CN115490212A - Near-infrared active periodic plasma heterojunction photo-anode material and preparation method thereof - Google Patents
Near-infrared active periodic plasma heterojunction photo-anode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a near-infrared active periodic plasma heterojunction photo-anode material and a preparation method thereof, wherein the near-infrared active periodic plasma heterojunction photo-anode material is prepared from Bi x /Bi 3 (Se 1‑y Te y ) 2 Periodic heterogeneous nanostructure composition; the Bi x /Bi 3 (Se 1‑y Te y ) 2 Periodic heterogeneous nano structure made of Bi 3 (Se 1‑y Te y ) 2 Passing of nanowiresOne-step solvent thermal synthesis. The photoanode material provided by the application adjusts Bi 3 (Se 1‑ y Te y ) 2 The ratio of Bi to Bi realizes the high-efficiency utilization of the surface plasma resonance effect, thereby improving the energy conversion efficiency of the photoelectrochemical process. The invention provides a new way for designing and developing photo-anode nano materials with high performance.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a near-infrared active periodic plasma heterojunction photo-anode material and a preparation method thereof.
Background
The Photoelectrochemical (PEC) conversion system can effectively utilize solar energy to produce clean energy, and is beneficial to relieving energy and environmental crisis and improving living environment. However, the commercial application of PEC conversion systems has been hindered by the energy conversion efficiency of the current photoelectrode materials, which is too low.
Most semiconductors used as photoelectrodes to date have a wide optical band gap, and thus cannot effectively utilize infrared light (λ >700 nm). However, infrared light occupies most of the energy of solar energy. In addition, the photogenerated charge recombination and low surface redox reaction kinetics of these semiconductors are also not conducive to efficient artificial photosynthesis processes.
Plasma-induced photoelectrocatalysis offers a promising solution to break through the limitations of photoelectrodes described above. In addition to broadening the spectral absorption range of the photoelectrode through Surface Plasmon Resonance (SPR) absorption, the SPR effect can effectively enhance the light absorption capability of the photoelectrode. Meanwhile, local electromagnetic field enhancement (LEMF) and photothermal effect generated by SPR effect can also improve the kinetics of charge transfer and surface redox reaction. Further, by coupling the plasmon metal and the semiconductor, a schottky barrier can be generated, separation of photogenerated carriers can be promoted, and the lifetime thereof can be extended. At present, most plasma metal/semiconductor nano-structures are mainly compounded by noble metals (Au, ag and the like) and semiconductor materials, such as Ag/TiO 2 Au/CdSe, etc. Although the position of the SPR resonance peak can be adjusted by changing the shape and the size of the metal particles, and the spectral absorption range of the material can be expanded, the expansion range is very limited. In addition, the SPR effect is localized in spatial distribution, and thus the localized electromagnetic field enhancement and photothermal effect it produces is also non-uniform in spatial distribution. They work most strongly at the plasma metal surface and their intensity decays rapidly with distance. This localization limits the influence of SPR effects on the enhancement of the photoelectrode performance.
Therefore, how to design a metal/semiconductor photoelectrocatalysis system which can overcome the problems and exert the SPR effect to the maximum extent is of great significance for realizing efficient and stable solar energy-fuel conversion.
Disclosure of Invention
In view of the above, the present invention aims to provide a near-infrared active periodic plasma heterojunction photoanode material and a preparation method thereof, wherein the photoanode material can realize efficient utilization of surface plasmon resonance effect, thereby improving energy conversion efficiency of a photoelectrochemical process.
The invention provides a near-infrared active periodic plasma heterojunction photo-anode material which is characterized by comprising Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; wherein x is more than or equal to 0;0<y<1。
In the present invention, the Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nano structure made of Bi 3 (Se 1-y Te y ) 2 The nano-wire is prepared by solvent thermal synthesis.
In the present invention, the Bi x And Bi 3 (Se 1-y Te y ) 2 The mass ratio of (3) is 0 to 2.
Based on the problem of low energy conversion efficiency of the photo-anode, the application provides a near-infrared active periodic plasma heterojunction photo-anode material, and the size and distribution periodicity of Bi nanoparticles are accurately adjusted by adjusting the amount of added plasma metal precursors, so that the efficient utilization of the surface plasma resonance effect is realized, and the energy conversion efficiency of the photoelectrochemical process is improved. Bi of the photo-anode material x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nano structure made of Bi 3 (Se 1-y Te y ) 2 The nano-wires are obtained by further solvothermal synthesis, and the Bi is x /Bi 3 (Se 1-y Te y ) 2 Bi in periodic heterogeneous nano structure 3 (Se 1-y Te y ) 2 And Bi x The amount ratio of the substances (C) may take any value.
The invention provides a preparation method of a near-infrared active periodic plasma heterojunction photo-anode material in the technical scheme, which comprises the following steps:
mixing Te m Se n @Se 1-m-n The nano-wire is dispersed in a solution containing a bismuth source and a reducing agent, and Bi is obtained through hydrothermal reaction 3 (Se 1-y Te y ) 2 A nanowire; 0<m<1；0<n<1；0<m+n<1；0<y<1；
Adding Bi 3 (Se 1-y Te y ) 2 The nano-wire is dispersed in a solution containing a bismuth source and a reducing agent, and Bi is obtained through solvothermal reaction x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; x is more than or equal to 0.
In the above Te m Se n @Se 1-m-n In the nanowires, the value of m larger than zero and smaller than 1, n represents the amount of Se element forming an alloy phase with Te element in the nanowires of the core-shell structure, and although the value cannot be specifically determined, the value thereof is larger than zero and smaller than 1. In the present invention, the bismuth source is selected from bismuth salts, more preferably from one or more of bismuth chloride, bismuth nitrate, bismuth oxide and bismuth acetate; the reducing agent is selected from one or more of hydrazine hydrate, ascorbic acid and sodium borohydride. The Bi 3 (Se 1-y Te y ) 2 Y in the nanowire is greater than 0 and less than 1, specifically, the y is selected from 0.33, 0.20, 0.14, 0.11, 0.08, or 0.06; in a specific embodiment, the value of y is 0.20.
In the invention, the temperature of the hydrothermal reaction is 140-180 ℃, preferably 160-180 ℃, and more preferably 160 ℃; the heating rate for heating to the temperature required by the hydrothermal reaction is 5-10 ℃/min, preferably 8-10 ℃/min, and more preferably 9 ℃/min; the time required for the temperature rise is 6 to 18 hours, preferably 10 to 12 hours, and more preferably 12 hours.
And after the hydrothermal reaction is finished, cooling. The cooling method is a cooling method known to those skilled in the art, and is not particularly limited; in the specific embodiment, natural cooling is adopted; cooling, centrifuging and washing to obtain Bi 3 (Se 1-y Te y ) 2 A nanowire; the washing is preferably carried out with hexane and ethanol.
This application is then directed to Bi 3 (Se 1-y Te y ) 2 Loading Bi nano particles on the surface of the nano wire to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; the Bi x /Bi 3 (Se 1-y Te y ) 2 The preferable synthesis method of the periodic heterogeneous nano structure is a solvothermal synthesis method, which specifically comprises the following steps:
adding Bi 3 (Se 1-y Te y ) 2 Mixing and heating the nano-wire, a bismuth source and a reducing agent in water and an alcohol solvent to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure. The alcohol solvent is selected from glycol and/or glycerol.
In the invention, bi is preferably firstly selected 3 (Se 1-y Te y ) 2 Dispersing the nano-wires in a solvent consisting of water and alcohols, then mixing with a bismuth source and a reducing agent, and promoting bismuth ions and Bi under ultrasound 3 (Se 1-y Te y ) 2 Fully mixing the nanowires; the ultrasonic treatment time is preferably 10-60 min, more preferably 20-50 min, and most preferably 30min;
in the invention, the temperature of the solvothermal reaction is 160-180 ℃, preferably 180 ℃; the heating rate of heating to the temperature required by the solvothermal reaction is 5-10 ℃/min, preferably 8-10 ℃/min, and more preferably 9 ℃/min; the time is 12 to 18 hours, preferably 16 to 18 hours. After the reaction is finished, the product is preferably precipitated, centrifuged and washed by ethanol to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; the washing is preferably with ethanol. The Bi x /Bi 3 (Se 1-y Te y ) 2 Bi in periodic heterogeneous nano structure 3 (Se 1-y Te y ) 2 And Bi x The amount ratio of the substances (C) may take any value. x represents the amount of the added bismuth source substance, and can be a value larger than 0 at will in terms of specific values; in a particular embodiment, said x is preferably 0.15,0.45,0.75.
The inventionIn (B) the Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructure Bi 3 (Se 1-y Te y ) 2 And Bi x The amount ratio of the substances of (a) is adjusted by changing the amount of the bismuth source added. By adjusting Bi 3 (Se 1-y Te y ) 2 The proportion of Bi to Bi can realize the adjustment of the size and the distribution periodicity of Bi nano particles, thereby realizing the high-efficiency utilization of the surface plasma resonance effect, finally improving the energy conversion efficiency in the photoelectrochemical process and providing a new way for designing and developing the photoanode nano material with high performance.
The invention provides a near-infrared active periodic plasma heterojunction photo-anode material, which is prepared from Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructure composition; the Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nano structure made of Bi 3 (Se 1-y Te y ) 2 The nanowires are obtained by further solvothermal synthesis. The photoanode material provided by the application adjusts Bi 3 (Se 1-y Te y ) 2 The ratio of Bi to Bi can realize the efficient utilization of the surface plasma resonance effect, thereby improving the energy conversion efficiency of the photoelectrochemical process.
Drawings
FIG. 1 is Te used in example 1 of the present invention m Se n @Se 1-m-n Nanowire Transmission Electron Microscopy (TEM) images;
FIG. 2 shows Bi prepared in example 1 of the present invention 3 (Se 1-y Te y ) 2 (BST) nanowire TEM images;
FIG. 3 shows Bi prepared in example 2 of the present invention x /Bi 3 (Se 1-y Te y ) 2 TEM images of (Bi/BST) periodic heterogeneous nanostructures;
FIG. 4 shows Bi prepared in examples 1 and 2 of the present invention 3 (Se 1-y Te y ) 2 (BST) nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 (Bi/BST) powder X-ray spectra of periodic heterogeneous nanostructures;
FIG. 5 shows Bi prepared in examples 1 and 2 of the present invention 3 (Se 1-y Te y ) 2 (BST) nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 (Bi/BST) high resolution transmission electron microscopy images of periodic heterogeneous nanostructures;
FIG. 6 shows Bi prepared in example 1 of the present invention 3 (Se 1-y Te y ) 2 (BST) EDS elemental plane distribution image of nanowires;
FIG. 7 shows Bi prepared in example 2 of the present invention x /Bi 3 (Se 1-y Te y ) 2 (Bi/BST) EDS elemental plane distribution images and EDS elemental line distribution maps of periodic heterogeneous nanostructures;
FIG. 8 shows Bi prepared in example 2 of the present invention x /Bi 3 (Se 1-y Te y ) 2 KPFM analysis images of (Bi/BST) periodic heterogeneous nanostructures;
FIG. 9 shows Bi prepared in examples 1 and 2 of the present invention 3 (Se 1-y Te y ) 2 (BST) nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 (Bi/BST) current-voltage spectra, incident monochromatic photon-electron conversion efficiency, current intensity-time spectra, electrochemical impedance spectra, and stability test spectra of periodic heterogeneous nanostructures.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe in detail a near-infrared active periodic plasma heterojunction photoanode material and a preparation method thereof, which should not be construed as limiting the scope of the present invention.
Example 1
Bi 3 (Se 1-y Te y ) 2 Preparing the nano wire: adding 1.35mmol of bismuth nitrate Bi (NO) 3 ) 3 ·5H 2 O, 0.9mmol of Te m Se n @Se 1-m-n (m is more than 0 and less than 1, n is more than 0 and less than 1, m + n is less than 1In an embodiment, m is preferably 0.20) nanowire, 57mL deionized water and 1mL hydrazine hydrate are mixed and stirred vigorously, and the mixed solution is transferred to a 100mL polytetrafluoroethylene lining and packaged in a stainless steel autoclave; then the stainless steel autoclave is sealed and heated at 160 ℃ for 12 hours; the heating rate of the heating reaction is 8-10 ℃/min; after the reaction is finished, cooling the reaction product to room temperature; the final product Bi was collected by centrifugation (10000rpm, 3min) 3 (Se 1-y Te y ) 2 Nanowires were washed 3 times with ethanol for further use.
Te used in example 1 was measured by a transmission electron microscope m Se n @Se 1-m-n The nanowires were analyzed and their tem images were obtained as shown in fig. 1; as can be seen from FIG. 1, te m Se n @Se 1-m-n The diameter of the nanowire is about 20nm, and the surface of the nanowire is smooth;
bi obtained in example 1 was subjected to transmission electron microscopy 3 (Se 1-y Te y ) 2 The nanowires were analyzed and their transmission electron microscopy images were obtained as shown in FIG. 2; as can be seen from FIG. 2, bi 3 (Se 1-y Te y ) 2 The diameter of the nanowire is about 50nm and the surface is rough.
Example 2
Bi x /Bi 3 (Se 1-y Te y ) 2 Preparing a periodic heterogeneous nano structure: 0.45mmol of Bi 3 (Se 1-y Te y ) 2 (0 < y < 1; in a specific embodiment, y is preferably 0.20) nanowires, a quantity of bismuth nitrate Bi (NO) of a substance 3 ) 3 ·5H 2 O (in the specific embodiment, the amounts of the bismuth nitrate are selected to be 0.15mmol, 0.45mmol and 0.75mmol respectively), 47mL of deionized water, 10mL of ethylene glycol and 1mL of hydrazine hydrate are mixed and stirred vigorously, and the mixed solution is transferred to a 100mL polytetrafluoroethylene lining and packaged in a stainless steel autoclave; then the stainless steel autoclave is sealed and heated at 180 ℃ for 18 hours; the heating rate of the heating reaction is 8-10 ℃/min; after the reaction is finished, cooling the reaction product to room temperature; the most abundant fractions were collected by centrifugation (10000rpm, 3min)End product Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructures and washed 3 times with ethanol for further use.
Bi in example 2 was analyzed by transmission electron microscope and X-ray diffraction x /Bi 3 (Se 1-y Te y ) 2 The periodic heterogeneous nanostructure was analyzed to obtain transmission electron microscopy images and X-ray spectra as shown in fig. 3 and 4; as can be seen from FIG. 3, bi x /Bi 3 (Se 1-y Te y ) 2 The periodic heterogeneous nano structure is formed by uniformly dispersing and compounding Bi nano particles in Bi with periodicity 3 (Se 1-y Te y ) 2 Nanowires are formed, and the size and distribution of the Bi nanoparticles can be periodically adjusted as the amount of Bi source added during synthesis is varied. As can be seen from FIG. 4, bi x /Bi 3 (Se 1-y Te y ) 2 All diffraction peaks in the X-ray diffraction pattern of the periodic heterogeneous nanostructure can be attributed to Bi in the hexagonal phase 3 Se 2 (JCPDS card number 40-0935, space group P-31 m) and rhombohedral Bi (JCPDS card number 44-1246, space group R-3 m).
Bi obtained in examples 1 and 2 was subjected to high-resolution transmission electron microscopy 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 And analyzing the periodic heterogeneous nano structure to obtain a high-resolution transmission electron microscope image of the periodic heterogeneous nano structure. As shown by i in fig. 5; bi in the image x /Bi 3 (Se 1-y Te y ) 2 The periodic hetero-nanostructures show lattice spacings of 0.325nm and 0.359nm, respectively ascribed to the (012) crystal plane of Bi of rhombohedral and Bi of hexagonal phase 3 Se 2 The (102) crystal plane of (1). As shown at ii in fig. 5; bi in the image 3 (Se 1-y Te y ) 2 The nanowires show a lattice spacing of 0.313nm, which is attributed to Bi in the hexagonal phase 3 Se 2 The (1010) crystal plane of (c).
Bi obtained in examples 1 and 2 was analyzed by an energy spectrometer 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 Analyzing the periodic heterogeneous nano-structure to obtain an EDS element surface distribution diagram and a line distribution diagram of the periodic heterogeneous nano-structure, as shown in FIGS. 6 and 7; as can be seen from FIG. 6, the elements Bi, se and Te are uniformly distributed throughout the entire Bi 3 (Se 1-y Te y ) 2 In a nanowire structure. As can be seen from FIG. 7, the Bi, se, and Te elements are uniformly distributed in the nanowire, but the element distribution of the nanoparticle structure is mainly Bi element, which fully proves that the Bi element is exactly Bi obtained in example 2 x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure.
Bi obtained in example 2 was subjected to Kelvin probe microscopy x /Bi 3 (Se 1-y Te y ) 2 Analyzing the periodic heterogeneous nano structure to obtain a height map and a surface potential distribution map under dark state and illumination conditions, as shown in fig. 8; as can be seen from FIG. 8, I in example 2 is Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure. As can be seen from ii in FIG. 8, the surface potential of Bi nanoparticles is higher than that of Bi in the absence of light 3 (Se 1-y Te y ) 2 Nanowires, which demonstrate that the work function of the nanoparticles is larger than that of nanowires. However, as can be seen from iii in FIG. 8, under light irradiation, bi nanoparticles and Bi 3 (Se 1-y Te y ) 2 The surface potential of the nanowires is increased, which indicates that a large number of photo-generated electrons are generated under illumination. As can be seen from the comparison of ii in FIG. 8 and iii in FIG. 8, bi is observed under light 3 (Se 1-y Te y ) 2 The surface potential of the nano-wire is improved more, and the photo-generated electrons are fully proved to be generated from Bi nano-particles to Bi 3 (Se 1-y Te y ) 2 And transferring the nanowire.
For Bi obtained in examples 1 and 2 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic differenceThe photoelectrochemical hydrogen production performance of the proton nanostructure was analyzed to obtain a current-voltage spectrum, an incident monochromatic photon-electron conversion efficiency, a current intensity-time spectrum, an electrochemical impedance spectrum, and a stability test spectrum, as shown in fig. 9.
The application simulates sunlight (lambda)>800nm，100mW·cm -2 ) Irradiation and Na 2 SO 3 /Na 2 S as hole sacrificial agent, their Photoelectrochemical (PEC) properties were tested using photoanodes of controlled thickness. By adjusting Bi 3 (Se 1-y Te y ) 2 Ratio of nanowire to Bi to adjust Bi x /Bi 3 (Se 1-y Te y ) 2 The size and distribution periodicity of Bi nanoparticles in the hetero-nanostructure optimizes the performance of these photoanodes. As shown by i in FIG. 9, bi x /Bi 3 (Se 1-y Te y ) 2 The initial potential of the heterogeneous nano-structure photo-anode is 0.5V RHE At 0.85V RHE It showed 8.3mA cm -2 Photocurrent of (2), and Bi 3 (Se 1-y Te y ) 2 The nano wire is at 0.85V RHE Only 5.0mA · cm was shown -2 The photocurrent of (c). The near-infrared active periodic plasma heterojunction photoanode fully shows that the efficient utilization of the SPR effect is realized, and the PEC hydrogen production performance is further improved.
Applicant has also shown that Bi 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 The incident monochromatic photon-electron conversion efficiency (IPCE) of the photoanode of the periodic heterogeneous nano structure is tested and compared, and all samples are tested under the conditions of one sunlight irradiation and 0.6V RHE At a given bias voltage, IPCE efficiency over a given time. From ii in FIG. 9, it can be seen that Bi is in the range of 800 to 1520nm x /Bi 3 (Se 1-y Te y ) 2 IPCE ratio Bi of heterogeneous nano-structure photo-anode 3 (Se 1-y Te y ) 2 The height of the nanowires is high. This is a good demonstration that rational adjustment of the size and periodicity of the distribution of the plasma metal contributes to the efficiency of photoelectrochemical catalysis.
Applicant has also investigated Bi 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 The transient current response and the electrochemical impedance spectrum of the photoanode of the periodic heterogeneous nano structure are tested and compared, and all samples are tested at 0.6V RHE Performance of the bias voltage of (c). Meanwhile, as shown in iii in FIG. 9, bi x /Bi 3 (Se 1-y Te y ) 2 The hetero-nanostructure has obviously stronger Bi property under specific voltage 3 (Se 1-y Te y ) 2 Photocurrent of the nanowire. And Bi as shown in iv of FIG. 9 x /Bi 3 (Se 1-y Te y ) 2 The electrochemical impedance spectrum radius of the heterogeneous nano structure is obviously smaller than that of Bi 3 (Se 1-y Te y ) 2 The radius of the electrochemical impedance spectrum of the nanowires. This also demonstrates the superiority of near-infrared active periodic plasma heterojunctions.
Applicant has also investigated Bi 3 (Se 1-y Te y ) 2 Nanowire and Bi x /Bi 3 (Se 1-y Te y ) 2 The stability of the photoanode of the periodic heterogeneous nano structure is tested and compared, and all samples are tested under the conditions of one sunlight irradiation and 0.6V RHE Current-time map at bias voltage. As shown by v in FIG. 9, bi 3 (Se 1-y Te y ) 2 The nano line photo anode is at 0.6V RHE The generated photocurrent is gradually reduced under the bias voltage, which indicates that the photo-generated carriers generated by the photo-anode can not participate in the oxidation-reduction reaction on the surface of the photo-anode in time, so that the photo-corrosion reaction is generated on the photo-anode. However, bi x /Bi 3 (Se 1-y Te y ) 2 The photoanode of the periodic heterogeneous nanostructure can fully utilize the SPR effect and sufficiently realize the efficient utilization of photon-generated carriers, so that the photo-corrosion reaction of the photoanode can be inhibited, and high stability is further realized. As shown by vi in FIG. 9, bi x /Bi 3 (Se 1-y Te y ) 2 The photoanode of the periodic heterogeneous nano structure is at 0.6V RHE Achieves a stability of nearly 90h under bias, which is far superior to Bi 3 (Se 1-y Te y ) 2 A nanowire photoanode.
From the above embodiments, the present invention provides a periodic non-noble metal/semiconductor hetero-nanostructure with SPR effect. Compared with noble metals with sharp SPR formants, non-noble metals (e.g. bismuth) can produce non-radiative damping throughout the uv-nir due to their unique interband transition processes, and thus have no sharp formants. Meanwhile, the design of the periodic heterostructure is beneficial to reducing the influence of the fast attenuation of the SPR effect on the spatial distribution, thereby realizing the effective utilization of the SPR effect. In addition, bismuth-based selenides have important potential applications in photocatalysis due to their unique optical properties.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The near-infrared active periodic plasma heterojunction photo-anode material is characterized by comprising Bi x /Bi 3 (Se 1- y Te y ) 2 A periodic heterogeneous nanostructure; wherein x is more than or equal to 0;0<y<1。
2. The near-infrared active periodic plasma heterojunction photoanode material of claim 1, wherein the Bi is x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nano structure made of Bi 3 (Se 1-y Te y ) 2 The nano-wire is prepared by solvent thermal synthesis.
3. The near-infrared active periodic plasma heterojunction photoanode material of claim 1, wherein the Bi is x And Bi 3 (Se 1-y Te y ) 2 Article ofThe mass ratio is 0 to 2.
4. A method for preparing the near-infrared active periodic plasma heterojunction photoanode material as defined in any one of claims 1 to 3, comprising the following steps:
te (Te) m Se n @Se 1-m-n The nano-wire is dispersed in a solution containing a bismuth source and a reducing agent, and Bi is obtained through hydrothermal reaction 3 (Se 1-y Te y ) 2 A nanowire; 0<m<1；0<n<1；0<m+n<1；0<y<1；
Adding Bi 3 (Se 1-y Te y ) 2 The nano-wire is dispersed in a solution containing a bismuth source and a reducing agent, and Bi is obtained through solvothermal reaction x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; x is more than or equal to 0.
5. The method of claim 4, wherein the bismuth source is selected from one or more of bismuth chloride, bismuth nitrate, bismuth oxide, and bismuth acetate;
the reducing agent is selected from one or more of hydrazine hydrate, ascorbic acid and sodium borohydride.
6. The method according to claim 4, wherein the solvent used in the solvothermal reaction is a mixture of water and an alcohol solvent;
the alcohol solvent is selected from glycol and/or glycerol.
7. The preparation method according to claim 4, wherein the temperature of the hydrothermal reaction is 140-180 ℃, the heating rate of the temperature required for heating to the hydrothermal reaction is 5-10 ℃/min, and the time is 6-18 h.
8. The preparation method according to claim 4, wherein the temperature of the solvothermal reaction is 160 to 180 ℃, the heating rate of the temperature to the temperature required by the solvothermal reaction is 5 to 10 ℃/min, and the time is 12 to 18 hours.
9. The method according to claim 4, wherein the Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructure Bi 3 (Se 1-y Te y ) 2 And Bi x The amount ratio of the substance(s) of (b) is adjusted by changing the amount of the bismuth source added.
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