Project description:Monoclinic bismuth vanadate (BiVO4) is an attractive material with which to fabricate photoanodes due to its suitable band structure and excellent photoelectrochemical (PEC) performance. However, the poor PEC stability originating from its severe photo-corrosion greatly restricts its practical applications. In this paper, pristine and Mo doped BiVO4 ceramics were prepared using the spark plasma sintering (SPS) method, and their photoelectrochemical properties as photoanodes were investigated. The as-prepared 1% Mo doped BiVO4 ceramic (Mo-BVO (C)) photoanode exhibited enhanced PEC stability compared to 1% Mo doped BiVO4 films on fluorine doped Tin Oxide (FTO) coated glass substrates (Mo-BVO). Mo-BVO (C) exhibited a photocurrent density of 0.54 mA/cm2 and remained stable for 10 h at 1.23 V vs. reversible hydrogen electrode (RHE), while the photocurrent density of the Mo-BVO decreased from 0.66 mA/cm2 to 0.11 mA/cm2 at 1.23 V vs. RHE in 4 h. The experimental results indicated that the enhanced PEC stability of the Mo-BVO (C) could be attributed to its higher crystallinity, which could effectively inhibit the dissociation of vanadium in BiVO4 during the PEC process. This work may illustrate a novel ceramic design for the improvement of the stability of BiVO4 photoanodes, and might provide a general strategy for the improvement of the PEC stability of metal oxide photoanodes.
Project description:BiVO4 as a promising semiconductor absorber is widely investigated as photoanode in photoelectrochemical water splitting. Herein, the rational design of 3D hierarchical ternary SnO2/TiO2/BiVO4 arrays is reported as photoanode for photoelectrochemical application, in which the SnO2 hierarchically hollow microspheres core/nanosheets shell arrays act as conductive skeletons, while the sandwiched TiO2 and surface BiVO4 are working as hole blocking layer and light absorber, respectively. Arising to the hierarchically ordered structure and synergistic effect between each component in the composite, the ternary SnO2/TiO2/BiVO4 photoanode enables high light harvesting efficiency as well as enhanced charge transport and separation efficiency, yielding a maximum photocurrent density of ≈5.03 mA cm-2 for sulfite oxidation and ≈3.1 mA cm-2 for water oxidation, respectively, measured at 1.23 V versus reversible hydrogen electrode under simulated air mass (AM) 1.5 solar light illumination. The results reveal that electrode design and interface engineering play important roles on the overall PEC performance.
Project description:Hydrogen production from water splitting using solar energy based on photoelectrochemical (PEC) cells has attracted increasing attention because it leaves less of a carbon footprint and has economic superiority of solar and hydrogen energy. Oxide semiconductors such as ZnO possessing high stability against photocorrosion in hole scavenger systems have been widely used to build photoanodes of PEC cells but under visible light their conversion efficiencies with respect to incident-photon-to-current conversion efficiency (IPCE) measured without external bias are still not satisfied. An innovative way is presented here to significantly improve the conversion efficiency of PEC cells by constructing a core-shell structure-based photoanode comprising Au@CdS core-shell nanoparticles on ZnO nanowires (Au@CdS-ZnO). The Au core offers strong electronic interactions with both CdS and ZnO resulting in a unique nanojunction to facilitate charge transfer. The Au@CdS-ZnO PEC cell under 400 nm light irradiation without any applied bias provides an IPCE of 14.8%. Under AM1.5 light illumination with a bias of 0.4 V, the Au@CdS-ZnO PEC cell produces H2 at a constant rate of 11.5 μmol h-1 as long as 10 h. This work provides a fundamental insight to improve the conversion efficiency for visible light in water splitting.
Project description:Modifying photoanodes with metal-organic frameworks (MOFs) as oxygen evolution reaction (OER) cocatalysts has emerged as a promising approach to enhance the efficiency of photoelectrochemical (PEC) water oxidation. However, designing OER-active MOFs with both high photo- and electrochemical stability remains a challenge, limiting the advancement of this research. Herein, we present a facile method to fabricate a MOF-modified photoanode by directly loading a pentanuclear Co-based MOF (Co-MOF) onto the surface of a Ti-doped hematite photoanode (Ti:Fe2O3). The resulting Co-MOF/Ti:Fe2O3 modified photoanode exhibits an enhanced photocurrent density of 1.80 mA∙cm-2 at 1.23 V, surpassing those of the Ti:Fe2O3 (1.53 mA∙cm-2) and bare Fe2O3 (0.59 mA∙cm-2) counterparts. Additionally, significant enhancements in charge injection and separation efficiencies, applied bias photon-to-current efficiency (ABPE), incident photon to current conversion efficiency (IPCE), and donor density (Nd) were observed. Notably, a minimal photocurrent decay of only 5% over 10 h demonstrates the extraordinary stability of the Co-MOF/Ti:Fe2O3 photoanode. This work highlights the efficacy of polynuclear Co-based MOFs as OER cocatalysts in designing efficient and stable photoanodes for PEC water splitting applications.
Project description:CdS/CdSe quantum dot-sensitized solar cells (QDSSCs) were fabricated on two types of TiO2 photoanodes, namely nanosheets (NSs) and nanoparticles. The TiO2 NSs with high (001)-exposed facets were prepared via a hydrothermal method, while the TiO2 nanoparticles used the commercial Degussa P-25. It was found that the pore size, specific surface area, porosity, and electron transport properties of TiO2 NSs were generally superior to those of P-25. As a result, the TiO2 NS-based CdS/CdSe QDSSC has exhibited a power conversion efficiency of 4.42%, which corresponds to a 54% improvement in comparison with the P-25-based reference cell. This study provides an effective photoanode design using nanostructure approach to improve the performance of TiO2-based QDSSCs.
Project description:Effectively regulating and promoting the charge separation and transfer of photoanodes is a key and challenging aspect of photoelectrochemical (PEC) water oxidation. Herein, a Ti-doped hematite photoanode with a CoFe-LDH cocatalyst loaded on the surface was prepared through a series of processes, including hydrothermal treatment, annealing and electrodeposition. The prepared CoFe-LDH/Ti:α-Fe2O3 photoanode exhibited an outstanding photocurrent density of 3.06 mA/cm2 at 1.23 VRHE, which is five times higher than that of α-Fe2O3 alone. CoFe-LDH modification and Ti doping on hematite can boost the surface charge transfer efficiency, which is mainly attributed to the interface interaction between CoFe-LDH and Ti:α-Fe2O3. Furthermore, we investigated the role of Ti doping in enhancing the PEC performance of CoFe-LDH/Ti:α-Fe2O3. A series of characterizations and theoretical calculations revealed that, in addition to improving the electronic conductivity of the bulk material, Ti doping also further enhances the interface coupling of CoFe-LDH/α-Fe2O3 and finely regulates the interfacial electronic structure. These changes promote the rapid extraction of holes from hematite and facilitate charge separation and transfer. The informative findings presented in this work provide valuable insights for the design and construction of hematite photoanodes, offering guidance for achieving excellent performance in photoelectrochemical (PEC) water oxidation.
Project description:Efficient carrier separation is important for improving photoelectrochemical water splitting. Here, the morphology modification and band structure engineering of Ta3N5 are accomplished by doping it with Cu and Zr using a two-step method for the first time. The initially interstitially-doped Cu atoms act as anchors to interact with subsequently doped Zr atoms under the influence of differences in electronegativity. This interaction results in Cu,Zrg-Ta3N5 having a dense morphology and higher crystallinity, which helps to reduce carrier recombination at grain boundaries. Furthermore, the gradient doping of Zr generates a band edge energy gradient, which significantly enhances bulk charge separation efficiency. Therefore, a photoanode based on Cu,Zrg-Ta3N5 delivers an onset potential of 0.38 VRHE and a photocurrent density of 8.9 mA cm-2 at 1.23 VRHE. Among all the Ta3N5-based photoanodes deposited on FTO, a Cu,Zrg-Ta3N5-based photoanode has the lowest onset potential and highest photocurrent. The novel material morphology regulation and band edge position engineering strategies described herein provide new ideas for the preparation of other semiconductor nanoparticles to improve the photoelectrochemical water splitting performance.
Project description:The glorious charge transfer efficiency of photoanode is an important factor for efficient photoelectrochemical (PEC) water oxidation. However, it is often limited by slow kinetics of oxygen evolution reaction. Herein, a dual transition metal-based metal-organic frameworks (MOF) cocatalyst, Fe@Ni-MOF, is introduced into a titanium-doped hematite (Fe2O3:Ti) photoanode. The combination of Ni and Fe can optimize the filling of 3d orbitals. Moreover, the introduction of Fe donates electrons to Ni in the MOF structure, thus, suppressing the irreversible (long-life-time) oxidation of Ni2+ into Ni3+. The resulting Fe@Ni-MOF/Fe2O3:Ti photoanode exhibits ∼threefold enhancement in the photocurrent density at 1.23 V versus the reversible hydrogen electrode. Kinetic analysis of the PEC water oxidation processes indicates that this performance improvement is primarily due to modulating the charge transfer efficiency of hematite photoanode. Further results show that a single transition metal-based MOF cocatalyst, Ni-MOF, exhibits slow charge transfer in spite of a reduction in surface charge recombination, resulting in a smaller charge transfer efficiency. These findings provide new insights for the development of photoelectrodes decorated with MOFs.
Project description:In this work, we demonstrate a facile successive ionic layer adsorption and reaction process accompanied by hydrothermal method to synthesize CdS nanoparticle-modified α-Fe2O3/TiO2 nanorod array for efficient photoelectrochemical (PEC) water oxidation. By integrating CdS/α-Fe2O3/TiO2 ternary system, light absorption ability of the photoanode can be effectively improved with an obviously broadened optical-response to visible light region, greatly facilitates the separation of photogenerated carriers, giving rise to the enhancement of PEC water oxidation performance. Importantly, for the designed abnormal type-II heterostructure between Fe2O3/TiO2, the conduction band position of Fe2O3 is higher than that of TiO2, the photogenerated electrons from Fe2O3 will rapidly recombine with the photogenerated holes from TiO2, thus leads to an efficient separation of photogenerated electrons from Fe2O3/holes from TiO2 at the Fe2O3/TiO2 interface, greatly improving the separation efficiency of photogenerated holes within Fe2O3 and enhances the photogenerated electron injection efficiency in TiO2. Working as the photoanodes of PEC water oxidation, CdS/α-Fe2O3/TiO2 heterostucture electrode exhibits improved photocurrent density of 0.62 mA cm- 2 at 1.23 V vs. reversible hydrogen electrode (RHE) in alkaline electrolyte, with an obviously negatively shifted onset potential of 80 mV. This work provides promising methods to enhance the PEC water oxidation performance of the TiO2-based heterostructure photoanodes.
Project description:The ultrasonic process has been examined to exfoliate layered materials and upgrade their properties for a variety of applications in different media. Our previous studies have shown that the ultra-sonication treatment in water without chemicals has a positive influence on the physical and electrochemical performance of layered materials and nanoparticles. In this work, we have probed the impact of ultrasonication on the physical properties and the oxygen evolution reaction (OER) of the NiFe LDH materials under various conditions, including suspension concentration (2.5-12.5 mg mL-1), sonication times (3-20 min) and amplitudes (50-90%) in water, in particular, sonication times and amplitudes. We found that the concentration, amplitude and time play significant roles on the exfoliation of the NiFe LDH material. Firstly, the NiFe LDH nanosheets displayed the best OER performance under ultrasonic conditions with the concentration of 10 mg mL-1 (50% amplitude and 15 min). Secondly, it was revealed that the exfoliation of the NiFe LDH nanosheets in a short time (<10 min) or a higher amplitudes (≥80%) has left a cutdown on the OER activity. Comprehensively, the optimum OER activity was displayed on the exfoliated NiFe LDH materials under ultrasonic condition of 60% (amplitude), 10 mg mL-1 and 15 min. It demanded only 250 mV overpotentials to reach 10 mA cm-2 in 1 M KOH, which was 100 mV less than the starting NiFe LDH material. It was revealed from the mechanism of sonochemistry and the OER reaction that, after exfoliation, the promoted OER performance is ascribed to the enriched Fe3+ at the active sites, easier oxidation of Ni2+ to Ni3+, and the strong electrical coupling of the Ni2+ and Fe3+ during the OER process. This work provides a green strategy to improve the intrinsic activity of layered materials.