CN114921797A - Oxide thin film photoelectrode with reconstructed oxygen vacancy and preparation method thereof - Google Patents
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Abstract
The invention discloses an oxide thin film photoelectrode for reconstructing oxygen vacancy and a preparation method thereof, belonging to the field of photoelectric materials. Using an n-type oxide film (. alpha. -Fe) 2 O 3 ,BiVO 4 ,ZnO,TiO 2 ) With p-type ultrathin catalysts (NiOOH, FeOOH, CoO) x ) And constructing a p-n heterojunction photoelectrode, and activating by treatment means such as Ar plasmon or anoxic atmosphere to prepare the p-n heterojunction photoelectrode. The invention reconstructs oxygen vacancy on the surface and in the body of the p-n heterojunction oxide film photoelectrode, and improves the oxide film photoelectrode by dynamically regulating and controlling the valence state of elementsThe conductivity of the oxide film photoelectrode reduces the surface carrier recombination, and obviously improves the carrier separation efficiency and the photoelectrochemistry 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 thin film photoelectrode for reconstructing oxygen vacancies and a preparation method thereof.
Background
Photoelectrochemical water splitting (PEC-WS) can convert solar energy into hydrogen energy, enabling the collection and storage of abundant solar energy into hydrogen fuel. Materials reported for PEC-WS semiconductor photoelectrode include oxides, sulfides, nitrides, III-V compounds. The oxide semiconductor has the characteristics of adjustable components, controllable band gap and the like, and is widely concerned, but the inherent defects of the oxide semiconductor, such as poor charge transport and serious surface charge recombination, limit the further popularization of the oxide semiconductor in the application of PEC-WS. Research is currently being conducted to improve PEC-WS performance mainly through improvement strategies such as improving light absorption efficiency, carrier separation efficiency, and transfer efficiency. Numerous studies have shown that surface engineering can effectively facilitate carrier separation and transfer by reducing surface recombination. Common surface engineering methods include the construction of oxygen evolution catalysts (i.e., FeOOH, NiOOH, Co-Pi, etc.), surface passivation layers (i.e., Al) 2 O 3 、TiO 2 ) Hetero-junction (i.e., Si/alpha-Fe) 2 O 3 、BiVO 4 /TiO 2 ) And the like.
Although the introduction of the catalyst through surface engineering can reduce surface defects and improve the solid-liquid contact surface, the surface catalyst itself has defects, and thus the surface defects of the photoelectrode are replaced by the surface catalyst defects. The surface catalyst has abundant dangling bonds, so that the surface of the catalyst is still a carrier recombination center. The surface defects can be treated by surface functionalization (i.e., Ar plasma, oxygen-deficient atmosphere treatment, etc.), but the range of action is limited. The surface functionalization treatment is combined with the ultrathin catalytic nano layer, so that not only can the surface catalytic layer be optimized, but also the surface of the photoelectrode oxide film can be optimized, and the surface defects of the photoelectrode can be synergistically improved.
There is no research on the PEC-WS performance of the oxide photoelectrode improved by the strategy, the analysis of carrier transport kinetics is not clear, and the evidence of relevant sites on oxygen vacancies is lacked, so that the search for further improvement of the PEC-WS performance of the oxide photoelectrode by reconstructing the oxygen vacancies on the ultrathin catalytic nanolayer is necessary.
Disclosure of Invention
The invention provides a method for reconstructing oxygen vacancy on the surfaces of a catalyst and an oxide film semiconductor based on the improvement of the transport of photon-generated carriers in a PEC-WS process by utilizing surface engineering so as to improve the PEC-WS performance of an oxide film photoelectrode.
The oxide thin film photoelectrode for reconstructing oxygen vacancy sequentially comprises the following components from bottom to top: FTO substrate, oxide film and ultra-thin catalyst, and the catalyst layer and oxide photoelectrode surface all have oxygen vacancy.
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 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 thin 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, an electrodeposition method or a hydrothermal method; the photoelectrode grows by taking FTO as a conductive substrate.
Further, in the above technical solution, the thickness of the oxide thin film photoelectrode (excluding the FTO substrate) is 450-550nm (preferably 500 nm). As the oxide thin film layer is deposited on the transparent conductive FTO substrate, the oxide thin film layer is in a planar structure, and 450-550nm (optimally 500nm) is favorable for ensuring good optical absorption and also can keep good conductivity.
Further, in the above technical solution, the thickness of the ultra-thin catalytic layer is 0.5-1.5nm (preferably 1 nm). The catalytic layer having a thickness of 0.5 to 1.5nm (preferably 1nm) after the oxygen deficient atmosphere treatment forms not only oxygen vacancies on the surface thereof but also oxygen vacancies on 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.
Further, in the above technical solution, the reconstructed oxygen vacancy is located in the oxide thin film photoelectrode modified by the ultra-thin catalyst as shown in fig. 1.
The preparation method of the oxide thin film photoelectrode with reconstructed oxygen vacancies comprises the following steps: using 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) is grown x ) And then carrying out surface treatment (Ar plasma treatment and oxygen-deficient atmosphere treatment) to obtain the oxide thin film photoelectrode with reconstructed oxygen vacancies.
The invention further provides an application of the oxide thin film photoelectrode adopting the reconstructed oxygen vacancy in photoelectrochemical decomposition of water.
Technical effects
1. The invention modifies oxygen vacancy on the surface of oxide film and ultrathin catalyst layer, and finds out the structure configuration with optimal carrier transport by regulating the thickness of oxide film, the thickness of ultrathin catalyst layer, the content of oxygen vacancy and other parameters. The oxide film and the ultrathin catalyst layer have the characteristic of adjustable chemical composition, and in order to maintain electric neutrality, after oxygen vacancies are introduced, the element valence state is dynamically changed, so that the conductivity is improved, and the carrier transport is promoted. The invention reconstructs oxygen vacancy on the oxide film photoelectrode modified by the ultrathin catalyst by utilizing an anoxic atmosphere treatment mode, thereby not only ensuring that the oxygen vacancy is introduced on the surfaces of the ultrathin catalyst layer and the oxide film, but also reducing the recombination center of the surface and the interface, ensuring the good crystallinity of the photoelectrode material and promoting the effective transportation of current carriers.
2. The invention prepares NiOOH modified alpha-Fe by using a hydrothermal method and a solution impregnation method 2 O 3 Photoelectrode, and treating Sn @ alpha-Fe with Ar plasma 2 O 3 The surface of the NiOOH photoelectrode is enabled to generate oxygen vacancy, and 1.23V is promoted RHE The current density is from 0.91mA/cm 2 Increased to 2.77mA/cm 2 And the initial potential is equal to that of pure Sn @ alpha-Fe 2 O 3 A photoelectrode generates-0 in the cathode direction2V displacement. The analysis of carrier transport kinetics shows that the introduced oxygen vacancy 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 site is not close to the oxygen vacancy, but actually farther away from it. The oxygen vacancy is constructed on the surface and in the body of the photoelectrode, so that the carrier separation and transfer efficiency is effectively promoted, and the PEC-WS performance is greatly improved.
Drawings
FIG. 1: a structural schematic diagram of an oxide thin film photoelectrode with reconstructed oxygen vacancies; wherein: FTO stands for growth substrate, Sn @ alpha-Fe 2 O 3 Representing an oxide film, NiOOH representing a catalyst, and oxygen vacancies being 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/NiOOH-Ar photoelectrode Scanning Electron Microscope (SEM) cross-sectional view;
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 A photocurrent change diagram of the/NiOOH-Ar photoelectrode under different bias voltages; wherein: at 1.23V RHE At a photocurrent density of NiOOH and Sn @ alpha-Fe 2 O 3 The photoelectrode photocurrent density of oxygen vacancy introduced on the surface of the photoelectrode reaches 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 photoelectrode with oxygen vacancy introduced on the surface has the 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 A variation diagram of absorption and separation efficiency of photo-generated carriers of the NiOOH-Ar photoelectrode under different bias voltages; wherein: 1.23V RHE At a photon-generated carrier separation efficiency of NiOOH and Sn @ alpha-Fe 2 O 3 Surface-introduced oxygen vacancy photoelectrode (38.3%) compared with pure Sn @ alpha-Fe 2 O 3 (21.4%) photoelectrode 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 variation graph of the transfer efficiency of the photon-generated carriers of the NiOOH-Ar photoelectrode under different bias voltages; wherein: 1.23V RHE At the transfer efficiency of photogenerated carriers in NiOOH and Sn @ alpha-Fe 2 O 3 Surface-introduced oxygen vacancy photoelectrode (56.5%) compared with pure Sn @ alpha-Fe 2 O 3 (39.7%) the photoelectrode increased by 42.3%;
FIG. 10: FTO/Sn @ alpha-Fe 2 O 3 The structure of the/NiOOH-Ar photoelectrode is shown schematically; wherein: circle (C)
Representing oxygen vacancy, and the left side is oxide semiconductor alpha-Fe 2 O 3 The right side is a catalyst NiOOH;
FIG. 11: FTO/Sn @ alpha-Fe 2 O 3 The structure of the/NiOOH-Ar photoelectrode is shown schematically; wherein: 1 # ，2 # To an active site closer to an oxygen vacancy, 3 # Is an active site further 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 NiOOH-Ar photoelectrodeGibbs free energy change diagram during PEC-WS oxygen production;
FIG. 13 is a schematic view of: calculation of FTO/Sn @ alpha-Fe Using DFT 2 O 3 A Gibbs free energy change diagram of different distances from an oxygen vacancy to an active site on a NiOOH-Ar photoelectric electrode in the process of generating oxygen from a PEC-WS.
Detailed Description
In order to more clearly illustrate the technical solution, the following is further described with reference to the accompanying drawings and embodiments:
preparation of alpha-Fe by hydrothermal reaction 2 O 3 Film formation: the FTO substrate was ultrasonically cleaned with ethanol, acetone, and deionized water for 15 minutes in sequence. FeCl is added 3 (1.5mmol) and urea (1.5mmol) were prepared as a 50ml aqueous solution which was poured into a teflon reaction kettle to submerge the FTO substrate. Heating the mixed solution to 100 ℃ for 12h, and obtaining the FeOOH film after reaction and cooling. Immersing FeOOH film into 0.1M SnCl 4 And (4) dissolving in ethanol for 15 minutes to obtain Sn @ FeOOH. The hydrothermal reaction and Sn doping process described above is referred to as a cycle, and FTO/Sn @ FeOOH is prepared after 5 cycles. The FTO/Sn @ FeOOH film is annealed for 2 hours at 550 ℃ and annealed for 15 minutes at 700 ℃ in the air atmosphere respectively to obtain the FTO/Sn @ alpha-Fe 2 O 3 。
Preparing a surface ultrathin catalyst by a solution impregnation method: mixing FTO/Sn @ alpha-Fe 2 O 3 Soaking in 0.1M NiSO 4 Mixing with 0.1M NaOH mixed aqueous solution, and controlling different soaking times (0.5h, 1h and 2h) to obtain NiOOH modified alpha-Fe with different thicknesses 2 O 3 And a photoelectrode. FTO/Sn @ alpha-Fe 2 O 3 And FTO/Sn @ alpha-Fe 2 O 3 The NiOOH photoelectrode is treated by using medium-power Ar plasma for different time (5 minutes, 10 minutes and 20 minutes) to prepare a photoelectrode containing a surface catalyst and oxygen vacancies (FTO/Sn @ alpha-Fe) 2 O 3 -NiOOH，FTO/Sn@α-Fe 2 O 3 -Ar and FTO/Sn @ alpha-Fe 2 O 3 A NiOOH-Ar photoelectrode.
As shown in FIG. 2, SEM images show FTO/Sn @ alpha-Fe 2 O 3 The surface of the/NiOOH-Ar photoelectrode has deep cracks, and the surface is composed 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 tightly packed. The TEM image showed the nanoparticle size to 50nm and a microcrystalline state as shown in fig. 4. XRD pattern proves that the phase of the prepared oxide film photoelectrode is alpha-Fe 2 O 3 And introducing oxygen vacancy pairs generated by NiOOH and Ar plasma treatment of surface catalysts to alpha-Fe 2 O 3 Without any influence, as shown in figure 5.
FIG. 6 shows Sn @ alpha-Fe 2 O 3 Photoelectrode PEC-WS performance with or without the introduction of NiOOH catalyst and Ar plasma treatment. And pure FTO/Sn @ alpha-Fe 2 O 3 FTO/Sn @ alpha-Fe as compared with a photoelectrode 2 O 3 the/NiOOH-Ar photoelectrode is at 1.23V RHE The photocurrent density is improved by 204 percent (from 0.91 mA/cm) 2 To 2.77mA/cm 2 ) And turn on the potential (U) on ) Shifted by 0.2V in the direction of the cathode. As shown in FIG. 7, 1.2V RHE Shows FTO/Sn @ alpha-Fe by photoelectrochemical impedance spectroscopy 2 O 3 the/NiOOH-Ar photoelectrode has a minimum radius, indicating that introduction of NiOOH and oxygen vacancies can effectively reduce the transport resistance.
As shown in FIG. 8, according to the presence or absence of H 2 O 2 Testing J-V curve under existing condition to calculate carrier separation efficiency (eta) sep ) And transfer efficiency (. eta.) tran )。FTO/Sn@α-Fe 2 O 3 Photoelectrode calculation of eta abs ×η sep 21.4% and is significantly less than FTO/Sn @ alpha-Fe 2 O 3 the/NiOOH-Ar photoelectrode (38.3%). Absorption efficiency (eta) of photoelectrode after NiOOH and Ar plasma treatment abs ) There is little change, so the calculated η abs ×η sep Can directly reflect eta sep Size. FTO/Sn @ alpha-Fe as shown in FIG. 9 2 O 3 the/NiOOH-Ar photoelectrode also exhibits a maximum η tran (56.5%) 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 vacancy and the ultrathin surface catalyst can effectively increase the separation efficiency and transfer of the photogenerated carriersEfficiency.
To reveal the reason for the improved PEC-WS performance, the OER process was calculated using DFT with and without oxygen vacancies α -Fe 2 O 3 The energy barrier on the NiOOH photoelectric electrode is established, and a corresponding model is established to calculate the corresponding Gibbs free energy change of each OER process, as shown in FIG. 10. Selection of adsorption sites at different positions (i.e., 1) # 、2 # 、3 # ) To study the alpha-Fe having oxygen vacancy 2 O 3 The actual active site on the NiOOH photoelectrode is shown in FIG. 11. The straight lines from left to right in fig. 12 represent the intermediates OH, O, OOH, respectively, the dashed lines represent the energy required for each step of the OER reaction, the rise represents the endothermic process and the fall represents the exothermic process. FIG. 13 compares the Gibbs free energies of three different active sites, finding 1 # (1.78eV) and 2 # The energy barrier of the (1.70eV) site is obviously stronger than 3 # (0.56eV) sites, indicating 1 near oxygen vacancy # And 2 # The site desorption energy barrier is larger and farther 3 # The site has a suitable desorption energy barrier. To maintain electroneutrality, oxygen intermediates are tightly adsorbed near the oxygen-vacancy active site, while oxygen intermediates are less energetic to adsorb away from the oxygen-vacancy active site. Comparative alpha-Fe 2 O 3 The NiOOH photoelectrode is 3 # Oxygen vacancy Gibbs free energy is not existed at the site, desorption energy barrier is 1.56eV, and alpha-Fe with oxygen vacancy is higher than the same position 2 O 3 the/NiOOH photoelectrode (0.56 eV). The results indicate that active sites far from the oxygen vacancy have higher activity.
These data fully illustrate the feasibility of using this approach to treat at Sn @ alpha-Fe using Ar plasma 2 O 3 Oxygen vacancy is introduced into a NiOOH photoelectrode and has the oxygen vacancy of FTO/Sn @ alpha-Fe 2 O 3 the/NiOOH-Ar photoelectrode showed excellent PEC-WS performance. And simple Sn @ alpha-Fe 2 O 3 Photoelectrode phase, J ph@1.23V From 0.91mA/cm 2 Increased to 2.77mA/cm 2 The turn-on potential had 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 electroneutrality, the valence of the element shows dynamic change, the conductivity is improved, the carrier recombination is reduced, and the conductivity is improvedCarrier 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 are at locations remote from the oxygen vacancies. The invention opens up a new way for realizing the deep reconstruction of the oxygen vacancy and improving the photoelectric conversion performance.
The foregoing embodiments have described the general principles, major 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 embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (10)
1. The oxide film photoelectrode for reconstructing oxygen vacancy sequentially comprises the following components from bottom to top: FTO base, oxide film and ultra-thin catalyst layer, its characterized in that: the catalyst layer and the oxide photoelectrode surface both have oxygen vacancies.
2. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the oxide film layer is selected from alpha-Fe 2 O 3 、TiO 2 、WO 3 ZnO or BiVO 4 。
3. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the ultra-thin catalyst is selected from NiOOH, FeOOH, CoOOH, NiFe-LDH or CoO x 。
4. The oxygen vacancy restructured oxide thin film photoelectrode of 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 by taking FTO as a conductive substrate.
5. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the oxygen vacancies are treated by Ar plasma or an oxygen-deficient atmosphere.
6. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the thickness of the oxide film layer is 450-550nm from the FTO substrate upwards.
7. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the thickness of the catalyst is 0.5-1.5 nm.
8. The oxygen vacancy restructured oxide thin film photoelectrode of claim 1, wherein: the oxide thin film semiconductor is an n-type semiconductor, and the catalyst is a p-type semiconductor, so that a p-n junction is constructed.
9. A method of making an oxide thin film photoelectrode of restructuring oxygen vacancies as in claim 1 comprising the steps of: and (3) annealing at high temperature by taking FTO as a substrate 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.
10. Use of the oxygen vacancy restructured oxide thin film photoelectrode of any one of claims 1-8 to photoelectrochemically decompose water.
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