Browsing by Author "Karadaş, Ferdi"
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Item Open Access 2D Network overtakes 3D for photocatalytic hydrogen evolution(Royal Society of Chemistry, 2022-07-18) Ahmad, Aliyu Aremu; Türkan Gamze Ulusoy, Ghobadi; Özbay, Ekmel; Karadaş, Ferdi3-Dimensional (3D) cyanide coordination polymers, typically known as Prussian blue Analogues (PBAs), have received great attention in catalysis due to their stability, easily tuned metal sites, and porosity. However, their high crystallinities and relatively low number of surface-active sites significantly hamper their intrinsic catalytic activities. Herein, we report the utilization of a 2-dimensional (2D) layered cobalt tetracyanonickelate, [Co–Ni], for the reduction of protons to H2. Relying on its exposed facets, layered morphology, and abundant surface-active sites, [Co–Ni] can efficiently convert water and sunlight to H2 in the presence of a ruthenium photosensitizer (Ru PS) with an optimal evolution rate of 30 029 ± 590 μmol g−1 h−1, greatly exceeding that of 3D Co–Fe PBA [Co–Fe] and Co–Co PBA [Co–Co]. Furthermore, [Co–Ni] retains its structural integrity throughout a 6 hour photocatalytic cycle, which is confirmed by XPS, PXRD, and Infrared analysis. This recent work reveals the excellent morphologic properties that promote [Co–Ni] as an attractive catalyst for the hydrogen evolution reaction (HER).Item Open Access A dormant reagent reaction-diffusion method for the generation of Co-Fe Prussian Blue analogue periodic precipitate particle libraries(Wiley-VCH GmbH, 2023-08-25) Tootoonchian, Pedram; Kwiczak-Yiğitbaşı, Joanna; Turab Ali Khan, Muhammad; Chalil Oglou, Ramadan; Holló, G.; Karadaş, Ferdi; Lagzi, I.; Baytekin, BilgeLiesegang patterns that develop as a result of reaction-diffusion can simultaneously form products with slightly different sizes spatially separated in a single medium. We show here a reaction-diffusion method using a dormant reagent (citrate) for developing Liesegang patterns of cobalt hexacyanoferrate Prussian Blue analog (PBA) particle libraries. This method slows the precipitation reaction and produces different-sized particles in a gel medium at different locations. The gel-embedded particles are still catalytically active. Finally, the applicability of the new method to other PBAs and 2D systems is presented. The method proves promising for obtaining similar inorganic framework libraries with catalytic abilities. © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.Item Open Access Angstrom thick ZnO passivation layer to improve the photoelectrochemical water splitting performance of a TiO 2 nanowire photoanode: The role of deposition temperature(Nature Publishing Group, 2018) Ghobadi, Amir; Ulusoy-Ghobadi, Türkan Gamze; Karadaş, Ferdi; Özbay, EkmelIn this paper, we demonstrate that angstrom thick single atomic layer deposited (ALD) ZnO passivation can signifcantly improve the photoelectrochemical (PEC) activity of hydrothermally grown TiO2 NWs. It is found that this ultrathin ZnO coating can passivate the TiO2 surface defect states without hampering the carrier’s transfer dynamics. Moreover, a substantial improvement can be acquired by changing the deposition temperature of the ZnO layer (80°C, and 250°C) and named as 80°C TiO2-ZnO, and 250°C TiO2-ZnO. It was found that the deposition of this single layer in lower temperatures can lead to higher PEC activity compared to that deposited in higher ones. As a result of our PEC characterizations, it is proved that photoconversion efciency of bare TiO2 NWs can be improved by a factor of 1.5 upon coating it with a single ZnO layer at 80°C. Moreover, considering the fact that this layer is a passivating coating rather than a continuous layer, it also keeps the PEC stability of the design while this feature cannot be obtained in a thick shell layer case. This paper proposes a bottom up approach to control the electron transfer dynamics in a heterojunction design and it can be applied to other metal oxide combinations.Item Open Access Corrigendum: Building an iron chromophore incorporating prussian blue analogue for photoelectrochemical water oxidation(Wiley-VCH Verlag GmbH & Co. KGaA, 2021-09-20) Ghobadi, T. Gamze Ulusoy; Ghobadi, Amir; Demirtaş, Merve; Büyüktemiz, M.; Kübra N., Özvural; Yıldız, E. A.; Erdem, E.; Yağlıgül, H. G.; Durgun, Engin; Dede, Y.; Özbay, Ekmel; Karadaş, FerdiThe replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.Item Open Access A cyanide-based coordination polymer for hydrogen evolution electrocatalysis(Springer New York LLC, 2018) Alsaç, Elif Pınar; Ülker, E.; Nune, Satya Vijaya Kumar; Karadaş, FerdiAbstract: Research on H2 production has recently been directed to the development of cost-efficient and robust heterogeneous catalysts for hydrogen evolution reaction (HER). Given the promising catalytic activities of several cobalt-based systems and the robustness of Prussian blue analogues in harsh catalytic processes including water oxidation, a Co-Co Prussian blue analogue was investigated as a HER catalyst for the first time. Co-Co Prussian Blue modified fluorine doped tin oxide (FTO) electrode demonstrated a significant HER activity with an onset overpotential of 257 mV, a Tafel slope of 80 mV dec−1, and a turnover frequency of 0.090 s−1 at an overpotential of 250 mV. Comparative XPS, Infrared, and XRD studies performed on pristine and post-catalytic electrodes confirm the stability of the catalyst.Item Open Access Effect of cobalt doping on photocatalytic water splitting activity of NiTi-layered double hydroxide(Royal Society of Chemistry, 2022-03-17) Samuei, Sara; Akbari, Sina Sadigh; Ülker, E.; Karadaş, FerdiMetal doping has been used as an effective strategy to tune the energy levels of semiconductors. Herein, we dope NiTi layered double hydroxide (NiTi-LDH) with cobalt to prepare a ternary LDH, CoNiTi-LDH, to enhance its photocatalytic performance towards both water oxidation and hydrogen evolution. A CoNiTi-LDH with smaller plate sizes and a higher degree of order is obtained, which allows the band gap to shrink from 2.7 eV to 2.4 eV. CoNiTi-LDH exhibits a photocatalytic water oxidation activity of 366 μmol g−1 h−1, which is more than two times higher than NiTi-LDH (166 μmol g−1 h−1). We observed that appropriate energy levels of CoNiTi-LDH allow it to be an efficient photocatalyst also for hydrogen evolution. We performed detailed characterization studies to elucidate the effect of Co-doping on photocatalytic activity.Item Open Access Electrocatalytic hydrogen evolution with cobalt–poly (4-vinylpyridine) metallopolymers(Springer Netherlands, 2018) Kap, Zeynep; Ülker, Emine; Nune, Satya Vijaya Kuma; Karadaş, FerdiAbstract: A facile synthetic pathway using poly(4-vinylpyridine) as a polypyridyl platform is reported for the formation of a metallopolymer. Electrochemical studies indicate that the metallopolymer acts as an efficient H2 evolution catalyst similar to cobalt polypyridyl complexes. It is also observed that the metallopolymer is transformed to cobalt particles when a cathodic potential is applied in the presence of an acid. Electrochemical measurements indicate that an FTO electrode coated with these cobalt particles also acts as an efficient hydrogen evolution catalyst. Approximately 80 µmoles of H2 gas can be collected during 2 h of electrolysis at − 1.5 V (vs. Fc+/0) in the presence of 60 mM of acetic acid. A comprehensive study of the electrochemical and electrocatalytic behavior of cobalt-poly(4-vinylpyridine) is discussed in detail. Graphical Abstract: Poly(4-vinylpyridine) as a precursor for electrodeposited cobalt particles: a cobalt coat derived by a metallopolymer acts as an efficient H2 evolution catalyst. It can transform to a cobalt coat when a potential above − 1.1 V is applied in acid medium. Exchange current density of 10−2.67 mA cm−2 was observed from the Co-coat at − 1.5 V (vs. Fc+/0).Item Open Access Electrodeposited cobalt hexacyanoferrate electrode as a non-enzymatic glucose sensor under neutral conditions(Elsevier B.V., 2021-10-19) Oglou, Ramadan Chalil; Ghobadi, T. Gamze Ulusoy; Özbay, Ekmel; Karadaş, FerdiA CoFe Prussian blue analogue (CoFe PB) modified FTO electrode, prepared via a facile electrodepositionmethod, is investigated as a non-enzymatic glucose sensor under neutral conditions. The electrode ex-hibits a linear detection of glucose in the 0.1e8.2 mmol/L range with a detection limit of 67mM, asensitivity of 18.69mA/mM.cm2, and a fast response time of less than 7 s under neutral conditions. Its stability is confirmed with both electrochemical experiments and characterization studies performed on the pristine and post-mortem electrode. We also conducted a comprehensive electrochemical analysis to elucidate the identity of the active site and the glucose oxidation mechanism on the Prussian blue surface.Item Open Access Enhancing oxygen evolution catalytic performance of nickel borate with cobalt dopingand carbon nanotubes(Wiley, 2023-02-16) Enez, S.; Karani Konuksever, V.; Samuei, S.; Karadaş, Ferdi; Ülker, E.Item Open Access Highly efficient semiconductor-based metasurface for photoelectrochemical water splitting: broadband light perfect absorption with dimensions smaller than the diffusion length(Springer, 2020) Ghobadi, Amir; Ulusoy-Ghobadi, Türkan Gamze; Karadaş, Ferdi; Özbay, EkmelIn this paper, we demonstrate a highly efficient light trapping design that is made of a metal-oxide-semiconductor-semiconductor (nanograting/nanopatch) (MOSSg/p) four-layer design to absorb light in a broad wavelength regime in dimensions smaller than the hole diffusion length of the active layer. For this aim, we first adopt a modeling approach based on the transfer matrix method (TMM) to find out the absorption bandwidth (BW) limits of a simple hematite (α-Fe2O3)-based metal-oxide-semiconductor (MOS) cavity design. Our modeling findings show that this design architecture can provide near-perfect absorption in shorter wavelengths. To extend the absorption toward longer wavelengths, a nanostructured semiconductor is placed on top of this MOS design. This nanostructure supports the Mie resonance and adds a new resonance in longer wavelengths without disrupting the lower wavelength absorption capability of MOS cavity. By this way, a polarization-insensitive absorption above 0.8 can be acquired up to λ=565 nm. Moreover, to have a better qualitative comparison, the water-splitting photocurrent of this design has been estimated. Our calculations show that a photocurrent as high as 10.6 mA cm−2 can be achieved with this design that is quite close to the theoretical limit of 12.5 mA cm−2 for hematite-based water-splitting photoanode. This paper proposes a design approach in which the superposition of cavity modes and Mie resonances can lead to a broadband, polarization-insensitive, and omnidirectional near-perfect light absorption in dimensions smaller than the carrier’s diffusion length. This can be considered as a winning strategy to design highly efficient and ultrathin optoelectronic designs in a variety of applications including photoelectrochemical water splitting and photovoltaics.Item Open Access Investigation of the ideal composition of metal hexacyanocobaltates with high water oxidation catalytic activity(TÜBİTAK, 2019) Karadaş, FerdiThe electrocatalytic activities of Prussian blue analogues (PBAs) have recently received much attention due to their robustness and efficiency. Considering that PBAs with hexacyanocobaltate building block stand forward among other PBAs, a systematic study on a family of metal hexacyanocobaltates is presented in this study. Metal hexacyanocobaltates (M = Co, Mn, Ni, and Fe) were prepared, characterized, and electrochemical studies were performed. A series of mixed-metal cobalt-iron hexacyanocobaltates has also been studied to determine the ideal composition of a metal hexacyanocobaltate for electrocatalytic water oxidation process. The overall study clearly indicates that cobalt hexacyanocobaltate exhibits the highest electrocatalytic activity among all.Item Open Access Large scale compatible fabrication of gold capped titanium dioxide nanoantennas using a shadowing effect for photoelectrochemical water splitting(Elsevier, 2020) T. Gamze, Ulusoy-Ghobadi; Ghobadi, Amir; Karadaş, Ferdi; Özbay, EkmelIn this paper, a visible light driven plasmonic based photoelectrochemical water splitting (PEC-WS) cell is designed with an elegant two-step fabrication route. First, titanium dioxide (TiO2) nanowires (NWs) were synthesized using the hydrothermal method. Then, angled deposition was used to selectively coat the tips of the NWs yielding Au-capped TiO2 NWs with multiple sizes and shapes. The provided randomness leads to a multi-resonant system where the superposition of these resonance modes leads to an overall broadband absorption. The excited localized surface resonance (LSPR) modes contribute to the performance enhancement of the cell via near field effects and a hot electron injection mechanism. Moreover, these nanotips can trigger the formation of Fabry-Pérot (FP) cavity modes. The combination of the above-mentioned mechanisms leads to a high performance visible light driven plasmonic cell. At an applied potential of 1.23 V vs RHE, a photocurrent value as high as 82 μA/cm2 is acquired for the plasmonic based photoanode. The proposed design strategy is a large scale compatible route with no material restriction. Therefore, vast variety of semiconductor-metal pairs can be fabricated to obtain highly efficient water splitting cell for hydrogen generation.Item Open Access Laser-ablation assisted strain engineering of gold nanoparticles for selective electrochemical CO2 reduction(Royal Society of Chemistry, 2022-04-19) Zhang, C.; Zhang, W.; Karadaş, Ferdi; Low, J.; Long, R.; Liang, C.; Wang, J.; Li, Z.; Xiong, Y.Strain engineering can endow versatile functions, such as refining d-band center and inducing lattice mismatch, on catalysts for a specific reaction. To this end, effective strain engineering for introducing strain on the catalyst is highly sought in various catalytic applications. Herein, a facile laser ablation in liquid (LAL) strategy is adopted to synthesize gold nanoparticles (Au NPs) with rich compressive strain (Au-LAL) for electrochemical CO2 reduction. It is demonstrated that the rich compressive strain can greatly promote the electrochemical CO2 reduction performance of Au, achieving a CO partial current density of 24.9 mA cm−2 and a maximum CO faradaic efficiency of 97% at −0.9 V for Au-LAL, while it is only 2.77 mA cm−2 and 16.2% for regular Au nanoparticles (Au-A). As revealed by the in situ Raman characterization and density functional theory calculations, the presence of compressive strain can induce a unique electronic structure change in Au NPs, significantly up-shifting the d-band center of Au. Such a phenomenon can greatly enhance the adsorption strength of Au NPs toward the key intermediate of CO2 reduction (i.e., *COOH). More interestingly, we demonstrate that, an important industrial chemical feedstock, syngas, can be obtained by simply mixing Au-LAL with Au-A in a suitable ratio. This work provides a promising method for introducing strain in metal NPs and demonstrates the important role of strain in tuning the performance and selectivity of catalysts.Item Open Access Light-driven water oxidation with ligand-engineered Prussian blue analogues(American Chemical Society, 2022-02-24) Ahmad, Aliyu Aremu; Ulusoy Ghobadi, Türkan Gamze; Büyüktemiz, Muhammed; Özbay, Ekmel; Dede, Yavuz; Karadaş, FerdiThe elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups. K0.1[Co(bpy)]2.9[Fe(CN)6]2([Cobpy-Fe]), K0.2[Co(phen)]2.8[Fe(CN)6]2([Cophen-Fe]), {[Co(bpy)2]3[Fe(CN)6]2}[Fe(CN)6]1/3([Cobpy2-Fe]), and {[Co(phen)2]3[Fe(CN)6]2}[Fe(CN)6]1/3Cl0.11([Cophen2-Fe]) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2′-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K0.1Co2.9[Fe(CN)6]2([Co-Fe]). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe], while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s-1, respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10-2s-1). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers. © 2022 American Chemical Society. All rights reserved.Item Open Access Low-pressure deuterium storage on palladium-coated titanium nanofilms: a versatile model system for tritium-based betavoltaic battery applications(American Chemical Society, 2023-08-30) Ghobadi, Türkan Gamze Ulusoy; Koçak, Yusuf; Jalal, Ahsan; Altınkaynak, Yağmur; Çelik, Gülşah; Semiz, Tolga; Çakır, Cihan; Bütün, Bayram; Özbay, Ekmel; Karadaş, Ferdi; Özensoy, EmrahDeuterium (D2(g)) storage of Pd-coated Ti ultra-thin films at relatively low pressures is fine-tuned by systematically controlling the thicknesses of the catalytic Pd overlayer, underlying Ti ultra-thin film domain, D2(g) pressure (PD2), duration of D2(g) exposure, and the thin film temperature. Structural properties of the Ti/Pd nanofilms are investigated via XRD, XPS, AFM, SEM, and TPD to explore new structure-functionality relationships. Ti/Pd thin film systems are deuterated to obtain a D/Ti ratio of up to 1.53 forming crystallographically ordered titanium deuteride (TiDx) phases with strong Tix+–Dy– electronic interactions and high thermal stability, where >90% of the stored D resides in the Ti component, thermally desorbing at >460 °C in the form of D2(g). Electronic interaction between Pd and D is weak, yielding metallic (Pd0) states where D storage occurs mostly on the Pd film surface (i.e., without forming ordered bulk PdDx phases) leading to the thermal desorption of primarily DOH(g) and D2O(g) at <265 °C. D-storage typically increases with increasing Ti film thickness, PD2, T, and t, whereas D-storage is found to be sensitive to the thickness and the surface roughness of the catalytic Pd overlayer. Optimum Pd film thickness is determined to be 10 nm providing sufficient surface coverage for adequate wetting of the underlying Ti film while offering an appropriate number of surface defects (roughness) for D immobilization and a relatively short transport pathlength for efficient D diffusion from Pd to Ti. The currently used D-storage optimization strategy is also extended to a realistic tritium-based betavoltaic battery (BVB) device producing promising β-particle emission yields of 164 mCi/cm2, an open circuit potential (VOC) of 2.04 V, and a short circuit current (ISC) of 7.2 nA.Item Open Access Manipulating intermetallic charge transfer for switchable external stimulus-enhanced water oxidation electrocatalysis(John Wiley and Sons Inc, 2023-10-26) Chalil Oglou, Ramadan; Ulusoy Ghobadi, Türkan Gamze; Hegner, F. S. .; Galán-Mascarós, J. R.; López, N; Özbay, Ekmel; Karadaş, FerdiElectrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co−Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm−2), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.Item Open Access Modification of mesoporous LiMn2O4 and LiMn2−xCoxO4 by SILAR method for highly efficient water oxidation electrocatalysis(Wiley, 2020-06) Karakaya, Irmak; Karadaş, Ferdi; Ulgut, Burak; Dağ, ÖmerIridium, ruthenium, and cobalt oxides are target materials as efficient and stable mesoporous metal oxide electrocatalysts for oxygen evolution reaction (OER). However, they are costly, toxic, and not practical for an efficient OER process. Here, a two‐step method is introduced, based on earth‐abundant manganese; molten salt‐assisted self‐assembly process to prepare mesoporous LiMn2−xCoxO4 (x = 0–0.5) modified electrodes, in which a systematic incorporation of Co(II) into the structure is performed using successive ionic layer adsorption and reaction followed by an annealing (SILAR‐AN) process. Applying SILAR‐AN over a stable m‐LiMn1.6Co0.4O4 electrode improves the OER performance; the Tafel slope and overpotential drop from 66 to 46 mV dec−1 and 304 to 265 mV (at 1.0 mA cm−2), respectively. The performance of the modified electrodes is comparable to benchmark IrO2 and RuO2 catalysts and much better than cobalt oxide electrodes. Electronic interactions between the neighboring Mn and Co sites synergistically amplify the OER performance of the m‐LiMn2−xCoxO4 electrodes. The data are compatible with an eight steps nucleophilic acid‐base reaction mechanism during OER.Item Open Access A Noble-Metal-Free Heterogeneous Photosensitizer-Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light(Wiley-VCH Verlag, 2018) Ulusoy-Ghobadi, Türkan Gamze; Yıldız, E. A.; Büyüktemiz, M.; Akbari, S. Sadigh; Topkaya, D.; İşçi, Ü.; Dede, Y.; Yağlioğlu, H. G.; Karadaş, FerdiAn entirely earth-abundant chromophore-relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore-Prussian blue analogue assembly. Light-driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron-transfer and co-operates with porphyrin in the charge separation process.Item Open Access Photocatalytic water oxidation with a CoFe prussian blue analogue–layered niobate hybrid material(American Chemical Society, 2021-11-22) Sadigh Akbari, Sina; Ünal, U.; Karadaş, FerdiA semiconductor–catalyst hybrid assembly for photocatalytic water oxidation was obtained by preparing CoFe Prussian blue particles on Dion–Jacobson type niobate nanosheets, which produces a p–n junction, as evidenced by the Mott–Schottky plot. The hybrid material with a precious-metal-free cocatalyst exhibits an enhanced photocatalytic activity (89.5 μmol g–1 h–1) in the presence of S2O82– as the electron scavenger. XPS, infrared, XRD, TEM, and SEM studies performed on both pristine and postcatalytic samples indicate that the hybrid assembly exhibits a proper band energy alignment for the photocatalytic water oxidation process and it is stable throughout a 12 h photocatalytic study.Item Open Access Photocatalytic water oxidation with a Prussian blue modified brown TiO2(Royal Society of Chemistry, 2020-12-04) Gündoğdu, Gülsüm; Ulusoy Ghobadi, Türkan Gamze; Sadigh Akbari, Sina; Özbay, Ekmel; Karadaş, FerdiA recently emerging visible light-absorbing semiconductor, brown TiO2 (b-TiO2), was coupled with a CoFe Prussian blue (PB) analogue to prepare an entirely earth-abundant semiconductor/water oxidation catalyst hybrid assembly. PB/b-TiO2 exhibits a sevenfold higher photocatalytic water oxidation activity compared to b-TiO2. An elegant band alignment unified with the optical absorption of b-TiO2 and excellent electronic dynamics of PB yield a high-performance photocatalytic system.