CN115490212B - 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 Bi is used for preparing the near infrared active periodic plasma heterojunction photo-anode material x /Bi 3 (Se 1‑y Te y ) 2 Periodic heterogeneous nanostructure composition; the Bi is x /Bi 3 (Se 1‑y Te y ) 2 Periodic heterogeneous nanostructure is composed of Bi 3 (Se 1‑y Te y ) 2 Nanowires are obtained by further solvothermal synthesis. The photo-anode material provided by the application is prepared by adjusting Bi 3 (Se 1‑ y Te y ) 2 The ratio of Bi to Bi realizes the efficient utilization of the surface plasmon resonance effect, thereby improving the energy conversion efficiency of the photoelectrochemical process. The invention provides a new way for designing and developing the photo-anode nano material 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
Photoelectrochemical (PEC) conversion systems can effectively utilize solar energy to produce clean energy, which is beneficial to alleviating energy and environmental crisis and improving living environment. However, the low energy conversion efficiency of existing photoelectrode materials has hampered the commercial application of PEC conversion systems.
To date, most semiconductors used as photoelectrodes have a relatively wide optical bandgap, and therefore they cannot effectively utilize infrared light (λ >700 nm). However, infrared light occupies most of the energy of solar energy. In addition, photo-generated charge recombination and low surface redox kinetics of these semiconductors are also detrimental to the realization of efficient artificial photosynthesis processes.
Plasma-induced photoelectrocatalysis provides a promising solution to break through the limitations of photoelectrodes described above. In addition to widening the spectral absorption range of the photoelectrode by Surface Plasmon Resonance (SPR) absorption, the SPR effect can also effectively enhance the photoelectrode's light absorption capacity. Meanwhile, local electromagnetic field enhancement (LEMF) and photo-thermal effects generated by the SPR effect can also effectively improve the kinetics of charge transfer and surface redox reactions. In addition, by combining plasma metal withThe semiconductor coupling can generate a Schottky barrier to promote the separation of photon-generated carriers, thereby prolonging the service life of the photon-generated carriers. Currently, most plasmonic metal/semiconductor nanostructures mainly employ a noble metal (Au, ag, etc.) in combination with a semiconductor material, such as Ag/TiO 2 Au/CdSe, etc. Although the position of the SPR resonance peak can be adjusted by changing the morphology and size of the metal particles, and thus the spectral absorption range of the material is extended, the extension range is very limited. In addition, the SPR effect is localized in spatial distribution, so that the local electromagnetic field enhancement and photothermal effects produced thereby are also non-uniform in spatial distribution. Their effect is strongest at the plasma metal surface and their intensity decays rapidly with distance. This locality limits the impact of the SPR effect on the photoelectrode performance enhancement.
Therefore, how to design a metal/semiconductor photoelectrocatalysis system which can overcome the above problems and exert the SPR effect to the maximum extent is of great importance 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, which can realize efficient utilization of surface plasmon resonance effect, thereby improving energy conversion efficiency of 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 nanostructure is composed of Bi 3 (Se 1-y Te y ) 2 The nano-wire is prepared by solvothermal synthesis.
In the present invention, the Bi x With Bi 3 (Se 1-y Te y ) 2 The mass ratio of the substances 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, which can accurately adjust the size and distribution periodicity of Bi nano-particles by adjusting the amount of the added plasma metal precursor, thereby realizing the efficient utilization of the surface plasma resonance effect and improving the energy conversion efficiency of the photoelectrochemical process. Bi of the photo-anode material x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructure is composed of Bi 3 (Se 1-y Te y ) 2 Nanowires are obtained by further solvothermal synthesis, the Bi x /Bi 3 (Se 1-y Te y ) 2 Bi in periodic heterogeneous nanostructures 3 (Se 1-y Te y ) 2 With Bi x The ratio of the amounts of the substances may take any value.
The invention provides a preparation method of the near infrared active periodic plasma heterojunction photo-anode material, which comprises the following steps:
te (Te) m Se n @Se 1-m-n The nano wire is dispersed in a solution containing bismuth source and reducing agent, 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；
Bi is mixed with 3 (Se 1-y Te y ) 2 The nano wire is dispersed in a solution containing bismuth source and 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.
Te of the above m Se n @Se 1-m-n In the nanowire, m is greater than zero and less than 1, and n represents the amount of Se element forming an alloy phase with Te element in the nanowire of core-shell structure, and although the value cannot be specifically determined, the value is greater than zero and less than 1. In the present invention, the bismuth source is selected from bismuth salts, more preferably one or more of bismuth chloride, bismuth nitrate, bismuth oxide and bismuth acetate; by a means ofThe reducing agent is selected from one or more of hydrazine hydrate, ascorbic acid and sodium borohydride. The Bi is 3 (Se 1-y Te y ) 2 Y is greater than 0 and less than 1 in the nanowire, specifically, 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 present invention, the temperature of the hydrothermal reaction is 140 to 180 ℃, preferably 160 to 180 ℃, more preferably 160 ℃; the heating rate to the temperature required for the hydrothermal reaction is 5-10deg.C/min, preferably 8-10deg.C/min, more preferably 9 deg.C/min; the time required for the temperature increase is 6 to 18 hours, preferably 10 to 12 hours, more preferably 12 hours.
After the hydrothermal reaction is finished, cooling. The cooling means are well known to those skilled in the art, and are not particularly limited; in a specific embodiment, natural cooling is adopted; preferably centrifuging and washing after cooling to obtain Bi 3 (Se 1-y Te y ) 2 A nanowire; the washing is preferably performed with hexane and ethanol.
The present application then describes Bi 3 (Se 1-y Te y ) 2 The Bi nano particles are loaded on the surface of the nanowire to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; the Bi is x /Bi 3 (Se 1-y Te y ) 2 The synthesis method of the periodic heterogeneous nanostructure is preferably a solvothermal synthesis method, and specifically comprises the following steps:
bi is mixed with 3 (Se 1-y Te y ) 2 Mixing and heating the nanowires, bismuth source and reducing agent in water and alcohol solvent to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructures. The alcohol solvent is selected from ethylene glycol and/or glycerol.
The invention preferably firstly uses Bi 3 (Se 1-y Te y ) 2 Dispersing the nanowires in a solvent composed of water and alcohols, then mixing with bismuth source and reducing agent, and promoting bismuth ions and Bi under ultrasound 3 (Se 1-y Te y ) 2 The nanowires are fully mixedThe method comprises the steps of carrying out a first treatment on the surface of the The time of the ultrasonic treatment is preferably 10 to 60 minutes, more preferably 20 to 50 minutes, and most preferably 30 minutes;
in the invention, the temperature of the solvothermal reaction is 160-180 ℃, preferably 180 ℃; the heating rate to the temperature required for the solvothermal reaction is 5-10 ℃/min, preferably 8-10 ℃/min, more preferably 9 ℃/min; the time is 12 to 18 hours, preferably 16 to 18 hours. After the reaction is finished, the product is 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 performed with ethanol. The Bi is x /Bi 3 (Se 1-y Te y ) 2 Bi in periodic heterogeneous nanostructures 3 (Se 1-y Te y ) 2 And Bi (Bi) x The ratio of the amounts of the substances may take any value. x represents the amount of the bismuth source substance added, and in a specific value, x can take any value greater than 0; in a specific embodiment, the x is preferably 0.15,0.45,0.75.
Bi as described in the present invention x /Bi 3 (Se 1-y Te y ) 2 Periodic hetero-nanostructure Bi 3 (Se 1-y Te y ) 2 With Bi x The ratio of the amounts of the substances added to the bismuth source is adjusted by varying the amount of the bismuth source added. By adjusting Bi 3 (Se 1-y Te y ) 2 And the Bi proportion can realize the adjustment of the Bi nano particle size and the distribution periodicity, thereby realizing the high-efficiency utilization of the surface plasmon resonance effect, finally improving the energy conversion efficiency of the photoelectrochemistry 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 is x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructure is composed of Bi 3 (Se 1-y Te y ) 2 Nanowire synthesis by further solvothermal synthesisObtained. The photo-anode material provided by the application is prepared by adjusting Bi 3 (Se 1-y Te y ) 2 The ratio of Bi to Bi can realize the efficient utilization of the resonance effect of surface plasma, thereby improving the energy conversion efficiency of the photoelectrochemical process.
Drawings
FIG. 1 shows Te used in example 1 of the present invention m Se n @Se 1-m-n A nanowire Transmission Electron Microscope (TEM) image;
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 image 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 pattern 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 High resolution transmission electron microscopy images of (Bi/BST) periodic heterogeneous nanostructures;
FIG. 6 shows Bi prepared in example 1 of the present invention 3 (Se 1-y Te y ) 2 An EDS elemental plane distribution image of (BST) 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 element face distribution images and EDS element line distribution maps of periodic heterostructures;
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 is a schematic illustration of an embodiment of the present inventionBi prepared in examples 1 and 2 3 (Se 1-y Te y ) 2 (BST) nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 A current-voltage profile of (Bi/BST) periodic heterogeneous nanostructures, an incident monochromatic photon-electron conversion efficiency, a current intensity-time profile, an electrochemical impedance profile, and a stability test profile.
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, but they should not be construed as limiting the scope of the present invention.
Example 1
Bi 3 (Se 1-y Te y ) 2 Preparation of nanowires: 1.35mmol of bismuth nitrate Bi (NO 3 ) 3 ·5H 2 O, 0.9mmol Te m Se n @Se 1-m-n (0 < m < 1;0 < n < 1;0 < m+n < 1; in a specific embodiment, m is preferably 0.20) nanowires, 57mL deionized water and 1mL hydrazine hydrate are mixed and vigorously stirred uniformly, and the mixture is transferred to a 100mL polytetrafluoroethylene liner and packaged in a stainless steel autoclave; the stainless steel autoclave was then 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 mixture to room temperature; the final product Bi was collected by centrifugation (10000 rpm,3 min) 3 (Se 1-y Te y ) 2 The nanowires were washed 3 times with ethanol for further use.
Te used in example 1 was examined by a transmission electron microscope m Se n @Se 1-m-n Analyzing the nanowire to obtain a transmission electron microscope image of the nanowire as shown in figure 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 is smooth;
bi obtained in example 1 was subjected to a transmission electron microscope 3 (Se 1-y Te y ) 2 The nanowire is analyzed to obtain a transmission electron microscope of the nanowireThe figure is shown in figure 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 Preparation of periodic heterogeneous nanostructures: 0.45mmol of Bi 3 (Se 1-y Te y ) 2 (0 < y < 1; in a specific embodiment, the y is preferably 0.20) nanowires, bismuth nitrate Bi (NO) in a certain amount 3 ) 3 ·5H 2 O (in the specific example, the bismuth nitrate amounts are respectively 0.15mmol, 0.45mmol and 0.75 mmol), 47mL deionized water, 10mL ethylene glycol and 1mL hydrazine hydrate are mixed and vigorously stirred uniformly, and the mixture is transferred to a polytetrafluoroethylene lining of 100mL and packaged in a stainless steel autoclave; the stainless steel autoclave was then 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 mixture to room temperature; the final product Bi was collected by centrifugation (10000 rpm,3 min) x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructures were washed 3 times with ethanol for further use.
Bi in example 2 was subjected to a transmission electron microscope and X-ray diffraction x /Bi 3 (Se 1-y Te y ) 2 Analyzing the periodic heterogeneous nano structure to obtain a transmission electron microscope image and an X-ray image of the periodic heterogeneous nano structure, wherein the transmission electron microscope image and the X-ray image are 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 with periodicity on Bi 3 (Se 1-y Te y ) 2 The nano wires are formed, and the size and distribution periodicity of the Bi nano particles can be adjusted according to the variation of the amount of Bi source added in the synthesis. 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 heterostructure can be attributed to Bi in the hexagonal phase 3 Se 2 (JCPDS card)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 Nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 And (5) analyzing the periodic heterogeneous nano structure to obtain a high-resolution transmission electron microscope image of the periodic heterogeneous nano structure. As shown in fig. 5 i; bi in image x /Bi 3 (Se 1-y Te y ) 2 The periodic hetero-nanostructure showed lattice spacing of 0.325nm and 0.359nm, which are respectively attributed to the (012) plane of the rhombohedral Bi and to the hexagonal Bi phase 3 Se 2 (102) crystal plane of (a). And as shown in fig. 5 ii; bi in image 3 (Se 1-y Te y ) 2 The nanowires showed a lattice spacing of 0.313nm, which is attributed to hexagonal-phase Bi 3 Se 2 (1010) crystal plane of (a).
Bi obtained in examples 1 and 2 was analyzed by an energy spectrometer 3 (Se 1-y Te y ) 2 Nanowires 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 linear distribution diagram of the periodic heterogeneous nano structure, as shown in fig. 6 and 7; as can be seen from FIG. 6, the Bi, se, te elements are uniformly distributed throughout Bi 3 (Se 1-y Te y ) 2 In nanowire structures. As can be seen from FIG. 7, the Bi, se, te elements are uniformly distributed in the nanowires, but the element distribution of the nanoparticle structure is mainly Bi elements, which fully demonstrates that it is Bi obtained in example 2 x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructures.
Bi obtained in example 2 was examined by a Kelvin probe microscope 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, bi is synthesized in example 2 x /Bi 3 (Se 1-y Te y ) 2 Periodic heterogeneous nanostructures. As can be seen from FIG. 8 ii, 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 greater than that of nanowires. However, as can be seen from FIG. 8 iii, under light, bi nanoparticles and Bi 3 (Se 1-y Te y ) 2 The surface potential of the nanowires is increased, which means that a large number of photo-generated electrons are generated under illumination. As can be seen from a comparison of ii in FIG. 8 and iii in FIG. 8, bi under light 3 (Se 1-y Te y ) 2 The surface potential of the nanowires is increased more, which fully proves that the photo-generated electrons are generated from Bi nano particles to Bi 3 (Se 1-y Te y ) 2 And (3) transferring the nanowires.
For Bi obtained in examples 1 and 2 3 (Se 1-y Te y ) 2 Nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 The photoelectrochemical hydrogen production performance of the periodic heterogeneous nanostructure was analyzed to obtain a current-voltage profile, an incident monochromatic photon-electron conversion efficiency, a current intensity-time profile, an electrochemical impedance profile and a stability test profile, as shown in fig. 9.
The application is in the simulation of sunlight (lambda)>800nm，100mW·cm -2 ) Irradiation and Na 2 SO 3 /Na 2 S was tested for their Photoelectrochemical (PEC) properties using a photo-anode of controllable thickness as hole-sacrificial agent. By adjusting Bi 3 (Se 1-y Te y ) 2 Ratio of nanowires to Bi to adjust Bi x /Bi 3 (Se 1-y Te y ) 2 The Bi nanoparticles in the heterogeneous nanostructures are periodic in size and distribution, and the present application optimizes the performance of these photoanodes. As shown in i in fig. 9, bi x /Bi 3 (Se 1-y Te y ) 2 The initial potential of the hetero-nanostructure photo-anode is 0.5V RHE At 0.85V RHE Exhibits a measurement of 8.3 mA.cm -2 And Bi is 3 (Se 1-y Te y ) 2 The nanowire is at 0.85V RHE Exhibits only 5.0 mA.cm -2 Is a photo-current of the (c) light source. This fully demonstrates that near infrared active periodic plasma heterojunction photoanode achieves efficient utilization of SPR effect, and further improves its PEC hydrogen production performance.
Applicants also to Bi 3 (Se 1-y Te y ) 2 Nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 The incident monochromatic photon-electron conversion efficiency (IPCE) of the periodically heterogeneous nanostructured photoanode was tested for comparison, all samples were tested under one solar irradiation and 0.6V RHE IPCE efficiency over a given time period under bias of (C). As can be seen from FIG. 9 ii, bi is present in the range of 800-1520nm x /Bi 3 (Se 1-y Te y ) 2 IPCE ratio Bi of hetero-nanostructure photoanode 3 (Se 1-y Te y ) 2 The nanowires are high. This is a good demonstration of the rational adjustment of the size and distribution periodicity of the plasmonic metal helping to increase the efficiency of photoelectrochemical catalysis.
Applicants also to Bi 3 (Se 1-y Te y ) 2 Nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 The transient current response and electrochemical impedance spectrum of the periodically heterogeneous nanostructured photoanode were tested for comparison, testing all samples at 0.6V RHE Is a performance manifestation of the bias voltage of (a). Meanwhile, as shown in iii in FIG. 9, bi x /Bi 3 (Se 1-y Te y ) 2 The hetero-nanostructure has a significantly stronger than Bi at a specific voltage 3 (Se 1-y Te y ) 2 Photocurrent of the nanowire. And as shown in FIG. 9 iv, bi x /Bi 3 (Se 1-y Te y ) 2 The electrochemical impedance spectrum radius of the heterogeneous nano structure is obviously smaller than Bi 3 (Se 1-y Te y ) 2 Electrochemical impedance spectroscopy radius of the nanowires. This also demonstrates the superiority of near infrared active periodic plasma heterojunction.
Applicants also to Bi 3 (Se 1-y Te y ) 2 Nanowires and Bi x /Bi 3 (Se 1-y Te y ) 2 The stability of the periodically heterogeneous nanostructured photoanode was tested and compared, and all samples were tested under one solar irradiation and 0.6V RHE Current-time profile under bias of (c). As shown by v in FIG. 9, bi 3 (Se 1-y Te y ) 2 The nanowire photo anode is at 0.6V RHE The photocurrent generated under the bias voltage of the photo-anode is gradually reduced, which indicates that the photo-generated carriers generated by the photo-anode cannot timely participate in the oxidation-reduction reaction of the surface of the photo-anode, so that the photo-corrosion reaction occurs on the photo-anode. However, bi x /Bi 3 (Se 1-y Te y ) 2 The photo-anode with the periodic heterogeneous nano structure can fully utilize the SPR effect, so that the efficient utilization of photo-generated carriers can be realized, the photo-corrosion reaction can be inhibited, and the high stability can be further realized. As shown in 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 Achieve a stability of approximately 90h under bias of (c), which is far superior to Bi 3 (Se 1-y Te y ) 2 A nanowire photoanode.
From the above examples, the present invention proposes a periodic non-noble metal/semiconductor hetero-nanostructure with SPR effect. Compared to noble metals with distinct SPR formants, non-noble metals (e.g., bismuth) can produce non-radiative damping in the entire uv-near ir due to their unique interband transition processes, and thus have no distinct formants. Meanwhile, the design of the periodic heterostructure is beneficial to reducing the influence of rapid attenuation of the SPR effect on spatial distribution, so that the effective utilization of the SPR effect is realized. In addition, bismuth-based selenides have important potential applications in photocatalysis due to their unique optical properties.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. Near infrared active periodic plasma heterojunction photo-anode material with Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; wherein x is>0；0<y<1；
The Bi is x With Bi 3 (Se 1-y Te y ) 2 The mass ratio of the substances is more than 0 and less than or equal to 2;
the preparation method of the near infrared active periodic plasma heterojunction photo-anode material comprises the following steps:
te (Te) m Se n @Se 1-m-n The nano wire is dispersed in a solution containing bismuth source and reducing agent, 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；
Bi is mixed with 3 (Se 1-y Te y ) 2 Mixing and heating the nanowires, bismuth source and reducing agent in water and alcohol solvent to obtain Bi x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; x is x>0；
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;
the alcohol solvent is selected from ethylene glycol and/or glycerol;
the temperature of the hydrothermal reaction is 140-180 ℃, the temperature rising rate from the temperature required by the hydrothermal reaction is 5-10 ℃/min, and the time is 6-18 h;
the temperature of the solvothermal reaction is 160-180 ℃, the temperature rising rate from the temperature required by the solvothermal reaction to the temperature required by the solvothermal reaction is 5-10 ℃/min, and the time is 12-18 h.
2. A method of preparing the near infrared active periodic plasma heterojunction photoanode material of claim 1, comprising the steps of:
te (Te) m Se n @Se 1-m-n The nano wire is dispersed in a solution containing bismuth source and reducing agent, 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；
Bi is mixed with 3 (Se 1-y Te y ) 2 Dispersing the nano wire in water and alcohol solvent containing bismuth source and reducer, and obtaining Bi through solvothermal reaction x /Bi 3 (Se 1-y Te y ) 2 A periodic heterogeneous nanostructure; x is x>0。
3. The production method according to claim 2, wherein the Bi x /Bi 3 (Se 1-y Te y ) 2 Periodic hetero-nanostructure Bi 3 (Se 1-y Te y ) 2 With Bi x The ratio of the amounts of the substances added to the bismuth source is adjusted by varying the amount of the bismuth source added.
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