Reaction Medium Research Articles

Evaluation of homogeneous and heterogeneous catalytic strategies for furfural production from sugar-derived biomass in a solvent-free green pressurized reaction media (subcritical water-CO2)

A green organic, solvent-free, subcritical water-CO2 (subW-CO2) system was proposed for the production of furfural from the main hemicellulose's sugar, xylose. Despite subW itself showed potential for furfural generation due to its catalytic properties under subcritical conditions; when CO2 was added into the system as pressurization agent, higher yields were reached due to its effect as a Brønsted acid when dissolved in water. Furthermore, its combination with different Lewis acidic catalysts showed a synergistic effect, further improving furfural yield. In a batch configuration, five homogeneous and four heterogeneous catalysts were tested at 180 °C and 5.5 MPa and compared for the first time in a subW-CO2 reaction medium. Different furfural production paths were determined for the two catalysts types, with higher xylose isomerization rates to xylulose when homogeneous trivalent metal catalysts were used. CrCl3 and Nafion NR50 resin were selected as best catalysts from each of the groups due to higher furfural production rates (51.9 ± 0.9 % yield/h) and higher furfural selectivity (60.9 %), respectively. Furthermore, Nafion NR50 catalytic activity remained unchanged after 10 runs at 180 °C. The green subW-CO2 system furfural yields were comparable to water-organic solvent biphasic ones, proving to be a promising green alternative.

How to Survive without Water: A Short Lesson on the Desiccation Tolerance of Budding Yeast.

Water is essential to all life on earth. It is a major component that makes up living organisms and plays a vital role in multiple biological processes. It provides a medium for chemical and enzymatic reactions in the cell and is a major player in osmoregulation and the maintenance of cell turgidity. Despite this, many organisms, called anhydrobiotes, are capable of surviving under extremely dehydrated conditions. Less is known about how anhydrobiotes adapt and survive under desiccation stress. Studies have shown that morphological and physiological changes occur in anhydrobiotes in response to desiccation stress. Certain disaccharides and proteins, including heat shock proteins, intrinsically disordered proteins, and hydrophilins, play important roles in the desiccation tolerance of anhydrobiotes. In this review, we summarize the recent findings of desiccation tolerance in the budding yeast Saccharomyces cerevisiae. We also propose that the yeast under desiccation could be used as a model to study neurodegenerative disorders.

Characterization and Application of Cyrene as a Biomass-Based Solvent for Homogeneous Heck-Coupling Reaction.

Cyrene, a renewable, non-toxic substance having negligible vapor pressure, even at high temperatures, was proposed as a reaction medium for homogeneous Pd-catalyzed Heck-coupling reactions. It was first characterized by its temperature-dependent physicochemical properties, i.e., vapor pressure, density, surface tension, heat capacity, and viscosity, the key parameters of its reaction and process chemistry. Its refractive indices in the function of temperature were also determined. Hereafter, the effect of reaction parameters (Pd source, nature of the base, the water content of the reaction mixture, leaving group (-I, -Br, -Cl, and -OTf of aromatic substrates) on Pd-catalyzed Heck-coupling reaction was investigated using iodobenzene and styrene as model substrates. Subsequently, 4-substituted iodobenzene and styrene derivatives were applied to investigate the effect of electronic parameters on the reaction efficiency and functional group tolerance. To demonstrate the applicability of the system, thirteen stilbene derivatives were isolated with good to high yields and purity (> 95%) using 0.2 mol% of Pd, 1.5 eq. of Et3N as a base, in 1 mL of Cyrene for 2 h at 100 °C.

Water-Dispersible, Magnetically Recyclable Heterogeneous Cobalt Catalyst for C-C and C-N Cross-Coupling Reactions in Aqueous Media.

A cobalt catalyst supported on an iron oxide core, denoted as γ-Fe2O3@PEG@THMAM-Co, has been prepared and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray mapping, thermogravimetry differential thermogravimetry, vibrating sample magnetometry, and inductively coupled plasma. Polyhydroxy end groups in the shell make the catalyst particles dispersible in water, allowing Hiyama, Suzuki, and C-N cross-coupling reactions of aryl iodides and bromides. The catalyst could be recovered by magnetic decantation and reused for at least five successive runs with a negligent decrease in its activity or changes in its morphology. Water as a solvent without requiring additives, surfactants, or organic co-solvents, as well as an abundant and low-cost cobalt catalyst combined with facile recovery, low leaching, and scalability, provides an environmentally and economically attractive alternative to established palladium-catalyzed C-C and C-N coupling reactions.

Supercritical hydrothermal synthesis of ultra-fine Cu powders

ABSTRACT Ultra-fine Cu powders were synthesized using supercritical water as a reaction medium and formic acid as a reducing agent. The effects of reducing agent, reaction temperature, and complexing agent on the phase constituents, particle size distributions and morphology of the synthesized ultra-fine Cu powders were investigated. A complex mixture of Cu2O and Cu powders formed by pure supercritical water while high purity homogeneous ultra-fine Cu powders can be synthesized by supercritical water with formic acid as a reducing agent. Moreover, fine tuning of particle size and morphology can be realized by the addition of Ethylenediamine tetraacetic acid (EDTA). The modification mechanism of EDTA on the surfaces of ultra-fine Cu powders was investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. EDTA adsorbed on the surfaces of nanoparticles by the dehydration reaction of carboxyl groups in the molecule of EDTA and hydroxyl groups on surfaces of copper nanoparticles (CuOH).

Facet-engineered ruthenium oxide on titanium oxide oxygen evolution electrocatalysts for proton-exchange membrane water electrolysis

Ruthenium oxide-based catalysts exhibit an active oxygen evolution reaction (OER) in acidic media but suffer from low stability, limiting their practical application in proton-exchange membrane water electrolyzers (PEMWEs). Herein, we present an effective acidic OER catalyst comprising RuO2 nanolayers on an isostructural rutile TiO2 support (NL-RuO2-250) that maximizes exposure to specific crystal orientations. RuO2 morphology and growth mechanism on the TiO2 surface were affected by the interfacial charge states during hydrothermal process, with the crystal structure similarity between the RuO2 catalyst and TiO2 support advantageous for maximizing compatibility at the interface. Density functional theory combined with experimental analyses revealed that NL-RuO2-250 is an optimized form for improving OER performance. As-prepared NL-RuO2-250 required a low overpotential (230 mV at 10 mA cm−2) and a PEMWE single cell assembled with NL-RuO2-250 exhibited an insignificant voltage drop for 24 h under 0.2 A cm−2, demonstrating a practical design strategy for acidic OER catalysts.

Crystal-Phase-Selective Etching of Heterophase Au Nanostructures.

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal-phase-selective etching has been rarely studied. Here, a crystal-phase-selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt-based alloy and the crystal-phase-selective etching of 4H-Au in 4H/face-centered cubic (fcc) Au nanowires, the well-defined ladder-like Au@PtAg nanoframes are prepared. In addition, the 2H-Au in the fcc-2H-fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof-of-concept application, the ladder-like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst.

Chaotic Transport of Solutes in Unsaturated Porous Media.

Unsaturated porous media, characterized by the combined presence of several immiscible fluid phases in the pore space, are highly relevant systems in nature, because they control the fate of contaminants and the availability of nutrients in the subsoil. However, a full understanding of the mechanisms controlling solute mixing in such systems is still missing. In particular, the role of saturation in the development of chaotic solute mixing has remained unexplored. Using three-dimensional numerical simulations of flow and transport at the pore scale, built upon X-ray tomograms of a porous medium at different degrees of liquid (wetting)-phase saturation, we show the occurrence of chaotic dynamics in both the deformation of the solute plume, as characterized by computed chaos metrics (Lyapunov exponents), and the mixing of the injected solute. Our results show an enhancement of these chaotic dynamics at lower saturation and their occurrence even under diffusion-relevant conditions over the medium's length, also being strengthened by larger flow velocities. These findings highlight the dominant role of the pore-scale spatial heterogeneity of the system, enhanced by the presence of an immiscible phase (e.g., air), on the mixing efficiency. This represents a stepping stone for the assessment of mixing and reactions in unsaturated porous media.

Unusual emission from 2F5/2 two lowest excited levels of Yb3+-doped LuPO4 nano/micro-crystalline materials

Yb3+-doped inorganic materials are constantly in demand due to a strong interest in fundamental and applied research. The simplicity of the 4f1³ electronic structure minimizes de-excitation processes and enables a quasi-three-level laser emission scheme at 1 μm employed for IR laser devices.In this work, we present an unusual simultaneous emission from two of the lowest levels of the 2F5/2 excited state observed at 77 K, measured for the first time and confirmed by the barycenter law for Yb3+-doped tetragonal LuPO4 revealing the lowest crystal field among Yb3+ ion-activated oxide crystals.Three series of tetragonal lutetium orthophosphate powders, containing various concentrations of Yb3+ ions (0.5–5 mol %), were analyzed in nano and micro-crystalline forms. The ionic liquid-assisted (IL) hydrothermal (HT) method was used for the nano-powders' preparation. This route enabled the fabrication of fine nano-powders with particle sizes of 15 nm in an ethylene glycol (GE) reaction medium and 30 nm in a water (W) medium, each exhibiting the desired well-crystallized single-phase phosphate. For comparative studies, the micro-crystalline samples were synthesized via reaction in the solid phase at a relatively high temperature.The Yb3+ ion also served as a structural probe, its spectroscopy i.e., absorption at 4.2 K, selectively excited luminescence at 77 K, and fluorescence decays were used to assign Yb3+ energy levels in only one D2d center precisely. This assignment was based on exceptional features due to the unique emissions observed from the two lowest levels of the 2F5/2 excited state, split only by 27 cm−1, confirmed by calculation of the crystal field parameters from Zeeman spectra.

Unlocking the Potential of Deep Eutectic Solvents and Ligand-to-Metal Charge Transfer Processes: A Reusable Iron-and-UV-Based System for Sustainable C-C Bond Formation.

Catalytic C-H functionalization has provided new opportunities to access novel organic molecules more sustainably and efficiently. However, these procedures typically rely on precious metals or complex organic catalysts as well as on hazardous solvents or reaction conditions. Herein, a pioneering methodology for direct C-C bond formation enabled by Ligand-to-Metal Charge Transfer (LMCT) and mediated by UV irradiation has been developed using Deep Eutectic Solvents (DESs) as sustainable reaction media. This direct C-H bond functionalization via a radical addition to electrophiles was successfully confirmed over a broad scope of substrates. More importantly, this is the first example of photocatalytic C-C bond formation in DESs. An inexpensive and abundant iron catalyst (FeCl3) was used under air and mild conditions. Different functional groups were well tolerated obtaining promising results that were comparable to those reported in the literature. Additionally, the reaction medium along with the catalyst could be reused for up to 5 consecutive cycles without a significant loss in the reaction outcome. Several green metrics were calculated and compared to those of conventional procedures, revealing the advantages of using DESs.

Kinetic insights and pollution mitigation in waste tire pyrolysis: Targeting sulfur, nitrogen, and PAHs emissions

Waste tires have potential to be used for generation of fuel via thermal degradation because of their non-biodegradable nature. Nevertheless, the formation of various pollutants such as sulfur-based and nitrogen-based are inevitable due to presence of nitrogen and sulfur containing compounds during waste tires production. The main purpose was to examine the effect of variating heating rates on pollutants release because heating rate is an important parameter which influences the pollutants releasing profile. Moreover, Ar and CO2 as reaction medium were used to identify their behavior for restraining the PAHs in gas phase. The present study investigates the influence of heating rates and carrier gas environment (Argon and CO2) to reduce the pollutants emission. Thermogravimetry-Mass Spectrum coupled with Fourier transform infrared spectrometer was used to evaluate the thermal degradation and pollutants formation. The major degradation of waste tires occurred between 300 and 500 ℃. The sulfur-based (H2S, CS2, COS, SO2, and CH3SH), nitrogen-based (NH3, HNCO, NO, and HCN) and 9 series of PAHs pollutants were detected. The higher heating rates promoted the pollutants emission. The degradation of compounds having sulfur content formed -SH radials and -SH helped in further release of sulfur based-pollutants. The NH3 releasing profile started after 200 ℃ and released till around 800 ℃ for 30 ⁰C/min and 40 ⁰C/min but its emission was very low after 600 ⁰C for heating rates 5 ⁰C/min, 10 ⁰C/min, and 20 ⁰C/min. The aromatic compounds fraction was more at higher heating rate due to short residence time for pyrolytic products to go through secondary reaction. The 5 ℃/min and 10 ℃/min were considered favorable heating rates in terms of achieving lowest activation energy in both gas environments. The thermodynamic parameters analysis suggested that waste tires pyrolysis was non-spontaneous and endothermic reaction as well as feedstocks showed potential to be utilized for waste conversion.

The Nanoarchitectonics of Sustainable Smart Window Design by LCST Modulation of Photoresponsive Molecular π‐Systems

AbstractLower Critical Solution Temperature (LCST) of macromolecular systems is important in thermoresponsive smart window design. However, controlling the LCST behavior and sustaining the shelf‐life are challenging tasks. Herein, how photochemistry can be tweaked to design sustainable smart windows that allow controlled transmission of solar radiation is described. The cyanostilbene substituted naphthalenes 1(Z) and 2(Z), show Z/E‐photoisomerization and subsequent Mallory cyclization resulting in significant modulation in clouding temperatures (Tcloud). At 1 mM concentration, the Tcloud of 1(Z), and 1(E) are 33 ± 0.1 and 28 ± 0.13 °C, respectively whereas 2(Z) and 2(E) exhibit Tcloud around 37 ± 0.1 and 30 ± 0.1 °C, respectively. The high thermal barrier for the E/Z back isomerization of 1(E) and 2(E) and removal of oxygen from the reaction medium allow control of the photoprocesses, thereby facilitating the construction of sustainable smart windows that respond to the surrounding temperature. A 30 × 30 cm2 window prototype containing an aqueous solution of 1(Z) (1 mM) exhibits a fully transmissive state at 25 °C and a nearly zero‐transmissive state at 33 °C for 10,000 cycles of operation.

Enzymatic Synthesis of Prebiotic Carbohydrates from Lactose: Integration of Osmotic Membrane Distillation with Batch Reactor System

AbstractThis study aimed to enhance galactooligosaccharide (GOS) yield by maintaining high lactose concentration levels using osmotic membrane distillation (OMD) throughout the synthesis. The main problem influencing GOS yield during transgalactosylation is the decrease of lactose concentration over extended reaction periods. By integrating OMD with a continuous stirred batch reactor, water was progressively removed from the reaction medium. Compared to a standard batch reactor, the OMD-integrated system not only increased GOS yield by a maximum of 20.1% but also reduced the time needed for equivalent lactose conversion about 15–90 min. This integration particularly boosted the formation of longer-chain GOS. A consistent GOS yield of 67% was achieved, with up to 28% lactose conversion, surpassing the non-integrated reactor’s performance. The proposed reactor design shows promise for enhancing GOS production efficiency while concurrently concentrating the reaction medium in a single step.

Nickel ferrite decorated noble metal containing nitrogen-doped carbon nanotubes as potential magnetic separable catalyst for dinitrotoluene hydrogenation

The 2,4-toluenediamine (TDA) is one of the most important chemicals in the polyurethane industry, produced by the catalytic hydrogenation of 2,4-dinitrotoluene (DNT). The development of novel catalysts that can be easily recovered from the reaction mixture is of paramount importance. In our work, a NiFe2O4/N-BCNT supported magnetic catalyst was prepared by a modified coprecipitation method. The catalyst support alone also showed activity in the synthesis of TDA. Platinum nanoparticles were deposited on the catalyst support surface by a fast, relatively simple, and efficient sonochemical method, resulting in a readily applicable catalytically active system. The prepared catalyst exhibited high activity in hydrogenation tests, which was proved by the exceptionally high DNT conversion (100% for 120 min at 333 K) and TDA yield (99%). Furthermore, the magnetic catalyst can be easily recovered from the reaction medium by the action of an external magnetic field, which can greatly reduce catalyst loss during separation.

Friedel Crafts Reactions Revisited: Some Applications in Heterogeneous Catalysis#

Abstract: Important organic reactions require the use of catalysts. The Friedel-Crafts reactions were discovered by Charles Friedel and James Mason Crafts in 1887. They are an essential catalytic process since they are widely applied in different areas such as fuels, cleaning, and pharmacological products. The reaction is usually carried out in the presence of Lewis acids or Brønsted acids in a homogeneous medium, with the nucleophilic aromatic substrate in excess. Although there is still work in the literature on the Friedel- Crafts reaction in a homogeneous medium using metal halides, the tendency is to replace these catalysts, which generate effluents that are harmful to the environment. Heterogeneous catalysts using solid acids show advantages over homogeneous catalysts, especially concerning separating products from the reaction medium, recycling, and reusing. This paper presents a mini-review focusing on the use of solid acids in Friedel-Crafts reactions.

Ion- and surface-sensitive interactions during oxygen evolution reaction in alkaline media

Abstract Clean and sustainable energy has turned towards electrochemical water splitting as a viable solution in minimizing carbon emissions. Electrolysis of water converts electrical energy to chemical energy, through the production of hydrogen and oxygen gases, which can be harnessed for potential applications without contributing to greenhouse emissions. While this energy storage process shows great potential, its efficiency is hindered by the sluggish kinetics of the oxygen evolution reaction (OER). As a result, its widespread application in green electrolytic technologies is limited hence investigations on improving OER kinetics are of utmost importance. Recent research breakthroughs indicate that alkali metal cations are more than passive observers. They play complex roles in the electric double layer (EDL), which positively influences the OER kinetics. The presence of numerous ions and their combinations presents a challenge of complexity. This study aims to delve into the impact of alkali metal cations on OER activity due to the variance in their hydration energies. Specific investigations focusing on different alkali metal cations in solution, such as Li+, Na+, and K+, was conducted on RuO2 to gain a deeper understanding of how these ions interact with both reactants and intermediate species in the reaction kinetics. Traditional electrochemical tests, including cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and accelerated degradation test (ADT) measurements were employed to elucidate critical aspects such as surface activation, electric double layer interactions, catalytic activity and stability, ohmic resistance, and mass and charge transport.

Metal halide perovskites for solar‐to‐chemical energy conversion in aqueous media

AbstractSolar‐driven energy conversion is a promising technology for a sustainable energy future and environmental remediation, and an efficient catalyst is a key factor. Recently, metal halide perovskites (MHPs) have emerged as promising photocatalysts due to their exceptional photoelectronic properties and low‐cost solution processing, enabling successful applications in H2 evolution, CO2 reduction, organic synthesis, and pollutant degradation. Despite these successes, the practical applications of MHPs are limited by their water instability. In this review, the recently developed strategies driving MHP‐catalyzed reactions in aqueous media are outlined. We first articulate the structures and properties of MHPs, followed by elaborating on the origin of instability in MHPs. Then, we highlight the advances in solar‐driven MHP‐based catalytic systems in aqueous solutions, focusing on developing external protection strategies and intrinsically water‐stable MHP materials. With each approach offering peculiar sets of advantages and challenges, we conclude by outlining potentially promising opportunities and directions for MHP‐based photocatalysis research in aqueous conditions moving forward. We anticipate that this timely review will provide some inspiration for the design of MHP‐based photocatalysts, manifestly stimulating their applications in aqueous environments for solar‐to‐chemical energy conversion.

Obtaining and characterization of doped lanthanum manganite through an unconventional method

Considering the growing concern for food safety, the development of fast detection methods with high sensitivity and repeatability of specific food constituents is a huge necessity. In this regard, the electrochemical methods can be an effective way due to certain advantages such as low cost, fast response signal, high sensitivity and ease of use. The detection efficiency of electrochemical sensors mainly depends on the electrochemical characteristics of the electrode materials. Perovskite-based materials are ideal candidates for the development of electrochemical sensors due to their excellent catalytic activity and redox properties. We report herein the synthesis, morpho-structural properties, and electrical performance assessment of Ca doped lanthanum manganite by ultrasonic method with immersed sonotrode in the reaction medium. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were performed on the synthesized samples. The results indicated a wellcrystallized perovskite-type structure, and 29 nm average crystallite sizes. The electron microscopy images showed that the presence of the dopant influenced the surface morphology.

Contextual Teaching and Learning Interactive Media in Redox Reaction Concept for Improving Critical Thinking and Self-efficacy

Many students find redox reactions challenging due to educators focusing solely on imparting knowledge without real-world connections. This approach limits critical thinking and reduces students' self-efficacy. To address these issues, fostering creativity and developing interactive learning materials are essential solutions. This research aims to create contextual teaching and learning (CTL) based interactive learning media for redox reactions. This media focuses on validity, practicality, and effectiveness in enhancing students' critical thinking skills and self-efficacy. The research framework employed in this study follows a research and development method with an analysis, design, development, implementation, and evaluation (ADDIE) model, with a research subject of 31 students. The results showed that interactive learning media was declared valid by media experts and material experts with an average score of 92.50% (high validity category). Media is very practical based on readability tests, students' responses, teachers' responses and observation sheets average percentage of 85.92%. It is also proven to increase critical thinking skills in high effective category (N-gain 0.81), and increase self-efficacy in moderate category (N-gain 0.65).

PH-Dependent Morphology of Copper (II) Oxide in Hydrothermal Process and Their Photoelectrochemical Application for Non-Enzymatic Glucose Biosensor

In this study, we investigated the influence of pH on the hydrothermal synthesis of copper (II) oxide CuO nanostructures with the aim of tuning their morphology. By varying the pH of the reaction medium, we successfully produced CuO nanostructures with three distinct morphologies including nanoparticles, nanorods, and nanosheets according to the pH levels of 4, 7, and 12, respectively. The observed variations in surface morphology are attributed to fluctuations in growth rates across different crystal facets, which are influenced by the presence of intermediate species within the reaction. This report also compared the structural and optical properties of the synthesized CuO nanostructures and explored their potential for photoelectrochemical glucose sensing. Notably, CuO nanoparticles and nanorods displayed exceptional performance with calculated limits of detection of 0.69 nM and 0.61 nM, respectively. Both of these morphologies exhibited a linear response to glucose within their corresponding concentration ranges (3–20 nM and 20–150 nM). As a result, CuO nanorods appear to be a more favorable photoelectrochemical sensing method because of the large surface area as well as the lowest solution resistance in electroimpedance analysis compared to CuO nanoparticles and nanosheets forms. These findings strongly suggest the promising application of hydrothermal-synthesized CuO nanostructures for ultrasensitive photoelectrochemical glucose biosensors.