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Carbon aerogels (CAs) have garnered significant attention due to their multifunctional applications. Biomass waste, abundantly generated by agriculture and industry, serves as a primary carbon source. However, developing a facile, sustainable, and efficient method to produce CAs from biomass waste remains challenging. In this study, a one‐step Zn2+ ion‐glue‐assisted carbonization technique was developed to produce large‐scale, high‐performance CAs. Various biomass materials (wood bits, peanut shells, bamboo bits, and straw waste) were treated in a molten salt system (ZnCl2/KCl) at 300 °C for 2 h to obtain large‐block CAs derived from biomass bits. Zn2+ ions cleave cellulose hydrogen bonds in natural biomass, facilitating the dehydration crosslinking reaction among cellulose, hemicellulose, and lignin, thus reconstructing the entire block structure. The resulting CAs exhibited high porosity (95 %) and low density (0.078 g/cm3). Numerous hydroxyl and carbonyl groups were preserved during the low‐temperature treatment, facilitating chemical modification for diverse applications. For instance, amidoxime functionalized CAs were utilized as filters for selective and highly efficient extraction of U(VI) from wastewater. The adsorption capacity and extraction efficiency reached 801.2 mg/g and 95 % with a flux rate of 6.1×103 L/m2 ⋅ h. [ABSTRACT FROM AUTHOR]

In single‐step conversion of glycerol to propene, the intricate catalytic pathways with molybdenum and niobium catalysts remain elusive. While these catalysts can effectively accelerate the hydrogenolytic cleavage of the glycerol CO bonds, resulting in a high selectivity to propene, the routes have not been thoroughly studied. This study explores the reaction routes and the role hydrogen plays in determining the product distribution. The hydrodeoxygenation (HDO) of glycerol was investigated using various glycerol purities in both batch and continuous reaction modes. Remarkably, Mo(PO4)x and Nb(PO4)x demonstrated catalytic performance with raw glycerol, indicating that impurities had no detrimental effect on the catalyst's activity. In batch mode, a propene selectivity of 53% was achieved over Mo(PO4)x as the catalyst, highlighting the catalyst's stability under these conditions. In continuous operation, the highest product selectivity to propene (12%) was observed at low temperatures (573 K), while more C2 to C6 alkanes were formed at increased temperatures (623 and 673 K). Whereas a hydrogen atmosphere promotes formation of 2‐propenol, as primary precursor to propene, an inert atmosphere leads to increased formation of propanal and dissociation products. Our work has elucidated new routes to upcycle biorenewable glycerol to propene over Mo(PO4)x and Nb(PO4)x catalysts. [ABSTRACT FROM AUTHOR]

Hydration and dehydration reactions play pivotal roles in plate tectonics and the deep water cycle, yet many facets of (de)hydration reactions remain unclear. Here, we study (de)hydration reactions where associated solid density changes are predominantly balanced by porosity changes, with solid rock deformation playing a minor role. We propose a hypothesis for three scenarios of (de)hydration front propagation and test it using one‐dimensional hydro‐mechanical‐chemical models. Our models couple porous fluid flow, solid rock volumetric deformation, and (de)hydration reactions described by equilibrium thermodynamics. We couple our transport model with reactions through fluid pressure: the fluid pressure gradient governs porous flow and the fluid pressure magnitude controls the reaction boundary. Our model validates the hypothesized scenarios and shows that the change in solid density across the reaction boundary, from lower to higher pressure, dictates whether hydration or dehydration fronts propagate: decreasing solid density causes dehydration front propagation in the direction opposite to fluid flow while increasing solid density enables both hydration and dehydration front propagation in the same direction as fluid flow. Our models demonstrate that reactions can drive the propagation of (de)hydration fronts, characterized by sharp porosity fronts, into a viscous medium with zero porosity and permeability; such propagation is impossible without reactions, as porosity fronts become trapped. We apply our model to serpentinite dehydration reactions with positive and negative Clapeyron slopes and granulite hydration (eclogitization). We use the results of systematic numerical simulations to derive a new equation that allows estimating the transient, reaction‐induced permeability of natural (de)hydration zones. Plain Language Summary: We investigate reactions of hydration, which is the incorporation of water into a rock, and dehydration, which is the liberation of water from a rock, with simple mathematical models. These reactions are critical in understanding processes like plate tectonics, but many aspects of how hydration or dehydration fronts move through a rock are unclear. Our research focuses on reactions where changes in density are mostly balanced by changes in pore space, termed porosity, rather than the deformation of the solid rock. We developed mathematical models that combine fluid flow, rock deformation, and hydration/dehydration reactions. We derived simple equations that predict changes in porosity during hydration and dehydration, even when the solid rock deforms simultaneously. We found that whether a rock hydrates or dehydrates depends on how its solid density changes with increasing pressure during the reaction. By systematically studying our model, we discovered that the speed of hydration and dehydration is not influenced by the interval of fluid pressure over which the reaction occurs or the relationship between porosity and permeability. We present an equation that can be used to estimate permeability from natural (de)hydration zones. Key Points: (De)hydration fronts propagate into zero‐permeability rock if the solid density of the reactant is smaller than the one of the productExternal fluid flux compensates the imbalance between fluid generated/consumed by reaction and fluid needed to fill generated porosityResults of systematic numerical simulations allow estimating the transient, reaction‐induced permeability of natural (de)hydration zones [ABSTRACT FROM AUTHOR]

5‐Hydroxymethylfurfural (HMF) was transformed into 2,5‐diformylfuran (DFF) with nitric acid as the oxidant. The initial HMF content was as high as 12.5 wt %, and water was the sole solvent. This is an intensely exothermic reaction along with the emission of NO2 gas. A high DFF yield of 83.2 % was achieved if the oxidation ability of nitric acid matched with the requirement of target oxidation reaction while mismatched those of side reactions by regulating the initial concentration of nitric acid (59.5 wt %) and reaction temperature (50–60 °C). The oxidation reaction of HMF, overoxidation of HMF, and skeleton‐cracking reaction of FDCA preferred concentrated HNO3, hot HNO3, and concentrated or hot HNO3, respectively. After liquid‐liquid extraction, filtration, and column chromatography, light‐yellow DFF powders with purity of 92.1 wt % and isolated yield of 40.2 % were obtained and confirmed by NMR, FTIR, UV‐Vis, and elemental analysis. HMF was the dominant impurity due to its affinity to DFF. In addition, chromogenic substances were obtained as a byproduct, and they were potential pH indicators. These chromogenic substances had highly conjugated molecular structures, and they were generated via successive β‐protonation‐based ring‐opening reaction of HMF, aldol reaction, and dehydration reaction. [ABSTRACT FROM AUTHOR]

Increases in temperature and pressure caused by rapid burial of sediments seaward of the Sumatra subduction zone have been hypothesized to trigger dehydration reactions that diagenetically strengthen sediments and contribute to the formation of an over‐pressured pre‐décollement, which together facilitate the occurrence of large shallow earthquakes. We present paleomagnetic, rock magnetic, and electron microscopic analyses from drill cores collected offshore Sumatra at Site U1480 during IODP Expedition 362 that support this hypothesis. The older pre‐fan units (Late Cretaceous to early Paleocene) were deposited when Site U1480 was moving rapidly northward with the Indian plate from a paleolatitude of 50° to 30°S, which would equate to expected absolute paleomagnetic inclinations of 70°–43°. Most of the older pre‐fan sediments, however, have shallow observed inclinations (shallower than ±20°), indicating that the sediments were overprinted when Site U1480 was located near the paleoequator, as it has been since the early Oligocene. Electron microscopic observations reveal that the pre‐existing detrital magnetite grains have undergone pervasive dissolution and alteration by hydrothermal fluids. The diagenesis observed is consistent with mineral dehydration, possibly driven by rapid burial of pelagic sediments by the ∼1250 m thick Nicobar Fan sequence. In addition, the elevated burial temperature also facilitated the smectite to illite conversion reaction. We hypothesize that chemical reactions resulted in the formation of fine‐grained magnetite that records a chemical remanent magnetization overprint. This overprint is consistent with the alteration occurring after burial by the thick Nicobar Fan sequence sometime in the past few million years. Plain Language Summary: Sediments and rocks commonly contain magnetic minerals that record the direction and intensity of Earth's magnetic field as they are being emplaced, thus preserving an ancient record of the geomagnetic field. Subsequent alteration of the magnetic minerals caused by heating and/or fluid circulation can result in the acquisition of secondary magnetizations (i.e., remagnetization) that may overprint or completely reset the primary ancient magnetization. Such remagnetization provides evidence of the physical and chemical changes that have occurred. Here through paleomagnetic, rock magnetic, and microscopic analyses of the deeper older (pre‐fan) stratigraphic sequence cored offshore Sumatra, we find that hydrothermal fluids, resulting from mineral dehydration driven by rapid burial of this sequence by younger, thick Nicobar Fan sediments, led to pervasive secondary remagnetization. Consequently, the newly formed magnetite recorded a much younger paleomagnetic field, leaving a shallow overprint that probably occurred sometime in the past few million years. The dehydration reactions also increased the strength of the sediments entering the subduction zone and aided in the formation of slip surfaces (called décollements), possibly contributing to the shallow, large earthquakes that have generated tsunamis off Sumatra. Key Points: The 60–67 Ma pre‐fan sediments offshore Sumatra were most likely remagnetized since deposition of the Nicobar Fan sediments, which began at ∼9 MaRemagnetization of pre‐fan sediments caused by mineral dehydration may be linked to shallow seismogenic slip off SumatraMagnetic properties of input sediments in the subduction margin record conditions that may have facilitated the generation of earthquakes [ABSTRACT FROM AUTHOR]

Inorganic perovskites, with Cs+ substituting volatile organic components, show great promise in photovoltaic applications due to their outstanding optoelectronic properties and thermal stability. However, the black‐to‐yellow phase transition of CsPbI3 remains a challenge for realizing high‐performance inorganic perovskite solar cells (IPSCs). Herein, an effective approach is reported via incorporating the self‐assembled molecule Me‐4PACz to synergistically stabilize the [PbI6]4− octahedra and form a hydrophobic layer at interface and grain boundaries. An in situ dehydration condensation reaction of Me‐4PACz is observed during film annealing, which favors the reduction of undesired aggregation of Me‐4PACz in humid air, thus leading to enhanced anchoring interaction and more effective hydrophobic protection of CsPbI3. Therefore, the air‐processed CsPbI3 perovskite films show dramatically improved phase purity and humid stability. This strategy also improves the energy level alignment between perovskite and charge transport layers. As a result, a champion efficiency of 20.21% is realized, representing one of the highest reported values for air‐processed inverted IPSCs. Furthermore, it is demonstrated that by combining Me‐4PACz with the previously reported ethacridine lactate (EAL) additive, the device performance can be further boosted to 21.38%, which is a record efficiency for the inverted IPSCs reported to date. [ABSTRACT FROM AUTHOR]

The conversion of Methyl 3‐hydroxypropionate (3‐HPM) to 1,3‐propanediol (1, 3‐PDO) is an important step in the pathway towards the longterm sustainable production of the ethylene oxide hydroesterification. However, 3‐HPM is prone to side reactions like hydroxyl β‐dehydration and low reaction efficiency, which hinders its development. This study presents the first‐ever report on highly efficient gallium‐promoted Cu/SiO2 catalysts prepared using ethanol‐assisted ammonia‐evaporation (Et‐AE) for converting 3‐HPM to 1,3‐PDO. The prepared Cu‐1Ga/SiO2 catalyst exhibited satisfactory catalytic activity and 1,3‐PDO selectivity in the hydrogenation reaction, with a conversion of 3‐HPM of 94 % and a selectivity to 1,3‐PDO of 91 %. The characterisation results show that the addition of Ga increases the specific surface area and the pore volume of the catalyst, and also increases the dispersion of the Cu species. And the promotional effect likely originates from interactions between Ga3+ and Cu0 species though enhanced ability of the latter to activate H2. In addition, the introduction of Ga into the catalyst increases the interaction between Cu and the support, making it more difficult for Cu+ to be completely reduced to Cu0. This increases the content of Cu+ in the catalyst, which is beneficial for improving the activity and stability of the catalyst. This study investigates modifying Cu catalysts to provide guidelines for obtaining high performing hydrogenation catalysts. [ABSTRACT FROM AUTHOR]

Antigorite is the high‐temperature member of the serpentine group minerals and is broadly considered a primary carrier of water in the subducting oceanic lithosphere. It has a wavy crystal structure along its a‐axis and several polysomes with different m‐values (m = 13–24) have been identified in nature. The m‐value is defined as the number of tetrahedra in one wavelength and is controlled by the misfit between the octahedral and tetrahedral layers. The degree of misfit primarily depends on the volumes of the MgO6 octehedra and SiO4 tetrahedra within the layers, which vary as a function of pressure and temperature. However, it is not well understood which m‐values of antigorite are stable at different pressure and temperature conditions. To investigate the pressure dependence of the stability of different m‐values in antigorite, we performed first‐principles calculations for several polysomes (m = 14–19) at high pressure from 0 to 14 GPa and compared their enthalpies at static 0 K. We found that although the energy differences between polysomes are small, polysomes with larger m‐values are more stable at ambient pressure, while polysomes with smaller m‐values are more stable at elevated pressures. This suggests that the structure of antigorite in the oceanic lithosphere subducting into the deep Earth may gradually evolve into a different polysome structure than the antigorite samples observed at ambient or near‐surface pressure conditions. These changes in the m‐values are accompanied by a minor dehydration reaction. By modulating the available amount of free water in the system, antigorite polysomatism may influence the distribution of intermediate‐depth seismicity, such as the observance of double seismic zones. Plain Language Summary: Antigorite is a hydrous mineral known for being an important carrier of water into the Earth's interior and a seismicity trigger at intermediate‐depths down to ∼200 km. However, its crystal structure is complex (e.g., Uehara, 1998), and thus it is not well understood which structural variant (polysome) of antigorite is stable or dominant at high pressures and temperatures during subduction. In this study, several crystal structures of antigorite were calculated by first‐principles calculations, and their enthalpies (i.e., Gibbs free energy of a system at static 0 K) were compared to determine the stable structure as a function of pressure. The results indicate that the structure and chemical composition of antigorite likely changes under high pressure, resulting in the gradual release of water during the subduction process. As antigorite is thought to be the main trigger of seismicity in the subducting lithospheric mantle, its metasomatism may contribute to explain the reported distributions of intermediate‐depth earthquakes. Key Points: Antigorite crystal structures with various values of m (14–19) were determined by first‐principles calculation under pressureThe relative enthalpy shows that antigorite with smaller m‐values are stabilized with increased pressureAntigorite in suducting slabs may gradually dehydrate under high pressure as a result of changes to stable m‐values [ABSTRACT FROM AUTHOR]

An intramolecular electrochemical dehydration reaction of dicarboxylic acids to their cyclic anhydrides is presented. This electrolysis allows dicarboxylic acids as naturally abundant, inexpensive, safe, and readily available starting materials to be transformed into carboxylic anhydrides under mild reaction conditions. No conventional dehydration reagent is required. The obtained cyclic anhydrides are highly valuable reagents in organic synthesis, and in this report, we use them in‐situ for acylation reactions of amines to synthesize amides. This work is part of the recent progress in electrochemical dehydration, which – in contrast to electrochemical dehydrogenative reactions for example – is an underexplored field of research. The reaction mechanism was investigated by 18O isotope labeling, revealing the formation of sulfate by electrochemical oxidation and hydrolysis of the thiocyanate‐supporting electrolyte. This transformation is not a classical Kolbe electrolysis, because it is non‐decarboxylative, and all carbon atoms of the carboxylic acid starting material are contained in the carboxylic anhydride. In total, 20 examples are shown with NMR yields up to 71 %. [ABSTRACT FROM AUTHOR]

Zinc‐organic batteries (ZOBs) are receiving widespread attention as up‐and‐coming energy‐storage systems due to their sustainability, operational safety and low cost. Charge carrier is one of the critical factors affecting the redox kinetics and electrochemical performances of ZOBs. Compared with conventional large‐sized and sluggish Zn2+ storage, non‐metallic charge carriers with small hydrated size and light weight show accelerated interfacial dehydration and fast reaction kinetics, enabling superior electrochemical metrics for ZOBs. Thus, it is valuable and ongoing works to build better ZOBs with non‐metallic ion storage. In this review, versatile non‐metallic cationic (H+, NH4+) and anionic (Cl−, OH−, CF3SO3−, SO42−) charge carriers of ZOBs are first categorized with a brief comparison of their respective physicochemical properties and chemical interactions with redox‐active organic materials. Furthermore, this work highlights the implementation effectiveness of non‐metallic ions in ZOBs, giving insights into the impact of ion types on the metrics (capacity, rate capability, operation voltage, and cycle life) of organic cathodes. Finally, the challenges and perspectives of non‐metal‐ion‐based ZOBs are outlined to guild the future development of next‐generation energy communities. [ABSTRACT FROM AUTHOR]

In this study, a zero‐gap flow‐through microfluidic reactor was constructed for the degradation of tetracycline and norfloxacin in water using a porous Ti/RuO2‐IrO2@Pt electrode as the anode and porous titanium plate as the cathode. The operation parameters included electrolyte type, electrolyte concentration, current density, initial concentration of pollutants and pH, were investigated. The degradation efficiency and energy consumption were calculated and compared with traditional electrolyzer. In the zero‐gap flow‐through microfluidic reactor, 100 % of both tetracycline and norfloxacin can be decomposed in 15 min, and high mineralization rate were achieved under the optimized reaction condition. And the reaction was consistent with pseudo‐first‐order kinetics with k value of 0.492 cm−1 and 1.010 cm−1, for tetracycline and norfloxacin, respectively. In addition, the energy consumption was 28.33 kWh ⋅ kg−1 TC and 8.36 kWh ⋅ kg−1 NOR, for tetracycline and norfloxacin, respectively, which was much lower than that of traditional electrolyzer. The LC–MS results showed that tetracycline underwent a series of demethylation, dehydration and deamination reactions, and the norfloxacin went through ring opening reaction, decarboxylation and hydroxylation reaction, and finally both produced CO2 and H2O. [ABSTRACT FROM AUTHOR]

A density functional theoretical (DFT) study is presented, implicating a 1O2 oxidation process to reach a dihydrobenzofuran from the reaction of the natural homoallylic alcohol, glycocitrine. Our results predict an interconversion between glycocitrine and an iso‐hydroperoxide intermediate [R(H)O+–O−] that provides a key path in the chemistry which then follows. Formations of allylic hydroperoxides are unlikely from a 1O2 'ene' reaction. Instead, the dihydrobenzofuran arises by 1O2 oxidation facilitated by a 16° curvature of the glycocitrine ring imposed by a pyramidal N‐methyl group. This curvature facilitates the formation of the iso‐hydroperoxide, which is analogous to the iso species CH2I+–I− and CHI2+–I− formed by UV photolysis of CH2I2 and CHI3. The iso‐hydroperoxide is also structurally reminiscent of carbonyl oxides (R2C=O+–O−) formed in the reaction of carbenes and oxygen. Our DFT results point to intermolecular process, in which the iso‐hydroperoxide's fate relates to O‐transfer and H2O dehydration reactions for new insight into the biosynthesis of dihydrobenzofuran natural products. [ABSTRACT FROM AUTHOR]

We study the interplay of the thermal structure within subducted oceanic slabs together with the stability fields of hydrous phases that control slab dehydration and the amount of water transported into the deeper mantle. We implement different published thermodynamic data for phase A and Mg‐sursassite into a model of 56 subduction zones and evaluate the effect of these phases on the global water budget. We modeled vertical fluid fluxes within the slab such that dehydration‐derived fluid was allowed to react with fluid‐undersaturated rocks in other parts of the slab. The effect of Mg‐sursassite on the global water budget is limited, because the Clapeyron slope of this dehydration reaction is steeper than most pressure‐temperature trajectories in subduction zones. Two sets of published thermodynamic data for phase A yield significantly different values for the amount of deeply subducted water, ranging between 8 × 108 Tg/Ma and 1.4 × 109 Tg/Ma. In some subduction zones, the differences span several orders of magnitude. The absolute modeled amount of deeply subducted water strongly depends on the depth and intensity of slab mantle hydration, but a comparison of modeled and experimental data indicates that the thermodynamic dataset that yielded higher values is more reliable and should be implemented in future thermodynamic models. Our results show that the stable phases around the choke point as well as the slope and position of the phase A‐out reaction influence the deep water release from the slab, but the slope and position of the phase A dehydration reaction mainly control the recycling of water into the deep mantle. Plain Language Summary: Water on our planet is constantly exchanged between the oceans and the interior of the Earth. This happens at subduction zones where hydrated oceanic crust is sinking into the Earth's mantle, thus bringing water to depths exceeding 300 km. We quantify this amount of water that is globally recycled into the deeper Earth in subduction zones through computer models that combine the temperature structure of the subducted rocks with the stability of hydrous phases. Knowledge about the global water budget is important to quantify the Earth's total water amount, to understand the water release from the subducting oceanic plate, and to interpret sea level changes in Earth's history. We compared thermodynamic datasets for two minerals, namely Mg‐sursassite and phase A, in the oceanic plate that can transfer large amounts of water into the deeper Earth. Our thermodynamic models show that the stability of phase A in the down going oceanic plate controls much of the recycled water in most subduction zones. Key Points: Mg‐sursassite has a limited influence on the global amount of subducted waterMg‐sursassite can transfer water to depths of up to 250 km and lead to deep dehydration and water release from the slabThe Clapeyron slope of the phase A dehydration reaction is sub‐parallel to many slab P‐T paths and mainly controls the deep water subduction [ABSTRACT FROM AUTHOR]

Dehydration reactions within subducted oceanic crust are important for fluid‐mediated element transfer within the subducting plate and potentially to the mantle wedge. The effects of metamorphic reactions and fluid flow on element recycling that occur during retrogression and exhumation of subducted continental crust from mantle depths are poorly understood. We study two metabasite pods with fresh eclogite cores and retrogressed amphibolite‐facies rims and surrounding host gneiss within the Western Gneiss Region (WGR), Norway, to better understand element mobility and mass transfer during exhumation of subducted continental crust. Bulk‐rock data were collected from samples taken across the pod and into the host gneiss. Phengite breakdown in eclogite and epidote recrystallization in veins and/or gneiss within pod cores contributed large ion lithophile elements and REE to retrogressed eclogite closest to the pod cores. In gneiss hosting the pods, phengite and epidote breakdown provided fluid that mediated elemental transfer and redistribution to the pod rim or tail. Compared to the studied pod in the southern WGR, the pod in the northern WGR underwent higher P‐T conditions, partial melting and higher strain rates. This resulted in the infiltration of external fluid farther into the pod interior from the rim and facilitated larger mass gain in trace elements in the amphibolite tail of the pod relative to fresh eclogite in the core. The results show clear evidence for retrogression dehydration reactions driving significant fluid‐mediated element redistribution as observed on the outcrop scale during exhumation following ultrahigh‐pressure metamorphism, which directly impacts element signatures within the exhuming crust. Plain Language Summary: A lot is not known about how fluids and metamorphic reactions recycle elements in continental crust as it is brought to the surface after being subducted to ∼100 km. We study two eclogite pods that are surrounded by gneiss in the Western Gneiss Region, Norway to study how different pressure‐temperatures (P‐T), deformation, and fluids control element movement in deep crust as it is exhumed. The pod cores have eclogite that record the rock conditions at ∼100 km, but the exteriors were altered during exhumation. We sampled transects from the pod cores to ∼20 m into the surrounding gneiss. Bulk‐rock and mineral trace‐element data show two situations of mineral breakdown that generated trace‐element‐rich fluid that reacted with and enriched metabasite in Rb, Sr, Ba, and light rare earth elements: (a) veins or gneiss in pod cores enriched adjacent eclogite, and (b) surrounding gneiss enriched the pod exteriors. As shown by the pod that experienced higher P‐T conditions and deformation than the second pod, larger amounts of elements were transferred into the pod rim, and fluid penetrated the pod, enriching eclogite near the pod rim. Clearly, exhumation conditions and mineral break‐down reactions are important for elemental recycling in crust during exhumation. Key Points: In the Western Gneiss Region, Norway, fluids redistribute elements during retrogression after ultrahigh‐pressure metamorphismRecrystallization of epidote‐group minerals and phengite in metabasite pod interiors facilitate elemental transfer within the podsHost gneiss‐derived fluids infiltrate amphibolite‐facies retrogressed pod rims, driving significant element redistribution and mass transfer [ABSTRACT FROM AUTHOR]

Understanding the molecular composition of high explosives during thermal decomposition is vital for predicting the sensitivity, safety, and performance of explosive materials. The thermal decomposition of 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) has been linked to the formation of furazans through a series of dehydration reactions of the NO2 and NH2 groups on the phenyl ring, along with breakdown into small molecules (≤120 amu). Molecular identification of compounds formed in this transformation of the furazans to light gases has been lacking. To address this, we have applied a pseudo‐confined sampling system in a cryo‐focused pyrolysis gas chromatography‐mass spectrometry (pyGC‐MS) system to molecularly identify these intermediates. By design, sublimation of TATB, which has complicated MS analyses of thermal degradation, was significantly reduced and additional compounds were identified with potential structural information. In addition to the known furazan compounds, one of these compounds forms from the loss of oxygen from benzo‐trifurazan (F3) and produces an open ring structure that may be the first step in the formation of lower molecular weight furazan breakdown products. The loss of a nitro group from benzo‐monofurazan (F1) was also discovered and implicates the formation of oxidizing NO2 gas in the thermal decomposition mechanism. These findings are vital for understanding the proper heat flow from energetic materials on a molecular level, necessary when measuring enthalpy and developing decomposition models based on kinetic parameters. [ABSTRACT FROM AUTHOR]

Nonthermal plasma (NTP), for the first time, was integrated in glycerol dehydration reaction catalyzed by silicotungstic acid supported on mesoporous silica with argon as the carrier and discharge gas. A range of reaction temperatures (220–320°C) and NTP discharge field strengths (2.06–6.87 kV/cm) were studied for the individual and interactive effects regarding the glycerol conversion and product selectivity. Results showed that the presence of NTP always improved the glycerol conversion, and NTP increased acrolein selectivity if properly conditioned. An optimal condition of 275°C and 4.58 kV/cm NTP field strength achieved a glycerol conversion of 94.4 mol%, acrolein selectivity of 88.0 mol%, with an acrolein yield of 83.1 mol%, representing a 10% improvement in acrolein production over that conducted at the same temperature but without NTP. Results of this study will also have significant implication for other heterogeneously catalyzed dehydration reactions. Simulation of the high‐voltage electric field distribution as function of NTP electrical conductivity and relative permittivity of catalyst materials also offers insight for the future design of reactors and catalysts. [ABSTRACT FROM AUTHOR]

Converting extensive sugars into value‐added 2,5‐furandicarboxylic acid (FDCA) has been considered to be a promising approach to developing sustainable substitutes for chemicals from fossil resources. The complicated conversion processes involved multiple cascade reactions and intermediates, which made the design of efficient multifunction catalysts challenging. Herein, we developed a catalyst by introducing phosphotungstic acid (PW) and Co sites into the UiO‐66, which achieved a one‐pot cascade conversion of fructose‐to‐FDCA with high conversion (>99 %) and yield (94.6 %) based on the controllable Lewis/Brønsted acid sites and redox sites. Controlled experiments and detailed characterizations show that the multifunctional PW/UiO(Zr, Co) catalysts successfully affords the direct synthesis of FDCA from fructose via dehydration and selective oxidation in the one‐pot reaction. Additionally, the MOF catalysts could also efficiently convert various sugars into FDCA, which has broad application prospects. This study provides new strategies for designing multifunctional catalysts to achieve efficient production of FDCA from biomass in the one‐pot reaction. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) hydrogenation to methanol (CH3OH) is one of the most promising approaches to provide this platform chemical and to close carbon cycles. In this minireview, we systematically analyze primary and secondary reactions which can take place in this reaction over Cu‐based catalysts. In addition to repeatedly discussed reverse water gas shift reaction (RWGS) and CH3OH production directly from CO2, we consider decomposition, dehydration, dehydrogenation, and steam reforming of the desired alcohol. These reactions are usually ignored in the studies dealing with CO2 hydrogenation to CH3OH but can worsen the catalyst efficiency. Apart from the corresponding thermodynamic analysis, proposed reaction mechanisms and active sites are described and discussed. The effects of co‐fed water, CH3OH and methyl formate on catalyst performance are critically scrutinized, too. We also provide several criteria for unambiguous comparison of different catalysts in terms of CH3OH selectivity and their activity. [ABSTRACT FROM AUTHOR]

Rationale: Microdroplet chemistry has attracted tremendous interest in recent years. We have previously reported that microdroplet mass spectrometry (MS) achieves reaction acceleration. Here we systematically investigated the effect of capillary heating of MS inlet and solvent polarity of microdroplets on the conversion ratios of dehydration and phosphorylation reactions. Methods: The micron‐sized droplets generated by high‐speed gas encapsulated the compounds. The conversion ratios of dehydration and phosphorylation reactions were investigated at different capillary temperatures of MS inlet between 30°C and 300°C. Subsequently, the effects of solvent polarity of different microdroplets (acetonitrile, acetonitrile/water [v/v: 9:1], and water) on microdroplet reactions were investigated. Results: The microdroplets could be used as reaction vessels for rapid dehydration and phosphorylation reactions. Microdroplet MS is characterized by the completion of the reaction in microseconds. The increase in capillary temperature increased the conversion ratio of dehydration reactions but had little effect on phosphorylation reactions. The stability of compounds supports this phenomenon. In addition, the increase in solvent polarity in microdroplets promoted the dehydration reaction but inhibited the nucleophilic substitution reaction (phosphorylation reaction). Conclusions: Microdroplet MS achieved an acceleration of the reaction, which was attributed to capillary temperature, microdroplet solvents, and the stability of reaction products. This finding suggested that the inlet capillary and solvent system should be considered in the study and interpretation of microdroplet MS. [ABSTRACT FROM AUTHOR]

In accretionary prisms, scaly clays structure might be the result of strain localization and weakening or strain delocalization and hardening. Therefore, it is not clear how they influence the mechanical behavior of the accretionary prism. Here, we investigate the effect of rock fabric on the mechanical properties of scaly clays sampled from a fossil accretionary prism in a range of pressure‐temperature conditions typical of burial within accretionary prisms. We performed triaxial experiments using a direct shear configuration on samples in which the natural scaly clay fabric and natural lithological boundaries were preserved, at confining pressures of 10–120 MPa and temperatures of 25–150°C. Samples with homogeneous composition and natural scaly fabrics display strain hardening behavior at all tested conditions. Shearing at high P‐T displays lower strength with respect to shearing at low P‐T. The samples containing a lithological contact display strain hardening at low P‐T and weakening at high P‐T conditions. After the experiments, the homogeneous samples show a distributed foliation and short, discontinuous shear surfaces at the contacts with the sample holder, while the samples including a contact developed a through‐going shear zone composed of a series of en‐echelon shear surfaces. A reduced smectite and water content is observed in the post‐deformation samples, suggesting that weakening may correlate with water release during dehydration reactions of clay minerals at 150°C. This shows how both dehydration reactions at high P‐T conditions and strain localization along lithological boundaries promote brittle behavior within scaly clays in subduction zones accretionary prisms. Plain Language Summary: In subduction zones, among the rocks that constitute the accretionary prism are claystones with a peculiar texture called "scaly clays." We investigated these rocks preserving their original scaly texture at deformation and temperature conditions typical of those occurring in the frontal part of subduction zone. In the deformed samples, only when a contact between two different scaly clays is present and it is deformed at the highest pressure and temperature, a decrease of strength occurs. This behavior is related to the simultaneous presence of a pre‐existing lithological contact across the sample and by the release of water by dehydration of the "scaly clays." The process, reproduced in the laboratory, might occur at a larger scale and control deformation within the natural subduction zones. Key Points: Experimental deformation of natural scaly clays at 10–120 MPa and 25–150°CStrain localization and weakening occur when a pre‐existing lithological contact is included in the sample and at high P‐T conditionsLithological contacts and water release enhance strain localization and weakening in natural accretionary prisms [ABSTRACT FROM AUTHOR]

Aldehydes and carboxylic acids are widely used as catalysts for efficient racemization process of amino acids. However, the detailed reaction mechanism remains unclear. This work aims to clarify the racemization mechanism of aspartic acid (Asp) catalyzed by salicylaldehyde and acetic acid by using computational approaches. Density functional theory was used to obtain the structures and relative energies of 10 intermediates and five transition states, thus characterizing the main stages of the reaction. The calculated energy diagram shows that the dehydration step has the highest energy barrier, followed by the reaction step to change the chirality of Asp, which is a crucial process for racemization. In the dehydration reaction, water molecules can induce a remarkable decrease in the required energy. [ABSTRACT FROM AUTHOR]

A novel ZnCl2‐promoted three‐component reaction strategy for the synthesis of hexahydrochromeno[2,3‐b]quinoline derivatives via the Aldol condensation/Michael addition/cycloaddition/dehydration cascade reaction of 2‐amino‐4H‐chromen‐4‐ones, aromatic aldehydes, and cyclohexane‐1,3‐dione was investigated. This procedure is environmentally friendly, highly efficient, and has a broad scope. The structures of the products obtained were determined based on x‐ray diffraction studies. [ABSTRACT FROM AUTHOR]

Total syntheses of the title marine natural products have been achieved and so confirming the structures originally assigned to them. Upon subjecting agesasine A and its corresponding ethyl ester to Mitsunobu conditions, a 1,5‐cyclodehydration reaction takes place to give 2‐oxazolines. In contrast, on subjecting agesasine B to the same Mitsunobu conditions, a simple dehydration reaction occurs to give the corresponding acrylate. A total synthesis of longamide E was achieved by engaging a 1,2‐disubstituted pyrrole in a lactam‐forming reaction and this was followed by a two‐fold and fully regio‐controlled bromination reaction. A distinctly different and possibly biomimetic route was used to synthesize, via the open‐chain natural product nakamurine B, longamide B and its methyl ester. Preliminary biological evaluations of the title alkaloids and various analogues against a small human cancer cell line panel reveals cytotoxic properties that vary significantly with structure. [ABSTRACT FROM AUTHOR]

Microwave heating was utilized as a dehydration method to produce gelatin membranes. The results demonstrated that the moisture content reduced drastically at higher microwave power, and the effective diffusivities were determined. The specific energy consumption was recorded at a higher range for 10 wt % but an opposite trend was observed for the moisture extraction rate. The spectra of all dehydrated gelatin membranes were quite similar to that of gelatin powder. Microwave dehydration increased the disordered structure of gelatin which enhanced the amphiphilicity. The surface morphology revealed a rough membrane surface which could aid the adhesion and growth of human skin cells. [ABSTRACT FROM AUTHOR]

The development of new strategies for synthesizing 1D cerium oxide (CeO2) hollow nanostructures has attracted much attention in recent years due to the importance of their superior properties and highly anisotropic geometry. This study reports an unpublished route of fabricating novel multiwalled CeO2‐δ nanotubes (CeO2‐δ NTs) in which the entire volume of functionalized multiwalled carbon nanotubes (f‐MWCNTs) is converted into the CeO2‐δ pseudomorph through oxidation and dehydration topotactic reactions. The stable CeO2‐δ (111) planes are topotactically grown on the curved C (002) planes, preferentially exposed along the nanotube axis. In their initial condition, the novel nanotubes consist of Ce oxyhydroxide (CeO2‐x(OH)x) with residual carbon. When heating the air up to 500 °C, CeO2‐x(OH)x transforms gradually by dehydration into CeO2‐δ, while the residual carbon is oxidized. Despite compositional changes, nanotubes maintain their multiwalled structural integrity up to ≈550 °C. The CeO2‐δ NTs exhibit an unusually high presence of Ce3+ ions and surface O vacancies, contributing to a low direct band gap ranging from 2.67 to 2.32 eV compared to their NPs counterparts (3.2 eV). [ABSTRACT FROM AUTHOR]

Efficient cleavage of β‐O‐4 bonds in lignin to high‐yield aromatic compounds for the potential production of fuels and chemicals is vital for the economics of the modern biorefinery industry. This work is distinct in that a detailed mechanistic analysis of the reaction pathways of veratrylglycero‐β‐guaiacyl ether (VGE) catalyzed by transition‐metal‐free solid acid zeolite in aqueous conditions at high hydrogen pressure has been performed. VGE degradation produced high monomers yields (≈87 %), including guaiacol (48.2 %), 1‐(3,4‐dimethoxyphenyl)ethanol (10.3 %), 1‐(3,4‐dimethoxyphenyl)‐2‐propanol (6.1 %), 3,4‐dimethoxyphenylpropanol (4.7 %), 3,4‐dimethoxycinnamyl alcohol (4.1 %), and 1,2‐dimethoxy‐4‐propylbenzene (2 %). The products were identified and confirmed by the in situ solid‐state magic angle spinning (MAS) 13C NMR spectroscopy in real‐time conditions and the two‐dimensional gas chromatography (GC×GC). A variety of products reveal the crucial role of hydrogen, water, and acid sites for heterolytic cleavage of the β‐O‐4 bond in VGE. Decarbonylation, hydrogenolysis, hydrogenation, and dehydration reaction pathways are proposed and further validated using first‐principles calculations. [ABSTRACT FROM AUTHOR]

This study reports the selective obtaining of butanediols, mainly 23BDO and 12BDO isomers, by C−O hydrogenolysis of erythritol on Ru (2 %wt.) supported on titania at 473 K and 25 bar H2 and their modification with Re species that improve the selectivity to C−O hydrogenolysis over other reactions (C−C hydrogenolysis, dehydration, etc). The dependence of the catalytic activity with reaction temperature and reactants concentrations is also discussed. Characterization by XPS, TEM and TPR indicates that the surface of rhenium modified Ru is formed by small particles (<3 nm) of Ru0 in contact with Re+IV (Re/Ru molar ratio ≈1). Over this catalyst (Ru/ReOx/TiO2) close or even higher BDO yields than previous values reported on other noble metals were obtained, making it very attractive since Ru is more economical than Pt, Ir or Rh metal. Furthermore, we demonstrate that Ru/ReOx/TiO2 was also stable and allowed to be reused in at least three consecutive reactions. [ABSTRACT FROM AUTHOR]

Dehydratase (DH), a domain located at polyketide synthase (PKS) modules, commonly catalyzes the dehydration of β‐hydroxy to an α,β‐unsaturated acyl intermediate. As a unique bifunctional dehydratase, AmbDH3 (the DH domain of module 3 of the ambruticin PKS) is verified to be responsible for both dehydration and the following pyran‐forming cyclization. Besides, in vitro studies showed that its catalytic efficiency varies with different chiral substrates. However, the detailed molecular mechanism of AmbDH3 remains unclear. In this work, the structural rationale for the substrate specificity (2R/2S‐ and 6R/6S‐substrates) in AmbDH3 was elucidated and the complete reaction pathways including dehydration and cyclization were presented. Both MD simulations and binding free energy calculations indicated AmbDH3 had a stronger preference for 2R‐substrates (2R6R‐2, 2R6S‐3) than 2S‐substrates (2S6R‐1), and residue H51 and G61 around the catalytic pocket were emphasized by forming stable hydrogen bonds with 2R‐substrates. In addition, AmbDH3's mild tolerance at C6 was explained by comparison of substrate conformation and hydrogen bond network in 6S‐ and 6R‐substrate systems. The QM/MM results supported a consecutive one‐base dehydration and cyclization mechanism for 2R6S‐3 substrate with the energy barrier of 25.2 kcal mol−1 and 24.5 kcal mol−1, respectively. Our computational results uncover the substrate recognition and catalytic process of the first bifunctional dehydratase‐cyclase AmbDH3, which will shed light on the application of multifunctional DH domains in PKSs for diverse natural product analogs and benefit the chemoenzymatic synthesis of stereoselective pyran‐containing products. [ABSTRACT FROM AUTHOR]

The reactivity of CO2 with a previously described PCcarbeneP cobalt(I) hydroxide is reported. Insertion of CO2 into the Co−OH bond followed by a dehydration reaction releasing water results in a cobalt(I) bridging carbonate species featuring fluctional κ1: κ1 and κ1: κ2 coordination of the central carbonate moiety. The reduction chemistry of the resulting cobalt(I) bridging carbonate species is explored utilizing deoxygenative reducing agents N,N′‐bis(trimethylsilyl)‐ and N,N′‐bis(pinacolatoboryl)‐4,4′‐bipyridinylidene. The three‐electron reduction produces the corresponding PCcarbeneP cobalt(I) siloxide or boroxide complex alongside a PCcarbeneP cobalt(0) monocarbonyl, silyl/boryl ether, and 4,4'‐bipyridine. [ABSTRACT FROM AUTHOR]

The spatial distribution of effective normal stress, σe ${\sigma }_{\mathrm{e}}$, is essential for understanding the fault motion. Although Rice (1992, https://doi.org/10.1016/s0074-6142(08)62835-1) proposed a steady‐state solution for a vertical strike‐slip fault zone with constant fluid properties, models that are based on the concept by Rice (1992, https://doi.org/10.1016/s0074-6142(08)62835-1) and are applicable for other tectonic settings have not yet been developed. Such a model is particularly important in subduction zones because the relationship between low σe ${\sigma }_{\mathrm{e}}$ and slow earthquakes is often discussed. To quantitatively examine the causes of a local decrease in σe ${\sigma }_{\mathrm{e}}$ on a shallow region of the subduction zone, we performed model calculations that incorporated mechanisms characteristic to subduction zones. Our basic model, which considers the effect of smectite dehydration and the mechanical effect of subduction, yields results that are consistent with those reported by Rice (1992, https://doi.org/10.1016/s0074-6142(08)62835-1): the gradient of σe ${\sigma }_{\mathrm{e}}$ remarkably decreases with the increase in depth, whereas the realistic fluid properties rule out nearly constant σe ${\sigma }_{\mathrm{e}}$ at depth. We obtained a monotonic increase in σe ${\sigma }_{\mathrm{e}}$ with the increase in depth for the physically sound solutions and failed to generate a local decrease in σe ${\sigma }_{\mathrm{e}}$. The presence of a splay fault and fluid leakage though it cannot decrease σe ${\sigma }_{\mathrm{e}}$ locally. We found that a local decrease in permeability decreased σe ${\sigma }_{\mathrm{e}}$ locally around an impermeable zone and, thus, possibly led to the occurrence of shallow slow earthquakes. The water release caused by the dehydration reaction may not be the dominant factor, although smectite dehydration releases silica and promotes its precipitation. Plain Language Summary: The development and deployment of observation networks over the last two decades allowed for the investigation of "slow earthquakes," slower fault slip events than regular earthquakes. The occurrence of these slow earthquakes in subduction zones is often discussed in association with high pressure of pore fluid in rocks along a subduction plate interface, whereas the dominant mechanism responsible for the high pore pressure is enigmatic and still under debate. In this study, we tackled this issue by developing new, sophisticated hydraulic models that consider various process characteristics of subduction zones. Our results indicate that the clogging process of conduits can induce such a local increase in pore pressure and, thus, potentially allow for the occurrence of slow earthquakes, whereas the effect of the dehydration reaction of smectite is only modest, which has been considered as a candidate mechanism for the high pore pressure. Our new hydraulic models consider more realistic and complex mechanisms in subduction zones than the previous models and may be directly applicable to more realistic earthquake cycle simulations in the future, which can elucidate fault motion in the crust. Key Points: We quantitatively calculated the distributions of effective normal stress along a plate interface using hydraulic models in subduction zonesNeither smectite dehydration nor the presence of a splay fault can generate a local decrease in effective normal stress at shallow regionsA locally low effective normal stress is realized when permeability locally decreases, potentially responsible for shallow slow earthquakes [ABSTRACT FROM AUTHOR]

The strength and sliding behavior of faults in the crust is largely controlled by friction and effective stress, which is itself modulated by fluid pressure. Most earthquake models assume a fixed pore fluid pressure despite widespread evidence that is varies strongly in time due to changes in permeability. Here we explore how dynamic changes in pore pressure influence the properties of earthquakes in the upper crust. To study this problem we develop a two dimensional model that incorporates slow tectonic loading and fluid pressure generation during the interseismic period with frictional sliding on a thrust fault whose permeability evolves with slip. We find that the presence of relatively modest fluid overpressures tends to reduce coseismic slip, stress drop, maximum sliding velocity, rupture velocity and the earthquake recurrence time compared to models without fluids. Our model produces a wide range of sliding velocities from rapid to slow earthquakes, which occur due to the presence of high pore pressures prior to rupture. The models also show evidence for aftershocks that are driven by fluid transfer along the fault plane after the mainshock. Overall, this study shows that fluids can exert an important influence on earthquakes in the crust, which is mostly due to modulation of the effective stress and variations in permeability, and to a lesser extent to poro‐elastic coupling. Plain Language Summary: In this study we use a numerical model to investigate how fluid pressures vary over the seismic cycle and how they interact with and influence the properties of earthquakes that occur in the upper crust. In the model, fluid overpressures are generated slowly during the interseismic period by phenomena such as dehydration reactions while they are episodically released during earthquakes due to fracturing and a dramatic increase in permeability. The models show that the presence of high fluid pressures has an important influence on earthquakes. High fluid pressures favor smaller, more frequent earthquakes. Also high fluid pressures may sometimes be responsible for aftershocks and for anomalously slow earthquakes that involve slip over several months rather than several seconds. Overall, we show that the presence of fluids in the crust plays an integral part in the earthquake process. Key Points: Properties of earthquakes are markedly influenced by the presence of fluid overpressuresRuptures in wet models have relatively low stress drops, sliding speed and rupture velocitySlow slip events and aftershocks might be a fingerprint of fluid overpressures [ABSTRACT FROM AUTHOR]

Benzyl phenyl sulfide is a kind of important chemicals with wide usage, which is mainly prepared through a nucleophilic reaction of thiophenol with benzyl chlorides or benzyl alcohols, suffering from inherent drawbacks, such as low efficiency, requirements for equivalent acid or base catalysts and formation of harmful byproducts and waste. Herein, we report a green route to access various benzyl phenyl sulfide derivatives in good to excellent yields under mild conditions via the reaction of thioanisoles with benzyl alcohols over ionic liquid 1‐propylsulfonate‐3‐methylimidazolium trifluoromethanesulfonate ([SO3HPrMIm][OTf]). Mechanism investigation indicates that the synergic effect of cation and anion of [SO3HPrMIm][OTf] activates thioanisoles and benzyl alcohols via hydrogen bonding, thus catalyzes the dehydration of benzyl alcohol to dibenzyl ether and the subsequent metathesis reaction between dibenzyl ether and benzyl phenyl sulfide, finally generating benzyl phenyl sulfide derivatives. This is a simple, highly efficient, and green approach to produce benzyl phenyl sulfide derivatives, which has promising application potentials. [ABSTRACT FROM AUTHOR]

Poly(amic acid)s (PAAs) alignment agents have been prepared from the alicyclic dianhydrides, including 1,2,3,4‐cyclobutanetetracarboxylic dianhydride (CBDA, I), 1,3‐dimethyl‐1,2,3,4‐cyclobutanetetracarboxylic dianhydride (DMCBDA, II), and ester‐linked aromatic diamines, including 4‐aminophenyl‐4′‐aminobenzoate (APAB, a) and bis(4‐aminophenyl)terephthalate (BPTP, b), respectively. The derived PAAs, including PAA‐Ia (CBDA‐APAB), PAA‐Ib (CBDA‐BPTP), and PAA‐IIa (DMCBDA‐APAB) exhibited the preferable molecular weights, while the PAA‐IIb (DMCBDA‐BPTP) showed the low one due to the low polymerization reactivity both for the DMCBDA dianhydride and the BPTP diamine. All the PAA solutions except PAA‐IIb were adopted as the alignment components to fabricate liquid crystal (LC) minicells with a mode of in‐plane switching (IPS). The polyimides (PI) alignment layers derived from the thermal dehydration reaction of the PAA precursors at 230°C for 30 min showed good alignments effects to the LC molecules, which exhibited the pretilt angles (θp) from 0.09 to 0.15° after being exposed by the linear polarized ultraviolet light sources with the wavelength of 254 nm. In addition, the PI alignment layers afforded good optoelectronic features to the minicells, including the voltage holding ratio values over 97% at room temperature, and the residual direct circuit voltages lower than 1.0 V. The anchoring energy results indicated that the PI‐IIa (DMCBDA‐APAB) alignment layer showed the highest interaction with the LC molecules, and thus exhibited the highest threshold voltage (Vth) in the voltage‐transmittance (V‐T) measurements for the minicells. [ABSTRACT FROM AUTHOR]

Catalytic dehydration of isopropanol was studied as a model reaction for the conversion of bio‐oil into light olefins. γ‐Alumina synthesized in the laboratory and commercial ultrastable Y (USY) zeolite were used as catalysts. The catalytic activity and the effects of temperature, N2 flow, and catalyst loading were investigated. The highest conversions of isopropanol were achieved by employing USY zeolite. The model reaction tests also showed that a higher temperature favors a rise in the conversion of isopropanol. The increase in nitrogen flow allows better desorption of water molecules that possibly inhibit the reaction, thus increasing conversion. A higher catalyst loading also promoted a higher conversion of isopropanol due to the number of acidic sites available. [ABSTRACT FROM AUTHOR]

The Puebla‐Morelos (Mexico) 2017 earthquake nucleated ∼250 km inland from the trench within the Cocos oceanic plate mantle. Here, we argue that the Puebla‐Morelos (Mexico) 2017 earthquake resulted from changes in effective stress due to the reaction brucite + antigorite = olivine + H2O leading to the reactivation of pre‐existing seafloor faults. Fluid release (∼185 kg of H2O per m3 of subducted hydrated harzburgite) and volume increase (ΔVrsolid+fluid = ∼0.8%) likely occur along subducted seafloor‐inherited faults. The amount of H2O released, and magnitude of volume change depends on the degree of faults hydration; only highly hydrated (>40% of hydration) faults will stabilize brucite and experience this reaction at depth. The brucite + antigorite dehydration reaction may be key for intermediate seismicity worldwide. Plain Language Summary: The Puebla‐Morelos (central Mexico) Mw7.1 earthquake occurred in an uncommon locality in Mexico compared to most of the catastrophic earthquakes that have occurred in this part of the world—it nucleated ∼250 km inland, almost below Mexico City. In this paper, we explore the role of mineralogical changes occurring in the Cocos tectonic plate, which is currently descending below the North America plate. Our model tracked the changes in the minerals within the rocks and show that the earthquake might have been triggered by the physical changes associated with the mineral reaction: brucite + antigorite = olivine + H2O. We suggest that this mineral reaction primarily occurred along faults in the subducting oceanic floor along which the mantle lithosphere was hydrated prior to subduction. The brucite + antigorite dehydration reaction may be key for intermediate seismicity worldwide. Key Points: The dehydration of antigorite + brucite has a positive total volume change and leads to fluid‐induced fault reactivationWe hypothesize that fluid‐induced fault reactivation triggered the Puebla‐Morelos 2017 earthquakeThe antigorite + brucite reaction only happens in highly hydrated regions of the upper lithospheric mantle [ABSTRACT FROM AUTHOR]

Acrylic acid, conventionally produced via propylene (non‐renewable fossil fuel route), is an industrially important chemical. The bio‐based feedstock process employing glycerol (a by‐product of biodiesel production) has attracted the attention of researchers due to its non‐polluting and renewable characteristics. Bi/multifunctional catalysts using a combination of zeolites, metal oxides, heteropoly acids, and phosphates have been mainly studied for the glycerol oxydehydration process. Brønsted acid sites favour acrolein generation over Lewis acid sites, whereas the redox sites convert the generated acrolein to acrylic acid. So far, the maximum acrylic acid yields of 60% and 59% have been reported on heteropoly acid and mixed metal oxide catalysts, respectively. Some DFT studies also revealed the deprotonation energy of acid sites and further helped in designing efficient catalysts. Despite these accomplishments, catalyst deactivation because of coking and stability remains a major problem. In this paper, various bi/multifunctional catalysts employed in glycerol oxydehydration to acrylic acid are critically reviewed. Different catalyst forms, preparation techniques, reaction kinetics, reaction mechanisms, deactivation, reactivation, process operating parameters, and sustainability are considered. In addition, the challenges associated with each catalyst type and strategies to overcome low yield, deactivation, and future directions are discussed. [ABSTRACT FROM AUTHOR]

Structurally diverse aldoximes were conveniently transformed within minutes to the corresponding nitriles by using tropylium BF4 as organocatalyst, in 1‐butyl‐3‐methylimidazolium ionic liquids (BMIM‐ILs) as solvent, under microwave irradiation. The scope of this convenient, cyanide free, process for nitrile synthesis was explored, and DFT computations were employed to shed light on the mechanistic steps of this catalytic reaction leading to dehydration. [ABSTRACT FROM AUTHOR]

A new method to determine fluid flux at high pressures and temperatures has been developed and used to study serpentinites at subduction zone conditions. Drill cores of a natural antigorite‐serpentinite with a strong foliation were used in multi‐anvil experiments in the range of 2–5 GPa and 450–800°C. Fluids released upon dehydration are fixed by the formation of brucite in an adjacent fluid sink. The amount and distribution of brucite serves as a proxy for fluid flow. In our specific setup the sample reacted with the surrounding fluid sink to form an additional layer of olivine, which has the potential to limit fluid flux within our experiments. For conditions prior to serpentine dehydration we used Al(OH)3 as fluid source. Fluid in this experiment did not migrate through the serpentinite, indicating that serpentine has a low diffusivity. The experiments also show that small deviatoric stresses have an influence on the fluid flux and can cause an anisotropic fluid flux. Comparison between the time scales of the determined fluid flux with fluid production rates indicates fluid pressure buildup during dehydration reactions. Adjacent less permeable layers can inhibit fluid flux and cause fluid pressure buildup even at conditions when an interconnected pore space formed. Plain Language Summary: Subduction zones are regions where tectonic plates are recycled into the Earth's interior. Prior to subduction, the plates experienced extensive chemical interaction with the ocean water, forming hydrous minerals. Serpentine is an important hydrous mineral that can transport significant amounts of water into the Earth's interior. During subduction both pressure and temperature increase whereby hydrous minerals break down and release their water. The fluid migrates into the overlying mantle wedge, where it accounts for hydration as well as melting processes. The global flux balances would require this process to be very effective. However, it was so far not possible to measure the fluid flux at the subduction zone conditions in laboratories. In this study, we present a new method to determine the fluid flux prior and during dehydration. We found that prior to dehydration, the fluid flux in serpentinites is small. During dehydration the rocks ability to let fluids pass through increases. However, adjacent rocks with a low ability for fluid transport can further inhibit a fluid flux at these conditions. Generally, our experimental setup can be used for any system that immobilizes migrating fluids by hydration reactions. Key Points: A new method to determine fluid flux at high pressure and temperature conditions is developedSlow fluid migration in serpentinites promotes brittle fracturing in subduction zonesFast fluid migration upon dehydration of serpentinites promotes large‐scale fluid flux, if not inhibited by adjacent less permeable layers [ABSTRACT FROM AUTHOR]

Geophysical observations indicate that patches of localized fracturing occur within otherwise viscous regions of subduction plate boundaries. These observations place uncertainty on the possible down‐dip extent of the seismogenic zone, and as a result the maximum magnitude of subduction thrust earthquakes. However, the processes controlling where and how localized fracturing occurs within otherwise viscous shear zones are unclear. We examined three exposures of exhumed plate boundary on Kyushu, Japan, which contain subducted sediments and hydrated oceanic crust deformed at ∼300 to ∼500°C. These exposures preserve subduction‐related viscous deformation, which in two of the studied exposures has a mutually overprinting relationship with quartz veins, indicating localized cyclical embrittlement. Where observed, fractures are commonly near lithological contacts that form viscosity contrasts. Mineral equilibrium calculations for a metabasalt composition indicate that exposures showing cyclical embrittlement deformed at pressure‐temperature conditions near dehydration reactions that consume prehnite and chlorite. In contrast, dominantly viscous deformation occurred at intervening pressure‐temperature conditions. We infer that at conditions close to metamorphic dehydration reactions, only small stress perturbations are required for transient embrittlement, driven by localized dehydration reactions reducing effective stress, and/or locally increased shear stresses along rheological contrasts. Our results show that the protolith composition of the subducting oceanic lithosphere controls the locations and magnitudes of dehydration reactions, and the viscosity of metamorphosed oceanic crust. Therefore, compositional variations might drive substantial variations in slip style. Plain Language Summary: Along tectonic plate boundaries, with increasing depth, pressure and temperature, plate movement by brittle fracturing is suppressed, and mechanisms allowing steady slip become more efficient. Along subduction plate boundaries, where one plate sinks beneath another, observations indicate that a proportion of slip sometimes occurs by fracturing at pressure‐temperature conditions where steady slip typically dominates. We use outcrops of an ancient, inactive plate boundary exposed on Kyushu, Japan to investigate the reason for this behavior. We found that chemical reactions, triggered by increasing temperature in sinking oceanic crust, produce water, with the effect of locally raising the fluid pressure within the plate boundary. We suggest that locally raised fluid pressures assist fracturing at pressure‐temperature conditions where steady slip typically dominates. In some outcrops, fractures are especially common along contacts between different rock types, suggesting that mixing of different materials along the plate boundary might also favor fracturing. Key Points: Brittle fracturing occurred locally within viscously deforming hydrated oceanic crust and subducted sedimentsFracturing is localized at viscosity contrasts and P‐T conditions of metamorphic dehydration reactionsRocks that deformed at P‐T conditions away from dehydration reactions record dominantly viscous behavior [ABSTRACT FROM AUTHOR]

Preparation of isosorbide from cellulose by a catalytic one‐pot method under hydrothermal conditions is studied. Phosphate tantalum (TaOPO4) was prepared and used as support for the preparation of Ni/TaOPO4 via impregnation of Ni. The catalyst was characterized by X‐ray diffraction, H2‐TPR, NH3‐TPD, pyridine FTIR and Raman spectroscopy analysis. Results showed that the 5Ni/TaOPO4 (5 % loading of Ni) with a Brønsted/Lewis site (B/L) ratio of 0.153 showed the best catalytic performance and the total yields of sorbitol and isosorbide from cellulose reached 43 % under the conditions of 200 °C and 3 MPa H2 for 24 h. Both Lewis and Brønsted acid sites played crucial roles for the decomposition and dehydration reactions. The synergy of surface acid sites and reduction sites enhanced the cascade dehydration and hydrogenation reactions during the conversion of cellulose to isosorbide. This research is expected to broach a solution for the development of novel solid acid catalysts for the conversion of sugars into platform compounds. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) as promising green drying agents were first proposed to natural gas (NG) dehydration. In this work, choline chloride (ChCl)‐based DESs were prepared using ChCl as hydrogen bond acceptor (HBA) and triethylene glycol (TEG), ethylene glycol (EG) or Urea as hydrogen bond donors (HBDs). To explore the potential application, methane (CH4) dehydration experiment was conducted to verify the dehydration performance using prepared DESs. The thermodynamic properties were predicted by COSMO‐RS model (Conductor‐like screening model for real solvents). The quantum chemistry calculation was applied to understand the separation mechanism at the molecular level. The absorption performance of H2O in DESs depends on the weak interaction between Cl atom (or N and O atom) of ChCl and H atom of H2O as well as the free volume of DESs. Molecular dynamics (MD) simulation discloses the intermolecular interaction between HBA and HBD. This work makes the first multi‐scale analysis on NG dehydration using DESs. [ABSTRACT FROM AUTHOR]

We report the catalysis of an enantioselective, intramolecular aldol reaction accelerated by an organocatalyst embedded in a series of multicomponent metal‐organic frameworks. By precisely programming the pore microenvironment around the site of catalysis, we show how important features of an intramolecular aldol reaction can be tuned, such as the substrate consumption, enantioselectivity, and degree of dehydration of the products. This tunability arises from non‐covalent interactions between the reaction participants and modulator groups that occupy positions in the framework remote from the catalytic site. Further, the catalytic moiety can be switched form one framework linker to another. Deliberately building up microenvironments that can influence the outcome of reaction processes in this way is not possible in conventional homogenous catalysts but is reminiscent of enzymes. [ABSTRACT FROM AUTHOR]

The dehydration of fructose to selectively produce 5‐HMF was catalytically developed in a new type of ionic liquids based on triazoles supported on alumina (Al2O3). The synthesis of triazoles by 1,3‐dipolar cycloaddition allows for creating a tailor‐made triazole, that was eventually used to design catalysts based on triazolium‐based ionic liquids. In this work, four catalysts based on triazolium‐ionic liquids supported on Al2O3 were synthesized to produce 5‐HMF from fructose in DMSO as the reaction solvent. According to their molecular structure, the catalysts were tagged as TR1/Al2O3, TR1‐HSO4/Al2O3, TR2/Al2O3, and TR2‐HSO4/Al2O3. [ABSTRACT FROM AUTHOR]

Major and trace elements in omphacite, including hydrogen, were determined in eclogites from two Variscan basement complexes in Germany: Erzgebirge (EG) and Fichtelgebirge (FG). Erzgebirge eclogite is derived from three units, showing different peak pressure (P) and temperature (T) conditions (Unit 1: 840–920°C/≥30 kbar, Unit 2: 670–730°C/24–26 kbar, Unit 3: 600–650°C/20–22 kbar). The peak conditions of FG eclogite (690–750°C/25–28 kbar) resemble those of EG Unit 2. Coesite eclogite occurs in EG Unit 1, and quartz eclogite in all other units. Omphacite from all samples shows four infrared (IR) absorption bands. Two prominent, sharp bands occur at 3,455 ± 10 cm−1 (band II) and 3,522 ± 10 cm−1 (band III). Band II is usually more prominent than band III, except for few samples with low jadeite content. A further, broad band is centred between 3,270 and 3,370 cm−1 (band I) and a fourth, minor band at 3,611–3,635 cm−1 (band IV). Bands II and III are due to hydrogen bound as structural OH− ions in omphacite. In most cases, this also applies to band IV. However, some spectra with extremely large type IV bands reflect phengite inclusions. The ambiguous band I may be due to different H2O species (molecular water, structural OH, and water in phengite). Omphacite of quartz eclogite has lower contents of TiO2, Zr, Hf, and REE, compared with that from coesite eclogite. By contrast, omphacite in quartz eclogite from both EG (H2O sample averages: 465–852 ppm) and FG (546–1,089 ppm) contains the same amount of structural OH (concentrations given in wt.‐ppm H2O) as omphacite in coesite eclogite (492–1,140 ppm). The obtained difference in the garnet‐omphacite H2O partition coefficient between quartz (0.01–0.03) and coesite eclogite (0.08–0.11) results from different H2O contents in garnet (coesite eclogite: 50–150 ppm; quartz eclogite: <2–50 ppm; Gose & Schmädicke, 2018). The total content of structural OH in omphacite is unrelated to its major and trace element composition. However, treating the individual IR bands separately, a relation between OH and mineral composition is observed. The OH amount defined by band II is positively correlated to Ti and tetrahedral Al, and that of band III shows a positive correlation with Ca and a negative one with Na (and jadeite). Both the total OH content of omphacite and the partial contents deduced from individual IR bands are unrelated to PT conditions. This implies that omphacite incorporated its structural H2O mainly in the quartz stability field, presumably during initial omphacite growth. Conversely, most OH in garnet was derived from the final breakdown of the last remaining calcic amphibole close to or within the coesite stability field. Our data suggest that coesite eclogite is able to transport a significant amount of H2O (average 550 ppm, maximum 730 ppm), corresponding to that in 3–4 vol.% calcic amphibole, via subduction to depths beyond 100 km. However, the majority of water liberated by dehydration reactions during subduction, including the breakdown of 5–10 vol.% eclogite facies and >10 vol.% pre‐eclogitic hydrous minerals, is not preserved in eclogite but liberated to the mantle wedge. [ABSTRACT FROM AUTHOR]

Catalytic performance of catalysts is influenced by process conditions. In this work the influence of temperature, residence time and C2H5OH feed concentration was investigated in ethanol dehydration reaction using the response surface methodology (RSM) for γ‐Al2O3 and CeZrO2 catalysts. The γ‐Al2O3 was prepared using calcination method and CeZrO2 precipitation method. The process indicators (conversion, yield, selectivity) were modeled through the RSM method, and the equations obtained showed a good fit to the experimental data. The optimization results indicate different optimum conditions for each catalyst. For γ‐Al2O3 at 420 °C, 23.5 % of ethanol concentration and 0.65 gs/L, 0.6 molethylene/molethanol is obtained and total conversion. For CeZrO2 at 495 °C, 59 % ethanol concentration and 300 gs/L, 0.38 molethylene/molethanol is obtained and total ethanol conversion. Catalyst characterization was performed using, XRD (x‐ray diffraction), BET (Brunauer‐Emmett‐Teller surface area analysis), TPR (Temperature‐programmed reduction) and TPD (Temperature‐programmed desorption). [ABSTRACT FROM AUTHOR]

Oligomers and polymers of lactic acid are generally synthesized through condensation reactions by dehydration at high emperature under catalysis. In the present work, ionization behaviors of lactic acid produced by atmospheric pressure chemical ionization were investigated. Influence of the sample concentration, the heating zone temperature, and the source fragmentor voltage on kinds and abundances of the product ions was examined. Complex formation of the product ions with neutral species was also investigated. Not only lactate, [M–H]− and its complexes but also ions of condended species, [nM–(n‐1)H2O–H]− with n = 2–5, and their complexes were observed. The condensation reactions occurred in an aerosol state generated in the heating zone for evaporation. By increasing the concentration of lactic acid, abundances of the product ions were increased and the increase of larger ones was noticeable. By increasing the heating zone temperature, abundances of the product ions were decreased and the decrease of larger ones was remarkable. By increasing the source fragmentor voltage, abundances of small product ions were increased and those of the complexes, [nM–(n‐2)H2O–H]− with n = 2–5, were significantly decreased. Complex formation of lactate with the neutral condensed species was more favorable than that of the condensed oligomer ions with a neutral lactic acid. The experimental results were explained by energies and structures of the product ions and neutral species obtained by theoretical calculations. [ABSTRACT FROM AUTHOR]

BACKGROUND: Acidic hydrolysis of a birch (Betula pendula) xylan produced by a novel semi‐industrial‐scale aqueous‐based and highly sustainable method was studied in a batch reactor. Five commercial acidic heterogeneous catalysts were screened and significant differences in their performance were observed. Dowex 50WX2‐100 was selected for further studies and the influence of the reaction parameters, including stirring speed, pH (0.5–1.5), temperature (115–145 °C) and catalyst particle size (50–400 mesh) were studied. The goal was to maximize xylose yield by balancing between the kinetics of hydrolysis and the undesired degradation of monosaccharides. RESULTS: The results show that the maximum achieved yield of xylose was 76%, but higher yields were hindered by the consecutive dehydration of sugars. It was also observed that the hydrolysis and dehydration reactions do not follow the same dependence on the experimental parameters, which leaves room for optimization of the yield. A kinetic model was developed based on the data, which takes into account the consecutive reaction pathway and the influence of the experimental conditions, and a very good fit of the model to the experimental data was achieved. An activation energy of 119 and 88 kJ mol–1 was obtained for the hydrolysis and dehydration steps, respectively. CONCLUSION: Hydrolysis results of this novel, well‐characterized hemicellulose extract have not been published previously, and they contribute significantly to the understanding of the hydrolysis and dehydration of real feedstock, instead of highly purified and typically very deacetylated model compounds with different characteristics and behaviour in hydrolysis. © 2021 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

Metamorphic transformation rates are classically determined on decimetre‐scale field samples and from laboratory experiments at smaller scales. Here we present a geophysical approach based on field data and joint geophysical–petrological modelling to quantify the average rate of metamorphic transformations at the 10–100‐kilometre and million‐year scales. The model simulates the eclogitization of Indian lower crust as it penetrates beneath southern Tibet. Metamorphic transformation of the lower crust is tracked by its densification, the effect of which is then compared to observed gravity anomalies. From the modelling we find that the Indian lower crust's overall densification requires a partially hydrated initial composition. Moreover, the modelled evolution of this densification compared to what is predicted by pressure–temperature–density grids is consistent with delayed, far‐from‐equilibrium metamorphism. The Indian lower crust descends underneath the Himalaya until beneath southern Tibet in a thermodynamically metastable state until the first dehydration reactions are reached. This observation is used to determine the average rate of metastable rock transformation to an eclogite facies assemblage, constrained at between ~6 × 10−9 and 5 × 10−7 g/cm2/year, and reaction affinity at 0.8–1.6 kJ/mol oxygen. Compared to field and laboratory data, this range of results matches the effective rates typically associated with regional metamorphism. This fit and correlation across the scales legitimates the use of transformation rates determined at small scales in large‐scale geodynamic studies. [ABSTRACT FROM AUTHOR]

Here, we describe the maximum production of 5‐HMF using glucose over Sn doped Ta2O5 in a binary solvent system. The analytical characterizations established that Sn4+ in the catalyst interacts with Ta2O5 and offers the Lewis acid sites favorable for glucose isomerization to fructose. Similarly, the Ta2O5 support offers both the Lewis and Brønsted acid sites to promote fructose dehydration to 5‐HMF. The catalyst provided favorable conditions for the sequential sugar(s) transformation, i. e. glucose isomerization followed by fructose dehydration, which resulted in a 5‐HMF yield as high as 57 % wt. and 80 % selectivity under modest reaction conditions in a water‐DMSO system using ST1 (1 % Sn on Ta2O5). The separate fructose to 5‐HMF conversion study verified the negligible influence of Sn on the dehydration reaction. Moreover, the catalyst's systematic sugar conversion enabled a >65 % fructose formation, which accounts for the enriched 5‐HMF synthesis. The neural network model best represented the 5‐HMF data (<4 % MAE for glucose and fructose conversions). [ABSTRACT FROM AUTHOR]

Sugar alcohol dehydration in hot water is an important reaction that allows for environmentally friendly biomass conversion without the use of organic solvents. Here, we report a free‐energy analysis by metadynamics (MTD) simulations based on ab initio density functional theory and semiempirical density‐functional tight‐binding method to understand the mechanism of dehydration reactions of d‐sorbitol (SBT) in hot acidic water. Comparing the results of ab initio and semiempirical MTD, it was found that the latter gives a reliable free energy surface of SBT dehydration reaction, although the results vary upon the inclusion of dispersion correction. It was found that the reaction proceeds consistently via an SN2 mechanism, whereby the free energy of protonation of the hydroxyl group created as an intermediate is affected by the acidic species. This mechanism was further verified by real‐time trajectories started from the transition state using ab initio molecular dynamics simulations. The free energy barriers of the reaction pathways leading to five‐membered ether products are lower than those leading to six‐membered ether products, in agreement with experiment. This outcome can be ascribed, in part, to our finding that the reaction barrier of the pathway is correlated to the stability of the SBT confined conformation at the initial stage of the reaction. [ABSTRACT FROM AUTHOR]