CN118147660A - Self-bias photoelectric catalytic system based on (In) GaN nano-pillar array and application thereof - Google Patents

Self-bias photoelectric catalytic system based on (In) GaN nano-pillar array and application thereof Download PDF

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CN118147660A
CN118147660A CN202410016355.3A CN202410016355A CN118147660A CN 118147660 A CN118147660 A CN 118147660A CN 202410016355 A CN202410016355 A CN 202410016355A CN 118147660 A CN118147660 A CN 118147660A
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林静
卢鑫宇
李晔
王军
潘科霖
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Wuyi University
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Wuyi University
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Abstract

The invention discloses a self-bias photoelectric catalytic system based on an (In) GaN nano-pillar array and application thereof, and the self-bias photoelectric catalytic system comprises the following components: a photo-anode and a photo-cathode; the photo anode comprises at least one of an integration of a single electrode of an (In) GaN nano-pillar array with a Si-based solar cell, an integration of a double electrode of an (In) GaN nano-pillar array with a Si-based solar cell, a single electrode of an (In) GaN nano-pillar array, and a double electrode of an (In) GaN nano-pillar array; the photocathode includes at least one of an (In) GaN nanorod photocathode and a platinum electrode. The self-bias photoelectrocatalysis hydrogen production is realized by simulating sunlight irradiation photoelectrode. The invention uses the self-bias photoelectric catalytic system based on the (In) GaN nano-pillar array, can widen spectral absorption, improve the required photovoltage for water decomposition, realize self-bias photoelectric water decomposition to produce hydrogen, and provide an effective strategy for preparing hydrogen energy by utilizing solar energy on a large scale.

Description

Self-bias photoelectric catalytic system based on (In) GaN nano-pillar array and application thereof
Technical Field
The invention relates to the fields of (In) GaN nanopillars, integration of photoelectrodes and solar cells, energy sources and catalysis, in particular to a self-bias photoelectrocatalysis system based on an (In) GaN nanopillar array and application thereof.
Background
Self-biased Photoelectrochemical (PEC) water splitting hydrogen production has shown great potential in solving global energy crisis and environmental problems. The (In) GaN nano-pillar has an adjustable band gap (0.65 eV-3.4 eV), and light absorption can be adjusted by changing the composition of indium, so that the (In) GaN nano-pillar becomes an ideal choice of a photoelectrode. In addition, the (In) GaN nano-pillar has energy band positions suitable for water oxidation-reduction reaction, long charge diffusion distance, high surface area to volume ratio and excellent theoretical solar energy to hydrogen energy (STH) efficiency (-27%), so that the (In) GaN nano-pillar is very favorable for photoelectrochemical total water decomposition. However, problems such as rapid recombination of bulk and surface charges of the (In) GaN nanopillars and slow oxidation reaction kinetics, result In the need for additional bias voltages to facilitate charge transfer. Therefore, development of a self-bias catalytic system based on an (In) GaN nano-pillar array has important research significance for preparation of hydrogen energy sources.
The construction of a common (In) GaN nano-pillar array-based self-bias PEC water decomposition system is mainly realized by the following two strategies: and (3) constructing a double-light-absorber single electrode and parallel irradiation type double-electrode system.
1) The double-light-absorber single-electrode system is mainly formed by connecting (In) GaN nano-pillar light absorbers with different In components through tunneling junctions so as to drive water decomposition by generated photovoltage. However, the preparation of a high-quality tunneling junction is difficult, the In component regulation and control of an ideal double-band-gap (In) GaN nano-pillar are difficult, and self-bias photolysis water is difficult to realize. Wang et al monolithically integrate single-junction (In) GaN nanopillar photocathodes on n-type Si substrates by using (In) GaN tunneling junctions, exhibiting 3.4% STH efficiency at 0v vs. pt, enabling unbiased photolysis of water without using any passivation layer, and exhibiting excellent stability over-300 h. The research shows that the tunneling junction In the double-light absorber single electrode is mainly composed of heavily doped (In) GaN or GaN, and particularly when the (In) GaN nano-pillar base photoelectrode with an ideal band gap is prepared, the heavily doped high indium component (In) GaN tunneling junction is required to be introduced. However, because of the difficulty in growing high indium component nanopillars, it is difficult to achieve high quality heavily doped (especially p-doped) tunneling junctions, resulting in reduced energy level separation and reduced generated photovoltage, and thus, it is very difficult to achieve self-biased photolysis for dual-absorber single-electrode-based PEC cells at present.
2) The parallel irradiation type double-electrode system adopts n-type and p-type (In) GaN nano-pillars as a photo-anode and a photo-cathode respectively, and simultaneously absorbs light with corresponding wavelength In two parallel light beams respectively. Similar to the double-acceptor single electrode, the accumulated photovoltage generated by the double-acceptor electrode drives unbiased photolysis water. Although the parallel irradiation type double-electrode system needs a relatively simple process, two beams of light are simultaneously required for irradiating the double-electrode system, and the requirements of low-energy consumption hydrogen production are not met.
Achieving efficient self-biasing water splitting hydrogen production with the PEC system constructed as described above also faces significant challenges, mainly due to two factors. First, considering that the Si substrate has advantages of low cost, rich property and large size, in addition, the Si substrate (band gap, -1.1 eV) can be used as bottom light absorber of photoelectrode to widen spectral absorption of the whole photoelectrode. Meanwhile, the light transmittance of the Si-based (In) GaN nanopillar photoelectrode is poor, the light loss is serious, and the effective integration of the PV-PEC and PEC series battery cannot be realized, so that the excellent power generation characteristic of the photovoltaic battery and the total absorption of the spectrum cannot be utilized. However, the thickness of the Si-based (In) GaN nanopillar photoelectrode substrate having light transmittance needs to be as thin as possible, which requires the introduction of a high-cost substrate thinning process, which not only increases the complexity of device fabrication, but also adversely affects the device performance.
In recent years, the two-dimensional material is used as a seed layer for the growth of the nano-pillars, so that the epitaxial relationship between the substrate and the nano-pillars can be effectively eliminated, the selection range of the substrate required by the growth of the nano-pillars can be enlarged, and the special functional requirement of the prepared device can be met. The graphene is a transparent and flexible two-dimensional material with high heat conductivity and high electric conductivity, is the earliest two-dimensional support material used for growing III-V group semiconductors, and opens up a great application prospect for preparing functional semiconductor devices. Although GaN nanopillar arrays perpendicular to the substrate are currently grown on graphene by MBE techniques, the exact epitaxial relationship between graphene and GaN is still somewhat controversial. In addition, the preparation process of the graphene film on the substrate (Si) is very complex (high-temperature growth of graphene, etching of a copper base and removal of PMMA), and residual Cu and PMMA in the wet transfer process of graphene reduce the photoelectric performance of the constructed device. Therefore, graphene is limited in the field of growth of GaN materials and device applications. Titanium carbide MXene (Ti 3C2Tx) is a novel two-dimensional transition metal carbide or carbonitride material, whose conductivity is comparable to that of graphene, and is widely used as a support material for electrochemical energy devices such as electrolytic cells, supercapacitors and solar cells, and has been attracting attention in recent years.
Therefore, it is an urgent need to provide a self-biased photocatalytic system based on an (In) GaN nanopillar array, which reduces the light loss In the (In) GaN nanopillar array and improves the photoelectric conversion efficiency.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a self-bias photoelectric catalytic system based on an (In) GaN nano-pillar array, which can widen spectral absorption, improve the required photovoltage for water decomposition and realize hydrogen production by self-bias photoelectric water decomposition.
According to an embodiment of the first aspect of the present invention, a self-biasing photo-catalytic system based on an (In) GaN nanopillar array is presented, comprising the following components: a photo-anode and a photo-cathode;
The photo anode comprises at least one of an integration of a single electrode of an (In) GaN nano-pillar array with a Si-based solar cell, an integration of a double electrode of an (In) GaN nano-pillar array with a Si-based solar cell, a single electrode of an (In) GaN nano-pillar array and a double electrode of an (In) GaN nano-pillar array;
in the photoanode, the (In) GaN nanopillar array comprises a substrate, an MXene layer on the substrate, and (In) GaN nanopillars grown on the MXene layer,
The photocathode includes at least one of an (In) GaN nanorod photocathode and a platinum electrode.
Embodiments according to the first aspect of the invention have at least the following advantageous effects:
The titanium carbide used in the invention not only widens the selection range of the substrate, but also can be used as a conductive electrode, thereby greatly reducing the cost; the titanium carbide can also form a Schottky barrier with the nano-column, which is favorable for separating photogenerated carriers, enhancing carrier transport performance and greatly improving photoelectric performance of the nano-column; meanwhile, the light transmittance of the titanium carbide can be used for preparing (In) GaN nano-pillar integrated photoelectrodes, so that the spectrum absorption can be widened, the required photovoltage for water decomposition can be improved, and the self-bias photoelectric water decomposition hydrogen production can be realized.
According to some embodiments of the invention, the substrate comprises a sapphire substrate.
According to some embodiments of the invention, the Si-based solar cell is a single cell or a double cell series-parallel connection.
According to some embodiments of the invention, in the self-biased photo-catalytic system based on an (In) GaN nanopillar array, the photo-anode preparation comprises the steps of:
s1, plating an MXene film on a sapphire substrate, drying, then placing the sapphire substrate into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 700-900 ℃ to obtain a clean surface and obtain a sapphire/MXene structure;
S2, controlling the temperature of the sapphire/MXene structure obtained In the step S1 to be 900-980 ℃ by adopting a molecular beam epitaxial growth process, controlling the rotating speed of the sapphire/MXene structure to be 10r/min, enabling the equivalent pressure of Ga beam to be 1.0X10 -7～3.5×10- 7 Torr, enabling the equivalent pressure of In beam to be 1.0X10 -8～2×10-8 Torr, enabling the flow of nitrogen to be 2-4 sccm, enabling the power of a plasma source to be 200-400W, enabling the growth time to be 1-5 h, and growing (In) GaN nano-pillars on the sapphire/MXene structure obtained In the step S1;
S3, connecting the lead with MXene by using an In-Ga alloy to obtain the photo-anode.
Under the preparation method, the MXene film is annealed to obtain a clean surface, so that surface impurities and defects are eliminated, and the contact performance and the crystallization quality are improved; the molecular beam epitaxial growth process is adopted to grow the nano-column, and growth parameters including temperature, gas flow, equivalent beam pressure and the like can be accurately controlled, so that the growth control of a monoatomic layer is realized, and the nano-column has uniform size and crystal quality; by adjusting growth parameters such as temperature, equivalent beam pressure, gas flow and the like, the size, morphology and crystal quality of the (In) GaN nano-column can be accurately controlled so as to meet different application requirements, and the nano-column has excellent photoelectrocatalysis performance; the In-Ga alloy is used for connecting the lead and the MXene film, so that the contact performance and the electron transmission efficiency can be effectively improved, and the performance and the service life of the photo-anode can be improved.
Compared with graphene, the MXene has the advantages of simple preparation process and low cost, and is more beneficial to industrialized application of devices. Furthermore, the MXene lattice constantAnd GaN/>In close proximity, sapphire is also commonly used as a growth substrate for group III nitrides, and therefore, the sapphire/MXene structure is advantageous for MBE self-assembled growth (In) GaN nanopillars compared to Si substrates. In addition, the introduction of the titanium carbide layer can not only relieve the problem of lattice mismatch between sapphire and (In) GaN, but also form a Schottky barrier between the titanium carbide and the semiconductor to receive electrons In the semiconductor, and simultaneously block holes from migrating into graphene, so that the recombination of electron-hole pairs on the surface of the semiconductor photocatalyst can be effectively inhibited. In addition, the titanium carbide can also be used as an electrode, so that the manufacturing process of the electrode is greatly simplified, and the cost is saved. Thus, MXene on-board (In) GaN nanopillar growth would be an effective strategy to build ideal, efficient self-biasing PEC cells.
According to some embodiments of the invention, in step S1, a method for preparing an MXene layer on a sapphire substrate includes: dip-coating, spin-coating or spray-coating.
According to some embodiments of the invention, the MXene layer has a thickness of 5 to 20nm.
The thickness of the MXene layer is In the range of 5-20 nm, so that a proper electron transmission path can be provided, good contact with the (In) GaN nano-pillars is maintained, resistance and electron transmission loss are reduced, and photoelectric conversion efficiency is improved.
According to some embodiments of the invention, the proportion of In atoms of the (In) GaN nanopillars grown on the MXene layer is 0% to 20% of the metal atoms (In, ga).
The energy band structure and energy level distribution of the nano-column can be changed by adjusting the proportion of In atoms, so that the light absorption and photoelectric conversion performance of the nano-column can be regulated and controlled, and the In atoms In the proportion can improve the photoelectric catalytic efficiency and stability.
According to some embodiments of the invention, the (In) GaN nanopillars grown on the MXene layer have a nanopillar height of 100-500 nm, a diameter of 50-80 nm, and a density of 100-400 μm -2.
The height of the nano-column under the height can increase the surface area of the nano-column, provide more active sites and enhance the light absorption capacity and the catalytic reaction activity; the above-described diameter and density contribute to improvement of photoelectric conversion efficiency while maintaining appropriate light absorption and carrier transport properties.
According to some embodiments of the invention, in the self-biased photo-catalytic system based on an (In) GaN nanopillar array, the (In) GaN nanopillar photocathode preparation comprises the steps of:
B1. Adopting a molecular beam epitaxial growth process, controlling the temperature of a photocathode substrate to be 800-980 ℃, controlling the rotating speed of the substrate to be 10r/min, controlling the equivalent pressure of Ga beam to be 1 multiplied by 10 -7～3.5×10-7 Torr, controlling the equivalent pressure of In beam to be 2.0 multiplied by 10 -7～5×10-7 Torr, controlling the flow of nitrogen to be 2-4 sccm, controlling the power of a plasma source to be 200-400W, and growing for 1-3 h, and growing (In) GaN nanopillars on the photocathode substrate;
B2. and connecting the lead with the back surface of the substrate by using an In-Ga alloy to obtain the photocathode.
By controlling the temperature of the substrate, the growth rate, the lattice structure and the quality of the nano-pillars can be influenced, so that the photoelectrocatalysis performance can be regulated and controlled, and the rapid growth of the high-quality nano-pillars is facilitated; the components and the lattice structure of the material are influenced by adjusting the equivalent pressure of Ga and In beams, so that the photoelectrocatalysis performance is further influenced, and the required chemical composition and material quality are realized; under the nitrogen flow, the plasma power and the growth time, the (In) GaN nano-pillar photocathode preparation with high quality, high efficiency and high stability can be realized.
According to some embodiments of the invention, the substrate of the (In) GaN nanopillar photocathode comprises an n-type Si substrate.
The (In) GaN nanopillar photocathode substrate is an n-type Si substrate (conductivity <0.005 Ω).
The n-type Si substrate provides a good electron transmission channel, which is beneficial to the improvement of the photoelectric catalytic efficiency.
According to some embodiments of the invention, the proportion of In atoms In the (In) GaN nanopillar photocathode is 30% -45% of the proportion of In atoms In the metal atoms (In and Ga).
The In content In the content can be used for adjusting the energy band structure, lattice defect and charge distribution of the material, so that the photoelectrocatalysis performance is improved, and In the content range, the light absorption capacity and the carrier transmission efficiency can be improved by increasing the In content, and the photoelectric conversion efficiency is further improved.
According to some embodiments of the invention, the (In) GaN nanopillar photocathode has a nanopillar height of 100 to 500nm, a diameter of 50 to 80nm, and a density of 100 to 400 μm -2.
The height, diameter and density parameters of the nano-pillars improve the photo-catalytic performance. The density and the diameter of the nano-pillars under the conditions can improve the light absorption efficiency and the effective surface area, enhance the photoelectric conversion efficiency, and the proper height of the nano-pillars can be matched with the wavelength of light, so that the light absorption efficiency is improved, and the photoelectrocatalysis material has higher activity under the same illumination condition by optimizing the parameters.
According to some embodiments of the invention, the (In) GaN nanopillar array-based self-biasing photocatalytic system further comprises the following components: electrolyte and light source.
According to some embodiments of the invention, the electrolyte has a pH of 0 to 14.
According to some embodiments of the invention, the electrolyte comprises H 2SO4 electrolyte.
According to some embodiments of the invention, the light source irradiates the electrode in a parallel light irradiation or a full light irradiation.
According to an embodiment of the second aspect of the present invention, there is provided the use of a self-biasing photoelectrocatalytic system based on an (In) GaN nanopillar array for the water-splitting hydrogen production.
The photo-anode is a photoelectrode-photovoltaic (PEC-PV) integrated photoelectrode or PEC electrode based on an (In) GaN nano-pillar array, is connected with a photocathode through a wire, is communicated with an external circuit, is placed In electrolyte, and is subjected to water-splitting hydrogen preparation by simulating sunlight irradiation.
(1) The invention uses MXene as a medium layer for growing (In) GaN nano-pillars, can expand the choice of the substrate, avoids poor quality of grown nano-pillar crystals caused by selecting substrate materials with high lattice mismatch degree with (In) GaN and good conductivity and low price, and can serve as a conductive electrode to reduce the preparation cost.
(2) The invention uses MXene as a Schottky barrier between the substrate and the (In) GaN nano-pillar to receive electrons In the semiconductor, and can block holes from migrating into graphene, thereby effectively inhibiting the recombination of electron-hole pairs, and greatly improving the photoelectric conversion efficiency of the (In) GaN nano-pillar photoelectrolysis water.
(3) When the self-bias photoelectric catalytic system of the (In) GaN nano-pillar array on the MXene is applied to hydrogen production by photoelectrolysis of water, the spectrum absorption can be widened, the required photovoltage for water decomposition can be improved, the hydrogen production by unbiased photoelectric water decomposition can be realized, and the hydrogen production by large-scale solar energy can be facilitated.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic view of a photo-anode structure In a self-biased photo-catalytic system based on an (In) GaN nano-pillar array according to this embodiment.
Fig. 2 is a schematic diagram of a photoelectrochemical cell structure In a self-biased photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Fig. 3 is a schematic diagram of a photoelectrochemical cell structure In a self-biased photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Fig. 4 is a schematic diagram of a photoelectrochemical cell structure In a self-biased photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Fig. 5 is a schematic diagram of a photocathode structure In a self-biased photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Fig. 6 is a schematic diagram of a parallel light irradiation photoelectrochemical cell structure In a self-bias photoelectrocatalysis system based on an (In) GaN nano-pillar array according to the present embodiment.
Fig. 7 is a schematic structural diagram of a full-illumination photoelectrochemical cell In a self-bias photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Fig. 8 is a schematic diagram of a photoelectrochemical cell structure In a self-biased photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the present application may be a mass unit known in the art such as μ g, mg, g, kg.
Example 1
The construction and application of the self-bias photo-catalytic system based on the (In) GaN nano-pillar array comprise the following steps:
(1) Preparation of a photo-anode: and (3) plating an MXene film with the thickness of 5nm on the sapphire substrate by adopting a lifting dipping method, drying, then placing the film into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 900 ℃ to obtain a clean surface and obtain the sapphire/MXene structure. Then, a molecular beam epitaxial growth process is adopted, the temperature of the sapphire/MXene is controlled to be 900 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is 1.0X10 -7 Torr, the equivalent pressure of In beam is 2× -8 Torr, the nitrogen flow is 4sccm, the power of a plasma source is 400W, the growth time is 5h, and the proportion of In atoms In metal atoms (In and Ga) In the (In) GaN nanopillar array on the obtained sapphire substrate is 20%. Finally, connecting a lead with the MXene layer by using an In-Ga alloy, and coupling the lead with the Si-based solar cell In series to prepare the photo-anode.
(2) Selection of photocathodes: a Pt electrode.
(3) Construction of photoelectrochemical cell: the photo-anode and the photo-cathode are connected in series, the electrolyte is 0.5M H 2SO4 electrolyte (pH=0), and the light source irradiates with parallel light.
As shown In fig. 1, the structure of a photo-anode In a self-biased photo-catalytic system based on an (In) GaN nano-pillar array according to this embodiment is schematically shown.
As shown In fig. 2, the structure of a photoelectrochemical cell In the self-biased photoelectrocatalysis system based on the (In) GaN nano-pillar array according to the present embodiment is schematically shown.
The self-bias photoelectrocatalysis system based on the (In) GaN nano-pillar array of the embodiment is used for generating hydrogen by solar energy, and the conversion efficiency of the obtained light to the hydrogen energy is 2.5%.
Example 2
The construction and application of the self-bias photo-catalytic system based on the (In) GaN nano-pillar array comprise the following steps:
(1) Preparation of a photo-anode: and (3) plating an MXene film with the thickness of 8nm on the sapphire substrate by adopting a lifting dipping method, drying, then placing the film into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 900 ℃ to obtain a clean surface and obtain the sapphire/MXene structure. Then, a molecular beam epitaxial growth process is adopted, the temperature of the sapphire/MXene is controlled to be 950 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is 2.0X10 -7 Torr, the equivalent pressure of In beam is 1.5X10 -8 Torr, the nitrogen flow is 5sccm, the power of a plasma source is 400W, the growth time is 5h, and the proportion of In atoms In metal atoms (In and Ga) In the (In) GaN nanopillar array on the obtained sapphire substrate is 10%. In addition, the temperature of the sapphire/MXene is controlled to be 900 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is controlled to be 1.0X10 -7 Torr, the equivalent pressure of In beam is controlled to be 2X 10 -8 Torr, the nitrogen flow is controlled to be 4sccm, the power of a plasma source is controlled to be 400W, the growth time is controlled to be 5h, and the proportion of In atoms In an (In) GaN nanopillar array on the titanium carbide on the obtained sapphire substrate to be 20% of metal atoms (In and Ga). Finally, connecting wires with the MXene under the two prepared nano-pillars by using an In-Ga alloy, and coupling the wires with a Si-based solar cell In series to prepare the photo-anode.
(2) Selection of photocathodes: a Pt electrode.
(3) Construction of photoelectrochemical cell: the photo-anode and the photo-cathode are connected in series, the electrolyte is 0.5M H 2SO4 electrolyte (pH=0), and the light source irradiates with parallel light.
As shown In fig. 3, the structure of a photoelectrochemical cell In the self-biased photoelectrocatalysis system based on the (In) GaN nano-pillar array according to the present embodiment is schematically shown.
The self-bias photoelectrocatalysis system based on the (In) GaN nano-pillar array of the embodiment is used for generating hydrogen by solar energy, and the conversion efficiency of the obtained light to the hydrogen energy is 3.5%.
Example 3
The construction and application of the self-bias photo-catalytic system based on the (In) GaN nano-pillar array comprise the following steps:
(1) Preparation of a photo-anode: and (3) plating an MXene film with the thickness of 10nm on the sapphire substrate by adopting a lifting dipping method, drying, then placing the film into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 900 ℃ to obtain a clean surface and obtain the sapphire/MXene structure. Then, a molecular beam epitaxial growth process is adopted, the temperature of the sapphire/MXene is controlled to be 900 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is 1.0X10 -7 Torr, the equivalent pressure of In beam is 2× -8 Torr, the nitrogen flow is 5sccm, the power of a plasma source is 400W, the growth time is 5h, and the proportion of In atoms In metal atoms (In and Ga) In the (In) GaN nanopillar array on the obtained sapphire substrate is 12%. Finally, connecting a lead with the MXene layer by using an In-Ga alloy, and coupling the lead with two Si-based solar cells In series to prepare the photo-anode.
(2) Selection of photocathodes: a Pt electrode.
(3) Construction of photoelectrochemical cell: the photo-anode and the photo-cathode are connected in series, the electrolyte is 0.5M H 2SO4 electrolyte (pH=0), and the light source irradiates with parallel light.
As shown In fig. 4, the structure of a photoelectrochemical cell In the self-biased photoelectrocatalysis system based on the (In) GaN nano-pillar array according to the present embodiment is schematically shown.
The self-bias photoelectrocatalysis system based on the (In) GaN nano-pillar array is used for generating hydrogen by solar energy, and the conversion efficiency of the obtained light to the hydrogen energy is 2%.
Example 4
The construction and application of the self-bias photo-catalytic system based on the (In) GaN nano-pillar array comprise the following steps:
(1) Preparation of a photo-anode: and (3) plating an MXene film with the thickness of 5nm on the sapphire substrate by adopting a spin coating method, drying, then placing the film into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 900 ℃ to obtain a clean surface, thereby obtaining the sapphire/MXene structure. Then, a molecular beam epitaxial growth process is adopted, the temperature of the sapphire/MXene is controlled to be 980 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is 3.5X10 -7 Torr, the equivalent pressure of In beam is 1× -8 Torr, the nitrogen flow is 5sccm, the power of a plasma source is 400W, the growth time is 5h, and the proportion of In atoms In metal atoms (In and Ga) In the (In) GaN nanopillar array on the obtained sapphire substrate is 0%. Finally, connecting the lead with the MXene layer by using an In-Ga alloy to prepare the photoanode.
(2) Preparing a photocathode: n-type Si was used as the substrate (conductivity <0.005 Ω). Then, a molecular beam epitaxial growth process is adopted, the substrate temperature is controlled to 980 ℃, the substrate rotating speed is 10r/min, the Ga beam equivalent pressure is 3.5X10 - 7 Torr, the In beam equivalent pressure is 2.0X10 -7 Torr, the nitrogen flow is 2sccm, the plasma source power is 200W, and the In atom ratio In the (In) GaN nano-column is prepared for 3 h. Finally, connecting the lead with the back of the Si substrate by using an In-Ga alloy to prepare the photocathode.
(3) Construction of photoelectrochemical cell: the photo-anode and photo-cathode were connected in series, the light source was either parallel light or total light, and the electrolyte was 1m naoh electrolyte (ph=14).
As shown In fig. 5, the embodiment is a schematic diagram of a photocathode structure In a self-biased photo-catalytic system based on an (In) GaN nano-pillar array.
As shown In fig. 6, the structure of a photoelectrochemical cell irradiated with parallel light In the self-biased photoelectrocatalysis system based on the (In) GaN nano-pillar array according to the present embodiment is schematically shown.
As shown In fig. 7, the structure of a full-illumination photoelectrochemical cell In a self-bias photoelectrocatalysis system based on an (In) GaN nanopillar array according to the present embodiment is schematically shown.
The self-bias photoelectric catalytic system based on the (In) GaN nano-pillar array is used for generating hydrogen by solar energy, and the conversion efficiency of the obtained light to the hydrogen energy is respectively 0.5 and 1 percent according to different illumination modes.
Example 5
The construction and application of the self-bias photo-catalytic system based on the (In) GaN nano-pillar array comprise the following steps:
(1) Preparation of a photo-anode: and (3) plating an MXene film with the thickness of 8nm on the sapphire substrate by adopting a spraying method, drying, then placing the film into a Molecular Beam Epitaxy (MBE) reaction chamber, and carrying out annealing treatment on the MXene film at 900 ℃ to obtain a clean surface, thereby obtaining the sapphire/MXene structure. Then, a molecular beam epitaxial growth process is adopted, the temperature of the sapphire/MXene is controlled to be 950 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is 2.0X10 -7 Torr, the equivalent pressure of In beam is 1.5X10 -8 Torr, the nitrogen flow is 5sccm, the power of a plasma source is 400W, the growth time is 5h, and the proportion of In atoms In metal atoms (In and Ga) In the (In) GaN nanopillar array on the obtained sapphire substrate is 10%. In addition, the temperature of the sapphire/MXene is controlled to be 900 ℃, the rotating speed of the sapphire/MXene is controlled to be 10r/min, the equivalent pressure of Ga beam is controlled to be 1.0X10 - 7 Torr, the equivalent pressure of In beam is controlled to be 2X 10 -8 Torr, the nitrogen flow is controlled to be 4sccm, the power of a plasma source is controlled to be 400W, the growth time is controlled to be 5h, and the proportion of In atoms In an (In) GaN nanopillar array on the titanium carbide on the obtained sapphire substrate to be 20% of metal atoms (In and Ga). Finally, connecting wires with the MXene under the two nano-pillars by using an In-Ga alloy to prepare the photo-anode.
(2) Preparing a photocathode: n-type Si was used as the substrate (conductivity <0.005 Ω). Then, a molecular beam epitaxial growth process is adopted, the substrate temperature is controlled to 980 ℃, the substrate rotating speed is 10r/min, the Ga beam equivalent pressure is 3.5X10 - 7 Torr, the In beam equivalent pressure is 2.0X10 -7 Torr, the nitrogen flow is 2sccm, the plasma source power is 200W, and the In atom ratio In the (In) GaN nano-column is prepared for 3 h. Finally, connecting the lead with the back of the Si substrate by using an In-Ga alloy to prepare the photocathode.
(3) Construction of photoelectrochemical cell: the photo-anode and photo-cathode were connected in series, the light source was irradiated with parallel light, and the electrolyte was 1m noh electrolyte (ph=7).
As shown In fig. 8, the structure of a photoelectrochemical cell In the self-biased photoelectrocatalysis system based on the (In) GaN nano-pillar array according to the present embodiment is schematically shown.
The self-bias photoelectrocatalysis system based on the (In) GaN nano-pillar array is used for generating hydrogen by solar energy, and the conversion efficiency of the obtained light to the hydrogen energy is 1.2%.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.

Claims (10)

1. A self-biasing photo-catalytic system based on an (In) GaN nanopillar array, comprising the following components: a photo-anode and a photo-cathode;
The photo anode comprises at least one of an integration of a single electrode of an (In) GaN nano-pillar array with a Si-based solar cell, an integration of a double electrode of an (In) GaN nano-pillar array with a Si-based solar cell, a single electrode of an (In) GaN nano-pillar array and a double electrode of an (In) GaN nano-pillar array;
in the photoanode, the (In) GaN nanopillar array comprises a substrate, an MXene layer on the substrate, and (In) GaN nanopillars grown on the MXene layer,
The photocathode includes at least one of an (In) GaN nanorod photocathode and a platinum electrode.
2. The self-biasing photoelectrocatalytic system based on (In) GaN nanopillar arrays according to claim 1, wherein the Si-based solar cell is a single cell or a double cell series-parallel connection.
3. The (In) GaN nanopillar array based self-biasing photo-catalytic system of claim 1, wherein the substrate comprises a sapphire substrate.
4. The self-biasing photoelectrocatalytic system based on an array of (In) GaN nanopillars according to claim 1, wherein the thickness of the MXene layer is 5-20 nm.
5. The self-biased photoelectrocatalytic system based on an array of (In) GaN nanopillars according to claim 1, wherein the proportion of In atoms of the (In) GaN nanopillars grown on the MXene layer to metal atoms (In, ga) is 0% to 20%, preferably the nanopillars of the (In) GaN nanopillars grown on the MXene layer have a height of 100 to 500nm, a diameter of 50 to 80nm, and a density of 100 to 400 μm -2.
6. The self-biasing photoelectrocatalytic system based on an array of (In) GaN nanopillars according to claim 1, wherein the substrate of the (In) GaN nanopillar photocathode comprises an n-type Si substrate.
7. The self-biasing photoelectrocatalytic system based on (In) GaN nanopillar arrays according to claim 1, wherein the proportion of In atoms In the (In) GaN nanopillar photocathode is 30% -45% of the metal atoms (In, ga); preferably, the (In) GaN nanopillar photocathode has nanopillar height of 100-500 nm, diameter of 50-80 nm, and density of 100-400 μm -2.
8. The (In) GaN nanopillar array based self-biasing photocatalytic system of claim 1, further comprising the following components: electrolyte and light source; preferably, the pH of the electrolyte is 0-14.
9. The self-biasing photoelectrocatalysis system based on (In) GaN nanopillar arrays according to claim 1, wherein the light source irradiates the electrode In a manner of parallel light irradiation or full irradiation.
10. Use of a self-biasing photoelectrocatalytic system based on an array of (In) GaN nanopillars according to any one of claims 1 to 9 for the production of hydrogen by water splitting.
CN202410016355.3A 2024-01-03 2024-01-03 Self-bias photoelectric catalytic system based on (In) GaN nano-pillar array and application thereof Pending CN118147660A (en)

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