CN114284366A - Artificial bionic tree leaf and preparation method thereof - Google Patents
Artificial bionic tree leaf and preparation method thereof Download PDFInfo
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- CN114284366A CN114284366A CN202111625519.5A CN202111625519A CN114284366A CN 114284366 A CN114284366 A CN 114284366A CN 202111625519 A CN202111625519 A CN 202111625519A CN 114284366 A CN114284366 A CN 114284366A
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Abstract
The invention provides an artificial bionic leaf and a preparation method thereof, wherein the artificial bionic leaf comprises a vein-like layer and a mesophyll-like layer; the vein-like layer comprises a first film and a metal conductor, wherein the metal conductor is in a vein shape and is attached to one surface of the first film; the mesophyll-imitated layer comprises a second film and photoelectric semiconductor particles, and the photoelectric semiconductor particles are attached to one surface of the second film; at least one of the first film and the second film is made of transparent materials, the simulated leaf vein layer and the simulated leaf flesh layer are combined together in a mode that the surface of the first film, to which the metal conductor is attached, is attached to the surface of the second film, to which the photoelectric semiconductor particles are attached, and the metal conductor leads out the photogenerated carriers generated by the photoelectric semiconductor particles. The invention uses the metallic conductor in the shape of veins to transfer the carriers in the separated photo-generated electron-hole pairs out of the region where the carriers are located, thereby effectively avoiding the combination with the photo-generated holes again.
Description
Technical Field
The invention relates to the field of photoelectric semiconductors, in particular to an artificial bionic leaf and a preparation method thereof.
Background
Solar energy is a green, nearly unlimited energy source, and becomes the most potential new energy source. Photoelectric semiconductors such as titanium dioxide, cadmium telluride and the like can generate photogenerated electron-hole pairs under the condition of illumination, and the conversion of light energy into electric energy is realized.
In recent years, bionics has been applied to the field of photovoltaic applications, for example, artificial bionic leaves can simulate photosynthesis, reduce carbon dioxide to methane, and the like. However, the photoelectric conversion efficiency of the existing artificial bionic leaves is relatively low. In order to improve the photoelectric conversion efficiency, on one hand, the photoresponse range of the photoelectric semiconductor can be improved, and the specific treatment means is doping treatment such as nitrogen doping; on the other hand, the utilization rate of the photon-generated carriers can be improved, and common processing means comprise heterojunction and noble metal doping, such as silver doping, so as to inhibit the recombination of the photon-generated carriers.
However, the modification treatment of the photoelectric semiconductor in the artificial bionic leaves adopts a homogenization treatment method, such as indiscriminately introducing noble metals which are randomly arranged on the surface of the photoelectric semiconductor; in the processing mode, although the separation efficiency of the generated photon-generated electron-hole pairs is remarkably improved, as the separated photon-generated carriers cannot be timely far away from the accumulation region of opposite charges, carrier recombination with a relatively high proportion still occurs, and the improvement of the photoelectric conversion efficiency is not obvious.
Disclosure of Invention
The invention aims to solve the technical problem that the photoelectric conversion efficiency of the artificial bionic leaves is relatively low, and provides the artificial bionic leaves and a preparation method thereof.
The technical scheme for solving the technical problems is that the invention provides an artificial bionic leaf, which comprises a vein-like layer and a mesophyll-like layer; the vein-like layer comprises a first film and a metal conductor, wherein the metal conductor is in a vein shape and is attached to one surface of the first film; the mesophyll-imitated layer comprises a second film and photoelectric semiconductor particles, and the photoelectric semiconductor particles are attached to one surface of the second film; at least one of the first film and the second film is made of transparent materials, the simulated leaf vein layer and the simulated leaf flesh layer are combined together in a mode that the surface of the first film, to which the metal conductor is attached, is attached to the surface of the second film, to which the photoelectric semiconductor particles are attached, and the metal conductor leads out the photogenerated carriers generated by the photoelectric semiconductor particles.
As a further improvement of the invention, the mesophyll-like layer comprises noble metal particles, the noble metal particles and the photoelectric semiconductor particles are mixed and then jointly attached to the surface of the second film, and the number ratio of the noble metal particles to the photoelectric semiconductor particles is 1: 1-1: 2.
as a further improvement of the present invention, the thickness of the noble metal particles and the photoelectric semiconductor particles on the second film is 2 to 5 μm, and the coverage of the noble metal particles and the photoelectric semiconductor particles on the surface of the second film is 50 to 75%.
As a further improvement of the invention, the particle size of the photoelectric semiconductor particles is 20-50 nm, and the particle size of the noble metal particles is 10-15 nm.
As a further improvement of the invention, the width and the height of the metal conductor are matched with the width and the thickness of the leaf vein of the tree leaf.
The invention also provides a preparation method of the artificial bionic leaf, which comprises the following steps:
(a) bonding a metallic conductor in a vein shape to one surface of the first film to form a vein-like layer;
(b) spraying photoelectric semiconductor particles on one surface of the second film to form a simulated mesophyll layer;
(c) and combining the vein-like layer and the mesophyll-like layer in a manner that the surface of the first film, which is attached with the metal conductor, is attached with the surface of the second film, which is attached with the photoelectric semiconductor particles.
As a further improvement of the present invention, the step (a) comprises:
(a1) taking the leaf vein as a template, preparing a continuous groove corresponding to the leaf vein on a soft base material, wherein the depth of the continuous groove is matched with the thickness of the leaf vein;
(a2) filling a salt solution of the intended metal into the continuous groove of the soft substrate;
(a3) reducing the salt solution of the intended metal in the groove of the soft base material to form a vein-shaped metal conductor;
(a4) and preparing a first film on the surface of the soft base material, so that the metal conductor is tightly combined with the first film to form a vein-like layer.
As a further improvement of the present invention, the step (a1) includes:
(a11) heating the soft base material to be softened;
(a12) placing the leaf vein on the surface of a soft base material which is softened by heating, and uniformly pressing the leaf vein by using a flat plate until the leaf vein is embedded into the surface of the soft base material;
(a13) stopping heating the soft base material and taking out the leaf veins.
As a further improvement of the present invention, the step (a1) includes:
(a14) three-dimensional scanning is carried out on the leaf veins to obtain leaf vein model data;
(a15) and using the vein model data and preparing and forming the continuous groove on the soft substrate by adopting a laser etching method.
As a further improvement of the present invention, the step (a2) includes:
(a21) immersing the leaf vein in a salt solution of an intended metal;
(a22) taking out the leaf vein and placing the leaf vein into a continuous groove of the soft base material so as to fill the salt solution of the intended metal carried on the leaf vein into the continuous groove;
(a23) repeating steps (a21) and (a22) until the salt solution of the intended metal fills the continuous groove of the flexible substrate.
The invention has the following beneficial effects: one carrier in the separated photo-generated electron-hole pairs is orderly moved out of the region by the metal conductor distributed in a vein shape, and the combination with the photo-generated holes is effectively avoided, so that the photoelectric conversion efficiency of the photoelectric semiconductor is greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of an artificial bionic leaf provided by an embodiment of the invention;
FIG. 2 is a schematic cross-sectional view of an artificial bionic leaf according to an embodiment of the present invention;
fig. 3 is a schematic flow chart of a preparation method of the artificial bionic leaves provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1 and fig. 2, the artificial bionic tree leaf provided by the embodiment of the present invention is a structural schematic diagram, and the artificial bionic tree leaf can simulate light and action under an illumination condition, and can realize organic matter degradation (for example, methane oxidation), carbon dioxide reduction, and the like by using energy provided by solar energy.
The artificial bionic leaf of the embodiment comprises a simulated vein layer 10 and a simulated mesophyll layer 20. Specifically, the vein-like layer 10 includes a first film 11 and a metal conductor 12, wherein the metal conductor 12 is vein-like and attached to one of the surfaces of the first film 11; the mesophyll-imitated layer 20 comprises a second film 21 and photoelectric semiconductor particles 22, and the photoelectric semiconductor particles 22 are attached to one surface of the second film 21. At least one of the first film 11 and the second film 21 is made of a transparent material, and the simulated vein layer 10 and the simulated mesophyll layer 20 are bonded together in such a manner that the surface of the first film 11 to which the metal conductor 12 is attached and the surface of the second film 21 to which the photoelectric semiconductor particles 22 are attached are adhered, for example, by bonding the first film 11 and the second film 21 together by spot bonding (i.e., bonding together by a plurality of bonding points).
Since at least one of the first thin film 11 and the second thin film 21 is made of a transparent material, light can be irradiated to the optoelectronic semiconductor particles 22 through the first thin film 11 or the second thin film 21, so that the optoelectronic semiconductor particles 22 generate photo-generated electron-hole pairs under the irradiation condition, and the metal conductor 12 is connected to an external circuit to have a certain electric potential, so that the metal conductor 12 and the nearby optoelectronic semiconductor particles form a local optoelectronic effect community. In the photoelectric effect community, the photogenerated holes are captured by the photoelectric semiconductor particles, the separated photogenerated carriers rapidly migrate to the nearby metal conductor 12, that is, the separated photogenerated carriers migrate from the photoelectric semiconductor particles 22 to the metal conductor 12, the metal conductor 12 forms the migration destination and the transport channel of the photogenerated carriers, and finally the photogenerated carriers generated by the photoelectric semiconductor particles 22 are led out to an external circuit by the metal conductor 12.
The artificial bionic leaf has the advantages that the current carriers in the photo-generated electron-hole pairs separated from the photoelectric semiconductor particles 22 are orderly moved out of the region where the photo-generated electron-hole pairs are located through the metal conductor 12, and the metal conductor 12 has a microstructure close to the veins of a real leaf, so that a local loop cannot be formed, combination with a photo-generated hole again can be effectively avoided, the photoelectric conversion efficiency of the photoelectric semiconductor is greatly improved, and the oxidation or reduction efficiency of corresponding gas is further improved. Meanwhile, the derived photon-generated carriers can form photon-generated current, and photovoltaic power generation is realized.
In one embodiment of the present invention, the width and height of the metal conductor 12 in the simulated leaf layer 10 may vary depending on the selected real leaf, ranging from hundreds of microns to hundreds of nanometers in size, to create a microstructure similar to the height of the leaf vein of the real leaf. The metal conductor 12 may be made of metal having high conductivity, such as gold, silver, or copper. Specifically, the metal conductor 12 may be embedded in the surface of the first film 11, or may be attached to the surface of the first film 11.
In one embodiment of the present invention, in order to further suppress recombination of the separated photo-generated electron-hole pairs, the mesophyll-like layer 20 may further include noble metal particles mixed with the photo-semiconductor particles 22 and attached to the surface of the second film 21, and the ratio of the number of the noble metal particles to the number of the photo-semiconductor particles 22 is 1: 1-1: 2. that is, the photo-semiconductor particles 22 are modified with the noble metal particles so that photo-generated carriers generated by the photo-semiconductor particles 22 can be "transported" by the noble metal particles to the metal conductor 12. The noble metal particles can be made of high-purity simple substance state gold, silver, copper and the like, and the particle size of the noble metal particles can be 10-15 nanometers. Specifically, the optoelectronic semiconductor particles 22 may be embedded on the surface of the second film 21, or may be attached on the surface of the second film 21.
The optoelectronic semiconductor particles 22 may specifically adopt cadmium telluride, gallium nitride, silicon carbide, tungsten oxide, etc., which are nano-sized particles, for example, having a particle size of 20 to 50 nm. Moreover, the thickness of the noble metal particles and the photoelectric semiconductor particles 22 on the second film 21 is 2-5 microns, and the coverage rate of the noble metal particles and the photoelectric semiconductor particles on the surface of the second film is 50-75%, so that the material loss can be reduced while the high performance is achieved.
The first film 11 and the second film can be made of polyurethane, acrylate, fluorocarbon resin and the like by a spin coating method, and the thickness of the first film and the second film can be 10-100 micrometers.
In an embodiment of the present invention, the overall shape of the artificial bionic leaf formed by combining the simulated vein layer 10 and the simulated mesophyll layer 20 may be leaf-shaped, or may be any shape such as circular, square, etc., as long as the metal conductor 12 of the simulated vein layer 10 can cover all areas.
Fig. 3 is a schematic flow chart of the method for preparing the artificial bionic leaves according to the embodiment of the present invention. The method specifically comprises the following steps:
step S31: and bonding a metallic conductor in a vein shape to one surface of the first film to form a vein-like layer.
In this step, the leaf vein can be used as a template to prepare a continuous groove corresponding to the leaf vein on a soft substrate (such as beeswax or polytetrafluoroethylene), and the depth of the continuous groove is adapted to the thickness of the leaf vein (usually less than 1 mm); then filling salt solution of the intended metal (for example, preparing a metal conductor made of silver, immersing the leaf vein into silver nitrate solution, or preparing a metal conductor made of copper, immersing the leaf vein into copper chloride solution) into the continuous groove of the soft base material; then, performing reduction treatment on the salt solution of the intended metal in the groove of the soft base material (for example, reducing metal ions into a simple substance metal material by adopting a method such as normal-temperature hydrogen plasma treatment and the like) to form a vein-shaped metal conductor; and finally, preparing a first film on the surface of the soft base material, so that the metal conductor is tightly combined with the first film to form a vein-like layer, and an embedded structure of the metal conductor and the first film is formed. Specifically, a transparent resin film with the thickness of about 100 microns is prepared on the surface of a soft base material with a metal conductor by adopting a spin coating method, a first film is formed after the transparent resin is naturally dried at normal temperature, the metal conductor is tightly connected with the first film and can be separated from the soft base body along with the first film, and thus the bionic vein layer can be obtained.
Specifically, the leaf vein of the tree can be prepared by the following steps: selecting complete real leaves, soaking the leaves in 80 ℃ sodium bicarbonate water solution for 30 minutes, taking out the leaves, and cleaning the leaves in clear water; then, the mesophyll of the leaves is removed by adopting a fine brush, the completeness of the leaves is ensured without damaging the vein structure; finally, cleaning the veins, and naturally drying to obtain the leaves and veins.
And, a continuous groove corresponding to the leaf vein of the tree leaf can be prepared on the soft base material by the following method: first, a soft substrate (e.g., beeswax) is heated to soften; then placing the leaf veins on the surface of the soft base material which is softened by heating, and uniformly applying pressure to the leaf veins by using a flat plate until the leaf veins are embedded into the surface of the soft base material; and finally, stopping heating the soft base material and taking out the leaf veins, thereby forming continuous grooves corresponding to the leaf veins on the surface of the soft base material.
In addition, the continuous grooves corresponding to the leaf veins of the leaves can be prepared on the soft base material by the following method: three-dimensional scanning is carried out on leaf veins to obtain vein model data; and then using vein model data and adopting a laser etching method to prepare and form a continuous groove on a soft substrate (such as polytetrafluoroethylene).
Filling the salt solution of the intended metal into the continuous grooves of the flexible substrate can be achieved by: immersing the leaf vein in a salt solution of the intended metal; then taking out the leaf vein and placing the leaf vein into a continuous groove of a soft base material so as to fill the salt solution of the intended metal carried on the leaf vein into the continuous groove, wherein the leaf vein and the continuous groove of the soft base material are required to be strictly matched in the process; repeating the above steps until the salt solution of the intended metal fills the continuous grooves of the soft substrate.
Step S32: and spraying photoelectric semiconductor particles on one surface of the second film to form a simulated mesophyll layer.
Specifically, the second film can be prepared by a spin coating method, photoelectric semiconductor particles (such as cadmium telluride nanoparticles, gallium nitride nanoparticles and the like, which can be modified by noble metal particles) are uniformly sprayed on one surface of the second film when the second film is not dried, the sprayed thickness is controlled to be 2-5 micrometers, then pressure is applied to embed the photoelectric semiconductor particles into the second film, so that a mosaic structure of the photoelectric semiconductor particles and the second film is formed, and the second film with the photoelectric semiconductor particles attached can be obtained after natural drying, so that the bionic leaf-flesh layer can be obtained.
Step S33: the simulated leaf vein layer and the simulated leaf flesh layer are combined together in a way that the surface of the first film, which is attached with the metal conductor, is attached with the surface of the second film, which is attached with the photoelectric semiconductor particles.
Specifically, the exposed surface of the metal conductor of the simulated vein layer and the exposed surface of the photoelectric semiconductor particles of the simulated mesophyll layer can be bonded by using a polyurethane adhesive and adopting a point bonding method, so that the artificial bionic leaf is obtained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An artificial bionic leaf is characterized by comprising a simulated vein layer and a simulated mesophyll layer; the vein-like layer comprises a first film and a metal conductor, wherein the metal conductor is in a vein shape and is attached to one surface of the first film; the mesophyll-imitated layer comprises a second film and photoelectric semiconductor particles, and the photoelectric semiconductor particles are attached to one surface of the second film; at least one of the first film and the second film is made of transparent materials, the simulated leaf vein layer and the simulated leaf flesh layer are combined together in a mode that the surface of the first film, to which the metal conductor is attached, is attached to the surface of the second film, to which the photoelectric semiconductor particles are attached, and the metal conductor leads out the photogenerated carriers generated by the photoelectric semiconductor particles.
2. The artificial bionic leaf as claimed in claim 1, wherein the simulated mesophyll layer comprises noble metal particles, the noble metal particles and photoelectric semiconductor particles are mixed and then attached to the surface of the second film, and the number ratio of the noble metal particles to the photoelectric semiconductor particles is 1: 1-1: 2.
3. the artificial bionic leaf as claimed in claim 2, wherein the thickness of the noble metal particles and the photoelectric semiconductor particles on the second film is 2-5 microns, and the coverage rate of the noble metal particles and the photoelectric semiconductor particles on the surface of the second film is 50-75%.
4. The artificial bionic leaf as claimed in claim 2, wherein the photoelectric semiconductor particles have a particle size of 20-50 nm, and the noble metal particles have a particle size of 10-15 nm.
5. The artificial bionic leaf according to claim 1, wherein the width and height of the metal conductor are adapted to the width and thickness of the leaf vein.
6. A method for preparing artificial bionic leaves as claimed in any one of claims 1-5, comprising the following steps:
(a) bonding a metallic conductor in a vein shape to one surface of the first film to form a vein-like layer;
(b) spraying photoelectric semiconductor particles on one surface of the second film to form a simulated mesophyll layer;
(c) and combining the vein-like layer and the mesophyll-like layer in a manner that the surface of the first film, which is attached with the metal conductor, is attached with the surface of the second film, which is attached with the photoelectric semiconductor particles.
7. The method of claim 6, wherein the step (a) comprises:
(a1) taking the leaf vein as a template, preparing a continuous groove corresponding to the leaf vein on a soft base material, wherein the depth of the continuous groove is matched with the thickness of the leaf vein;
(a2) filling a salt solution of the intended metal into the continuous groove of the soft substrate;
(a3) reducing the salt solution of the intended metal in the groove of the soft base material to form a vein-shaped metal conductor;
(a4) and preparing a first film on the surface of the soft base material, so that the metal conductor is tightly combined with the first film to form a vein-like layer.
8. The method of claim 7, wherein the step (a1) includes:
(a11) heating the soft base material to be softened;
(a12) placing the leaf vein on the surface of a soft base material which is softened by heating, and uniformly pressing the leaf vein by using a flat plate until the leaf vein is embedded into the surface of the soft base material;
(a13) stopping heating the soft base material and taking out the leaf veins.
9. The method of claim 7, wherein the step (a1) includes:
(a14) three-dimensional scanning is carried out on the leaf veins to obtain leaf vein model data;
(a15) and using the vein model data and preparing and forming the continuous groove on the soft substrate by adopting a laser etching method.
10. The method of claim 7, wherein the step (a2) includes:
(a21) immersing the leaf vein in a salt solution of an intended metal;
(a22) taking out the leaf vein and placing the leaf vein into a continuous groove of the soft base material so as to fill the salt solution of the intended metal carried on the leaf vein into the continuous groove;
(a23) repeating steps (a21) and (a22) until the salt solution of the intended metal fills the continuous groove of the flexible substrate.
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| CN102923639A (en) * | 2012-08-08 | 2013-02-13 | 西安交通大学 | Precise molding method of biomimetic micro-channel system based on plant veins |
| CN103606418A (en) * | 2013-10-22 | 2014-02-26 | 华南师范大学 | Preparation method of leaf-shaped transparent conductive electrode |
| CN108722401A (en) * | 2018-05-31 | 2018-11-02 | 吉林大学 | A kind of bionic plant foliaceous Au/ZnO heterojunction photocatalysts and preparation method thereof |
| US20190358605A1 (en) * | 2016-09-08 | 2019-11-28 | King Abdullah University Of Science And Technology | Flexible artificial leaves for hydrogen production and methods for making |
| CN111180110A (en) * | 2019-12-27 | 2020-05-19 | 华南师范大学 | Preparation method of composite metal network transparent conductive electrode |
| CN113311628A (en) * | 2021-05-18 | 2021-08-27 | 电子科技大学 | Self-repairing integrated electrochromic bionic leaf for intelligent stealth |
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2021
- 2021-12-27 CN CN202111625519.5A patent/CN114284366B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923639A (en) * | 2012-08-08 | 2013-02-13 | 西安交通大学 | Precise molding method of biomimetic micro-channel system based on plant veins |
| CN103606418A (en) * | 2013-10-22 | 2014-02-26 | 华南师范大学 | Preparation method of leaf-shaped transparent conductive electrode |
| US20190358605A1 (en) * | 2016-09-08 | 2019-11-28 | King Abdullah University Of Science And Technology | Flexible artificial leaves for hydrogen production and methods for making |
| CN108722401A (en) * | 2018-05-31 | 2018-11-02 | 吉林大学 | A kind of bionic plant foliaceous Au/ZnO heterojunction photocatalysts and preparation method thereof |
| CN111180110A (en) * | 2019-12-27 | 2020-05-19 | 华南师范大学 | Preparation method of composite metal network transparent conductive electrode |
| CN113311628A (en) * | 2021-05-18 | 2021-08-27 | 电子科技大学 | Self-repairing integrated electrochromic bionic leaf for intelligent stealth |
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