Környezetvédelmileg ártalmas anyagok csökkentése arany és ezüst katalizátorral: a szerkezetfüggés modellezése = Gold and silver catalysts for abatement of environmentally harmful materials: modelling the structure dependency

A gépkocsik kipufogó gázaiban nagy mennyiségű NOx, CO és szénhidrogén-származék található, amelyek ártalmasak az emberi szervezetre. Ezek a komponensek drasztikusan csökkenthetők a háromutas katalizátor alkalmazásával. A napjainkban alkalmazott háromutas katalizátorokban Pt, Pd és Rh található cirkónium-oxid stabilizált cérium-oxid, cirkónium-oxid és α-alumínium-oxid hordozón. A jelen munka célja volt Au és Ag alapú katalizátor család fejlesztése a drága Pt és Rh helyettesítésére. Au-Ag kétfémes és az egyfémes Au és Ag mintákat SiO2, TiO2 és CeO2 hordozón állítottunk elő szol adszorpciós módszerrel, hogy vizsgáljuk a két fém egymásra hatását az ötvözet fázisban, és a hordozó hatást. Au/ és Ag/redukálható fémoxid határfelületek hatását különböző jól definiált szerkezetű modell katalizátorokon vizsgáltuk. Ezért Au és Ag nanorészecskéket és rétegeket párologtattunk kontrolált körülmények között a natív SiO2-vel borított Si(100) felületekre különböző módszerekkel (PLD, MBE, magnetron porlasztás). Redukálható oxid (pl. TiO2 FeOx és CeO2) Au-val és Ag-vel alkotott határfelületét többféle szerkezettel hoztuk létre, különböző sorrendben építve egymásra a részecskés vagy a vékonyréteg szerkezetű komponenseket. A minták jellemzését különböző módszerekkel végeztük (XPS, AFM, TEM, XRD, SIMS), valamint vizsgáltuk őket CO oxidációban és NOx redukciójában, valamint kiegészítésként glükóz szelektív oxidációjában. | Automotive exhaust gas contains high concentrations of NOx, CO, and hydrocarbons, which are harmful to human health. These components can be reduced drastically by the use of a three-way catalyst. All commercial three way catalysts in use at present are based on Pt, Pd, and Rh on a support comprised of zirconia-stabilized ceria, zirconia and α-alumina. The present project was aimed at developing a novel family of catalysts, based on Au and Ag, the most promising alternative candidates, to replace the more expensive Pt and Rh. We produced SiO2, TiO2 and CeO2 supported bimetallic Au-Ag and monometallic Au and Ag particles using sol preparation and adsorption method to clarify the cooperation of the two metals in the alloyed phase, and the support effect. The effect of the Au/, Ag/reducible metal oxide interface was studied with model catalysts of well defined various structures produced by different techniques. For this purpose Au and Ag nanoparticles and layers were evaporated in controlled ways onto Si(100) wafers using different new techniques (PLD, MBE, magnetron sputtering). Interface of gold and different oxides like TiO2, FeOx and CeO2 were created in different morphology fabricating of the layers or particles of the two components and changing of the order of the deposition. The samples were characterized by different techniques (XPS, AFM, TEM, XRD, SIMS), and studied in CO oxidation and NOx reduction as well as additionally in glucose selective oxidation

Electrodeposition of Fe-Complexes on Oxide Surfaces for Efficient OER Catalysis

Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the molecular unit for surface adsorption, thus set less rigorous pre-requisites. Herein, we report efficient electrodeposition (ED) of two Fe(III) complexes prepared with closely related NN’N pincer ligands yielding stable and active ad-layers for the electrocatalysis of the oxygen-evolving reaction (OER). The ED method is based on the utilization of a chloride precursor complex [FeIIICl2(NN’N)], which is dissolved in an organic electrolyte undergoes chloride/aqua ligand exchange upon addition of water. ED provides patchy distribution of a chloride-depleted catalyst layer on indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) surfaces, which can be applied for long periods as OER electrocatalysts. Compared to drop-casting or layering of [FeIIICl2(NN’N)] with Nafion (a commonly used support for molecular electrocatalysts), the surface modification by ED is a material saving and efficient method to immobilize catalysts

Photoelectrocatalytic Water Splitting by Conformal Copper‐Oxide on Hematite Nanostructures: Dependence on Surface‐States

Abstract Understanding the pivotal role of surface co‐catalysts is paramount in the strategic design of forthcoming photoelectrodes. However, the nuanced impacts of co‐catalysts remain elusive, particularly in promoting the water oxidation reaction on hematite, especially in connection to surface states denoted as S1 (higher energy) and S2 (lower energy). For this purpose, we tailored two isomorphous hematite nanoarrays with a thin layer of amorphous copper oxide (CuOx), composed of a blend of Cu(I) and Cu(II) species, via a soft electrodeposition technique. Remarkably, we discovered that in pristine hematite (α‐Fe2O3), the S2 state played a pivotal role in activating the CuOx ad‐layer for water oxidation. At lower external biases (approximately 0.9–1.1 VRHE), CuOx served as charge reservoir in equilibrium with the S2 state. Notably, beyond 1.1 VRHE, where the high‐energy holes of the S1 state became available, CuOx was activated indirectly through the equilibrium with the S2 state, and a pronounced enhancement in photocurrent was observed. Conversely, in the case of Ti‐doped hematite (Ti : α‐Fe2O3) devoid of the S2 state, the presence of CuOx resulted in a decline in charge transfer efficiency. Instead of facilitating water oxidation, CuOx adversely affected the S1 surface sites and reduced the charge carrier density in Ti : α‐Fe2O3