Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe2O3@K-OMS-2 Branched Core-Shell Nanoarrays.

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe2O3@K-OMS-2 branched core-shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core-shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe2O3 were confirmed by grazing incidence X-ray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn3O4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 VRHE, compared to the pristine Fe2O3 photoanode (0.33 mA/cm2), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm2. Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core-shell structure, the conductive K-OMS-2 core, and the formation of the Mn3O4 thin layer formed between the core and shell.

Cobalt-doped V2O5 hexagonal nanosheets for superior photocatalytic toxic pollutants degradation, Cr (VI) reduction, and photoelectrochemical water oxidation performance.

The worldwide energy calamity and ecological disturbances demand materials that can remove harmful contaminants from the polluted water. Recently, semiconductor-based catalytic dye removal has created much consideration due to its high efficacy and eco-friendly contaminated water treatment processes. Vanadium oxide (V2O5) has attracted superior attention as a catalyst due to its robust oxidation power, chemical inertness, and stability against photodegradation. In this study, pristine and cobalt (Co)-doped V2O5 samples were synthesized by solvothermal method and examined for their photo-degradation activity and photoelectrochemical (PEC) water oxidation properties. The orthorhombic crystal phase was confirmed by X-ray diffraction (XRD), hexagonal-shaped morphology was observed by scanning electron microscope (SEM) and reduced optical band gap (2.01 eV) was noticed for doped V2O5 catalyst compared to the pristine (2.20 eV) catalyst. The doped V2O5 catalyst exhibited enhanced photodegradation of crystal violet CV (92.7%) and Cr (VI) reduction (90.5%) after 100 min of light irradiation. The doped photocatalyst exhibited approximately 2.1 and 1.9-fold enhancement of photodegradation of CV and Cr(VI) reduction, respectively. The doped electrode showed improved photocurrent density (0.54 mA/cm-2) compared to pristine electrode (0.12 mA/cm-2). Moreover, the doped electrode showed reduced charge-transfer resistance and enhanced charge-transfer properties compared to those of the pristine electrode. Hence, the prepared hexagonal-shaped V2O5 is a suitable material for the elimination of environmental contaminants from the polluted water as well as water splitting for hydrogen generation.

Facile Zn and Ni Co-Doped Hematite Nanorods for Efficient Photocatalytic Water Oxidation.

In this work, we report the effect of zinc (Zn) and nickel (Ni) co-doping of hydrothermally synthesized hematite nanorods prepared on fluorine-doped tin oxide (FTO) substrates for enhanced photoelectrochemical (PEC) water splitting. Seeded hematite nanorods (NRs) were facilely doped with a fixed concentration of 3 mM Zn and varied concentrations of 0, 3, 5, 7, and 9 mM Ni. The samples were observed to have a largely uniform morphology of vertically aligned NRs with slight inclinations. The samples showed high photon absorption within the visible spectrum due to their bandgaps, which ranged between 1.9-2.2 eV. The highest photocurrent density of 0.072 mA/cm2 at 1.5 V vs. a reversible hydrogen electrode (RHE) was realized for the 3 mM Zn/7 mM Ni NRs sample. This photocurrent was 279% higher compared to the value observed for pristine hematite NRs. The Mott-Schottky results reveal an increase in donor density values with increasing Ni dopant concentration. The 3 mM Zn/7 mM Ni NRs sample produced the highest donor concentration of 2.89 × 1019 (cm-3), which was 2.1 times higher than that of pristine hematite. This work demonstrates the role of Zn and Ni co-dopants in enhancing the photocatalytic water oxidation of hematite nanorods for the generation of hydrogen.

Efficient Oxygen Evolution Reaction on Polyethylene Glycol-Modified BiVO4 Photoanode by Speeding up Proton Transfer.

The rate-determining step of the oxygen evolution reaction based on a semiconductor photoanode is the formation of the OO bond. Herein, polyethylene glycol (PEG)-modified BiVO4 photoanodes are reported, in which protons can be transferred quickly due to the high proton conductivity of PEG, resulting in the acceleration of the OO bond formation rate. These are fully demonstrated by different kinetic isotope effect values. Moreover, the open-circuit voltage (Uoc ) further illustrates that PEG passivates the surface states and surface charge recombination is reduced. The composite photoanode can achieve a maximum photocurrent density of 3.64 mA cm-2 at 1.23 V compared to 1.04 mA cm-2 for pure BiVO4 , and an onset potential of 170 mV, which is a 230 mV negative shift compared to pure BiVO4 . This work provides a new strategy to accelerate water oxidation kinetics for photoanodes by speeding up the transfer of the proton and the OO bond formation rate.

Pt nanoparticles coupled with perylene-based small molecule deposited on Ti3+ self-doped TiO2 nanorods-An inorganic/organic type-II nanoheterostructure for efficient visible-light photoelectrochemical water oxidation.

In the work reported in this article, we have coupled Ti3+-self-doped TiO2 nanorods (NRs) with a newly synthesized tetrathiophene coupled perylene-based molecule (tThTMP) to form type-II inorganic/organic nanoheterostructures (NHs) for visible-light-driven water oxidation. The small organic molecule helps in better utilizing a wide range of the visible light spectrum, facilitates a faster delocalization of the photogenerated carriers at the inorganic/organic heterojunction, and exhibits improved photoelectrochemical performances. We have further decorated the NHs with platinum nanoparticles (NPs). The decoration of the Pt NPs significantly augments the various aspects of photoelectrochemical performances. The Pt NPs decorated NHs photoanode exhibits a photocurrent density of 0.83 mA/cm2 at 1.23 V vs. RHE (@10 mV/s scan rate), a photoconversion efficiency of 0.26%, a substantial cathodic shift in the water oxidation onset potential and flat band potential, impressively reduced charge transfer resistance, improved photocarrier concentration, photovoltage, and stability.

Facile loading of cobalt oxide on bismuth vanadate: Proved construction of p-n junction for efficient photoelectrochemical water oxidation.

Cobalt oxide is an excellent water oxidation cocatalyst used in photoelectrochemical (PEC) water splitting field. Finding a facial way to load cobalt oxide on a semiconductor anode is important to effectively realize PEC water splitting on a large scale. In this work, a simple impregnation and calcination method is developed to fabricate CoOx/BiVO4 anode. The constructed CoOx/BiVO4 anode provides a photocurrent of 3.1 mA cm-2 at 1.23 V vs. RHE, about 2.8 times that of BiVO4 anode (1.1 mA cm-2). Furthermore, both the charge separation and injection efficiency are improved by loading CoOx nanoparticles onto the BiVO4 layer. Importantly, input voltage-output current characteristic curves are used for the first time to prove the formation of p-n junction between CoOx and BiVO4, which benefits to the separation of photogenerated holes and electrons. All results indicate that the impregnation and calcination method is efficacious for facile fabrication of CoOx/BiVO4 photoanode with high performance.

Copper-doped ZrO2 nanoparticles as high-performance catalysts for efficient removal of toxic organic pollutants and stable solar water oxidation.

Doping effect on the photoelectrochemical (PEC) water splitting efficiency and photocatalytic activities of ZrO2 under visible light are reported. The XRD analysis revealed that pure, 0.1 and 0.3 mol% doped samples showed mixed crystal phases (tetragonal and monoclinic) and 0.5 mol% doped sample showed a pure tetragonal phase. Under visible light, 90% of methyl orange dye degradation was achieved with in 100 min. Moreover, the optimal doped sample showed a significant degradation rate constant over other samples. The doped photoelectrodes display a better PEC water oxidation performance over pure photoelectrode. Furthermore, the optimal doped (0.3 mol %) electrode shows 0.644 mAcm-2 photocurrent density, corresponding to an approximate 50-fold enhancement over pure electrode (0.013 mAcm-2). The optimized doped sample achieved 98% degradation of methyl orange within 100 min of light irradiation. The superior PEC water oxidation and photocatalytic activity of optimal doped samples under visible light are credited to suitable doping content, crystalline size, greater surface area, suitable bandgap, a lower charge carrying resistance, surface properties and the ability for decreasing the charge carrier's recombination rate.

Atomic layer deposition of metastable ß-Fe2O3 via isomorphic epitaxy for photoassisted water oxidation.

We report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (ß-Fe2O3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In2O3). As a photoanode, unoptimized ß-Fe2O3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ∼0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phases as new PEC materials.