Milivoj Plodinec

Milivoj Plodinec
Fritz Haber Institute of the Max Planck Society | FHI · Department of Inorganic Chemistry

PhD

About

63
Publications
7,141
Reads
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980
Citations
Additional affiliations
October 2016 - present
Fritz Haber Institute of the Max Planck Society
Position
  • PostDoc Position
Description
  • Operando Electron microscopy with focus on catalysis
November 2015 - December 2015
Fritz Haber Institute of the Max Planck Society
Position
  • Guest scientist
October 2011 - April 2012
Jožef Stefan Institute
Position
  • Guest scientist

Publications

Publications (63)
Article
The increasing demand for short chain olefins like propene for plastics production and the availability of shale gas make the development of highly performing propane dehydrogenation (PDH) catalysts, robust toward industrially applied harsh regeneration conditions, a highly important field of research. A combination of surface organometallic chemis...
Preprint
The increasing demand for short chain olefins like propene for plastics production and the availability of shale gas make the development of highly performing propane dehydrogenation (PDH) catalysts, robust towards industrially applied harsh regeneration conditions, a highly important field of research. A combination of surface organometallic chemi...
Preprint
The increasing demand for short chain olefins like propene for plastics production and the availability of shale gas make the development of highly performing propane dehydrogenation (PDH) catalysts, robust towards industrially applied harsh regeneration conditions, a highly important field of research. A combination of surface organometallic chemi...
Article
The cover picture show double‐helical SnBrP crystals grown in a vapor transport process and an illustration of the double helical structure with an outer [SnBr] and an inner [P]‐helix. The inset above the structure denotes the results of an HR‐TEM experiment where the rotating lattice character of SnBrP becomes obvious. As a result of very weak van...
Article
One-dimensional semiconductors are interesting materials due to their unique structural features and anisotropy, which grant them intriguing optical, dielectric and mechanical properties. In this work, we report on SnBrP, a lighter homologue of the first inorganic double helix compound SnIP. This class of compounds is characterized by intriguing me...
Article
Full-text available
Metallic copper generally adopts an FCC structure. In this work, we detect highly unusual BCC-structured Cu nanoparticles as a transient intermediate during the H 2 reduction of a Cu I precursor, [Cu 4 O t Bu 4 ],...
Article
Full-text available
Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru-and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniqu...
Article
As-prepared materials tested for a catalytic reaction are usually only precatalysts that become active and/or selective under specific conditions. During this initial formation phase, catalysts can undergo a change in their structure, morphology, chemical state, or even composition. This dynamic behavior has a vital impact on reactivity, and we ide...
Preprint
Full-text available
Iridium and its oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotential and the high corrosion resistance observed for Ir-based anodes. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode n...
Article
Full-text available
During the last decade, modern micro-electro-mechanical systems (MEMS) technology has been used to create cells that can act as catalytic nanoreactors and fit into the sample holders of transmission electron microscopes. These nanoreactors can maintain atmospheric or higher pressures inside the cells as they seal gases or liquids from the vacuum of...
Article
Full-text available
Titanium silicalite-1 (TS-1) is a zeolitic material with MFI framework structure, in which 1 to 2 per cent of the silicon atoms are substituted for titanium atoms. It is widely used in industry owing to its ability to catalytically epoxidize olefins with hydrogen peroxide (H2O2), leaving only water as a byproduct1,2; around one million tonnes of pr...
Article
Full-text available
The local composition of heterogeneous catalysts can deviate from average values obtained by integral techniques. However, due to the difficulties in capturing nontranslational parts, they are often not determined. We have examined local alterations in the metal cation distribution of open-structured orthorhombic (Mo,V)Ox by scanning transmission e...
Article
Direct Insight into the Reactivity of Pt Nanoparticles in CO Oxidation by Operando TEM and the Impact of Electron Dose Rate on Their Coarsening - Milivoj Plodinec, Hannah Nerl, Robert Schlögl, Thomas Lunkenbein
Article
Full-text available
How a catalyst behaves microscopically under reaction conditions, and what kinds of active sites transiently exist on its surface, is still very much a mystery to the scientific community. Here we present an in situ study on the red-ox behaviour of copper in the model reaction of hydrogen oxidation. Direct imaging combined with on-line mass spectro...
Article
Full-text available
Copper is a widely studied catalyst material for the electrochemical conversion of carbon dioxide to valuable hydrocarbons. In particular, copper-based nanostructures expressing predominantly {100} facets have shown high selectivity toward ethylene formation, a desired reaction product. However, the stability of such tailored nanostructures under r...
Article
Full-text available
Ag doped TiO2 photocatalysts (Ag@TiO2) were prepared with an aim to extend the absorption range of TiO2 into the visible region, for tentative application under solar irradiation. Photocatalyst synthesized by the novel method using chitosan for reduction of Ag+ to Ag0 nanoparticles was compared to similar catalysts previously reported. The photocat...
Article
Mechanical properties and stability of porous tetragonal yttria-stabilised zirconia (Y-TZ) ceramics, biomimetically coated with calcium deficient hydroxyapatite (CaDHA) to obtain a bioactive material, were investigated. The 5.7 mol% yttria-stabilised tetragonal zirconia was obtained by sol-gel process and sintered at different temperatures to obtai...
Article
Full-text available
The authors note that the formula converting the potential measured against a Ag/AgCl reference electrode to the reversible hydrogen electrode (RHE) scale (see Supporting Information of the original article) contains a sign error. It should befor EAg/AgCl0 = 0.197 V NHE and pH = 0.96. Because of this sign error, all potentials given in the publica...
Article
The Cover Feature shows an ensemble of Ag atoms differently enriched with oxygen for the ethylene epoxidation reaction. In their Full Paper, M. Lamoth et al. demonstrate that the oxygen concentration in/on Ag defines the selectivity of the Ag catalysts. Ethylene epoxide is preferentially formed on oxygen poor Ag. This effect is directly coupled to...
Article
In the present work, we report on a comparative study of model catalysts in the ethylene epoxidation reaction consisting of Ag nanoparticles < 6 nm and a reference sample ~ 100 nm operated under industrially relevant conditions. Combining catalytic data with transmission electron microscopy, thermal desorption spectroscopy, and density functional t...
Article
The structures of solids can locally differ from the macroscopic picture obtained by structural averaging techniques. This difference significantly influences the performance of any functional material. Measurements of these local structures are challenging. Thus, the description of defects is often disregarded. However, in order to understand the...
Article
Full-text available
Understanding how catalysts work during chemical reactions is crucial when developing efficient catalytic materials. The dynamic processes involved are extremely sensitive to changes in pressure, gas environment and temperature. Hence, there is a need for spatially resolved operando techniques to investigate catalysts under working conditions and o...
Article
Full-text available
Synthesis gas, composed of H2 and CO, is an important fuel which serves as feedstock for industrially relevant processes, such as methanol or ammonia synthesis. The efficiency of these reactions depends on the H2: CO ratio, which can be controlled by a careful choice of reactants and catalyst surface chemistry. Here, using a combination of environm...
Article
Full-text available
The functionality of heterogeneous catalysts is influenced by a delicate interplay of multiple parameters, including morphology and structure, chemical potential gradients and related dynamics. Here, we report on how these factors are interconnected. Combining time-resolved transmission electron microscopy imaging and selected area electron diffrac...
Article
Full-text available
ZnO has prominent electron transport and optical properties, beneficial for photovoltaic application, but its surface is prone to the formation of defects. To overcome this problem, we deposited nanostructured TiO2 thin film on ZnO nanorods to form a stable shell. ZnO nanorods synthesized by wet-chemistry are single crystals. Three different proced...
Article
Thin-films of vertically aligned titanium dioxide nanotubes are key constituents of charge transfer layers in 3rd generation photovoltaics. The beneficial charge transport primarily occurs due to the favourable microstructural features, i.e. the large effective surface-to-volume ratio. Here measuring methods are selected which are sensitive to micr...
Article
Full-text available
Multimodal Operando Electron Microscopy Approach to Study Pt Catalyst During CO Oxidation Reaction - Volume 25 Supplement - M. Plodinec, E. Stotz, L. Sandoval-Diaz, R. Schlögl, T. Lunkenbein
Article
Invited for the cover of this issue are Dr. Elias Frei and co‐workers from the Inorganic Chemistry Department of the Fritz‐Haber‐Institute of the Max‐Planck‐Gesellschaft, Berlin, and Dr. Frank Rosowski from BasCat/BASF, Ludwigshafen, Germany. The cover image shows three different hourglasses underlining the importance of the reaction time for the h...
Article
Full-text available
The Front Cover shows hexagonal platelets of various delafossites AgBO2 (B: Al, Ga, In) obtained from rapid hydrothermal synthesis. Due to their metastable nature under hydrothermal conditions, the synthesis time is crucial, as indicated by the hourglass designs. The selected isoelectronic group 13 B‐site atoms, symbolized by the colors of the plat...
Article
Full-text available
Supported Ag catalysts on silica and corundum have been synthesized applying an improved impregnation technique. The resulting Ag parti-cle sizes can be divided into three categories concerning: (I) bulk-like, (II) nanoparticles of 1 – 6 nm and (III) in-situ created Ag clusters below 1 nm. Ag nanoparticles and bulk-like Ag are investigated concerni...
Article
Full-text available
During the electrochemical reduction of oxygen, platinum catalysts are often (partially) oxidized. While these platinum oxides are thought to play a crucial role in fuel cell degradation, their nature remains unclear. Here, we studied the electrochemical oxidation of Pt nanoparticles using in situ XPS. By sandwiching the particles between a graphen...
Article
Iridium oxide based catalysts are uniquely active and stable in the oxygen evolution reaction. Theoretical work attributes their activity to oxyl, or µ1-O, species. Verifying this intermediate experimentally has, however, been challenging. In the present study, these challenges were overcome by combining theory with new experimental strategies. Ab...
Article
A single‐step rapid hydrothermal low‐temperature process for the formation of high purity polycrystalline Ag‐based delafossite oxides 3R‐AgBO2 (B: Al, Ga, In) is reported. For the synthesis process reusable and widely available PTFE‐lined pressure vessels are used. The presence of an elemental Ag by‐phase is traced back to the metastability of the...
Article
An electrode for the oxygen evolution reaction based on a conductive bi-layered free standing graphene support functionalized with iridium nanoparticles was fabricated and characterized by means of potentiometric and advanced X-ray spectroscopic techniques. It was found that the electrocatalytic activity of iridium nanoparticles is associated to th...
Article
Novel forms of black TiO2 nanotubes-based photocatalysts for water purification were prepared. Two features were combined: decoration of TiO2 nanotube arrays with Ag nanoparticles (sample TiO2-NT'[email protected]) and further hydrogenation of this material (TiO2-NT'[email protected]). Obtained photocatalysts show high efficiency for degradation of...
Article
The properties of nanocrystals are highly depending on their morphology, composition and structure. Tailored synthesis over these parameters is successfully applied for the production of nanocrystals with desired properties for specific applications. However, in order to get a full control over the properties, the behavior of nanocrystals under ext...
Article
Spontaneous precipitation of CaCO3 polymorphs in the presence of selected amino acids (AA) has been investigated. The L-aspartic acid (Asp), L-lysine (Lys), L-asparagine (Asn), L-tyrosine (Tyr), L-phenylalanine (Phe), L-serine (Ser) and L-alanine (Ala) were selected because of different charge and polarity of their side chains at applied experiment...
Article
Amorphous calcium carbonate (ACC) and calcium phosphate (ACP) increasingly attract attention as initial solid phases in vertebrate and invertebrate hard tissue formation, as well as in materials science as a possible new synthetic route for advanced materials preparation. Although much is known about these two amorphous phases and similarities in t...
Article
We prepared the anatase nanotubes (NT) and other nanostructured titania as electron accepting/transmitting layers in solar cells, using titanium anodization. Upon gaining control over the anodization, the parameters were held constant in order to observe the role of the deposited layers (by electron beam evaporation and magnetron sputtering) on the...
Poster
Full-text available
Besides geological forms, calcium carbonate occurs as an important biomineral, organic-inorganic hybrid material, formed by biological organisms. Morphology of such crystals is predominantly controlled by present organic macromolecules, mostly glycoproteins, responsible for gel-like properties of matrix. Crystals formed in such environment meet var...
Article
Titania powders were prepared by solvothermal process from titanium n-butoxide and ethyl acetoacetate modified titanium n-butoxide. The prepared samples were characterized using X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM/TEM) with selected area electron diffraction (SAED), differential thermal and thermo-gravimetric...
Chapter
TiO2 nanostructures with promising physical and chemical properties, such as a high specific surface area, a high photo-activity and environmental stability, but also the low costs of synthesis inspire numerous studies over the past three decades. Titania nanostructures can be used for photo-catalysis, in solar cells (DSSC) and sensors, still it ca...
Chapter
Full-text available
TiO2 as the material exhibits properties that allow its use in various applications such as photocatalysts, solar cells, gas sensors, and biomedical applications. The typical organic solar cells are produced on transparent conductive layers covered with nanostructured TiO2. The surface roughness is one of the key parameters for high efficiency. In...
Chapter
TiO2 is known as material with excellent chemical and photochemical stability. It exists in three different crystalline phases: anatase, rutile and brookite. It was found that anatase is photocatalytically more active than rutile due to its large surface area. This activity depends not only on the phase of TiO2 but also on the crystallite size and...
Poster
In this research the crystallization of calcium carbonate in alginate hydrogel matrix, containing the amino acids (Tyr, Asp) which are found at significant amount in proteins supposed to be relevant for biomineralization, is investigated. The precipitation model system comprised alginate hydrogel beads, made by ionotropic gelation and mineralized b...
Article
Full-text available
Thin ZnO:Al layers were deposited by pulsed laser deposition in vacuum and in oxygen atmosphere at gas pressures between 10 and 70 Pa and by applying radio-frequency (RF) plasma. Grazing incidence small angle x-ray scattering and grazing incidence x-ray diffraction (GIXRD) data showed that an increase in the oxygen pressure leads to an increase in...
Article
Full-text available
Nano-rippled graphene, a structurally modified graphene, presents a novel material with a large range of possible applications including sensors, electrodes, coatings, optoelectronics, spintronics and straintronics. In this work we have synthesized macroscopic single layer graphene with well-defined uniaxial periodic modulation on a stepped Ir(332)...
Poster
Calcium carbonates could be biomineralized by different invertebrate organisms, either in a form of certain polymorph (calcite, vaterite and aragonite) or hydrated modification. The formation of specific crystal modification or appearance of appropriate morphological form can be influenced by parameters like temperature, pH or supersaturation, as w...
Article
The present research focuses on the comparative investigation of the acid–base surface properties (the isoelectric point, pHiep and point of zero charge, pHpzc) of one-dimensional TiO2 nanomaterials. Different one-dimensional TiO2 nanomaterials, nanotubes (NTs) and nanowires (NWs) were prepared by an alkaline hydrothermal synthesis procedure. The s...
Article
This work highlights the importance of in situ experiments for an improved understanding of graphene growth on copper via metal-catalyzed chemical vapor deposition (CVD). Graphene growth inside the chamber of a modified environmental scanning electron microscope under relevant low-pressure CVD conditions allows visualizing structural dynamics of th...
Article
Full-text available
The persistent photoconductivity (PPC) effect in nanotube arrays of barium titanate and TiO2 (BTO/TiO2NT) was studied at room temperature under daylight illumination. The BTO/TiO2NT heterostructures exhibited a giant PPC effect that was six orders of magnitude higher than the dark conductivity, followed by a slow relaxation for 3 h. The PPC in this...
Article
Full-text available
Protonated titanate nanotubes (TiNT-H) were surface-modified with (3-aminopropyl)trimethoxy silane (APTMS) by a novel method suitable for the syntheses of large amounts of materials at a low cost. The usage of prepared nanotubes for polymer reinforcement was studied. Since the thermal stability of the nanofiller was important to preserve its functi...
Article
Titanate nanotubes (TiNTs) and silver-decorated titanate nanotubes (TiNTs@Ag) were synthesized using the hydrothermal method. In the decorated nanotubes the silver particles were obtained by the photoreduction of AgNO3 under UV light. Pure and Ag-decorated nanotubes were high-temperature heat treated at 550 °C in a hydrogen atmosphere and the “core...
Article
In the present work, multiphase polycrystalline BTO nanorods were synthesized using template-assisted sol–gel deposition and their structural evolution was studied using thermo Raman spectroscopy, X-ray diffractometry and high-resolution transmission electron microscopy (HRTEM). In the BTO nanorods, the tetragonal phase was the dominant one, while...
Article
Structural stability of nanostructured titanates was investigated for further processing and possible applications. With the aim to investigate their mechanochemical stability we applied highenergy ball milling and studied induced phase transitions. Hydrogen titanates having two different morfologies, microcrystals and nanotubes, were taken into co...
Article
Titanate nanotubes were synthesized by hydrothermally treating the TiO2 powder with NaOH solution. Their formation and thermal stability was discussed in the view of different TiO2 precursors and Na+ content. The starting precursors for nanotube synthesis were either anatase or the mixture of anatase, rutile and high-pressure TiO2 II phase (TiO2 II...

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Projects

Projects (4)
Project
The development of in situ/operando electron microscopy techniques that enable characterizations of the active catalyst and associated dynamic processes under relevant catalytic conditions. The aim is to obtain key insights into better understanding of the structure-function relationships on a atomic scale in order to establish guidelines for a rational design of better catalysts.
Project
The aim of the project is to study surface composition changes of macro-porous beta-tricalcium phosphate scaffolds for bone implants induced during immersion in cells media. The purpose is to understand the influence of shape and size of the pores in ceramics on response of MG63 osteoblasts cells on bio-ceramics, as well as the influence of cells and/or cell solution on phase transition of ceramic materials, beta-tricalcium phosphates (β-TCP).
Archived project
Bioinspired materials – Formation Mechanisms and Interaction (Bio-Mat-Form) is a project supported by Croatian science foundation. It combines biomineralization and material chemistry.