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25 pages, 5735 KB  
Article
Surface Modification of AZ31 Mg Alloy Based on PLA or PLGA with Caffeic Acid for Bioengineering Applications
by Karol Kyzioł, Janusz Prażuch, Marcin Gołąbczak, Agnieszka Kyzioł, Marek Hebda and Stanisława Kluska
Coatings 2025, 15(11), 1309; https://doi.org/10.3390/coatings15111309 - 10 Nov 2025
Abstract
The study is focused on the technology for surface modification of AZ31 magnesium alloy for biomedical applications, in particular in implantology. The experimental procedure consists of intentional stages that involve chemical treatment in piranha solution, plasma chemical activation of the alloy surface using [...] Read more.
The study is focused on the technology for surface modification of AZ31 magnesium alloy for biomedical applications, in particular in implantology. The experimental procedure consists of intentional stages that involve chemical treatment in piranha solution, plasma chemical activation of the alloy surface using Ar and O2 as gaseous precursors, and biopolymer coatings deposition—based on polylactic acid (PLA) and poly(lactic-co-glycolic acid) (PLGA) with the addition of caffeic acid—utilizing the immersion method. In the course of the experiment, the validity of the investigated technology of surface modification of AZ31 magnesium alloy was confirmed. The pre-treatment step guaranteed obtaining a higher surface roughness, resulting in homogeneous and stable biopolymer coatings with proper adhesion to the substrate. Moreover, the corrosion studies conducted confirmed better corrosion behaviour of the modified samples in SBF corrosive medium, and no significant release of the alloy-related ions was observed. Furthermore, the biopolymer coatings ensured non-cytotoxicity towards the MG-63 cell line and promoted cell proliferation with proper morphology. Based on the obtained results, it may be concluded that the proposed technology can be treated as an interesting and promising surface-engineering strategy for implantology and biodegradable materials applications. Full article
(This article belongs to the Special Issue Recent Advances in Surface Functionalisation, 2nd Edition)
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15 pages, 15535 KB  
Article
Oxide Uniformity and Oxygen Scavenging Correlate with Rapid Formation of Atomically Flat Si(111)–H Surfaces
by Peng-Mou Chen and Yit Lung Khung
Surfaces 2025, 8(4), 75; https://doi.org/10.3390/surfaces8040075 - 24 Oct 2025
Viewed by 281
Abstract
The formation of atomically flat Si(111)–H surfaces was critical for molecular electronics, nanoscale device fabrication, and surface chemistry studies. We systematically investigated how initial oxide composition and dissolved oxygen affected terrace-formation kinetics during ammonium fluoride (NH4F) etching. N-type Si(111) was cleaned [...] Read more.
The formation of atomically flat Si(111)–H surfaces was critical for molecular electronics, nanoscale device fabrication, and surface chemistry studies. We systematically investigated how initial oxide composition and dissolved oxygen affected terrace-formation kinetics during ammonium fluoride (NH4F) etching. N-type Si(111) was cleaned with either oxygen plasma or piranha solution to generate, respectively, a more uniform versus a chemically heterogeneous oxide, and then etched in NH4F containing 0–5% (w/v) ammonium sulfite (AS) as an oxygen scavenger. AFM acquired every 2 min over 20 min revealed that plasma-pretreated surfaces reached atomically flat terraces earlier and more reproducibly than piranha-pretreated surfaces. Increasing AS concentration suppressed oxygen-induced etch pits and promoted the earlier appearance of large, well-ordered terraces, whereas prolonged etching led to roughening. XPS and ATR-FTIR corroborated differences in the starting oxides and confirmed post-etch H-termination. Collectively, the results indicated that oxide uniformity together with oxygen scavenging correlated with faster attainment and greater persistence of low-roughness terraces, providing a practical framework for reproducibly preparing hydrogen-terminated Si(111)–H surfaces. Full article
(This article belongs to the Collection Featured Articles for Surfaces)
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14 pages, 1641 KB  
Article
Time-Dependent Piranha Solution Treatment as an Alternative to Sandblasting for Improving Zirconia–Resin Cement Bond Strength
by Apichai Maneenacarith, Nantawan Krajangta, Thanasak Rakmanee and Awiruth Klaisiri
Ceramics 2025, 8(4), 123; https://doi.org/10.3390/ceramics8040123 - 2 Oct 2025
Viewed by 440
Abstract
This study investigated the effect of piranha solution etching duration on the shear bond strength of zirconia ceramics bonded to resin cement, comparing it to conventional sandblasting treatment. Fifty fully sintered zirconia specimens (6.0 mm diameter, 4.0 mm thickness) were prepared and randomly [...] Read more.
This study investigated the effect of piranha solution etching duration on the shear bond strength of zirconia ceramics bonded to resin cement, comparing it to conventional sandblasting treatment. Fifty fully sintered zirconia specimens (6.0 mm diameter, 4.0 mm thickness) were prepared and randomly divided into five groups (n = 10): sandblasting control and piranha solution treatment for 1, 2, 3, and 4 min. Piranha solution was prepared by mixing 98% H2SO4 and 35% H2O2 in a 3:1 ratio. All specimens were bonded to resin composite cylinders using dual-cure resin cement. Shear bond strength testing was performed using a universal testing machine at a 0.5 mm/min crosshead speed. Failure modes were analyzed using a stereomicroscope and classified as adhesive, cohesive, or mixed failures. One-way ANOVA revealed significant differences between groups (p < 0.05). Tukey’s post hoc test showed that 1-min piranha treatment produced significantly lower bond strength (7.64 ± 2.02 MPa) compared to all other groups. The 2-min (15.17 ± 2.79 MPa), 3-min (14.99 ± 3.27 MPa), and 4-min (18.34 ± 3.15 MPa) piranha treatments showed no significant differences compared to sandblasting (15.41 ± 2.61 MPa). Failure mode analysis revealed 100% adhesive failures for the 1-min group, while all other groups showed 80% adhesive and 20% mixed failures. Piranha solution treatment duration significantly affected zirconia bonding performance. While 1-min treatment proved inadequate, 2–4 min treatments achieved bond strengths comparable to sandblasting. The findings suggest that piranha solution treatment for 2–4 min represents a viable alternative to sandblasting for zirconia surface preparation, with the 2-min protocol being the most efficient choice for clinical application. Full article
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27 pages, 2815 KB  
Article
Machine Learning-Augmented Triage for Sepsis: Real-Time ICU Mortality Prediction Using SHAP-Explained Meta-Ensemble Models
by Hülya Yilmaz Başer, Turan Evran and Mehmet Akif Cifci
Biomedicines 2025, 13(6), 1449; https://doi.org/10.3390/biomedicines13061449 - 12 Jun 2025
Cited by 1 | Viewed by 2412
Abstract
Background/Objectives: Optimization algorithms are acknowledged to be critical in various fields and dynamical systems since they provide facilitation in identifying and retrieving the most possible solutions concerning complex problems besides improving efficiency, cutting down on costs, and boosting performance. Metaheuristic optimization algorithms, on [...] Read more.
Background/Objectives: Optimization algorithms are acknowledged to be critical in various fields and dynamical systems since they provide facilitation in identifying and retrieving the most possible solutions concerning complex problems besides improving efficiency, cutting down on costs, and boosting performance. Metaheuristic optimization algorithms, on the other hand, are inspired by natural phenomena, providing significant benefits related to the applicable solutions for complex optimization problems. Considering that complex optimization problems emerge across various disciplines, their successful applications are possible to be observed in tasks of classification and feature selection tasks, including diagnostic processes of certain health problems based on bio-inspiration. Sepsis continues to pose a significant threat to patient survival, particularly among individuals admitted to intensive care units from emergency departments. Traditional scoring systems, including qSOFA, SIRS, and NEWS, often fall short of delivering the precision necessary for timely and effective clinical decision-making. Methods: In this study, we introduce a novel, interpretable machine learning framework designed to predict in-hospital mortality in sepsis patients upon intensive care unit admission. Utilizing a retrospective dataset from a tertiary university hospital encompassing patient records from January 2019 to June 2024, we extracted comprehensive clinical and laboratory features. To address class imbalance and missing data, we employed the Synthetic Minority Oversampling Technique and systematic imputation methods, respectively. Our hybrid modeling approach integrates ensemble-based ML algorithms with deep learning architectures, optimized through the Red Piranha Optimization algorithm for feature selection and hyperparameter tuning. The proposed model was validated through internal cross-validation and external testing on the MIMIC-III dataset as well. Results: The proposed model demonstrates superior predictive performance over conventional scoring systems, achieving an area under the receiver operating characteristic curve of 0.96, a Brier score of 0.118, and a recall of 81. Conclusions: These results underscore the potential of AI-driven tools to enhance clinical decision-making processes in sepsis management, enabling early interventions and potentially reducing mortality rates. Full article
(This article belongs to the Section Molecular and Translational Medicine)
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19 pages, 3576 KB  
Article
A Study on the Oxidative Functionalization of a Poplar Biochar
by Antonella Di Vincenzo, Ettore Madonia, Calogero Librici, Paola Bambina, Delia Chillura Martino, Susanna Guernelli, Paolo Lo Meo and Pellegrino Conte
Molecules 2025, 30(5), 1048; https://doi.org/10.3390/molecules30051048 - 25 Feb 2025
Cited by 2 | Viewed by 1047
Abstract
This study investigates the functionalization of a poplar biochar (PB), obtained by high-temperature pyrolysis, under oxidative conditions typically used in organic synthesis. In particular, concentrated nitric acid, a sulfonitric mixture and a piranha mixture were applied as oxidants at different temperatures and reaction [...] Read more.
This study investigates the functionalization of a poplar biochar (PB), obtained by high-temperature pyrolysis, under oxidative conditions typically used in organic synthesis. In particular, concentrated nitric acid, a sulfonitric mixture and a piranha mixture were applied as oxidants at different temperatures and reaction times. In order to assess the outcome of the reaction conditions on the characteristics of the resultant products, these were characterized by a combination of imaging (SEM), spectroscopic (ATR-FTIR, RAMAN) and FFC-NMR relaxometric techniques. The latter techniques, rationalized in terms of the Kohlrausch-type stretched exponential kinetic model, were analyzed using a recently developed heuristic Monte Carlo method, providing insights into the water dynamics within material pore networks. Additionally, the water-holding capacity of the modified biochars and their abilities to adsorb some model dyes were evaluated. The results clarify the relationship between oxidative treatment conditions and biochar properties, highlighting their impact on both structural modifications and water dynamics within the porous network, and enabling us to identify the best reaction conditions for optimizing the features of the oxidized product. Full article
(This article belongs to the Section Materials Chemistry)
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24 pages, 7291 KB  
Article
Piranha Foraging Optimization Algorithm with Deep Learning Enabled Fault Detection in Blockchain-Assisted Sustainable IoT Environment
by Haitham Assiri
Sustainability 2025, 17(4), 1362; https://doi.org/10.3390/su17041362 - 7 Feb 2025
Cited by 3 | Viewed by 1431
Abstract
As the acceptance of Internet of Things (IoT) systems quickens, guaranteeing their sustainability and reliability poses an important challenge. Faults in IoT systems can result in resource inefficiency, high energy consumption, reduced security, and operational downtime, obstructing sustainability goals. Thus, blockchain (BC) technology, [...] Read more.
As the acceptance of Internet of Things (IoT) systems quickens, guaranteeing their sustainability and reliability poses an important challenge. Faults in IoT systems can result in resource inefficiency, high energy consumption, reduced security, and operational downtime, obstructing sustainability goals. Thus, blockchain (BC) technology, known for its decentralized and distributed characteristics, can offer significant solutions in IoT networks. BC technology provides several benefits, such as traceability, immutability, confidentiality, tamper proofing, data integrity, and privacy, without utilizing a third party. Recently, several consensus algorithms, including ripple, proof of stake (PoS), proof of work (PoW), and practical Byzantine fault tolerance (PBFT), have been developed to enhance BC efficiency. Combining fault detection algorithms and BC technology can result in a more reliable and secure IoT environment. Thus, this study presents a sustainable BC-Driven Edge Verification with a Consensus Approach-enabled Optimal Deep Learning (BCEVCA-ODL) approach for fault recognition in sustainable IoT environments. The proposed BCEVCA-ODL technique incorporates the merits of the BC, IoT, and DL techniques to enhance IoT networks’ security, trustworthiness, and efficacy. IoT devices have a substantial level of decentralized decision-making capacity in BC technology to achieve a consensus on the accomplishment of intrablock transactions. A stacked sparse autoencoder (SSAE) model is employed to detect faults in IoT networks. Lastly, the Piranha Foraging Optimization Algorithm (PFOA) approach is used for optimum hyperparameter tuning of the SSAE approach, which assists in enhancing the fault recognition rate. A wide range of simulations was accomplished to highlight the efficacy of the BCEVCA-ODL technique. The BCEVCA-ODL technique achieved a superior FDA value of 100% at a fault probability of 0.00, outperforming the other evaluated methods. The proposed work highlights the significance of embedding sustainability into IoT systems, underlining how advanced fault detection can provide environmental and operational benefits. The experimental outcomes pave the way for greener IoT technologies that support global sustainability initiatives. Full article
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15 pages, 6241 KB  
Article
Osseointegration of Implants Through Ti Biofunctionalization with Biomass from Chlorella sorokiniana UTEX 1230 and Synechococcus sp. PCC 7002
by Yarelis Bravo, Alejandra M. Miranda, Fabian Hernandez-Tenorio, Alex A. Sáez and Virginia Paredes
Int. J. Mol. Sci. 2024, 25(23), 13161; https://doi.org/10.3390/ijms252313161 - 7 Dec 2024
Cited by 1 | Viewed by 1229
Abstract
The inadequate osseointegration of titanium implants remains a significant challenge in orthopedics, limiting the long-term efficacy of prostheses and medical devices. It has been determined that biological aging of the titanium surface compromises the implant–bone tissue interaction due to increased hydrophobicity and accumulation [...] Read more.
The inadequate osseointegration of titanium implants remains a significant challenge in orthopedics, limiting the long-term efficacy of prostheses and medical devices. It has been determined that biological aging of the titanium surface compromises the implant–bone tissue interaction due to increased hydrophobicity and accumulation of organic molecules. To address this issue, an innovative strategy has been proposed: the biofunctionalization of Ti6Al4V surfaces utilizing biomass derived from Chlorella sorokiniana UTEX 1230 and Synechococcus sp. PCC 7002. This research was structured to encompass microalgal culture optimization through biocompatibility evaluation of biofunctionalized surfaces. Biofunctionalization stages were analyzed using contact angle measurements, EDS, SEM, and cellular assays. It was observed that piranha solution activation generated a hydrophilic surface, while silanization was more efficient in samples treated for 14 h. It was found that Synechococcus sp. PCC 7002 presented a higher biomass concentration on the surface compared to C. sorokiniana UTEX 1230. Cytotoxicity assays revealed that the coating with Synechococcus sp. PCC 7002 was potentially non-cytotoxic, with a cell viability of 86.8%. SEM images showed a significant number of cells adhered to the treated sample. In conclusion, the potential of using microalgal biomass to biofunctionalize titanium surfaces has been demonstrated, offering an innovative alternative to improve implant–tissue interaction and, consequently, the osseointegration process in orthopedic applications. Full article
(This article belongs to the Section Molecular Microbiology)
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17 pages, 4176 KB  
Article
Using an Automated Operant Conditioning Procedure to Test Colour Discrimination in Two Juvenile Piranhas, Pygocentrus nattereri: A Lesson on Failures and Pitfalls and How to Avoid Them
by Christian Agrillo and Alessandra Pecunioso
Animals 2024, 14(22), 3187; https://doi.org/10.3390/ani14223187 - 6 Nov 2024
Viewed by 1673
Abstract
Most studies on the cognitive abilities of fish have focused on model organisms adopted in behavioural neuroscience. To date, little attention has been devoted to characiformes fish and we record a lack of cognitive investigation on the piranha. In this study, we conducted [...] Read more.
Most studies on the cognitive abilities of fish have focused on model organisms adopted in behavioural neuroscience. To date, little attention has been devoted to characiformes fish and we record a lack of cognitive investigation on the piranha. In this study, we conducted a preliminary set of experiments to assess whether red-bellied piranhas (Pygocentrus nattereri) can solve an automated operant conditioning task, specifically, a reversal learning task. In Experiment 1, the fish were required to discriminate between red and green, while in Experiment 2, they had to discriminate between white and yellow. In either case, we found no evidence of learning capacities with our protocol after extensive training exceeding one thousand trials overall. In Experiment 3, we simplified the learning task by using achromatic stimuli (black and white discrimination) and always presenting the reinforced stimulus on the same side of the tank (a combination of response learning and place learning). Subjects did learn how to discriminate between the colours, although no subject was able to reach the criterion in the subsequent reversal learning task, suggesting that piranhas may be limited in their cognitive flexibility. However, our training procedure may have been inefficient in addressing this issue. We outline some potential limitations of the current methodology to help to establish a more effective approach for investigating operant conditioning in this species. Full article
(This article belongs to the Section Human-Animal Interactions, Animal Behaviour and Emotion)
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13 pages, 9550 KB  
Article
Piranha Solution-Assisted Surface Engineering Enables Silicon Nanocrystals with Superior Wettability and Lithium Storage
by Tingting Li, Yangfan Li, Fan Zhang, Naiwen Liang, Jiang Yin, Haihong Zhao, Yahui Yang, Bo Chen and Lishan Yang
Crystals 2023, 13(7), 1127; https://doi.org/10.3390/cryst13071127 - 19 Jul 2023
Cited by 11 | Viewed by 3907
Abstract
Silicon anodes with a high theoretical capacity possess great potential applications in power batteries for electric vehicles, while their volume expansion always leads to crystal pulverization and electrode polarization. An ideal solution to alleviate such pulverization and polarization of silicon crystals is to [...] Read more.
Silicon anodes with a high theoretical capacity possess great potential applications in power batteries for electric vehicles, while their volume expansion always leads to crystal pulverization and electrode polarization. An ideal solution to alleviate such pulverization and polarization of silicon crystals is to simultaneously use nano-sized silicon crystals and introduce high viscosity and elasticity polymer binders. This work has achieved the adjustable introduction of hydroxyl groups to silicon nanocrystals under the optimal reaction temperature (e.g., 80 °C) and appropriate piranha solution composition (e.g., H2SO4/H2O2 = 3:1 v/v), ultimately forming an amorphous coating layer of ~1.3 nm on the silicon surface. The optimized silicon anode exhibits superior electrochemical performance (with an initial Coulombic efficiency of 85.5%; 1121.4 mA h g−1 at 1 A g−1 after 200 cycles) and improved hydrophilicity. The introduced hydroxyl groups significantly enhance the hydrophilicity of silicon in the electrolyte and the electrochemical activity of the silicon anodes. The hydroxyl groups achieve stronger bonding between silicon and polymer binders, ultimately improving the mechanical strength and stability of the electrode. The introduction of hydrophily functional groups on the surface of silicon crystals can be explored as an active strategy to solve the above issues. This surface engineering method could be extended to more fields of infiltrating silicon-based functional materials. Full article
(This article belongs to the Special Issue Emerging Low-Dimensional Materials II)
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11 pages, 3551 KB  
Article
Optimization of Biomethane Yield of Xyris capensis Grass Using Oxidative Pretreatment
by Kehinde O. Olatunji and Daniel M. Madyira
Energies 2023, 16(10), 3977; https://doi.org/10.3390/en16103977 - 9 May 2023
Cited by 10 | Viewed by 1503
Abstract
Biogas production from lignocellulose feedstocks has become an acceptable energy source globally due to their availability and economy. Lignocellulose materials have a complex arrangement that hinders digestion during the process. Therefore, applying the pretreatment process to lower the recalcitrant properties is required to [...] Read more.
Biogas production from lignocellulose feedstocks has become an acceptable energy source globally due to their availability and economy. Lignocellulose materials have a complex arrangement that hinders digestion during the process. Therefore, applying the pretreatment process to lower the recalcitrant properties is required to utilize the full potential of the feedstock. This study, therefore, examines the influence of the oxidative pretreatment on the microstructural arrangement and biomethane yield of Xyris capensis. Piranha solution was prepared using H2O2 and H2SO4 at 100, 95:5, 85:15, and 75:25% of H2O2:H2SO4, respectively, and Xyris capensis grass was soaked in the prepared solution. The pretreated and untreated feedstocks were examined under the scanning electron microscope (SEM) to study the effect of the pretreatment on the microstructural arrangement. The effect of the pretreatment on biomethane yield was investigated during anaerobic digestion in a laboratory-scale batch digester at a mesophilic temperature (37 °C). The SEM analysis shows that the oxidative pretreatment method significantly affects the substrate’s microstructure, and the pretreatment’s severity depends on the percentage of H2SO4 added. A biomethane yield of 174.41, 188.61, 192.23, 207.51, and 139.71 mL CH4/g VSadded was observed, and the yield was increased by between 24.84 and 48.52% compared to the untreated substrate. Therefore, applying oxidative pretreatment using low-cost H2O2 is a clear method of improving the biomethane yield of lignocellulose feedstocks. Full article
(This article belongs to the Section A4: Bio-Energy)
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12 pages, 9478 KB  
Article
Novel Functionalized Boron Nitride Nanosheets Achieved by Radiation-Induced Oxygen Radicals and Their Enhancement for Polymer Nanocomposites
by Xin Yang, Bingling Zhao, Liudi Ji, Peng Hu, Xiaoming Zhu and Zeyu Li
Molecules 2023, 28(8), 3444; https://doi.org/10.3390/molecules28083444 - 13 Apr 2023
Cited by 5 | Viewed by 2710
Abstract
Boron nitride nanosheets (BNNSs) exfoliated from hexagonal boron nitride (h-BN) show great potential in polymer-based composites due to their excellent mechanical properties, highly thermal conductivity, and insulation properties. Moreover, the structural optimization, especially the surface hydroxylation, of BNNSs is of importance to promote [...] Read more.
Boron nitride nanosheets (BNNSs) exfoliated from hexagonal boron nitride (h-BN) show great potential in polymer-based composites due to their excellent mechanical properties, highly thermal conductivity, and insulation properties. Moreover, the structural optimization, especially the surface hydroxylation, of BNNSs is of importance to promote their reinforcements and optimize the compatibility of its polymer matrix. In this work, BNNSs were successfully attracted by oxygen radicals decomposed from di-tert-butylperoxide (TBP) induced by electron beam irradiation and then treated with piranha solution. The structural changes of BNNSs in the modification process were deeply studied, and the results demonstrate that the as-prepared covalently functionalized BNNSs possess abundant surface hydroxyl groups as well as reliable structural integrity. Of particular importance is that the yield rate of the hydroxyl groups is impressive, whereas the usage of organic peroxide and reaction time is greatly reduced due to the positive effect of the electron beam irradiation. The comparisons of PVA/BNNSs nanocomposites further indicate that the hydroxyl-functionalized BNNSs effectively promote mechanical properties and breakdown strength due to the enhanced compatibility and strong two-phase interactions between nanofillers and the polymer matrix, which further verify the application prospects of the novel route proposed in this work. Full article
(This article belongs to the Special Issue Chemical Functionalization of Two-Dimensional Materials)
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12 pages, 4079 KB  
Communication
Cleaning Effect of Atmospheric-Plasma-Sprayed Y2O3 Coating Using Piranha Solution Based on Contamination Particle Measurement
by Hyuksung Kwon, Minjoong Kim, Jongho So, Seonjeong Maeng, Jae-Soo Shin and Ju-Young Yun
Coatings 2023, 13(3), 653; https://doi.org/10.3390/coatings13030653 - 20 Mar 2023
Cited by 6 | Viewed by 3891
Abstract
A Y2O3 coating was prepared using the atmospheric plasma spraying (APS) technique. On exposing the coating to CF4/O2/Ar plasma, a fluorine contamination layer (YOxFy) was formed, which was the main cause of [...] Read more.
A Y2O3 coating was prepared using the atmospheric plasma spraying (APS) technique. On exposing the coating to CF4/O2/Ar plasma, a fluorine contamination layer (YOxFy) was formed, which was the main cause of process drift and contamination particle generation on the APS–Y2O3 coating surface. To remove the YOxFy layer on the coating surface, a piranha solution, which is a mixture of sulfuric acid and hydrogen peroxide, was employed for cleaning. The piranha solution was found to be an excellent medium for removing the YOxFy layer. The amount of contamination particle generated could be reduced by approximately 37% after cleaning with a 3:1 piranha solution compared with before cleaning. Full article
(This article belongs to the Section Plasma Coatings, Surfaces & Interfaces)
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18 pages, 7822 KB  
Article
A Study on the Synthesis and Proton Transport Behavior of Multilayered ZSM-5 Zeolite Nanosheet Membranes Laminated on Polymer Substrates
by Zishu Cao, Landysh Iskhakova, Xinhui Sun and Junhang Dong
Membranes 2023, 13(3), 305; https://doi.org/10.3390/membranes13030305 - 6 Mar 2023
Cited by 2 | Viewed by 2497
Abstract
Single crystalline ZSM-5 ZNs with thicknesses around 6 nm were obtained by secondary growth of silicalite nanoparticles using diquaternary bis-1,5(tripropyl ammonium) pentamethylene diiodide (dC5) as a structure-directing agent (SDA). The dC5 could be effectively removed from the ZN pores by [...] Read more.
Single crystalline ZSM-5 ZNs with thicknesses around 6 nm were obtained by secondary growth of silicalite nanoparticles using diquaternary bis-1,5(tripropyl ammonium) pentamethylene diiodide (dC5) as a structure-directing agent (SDA). The dC5 could be effectively removed from the ZN pores by either high-temperature calcination or UV irradiation in air at room temperature but not by the piranha solution treatment. Ultrathin ZN-laminated membranes (ZNLMs) were fabricated by sandwiching a UV-activated multilayered ZN film between two recast Nafion® layers (ZNLM-Nafion) and by filtration coating from a suspension of thermally activated ZNs on a nonionic porous PVDF (ZNLM-PVDF). The ZNLMs on both supports demonstrated the ability of highly proton-selective ion conduction with low resistances in aqueous electrolyte solutions. The ZNLM-PVDF with PVDF binder was structurally stable, and it achieved a comparably low ASR but much higher proton selectivity compared with a Nafion membrane of same overall thickness. However, detachment between the ZNLM and Nafion layers occurred when the ZNLM-Nafion operated in aqueous electrolyte solutions. Results of this study show the potential for developing ZNLMs as efficient proton-conducting membranes without using expensive ionic polymer matrices. However, the development of polymer-supported ZNLMs is hindered by the current inefficiency in preparing well-dispersed suspensions of open-pore ZNs. Future development of efficient methods for synthesizing open-pore ZNs in dispersed states is key to realizing high-performance ZNLMs on polymers. Full article
(This article belongs to the Special Issue Recent Progress in Synthesis and Application of Zeolite Membrane)
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13 pages, 3016 KB  
Article
A Simple Strategy Stabilizing for a CuFe/SiO2 Catalyst and Boosting Higher Alcohols’ Synthesis from Syngas
by Nana Gong, Yingquan Wu, Qingxiang Ma and Yisheng Tan
Catalysts 2023, 13(2), 237; https://doi.org/10.3390/catal13020237 - 19 Jan 2023
Cited by 8 | Viewed by 2893
Abstract
Stable F-T-based catalyst development in direct CO hydrogenation to higher alcohols is still a challenge at present. In this study, CuFe/SiO2 catalysts with a SiO2 support treated with a piranha solution were prepared and evaluated in a long-term reaction. The treated [...] Read more.
Stable F-T-based catalyst development in direct CO hydrogenation to higher alcohols is still a challenge at present. In this study, CuFe/SiO2 catalysts with a SiO2 support treated with a piranha solution were prepared and evaluated in a long-term reaction. The treated catalyst showed higher total alcohols’ selectivity and great stability during a reaction of more than 90 h. It was found that the treatment with the piranha solution enriched the surface hydroxyl groups on SiO2, so that the Cu–Fe active components could be firmly anchored and highly dispersed on the support, resulting in stable catalytic performance. Furthermore, the in situ DRIFTS revealed that the adsorption strength of CO on Cu+ on the treated catalyst surface was weakened, which made the C-O bond less likely to be cleaved and thus significantly inhibited the formation of hydrocarbon products. Meanwhile, the non-dissociated CO species were obviously enriched on the Cu0 surface, promoting the formation of alcohol products, and thus the selectivity of total alcohols was increased. This strategy will shed light on the design of supported catalysts with stabilized structures for a wide range of catalytic reactions. Full article
(This article belongs to the Special Issue Catalysis for Selective Hydrogenation of CO and CO2)
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12 pages, 3742 KB  
Article
Halloysite Nanotubes as Bimodal Lewis/Brønsted Acid Heterogeneous Catalysts for the Synthesis of Heterocyclic Compounds
by Jiaying Yu, Javier Mateos and Mauro Carraro
Nanomaterials 2023, 13(3), 394; https://doi.org/10.3390/nano13030394 - 18 Jan 2023
Cited by 11 | Viewed by 3553
Abstract
Halloysite nanotubes can be used for the preparation of solid catalysts. Owing to their natural availability at low-cost as well as to their large and easy-to-functionalize surface, they can be conveniently activated with mineral acids or derivatized with acidic groups. Nevertheless, the use [...] Read more.
Halloysite nanotubes can be used for the preparation of solid catalysts. Owing to their natural availability at low-cost as well as to their large and easy-to-functionalize surface, they can be conveniently activated with mineral acids or derivatized with acidic groups. Nevertheless, the use of HNTs as catalysts in complex transformations is still limited. Herein, we report two strategies to utilize HNT-based materials as solid acidic catalysts for the Biginelli reaction. To this aim, two methods for increasing the number of acidic sites on the HNTs were explored: (i) the treatment with piranha solution (Pir-HNTs) and (ii) the functionalization with phenylboronic acid (in particular with benzene-1,4-diboronic acid: the sample is denoted as HNT-BOA). Interestingly, both strategies enhance the performance of the multicomponent reaction. Pir-HNTs and HNT-BOA show an increased reactivity (72% and 89% yield, respectively) in comparison with pristine HNTs (52%). Additionally, Pir-HNTs can be reused up to five times without significant performance loss. Moreover, the method also displays good reaction scope, as demonstrated by the preparation of 12 different 3,4-dihydropyrimidinones in up to 71% yield. Therefore, the described strategies are promising for enhancing the acidity of the HNTs as catalysts for the organic reaction. Full article
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