Ethylene Molecules Research Articles

Aqua-tri-fluorido-boron-1,3-dioxolan-2-one (1/2).

The crystal structure of the co-crystal of aqua-tri-fluorido-boron with two ethyl-ene carbonate (systematic name: 1,3-dioxolan-2-one) mol-ecules, BF3H2O·2OC(OCH2)2, was determined by low-temperature single-crystal X-ray diffraction. The co-crystal crystallizes in the ortho-rhom-bic space group P212121 with four formula units per unit cell. The asymmetric unit consists of an aqua-tri-fluorido-boron mol-ecule and two ethyl-ene carbonate mol-ecules, connected by O-H⋯O=C hydrogen bonds. This crystal structure is an inter-esting example of a superacidic BF3H2O species co-crystallized with an organic carbonate.

Synthesis and Behavior of Hexamethylenetetramine-Based Ionic Liquids as an Active Ingredient in Latent Curing Formulations with Ethylene Glycol for DGEBA

The paper presents the preparation of new ionic liquids based on hexamethylenetetramine with bis(trifluoromethanesulfonyl)imide and dicyanamide anion, which were characterized in detail in terms of their purity (Ion Chromatography) and thermal properties (Differential Scanning Calorimetry), as well as stability. The obtained substances were used to develop curing systems with ethylene glycol, which were successfully tested for their application with bisphenol A diglycidyl ether molecule. In addition, the curing process and its relationship to the structure of the ionic liquid are characterized in detail. The research showed that hexamethylenetetramine-based new ionic liquids can be successfully designed using well-known and simple synthetic methods-the Delepine reaction. Moreover, attention was paid to their stability, related limitations, and the application of hexamethylenetetramine-based ionic liquids in epoxy-curing systems.

Durable semi-crystalline interphase engineering to stabilize high voltage Ni-rich cathode in dilute ether electrolyte

Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability. However, their oxidation stability has been mostly relying on the high concentration approach, and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte. In this work, we construct a semi-crystalline interfacial layer on the surface of Li(Ni0.8Co0.1Mn0.1)O2 cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules. Different from traditional brittle crystalline interphases, the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer. Due to this design, the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability (84% capacity retention after 300 cycles). This article provides a solution to address the oxidation instability issue of ether-based electrolytes.

Nanoscale Ultrafine Zinc Metal Anodes for High Stability Aqueous Zinc Ion Batteries

Aqueous Zn batteries (AZBs) are a promising energy storage technology, due to their high theoretical capacity, low redox potential, and safety. However, dendrite growth and parasitic reactions occurring at the surface of metallic Zn result in severe instability. Here we report a new method to achieve ultrafine Zn nanograin anodes by using ethylene glycol monomethyl ether (EGME) molecules to manipulate zinc nucleation and growth processes. It is demonstrated that EGME complexes with Zn2+ to moderately increase the driving force for nucleation, as well as adsorbs on the Zn surface to prevent H-corrosion and dendritic protuberances by refining the grains. As a result, the nanoscale anode delivers high Coulombic efficiency (ca. 99.5%), long-term cycle life (over 366 days and 8800 cycles), and outstanding compatibility with state-of-the-art cathodes (ZnVO and AC) in full cells. This work offers a new route for interfacial engineering in aqueous metal-ion batteries, with significant implications for the commercial future of AZBs.

Direct observation of pressure-induced amorphization of methane/ethane hydrates using Raman and infrared spectroscopy.

The pressure-induced amorphization (PIA) of ice and clathrate hydrates occurs at temperatures significantly below their melting and decomposition points. The PIA of type I clathrate hydrates containing methane and ethane as guest molecules was investigated using Raman and infrared (IR) spectroscopy. With isothermal compression at 100 K, methane hydrate (MH) underwent PIA at 2-3.5 GPa, whereas ethane hydrate (EH) underwent PIA at 4.0-5.5 GPa. The type I clathrate structure consists of small (512) and large (51262) cages. The Raman results revealed that the collapsed small and large cages in the amorphous forms of MH and EH were not distinguishable. The collapsed cages, including the methane and ethane molecules, were similar to the small and large cages, respectively. Their water networks were folded or expanded during the PIA process so that the cavity sizes of the collapsed cages were compatible with those of the guest molecules. Peaks in the IR spectra of crystalline MH assignable to the ro-vibrational transition of methane in large cages were observed in the C-H stretching wavenumber region below 40 K. The ro-vibrational IR band disappeared after amorphization, suggesting that the rotational motion of the methane molecule in the large cage was frozen by the collapse, as reported in previous dielectric spectroscopic and simulation studies. This study contributes to a better understanding of the changes in the local structure around guest molecules during PIA and the dynamics of the guest molecules.

Synthesis of mixed methane-ethylene hydrate with ice powder

The study of gas hydrate researched by the ice powder method is helpful for us to understand the storage, separation, transportation and transformation of gas on the solid surface. In this work, the change regulation has been studied that temperature, pressure, hydrate saturation, and conversion rate in the formation process of methane-ethylene mixed hydrate, which exploring the internal action mode of the methane-ethylene mixed hydrate. The experimental results show that under the condition of −4.0 °C and 4 MPa, the conversion rates of methane, methane-ethylene (with mole ratios 2, 1, and 0.5), and ethylene hydrate are 5.30%, 11.95%, 16.57%, 19.93%, and 26.84%, respectively. And more, the conversion efficiencies of hydrate are 0.36, 0.81, 0.96, 1.58, and 6.58, respectively. The above data show that with the increase of ethylene content, the formation of hydrate is easier, which proves that ethylene can promote the formation efficiency of methane hydrate. The above results have reference value for understanding the formation of natural gas hydrates, so as to promote the development and application of gas hydrate. • There is no induction period in the process of ice powder generating methane, ethylene, and methane-ethylene mixed hydrate. • The ethylene molecules in the methane hydrate formation process can increase the reaction rate of the system. • It provides theoretical support for the development and utilization of natural gas hydrates.

Revisiting the bonding evolution theory: a fresh perspective on the ammonia pyramidal inversion and bond dissociations in ethane and borazane.

This work offers a comprehensive and fresh perspective on the bonding evolution theory (BET) framework, originally proposed by Silvi and collaborators [X. Krokidis, S. Noury and B. Silvi, Characterization of elementary chemical processes by catastrophe theory, J. Phys. Chem. A, 1997, 101, 7277-7282]. By underscoring Thom's foundational work, we identify the parametric function characterizing bonding events along a reaction pathway through a three-step sequence to establish such association rigorously, namely: (a) computing the determinant of the Hessian matrix at all potentially degenerate critical points, (b) computing the relative distance between these points, and (c) assigning the unfolding based on these computations and considering the maximum number of critical points for each unfolding. In-depth examination of the ammonia inversion and the dissociation of ethane and ammonia borane molecules yields a striking discovery: no elliptic umbilic flag is detected along the reactive coordinate for any of the systems, contradicting previous reports. Our findings indicate that the core mechanisms of these chemical reactions can be understood using only two folds, the simplest polynomial of Thom's theory, leading to considerable simplification. In contrast to previous reports, no signatures of the elliptic umbilic unfolding were detected in any of the systems examined. This finding dramatically simplifies the topological rationalization of electron rearrangements within the BET framework, opening new approaches for investigating complex reactions.

Theoretical screening of M3(btc)2 metal–organic frameworks for ethylene and 1-methylcyclopropene storage

Metal-organic frameworks (MOFs) can find numerous potential applications due to their ability of (selective) gas sorption, separation, storage, and release. One such application is active food packaging, in which controlled levels of ethylene and 1-methylcyclopropene (1-MCP) gasses can speed up or slow down fruit ripening. Following our recent experimental study of Cu3(btc)2 (HKUST-1) MOF, this work is aimed to theoretical screening isostructural M3(btc)2 (M = Cr, Mn, Fe, Co, Ni, Cu, Zn) materials for potential ethylene and 1-MCP storage and release. The optimal geometries and bonding energies were calculated for ethylene, 1-MCP and water molecules adsorbed in different configurations on open metal sites of M3(btc)2 at B3LYP-D3 level of theory. The results are discussed in frame of potential practical application and correlated with the available experimental data.

Catalyst-free diboration and silaboration of alkenes and alkynes using bis(9-heterofluorenyl)s.

Diboration and silaboration reactions are prominent tools to introduce valuable functional groups into organic substrates. To date, most diboranes(4) and silylboranes used for this purpose are electronically and/or kinetically stabilized and require activation by a catalyst. We show here that the tetraaryl (μ-hydrido)diborane(4) anion [3]- and the silyl (hydrido)borate ([4]-)/Me3SiBr system react spontaneously with the archetypal olefin ethylene in the absence of a catalyst. The actual active species in both cases are the valence isoelectronic intermediates [FluB-B(H)Flu]- ([1]-) and FluB-Si(H)Flu (2), which consist of two 9-heterofluorenyl halves that get attached to the 1 and 2 positions of ethylene. At room temperature, [1]- is present in a dynamic equilibrium with its isolable isomer [3]-, while 2 has to be released in situ at low temperatures by H- abstraction from [4]-. Quantum-chemical calculations show qualitatively identical reaction mechanisms for [1]- and 2. Since the reactions start with π coordination of the ethylene molecule to a vacant B(pz) orbital, the high Lewis acidity and low steric hindrance of the 9-borafluorenyl fragments are the keys to success. As the reaction proceeds, back-donation from the B-E bond into the ethylene π* orbital becomes increasingly important (E = B, Si). The scope of the reactions has been extended to tBu(H)C[double bond, length as m-dash]CH2 and tBuC[triple bond, length as m-dash]CH on the one hand and FluB-Si(Cl)Flu as well as FluB-Si(Cl)Ph2 on the other.

Explaining the High Catalytic Activity in Bis(indenyl)methyl Zirconium Cation Using Combined EDA-NOCV/QTAIM Approach.

The main purpose of this study is to elucidate some discrepancies already observed in the catalytic activity values of some zirconocene methyl cations. The EDA-NOCV scheme was employed for a theoretical description of the interactions between an ethylene molecule and five catalysts of zirconocene methyl cation. The nature of the chemical interactions has been elucidated through the QTAIM topological analysis. The steric hindrance due to the ligands was evaluated qualitatively by means of an IRI-based analysis and quantitively through Fisher information. The findings prove that the indenyl ligand seems to favor the orbital interaction between the ethylene molecule and the metal centre of zirconocene methyl cation. Both electrostatic and orbital contributions play a crucial role in stabilising the studied complexes. Based on the NOCV deformation density contributions, the strongest orbital interaction is reached with the bis(indenyl)methyl zirconium cation, which is the only one exhibiting covalent interactions. Especially, the strong contribution of π-back donation (occurring from the occupied orbitals of the zirconium atom to the π* anti-bonding orbital of ethylene) may be a key to understand why this catalyst has a higher polymerisation yield than the other studied catalysts. This work suggests a perspective for predicting values of catalytic activity when theoretically designing novel catalysts of zirconocene type.

Fluorinated ether decomposition in localized high concentration electrolytes

Localized high concentration electrolytes (LHCEs) are a promising class of battery materials to enable stable cycling of the lithium metal anode. Here, we report the use of operando nuclear magnetic resonance (NMR) spectroscopy to observe electrolyte decomposition during Li stripping/plating and identify the influence of individual components in LHCEs on Li metal battery performance. Data from operando19F solution NMR indicates that both bis(fluorosulfonyl)imide (FSI−) salt and bis(2,2,2-trifluoroethyl) ether (BTFE) diluent molecules play a key role in solid electrolyte interphase (SEI) formation. Three-electrode electrochemical impedance spectroscopy (EIS) of commercial pouch cells also shows differences in interfacial resistances between LHCE and standard high concentration electrolytes (HCEs) that may be explained by incorporation of BTFE and BTFE reaction products into the SEI. Based on solid-state NMR and X-ray photoelectron spectroscopic characterization, we find that BTFE diluents decompose to form CF2- and CF3-containing fragments within a LiF-rich SEI deposited on the anode surface. The CEI on the cathode (here, LiNi0.8Mn0.1Co0.1O2) side of the battery also contains higher quantities of LiF and trapped LiFSI after cycling in the LHCE compared to a HCE that are attributed to diluent decomposition and correlated with lower impedance at the cathode. Overall, this work provides a new framework to consider highly fluorinated ether molecules—instead of functioning purely as diluting agents in LHCEs, these fluorinated ethers exhibit tunable interfacial reactivity that can be leveraged to control Li deposition behavior.

Ethylene removal by adsorption and photocatalytic oxidation using biocarbon –TiO2 nanocomposites

A series of adsorbents and photocatalysts were developed using agricultural residues (olive stones) as raw materials. Activated carbons (ACs) were synthesized by physical activation and posteriorly, impregnated with TiO2 by a hydrothermal method. Both adsorbents (ACs) and composites (carbon-TiO2) were texturally, morphologically and chemically characterized by using complementary techniques (i.e., SEM, gas adsorption, TG, XRD, pHPZC, and so on) and then, the affinity of these samples for the ethylene molecules was tested in columns under dynamic conditions. The corresponding breakthrough curves were determined obtaining the amounts adsorbed at the breakthrough and saturation points. Finally, the photooxidation of ethylene to CO2 using carbon-TiO2 composites was analysed under UV-Vis and near UV-Vis irradiations. The physicochemical characteristics of supports and composites were correlated with their ability to remove ethylene, looking to identify the parameters allowing to improve the performance of the samples.

Superhydrophobic 3D-Assembled Metallic Nanoparticles for Trace Chemical Enrichment in SERS Sensing.

The performance of surface-enhanced Raman spectroscopy (SERS) is determined by the interaction between highly diluted analytes and boosted localized electromagnetic fields in nanovolumes. Although superhydrophobic surfaces are developed for analyte enrichment, i.e., to concentrate and transfer analytes toward a specific position, it is still challenging to realize reproducible, uniform, and sensitive superhydrophobic SERS substrates over large scales, representing a major barrier for practical sensing applications. To overcome this challenge, a superhydrophobic SERS chip that combines 3D-assembled gold nanoparticles on nanoporous substrates is proposed, for a strong localized field, with superhydrophobic surface treatment for analyte enrichment. Intriguingly, by concentrating droplets in the volume of 40µL, the sensitivity of 1nm is demonstrated using 1,2-bis(4-pyridyl)-ethylene molecules. In addition, this unique chip demonstrates a relative standard deviation (RSD) of 2.2% in chip-to-chip reproducibility for detection of fentanyl at 1µgmL-1 concentration, revealing its potential for quantitative sensing of chemicals and drugs. Furthermore, the trace analysis of fentanyl and fentanyl-heroin mixture in human saliva is realized after a simple pretreatment process. This superhydrophobic chip paves the way toward on-site and real-time drug sensing to tackle many societal issues like drug abuse and the opioid crisis.

First-Principles-Based Optimized Design of Fluoride Electrolytes for Sodium-Ion Batteries.

Because of the abundance and low cost of sodium, sodium-ion batteries (SIBs) are next-generation energy storage mediums. Furthermore, SIBs have become an alternative option for large-scale energy storage systems. Because the electrolyte is a critical component of SIBs, fluorination is performed to improve the cycling performance of electrolytes. Based on the first-principles study, we investigated the effects of the type, quantity, and relative position relationships of three fluorinated units, namely -CF1, -CF2, and -CF3, on the cyclic ester molecule ethylene carbonate (EC) and the linear ether molecule 1,2-dimethoxylethane (DME). The optimal fluorination was proposed for EC and DME by studying the bond length, highest occupied molecular orbital, lowest unoccupied lowest orbital, and other relevant parameters. The results revealed that for EC, the optimal fluorination is 4 F fluorination based on four -CF1 units; for DME, CF3CF1CF1-, CF3CF2CF2-, CF3CF1CF2CF3, and CF3CF2CF2CF3, four combinations of three -CF1, -CF2, and -CF3 units are optimal. The designed fluorinated EC and DME exhibited a wide electrochemical stability window and high ionic solvation ability, which overcomes the drawback of conventional solvents and can improve SIB cycling performance.

Kinetics of the simultaneous syntheses of ethyl tert-butyl ether (ETBE) and butyl tert-butyl ether (BTBE) over AmberlystTM 35

The kinetics of the simultaneous syntheses of ethyl tert-butyl ether (ETBE) and butyl tert-butyl ether (BTBE) over Amberlyst™ 35 (A35) has been studied at 315–353 K in the liquid phase. Different kinetic modeling approaches—namely, empirical power-law modeling, mechanistic modeling based on Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Eley-Rideal (ER) formalisms, and information-based modeling—have been compared. Empirical kinetic equations yield optimal quality of the fit, whereas mechanistic equations can explain the mechanisms of the studied reactions. The best mechanistic equation for both reactions corresponds to an ER-type mechanism in which an alcohol molecule (ethanol or 1-butanol) is adsorbed on one active site and reacts with isobutene from solution to produce the corresponding adsorbed ether molecule (ETBE or BTBE), which desorbs. A model built based on previous data has been used to check the validity of the inferred mechanism, while significantly reducing the number of adjustable parameters in the model.

Strong Cluster-Supported Brønsted Acids: Hexanuclear Niobium Cluster Compounds with Protonated Crown Ether Cations: (Crown-H)2[Nb6Cl12iX6a] (X = Cl or Br) and the Intermediate [Nb6Cl16(H2O)2]·4 dioxane.

Six cluster salts which consist of hexanuclear cluster anions [Nb6Cl12iX6a]2- (X = Cl or Br) and protonated crown ether molecules (15-crown-5 (15cr5) and 12-crown-4 (12cr4)) or crown ether-stabilized oxonium cations as well as one compound consisting of neutral cluster units, [Nb6Cl16(H2O)2]·4 dioxane, were synthesized in good to high yields. The single-crystal X-ray structures of six of these compounds were determined. The cation/anion ratios and the bond distances confirm in all cases oxidized cluster cores with 14 cluster-based electrons. The cations of the cluster salts are either sandwich-type dimers of the formula [(15cr5)H]22+ or [(15cr5)(H3O)]22+ with the protons or oxonium ions embedded in between the crown ether rings or monomeric units in the case of [(12cr4)H]+. 1H NMR investigations show that the cluster salts are strong Brønsted acids. The fact that the cluster core of [Nb6Cl16(H2O)2]·4 dioxane is oxidized but still carries water ligands indicates that within the multi-step reaction sequence of the formation of the cluster-supported acids, the oxidation step happens much faster than the ligand exchange steps. Temperature-dependent 2H MAS NMR spectra of deuterium-exchanged [(15cr5)H]2[Nb6Cl18]·2 CHCl3 are indicative of dynamic processes of the hydrogen-bonded protons within the crown ether molecule.

Caspase 3-like protease is involved in ethylene-induced programmed cell death during aerenchyma formation in Helianthus annuus stem.

Previous research has reported that hypoxic conditions and ethylene treatments greatly trigger programmed cell death (PCD) occurrence and induce the formation of aerenchyma to adapt stress environment in Helianthus annuus stem. Caspase 3-like protease (CLP) as regulatory signals, also be involved in the process of PCD to adapt the low oxygen environment. However, the relationships between ethylene and CLP have seldom been reported. Herein, To understand the regulatory role of ethylene and CLP signaling molecules in aerenchyma formation, we investigated the effects of exogenous ethephon (ET), ethylene perception inhibitor 1-methylcyclopropene (1-MCP), and the treatment of 1-MCP + ET on morphological, physiological characteristics and aerenchyma formation in H. annuus stem. The results showed that lysigenous aerenchyma formation in H. annuus stem is induced by ET, and immunohistochemistry assay indicate CLP activity is raised at the formation stage of aerenchyma formation, and decreased at the expanding phase of aerenchyma formation. Western blotting illustrate the expression of CLP is also increased within 8h after ethylene signaling inducing aerenchyma formation, and the activities of CLP are higher in ET treated seedlings than the control and 1-MCP treated seedlings. The same phenomenon was also observed by caspase-3 activity assay. These results revealed there is a causal and interdependent relationship between ET and CLP signaling during the process of aerenchyma formation, which regulating PCD initiation in H. annuus stem.

Effects of the ZSM-5 zeolites on hydrocarbon emission control of gasoline engine under cold start

The feasibility of ZSM-5 zeolite for controlling hydrocarbon (HC) emissions during cold start period of gasoline engine was studied by temperature programmed desorption (TPD) experiment and molecular simulation (MS). Acetylene, 1-butene, propylene, ethylene, acetaldehyde and benzene molecules were selected as representative HCs based on the HC emission components of gasoline engine cold start experiment. TPD experiment was carried on commercial ZSM-5, and desorption intensity curve of ZSM-5 zeolite for main cold start hydrocarbons was obtained. TPD results indicated that ZSM-5 zeolite can retain most of the hydrocarbons after 472 K, and the overall desorption intensity on ZSM-5 zeolite is acetaldehyde>1-butene > acetylene. Then adsorption and diffusion properties of the six main cold start hydrocarbon components on Na-ZSM-5 zeolite with different Si/Al ratio were studied by grand canonical Monte Carlo (GCMC) method and canonical ensemble Molecular Dynamics (MD) method. The results showed that the adsorption and diffusion of single-component hydrocarbons on ZSM-5 zeolite were affected by the number of exchange cations of zeolite, environment temperature, diameter of HC molecules and covalent bond types of HC molecules, and the adsorption capacity and diffusion coefficient were also affected by the competitive effect between the HC components. In competitive adsorption, molecules with large diameters such as acetaldehyde, 1-butene and benzene occupied the main adsorption sites of zeolite, so the adsorption capacity of these three HC molecules was large, while the adsorption capacity of smaller molecules such as ethylene, acetylene and propylene were small.

Molecular dynamic simulations of modeling aluminum-based composite nanoparticle in liquid Cellulose dinitrate decamer sol

Aluminum nanoparticle (ANP) in liquid Cellulose dinitrate decamer sol was investigated by ReaxFF molecular dynamics simulations. The mechanism of nitrocellulose (NC) single chain adsorption was researched as a chemisorption process. New Al–O bonds are formed by dehydrogenation and denitrification of the nitrate ester groups. The adsorbed part of the NC chain drags other parts to the surface as a horizontal adsorption state. We also simulated the processes of liquid Cellulose dinitrate decamer sol (ethanol, diethyl ether, and NC three components) coating the ANPs at different temperatures. The results indicate that the organic coating near surface is mainly consisted of ethanol and diethyl ether molecules. The NC chains are adsorbed on the ANPs surface in two states, including the horizontal adsorption or the nearly vertical adsorption. Heating can increase the coating rate without significantly changing the composition of the coating. Finally, the oxidation simulation shows that the organic layer can maintain good stability and oxidation resistance.

Topochemical, Single-Crystal-to-Single-Crystal [2+2] Photocycloadditions Driven by Chalcogen-Bonding Interactions.

The face‐to‐face association of (E)‐1,2‐di(4‐pyridyl)ethylene (bpen) molecules into rectangular motifs stabilized for the first time by chalcogen bonding (ChB) interactions is shown to provide photoreactive systems leading to cyclobutane formation through single‐crystal‐to‐single‐crystal [2+2] photodimerizations. The chelating chalcogen bond donors are based on original aromatic, ortho‐substituted bis(selenocyanato)benzene derivatives 1–3, prepared from ortho‐diboronic acid bis(pinacol) ester precursors and SeO2 and malononitrile in 75–90 % yield. The very short intramolecular Se⋅⋅⋅Se distance in 1–3 (3.22–3.24 Å), a consequence of a strong intramolecular ChB interaction, expands to 3.52–3.54 Å in the chalcogen‐bonded adducts with bpen, a distance (<4 Å) well adapted to the face‐to‐face association of the bpen molecules into the reactive position toward photochemical dimerization.