Important Reactions Research Articles

Integrating photothermal and plasmonic catalysis induced by near-infrared light for efficient reduction of 4-nitrophenol

The reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) is an important reaction in both chemical manufacturing and environmental protection. The design of a highly active, multifunctional and reusable catalyst for efficient 4-NP decontamination/valorization is therefore crucial to bring in economic and societal benefits. Herein, we achieve an efficient plasmonic-photothermal catalyst of Pd nanoparticles by growing them on graphene-polyelectrolytes self-assembly nanolayers via an in situ green reduction approach using polyelectrolyte as the reductant. The as-fabricated catalyst shows high catalytic behaviors and good stability (maintained over 92.5 % conversion efficiency after ten successive cycles) for 4-NP reduction under ultra-low catalyst dose. The rate constant and turnover frequency were calculated at 0.197 min−1 and 7.79 mmol g−1 min−1, respectively, which were much higher than those of most reported catalysts. Moreover, the as-prepared catalyst exhibited excellent photothermal conversion efficiency of ∼77 % and boosted 4-NP reduction by ∼2-fold under near-infrared irradiation (NIR). This study provides valuable insights into the design of greener catalytic materials and facilitates the development of multifunctional plasmonic-photothermal catalysts for diverse environmental, chemical, and energy applications using NIR.

Femtoliter oil droplets act as CO2 micropumps for uninterrupted electrochemiluminescence at the water|oil interface

Interfacial effects are well-known to significantly alter chemical reactivity, especially in confined environments, where the surface to volume ratio increases. Here, we observed an inhomogeneity in the electrogenerated chemiluminescence (ECL) intensity decrease over time in a multiphasic system composed of femtoliter water droplets entrapping femtoliter volumes of the 1,2-dichloroethane (DCE) continuous phase. In usual electrochemiluminescence (ECL) reactions involving an ECL chromophore and oxalate ([C2O4]2−), the build-up of CO2 diminishes the ECL signal with time because of bubble formation. We hypothesised that relative solubilities of chemical species in these environments play a dramatic role in interfacial reactivity. Water droplets, loaded with the ECL luminophore [Ru(bpy)3]2+ and the coreactant [C2O4]2− were allowed to stochastically collide and adsorb at the surface of a glassy carbon macroelectrode. When water droplets coalesce on the surface, they leave behind femtoliter droplets of the DCE phase (inclusions). We report the surprising finding that the addition of multiple interfaces, due to the presence of continuous phase’s femtoliter inclusions, allows sustained ECL over time after successive potential applications at the triple-phase boundary between water droplet|electrode|DCE inclusion. When femtoliter droplets of DCE form on the electrode surface, bright rings of ECL are observed during the simultaneous oxidation of [Ru(bpy)3]2+ and [C2O4]2−. Control experiments and finite element modelling allowed us to propose that these rings arise because CO2 that is generated near the 1,2-dichloroethane droplet partitions in due to relative solubility of CO2 in 1,2-dichloroethane and builds up and/or is expelled at the top of the droplet. The small droplets of the DCE phase act as micropumps, pumping away carbon dioxide from the interface. These results highlight the unexpected point that confined microenvironments and their geometry can tune chemical reactions of industrial importance and fundamental interest.

CO Oxidation Promoted by NO Adsorption on RhMn2O3- Cluster Anions.

CO oxidation represents an important model reaction in the gas phase to provide a clear structure-reactivity relationship in related heterogeneous catalysis. Herein, in combination with mass spectrometry experiments and quantum-chemical calculations, we identified that the RhMn2O3- cluster cannot oxidize CO into gas-phase CO2 at room temperature, while the NO preadsorbed products RhMn2O3-[(NO)1,2] are highly reactive in CO oxidation. This discovery is helpful to get a fundamental understanding on the reaction behavior in real-world three-way catalytic conditions where different kinds of reactants coexist. Theoretical calculations were performed to rationalize the crucial roles of preadsorbed NO where the strongly attached NO on the Rh atom can greatly stabilize the products RhMn2O2-[(NO)1,2] during CO oxidation and at the same time works together with the Rh atom to store electrons that stay originally in the attached CO2- unit. The leading result is that the desorption of CO2, which is the rate-determining step of CO oxidation by RhMn2O3-, can be greatly facilitated on the reactions of RhMn2O3-[(NO)1,2] with CO.

Ceria-Catalyzed Hydrolytic Cleavage of Sulfonamides.

Nanoceria is a promising nanomaterial for the catalytic hydrolysis of a wide variety of substances. In this study, it was experimentally demonstrated for the first time that CeO2 nanostructures show extraordinary reactivity toward sulfonamide drugs (sulfadimethoxine, sulfamerazine, and sulfapyridine) in aqueous solution without any illumination, activation, or pH adjustment. Hydrolytic cleavage of various bonds, including S-N, C-N, and C-S, was proposed as the main reaction mechanism and was indicated by the formation of various reaction products, namely, sulfanilic acid, sulfanilamide, and aniline, which were identified by HPLC-DAD, LC-MS/MS, and NMR spectroscopy. The kinetics and efficiency of the ceria-catalyzed hydrolytic cleavage were dependent on the structure of the sulfonamide molecule and physicochemical properties of Nanoceria prepared by three different precipitation methods. However, in general, all three ceria samples were able to cleave SA drugs tested, proving the robust and unique surface reactivity toward these compounds inherent to cerium dioxide. The demonstrated reactivity of CeO2 to molecules containing sulfonamide or even sulfonyl (and similar) functional groups may be significant for both heterogeneous catalysis and environmentally important degradation reactions.

Hydrodeoxygenation of Carbonyl Compounds Biomass Derivatives Using CaH2 over Pd/C

AbstractThe high content of oxygenated compounds present in the biomass constitutes an important drawback to transforming it into a suitable alternative of chemical entities. In this sense, hydrodeoxygenation (HDO) is an important reaction for the cleavage of the strong C−O bond. Herein we report our findings about the use of Pd/C and CaH2 system for the HDO of several aromatic and aliphatic aldehydes and ketones.

Contribution of Hydroxycinnamic Acids to Color Formation in Nonenzymatic Browning Reactions with Key Maillard Reaction Intermediates.

The Maillard reaction is a vital part of food processing, involving a vast number of complex reaction pathways, resulting in high-molecular-weight colorants. So far, studies have been focused on the conversion of carbohydrates and amino compounds, but the literature elaborating the contribution of phenolic compounds to the formation of the colored end-products is still rare. The aim of this study was to characterize early reactions, underlying the formation of phenol-containing melanoidins. For this purpose, binary model systems of the prominent phenolic compounds caffeic acid and ferulic acid combined with α-dicarbonyl compounds typically formed in the Maillard reaction such as glyoxal, methylglyoxal, and diacetyl were analyzed after heat treatment. High-resolution mass spectrometry revealed that decarboxylation, aromatic electrophilic substitution, and nucleophilic addition are important reaction steps that lead to colored heterogeneous oligomers. Polymerization was favored for phenolic compounds with a high electron density in the aromatic system and for α-dicarbonyl compounds carrying aldehyde functions.

Unraveling FeOx Nanoparticles Confined on Fibrous Mesoporous Silica Catalyst Construction and CO Catalytic Oxidation Performance

Catalytic oxidation is used to control carbon monoxide (CO) emissions from industrial exhaust. In this study, a mesoporous silica material, KCC-1, was synthesized and used as a carrier with a high specific surface area to confine active component FeOx nanoparticles (NPs), and the CO catalytic oxidation performance of x%Fe@KCC-1 catalysts (x represents the mass loading of Fe) was studied. The experimental results showed that due to its large specific surface area and abundant mesopores, the FeOx NPs were highly dispersed on the surface of the KCC-1 carrier. The particle size of FeOx was very small, resulting in strong interactions between FeOx NPs and KCC-1, which enhanced the catalytic oxidation reaction on the catalyst. The FeOx loading improved the CO adsorption capability of the catalyst, which facilitated the catalytic oxidation of CO, with the 7%Fe@KCC-1 catalyst achieving 100% CO conversion at 160 °C. The CO catalytic removal mechanism was investigated by a combination of in-situ DRIFTS and DFT calculations. This study advances scientific understanding of the application potential of nano-catalysts in important oxidation reactions and provides valuable insights into the development of efficient CO oxidation catalysts.

The sweat rate as a digital biomarker in clinical medicine beyond sports science

Sweating is an important physiological reaction and a clinical symptom in a variety of diseases. However, it remains underrated in clinical use. Gold standards to measure the sweat rate are neither continuous nor easily or lab-independently applicable. With the emergence of novel wearable devices, using the sweat rate as a digital biomarker shows promise for clinical monitoring and diagnostics. In this Commentary, we discuss the potential and importance of the sweat rate as a digital biomarker in clinical medicine beyond sports science.

Defluorination of perfluorooctanoic acid and perfluorooctane sulfonic acid by heterogeneous catalytic system of Fe-Al2O3/O3: Synergistic oxidation effects and defluorination mechanism

In this study, catalytic ozonation by Fe-Al2O3 was used to investigate the defluorination of PFOA and PFOS, assessing the effects of different experimental conditions on the defluorination efficiency of the system. The oxidation mechanism of the Fe-Al2O3/O3 system and the specific degradation and defluorination mechanisms for PFOA and PFOS were determined. Results showed that compared to the single O3 system, the defluorination rates of PFOA and PFOS increased by 2.32- and 5.92-fold using the Fe-Al2O3/O3 system under optimal experimental conditions. Mechanistic analysis indicated that in Fe-Al2O3, the variable valence iron (Fe) and functional groups containing C and O served as important reaction sites during the catalytic process. The co-existence of 1O2, OH, O2− and high-valence Fe(IV) constituted a synergistic oxidation system consisting of free radicals and non-radicals, promoting the degradation and defluorination of PFOA and PFOS. DFT theoretical calculations and the analysis of intermediate degradation products suggested that the degradation pathways of PFOA and PFOS involved Kolbe decarboxylation, desulfonation, alcoholization and intramolecular cyclization reactions. The degradation and defluorination pathways of PFOA and PFOS consisted of the stepwise removal of -CF2-, with PFOS exhibiting a higher defluorination rate than PFOA due to its susceptibility to electrophilic attack. This study provides a theoretical basis for the development of heterogeneous catalytic ozonation systems for PFOA and PFOS treatment.

Cooperative Triple Catalysis Enables Deaminative α-Indolmethylation of Carbonyl Compounds with Gramines.

α-Functionalization of carbonyl compounds is an important reaction in synthetic chemistry. However, the development of novel synthetic strategies to realize this reaction is challenging. This study describes the α-indolmethylation of carbonyl compounds using cooperative copper, amine, and hydrogen-bond catalysis. This reaction provides a novel and efficient strategy for developing indolmethylated carbonyl compounds by deaminative coupling of gramines.

L-proline-based deep eutectic solvents as green and enantioselective organocatalyst/media for aldol reaction

The use of chiral deep eutectic solvents (DESs) based on the natural amino acid L-proline and various glycols presents an environmentally friendly approach for important CC bond formation reactions. These DESs serve as both organocatalysts and reaction media in the aldol reaction, reducing the need for additional toxic or hazardous chemicals. By employing these DESs, we were able to activate the desired reaction through the condensation of ketones and L-proline via enamine activation. This approach eliminates the requirement for traditional, often environmentally harmful, organic solvents. Notably, diethylene glycol played a crucial role in modulating the reaction performance, including conversion and enantioselectivity. Diethylene glycol is a relatively safer alternative compared to other commonly used solvents or additives with potential environmental and health risks. Moreover, reducing the L-proline content in the DESs led to a slight increase in the enantiomeric excess of the predominant diastereomeric product. This finding suggests the possibility of minimizing the use of L-proline, which can be advantageous from both cost and environmental perspectives.The results of these reactions demonstrate promising green outcomes, with a diastereomeric ratio up to 25:1 for the major anti-isomer, showcasing excellent selectivity (>90 % ee). In addition to these high enantiomeric excess values, quantitative yields in the aldol reaction highlight the potential for high efficiency and reduced waste production.Overall, the utilization of chiral DESs based on L-proline and glycols offers a greener alternative for enantioselective organocatalytic reactions. This approach minimizes the use of hazardous catalysts, reduces waste generation, and demonstrates impressive selectivity, paving the way for more sustainable synthetic methodologies.

The Relevance of the Interfacial Water Reactivity for Electrochemical CO Reduction on Copper Single Crystals.

The electrochemical reduction of CO2 is an important electrolysis reaction that enables the conversion of a waste gas to fuels or value-added chemicals. To make this reaction viable, a profound understanding of central intermediate steps, such as the CO electroreduction, is required. On Cu, the CO reduction reaction (CORR) is intimately linked to the hydrogen evolution reaction (HER) that proceeds via the reduction of water in alkaline or neutral electrolytes. Here, we demonstrate that the interaction of water or more specifically the water reduction kinetics on differently smooth Cu(100) and Cu(111) surfaces during the CORR in alkaline media significantly governs the CORR. On Cu(111), faster HER kinetics and the highest CORR activity are observed, even though HER and CORR onsets are more negative. While on Cu(100) small Cu ad-island clusters form in the cathodic potential range only when CO is present, structural changes appear on a larger length scale on Cu(111) both under CORR conditions and when no CO is present. These differences in the reconstruction characteristics may be attributed to the dominance of either the CORR and its intermediates or the HER on the different Cu surfaces. Therefore, the interfacial water reactivity is considered an essential activity descriptor for the CORR on Cu in alkaline media.

A numerical study of NOX and soot emissions in ethylene-ammonia diffusion flames with oxygen enrichment

Blending ammonia with hydrocarbon fuels is gaining interest due to its potential to significantly reduce carbon emissions from the combustion of these blends. Additionally, studies have provided strong evidence of oxygen enhanced combustion to reduce soot emissions and improve flame stability. The present work attempts to leverage the benefits of both strategies, ammonia doping and oxygen enhanced combustion, by considering ethylene diffusion flames. Simulations are performed using the CHEMKIN-Pro software. A reaction mechanism with 372 species and 13,847 reactions is developed by combining gas phase chemistries for ethylene, NH3 and NOX, along with a detailed soot mode. The mechanism is extensively validated for a range of fuel blends in terms of flame structure, intermediate hydrocarbons, soot precursors and soot. Oxygen enrichment is achieved by removing certain amount of nitrogen from oxidizer stream and adding it to fuel stream, and thereby maintaining a nearly constant flame temperature. Extensive analysis is carried out to characterize the chemical and dilution effects of ammonia doping on flame structure, soot precursors, soot, and NOX in ethylene flames with varying levels of oxygenation. Further, dominant reaction pathways for several soot precursors and NOx are identified through detailed rate of production analyses. Results indicate that ammonia doping in ethylene flames leads to substantial increase in NOX emissions, while oxygenation has negligible influence on NOX emissions. In contrast, both NH3 doping and oxygenation provide significant reduction in the formation of soot precursors and soot. Oxygenation achieves this reduction through both hydrodynamic and flame structure effects, as the flame shifts from oxidizer side to fuel side. On the other hand, NH3 doping reduces the rates of important reactions for the formation of soot precursors, as the concentrations of relevant species (C2H2, C3H3, C3H3-P, C3H3-A etc.) decrease due to their consumption through reactions with species like NCO and CN formed from NH3. Moreover, the effectiveness of NH3 doping is further enhanced when combined with oxygenation. Hence, NH3 doping and oxygenation are found to be effective and synergistic strategies in reducing soot emissions, and their proper combination could provide near zero soot emissions.

Experimental study on the preparation of monodisperse nano-silver by hydrothermal synthesis

As a new material with wide application prospect, nano-silver is getting high attention. Hydrothermal synthesis has the advantages of green, easy operation and low cost, and is a promising technology for the preparation of nano-silver. In this paper, the effects of reaction time, reaction temperature, precursor concentration, PVP concentration and modifier addition on the particle size distribution and surface morphology of nano-silver during the subcritical hydrothermal reaction were optimized by comparing the supercritical and subcritical hydrothermal methods. Then, the important role and reaction mechanism of PVP as a modifier and the formation mechanism of spherical nano-silver particles were analyzed. The experimental results showed that the average particle size of 23.68 nm can be obtained by using NaHCO3 and PVP as reducing and dispersing agents, the reaction time is 5 h, the reaction temperature is 180 °C, and the concentrations of AgNO3 and PVP are 0.1 M and 0.3 M, respectively, to obtain the more uniformly dispersed silver nanoparticles. The results provide an important reference for future research on the preparation of conductive pastes.

Hydrogen Storage System Attained by HCOOH-CO2 Couple: Recent Developments in Pd-Based Carbon-Supported Heterogeneous Catalysts

The present review revisits representative studies addressing the development of efficient Pd-based carbon-supported heterogeneous catalysts for two important reactions, namely, the production of hydrogen from formic acid and the hydrogenation of carbon dioxide into formic acid. The HCOOH-CO2 system is considered a promising couple for a hydrogen storage system involving an ideal carbon-neutral cycle. Significant advancements have been achieved in the catalysts designed to catalyze the dehydrogenation of formic acid under mild reaction conditions, while much effort is still needed to catalyze the challenging CO2 hydrogenation reaction. The design of Pd-based carbon-supported heterogeneous catalysts for these reactions encompasses both the modulation of the properties of the active phase (particle size, composition, and electronic properties) and the modification of the supports by means of the incorporation of nitrogen functional groups. These approaches are herein summarized to provide a compilation of the strategies followed in recent studies and to set the basis for a hydrogen storage system attained using the HCOOH-CO2 couple.

Characterization of Dominant Hydrogeochemical Processes in Groundwater in Onitsha Area, Southeastern Nigeria

The characterization of the dominant hydrogeochemical processes in groundwater in Onitsha area, southeastern Nigeria was carried out. This is to identify the dominant mechanisms responsible for the evolution and the chemical composition of the water sources. A total of fifteen (15) groundwater samples were collected from different locations in the study area in August 2022 and these samples were subjected to chemical analysis using standard methods. The results indicated that the water quality parameters were within the World Health Organization acceptable limits for drinking quality although turbidity in six of the samples exceeded the guideline values. The hydrochemical facies were determined using various plots. Piper diagrams indicated that Ca2+ - Mg2+ - Cl- – SO42- was the dominant facies with Ca2+ and Cl- as the dominant ions. The Durov diagram indicate recharge water in limestone and sandstone aquifers and influenced by important ion exchange reactions. However, the Gibbs plots mainly plotted in the rock dominance zone indicating that the major processes controlling water chemistry in the study area were water-rock interaction and dissolution of rock minerals. The ionic ratio plots were employed to determine the mechanisms and reactions prevalent in the study area that influenced the water chemistry. Na/Cl plot indicated that the excess of Cl- over Na+ was balanced by Ca2+ and Mg2+ while the depletion of Na+ with respect to Clindicated ion exchange reaction which could be attributed to silicate weathering confirming the Na/Cl plot conclusions. The relative abundance of anionic facies shows that Cl- + SO42- were more abundant than HCO3- and the plot of Ca2+ + Mg2+ ions against HCO3- ions depict samples with excess Ca2+ + Mg2+. However, Ca2+ +Mg/HCO3 ratio was less than one (<1) and indicated fresh recharge water.

Kinetic multilayer models for surface chemistry in indoor environments.

Multiphase interactions and chemical reactions at indoor surfaces are of particular importance due to their impact on air quality in indoor environments with high surface to volume ratios. Kinetic multilayer models are a powerful tool to simulate various gas-surface interactions including partitioning, diffusion and multiphase chemistry of indoor compounds by treating mass transport and chemical reactions in a number of model layers in the gas and condensed phases with a flux-based approach. We have developed a series of kinetic multilayer models that have been applied to describe multiphase chemistry and interactions indoors. They include the K2-SURF model treating the reversible adsorption of volatile organic compounds on surfaces, the KM-BL model treating diffusion through an indoor surface boundary layer, the KM-FILM model treating organic film formation by multi-layer adsorption and film growth by absorption of indoor compounds, and the KM-SUB-Skin-Clothing model treating reactions of ozone with skin lipids in skin and clothing. We also developed the effective mass accommodation coefficient that can treat surface partitioning by effectively taking into account kinetic limitations of bulk diffusion. In this study we provide detailed instructions and code annotations of these models for the model user. Example sensitivity simulations that investigate the impact of input parameters are presented to help with familiarization to the codes. The user can adapt the codes as required to model experimental and indoor field campaign measurements, can use the codes to gain insights into important reactions and processes, and can extrapolate to new conditions that may not be accessible by measurements.

Development of supported intermetallic compounds: advancing the Frontiers of heterogeneous catalysis.

Intermetallic compound (IMC) catalysts have garnered significant attention due to their unique surface and electronic properties, which can lead to enhanced catalytic performance compared to traditional monometallic catalysts. However, developing IMC materials as high-performance catalysts has been hindered by the inherent complexity of synthesizing nanoparticles with well-defined bulk and surface compositions. Achieving precise control over the composition of supported bimetallic IMC catalysts, especially those with high surface area and stability, has proven challenging. This review provides a comprehensive overview of the recent progress in developing supported IMC catalysts. We first examine the various synthetic approaches that have been explored to prepare supported IMC nanoparticles with phase-pure bulk structures and tailored surface compositions. Key factors influencing the formation kinetics and compositional control of these materials are discussed in detail. Then the strategies for manipulating the surface composition of supported IMCs are delved into. Applications of high-performance supported IMCs in important reactions such as selective hydrogenation, reforming, dehydrogenation, and deoxygenation are comprehensively reviewed, showcasing the unique advantages offered by these materials. Finally, the prevailing research challenges associated with supported IMCs are identified, including the need for a better understanding of the composition-property relationships and the development of scalable synthesis methods. The prospects for the practical implementation of these versatile catalysts in industrial processes are also highlighted, underscoring the importance of continued research in this field.

Unlocking the secrets of porous silicon formation: insights into magnesiothermic reduction mechanism using in situ powder X-ray diffraction studies.

The magnesiothermic reduction of SiO2 is an important reaction as it is a bulk method that produces porous Si for a wide range of applications directly from SiO2. While its main advantage is potential tunability, the reaction behavior and final product properties are heavily dependent on many parameters including feedstock type. However, a complete understanding of the reaction pathway has not yet been achieved. Here, using in situ X-ray diffraction analysis, for the first time, various pathways through which the magnesiothermic reduction reaction proceeds were mapped. Further, the key parameters and conditions that determine which pathways are favored were determined. It was discovered that the reaction onset temperatures can be as low as 348 ± 7 °C, which is significantly lower when compared to previously reported values. The onset temperature is dependent on the size of Mg particles used in the reaction. Further, Mg2Si was identified as a key intermediate rather than a reaction byproduct during the reduction process. Its rate of consumption is determined by the reaction temperature which needs to be >561 °C. These findings can enable process and product optimization of the magnesiothermic reduction process to manufacture and tune porous Si for a range of applications.

The Prothrombin-Prothrombinase Interaction.

The hemostatic response to vascular injury entails a sequence of proteolytic events where several inactive zymogens of the trypsin family are converted to active proteases. The cascade starts with exposure of tissue factor from the damaged endothelium and culminates with conversion of prothrombin to thrombin in a reaction catalyzed by the prothrombinase complex composed of the enzyme factor Xa, cofactor Va, Ca2+, and phospholipids. This cofactor-dependent activation is paradigmatic of analogous reactions of the blood coagulation and complement cascades, which makes elucidation of its molecular mechanism of broad significance to the large class of trypsin-like zymogens to which prothrombin belongs. Because of its relevance as the most important reaction in the physiological response to vascular injury, as well as the main trigger of pathological thrombotic complications, the mechanism of prothrombin activation has been studied extensively. However, a molecular interpretation of this mechanism has become available only recently from important developments in structural biology. Here we review current knowledge on the prothrombin-prothrombinase interaction and outline future directions for the study of this key reaction of the coagulation cascade.