CN114921797B - Oxide film photoelectrode capable of reconstructing oxygen vacancy and preparation method thereof - Google Patents
Oxide film photoelectrode capable of reconstructing oxygen vacancy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an oxide film photoelectrode for reconstructing oxygen vacancies and a preparation method thereof, belonging to the field of photoelectric materials. Using an n-oxide film (alpha-Fe 2 O 3 ,BiVO 4 ,ZnO,TiO 2 ) With p-type ultra-thin catalyst (NiOOH, feOOH, coO) x ) And (3) constructing a p-n heterojunction photoelectrode, and activating the p-n heterojunction photoelectrode by treatment means such as Ar plasmons or anoxic atmosphere and the like to prepare the p-n heterojunction photoelectrode. The invention reconstructs oxygen vacancies on the surface and in vivo of the p-n heterojunction oxide film photoelectrode, improves the conductivity of the oxide film photoelectrode through dynamic regulation and control of element valence state, reduces surface carrier recombination, and obviously improves the carrier separation efficiency and photoelectrochemical water decomposition performance of the oxide film photoelectrode.
Description
Technical Field
The invention belongs to the field of photoelectric materials, and relates to an oxide film photoelectrode capable of reconstructing oxygen vacancies and a preparation method thereof.
Background
Photoelectrochemical decomposition of water (PEC-WS) converts solar energy into hydrogen energy, enabling the collection and storage of abundant solar energy into hydrogen fuel. Reported materials for PEC-WS semiconductor photoelectrodes include oxides, sulfides, nitrides, III-V compounds. Oxide semiconductors have the characteristics of adjustable components, controllable band gaps and the like, and are widely focused, but have inherent defects such as poor charge transport and serious surface charge recombination, so that the oxide semiconductors are limited to be further popularized in PEC-WS applications. The current research mainly improves PEC-WS performance by improving strategies such as light absorption efficiency, carrier separation efficiency, transfer efficiency and the like. Numerous studies have shown that surface engineering can effectively promote carrier separation and transfer by reducing surface recombination. The common surface engineering method comprises the construction of oxygen evolution catalyst (i.e. FeOOH, niOOH, co-Pi, etc.), surface passivation layer (i.e. Al 2 O 3 、TiO 2 )、Heterojunction (i.e. Si/alpha-Fe 2 O 3 、BiVO 4 /TiO 2 ) Etc.
Although the introduction of the catalyst by surface engineering can reduce surface defects and improve solid-liquid contact surface, the surface catalyst itself has defects, so that the photoelectrode surface defects are replaced by surface catalyst defects. The surface catalyst has rich dangling bonds, so that the surface is still a carrier recombination center. The surface defect can be performed by surface functionalization treatment (i.e., ar plasma, anoxic atmosphere treatment, etc.), but the range of application is limited. The surface functionalization treatment is combined with the ultrathin catalytic nano layer, so that the surface catalytic layer can be optimized, the surface of the photoelectrode oxide film can be optimized, and the surface defect of the photoelectrode can be synergistically improved.
At present, no research for improving the performance of the oxide photoelectrode PEC-WS through the strategy is available, carrier transport dynamics analysis is not clear, and the real active site on the oxygen vacancy lacks relevant evidence, so that the research is necessary to further improve the performance of the oxide photoelectrode PEC-WS through reconstructing the oxygen vacancy on the ultrathin catalytic nano-layer.
Disclosure of Invention
The invention provides a method for reconstructing oxygen vacancies on the surfaces of a catalyst and an oxide film semiconductor based on improving the transportation of photogenerated carriers in the PEC-WS process by utilizing surface engineering so as to improve the PEC-WS performance of the oxide film photoelectrode.
The oxide film photoelectrode for reconstructing oxygen vacancies comprises the following components in sequence from bottom to top: the FTO substrate, the oxide film and the ultrathin catalyst are provided with oxygen vacancies on the surfaces of the catalyst layer and the oxide photoelectrode.
Further, in the above technical solution, the oxide thin film layer includes: alpha-Fe 2 O 3 、TiO 2 、WO 3 ZnO or BiVO 4 . These several oxide thin film semiconductors can be used as photoelectrodes.
Further, in the above technical solution, the catalyst includes: niOOH, feOOH, coOOH, niFe-LDH or CoO x 。
Further, in the above technical solution, the oxide film is obtained by a hydrothermal method, an atomic layer deposition method, and a thermal decomposition method; the catalyst is obtained by an adsorption method, electrodeposition or a hydrothermal method; the photoelectrode grows with FTO as a conductive substrate.
Further, in the above technical solution, the thickness of the oxide thin film photoelectrode (except for the FTO substrate) is 450-550nm (preferably 500 nm). The oxide film layer is deposited on the transparent conductive FTO substrate, and the appearance of the oxide film layer is of a planar structure, and 450-550nm (the best is 500 nm) is beneficial to ensuring good optical absorption and keeping good conductivity.
Further, in the above technical solution, the thickness of the ultrathin catalytic layer is 0.5-1.5nm (preferably 1 nm). After the anoxic atmosphere treatment, the catalytic layer having a thickness of 0.5 to 1.5nm (preferably 1 nm) forms not only oxygen vacancies at the surface thereof but also oxygen vacancies at the surface of the oxide thin film.
Further, in the above technical solution, the oxide thin film semiconductor is an n-type semiconductor, and the corresponding catalyst is a p-type semiconductor.
Further, in the above technical scheme, the reconstructed oxygen vacancy is located in the ultrathin catalyst modified oxide thin film photoelectrode as shown in fig. 1.
The preparation method of the oxide film photoelectrode for reconstructing oxygen vacancies comprises the following steps: taking FTO as a substrate, and annealing at high temperature to obtain an oxide film (alpha-Fe 2 O 3 ,TiO 2 ,WO 3 ZnO or BiVO 4 ) On the surface of which a catalyst layer (NiOOH, feOOH, coOOH, niFe-LDH or CoO x ) And then carrying out surface treatment (Ar plasma treatment and anoxic atmosphere treatment) to obtain the oxide film photoelectrode with the reconstructed oxygen vacancies.
The invention further provides application of the oxide film photoelectrode for reconstructing oxygen vacancies in photoelectrochemical decomposition of water.
Technical effects
1. The invention discloses a structural configuration with optimal carrier transport by commonly modifying oxygen vacancies on the surfaces of an oxide film and an ultrathin catalytic layer and regulating and controlling the thickness of the oxide film, the thickness of the ultrathin catalytic layer, the content of the oxygen vacancies and other parameters. The oxide film and the ultrathin catalytic layer have the characteristic of adjustable chemical composition, and in order to maintain electric neutrality, after oxygen vacancies are introduced, the valence state of the element is dynamically changed, thereby being beneficial to improving the conductivity and promoting the carrier transportation. The oxygen vacancy is reconstructed on the oxide film photoelectrode modified by the ultrathin catalyst by using the anoxic atmosphere treatment mode, so that the oxygen vacancy is introduced on the surfaces of the ultrathin catalytic layer and the oxide film, the composite center of the surface and the interface is reduced, the good crystallinity of the photoelectrode material is ensured, and the effective transport of carriers is promoted.
2. The invention prepares the alpha-Fe modified by NiOOH by a hydrothermal method and a solution impregnation method 2 O 3 Photoelectrodes and treatment of Sn@ alpha-Fe with Ar plasma 2 O 3 The surface of the NiOOH photoelectrode is made to generate oxygen vacancies to promote 1.23V RHE The current density at time is from 0.91mA/cm 2 Increase to 2.77mA/cm 2 And the initial potential is equal to that of pure Sn@ alpha-Fe 2 O 3 The photoelectrode is displaced by 0.2V in the cathode direction. Carrier transport kinetics analysis shows that the introduced oxygen vacancies can reduce NiOOH and alpha-Fe 2 O 3 Surface defects and promote carrier separation and transfer by reducing surface recombination. Density Functional Theory (DFT) reveals that the true active sites are not close to oxygen vacancies, but are actually far from oxygen vacancies. The construction of oxygen vacancies on the surface and in vivo of photoelectrode effectively promotes the separation and transfer efficiency of carriers and greatly improves the PEC-WS performance.
Drawings
Fig. 1: reconstructing an oxide film photoelectrode structure schematic diagram of oxygen vacancies; wherein: FTO stands for growth substrate, sn@ alpha-Fe 2 O 3 Represents an oxide film, niOOH represents a catalyst, and oxygen vacancies are located on the surfaces of the catalyst and the oxide film;
fig. 2: FTO/Sn@ alpha-Fe 2 O 3 A NiOOH-Ar photoelectrode Scanning Electron Microscope (SEM) top view;
fig. 3: FTO/Sn@ alpha-Fe 2 O 3 A cross-sectional view of a NiOOH-Ar photoelectrode Scanning Electron Microscope (SEM);
fig. 4: FTO/Sn@ alpha-Fe 2 O 3 A NiOOH-Ar photoelectrode Transmission Electron (TEM) micrograph;
fig. 5: FTO/Sn@ alpha-Fe 2 O 3 、FTO/Sn@α-Fe 2 O 3 -Ar、FTO/Sn@α-Fe 2 O 3 NiOOH and FTO/Sn@ alpha-Fe 2 O 3 A NiOOH-Ar photoelectrode X-ray diffraction (XRD) spectrum;
fig. 6: FTO/Sn@ alpha-Fe 2 O 3 、FTO/Sn@α-Fe 2 O 3 -Ar、FTO/Sn@α-Fe 2 O 3 NiOOH and FTO/Sn@ alpha-Fe 2 O 3 Photo current change patterns of the NiOOH-Ar photoelectrode under different bias voltages; wherein: at 1.23V RHE At photocurrent density of NiOOH and Sn@ alpha-Fe 2 O 3 Photoelectrode surface with oxygen vacancy introduced has photoelectrode light current density up to 2.77mA/cm 2 Compared with the pure FTO/Sn@ alpha-Fe 2 O 3 The photoelectrode is improved by 204%;
fig. 7: FTO/Sn@ alpha-Fe 2 O 3 、FTO/Sn@α-Fe 2 O 3 -Ar、FTO/Sn@α-Fe 2 O 3 NiOOH and FTO/Sn@ alpha-Fe 2 O 3 The NiOOH-Ar photoelectrode is at 1.2V RHE Lower photoelectrochemical impedance spectroscopy; wherein: in NiOOH and Sn@ alpha-Fe 2 O 3 The surface of the oxygen vacancy introducing photoelectrode has minimum transmission resistance;
fig. 8: FTO/Sn@ alpha-Fe 2 O 3 、FTO/Sn@α-Fe 2 O 3 -Ar、FTO/Sn@α-Fe 2 O 3 NiOOH and FTO/Sn@ alpha-Fe 2 O 3 Photo-generated carrier absorption and separation efficiency change diagrams of the NiOOH-Ar photoelectrode under different bias voltages; wherein: 1.23V RHE Photo-generated carrier separation efficiency in NiOOH and Sn@ alpha-Fe 2 O 3 Surface-introduced oxygen vacancy photoelectrode (38.3%) compared to Sn@. Alpha. -Fe alone 2 O 3 (21.4%) the photoelectrode was improved by 78.9%;
fig. 9: FTO/Sn@ alpha-Fe 2 O 3 、FTO/Sn@α-Fe 2 O 3 -Ar、FTO/Sn@α-Fe 2 O 3 NiOOH and FTO/Sn@ alpha-Fe 2 O 3 A photo-generated carrier transfer efficiency change chart of the NiOOH-Ar photoelectrode under different bias voltages; wherein: 1.23V RHE Photo-generated carrier transfer efficiency at NiOOH and Sn@ alpha-Fe 2 O 3 Surface-introduced oxygen vacancy photoelectrode (56.5%) compared to Sn@. Alpha. -Fe alone 2 O 3 (39.7%) the photoelectrode was improved by 42.3%;
fig. 10: FTO/Sn@ alpha-Fe 2 O 3 A structural schematic diagram of a NiOOH-Ar photoelectrode; wherein: circleRepresenting oxygen vacancy, oxide semiconductor alpha-Fe on the left 2 O 3 The right is a catalyst NiOOH;
fig. 11: FTO/Sn@ alpha-Fe 2 O 3 A structural schematic diagram of a NiOOH-Ar photoelectrode; wherein: 1 # ，2 # To be closer to the oxygen vacancy than the active site, 3 # Is an active site farther from the oxygen vacancy;
fig. 12: calculation of FTO/Sn@ alpha-Fe Using DFT 2 O 3 /NiOOH、FTO/Sn@α-Fe 2 O 3 A Gibbs free energy change diagram of the NiOOH-Ar photoelectrode in the PEC-WS oxygen production process;
fig. 13: calculation of FTO/Sn@ alpha-Fe Using DFT 2 O 3 Gibbs free energy change diagram of active sites on NiOOH-Ar photo electrode at different distances from oxygen vacancy during PEC-WS oxygen production.
Detailed Description
For a clearer description of the present technical solution, the following is further described with reference to the accompanying drawings and examples:
preparation of alpha-Fe by hydrothermal reaction 2 O 3 Film: the FTO substrate was ultrasonically cleaned with ethanol, acetone, and deionized water sequentially for 15 minutes. FeCl is added 3 (1.5 mmol) and urea (1.5 mmol) were prepared as 50ml of aqueous solution which was poured into a polytetrafluoroethylene reaction kettle to submerge the FTO substrate. And heating the mixed solution to 100 ℃ and keeping for 12 hours, and cooling the reaction to obtain the FeOOH film. Immersing FeOOH film into 0.1M SnCl 4 And (3) carrying out ethanol solution for 15 minutes to obtain Sn@FeOOH. The hydrothermal reaction and Sn doping process described above is referred to as one cycle, and FTO/sn@feooh is prepared after 5 cycles. By annealing the FTO/Sn@FeOOH film at 550 ℃ for 2 hours in an air atmosphereAnnealing at 700 ℃ for 15 minutes to obtain the FTO/Sn@ alpha-Fe 2 O 3 。
Preparing a surface ultrathin catalyst by a solution impregnation method: FTO/Sn@ alpha-Fe 2 O 3 Soaking in 0.1M NiSO 4 And 0.1M NaOH mixed water solution, and different soaking time (0.5 h, 1h, 2 h) are controlled to obtain NiOOH modified alpha-Fe with different thickness 2 O 3 And a photoelectrode. FTO/Sn@ alpha-Fe 2 O 3 And FTO/Sn@ alpha-Fe 2 O 3 The NiOOH photoelectrode was treated with a medium power Ar plasma for various times (5 minutes, 10 minutes, 20 minutes) to prepare a photoelectrode FTO/Sn@. Alpha. -Fe containing a surface catalyst and oxygen vacancies, respectively 2 O 3 -NiOOH，FTO/Sn@α-Fe 2 O 3 Ar and FTO/Sn@ alpha-Fe 2 O 3 NiOOH-Ar photoelectrode.
As shown in FIG. 2, SEM image shows FTO/Sn@. Alpha. -Fe 2 O 3 The surface of the/NiOOH-Ar photoelectrode has very deep cracks, and the surface consists of nano particles. FIG. 3 shows FTO/Sn@ alpha-Fe 2 O 3 The thickness of the NiOOH-Ar photoelectrode is 500nm, and the nano particles are closely packed. TEM images show nanoparticle sizes of 50nm and a microcrystalline state, as shown in FIG. 4. XRD pattern proves that the prepared oxide film photoelectrode phase is alpha-Fe 2 O 3 Introducing oxygen vacancy generated by surface catalyst NiOOH and Ar plasma treatment to alpha-Fe 2 O 3 Without any effect on the phase of (c) as shown in figure 5.
FIG. 6 shows Sn@. Alpha. -Fe 2 O 3 Photoelectrodes PEC-WS performance with or without the introduction of NiOOH catalysts and Ar plasma treatments. With FTO/Sn@ alpha-Fe alone 2 O 3 FTO/Sn@ alpha-Fe compared with photoelectrode 2 O 3 The NiOOH-Ar photoelectrode is at 1.23V RHE The photocurrent density is increased by 204 percent (from 0.91mA/cm 2 To 2.77mA/cm 2 ) And turn on the potential (U on ) Moving 0.2V in the cathode direction. As shown in FIG. 7, 1.2V RHE The photoelectrochemical impedance spectrum shows FTO/Sn@ alpha-Fe 2 O 3 The NiOOH-Ar photoelectrode has the smallest radius, which shows that the transmission resistance can be effectively reduced by introducing NiOOH and oxygen vacancies。
As shown in fig. 8, according to the presence or absence of H 2 O 2 Testing J-V curve in the presence to calculate the Carrier separation efficiency (. Eta sep ) And transfer efficiency (. Eta.) tran )。FTO/Sn@α-Fe 2 O 3 Photoelectrode calculation η abs ×η sep 21.4% and significantly less than FTO/Sn@ alpha-Fe 2 O 3 NiOOH-Ar photoelectrode (38.3%). Absorption efficiency (. Eta.) of photoelectrode after treatment with NiOOH and Ar plasma abs ) Little change, thus calculated eta abs ×η sep Can directly reflect eta sep Size of the product. As shown in FIG. 9, FTO/Sn@ alpha-Fe 2 O 3 The NiOOH-Ar photoelectrode also exhibits a maximum η tran (56.5%) which is significantly greater than FTO/Sn@ alpha-Fe 2 O 3 (39.7％)、FTO/Sn@α-Fe 2 O 3 -Ar(48.3％)、FTO/Sn@α-Fe 2 O 3 NiOOH (51.2%) photoelectrode. Therefore, the introduced oxygen vacancies and the ultrathin surface catalyst can effectively increase the separation efficiency and transfer efficiency of the photogenerated carriers.
To reveal the cause of the PEC-WS performance improvement, the OER process was calculated with and without oxygen vacancies alpha-Fe using DFT 2 O 3 The energy barrier on the/NiOOH photoelectrode and a corresponding model was built to calculate the corresponding gibbs free energy change for each OER process as shown in figure 10. Selection of adsorption sites at different locations (i.e. 1 # 、2 # 、3 # ) To study alpha-Fe having oxygen vacancy 2 O 3 The true active site on the/NiOOH photo-electrode is shown in FIG. 11. The straight lines from left to right in fig. 12 represent intermediates of OH, O, OOH, respectively, the dashed lines represent the energy required for each step of the OER reaction, the rising represents the endothermic process, and the falling represents the exothermic process. FIG. 13 compares the gibbs free energy of three different active sites, found 1 # (1.78 eV) and 2 # The (1.70 eV) site energy barrier is significantly stronger than 3 # (0.56 eV) site, indicating 1 near oxygen vacancies # And 2 # The site resolution energy barrier is larger and is 3 farther # The sites have suitable solution barriers. To maintain electroneutrality, the active sites near oxygen vacancies adsorb tightly to the oxygen intermediate, while the active sites far from oxygen vacancies pair oxygenThe adsorption energy of the intermediate is lower. Comparison of alpha-Fe 2 O 3 NiOOH photoelectrode at 3 # The free energy of Gibbs with site free oxygen vacancy is 1.56eV, which is higher than alpha-Fe with oxygen vacancy at the same position 2 O 3 NiOOH photoelectrode (0.56 eV). The results indicate that active sites far from oxygen vacancies have higher activity.
These data fully demonstrate that the use of the present approach is feasible with Ar plasma treatment at Sn@ alpha-Fe 2 O 3 Introducing oxygen vacancy into NiOOH photoelectrode, and having oxygen vacancy FTO/Sn@ alpha-Fe 2 O 3 The NiOOH-Ar photoelectrode exhibits excellent PEC-WS properties. And pure Sn@ alpha-Fe 2 O 3 Photoelectrode ratio J ph@1.23V From 0.91mA/cm 2 Increase to 2.77mA/cm 2 The on-potential has a cathode displacement of 0.2V. First, ar plasma treatment reduces surface recombination and improves surface carrier transport efficiency. Secondly, in order to maintain the electric neutrality, the valence of the element shows dynamic change, thereby improving the conductivity, reducing the carrier recombination and improving the carrier separation efficiency. Finally, the introduction of oxygen vacancies increases the active sites, and the primary active sites are not dispersed around the oxygen vacancies, but rather at a location remote from the oxygen vacancies. The invention opens up a new way for realizing the depth reconstruction of oxygen vacancies and improving the photoelectric conversion performance.
The foregoing embodiments illustrate the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the principles of the invention, which are defined in the appended claims.
Claims (9)
1. The oxide film photoelectrode for reconstructing oxygen vacancies comprises the following components in sequence from bottom to top: FTO substrate, oxide film and ultra-thin catalyst layer, its characterized in that: the photoelectric electrode is FTO-Sn@ alpha-Fe 2 O 3 NiOOH, catalyst layer of the photoelectrode and oxide Sn@ alpha-Fe 2 O 3 Oxygen vacancies are arranged on the surface;the oxide film layer is selected from Sn@ alpha-Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The ultra-thin catalyst is selected from NiOOH.
2. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the oxide film is obtained by a hydrothermal method, an atomic layer deposition method or a thermal decomposition method; the catalyst layer is obtained by an adsorption method, electrodeposition or a hydrothermal method; the photoelectrode grows with FTO as a conductive substrate.
3. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the oxygen vacancies are treated by Ar plasma.
4. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the oxygen vacancies are treated by an anoxic atmosphere.
5. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the oxide film layer thickness is 450-550nm a from the FTO substrate.
6. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the thickness of the catalyst is 0.5-1.5. 1.5 nm.
7. An oxide thin film photoelectrode for the reconstruction of oxygen vacancies according to claim 1, wherein: the oxide film semiconductor is an n-type semiconductor, and the catalyst is a p-type semiconductor, so that a p-n junction is constructed.
8. A method for producing the oxide thin film photoelectrode for reconstructing oxygen vacancies according to claim 1, comprising the steps of: taking FTO as a substrate, annealing at high temperature to obtain an oxide film, growing a catalyst layer on the surface of the oxide film, and performing surface treatment to obtain the oxide film photoelectrode with reconstructed oxygen vacancies.
9. Use of the oxide thin film photoelectrode of any of claims 1 to 7 for the photoelectrochemical decomposition of water.
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