Search Results (30)

In this study, tin oxide (SnO₂) resistive random-access memory (RRAM) thin films were fabricated using the thermal evaporation and radiofrequency and dc frequency sputtering techniques for metal–insulator–metal (MIM) structures. The fabrication process began with the deposition of a silicon dioxide (SiO₂) layer onto a silicon (Si) substrate, followed by the deposition of a titanium nitride (TiN) layer to serve as the bottom electrode. Subsequently, the tin oxide (SnO₂) layer was deposited as the resistive switching insulator. Two types of top electrodes were developed to investigate the influence of different oxygen concentrations on the bipolar switching, electrical characteristics, and performance of memory devices. An aluminum (Al) top electrode was deposited using thermal evaporation, while a platinum (Pt) top electrode was deposited via dc sputtering. As a result, two distinct metal–insulator–metal (MIM) memory RRAM device structures were formed, i.e., Al/SnO₂/TiN/SiO₂/Si and Pt/SnO₂/TiN/SiO₂/Si. In addition, the symmetry bipolar switching characteristics, electrical conduction mechanism, and oxygen concentration factor of the tin oxide-based memory devices using rapid thermal annealing and different top electrodes were determined and investigated by ohmic, space-charge-limit-current, Schottky, and Poole–Frenkel conduction equations in this study. Full article

The effects of Ce incorporation into trimetallic PtSnIn-supported catalysts were investigated for a propane dehydrogenation reaction with advanced characterization techniques. It was found that some Ce species exist in the form of CeAlO₃ on the reduced PtSnIn/xCe-Al catalyst, significantly enhancing the thermal stability of the alumina support. The NH₃-TPD measurements verified that the total acidity of the PtSnIn/xCe-Al catalysts decreases with the addition of Ce. The PtSnIn/1.5Ce-Al catalyst exhibits the optimal particle distribution with the smallest Pt particle size of 8.0 nm, which was revealed by TEM. The H₂-TPR and XPS results suggest that more oxidized-state Sn species form on catalyst surfaces, and the metal–support interaction can be strengthened when Ce is introduced. Furthermore, TG analysis demonstrates that Ce incorporation substantially reduces coke formation on the spent catalysts. The PtSnIn/1.5Ce-Al catalyst exhibits exceptional catalytic performance, achieving an initial propane conversion of 62.6% and maintaining a conversion of 57.2% after a 120 min reaction. In addition, the PtSnIn/1.5Ce-Al catalyst possesses high long-term stability. Over 40.0% propane conversion can be maintained after a 53 h continuous PDH reaction. These findings highlight the pivotal role of Ce in improving the structural properties and catalytic performance of PtSnIn-based catalysts for propane dehydrogenation, offering valuable insights for the design of highly efficient and stable dehydrogenation catalysts. Full article

A huge variety of chemical commodities are built from propylene molecules, and its conventional production technologies (naphtha steam cracking and fluid catalytic cracking) are unable to satisfy C₃H₆’s increasing requirements. In this scenario, Direct Propane Dehydrogenation (PDH) provides a practical and reliable route for supplying this short demand due to the economic availability of the raw material (C₃H₈) and the high propylene selectivities. The main challenges of propane dehydrogenation technology are related to the design of very active catalysts with negligible byproduct formation. In particular, the issue of catalyst deactivation by coke deposition still requires further development. In addition, PDH is a considerable endothermic reaction, and the efficiency of this technology is strictly related to heat transfer management. Thus, this current review specifically discusses the recent advances in highly dispersed bimetallic and trimetallic catalysts proposed for the PDH reaction in both conventional-heated and microwave-heated reactors. From the point of view of catalyst development, the recent research is mainly addressed to obtain nanometric and single-atom catalysts and core–shell alloys: atomically dispersed metal atoms promote the desorption of surface-bonded propylene and inhibit its further dehydrogenation. The discussion is focused on the alternative formulations proposed in the last few years, employing active species and supports different from the classical Pt-Sn/Al₂O₃ catalyst. Concerning the conventional route of energy-supply to the catalytic bed, the advantage of using a membrane as well as fluidized bed reactors is highlighted. Recent developments in alternative microwave-assisted dehydrogenation (PDH) employing innovative catalytic systems based on silicon carbide (SiC) facilitate selective heating of the catalyst. This advancement leads to improved catalytic activity and propylene selectivity while effectively reducing coke formation. Additionally, it promotes environmental sustainability in the ongoing electrification of chemical processes. Full article

The tuning sensitivity towards CO₂ detection under in-field-like conditions was investigated using SnO₂-sensitive material deposited onto Al₂O₃ substrates provided with platinum electrodes with interdigital gaps of 100 µm and 30 µm. X-ray diffraction, low-magnification and high-resolution transmission electron microscopy, and electrical and contact potential difference investigations were employed to understand the sensing mechanism involved in CO₂ detection. The morpho-structural analysis revealed that the SnO₂ nanoparticles exhibit well-defined facets along the (110) and (101) crystallographic planes. Complex phenomenological investigations showed that moisture significantly affects the gas sensing performance. The experimental results corroborated the literature evidence, highlighting the importance of Pt within the interdigital electrodes subsequently reflected in the increase in the CO₂ sensing performance with the decrease in the interdigital gap. The catalytic efficiency is explained by the distribution of platinum at the gas-Pt-SnO₂ three-phase boundary, which is critical for enhancing the sensor performance. Full article

Autothermal oxidative coupling of methane (OCM) is a highly attractive approach for methane utilization. If platinum-based catalysts are operated in short-contact-time reactors with high space velocities, high methane conversion can be achieved. Using a 1 wt.% Pt/Al₂O₃ catalyst as a benchmark, the present study elucidates how different dopants, namely Ni, Sn, and V₂O₅, affect the OCM reaction. Kinetic catalyst tests reveal that acetylene (C₂H₂) is the predominant C₂ product, irrespective of the catalyst formulation or operation conditions. Furthermore, the use of bimetallic catalysts allows either for the maintenance or even the improvement of the C₂ selectivity during OCM, which is attributed to synergistic effects that occur when expensive Pt is partially replaced by cheaper dopants. In particular, the 1 wt.% Pt/Al₂O₃ reference catalyst yielded a maximum C₂ selectivity of 8.2%, whereas the best-performing doped sample 0.25 wt.% Pt 0.75 wt.% V₂O₅/Al₂O₃ yielded a total C₂ selectivity of 11.3%. Full article

In this study, a PtSn/Al₂O₃ catalyst with bimetallic uniform distribution in the sphere was synthesized. The PDH performance and characterization analyses, such as with FTIR, XPS, and NH₃-TPD, were investigated. The effects of acid on the PDH performance were analyzed. Citric acid (CA) acted as a competing adsorbent in the preparation process of the PtSn/Al₂O₃ catalyst to synthesize the uniform catalyst. Water washing and alkali-treated samples were also studied. SEM line scanning revealed that increased the apparent concentration of Pt metal from 0.23 to 0.30 with citric acid. In contrast to the fresh PtSn/Al₂O₃ catalyst, the addition of citric acid increased the PDH selectivity from 74% to 93%. After alkali or water washing treatments, the catalyst’s selectivity further increased to 96%. Strong acid sites promoted the breaking of C–C bonds during the PDH reaction, resulting in more methane and ethylene byproducts, and decreased catalyst selectivity for fresh PtSn/Al₂O₃. From the PDH reaction thermodynamic analysis, a relatively sub-atmospheric pressure environment with a lower propane pressure could be the reasonable choice. Full article

In the propane dehydrogenation process, the structure and catalytic performance stability of the catalyst are determined by its regeneration process, which includes oxidation of coke and oxychlorination to redisperse the supported metal particles. A commercial Pt-Sn catalyst was used in this work to investigate the impact of oxidation temperature on oxychlorination performance. The catalysts after oxidation and oxychlorination were characterized by H₂-TPR, CO-DRIFTS, HAADF-STEM, XPS, and CO chemisorption. It was found that mild sintering of Pt occurred during oxidation in the temperature range of 550–650 °C, and the catalyst could be fully restored in the subsequent oxychlorination treatment. Upon oxidation of the catalyst at 700 °C, a severe aggregation of Pt and SnOx could be observed, and the catalyst could not be fully regenerated under the given oxychlorination conditions. However, PDH catalyst deactivation caused by sintering is not irreversible. By tailoring the oxychlorination conditions, the detrimental effect of high oxidation temperature on regeneration could be ruled out. During the oxidation and oxychlorination treatment, the metal tends to migrate to anchor on sites with stronger metal–support interaction, which was helpful for enhancing the catalytic activity. Full article

Increased demand for ethylene has motivated direct ethane dehydrogenation over Pt-based catalysts. PtSn/γ-Al₂O₃ and PtSnZnCa/γ-Al₂O₃ catalysts were investigated with the aim of understanding the effect of the pretreatment environment on the state of dispersed Pt for ethane dehydrogenation. The catalysts were prepared by the impregnation method and pretreated in different environments like static air (SA), flowing air (FA), and nitrogen (N₂) atmospheres. A comprehensive characterization of the catalysts was performed using Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR), NH₃ Temperature-Programmed Desorption (NH₃-TPD), X-ray photoelectron spectroscopy (XPS), and Transmission Electron Microscopy (TEM) techniques. The results reveal that the PtSn on Al₂O₃ catalyst pretreated in the static air environment (PtSn-SA) exhibits 21% ethylene yield with 95% selectivity at 625 °C. XPS analysis found more platinum and tin on the catalyst surface after static air treatment. The overall acidity of the catalysts decreased after thermal treatment in static air. Elemental mapping demonstrated that Pt agglomeration was pronounced in catalysts calcined under flowing air and nitrogen. These factors are responsible for the enhanced activity of the PtSn-SA catalyst compared to the other catalysts. The addition of Zn and Ca to the PtSn catalysts increases the yield of the catalyst calcined in static air (PtSnZnCa-SA). The PtSnZnCa-SA catalyst showed the highest ethylene yield of 27% with 99% selectivity and highly stable activity at 625 °C for 10 h. Full article

Printed circuit boards (PCBs) are the main components of e-waste. In order to reduce the negative impact of waste PCBs on human health and the environment, they must be properly disposed of. A new method is demonstrated for recycling waste PCBs. It is referred to as the high-temperature thermo-mechano-chemical gasification (TMCG) of PCBs by the detonation-born gasification agent (GA), which is a blend of H₂O and CO₂ heated to a temperature above 2000 °C. The GA is produced in a pulsed detonation gun (PDG) operating on a near-stoichiometric methane–oxygen mixture. The PDG operates in a pulsed mode producing pulsed supersonic jets of GA and pulsed shock waves possessing a huge destructive power. When the PDG is attached to a compact flow reactor filled with waste PCBs, the PCBs are subject to the intense thermo-mechano-chemical action of both strong shock waves and high-temperature supersonic jets of GA in powerful vortical structures established in the flow reactor. The shock waves grind waste PCBs into fine particles, which undergo repeated involvement and gasification in the high-temperature vortical structures of the GA. Demonstration experiments show full (above 98%) gasification of the 1 kg batch of organic matter in a setup operation time of less than 350 s. The gaseous products of PCB gasification are mainly composed of CO₂, CO, H₂, N₂, and CH₄, with the share of flammable gas components reaching about 45 vol%. The solid residues appear in the form of fine powder with visible metal inclusions of different sizes. All particles in the powder freed from the visible metal inclusions possess a size less than 300–400 μm, including a large fraction of sizes less than 100 μm. The powder contains Sn, Pb, Cu, Ni, Fe, In, Cd, Zn, Ca, Si, Al, Ti, Ni, and Cl. Among these substances, Sn (10–20 wt%), Pb (5–10 wt%), and Cu (up to 1.5 wt%) are detected in the maximum amounts. In the powder submitted for analysis, precious elements Ag, Au, and Pt are not detected. Some solid mass (about 20 wt% of the processed PCBs) is removed from the flow reactor with the escaping gas and is partly (about 10 wt%) trapped by the cyclones in the exhaust cleaning system. Metal inclusions of all visible sizes accumulate only in the flow reactor and are not detected in powder samples extracted from the cyclones. The gasification degree of the solid residues extracted from the cyclones ranges from 76 to 91 wt%, i.e., they are gasified only partly. This problem will be eliminated in future work. Full article

Printed circuit boards (PCBs) from antiquated electronic goods were processed by a pyrometallurgical route to produce and separate alloy and slag phases. The process involved initial size reduction of PCBs, followed by pyrolysis at 500 °C for 6 h and finally smelting of the solid materials in an electric furnace. A preliminary smelting test was performed at 1600 °C to estimate the composition of the slag generated. In later kilogram-scale smelting experiments, B₂O₃ flux was added along with CaO and SiO₂ to decrease the liquidus temperature required to smelt the PCBs. The level of fluxing was adapted from earlier phase equilibria studies of the CaO-Al₂O₃-SiO₂-B₂O₃ slag system. Results showed that the flux decreased the melting temperature and assisted the recovery of most valuable metals within the alloy phase at 1350 °C smelting temperature. The alloy phase recovered 99.8% of Cu, 99% of Sn, and 100% of precious metals (Au, Ag, Pt). A fluxing strategy for smelting high Al₂O₃ containing e-waste PCBs was proposed based on the experimental findings of this research. Full article

In order to improve the response characteristics of the surface acoustic wave (SAW) sensor to trace gases, a SAW CO gas sensor based on a Pd–Pt/SnO₂/Al₂O₃ film with a high-frequency response performance is proposed in this paper. The gas sensitivity and humidity sensitivity of trace CO gas are tested and analyzed under normal temperatures and pressures. The research results show that, compared with the frequency response of the Pd–Pt/SnO₂ film, the CO gas sensor based on a Pd–Pt/SnO₂/Al₂O₃ film has a higher frequency response performance, and the sensor has high-frequency response characteristics to CO gas with a concentration in the range of 10–100 ppm. The average response recovery time of 90% ranges from 33.4 s to 37.2 s, respectively. When the CO gas with a concentration of 30 ppm is tested repeatedly, its frequency fluctuation is less than 5%, indicating that the sensor has good stability. In the range of relative humidity (RH) from 25% to 75%, it also has high-frequency response characteristics for CO gas with a 20 ppm concentration. Full article

Herein, the hierarchical porous catalyst of 3-dimensional ordered macro-mesoporous (3DOMM) Al₂O₃ supported active PtSn nanoparticles (NPs) was prepared by the combined synthesized path of evaporation-induced self-assembly with colloid crystal template (EISA-CCT) methods. The hierarchical macro-mesoporous composite structure can markedly increase the specific surface area, accommodate the diffusion of propene, and decrease the number of surface acid sites. In addition, the special surface property and pore structure of 3DOMM-Al₂O₃ can modify the interaction between metals and substrates, as well as stabilize the metal nanoparticle, which promotes the formation of a highly active and stable PtSn phase. The PtSn/3DOMM-Al₂O₃ catalyst exhibits higher productivity and stability than PtSn/Al₂O₃ catalysts with macropore and mesopore structures. The PtSn/3DOMM-Al₂O₃ catalyst displays the best catalytic performance with propylene selectivity over 95% at a propane conversion of 33.9%. The study of the ordered hierarchical porous structure of PtSn/3DOMM-Al₂O₃ catalysts can contribute to obtaining improved catalysts in industrial processes. Full article

The atmospheric pressure solvothermal (APS) synthesis of nanocrystalline SnO₂ (average size of coherent scattering regions (CSR)—7.5 ± 0.6 nm) using tin acetylacetonate as a precursor was studied. The resulting nanopowder was used as a functional ink component in microextrusion printing of a tin dioxide thick film on the surface of a Pt/Al₂O₃/Pt chip. Synchronous thermal analysis shows that the resulting semiproduct is transformed completely into tin dioxide nanopowder at 400 °C within 1 h. The SnO₂ powder and the resulting film were shown to have a cassiterite-type structure according to X-ray diffraction analysis, and IR spectroscopy was used to establish the set of functional groups in the material composition. The microstructural features of the tin dioxide powder were analyzed using scanning (SEM) and transmission (TEM) electron microscopy: the average size of the oxide powder particles was 8.2 ± 0.7 nm. Various atomic force microscopy (AFM) techniques were employed to investigate the topography of the oxide film and to build maps of surface capacitance and potential distribution. The temperature dependence of the electrical conductivity of the printed SnO₂ film was studied using impedance spectroscopy. The chemosensory properties of the formed material when detecting H₂, CO, NH₃, C₆H₆, C₃H₆O and C₂H₅OH, including at varying humidity, were also examined. It was demonstrated that the obtained SnO₂ film has an increased sensitivity (the sensory response value was 1.4–63.5) and selectivity for detection of 4–100 ppm C₂H₅OH at an operating temperature of 200 °C. Full article

In this work, the fluidized bed membrane reactor (FBMR) technology for the direct dehydrogenation of propane (PDH) was demonstrated at a laboratory scale. Double-skinned PdAg membranes were used to selectively remove H₂ during dehydrogenation tests over PtSnK/Al₂O₃ catalyst under fluidization. The performance of the fluidized bed membrane reactor was experimentally investigated and compared with the conventional fluidized bed reactor (FBR) by varying the superficial gas velocity over the minimum fluidization velocity under fixed operating conditions (i.e., 500 °C, 2 bar and feed composition of 30vol% C₃H₈-70vol% N₂). The results obtained in this work confirmed the potential for improving the PDH performance using the FBMR system. An increase in the initial propane conversion of c.a. 20% was observed, going from 19.5% in the FBR to almost 25% in the FBMR. The hydrogen recovery factor displayed a decrease from 70% to values below 50%, due to the membrane coking under alkene exposure. Despites this, the hydrogen extraction from the reaction environment shifted the thermodynamic equilibrium of the dehydrogenation reaction and achieved an average increase of 43% in propylene yields. Full article

This study primarily addresses the development of dynamic, selective and economical metal–acid (bifunctional) catalysts for one-pot menthol production by citral hydrogenation. Specifically, various metals such as Pd, Pt, Ni, Cs and Sn were doped over alumina support. Additionally, bifunctional composite catalysts were also prepared with the impregnation of heteropoly acids and Pd precursors over alumina support. Analytical techniques (e.g., BET, PXRD, FT-IR, pyridine adsorption and amine titration methods) were applied for characterization of the most efficient and selective catalysts (e.g., Al₂O₃ and PTA-Cat-I). Similarly, most of the essential operational variables (e.g., loading rate of metal precursor, type of heteropoly acid, temperature, gas pressure and reaction time) were examined during this study. The experimental data shows that the bifunctional catalyst (PTA-Cat-I) produced 45% menthol at full citral substrate conversion (r = 0.038 mmoles.min⁻¹) in liquid-phase citral hydrogenation (at optimized operating conditions: 70 °C, 0.5 MPa and 8 h). However, the heteropoly acid-supported bifunctional catalysts (e.g., PTA-Cat-I, PMA-Cat-I, SMA-Cat-I and STA-Cat-I) resulted in cracking and the dehydration of isopulegol/menthol by the generation of side products (e.g., 4-isopropyl-1-methyl, cyclohex-1-ane/ene); therefore, menthol yield was extensively diminished. On the other hand, non-acidic catalysts (e.g., Cat-I, Cat-II, Cat-III, Cat-IV and Cat-V) readily promoted hydrogenation reactions. The optimum menthol yield occurred due to the presence of strong Lewis and weak Bronsted acid sites. Mass transfer and reaction rate were substantially diminished due to acidity strength, heteropoly acid type and blockage of pores by the applied bifunctional catalysts. Full article