Two series of new mononuclear ruthenium complexes with hydrophobic or hydrophilic ligands [Ru(bda)L2] and [Ru(pdc)L3] (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; H2pdc = 2,6-pyridinedicarboxylic acid; L = pyridyl ligands) were synthesized and their electrochemical properties and catalytic activity toward water oxidation were examined. It was revealed that the hydrophobic ligands introduced to [Ru(bda)L2 ] improved the catalytic performance, ahnost twofold TON and TOF values were achieved compared to the [Ru(bda)] catalyst with hydrophilic ligands. The cyclic voltammogram of [Ru(bda)L2] exhibited marginal difference between the catalysts with hydrophobic ligands and hydrophilic ones, implying that the hydrophobic ligands promoted the catalytic activity by :lacilitating formation of a reaction intermediate dimer.

<div><br></div><div><p>Noble metal nanoparticles have been studied extensively as heterogeneous catalysts for electrocatalytic and thermal reactions. In particular, the support material for the catalytic species is known to play a role in influencing the geometric and electronic properties of the active site as well as its catalytic performance. Polycrystalline gold electrodes have been used as a support to modify the electrocatalytic behavior of adsorbed molecular species. Here, we have studied two electrocatalytic processes- the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR), using Au nanoparticle-based catalysts.</p> <p>Transition metal dichalcogenides are well-known HER catalysts that show structure-sensitive catalytic activity. In particular, undercoordinated sulfur sites at the edges of bulk materials as well as amorphous clusters and oligomers tend to show the highest reactivity. The hydrogen adsorption energy of MoS_x nanoclusters can be further tuned through the metallic support. Here, we synthesize colloidal Au@MoS₄^2-, Au@WS₄^2-and Au@MoS₄^2--WS₄^2- using a biphasic ligand-exchange method. The MoS₄^2- and WS₄^2- complexes show higher HER activity when supported on Au nanoparticles than on to a carbon control, illustrating the electronic role played by the support material.</p> <p>In the second project, Au nanoparticle cores are utilized as supports for Pd submonolayer and monolayer surfaces in order to catalyze the two-electron reduction of O₂ to generate hydrogen peroxide. Bulk surfaces of Pt and Pd are excellent catalysts for the four-electron reduction of O₂ to H₂O. In order to achieve high selectivity for H₂O₂, we postulate that the ensemble geometry of the Pd surface must be reduced to small islands or single atoms based on literature studies that have shown that large Pd ensembles are required for O–O bond cleavage. In this study, we synthesize several submonolayers surface coverages of Au@Pd core-shell nanoparticles using a biphasic ligand-exchange method. As the Pd coverage decreases from monolayer to submonolayer, the peroxide selectivity rises but is accompanied by an increase in catalytic overpotential. The highest peroxide selectivity was observed for 0.1 layers of Pd on Au, which likely exhibits the highest fraction of isolated atom and small cluster geometric ensembles of Pd.</p><br></div>

>Magister Scientiae - MSc / The majority of the global energy is sourced from conventional fossil fuels. The high demand for energy is accelerating along with the depletion of these fossil fuels. Hence, the shift to renewable energy sources and technology becomes indispensable. Hydrogen is considered a promising alternative to fossil fuels. Polymer electrolyte membrane water electrolysers offer an environmentally friendly technique for the production of hydrogen from renewable energy sources. However, the high overpotential and acidic environment at the anode is one of the challenges faced by polymer electrolyte membrane water electrolysers. This harsh environment requires distinct electrocatalysts which currently consist of expensive precious metals such as Ir, Ru and their oxides.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20397号 / 工博第4334号 / 新制||工||1672(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The growing interest of renewable fuel and energy sources has steadily increased over time due to climate changes. Research is being made around the world to find solutions for the different problems; one possible solution is to produce hydrogen gas to help phase out the usage of fossil fuels. So far, the technology for the hydrogen gas production is expensive for various reasons, one of the challenges is to minimize the energy usage for the production. Hydrogen could be used in fuel cells which can be used to fuel an electric car. In a fuel cell, hydrogen and oxygen gas are mixed to produce electrical energy as the main product, but it also forms thermal energy and water. Hydrogen gas can be produced from the reversed reaction; by electrolysis of water. This reaction requires energy and one way to minimize the energy usage for this is by using acatalyst. The goal with this master thesis was to see how the reaction rate of the oxygen evolution reaction can be affected by different single atom catalyst systems. The main structure for this catalyst in this thesis is aporphyrin molecule where different transition metals were tried as the active site. Different modifications on the structure were also made by exchanging some of the structures atoms and by adding different ligands.The purpose of this is to see how these modifications change the activity of the catalyst. The catalysts were optimized and calculated in a computational chemistry program called Gaussian 16. The calculations was made by using the DFT functional PBE0 and the basis sets Def2svp and Def2tzvpp. The results show that different modifications do affect the activity of the catalyst. The biggest variations in activity are from placing ligands under the active site while exchanging hydrogens to other substituents on the outer radial position can fine tune the results. The best active sites for this system came by using iridium, rhodium and cobalt which are all elements in group 9 of the periodic table. The lowest overpotential of 0.513 V was given by an iridium based system with four hydrogens exchanged by fluorides. / Runt om i världen finns ett ökat intresse för förnyelsebara energi och bränslekällor för att tackla klimat förändringarna. Stor del av forskningen som görs idag har i syfte att hitta nya lösningar för att minska klimatpåverkan i olika områden. Ett av forskningsområderna är hitta vägar till en miljövänligare vätgasproduktion där vätgasen skulle kunna användas i bränsleceller. Dessa celler kan sättas i elbilar och på så sätt fasa ut användingen av fossila bränslen. En av utmaningarna för vätgasproduktionen är att den idag är kostsam och kräver mycket energi. Forskare försöker hitta olika katalysatorer som kan minska energiåtgången som krävs vid elektrolys av vatten där syrgas och vätgas produceras. Målet med det här examensarbetet är att se hur en single atom catalyst kan påverka reaktionskinitiken för den syrgasbildande reaktionen vid elektrolys av vatten. Huvudstrukturen för katalysatorn som beräkningarna är gjorda på är en porphyrinmolekyl där olika övergångsmetaller kommer testas som det aktiva sätet i katalysatorn. Olika ligander kommer även tillsättas systemet samt utbyte av några väteatomer till olika substituenter i porfyrinstrukturen. Katalysatorn optimerades i det kvantkemiska beräkningsprogrammet Gaussian 16 med funktionalen PBE0 med basset Def2svp och Def2tzvpp. Resultaten visade att olika modifikationer på systemet hade en påverkan på katalysatorns aktivitet. Den största påverkan hade de olika liganderna som placerades under det aktiva sätet jämfört med de olika substituenterna. De bästa metallerna för katalysatorn var iridium, rhodium och kobolt vilket alla ligger i grupp nio i det periodiska systemet. Den lägsta överpotentialen på 0.513 V gavs av iridium systemet med fyra utbyta väten till fluor.

In the chlorate process, natural convection arises thanks to the hydrogen evolving cathode. This increases the mass transport of the different species in the chlorate electrolyte. There is a strong connection between mass transport and the kinetics of the electrode reactions. A better knowledge about these phenomena and their interactions is desirable in order to understand e.g. the reasons for deactivation of anode coatings and what process conditions give the longest lifetime and the highest efficiency. One of the aims of his work was to understand how the chlorate process has to be run to avoid exceeding the critical anode potential (Ecr) in order to keep the potential losses low and to achieve a long lifetime of the DSAs. At Ecr anodic polarisation curves in chlorate electrolyte bend to higher Tafel slopes, causing increasing potential losses and accelerated ageing of the anode. Therefore the impact on the anode potential and on Ecr of different electrolyte parameters and electrolyte impurities was investigated. Additionally, the work aimed to investigate the impact of an addition of chromate on oxygen evolution and concentration profiles under conditions reminiscent of those in the chlorate process (high ionic strength, 70 °C, ruthenium based DSA, neutral pH), but without chloride in order to avoid hypochlorite formation. For this purpose a model, taking into account mass transport as well as potential- and concentration-dependent electrode reactions and homogeneous reactions was developed. Water oxidation is one of the side reactions considered to decrease the current efficiency in chlorate production. The results from the study increase the understanding of how a buffer/weak base affects a pH dependent electrode reaction in a pH neutral electrolyte in general. This could also throw light on the link between electrode reactions and homogeneous reactions in the chlorate process. It was found that the mechanism for chloride oxidation is likely to be the same for potentials below Ecr as well as for potentials above Ecr. This was based on the fact that the apparent reaction order as well as αa seem to be of the same values even if the anode potential exceeds Ecr. The reason for the higher slope of the polarisation curve above Ecr could then be a potential dependent deactivation of the active sites. Deactivation of active ruthenium sites could occur if ruthenium in a higher oxidation state were inactive for chloride oxidation. Concentration gradients of H+, OH-, CrO4 2- and HCrO4 - during oxygen evolution on a rotating disk electrode (RDE) were predicted by simulations. The pH dependent currents at varying potentials calculated by the model were verified in experiments. It was found that an important part of the chromate buffering effect at high current densities occurs in a thin (in the order of nanometers) reaction layer at the anode. From comparisons between the model and experiments a reaction for the chromate buffering has been proposed. Under conditions with bulk pH and chromate concentration similar to those in the chlorate process, the simulations show that the current density for oxygen evolution from OH- would be approximately 0.1 kA m-2, which corresponds to about 3% of the total current in chlorate production. / QC 20101122

A major contribution to global warming is CO2 emitted from the combustion of fossil fuels. Electrochemical processes can help to mitigate the elevated CO2 emissions through either the conversion of CO2 into value-added chemicals or the replacement of fossil fuels with clean fuels such as hydrogen produced from water oxidation. The present dissertation focuses on the mechanistic aspects of electrochemical processes. Electrochemical water oxidation is hindered by the low efficiency of oxygen evolution reaction (OER) at the anode whereas electrochemical reduction of CO2 (ERCO2) is hampered by high overpotentials and poor product selectivity. In this dissertation, we studied the catalytic activity of transition metal-based catalysts, including FeNi spinels, metal-oxide/copper, and d metal cyclam complexes, for both OER and ERCO2 using the density functional theory (DFT) computational approach.We report a combined effort of fabricating FeNi oxide catalysts and identifying the active component of the catalyst for OER. Our collaborators at the University of California, Santa Cruze fabricated a series of FeNi spinels-based materials including Ni(OH)Fe2O4(Cl), Ni(OH)Fe2O4, Fe(OH)Fe2O4(Cl), Fe(OH)Fe2O4, Ni(OH)O(Cl), Ni(OH)O and some show exceptional activity for OER. Combined experimental characterization and computational mechanistic study based on the computational hydrogen electrode (CHE) model revealed that Ni(OH)Fe2O4(Cl) is the active ensemble for exceptional OER performance. We also investigated CO2 reduction to C1 products at the metal-oxide/copper interfaces ((MO)4/Cu(100), M = Fe, Co and Ni) based on the CHE model. The effect of tuning metal-oxide/copper interfaces on product selectivity and limiting potential was clearly demonstrated. This study showed that the catalyst/electrode interface and solvent can be regulated to optimize product selectivity and lower the limiting potential for ERCO2. Applied potential affects the stability of species on the surface of the electrode. The proton-coupled electron transfer (PCET) equilibrium assumed in the CHE model does not capture the change in free energy under the influence of the applied potential. In contrast, the constant electrode potential (CEP) model captures changes in free energy due to applied potential, we applied the CEP model to ERCO2 and OER on (MO)4/Cu(100) and compared the results with those from the CHE model. The results demonstrate that the CHE and the CEP models predict different limiting potentials and product selectivity for ERCO2, but they predict similar limiting potentials for OER. The results demonstrate the importance of accounting for the applied potential effect in the study of more complex multi-step electrochemical processes. We also studied transition metal-based homogeneous catalysts for ERCO2. We examined the performance of transition metal(M) - cyclam(L) complexes as molecular catalysts for the reduction of CO2 to HCOO- and CO, focusing on the effect of changing the metal ions in cyclam on product selectivity (either HCOO- or CO), limiting potential and competitive hydrogen evolution reaction. Our results show that among the complexes, [LNi]2+ and [LPd]2+ can catalyze CO2 reduction to CO, and [LMo]2+ and [LW]3+ can reduce CO2 to HCOO-. Notably, [LMo]2+, [LW]3+, [LW]2+ and [LCo]2+ have a limiting potential less negative than -1.6 V and are based on earth-abundant elements, making them attractive for practical application. In summary, the dissertation demonstrates high-performance catalysts can be designed from earth-abundant transition metals for electrochemical processes that would alleviate the high CO2 level in the environment. On the other hand, completely reversing the increasing trend of CO2 level in the atmosphere requires a collective human effort.

Environmental pollution and health problems created by fossil fuels have led to the development of alternative energies such as solar and wind energies, hydroelectric power, and green hydrogen. The use of biohybrid materials in the development of this type of alternative energies is recent. Biohybrid materials are a unique type of advanced materials that have a biological component that can be a biomolecule or a whole cell and an abiotic or non-biological component that can be a ceramic, a synthetic polymer, or a metal, among others. They have applications in different fields that range from construction (such as bioconcrete) to catalysis (such as artificial enzymes). There are examples in the literature in which bacteria are hybridized with reduced graphene oxide or manganese oxide to catalyze the oxygen evolution of the electrochemical water splitting reaction that produces green hydrogen. The focus of this dissertation is to synthesize efficient biohybrid catalysts following a whole cell approach using electroactive bacteria as the biological component and metallic precursors that form particles ranging from single atoms, nanoclusters, and nanoparticles as the abiotic component. The Fe molecule that is part of the heme group of C-type cytochromes in the outer membrane of Geobacter sulfurreducens acted as the reduction center that allowed the synthesis and hybridization of the metals with the bacteria. Single atom metal catalyst of Ir, Pt, Ru, Cu, and Pd were synthesized and demonstrated a bifunctional catalytic activity towards the hydrogen evolution reaction and the oxygen evolution reaction. Ni single atoms were also synthesized with excellent activity in the water splitting reactions making this biohybrid catalyst very efficient but also green, as Ni is an abundant and cheap metal. Pd nanoclusters with size-control were synthesized by controlling the metal concentration, dosing, and incubation times and were tested in the electrochemical water splitting. Overall, the findings of these studies provide new knowledge on the field of biohybrid materials by contributing with novel methodologies for the synthesis of these materials and the application in the green hydrogen production with high efficiencies.

In the area of sustainable energy, a major focus has been to design robust electrocatalysts that can be used for the electrolysis of water to produce H2 with a sustainable energy source such as solar. Sustainable H2 generation would potentially be a prelude to the adoption of a hydrogen economy, allowing the phasing out of fossil fuels as a primary fuel source. Toward this end, there is a global research effort to develop electrocatalysts that would facilitate the kinetics of the two half-reactions that make up the water-splitting process: the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER). A challenge is to develop active electrocatalysts that are largely composed of earth-abundant elements and show catalytic stability during water splitting at low pH, where the scientific community feels that commercial electrolysis will operate most efficiently. Currently, iridium oxide (IrO2) is being looked at for low pH water splitting because of its stability at low pH, but its relative scarcity (e.g., it is a precious metal) may well make it an unacceptable choice in the long run.In this dissertation, we focus on understanding the scientific issues that will allow the development of earth-abundant catalysts that contain a loading of Ir that is low as possible, while maintaining suitable activity and stability. We began by synthesizing a series of Ir-based OER electrocatalysts by incorporating varying amounts of Ir into 2D layered MnO2 (birnessite, nominally δ-MnO2) and 3D MnO2 (pyrolusite, β-MnO2) phases. The Ir-incorporated δ-MnO2 (Ir/δ-MnO2) electrocatalysts with 16-22 wt% Ir were synthesized by a wet chemical method using a ligating agent, such that Ir was present on the surface and partially intercalated into the interlayer of δ-MnO2. Ir-incorporated β-MnO2 (Ir/β-MnO2) was prepared for the first time via a thermally induced phase transition of Ir/δ-MnO2. This phase transition of δ-MnO2 to β-MnO2 was facilitated by the presence of Ir in the structure, as both Ir in IrO2 and Mn in β-MnO2 could adopt the more thermodynamically stable rutile structure. Extended X-ray absorption fine structure (EXAFS) of Ir/β-MnO2 showed that the catalyst consisted of Ir substituted into the crystalline β-MnO2 lattice, additionally, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and scanning electron microscopy (SEM) imaging revealed micron-sized particles with non-uniform distribution of Ir in the MnO2. In 0.5 M H2SO4 electrolyte, 22 wt% Ir/β-MnO2 (60 〖μg〗_Ir cm_geo^(-2)) resulted in the most active catalyst with an η@10 (overpotential at 10 mA cm_geo^(-2)) of 337 mV and stability of 6 h. This electrocatalyst outperformed a commercial IrO2 on a per Ir mass basis. EXAFS, HAADF-STEM and X-ray absorption near edge structure (XANES) showed that 22 wt% Ir/β-MnO2 had a strained structure containing ~41% Mn3+, an OER active species, along with a modified Ir bonding due to the presence of Ir-O-Ir and Ir-O-Mn. Density functional theory (DFT) computation has demonstrated that this modified bonding environment in Ir/β-MnO2 has contributed to enhancing the thermodynamic stability of the structure. Furthermore, the literature suggests that the presence of Ir-O-Mn bond can favorably tune the d-orbital energy of Ir, enabling superior performance in the Ir/β-MnO2 compared to IrO2. The thesis research also included the investigation of the activity and stability of Ir/β-MnO2 that was synthesized via a novel strategy. The resulting material maintained a homogeneous distribution of Ir in the MnO2 lattice and exhibited excellent OER activity and stability. A surfactant-assisted (SA) synthesis method was carried out to achieve uniform doping of 22-28 wt.% Ir in 3D MnO2 (ramsdellite, R-MnO2). Upon annealing, Ir/R-MnO2 transformed to Ir/β-MnO2 (SA), composed of nano-sized particles. Electrochemical studies in 0.5 M H2SO4 showed that, Ir/β-MnO2 (SA) with 75.6 〖µg〗_Ir cm_geo^(-2) exhibited an η of 327 mV and exceptional stability (up to 50 h). At similar Ir mass loadings, the Ir/β-MnO2 (SA) outperformed Ir/R-MnO2 (SA) and commercial IrO2. This enhanced activity and stability was attributed to a thermodynamically stable structure composed of uniform distribution of Ir (Ir-O-Mn) in the MnO2 lattice. Overall, the research results presented in this dissertation contributed towards designing a novel class of Ir-MnO2 catalysts, which potentially will point the scientific community in the right direction for designing future noble metal-incorporated earth-abundant metal oxides for electrocatalytic energy conversion reactions. / Chemistry

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