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Cataloged from PDF version of article. Thesis (Ph.D.): Bilkent University, Department of Chemistry, İhsan Doğramacı Bilkent University, 2022. Includes bibliographical references (leaves 122-153). The storage and conversion of solar energy appear to be a highly promising solution to the global energy dilemma due to the sustainability and abundance of sunlight. Among various strategies, artificial photosynthesis, in which solar energy is directly converted to chemical bonds, has gained a great deal of attraction over the past decades. Such a design requires a catalyst coupled with a semiconductor and/or a photosensitizer as light-harvesting components with proper band levels for efficient charge separation. Therefore, the development of an earth-abundant, robust, and visible-light absorbing photocatalytic assembly has been one of the bottlenecks for the advancement of scalable cells. This work aims to overcome this critical challenge by developing new cyanide-based hybrid assemblies for light-driven water splitting and CO2 reduction. CoFe Prussian blue analogues (CoFe-PBAs) have recently emerged as active water oxidation catalysts with excellent long-term stabilities. In the first study, a ZnCr layered double hydroxide (ZnCr-LDH) with a two-dimensional (2D) morphology and a CoFe-PBA are combined to afford a precious metal-free photocatalytic assembly involving a visible light-absorbing semiconductor (SC) and a water oxidation catalyst (WOC). The SC−WOC hybrid materials exhibit a threefold enhancement in activity compared to bare ZnCr-LDH, which is maintained for 6 h under photocatalytic conditions. The band energy diagram was extracted from optical and electrochemical studies to clarify the origin of the improved photocatalytic performance. The assembly is observed to have an appropriate band energy alignment that facilitates charge transfer from the valence band of ZnCr-LDH to the HOMO level of CoFe-PBA for the water oxidation process. In a follow-up study, we move one step forward by coupling exfoliated Dion−Jacobson type niobate nanosheets as a 2D semiconductor with the CoFe-PBA to construct an SC−WOC hybrid structure, which produces a p−n junction. The assembly exhibits a promoted activity (89.5 μmol g−1 h−1) with a proper band energy alignment for the photocatalytic water oxidation process, and it is stable throughout a 12 h photocatalytic study. These studies mark a straightforward pathway to developing low-cost and precious metal-free assemblies for light-driven water oxidation. Metal dicyanamides are another well-known cyanide-based materials, which can be employed as a catalyst for hydrogen evolution reaction (HER) and CO2 reduction due to the partial electron delocalization and the proper coordination environment of metal ions. Herein, we promote a cobalt dicyanamide coordination polymer, Co-dca, for the first time, as a selective catalyst to reduce CO2 to CO in the presence of a ruthenium photosensitizer (Ru PS) under visible light irradiation. A series of photocatalytic experiments under various reaction conditions were performed to reveal the role of the PS, the scavenger, and the solvent in the selectivity and the activity of the photocatalytic process. We find that Co-dca exhibits an activity of 254 µmol h−1 g−1 and a CO selectivity as high as 93%. Furthermore, cobalt dicyanamide also displayed enhanced H2 evolution activity (25000 µmol h−1 g−1), which is maintained for at least 12 h in a mixed aqueous solution containing a Ru-based photosensitizer and a sacrificial electron donor. The effect of various reaction parameters on the photocatalytic activity of the system was investigated. Overall, this thesis presents various low-cost and stable SC-WOC hybrid assemblies based on CoFe-PBA for the light-driven water oxidation process. Moreover, we suggest the use of Co-dca, for the first time, as catalysts for HER and CO2 reduction reactions. by Sina Sadigh Akbari Ph.D.

A 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 mu mol 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.

The development of earth‐abundant photocatalytic assemblies has been one of the bottlenecks for the advancement of scalable water splitting cells. In this study, a ZnCr layered double hydroxide and a CoFe Prussian blue analogue are combined to afford an earth‐abundant photocatalytic assembly involving a visible light‐absorbing semiconductor (SC) and a water oxidation catalyst (WOC). Compared to bare ZnCr‐LDH, the SC‐WOC hybrid assembly exhibits a threefold enhancement in photocatalytic activity, which is maintained for 6 h under photocatalytic conditions at pH 7. The band energy diagram was extracted from optical and electrochemical studies to elucidate the origin of the enhanced photocatalytic performance. This study marks a straightforward pathway to develop low‐cost and precious metal‐free assemblies for visible light‐driven water oxidation.

The utilization of cocatalysts on the photoelectrode surface is a feasible strategy to achieve a high photocurrent density in the photoelectrochemical water oxidation process. The catalysts can enhance the activity by improving the reaction kinetics, retarding charge carrier recombination, or accumulating charge carriers. In this work, we have utilized a CuFe–CoFe Prussian blue (PB) catalyst layer on the BiVO4 photoanode surface to enhance its water oxidation activity. The hybrid catalyst, in which the semiprecious cobalt ions are partially substituted with earth-abundant copper ions, exhibits 56% higher photocurrent density than the CoFe PB-modified BiVO4. We show that photogenerated hole accumulation is present in the CuFe PB layer, which results in higher charge extraction from the BiVO4 surface. The CoFe PB layer on top of the CuFe one facilitates the charge transfer due to its catalytic activity toward the oxygen evolution reaction (OER).

Photocatalytic conversion of CO2 into chemical fuels is a promising approach to tackle carbon emission and global warming. Herein, we promote a cobalt dicyanamide coordination compound, Co-dca, for the first time, as a selective catalyst to reduce CO2 to CO in the presence of a ruthenium photosensitizer (Ru PS) under visible light irradiation. Co-dca was prepared by a facile precipitation method and characterized by Infrared, UV-Vis, XRD, SEM, TEM, and XPS studies. A series of photocatalytic experiments under various reaction conditions were performed to reveal the role of the PS, the scavenger, and the solvent in the selectivity and the activity of the photocatalytic process. We find that Co-dca exhibits an activity of 254 μmol h−1 g−1 and a CO selectivity as high as 93%.

Metal 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.

One of the most critical steps in the transition to carbon-free energy systems is sustainable hydrogen evolution from water. In this research, a cobalt borophosphate crystalline compound consisting of phosphate and borate anions was synthesized with a solid-state reaction. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray Photoelectron (XPS) was employed to investigate the structure, composition, and morphology of Co3BPO7. Electrocatalytic performances of the catalyst towards oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) have been investigated on nickel foam (NF) electrode in 1.0 M KOH (pH 13.6) by linear sweep voltammetry, chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy. For OER, the catalyst exhibits an overpotential of 230 mV at 10 mA cm−2 with a Tafel slope of 130 mV dec−1, which is comparable to that of the benchmark RuO2 electrocatalyst, and 220 mV overpotential for a current density of 10 mA cm−2 with a Tafel slope of 147 mV dec−1 for HER process. Long-term chronoamperometry and multiple cyclic voltammetric experiments indicate the catalyst is stable throughout both HER and OER processes. Electrochemical experiments and characterization studies performed on the pristine and post-catalytic electrode indicate that the catalyst is robust under alkaline electrocatalytic conditions (pH 13.6).