Catalysts

Journal: Catalysts

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MDPI

ISSN

2073-4344

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Publications 1 - 10 of 11

Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach
Köpfle, Norbert; Ploner, Kevin; Lackner, Peter; et al. (2020)
Catalysts
Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.
Strong Activity Enhancement of the Photocatalytic Degradation of an Azo Dye on Au/TiO2 Doped with FeOx
Waheed, Ammara; Shi, Quanquan; Maeda, Nobutaka; et al. (2020)
Catalysts
The doping of Au/TiO2 with FeOx is shown to result in a strong enhancement of its photocatalytic activity in the degradation of the azo dye Orange II. In order to examine the source of this enhancement, Au-FeOx/TiO2 nanocomposites containing different molar ratios of Au:Fe were synthesized, and X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), and high-resolution transmission electron microscope (HRTEM) analyses indicated that the TiO2-supported Au nanoparticles were partially covered with an amorphous layer of FeOx species, in which the iron was present as Fe2+ and Fe3+. The metal-semiconductor system, i.e., Au/TiO2, showed only a moderate degradation rate, whereas doping with FeOx strongly enhanced the degradation activity. The bandgap energy decreased gradually from Au/TiO2 (3.13 eV) to the catalyst with the highest FeOx loading Au-FeOx (1:2)/TiO2 (2.23 eV), and this decrease was accompanied by a steady increase in the degradation activity of the catalysts. XPS analyses revealed that compared to Au/TiO2, on Au-FeOx/TiO2 a much higher population density of chemisorbed and/or dissociated oxygen species was generated, which together with the decreased bandgap resulted in the highest photocatalytic activity observed with Au-FeOx (1:2)/TiO2. The processes occurring during reaction on the catalyst surface and in the bulk liquid phase were investigated using operando attenuated total reflection IR spectroscopy (ATR-IR) combined with modulation excitation spectroscopy (MES), which showed that the doping of Au/TiO2 with FeOx weakens the interaction of the dye with the catalyst surface and strongly enhances the cleavage of the azo bond.
Bimetallic metal-organic framework mediated synthesis of Ni-Co catalysts for the dry reforming of methane
Khan, Il Son; Ramirez Galilea, Adrian; Shterk, Genrikh; et al. (2020)
Catalysts
Dry reforming of methane (DRM) involves the conversion of CO2 and CH4, the most important greenhouse gases, into syngas, a stoichiometric mixture of H2 and CO that can be further processed via Fischer–Tropsch chemistry into a wide variety of products. However, the devolvement of the coke resistant catalyst, especially at high pressures, is still hampering commercial applications. One of the relatively new approaches for the synthesis of metal nanoparticle based catalysts comprises the use of metal-organic frameworks (MOFs) as catalyst precursors. In this work we have explored MOF-74/CPO-27 MOFs as precursors for the synthesis of Ni, Co and bimetallic Ni-Co metal nanoparticles. Our results show that the bimetallic system produced through pyrolysis of a Ni-Co@CMOF-74 precursor displays the best activity at moderate pressures, with stable performance during at least 10 h at 700 °C, 5 bar and 33 L·h−1·g−1.
Fe-doping in double perovskite prbaco2(1-x)fe2xo6-б: Insights into structural and electronic effects to enhance oxygen evolution catalyst stability
Kim, Bae-Jung; Fabbri, Emiliana; Castelli, Ivano E.; et al. (2019)
Catalysts
Perovskite oxides have been gaining attention for its capability to be designed as an ideal electrocatalyst for oxygen evolution reaction (OER). Among promising candidates, the layered double perovskite—PrBaCo2O6-δ (PBC)—has been identified as the most active perovskite electrocatalyst for OER in alkaline media. For a single transition metal oxide catalyst, the addition of Fe enhances its electrocatalytic performance towards OER. To understand the role of Fe, herein, Fe is incorporated in PBC in different ratios, which yielded PrBaCo2(1-x)Fe2xCo6-δ (x = 0, 0.2 and 0.5). Fe-doped PBCF’s demonstrate enhanced OER activities and stabilities. Operando X-ray absorption spectroscopy (XAS) revealed that Co is more stable in a lower oxidation state upon Fe incorporation by establishing charge stability. Hence, the degradation of Co is inhibited such that the perovskite structure is prolonged under the OER conditions, which allows it to serve as a platform for the oxy(hydroxide) layer formation. Overall, our findings underline synergetic effects of incorporating Fe into Co-based layered double perovskite in achieving a higher activity and stability during oxygen evolution reaction.
Structured Perovskite-Based Catalysts and Their Application as Three-Way Catalytic Converters
Keav, Sylvain; Matam, Santhosh Kumar; Ferri, Davide; et al. (2014)
Catalysts
Automotive Three-Way Catalysts (TWC) were introduced more than 40 years ago. Despite that, the development of a sustainable TWC still remains a critical research topic owing to the increasingly stringent emission regulations together with the price and scarcity of precious metals. Among other material classes, perovskite-type oxides are known to be valuable alternatives to conventionally used TWC compositions and have demonstrated to be suitable for a wide range of automotive applications, ranging from TWC to Diesel Oxidation Catalysts (DOC), from NOx Storage Reduction catalysts (NSR) to soot combustion catalysts. The interest in these catalysts has been revitalized in the past ten years by the introduction of the concept of catalyst regenerability of perovskite-based TWC, which is in principle well applicable to other catalytic processes as well, and by the possibility to reduce the amounts of critical elements, such as precious metals without seriously lowering the catalytic performance. The aim of this review is to show that perovskite-type oxides have the potential to fulfil the requirements (high activity, stability, and possibility to be included into structured catalysts) for implementation in TWC.
Enhanced Visible-Light Driven Photocatalytic Activity of Ag@TiO2 Photocatalyst Prepared in Chitosan Matrix
Grčić, Ivana; Gajović, Andreja; Plodinec, Milivoj; et al. (2020)
Catalysts
Ag doped TiO(2)photocatalysts (Ag@TiO2) were prepared with an aim to extend the absorption range of TiO(2)into the visible region, for tentative application under solar irradiation. Photocatalyst synthesized by the novel method using chitosan for reduction of Ag(+)to Ag(0)nanoparticles was compared to similar catalysts previously reported. The photocatalytic activity of Ag@TiO(2)obtained by a simple novel method was evaluated based on degradation of salicylic acid as a model compound. The higher activity under visible irradiation can be attributed to the surface plasmon resonance and suppression of the electron-hole recombination when deposition of Ag nanoparticles on TiO(2)was achieved using chitosan. The photocatalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), high resolution TEM (HRTEM), energy dispersive X-ray spectroscopy (EDXS), selected area diffraction (SAED), and diffuse reflectance spectroscopy (DRS). The photochromism of Ag was observed and explained.
Tuning the Co Oxidation State in Ba0.5Sr0.5Co0.8Fe0.2O3-δ by Flame Spray Synthesis Towards High Oxygen Evolution Reaction Activity
Aegerter, Dino; Borlaf, Mario; Fabbri, Emiliana; et al. (2020)
Catalysts
The perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) is known as a highly active and stable oxygen evolution reaction (OER) electrocatalyst composited out of non-noble metals. The possibility of using the scalable flame spray synthesis (FSS) technique for the production of BSCF nanoparticles intensified the interest in this material for a future application in an alkaline water electrolyzer. A possible scale-up would require the optimization of the synthesis parameters to maximize the production rate. To further understand the influence of the synthesis parameters of the tunable FSS on the OER activity of BSCF, a systematic study was carried out by producing BSCF with different total metal concentrations (CTM), flow rates of the precursor solution (FRPS) and of the dispersion gas (FRDG). This study reveals that all three parameters have a direct impact on the OER activity of BSCF—measured in a rotating disc electrode (RDE) setup—due to the controllability of the initial Co and Fe oxidation state—indicated by X-ray absorption spectroscopy (XAS) measurements—and with that also of the oxygen vacancy concentration in the as-synthesized BSCF. This controllability enables the optimization of the OER activity of BSCF and emphasizes the importance of having Co in a lower initial oxidation state for reaching a high electrocatalytic performance.
Thermal Stability and Utilization of 1D-Nanostructured Co3O4 Rods Derived by Simple Solvothermal Processing
Mandić, Vilko; Kurajica, Stanislav; Plodinec, Milivoj; et al. (2022)
Catalysts
For p-type semiconductor nanoparticles, such as the cobalt oxide spinel, enhancing the nanoparticle geometry can expose more of the surface and bring up the sensitivity and applicability, pointing to even more advantageous behaviour in comparison to n-type semiconductors which are known for a somewhat faster reactivity. Here, we present a strategy that relies on fostering a simple synthetic route that can deliver reasonably or comparably performing p-type-semiconducting partially 1D-Co3O4 material prepared under less technically and economically demanding conditions. Structurally monophasic Co3O4 nanoparticles with a spinel structure were indicated by powder X-ray diffraction, while the presence of traces of organic-phase residuals in otherwise chemically homogeneous material was observed by Fourier-transform infrared spectroscopy. Scanning electron microscopy further showed that the observed fine nanoparticle matter formed agglomerates with the possible presence of rod-like formations. Interestingly, using transmission electron microscopy, it was possible to reveal that the agglomerates of the fine nanoparticulated material were actually nanostructured, i.e., the presence of 1D-shaped Co3O4 rods embedded in fine nanoparticulated matrix was confirmed. In conjunction with the N2 adsorption–desorption isotherms, discussion about the orientation, exposure of nanostructured rod domains, and derivative geometry parameters was possible. The nanostructured Co3O4 material was shown to be stable up to 800 °C whereat the decomposition to CoO takes place. The specific surface area of the nanostructured sample was raised. For the purpose of testing the photoactivity of the prepared samples, simple sorption/photodegradation tests using methylene blue as the model pollutant were performed. The degradation performance of the prepared nanostructured Co3O4 was better described by a pseudo-second-order fit, suggesting that the prepared material is worth further development toward improved and stable immobilized photocatalysts.
Synthesis and reactivity of poly(Propyleneimine) dendrimers functionalized with cyclopentadienone n-heterocyclic-carbene ruthenium(0) complexes
Cesari, Cristiana; Conti, Riccardo; Cingolani, Andrea; et al. (2020)
Catalysts
Ligand design in metal chemistry is a fundamental step when pursuing compounds with specific reactivity. In this paper, the functionalization of the OH group in the lateral chain of the N-heterocyclic-carbene (NHC) ligand bound to a bis-carbonyl cyclopentadienone NHC ruthenium(0) complex allowed the decoration of five generations of poly(propyleneimine) (PPIs) dendrimers with up to 64 organometallic moieties. The coupling was achieved by employing carbonyldiimidazole and the formation of carbamate linkages between dendritic peripheral NH2 and lateral OH groups on ruthenium complexes. The synthetic procedure, chemical purification, and spectroscopic characterization of the five generations of dendrimers (3g1–5) are here described. The ruthenium-modified dendrimers were activated as catalysts in the transfer hydrogenation of the model compound 4-fluoroacetophenone in the presence of cerium ammonium nitrate as their mononuclear congeners. The catalytic activity, being similar for the five generations, shows a decrease if compared to mononuclear complexes. This detrimental effect might be ascribed to the –CH2NH– functionalization, largely present in dendrimer skeleton and that can compete with the hydrogen transfer mechanism, but also partially to a dendritic effect caused by steric encumbrance.
PtRu Nanoparticles Deposited by the Sulfite Complex Method on Highly Porous Carbon Xerogels: Effect of the Thermal Treatment
Alegre, Cinthia; Sebastian, David; Galvez, Maria E.; et al. (2013)
Catalysts
Highly porous carbon xerogels (CXGs) were synthesized to be used as support for PtRu nanoparticles. Metal particles were deposited on CXGs by means of the sulfite complex method for the first time. Catalysts so-obtained were submitted to thermal treatment in H2, at different temperatures, in order to increase the particle size and thus the intrinsic activity. Physico-chemical characterizations included N2 physisorption, X-Ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Highly dispersed alloyed PtRu particles were obtained, with crystal sizes ranging from 1.6 to 2.0 nm. PtRu-catalysts were tested in half-cell for the methanol oxidation reaction (MOR). The resulting thermal treatment was effective in increasing both particle size and catalytic activity toward MOR.

Publications 1 - 10 of 11

Journal: Catalysts

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