Surface Chemistry and Catalysis / "Ilie Murgulescu" Institute of Physical Chemistry of Romanian Academy "Ilie Murgulescu" Institute of Physical Chemistry of Romanian Academy
Ti-zeolite Y based nanocomposites modified with Au and CeO2 with photocatalytic activity in visible light Gabriela Petcu, Elena M. Anghel, Irina Atkinson, Florica Papa, Nicoleta G. Apostol, Adriana Baran, Simona Petrescu, Bogdan Trica, Krasimir Tenchev, Silviya Todorova, Viorica Parvulescu Catalysis Today, 2025 Two series of photocatalysts (TYAu, TYCeAu) were obtained. Ti was incorporated by direct synthesis with zeolite Y, while Ce and Au were immobilized by double incipient wetness impregnation method. The experimental weight percents (XRF analysis) were for titanium (0.7%, 1.9%, 3.5%), Ce (1%), and Au (0.3%, 0.1). The typical crystalline structure of zeolite Y was preserved in all samples except those with 3.5% Ti, where XRD revealed reduced pattern intensity. SEM and TEM analyses showed morphological changes at higher Ti contents. CO₂-TPD confirmed a decrease in basicity with increasing Ti, consistent with the diminished zeolite contribution. XPS analysis indicated the presence of varying Au 0 /Au⁺ and Ce³ + /Ce 4+ ratios on the surface, depending on the Ti content. The intra- and extraframework TiO 2 as amorphous or anatase phases were Raman confirmed in cerium-containing samples. For materials with high Ti content, the dominant effect was from the Ce and Ti species, accentuated by gold. The surface plasmon resonance effect of Au nanoparticles and decreasing in band gap energy after Ce immobilization was evidenced by UV-Vis spectroscopy. The photocatalytic properties of the synthesized materials were evaluated in CO 2 reduction with water and H 2 production via water splitting under visible light (525 nm). Higher Ti content enhanced CO 2 conversion and reduced CH 4 selectivity, favoring the production of CH 3 OH and CH 2 O. A greater amount of hydrogen was produced by the samples with the lowest Ti concentration while the reaction was favored by the presence of cerium in the rich titanium samples.
Effect of Modifying NiNbO Catalyst with Tetravalent (Sn, Ti) and Pentavalent (Sb, Ta) Cations on Its Ethane Oxidative Dehydrogenation Performance Ştefan-Bogdan Ivan, Ionel Popescu, Catalin Negrilă, Florica Papa, Stéphane Loridant, Ioan-Cezar Marcu Industrial and Engineering Chemistry Research, 2025 The purpose of this study was to investigate the effect of the addition of a third cation, M (M = Ti, Sn, Sb and Ta) on the physicochemical properties and catalytic performance of the Nb-containing NiO catalyst (Ni 0.85 Nb 0.15 O) during ethane oxidative dehydrogenation to ethylene. Hydrothermal and solvent evaporation methods were used for the preparation of tricationic oxides of type Ni 0.765 Nb 0.135 M 0.1 O, which were then calcined at 450 °C. The catalysts were characterized by XRD, SEM-EDX, H 2 -TPR, MicroRaman, and XPS, and evaluated via in situ electrical conductivity measurements under varying conditions. The findings indicate that the addition of a third cation substantially changes the structural, electronic and redox properties of the NiNbO system, with considerable effects on its catalytic activity in the oxidative dehydrogenation of ethane. Among all the catalysts tested, the Ta(5)–NiNbO-8 sample─a 5 at % Ta-doped NiNbO catalyst prepared under alkaline conditions (pH 8)─exhibited the best performance: 40% ethane conversion and 75% ODH selectivity at 350 °C. It outperforms the undoped NiNbO system in terms of both ethane conversion and ethylene selectivity over the whole temperature range studied. Its superior behavior is attributed to an optimal balance between redox ability and surface composition, particularly a reduced density of nonselective active species and enhanced lattice oxygen exchangeability under reaction conditions. However, none of the catalysts, including Ta(5)–NiNbO-8, demonstrated sustained stability at 400 °C. Progressive deactivation was linked to a gradual loss of p-type conductivity and diminished reoxidation capacity, consistent with a decrease in the density of active lattice O – species. Surface compositional changes together with structural changes were also associated with catalyst deactivation. These results demonstrate how important the type of dopant is in adjusting the physicochemical characteristics and catalytic activity of Nb-promoted NiO systems for ethane ODH. Future efforts will focus on exploring additional high-valence dopants and surface modifications to improve long-term stability and ODH selectivity.
Mono-(Ni, Au) and Bimetallic (Ni-Au) Nanoparticles-Loaded ZnAlO Mixed Oxides as Sunlight-Driven Photocatalysts for Environmental Remediation Monica Pavel, Liubovi Cretu, Catalin Negrila, Daniela C. Culita, Anca Vasile, Razvan State, Ioan Balint, Florica Papa Molecules, 2025 A facile and versatile strategy to obtain NPs@ZnAlO nanocomposite materials, comprising controlled-size nanoparticles (NPs) within a ZnAlO matrix is reported. The mono-(Au, Ni) and bimetallic (Ni-Au) NPs serving as an active phase were prepared by the polyol-alkaline method, while the ZnAlO support was obtained via the thermal decomposition of its corresponding layered double hydroxide (LDH) precursors. X-ray diffraction (XRD) patterns confirmed the successful fabrication of the nanocomposites, including the synthesis of the metallic NPs, the formation of LDH-like structure, and the subsequent transformation to ZnO phase upon LDH calcination. The obtained nanostructures confirmed the nanoplate-like morphology inherited from the original LDH precursors, which tended to aggregate after the addition of gold NPs. According to the UV-Vis spectroscopy, loading NPs onto the ZnAlO support enhanced the light absorption and reduced the band gap energy. ATR-DRIFT spectroscopy, H2-TPR measurements, and XPS analysis provided information about the functional groups, surface composition, and reducibility of the materials. The catalytic performance of the developed nanostructures was evaluated by the photodegradation of bisphenol A (BPA), under simulated solar irradiation. The conversion of BPA over the bimetallic Ni-Au@ZnAlO reached up to 95% after 180 min of irradiation, exceeding the monometallic Ni@ZnAlO and Au@ZnAlO catalysts. Its enhanced activity was correlated with good dispersion of the bimetals, narrower band gap, and efficient charge carrier separation of the photo-induced e−/h+ pairs.
Effect of Mg/Al Molar Ratio on the Catalytic Performance of Cu-MgAlO Mixed Oxide Catalysts in the Hydrodeoxygenation of Benzyl Alcohol Claudiu-Eduard Rizescu, Chao Sun, Florica Papa, Paul Mereuţă, Constantin Cătălin Negrilă, Ionel Popescu, Patrick Da Costa, Adriana Urdă, Ioan-Cezar Marcu Energy and Fuels, 2025 The catalytic hydrodeoxygenation (HDO) of lignocellulose-derived pyrolysis oil is a critical process for producing high-quality biofuels. This study investigates the effect of the Mg/Al molar ratio on the catalytic performance of CuMg(Al)O mixed oxide catalysts in the HDO reaction of benzyl alcohol as a model oxygenated compound. They were synthesized by coprecipitation with a fixed Cu content of 15 at. %, with respect to cations, and different Mg/Al molar ratios (0/1, 1/1, 3/1, 5/1, and 1/0). The catalysts were characterized using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), UV–vis spectroscopy, nitrogen adsorption–desorption isotherms, temperature-programmed reduction with hydrogen (H 2 -TPR), and temperature-programmed desorption (TPD) of CO 2 and NH 3 . It has been shown that the Mg/Al molar ratio strongly influences the physicochemical characteristics of the CuMg(Al)O mixed oxides and, hence, their catalytic performance. Catalytic tests were conducted in a stainless-steel autoclave reactor and the obtained results indicated that the systems with Mg/Al molar ratios of 3/1 and 5/1, issued from layered double hydroxide precursors, exhibited the highest activity, with yields to toluene higher than 85%. This superior performance is attributed to the well-dispersed copper species on the catalyst surface combined with appropriate acid–base properties. As the CuMg(Al)O system with Mg/Al molar ratio of 5/1 was the best in terms of benzyl alcohol conversion, i.e., ca. 98% at 230 °C, under 5 atm of H 2, for 3 h of reaction time, with high selectivity to toluene of ca. 87%, the influence of the reaction time, temperature and reusability over multiple reaction cycles on its performance were investigated.
The Effect of the Metal Oxide as the Support for Silver Nanoparticles on the Catalytic Activity for Ammonia Ozonation Razvan-Nicolae State, Maria-Alexandra Morosan, Liubovi Cretu, Alexandru-Ioan Straca, Anca Vasile, Veronica Bratan, Daniela Culita, Irina Atkinson, Ioan Balint, Florica Papa Catalysts, 2025 Ammonia is one of the common inorganic pollutants in surface waters. It can come from a wide range of sources through the discharge of wastewater (industry, agriculture, and municipal waters). Catalytic ozonation reaction can efficiently remove ammonia nitrogen without introducing other pollutants and improve the nitrogen selectivity of reaction products by controlling the reaction conditions. Catalysts based on silver nanoparticles (Ag NPs) have shown excellent O3 decomposition performance; therefore, they are promising catalysts for catalytic ammonia ozonation due to their high reactivity, stability, and selectivity to N2. In this study, we synthesized well-defined silver nanoparticles (Ag NPs) using a modified alkaline polyol method and then dispersed them on solid oxide supports (Fe3O4, TiO2, and WO3). Before being deposited on the oxide support, the silver nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-VIS spectroscopy. The obtained catalysts, Ag_Fe3O4, Ag_TiO2, and Ag_WO3 were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area analysis, UV-VIS spectroscopy, temperature-programmed reduction (H2-TPR), and temperature-programmed desorption (TPD) of CO2 and NH3. It has been demonstrated that the nature of the support significantly influences the physicochemical properties of the catalysts, as well as their catalytic performance in ammonia ozonation reaction.
Optimizing nanocasting techniques for stable bismuth-mesoporous silica composites in thermal energy storage application Daniel Lincu, Simona Ioniță, Mihaela Deaconu, Florica Papa, Bogdan Trică, Cristian Matei, Daniela Berger, Raul-Augustin Mitran Sustainable Materials and Technologies, 2024 Economically storing solar energy for use throughout the night is a major challenge facing the widespread transitions towards green energy generation and combating global warming. While most efforts are focused on electrochemical batteries, storing solar energy as heat is a viable alternative. Phase change materials (PCMs) utilize the solid – liquid transition to reversibly store heat at a constant temperature. The leakage of the molten phase limits the use of PCMs, but it can be alleviated by impregnation into porous matrices. Metals can be used for high temperature stationary heat storage, but are incompatible with oxide matrices due to the large difference in density and surface tension. The optimization of mesoporous silica – bismuth composites synthesis through nanocasting followed by reduction is reported. The resulting materials exhibit metallic bismuth both inside the mesopores and as an interparticle phase, leading to materials with stability towards oxidation, reversible heat storage, shape stability and reliability. A nanoconfined Bi phase could be obtained for low reaction times (4 h) and temperatures (125 °C) and it is correlated with increased stability towards oxidation in air. The samples with 50 % wt. metal retain their macroscopic shape above the metal melting point without leakage. All composites retain 50–96 % of their theoretical heat of fusion, which remains unchanged after 50 heating – cooling cycles. Nanocasting metal salts under hydrophobic solvents is a promising route for obtaining nanocomposites for thermal energy storage with both nanoconfined and interparticle metal phases. • Mesoporous silica (MSN) acts as matrix for molten bismuth. • Shape-stabilized phase change materials obtained through nanocasting. • Distinct melting/crystallization evens for interparticle and bulk metal phases. • Low temperatures and reaction times are the optimum synthesis conditions.
Correlation of the Sr-dopant content in La1-XSrXCoO3 with catalytic activity for hydrogen peroxide decomposition Revue Roumaine De Chimie, 2018
Oxide powders from tartaric acid Mg/Zr coordination compounds with CO2 adsorption properties Revista Romana De Materiale Romanian Journal of Materials, 2018
Enhanced photocatalytic activity of ZnO nanoparticles obtained by “green” synthesis with well dispersed Pd-Au bimetallic nanoparticles Revue Roumaine De Chimie, 2018
Impact of RbLaTa2O7 layered perovskite synthesis conditions on their activity for photocatalytic abatement of trichloroethylene Revue Roumaine De Chimie, 2018
Thermosensitive triblock copolymer templated synthesis of Pt-Cu supported on TiO2: Investigation of their catalytic activity for CO oxidation reaction Revue Roumaine De Chimie, 2018
Synthesis and characterization of pvp (Polyvinyl pyrrolidone) stabilized gold nanoparticles Revista Romana De Materiale Romanian Journal of Materials, 2015