Gas-phase Hydrolysis Research Articles

Correction to: Sustainable Production of Microcrystalline Cellulose Through Gas Phase Hydrolysis for Pharmaceutical Applications: Characterization and Life Cycle Assessment

Correction to: Sustainable Production of Microcrystalline Cellulose Through Gas Phase Hydrolysis for Pharmaceutical Applications: Characterization and Life Cycle Assessment

Sustainable Production of Microcrystalline Cellulose Through Gas Phase Hydrolysis for Pharmaceutical Applications: Characterization and Life Cycle Assessment

Sustainable Production of Microcrystalline Cellulose Through Gas Phase Hydrolysis for Pharmaceutical Applications: Characterization and Life Cycle Assessment

High-efficiency photocatalytic degradation of Rhodamine B and tetracycline by Z-scheme nanostructured Ag/Ag3PO4/Ti3+-TiO2 mesocrystals heterojunctions under visible light

This paper discusses the photocatalytic properties of Ag/Ag3PO4/Ti3+-TiO2 composites. The nanostructured composites were synthesized by gas-phase hydrolysis, precipitation, and photoreduction methods. The photocatalytic performance of the photocatalysts was evaluated by degrading RhB and TC under visible light. The degradation efficiency of AT4 for RhB and TC reached 99.9 % and 78.2 % under visible light irradiation for 20 min and 2.5 min, respectively. The superior performance of AT4 is facilitated by the combined influence of the heterojunction and the SPR. The free radical capture test proved that h+ and •O2− were the major reactive groups, and in conjunction with UV–vis DRS curves and Mott-Schottky curves, a probable reaction mechanism was proposed.

CO2/CH4 separation performance of SiO2/PES composite membrane prepared by gas phase hydrolysis and grafting coating in gas-liquid membrane contactor: A comparative study

The gas-liquid membrane contactor (GLMC) is a new and promising kind of gas separation technique, but still exhibits limitations, especially in membrane performance. In order to solve the above problems, we fabricated and characterized novel OH/SiO2/PES composite membranes using gas phase hydrolysis and graft coating methods, respectively. In the preparation process, whether to use alkali to pretreat the membrane was used as an evaluation index. The CO2/CH4 separation performance was tested using the modified OH/SiO2/PES hollow fiber membrane as the membrane contactor in GLMC. In the experiment, we conducted a single factor experiment with diethanolamine (DEA) as the adsorbent to analyze the effect of the flow rate and concentration of DEA on the separation of CO2/CH4. The collected gas had a CH4 content of 99.92% and a CO2 flux of 10.1059 × 10−3 mol m−2 s−1 while DEA at a concentration of 1 mol/L was flowing at a rate of 16 L/h. The highest separation factor occurred at this moment, which was 833.67. Overall, the CO2/CH4 separation performance in GLMC was enhanced with the use of the fluorinated OH/SiO2/PES composite membrane.

Theoretical Study of the Gas-Phase Hydrolysis of Formaldehyde to Produce Methanediol and Its Implication to New Particle Formation.

Aldehydes were speculated to be important precursor species in new particle formation (NPF). The direct involvement of formaldehyde (CH2O) in sulfuric acid and water nucleation is negligible; however, whether its atmospheric hydrolysate, methanediol (CH2(OH)2), which contains two hydroxyl groups, participates in NPF is not known. This work investigates both CH2O hydrolysis and NPF from sulfuric acid and CH2(OH)2 with quantum chemistry calculations and atmospheric cluster dynamics modeling. Kinetic calculation shows that reaction rates of the gas-phase hydrolysis of CH2O catalyzed by sulfuric acid are 11-15 orders of magnitude faster than those of the naked path at 253-298 K. Based on structures and the calculated formation Gibbs free energies, the interaction between sulfuric acid/its dimer/its trimer and CH2(OH)2 is thermodynamically favorable, and CH2(OH)2 forms hydrogen bonds with sulfuric acid/its dimer/its trimer via two hydroxyl groups to stabilize clusters. Our further cluster kinetic calculations suggested that the particle formation rates of the system are higher than those of the binary system of sulfuric acid and water at ambient low sulfuric acid concentrations and low relative humidity. In addition, the formation rate is found to present a negative temperature dependence because evaporation rate constants contribute significantly to it. However, cluster growth is essentially limited by the weak formation of the largest clusters, which implies that other stabilizing vapors are required for stable cluster formation and growth.

Preparation of OH/TiO2/PES composite membrane by a novel gas-phase hydrolysis method in gas-liquid membrane contactor to improve the separation efficiency of CO2 and CH4

Conventional gas separation methods are very limited for CO2 separation in terms of separation efficiency and cost. In this study, We obtained fluorinated TiO2/polyethersulfone (PES) composite membranes by gas-phase hydrolysis and compared the characterization results with the composite membranes prepared by the graft coating method. In the mixed gas separation experiment, we used diethanolamine (DEA) as the absorbent to test the separation performance of CO2/CH4 using the composite membranes prepared by gas phase hydrolysis in a gas-liquid membrane contactor (GLMC) system. DEA flow rate and concentration and feed gas flow were found to have a significant effect on separation performance. When the feed gas flow rate was kept constant at 30 ml/min and the DEA flow rate and concentration were 16 L/h and 1 mol/L, respectively, the collected CH4 concentration was 99.4 %. Meanwhile, the CO2 flux was 10.096 × 10−3 mol m−2 s−1, and the separation factor reached 110.444. Collectively, the application of TiO2/PES composite membranes in GLMC is an efficient method for CO2 capture and mixed gas separation.

Combining density functional theory and CFD-PBM model to predict TiO2 nanoparticle evolution during chemical vapor deposition

Preparation of TiO2 nanoparticles by TiCl4 hydrolysis during chemical vapor deposition (CVD) is one of the effective techniques for producing TiO2 nanoparticles, while the mechanisms of TiO2 nanoparticle evolution are not well understood. This paper uses computational fluid dynamics (CFD) population balance model (PBM) to predict particle size distribution during CVD, and density functional theory (DFT) calculations to explore reaction mechanisms. DFT calculations reveal that the gas phase hydrolysis reaction can be simplified into two processes, the hydrolysis of TiCl4 to form TiO(OH)2 and the decomposition of TiO(OH)2 to TiO2. During the surface reactions, the energy barriers of TiO(OH)2 decomposition reactions on the surfaces of (TiO2)n nanoclusters (n = 1–8) are generally lower than those in the gas phase reactions, and the largest energy barrier of the surface reaction occurs on the surface of (TiO2)6 nanoclusters. Simulations using a perfect stirred reaction model indicate that Ti(OH)4 is the dominant hydrolysis products when the temperature is lower than 548 K, while TiO2 production starts at ∼610 K, indicating reaction temperature is a crucial factor that governs the products of TiCl4 hydrolysis. CFD-PBM model predict the evolution of Particle Size Distribution (PSD) of nanoparticles in a CVD reactor, which is agreed with experimental measurements in the literature. Increasing the reaction temperature results in an increase of the peak of the PSD of nanoparticles in the reactor. This study provides atomic insights into the nanoparticle evolution and a practical model to predict the nanoparticle evolution during the CVD process.

Resolving the amine-promoted hydrolysis mechanism of N2O5 under tropospheric conditions

Hydrolysis of N2O5 under tropospheric conditions plays a critical role in assessing the fate of O3, OH, and NOx in the atmosphere. However, its removal mechanism has not been fully understood, and little is known about the role of entropy. Herein, we propose a removal path of N2O5 on the water clusters/droplet with the existence of amine, which entails a low free-energy barrier of 4.46 and 3.76 kcal/mol on a water trimer and droplet, respectively, at room temperature. The free-energy barrier exhibits strong temperature dependence; a barrierless hydrolysis process of N2O5 at low temperature (≤150 K) is observed. By coupling constrained ab initio molecular dynamics (constrained AIMD) simulations with thermodynamic integration methods, we quantitively evaluated the entropic contributions to the free energy and compared NH3-, methylamine (MA)-, and dimethylamine (DMA)-promoted hydrolysis of N2O5 on water clusters and droplet. Our results demonstrate that methylation of NH3 stabilizes the product state and promotes hydrolysis of N2O5 by reducing the free-energy barriers. Furthermore, a quantitative analysis of the internal coordinate distribution of the reaction center and the relative position of surrounding species reveals that the significant entropic contribution primarily results from the ensemble effect of configurations observed in the AIMD simulations. Such an ensemble effect becomes more significant with more water molecules included. Lowering the temperature effectively minimizes the entropic contribution, making the hydrolysis more exothermic and barrierless. This study sheds light on the importance of the promoting effect of amines and the entropic effect on gas-phase hydrolysis reactions, which may have far-reaching implications in atmospheric chemistry.

Отбелка микрокристаллической целлюлозы, полученной методом газофазного гидролиза

One of the main consumers of microcrystalline cellulose (MCC) is the pharmaceutical industry, where MCC is used as a binder and filler in direct compression of tablets. MCC is produced by acidic hydrolysis of cellulose, which usually results in a decrease in whiteness. This is due to the destruction of sugars formed during hydrolysis and the subsequent formation of colored products. The composition and properties of these products depend on the method of hydrolysis, acid concentration, temperature, and process duration. One of the most promising methods for producing MCC is gas-phase hydrolysis of cellulose with hydrogen chloride gas-air mixtures. The method has a high rate of hydrolysis, low reagent and energy consumption. The requirements of the pharmaceutical industry determine the need to produce MCC with high whiteness. The research purpose is to select bleaching modes for MCC using sodium hypochlorite and hydrogen peroxide as bleaching agents. MCC produced by gas-phase hydrolysis of bleached wood pulp was used during the study. The whiteness and intensity of the yellow tint of MCC in the bleaching process were determined by digital colorimetry on a flatbed scanner. The paper shows that sodium hypochlorite and hydrogen peroxide allow achieving the whiteness not less than 90 % and the intensity of the yellow tint not more than 3 standard units. High-quality bleaching can be carried out even for MCC samples with an initial whiteness of about 40 %. The most effective bleaching agent is sodium hypochlorite when the pH of the bleaching solution is 2–3. Hydrogen peroxide also provides high whiteness of MCC at pH of 10–11. However, the consumption of active oxygen (AO) for bleaching is more than three times higher in comparison with the consumption of active chlorine (ACh). It was found that the dyes of MCC produced by gas-phase hydrolysis consist of two chromophore groups that decolorize at different rates. The easily oxidized group of components makes up about 90 % of the total amount of dyes, and the resistant to oxidation components make up about 10 % and determine the intensity of the yellow tint of MCC. The modes of bleaching MCC with sodium hypochlorite and hydrogen peroxide to product samples with whiteness comparable to that of imported samples were determined. For citation: Sizov A.I., Pimenov S.D., Stroiteleva A.D., Stroiteleva K.D. Bleaching of Microcrystalline Cellulose Produced by Gas-Phase Hydrolysis. Lesnoy Zhurnal [Russian Forestry Journal], 2021, no. 6, pp. 173–183. DOI: 10.37482/0536-1036-2021-6-173-183

An Ab Initio Molecular Dynamics Study of the Hydrolysis Reaction of Sulfur Trioxide Catalyzed by a Formic Acid or Water Molecule.

Ab initio molecular dynamics (AIMD) calculations have been performed to investigate the role of dynamical and steric effects in formic acid (FA) or H2O-catalyzed gas phase hydrolysis of SO3 to form sulfuric acid. This was done by colliding FA or H2O with the SO3-H2O complex and the water dimer with the SO3 molecule and analyzing the outcomes of 230 AIMD trajectories. Our calculations show that, within simulation times used, sulfuric acid is formed in 5% of FA collisions but is not produced when H2O collides with the SO3-H2O complex or when the water dimer collides with the SO3 molecule. We also find that FA collisions have about 2 times higher probability to form the prereactive complex than H2O collisions. Moreover, our simulations show that the SO3-H2O-FA prereactive complex is more stable in time than the SO3-H2O-H2O prereactive complex. These findings indicate that the FA-catalyzed mechanism is favored over the H2O one when looking from the steric and dynamic effect point of view. Additionally, AIMD simulations starting from the optimized structure of the SO3-H2O-FA prereactive complex have been computed to qualitatively estimate the rate of the sulfuric acid formation. Collisional energy has been observed to promote sulfuric acid formation more effectively than thermal excitation.

Insights into Catalytic Gas-Phase Hydrolysis of Organophosphate Chemical Warfare Agents by MOF-Supported Bimetallic Metal-Oxo Clusters.

Zirconium-based metal-organic frameworks (Zr-MOFs) have been reported to be efficient catalysts for the hydrolysis of organophosphate chemical warfare agents (CWAs) in buffered solutions. However, for the gas-phase reaction, which is more relevant to the situation in a battlefield gas mask application, the kinetics of Zr-MOF catalysts may be severely hindered by strong product inhibition. To improve the catalytic performance, we computationally screened a series of synthetically accessible Zr-MOF-supported bimetallic metal-oxo clusters in which the metal-oxygen-metal active motif is preserved, aiming to find catalysts that have lower binding affinities to the hydrolysis product. For the promising catalyst Al2O2(OH)2@NU-1000 identified from the screening using density functional theory, we mapped out the full reaction pathway of gas-phase dimethyl p-nitrophenolphosphate (DMNP) hydrolysis and analyzed the free energy profile as well as the turnover frequency (TOF). We found that the catalytic mechanism on the new catalyst is slightly different from the one on NU-1000, which also led to a different TOF-limiting step. Additional factors that can affect the overall catalytic performance in practical application, such as the amount of ambient moisture and the existence of acid gases that may poison the catalyst, have also been evaluated.

Hydrolysis of ketene catalysed by nitric acid and water in the atmosphere

Environmental contextThe detailed mechanism of hydrolysis of gas-phase ketene to form acetic acid is critical for understanding the formation of certain atmospheric contaminants. This study explores the effect of nitric acid and water on the hydrolysis of ketene in the atmosphere. The calculated results show that nitric acid is an effective catalyst in the hydrolysis of ketene to form acetic acid in atmospheric water-restricted environments. AbstractThe gas-phase hydrolysis of ketene and the unimolecular reaction of 1,1-enediol catalysed by nitric acid and water have been investigated using quantum chemical methods and conventional transition state theory with Eckart tunnelling. The theoretical calculation results show that nitric acid exerts a strong catalytic effect on the hydrolysis of ketene in the gas-phase. The calculated energy barrier for the direct reaction mechanistic pathway is reduced from 42.10kcal mol−1 in the reaction of ketene with water to 3.40kcal mol−1 in the reaction of ketene with water catalysed by HNO3. The catalytic ability of nitric acid is further proven in the hydrogen shift reaction of 1,1-enediol because the energy barrier of the unimolecular reaction of 1,1-enediol is decreased from 44.92kcal mol−1 to −4.51kcal mol−1. In addition, the calculated results indicate that there is competition between the direct and indirect mechanistic pathways with the increase of additional water molecules in the reaction of ketene with water catalysed by HNO3 and (H2O)n (n=1, 2). The calculated kinetics results show that the CH2=C=O+H2O+HNO3 reaction is significant in the gas phase of the atmosphere and the other reactions are negligible owing to the slow reaction rates. However, compared with the CH2=C=O+OH reaction, the CH2=C=O+H2O+HNO3 reaction is very slow and cannot compete with the CH2=C=O+OH reaction. CH2=C=O+OH is the main elimination pathway of ketene in the gas phase of the atmosphere. Our findings reveal that acetic acid may be formed through the hydrolysis of ketene in atmospheric water-restricted environments of the surfaces of aqueous, aerosol and cloud droplets.

Computational Screening of Metal–Organic Framework-Supported Single-Atom Transition-Metal Catalysts for the Gas-Phase Hydrolysis of Nerve Agents

Recent studies have suggested that the gas-phase hydrolysis of nerve agents by Zr-based metal–organic frameworks (MOFs) may be limited by product inhibition resulting from strong bidentate binding of the hydrolysis products to the Zr6-nodes. A potential method to avoid this problem is to deposit single-atom catalysts on the nodes so that the products bind in a more favorable monodentate mode. Such catalytic active sites can be characterized with atomic precision, enabling detailed computational mechanistic studies. Thus, we used density functional theory to perform a comprehensive screening of single-atom transition-metal catalysts, in varying oxidation states, deposited on NU-1000 nodes for the gas-phase hydrolysis of the nerve agent sarin. By calculating the complete reaction pathways for M–NU-1000 systems, we discovered that the highest reaction barrier varies between catalysts, highlighting the need to consider more than a single reaction step when screening a large number of diverse materials. The si...

Hydrolysis of Formyl Fluoride Catalyzed by Sulfuric Acid and Formic Acid in the Atmosphere.

Formyl fluoride (HFCO) is an important atmospheric molecule, and its reaction with the OH radical is an important pathway when degradation of HFCO is considered in earth’s troposphere. Here, we study the hydrolysis of formyl fluoride (HFCO + H2O) with sulfuric acid (H2SO4) and formic acid (HCOOH) acting as catalysts by utilizing M06-2X, CCSD(T)-F12a, and conventional transitional state theory with Eckart tunneling to explore the atmospheric impact of the above-said hydrolysis reactions. Our calculated results show that H2SO4 has a remarkably catalytic role in the gas-phase hydrolysis of HFCO, as the energy barriers of the HFCO + H2O reaction are reduced from 39.22 and 41.19 to 0.26 and −0.63 kcal/mol with respect to the separate reactants, respectively. In addition, we also find that H2SO4 can significantly accelerate the decomposition of FCH(OH)2 into hydrogen fluoride (HF) and HCOOH. This is because while the barrier height for the unimolecular decomposition of FCH(OH)2 into HF and HCOOH is 31.63 kcal/mol, the barrier height for the FCH(OH)2 + H2SO4 reaction is predicted to be −5.99 kcal/mol with respect to separate reactants. Nevertheless, the comparative relative rate analysis shows that the reaction between HFCO and the OH radical is still the most dominant pathway when the tropospheric degradation of HFCO is taken into account and that the gas-phase hydrolysis of HFCO may only occur with the help of H2SO4 when the atmospheric concentration of OH is about 101 molecules cm–3 or less. Having an understanding from the present study that the gas-phase hydrolysis of HFCO in the presence of H2SO4 has very limited role possibly in the absence of sunlight, we also prefer here to emphasize that the HFCO + H2O + H2SO4 reaction may occur on the surface of secondary organic aerosols for the formation of HCOOH.

The Role of Clouds in the Tropospheric NOx Cycle: A New Modeling Approach for Cloud Chemistry and Its Global Implications

AbstractWe present a new method for simulating heterogeneous (surface and multiphase) cloud chemistry in atmospheric models that do not spatially resolve clouds. The method accounts for cloud entrainment within the chemical rate expression, making it more accurate and stable than other approaches. Using this “entrainment‐limited uptake,” we evaluate the role of clouds in the tropospheric NOx cycle. Past literature suggests that on large scales, losses of N2O5 and NO3 in clouds are much less important than losses on aerosols. We find, however, that cloud reactions provide 25% of tropospheric NOx loss in high latitudes and 5% of global loss. Homogeneous, gas phase hydrolysis of N2O5 is likely 2% or less of global NOx loss. Both clouds and aerosols have similar impacts on global tropospheric O3 and OH levels, around 2% each. Accounting for cloud uptake reduces the sensitivity of atmospheric chemistry to aerosol surface area and uptake coefficient since clouds and aerosols compete for the same NO3 and N2O5.

Frontispiece: Gas Phase Hydrolysis and Oxo‐Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium

Frontispiece: Gas Phase Hydrolysis and Oxo‐Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium

Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series.

Computational study on the hydrolysis of halomethanes

The hydrolysis reactions of methane and halomethanes have been systematically investigated using density functional theory. These reactions may occur via a metathesis mechanism and a direct-elimination mechanism, metathesis being the predominant pathway with the formation of methanol and HX (X = H, F, Cl, Br, I). The energy barriers of the predominant gas-phase hydrolysis pathway for CH4, CH3F, CH3Cl, CH3Br, and CH3I are 92.9, 19.3, 25.1, 18.8, and 20.8 kcal/mol, respectively. These values change to 92.6, 20.0, 22.8, 16.3, and 18.3 kcal/mol, respectively, when polarizable continuum model implicit solvent effect is employed. The catalytic influence of molecular water and the bulk solvent effect of water have been revealed. It was also determined that the energy barrier initially decreased and then increased with an increase in the number of water molecules. For CH4 and CH3F, there are four reactive H2O molecules taking part in the proton transfer during hydrolysis to form ten-member rings in the transition state, and two other H2O molecules participate as solvents in the predominant route. For CH3Cl, CH3Br, and CH3I, there are three H2O molecules that form eight-member rings transition state and other 2H2O molecules that act as solvent in the predominant hydrolysis pathway. Additional H2O molecules as an explicit solvent are investigated using the ONIOM model, and the coulomb interaction between adjacent atoms of the transition state is calculated to investigate the inherent reason for the formation of HF in the gas phase and (H3O+ + F−) in a solvent. These intrinsic mechanistic insights should facilitate a deeper understanding of halomethanes hydrolysis.

Sulphur dioxide cooperation in hydrolysis reactions of vanadium oxide and hydroxide cluster dianions

Gas-phase hydrolysis takes place due to the synergistic action of SO2and vanadium-containing dianions that succeeds in tightening hydrogen bonds.

Mononuclear thorium halide clusters ThX4 (X = F, Cl): gas-phase hydrolysis reactions.

Density functional theory (DFT) calculations have been performed to explore the gas-phase hydrolysis reaction of mononuclear thorium halide clusters ThX4 (X = F, Cl). We have found that the hydrolysis of ThCl4 is easier than that of ThF4. Furthermore, their hydrolysis reactions favor pathways of direct dehydration of Th(OH)4 instead of further hydrolysis of ThOX2. There are some differences between the hydrolysis of ThCl4 and that of MCl4 (M = Ti, Zr and Hf). The X-HY (X = F, Cl; Y = F, Cl and OH) hydrogen bonds play an important role in the hydrogen transfer process of the hydrolysis reaction. The differences in the steric effects and bonding may be important factors that are related to the disparities in the hydrolysis of the above-mentioned metal halides.