than that of TiO2The conduction band bottom of GeSe is higher than that of TiO2The price band of (c).
The GeSe material is a double-layer GeSe material, and the thickness of the GeSe material is between 3 and 6 nm.
Selected TiO2Has anatase structure.
The catalytic mechanism is the Z-scheme mechanism.
The GeSe material is two-dimensional nano material.
The heterojunction GeSe/TiO2The preparation method of the composite photocatalyst comprises the following steps:
a. preparing GeSe nanosheet dispersion liquid:
b. preparing TiO2:
Selecting pure TiO2Annealing the powder at 500 ℃ for 4 hours to remove organic impurities;
c. preparing a photocatalyst:
adding the pure anatase titanium dioxide powder obtained in the step b into the prepared GeSe nanosheet dispersion liquid, stirring the mixed solution, and stirring for reaction; centrifuging with high speed centrifuge, and removing supernatant ethanol solution; putting the sample at the bottom in a vacuum drying oven for drying until the sample is completely dried; grinding the completely dried sample, and finallyPreparation of GeSe/TiO2A composite photocatalyst is provided.
The specific method for preparing the GeSe nanosheet dispersion liquid in the step a comprises the following steps: ge powder and Se powder are mixed according to a molar ratio of 1:1, then heating reaction is carried out under a vacuum condition to obtain a GeSe block material, then the block material is dissolved in ethanol to form GeSe-ethanol suspension, then the GeSe-ethanol suspension is placed in a cell crusher to carry out liquid phase stripping, Van der Waals force between GeSe layers is gradually destroyed in ultrasonic oscillation, the GeSe layer is slowly stripped from the block, and finally a single-layer or few-layer GeSe nanosheet dispersion liquid is formed.
The centrifugal speed in step c is 9500 rpm.
Has the advantages that:
1. according to the invention, the black phosphorus-like material GeSe and titanium dioxide are selected to be compounded to form the photocatalyst, and the GeSe has better stability compared with materials such as phosphorus alkene. The GeSe material is a two-dimensional nano material, has an ultrahigh specific surface area, and has a larger contact area and more redox sites compared with a bulk catalyst.
The forbidden band width of the GeSe material is smaller, and the band gap is relative to that of TiO2Smaller, wider light absorption range, wide photocatalytic response range and high light utilization efficiency, thereby better utilizing solar energy.
GeSe and TiO2The formed II type heterojunction can effectively separate the photo-generated electron hole pair and prevent the recombination process of the photo-generated electron hole pair, thereby improving the photocatalysis performance. The so-called type ii heterostructure is generally defined as the band structure of the heterojunction behaves as: the conduction band and the valence band bottom of one of the two materials are higher than those of the other material, namely the signs of Δ Ec (narrow-band to wide-band conduction band bottom energy difference) and Δ Ev (narrow-band to wide-band valence band top energy difference) are the same, and the conduction band bottom of the lower conduction band material is higher than the valence band bottom of the higher material.
4. Photocatalyst GeSe/TiO2The reaction mechanism of (a) is Z-scheme, GeSe and TiO2Under the illumination condition, the material can excite electrons from a valence band to a conduction band, and the valence band and TiO of GeSe2Are very close, so that electrons are easily transferred from the TiO2The conduction band of (A) is transferred to the valence band and GeSe of GeSeThe holes are compounded, so that the GeSe conduction band electrons and the valence band holes are prevented from being compounded, the stability of the GeSe conduction band electrons is improved, meanwhile, the oxidation active sites and the reduction active sites are effectively separated because the oxidation active sites and the reduction active sites are positioned at different positions, the oxidation reduction reaction is separated, the service life of the photo-generated electrons is prolonged better, and the overall photocatalytic activity is improved.
5. TiO selected by the invention2Has anatase structure, higher photocatalytic activity than rutile TiO2, and good stability at room temperature
Drawings
Fig. 1 is a diagram showing an energy band distribution of a photocatalyst material provided by the present invention.
Fig. 2 is a side view and a top view of a GeSe bilayer.
FIG. 3 is TiO2And TiO2A GeSe composite photocatalyst absorption coefficient diagram.
The specific implementation mode is as follows:
heterojunction semiconductor laser, black phosphorus-like material GeSe and TiO2A type ii heterojunction will form, which is generally defined as a band structure of the heterojunction exhibiting: the conduction band bottom and the valence band bottom of one material in the two materials are higher than those of the other material, namely the signs of delta Ec (energy difference between the narrowband and the broadband conduction band bottom) and delta Ev (energy difference between the narrowband and the broadband valence band top) are the same, and the conduction band bottom of the conduction band lower material is higher than the valence band bottom of the higher material; GeSe in the patent has a conduction band higher than TiO2And the conduction band bottom of GeSe is higher than the valence band bottom of TiO 2. The heterojunction structure can effectively separate photo-generated electron hole pairs and effectively improve the photocatalysis efficiency.
The heterojunction photocatalyst is mainly a double-layer GeSe material, and the thickness of the double-layer GeSe material is 3-6 nm.
Selected TiO2Is anatase structure, compared with rutile structure TiO2Has higher photocatalytic activity and good stability at normal temperature.
The catalytic mechanism is the Z-scheme mechanism. GeSe and TiO2In the light ofUnder the condition, the crystal can excite electrons from a valence band to a conduction band, the valence band of GeSe and TiO2Are very close, so that electrons are easily transferred from the TiO2The conduction band is transferred to the valence band of GeSe to be compounded with the hole on the GeSe, so that the compounding of GeSe conduction band electrons and the hole on the valence band of the GeSe is prevented, the stability of the GeSe conduction band electrons is improved, meanwhile, the oxidation-reduction reaction is separated because the oxidation active site and the reduction active site are positioned at different positions, the service life of photo-generated electrons is better prolonged, and the photocatalytic activity is improved.
The GeSe material is a two-dimensional nano material, has an ultrahigh specific surface area, and has a larger contact area and more redox sites compared with a bulk catalyst.
The selected GeSe has smaller forbidden band width, wide photocatalytic response range and high light utilization efficiency.
A preparation method of the heterojunction photocatalyst comprises the following steps:
a. preparation of GeSe nanosheet dispersion
Ge powder and Se powder are mixed in a ratio of 1:1 to make the mass sum of the Ge powder and the Se powder be 4mg, and then the mixture is heated to 690 ℃ under the vacuum condition for 48 hours to obtain a GeSe bulk material. Then dissolving the block powder into ethanol to form GeSe-ethanol suspension, and then putting the GeSe-ethanol suspension into a cell crusher for liquid phase stripping. Van der Waals force between the GeSe layers can gradually find damage in ultrasonic oscillation, and the GeSe nanosheet is slowly stripped from the block body to finally form a single-layer or few-layer GeSe nanosheet dispersion liquid.
b. Preparing TiO2
Selecting pure TiO2The powder was annealed at 500 ℃ for 4 hours to remove organic impurities.
c. Preparation of the photocatalyst
B, adding 160mg of the pure anatase titanium dioxide powder obtained in the step b into the prepared GeSe nanosheet dispersion liquid, and stirring the mixed solution for about 3 hours; centrifuging for 25 minutes by using a high-speed centrifuge at the rotating speed of 9500rpm, and removing the supernatant ethanol solution after centrifuging; the sample at the bottom is placed in a vacuum drying oven at 45 deg.CDrying the sample, and waiting for the sample to be completely dried; grinding the completely dried sample to obtain GeSe/TiO2A composite photocatalyst is provided.
Examples
a. Preparation of GeSe nanosheet dispersion
Ge powder and Se powder are mixed according to a molar ratio of 1:1 to make the mass sum of the Ge powder and the Se powder be 4mg, and then the mixture is heated to 690 ℃ under a vacuum condition for 48 hours to obtain a GeSe bulk material. Then dissolving the block powder into ethanol to form GeSe-ethanol suspension, and then putting the GeSe-ethanol suspension into a cell crusher for liquid phase stripping. Van der Waals force between the GeSe layers can gradually find damage in ultrasonic oscillation, and the GeSe nanosheet is slowly stripped from the block body to finally form a single-layer or few-layer GeSe nanosheet dispersion liquid.
b. Preparing TiO2
Selecting pure TiO2The powder was annealed at 500 ℃ for 4 hours to remove organic impurities.
c. Preparation of the photocatalyst
B, adding 160mg of the pure anatase titanium dioxide powder obtained in the step b into the prepared GeSe nanosheet dispersion liquid, and stirring the mixed solution for about 3 hours; centrifuging for 25 minutes by using a high-speed centrifuge at the rotating speed of 9500rpm, and removing the supernatant ethanol solution after centrifuging; putting the sample at the bottom in a vacuum drying oven to dry at the temperature of 45 ℃ and waiting for the sample to be completely dried; grinding the completely dried sample to obtain GeSe/TiO2A composite photocatalyst is provided.
Claims (8)
1. Heterojunction GeSe/TiO2The composite photocatalyst is characterized in that the material similar to black phosphorus is GeSe and TiO2Forming type II heterojunction, with GeSe conduction band bottom higher than that of TiO2The conduction band bottom of GeSe is higher than that of TiO2The price band of (c).
2. The heterojunction GeSe/TiO of claim 12The composite photocatalyst is characterized in that the composite photocatalyst is a double-layer GeSe material, and the thickness of the composite photocatalyst is 3-6 nm.
3. The heterojunction GeSe/TiO of claim 12Composite photocatalyst, which is characterized in that TiO is selected2Has anatase structure.
4. The heterojunction GeSe/TiO of claim 12The composite photocatalyst is characterized in that the catalysis mechanism is a Z-scheme mechanism.
5. The heterojunction GeSe/TiO of claim 12The composite photocatalyst is characterized in that GeSe is a two-dimensional nano material.
6. The heterojunction GeSe/TiO of any one of claims 1 to 52The preparation method of the composite photocatalyst is characterized by comprising the following steps:
a. preparing GeSe nanosheet dispersion liquid:
b. preparing TiO2:
Selecting pure TiO2Annealing the powder at 500 ℃ for 4 hours to remove organic impurities;
c. preparing a photocatalyst:
adding the pure anatase titanium dioxide powder obtained in the step b into the prepared GeSe nanosheet dispersion liquid, stirring the mixed solution, and stirring for reaction; centrifuging with high speed centrifuge, and removing supernatant ethanol solution; putting the sample at the bottom in a vacuum drying oven for drying until the sample is completely dried; grinding the completely dried sample to obtain GeSe/TiO2A composite photocatalyst is provided.
7. A heterojunction GeSe/TiO as claimed in claim 62The preparation method of the composite photocatalyst is characterized in that the specific method for preparing the GeSe nanosheet dispersion liquid in the step a is as follows: mixing Ge powder and Se powder in a molar ratio of 1:1, heating and reacting under a vacuum condition to obtain a GeSe bulk material, dissolving the GeSe bulk material into ethanol to form a GeSe-ethanol suspension, and adding the GeSe-ethanol suspensionAnd (3) carrying out liquid phase stripping in the cell crusher, gradually damaging Van der Waals force between the GeSe layers in ultrasonic oscillation, slowly stripping the GeSe from the block body, and finally forming a single-layer or few-layer GeSe nanosheet dispersion liquid.
8. A heterojunction GeSe/TiO as claimed in claim 62The preparation method of the composite photocatalyst is characterized in that the centrifugal rotation speed in the step c is 9500 rpm.
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CN109081316A (en) * | 2017-06-13 | 2018-12-25 | 天津大学 | A kind of preparation method of the Germanium selenide two-dimensional material based on solvent heat graft process |
CN109502545A (en) * | 2018-10-10 | 2019-03-22 | 华南师范大学 | Germanium selenide base sun photodegradation aquatic products hydrogen electronic device, electrode system and preparation method thereof |
CN111375427A (en) * | 2020-04-16 | 2020-07-07 | 安徽理工大学 | Two-dimensional SnS2@TiO2Preparation of photocatalytic composite material |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109081316A (en) * | 2017-06-13 | 2018-12-25 | 天津大学 | A kind of preparation method of the Germanium selenide two-dimensional material based on solvent heat graft process |
CN109502545A (en) * | 2018-10-10 | 2019-03-22 | 华南师范大学 | Germanium selenide base sun photodegradation aquatic products hydrogen electronic device, electrode system and preparation method thereof |
CN111375427A (en) * | 2020-04-16 | 2020-07-07 | 安徽理工大学 | Two-dimensional SnS2@TiO2Preparation of photocatalytic composite material |
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