1. Non-oxidative calcination enhances the methane dry reforming performance of ▫$Ni/CeO_{2−x}$▫ catalysts under thermal and photo-thermal conditionsKristijan Lorber, Vasyl Shvalya, Janez Zavašnik, Damjan Vengust, Iztok Arčon, Matej Huš, Andraž Pavlišič, Janvit Teržan, Uroš Cvelbar, Blaž Likozar, Petar Djinović, 2024, izvirni znanstveni članek Opis: We analyzed the effect of the calcination atmosphere and visible-light contribution to an accelerated
reaction rate and improved H2 selectivity over 2 wt% Ni/CeO2−x nanorod catalysts. Spectroscopic and
structural characterization was performed by operando DRIFTS, in situ Raman, UV-vis and XAS
techniques, which were complemented by DFT calculations. Calcination in an argon or H2 atmosphere
yields 15% more active catalysts in the thermally driven reaction, which are also more susceptible to
light-induced rate acceleration compared to the catalyst calcined in air. The most active 2Ni/CeO2
catalyst calcined in hydrogen converts methane with a rate of 7.5 mmol (gcat min)−1 and produces a H2/
CO ratio of 0.6 at 460 °C when stimulated by a combination of visible light and thermal energy. In the
absence of visible light illumination and at an identical catalyst temperature, the achieved methane rate
was 4.2 mmol (gcat min)−1 and the H2/CO ratio was 0.49. The non-oxidative calcination improves nickel
dispersion and the formation of subnanometer sized Ni clusters, together with a higher abundance of
surface and bulk oxygen vacancies in ceria nanorods. The Ni–Ov–Ce3+components constitute the
catalytically active sites under visible light illumination, which enable the DRM reaction to proceed with
an Ea value of 20 kJ mol−1. Visible light also induces the following changes in the 2Ni/CeO2−x catalyst
during the DRM reaction: (1) decomposition and desorption of carbonates from the nickel–ceria
interface sites, (2) reduced population of nickel surface with carbonyl species and (3) promoted
adsorption and dissociation of methane.
Ključne besede: methane dry reforming performance, calcination
Objavljeno v RUNG: 05.07.2024; Ogledov: 1079; Prenosov: 18
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2. Polythiacalixarene-embedded gold nanoparticles for visible-light-driven photocatalytic CO [sub] 2 reductionTina Škorjanc, Kamal Khaja Mohaideen, Ayesha Alkhoori, Gregor Mali, Abdul Khayum Mohammed, Zouhair Asfari, Kyriaki Polychronopoulou, Blaž Likozar, Ali Trabolsi, Dinesh Shetty, 2022, izvirni znanstveni članek Ključne besede: Gold, Materials, Metal nanoparticles, Photocatalysis, Polymers
Objavljeno v RUNG: 13.07.2022; Ogledov: 2424; Prenosov: 0
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3. CO[sub]2 activation over nanoshaped CeO[sub]2 decorated with nickel for low-temperature methane dry reformingKristijan Lorber, Janez Zavašnik, Iztok Arčon, Matej Huš, Janvit Teržan, Blaž Likozar, Petar Djinović, izvirni znanstveni članek Opis: Dry reforming of methane (DRM) is a promising way to
convert methane and carbon dioxide into H2 and CO (syngas). CeO2
nanorods, nanocubes, and nanospheres were decorated with 1−4 wt % Ni.
The materials were structurally characterized using TEM and in situ
XANES/EXAFS. The CO2 activation was analyzed by DFT and
temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO2 morphologies expose {111} and {100} terminating facets,
varying the strength of the CO2 interaction and redox properties, which
influence the CO2 activation. Temperature-programmed CO2 DRIFTS
analysis revealed that under hydrogen-lean conditions mono- and bidentate
carbonates are hydrogenated to formate intermediates, which decompose
to H2O and CO. In excess hydrogen, methane is the preferred reaction
product. The CeO2 cubes favor the formation of a polydentate carbonate
species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria’s surface, resulting in
less-abundant surface sites for CO2 dissociation
Ključne besede: surface carbonates, in situ characterization, Ni XANES, Ni EXAFS, spectator species, CeO2 nanoshapes, CO2 activation
Objavljeno v RUNG: 13.07.2022; Ogledov: 2540; Prenosov: 0
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4. Photo-Chemically-Deposited and Industrial Cu/ZnO/Al2O3 Catalyst Material Surface Structures During CO2 Hydrogenation to Methanol: EXAFS, XANES and XPS Analyses of Phases After Oxidation, Reduction, and ReactionMaja Pori, Iztok Arčon, Venkata Dasireddy, Blaž Likozar, 2021, izvirni znanstveni članek Opis: Industrial Cu/ZnO/Al2O3 or novel rate catalysts, prepared with a photochemical deposition method, were studied under functional CH3OH synthesis conditions at the set temperature (T) range of 240–350 °C, 20 bar pressure, and stoichiometric carbon dioxide/hydrogen composition. Analytical scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray adsorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) methods were systematically utilized to investigate the interfaces, measured local geometry, and chemical state electronics around the structured active sites of commercially available Cu/ZnO/Al2O3 material or synthesized Cu/ZnO. Processed Cu K-edge EXAFS analysis suggested that various Cu atom species, clusters, metallic fcc Cu, Cu oxides (Cu2O or CuO) and the Cu0.7Zn2 alloy with hexagonal crystalline particles are contained after testing. It was proposed that in addition to the model’s Cu surface area, the amount, ratio and dispersion of the mentioned bonded Cu compounds significantly influenced activity. Additionally, XPS revealed that carbon may be deposited on the commercial Cu/ZnO/Al2O3, forming the inactive carbide coating with Cu or/and Zn, which may be the cause of basicity’s severe deactivation during reactions. The selectivity to methanol decreased with increasing T, whereas more Cu0.7Zn2 inhibited the CO formation through reverse water–gas shift (RWGS) CO2 reduction.
Ključne besede: CH3OH synthesis, Cu/ZnO-based catalyst, XPS, XANES, EXAFS analyses, Catalyst selectivity and activity
Objavljeno v RUNG: 03.06.2021; Ogledov: 3246; Prenosov: 0
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5. Effect of Na, Cs and Ca on propylene epoxidation selectivity over CuOx/SiO2 catalysts studied by catalytic tests, in-situ XAS and DFTJanvit Teržan, Matej Huš, Iztok Arčon, Blaž Likozar, Petar Djinović, 2020, izvirni znanstveni članek Opis: This research focuses on epoxidation of propylene over pristine, Na, Ca and Cs modified
CuOx/SiO2 catalysts using O2. The selectivity of the reaction is analyzed using a combination
of catalytic tests, in-situ XAS and DFT calculations. The initially present subnanometer CuO
clusters are present in all catalysts which re-disperse/flatten during reaction. During catalytic
reaction, the Cu1+ becomes the predominant oxidation state. There is no correlation between
propylene oxide (PO) selectivity and copper oxidation state. DFT analysis of the propylene
reaction pathway revealed that Na, Cs, and Ca addition decreases the bonding strength of
propylene to CuO and decreases the O2 activation barrier, while simultaneously increase the
exothermicity of O2 dissociation. The Na induced Cu-O bond modification decreases the
activation barrier from 0.87 to 0.71 eV for the oxametallacycle (OMC) ring closure (first step
in the reaction pathway favoring selectivity towards PO) compared to pristine 5Cu catalyst.
At the same time, we observed an increase (from 0.45 to 0.72 eV) of the barrier for the
abstraction of allylic hydrogen. The opposite effect is achieved by Ca addition: the activation
barrier for OMC ring closure increases to 1.08 eV and that for allylic hydrogen stripping
decreases to 0.16 eV.
Ključne besede: Alkali modification, propylene epoxidation, reaction mechanism, copper oxide, activation barrier.
Objavljeno v RUNG: 05.06.2020; Ogledov: 3705; Prenosov: 0
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6. Synthesis of a Cu/ZnO Nanocomposite by Electroless Plating for the Catalytic Conversion of CO2 to MethanolMaja Pori, Iztok Arčon, Damjan Lašič Jurković, Marjan Marinšek, Goran Dražić, Blaž Likozar, Zorica Crnjak Orel, 2019, izvirni znanstveni članek Opis: The process of methanol synthesis based on the hydrogenation of CO2
was investigated over binary Cu/ZnO catalyst materials,
prepared by applying a novel electroless plating fabrication method. The activity of the produced catalytic samples
was determined at temperature range between 200 and 300 °C and the feedstock conversion data were supplemented with
a detailed microstructure analysis using high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction
(XRD) and Cu and Zn K-edge, X-ray absorption near-edge structure (XANES) measurements and extended X-ray
absorption fine-structure (EXAFS) measurements. It was confirmed that the disorder in the Cu crystallites created unique
geometrical situations, which acted as the additional reactive centres for the adsorption of the reactant molecule species.
Copper and zinc structural synergy (spill-over) was also demonstrated as being crucial for the carbon dioxide’s activation.
EXAFS and XANES results provide strong evidence for surface alloying between copper and zinc and thus the present results
demonstrate new approach applicable for explaining metal–support interactions.
Ključne besede: EXAFS, CuZn alloy, Spillover mechanism, CO2 valorization, Electroless deposition method, Heterogeneous
catalysis
Objavljeno v RUNG: 12.04.2019; Ogledov: 4593; Prenosov: 0
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7. Okolju prijazna sinteza metanola s hidrogeniranjem ogljikovega dioksida preko trikomponentnih katalizatorjevTeja Cankar, 2017, diplomsko delo Opis: Zaradi naraščanja koncentracije CO2 v ozračju in njenega negativnega vpliva na okolje, se išče načine, s katerimi bi to koncentracijo zmanjšali. Ena izmed možnosti je direktna hidrogenacija atmosferskega CO2 do metanola, s čimer bi CO2 uporabili kot surovino, hkrati pa pridobili metanol, ki je uporabna kemikalija. Ta proces zahteva uporabo učinkovitega in stabilnega katalizatorja ter optimalne reakcijske pogoje. V tem raziskovalnem delu smo s katalitičnimi testi proučevali vpliv reakcijskih pogojev, različnih komponent katalizatorja in sinteznih metod na učinkovitost katalizatorjev za sintezo metanola. Kot optimalna temperatura in tlak sta se izkazala območja od 220 do 240 °C in od 40 do 50 barov, kjer je reakcija dovolj hitra, hkrati pa še ni bistveno termodinamsko zavrta, in pride do zadostne količine sintetiziranega metanola. Kot najbolj učinkovito molsko razmerje plinov se je izkazalo H2 : CO2 = 3 : 1 in kot najbolj učinkovita plinska urna prostorska hitrost 6000 h-1. To sta pogoja, kjer je količina sintetiziranega metanola zadosti velika ob sprejemljivi porabi reaktantov. Kot najbolj učinkovit katalizator se je izkazal komercialno uporabljen HiFUEL®, dobre lastnosti pa sta pokazala tudi CuO/MgO/Al2O3 in CuO/ZnO/CeO2. CuO/MgO/Al2O3 katalizator je dobro aktiven v širšem temperaturnem območju (220–260 °C), njegova aktivnost je okoli 0,6 molCH3OH•l-1•h-1. Prednost CuO/ZnO/CeO2 katalizatorja pa je izredno visoka selektivnost, in sicer pri 220 °C približno 65 %.
Ključne besede: hidrogenacija CO2, sinteza metanola, učinkovitost katalizatorjev, reakcijski pogoji, različna sestava katalizatorjev
Objavljeno v RUNG: 17.11.2017; Ogledov: 6836; Prenosov: 265
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