Decomposition Products Research Articles

Conformal Li2O2 Growth and Decomposition Within 3D Lithiophilic Nanocages of Metal–Organic Frameworks for High‐Performance Li─O2 Batteries

AbstractLi─O2 batteries (LOBs) have the largest theoretical capacity among current batteries, but the irreversible growth and decomposition of Li2O2 products in positive electrodes cause dramatic degradation of their capacities over charging–discharging cycles. Herein, a metal–organic framework is reported with bipyridinic N linkers attached to graphene (bpyN‐MOF/g) as a positive electrode material to overcome the challenge. The bpyN‐MOF/g promotes conformal Li2O2 growth during discharging, while allowing Li2O2 decomposition at a low overpotential (0.487 V vs Li+/Li at 200 mA gc−1) during charging process, outperforming the Pt/C‐based electrode (0.857 V). Moreover, 3D‐tomography and density functional theory calculations consistently support the Li2O2 growth and decomposition mechanism inside bpyN‐MOF/g. Furthermore, bpyN‐MOF/g//Li LOBs achieve an exceptional discharge capacity (17 275 mAh gc−1 at 100 mA gc−1) and steady cycling for 270 cycles at 1000 mAh gc−1 under 2000 mA gc−1. Additionally, high gravimetric capacity at low mass loadings (0.27–0.44 mg cm−2) and stable cycle operation at a high areal current density (0.5 mA cm−2) open new opportunities for various practical applications.

Considerations for the safe handling and processing of unstable materials

AbstractWe evaluate the instability hazards of initiators, monomers, and other unstable materials during storage and handling in individual containers, pallets of containers, and storage and process vessels. We propose a simplistic model to analyze the temperature–time profile of an unstable chemical, given heat transfer from/to the environment, heat generation due to decomposition and other reaction kinetics, and heat generated from auxiliary equipment (e.g., agitators/mixers, pumps, vessel jackets). Lumped capacitance‐based heat transfer and decomposition kinetics are integrated to predict self‐accelerating decomposition temperature (SADT), self‐accelerating polymerization temperature (SAPT), and the temperature profile given exposure conditions (e.g., ambient temperature and additional sources of heat). Case studies related to the storage and processing of unstable liquid monomers (i.e., methyl methacrylate, MMA), and organic peroxides, (i.e., tert‐butyl peroxybenzoate, TBPB), are presented. We also provide recommendations on determining safe storage and processing temperatures and steps to prevent emergency situations and include an overview of thermal analysis and data treatment procedures which might affect chemical process safety recommendations.

Fluorinated functional groups enhanced composite in-situ gel electrolytes for high voltage cathode of quasi solid-state lithium battery

Gel electrolyte is an ideal system for improving the cycling stability and safety of lithium metal battery. However, traditional gel system with acrylic ester system is still not suitable for high-voltage battery system limited by its intrinsic structure and unstable interface. The polymer structures with -CF3 modified acrylic ester are proposed to improve the stability of both structure and interface in high-voltage battery systems. The LiF-rich anode-electrolyte interface assisted by fluorine contained in-situ gel electrolyte ensures stable cycling of lithium anode. The quasi-solid state lithium battery assembled with the LiFePO4 can still achieve a capacity retention rate of 81.2 % after 900 cycles at a rate of 1 C. Furthermore, the uniform organic cathode-electrolyte interface constructed by crosslinked -CF3 modified polymer effectively inhibits the corrosion of HF on the cathode material. The interaction between the anion and solvent molecules prevents the continuous decomposition reaction of the electrolyte on the surface of the LiCoO2 cathode at high voltage, which guarantees LiCoO2 battery can still achieve a capacity retention rate of 82.1 % after 500 cycles at a voltage of 4.45V. Design of fluorine contained in-situ polymer gel electrolyte could promote the development of quasi solid-state battery in practical industrial application.

Assessing vitamin E acetate as a proxy for E-cigarette additives in a realistic pulmonary surfactant model

Additives in vaping products, such as flavors, preservatives, or thickening agents, are commonly used to enhance user experience. Among these, Vitamin E acetate (VEA) was initially thought to be harmless but has been implicated as the primary cause of e-cigarette or vaping product use-associated lung injury, a serious lung disease. In our study, VEA serves as a proxy for other e-cigarette additives. To explore its harmful effects, we developed an exposure system to subject a pulmonary surfactant (PSurf) model to VEA-rich vapor. Through detailed analysis and atomic-level simulations, we found that VEA tends to cluster into aggregates on the PSurf surface, inducing deformations and weakening its essential elastic properties, critical for respiratory cycle function. Apart from VEA, our experiments also indicate that propylene glycol and vegetable glycerin, widely used in e-liquid mixtures, or their thermal decomposition products, alter surfactant properties. This research provides molecular-level insights into the detrimental impacts of vaping product additives on lung health.

Insight into the mechanism of H2O promoted CaCO3 decomposition in CO2 atmosphere

Calcium looping is one of the most promising CO2 capture technology. The flus gas during the calcination stage of the calcium looping contains both CO2 and H2O. However, the effect of H2O on the decomposition of carbonation in the CO2 atmosphere remains inconclusive. This study employed the Reactive Force Field molecular dynamics (ReaxFF-MD) simulations to investigate the influence of H2O on the decomposition of calcium carbonate in a CO2 atmosphere. The TGA experiments demonstrated that H2O increases the decomposition rate of calcium carbonate and also reduces the reaction temperature. Subsequently, the effects of varying CO2 and H2O concentrations on the decomposition of calcium carbonate were examined using ReaxFF-MD simulations. The simulation results for calcium carbonate decomposition, with the addition of CO2 and H2O, aligned with the experimental trends, verifying the reliability of the models. By tracking and labeling carbon, oxygen and hydrogen atom sources in the simulation, the decomposition, carbonation and hydrolysis reaction network for the CaCO3 decomposition in CO2 atmosphere was systematically constructed. Analysis of the chemical reactions and atomic distribution indicated that H2O primarily facilitates calcium carbonate decomposition by generating HCO3− through surface hydrolysis, which reduces the activation energy of the reaction. Moreover, the hydroxyl groups formed by hydrolysis compete with atmospheric CO2 for active sites on CaO, further inhibiting the carbonation reaction and increasing the calcination rate.

Interactions between nanobiochar and arsenic: Effects of biochar aging methods on arsenic binding capacity and mechanisms

Nano-biochar (nanoBC), produced from biochar aging, exhibits significant molecular heterogeneity that may affect the fate and toxicity of co-occurring pollutants. However, the interaction between nanoBC and arsenic (As) remains unclear. Herein, we simulated biochar aging through water erosion, photoaging, and thermal chemical decomposition to generate three types of nanoBC (nUBC, nPBC, and nHBC). We then investigated their distinct binding affinities and interaction mechanisms with arsenite (AsIII) and arsenate (AsV). Complementary analysis using optical spectrophotometer and high-resolution mass spectrometry revealed significant differences in properties and chemical compositions among the three nanoBCs at a size of 100 nm. Specifically, nHBC had higher yield, nPBC had higher aromaticity, and nUBC had more intricate molecular compositions and larger molecular weights. Binding experiments showed that nHBC and nUBC exhibited the highest conditional distribution coefficient (KD) for AsIII and AsV, respectively. In nHBC, a higher proportion of humic-like fluorescent component C3 enhanced its affinity for AsIII, attributed to lignin-like molecules with CHONS formulas where thiol acted as active binding sites. In contrast, the robust AsV binding capacity of nUBC stemmed from its richness in humic-like fluorescent component C1 and tryptophan-like fluorescent component C2. This is facilitated by lipid-like molecules and CHO formulas in C1 and aliphatic/peptide-like molecules and CHON formulas in C2, which provided oxygenic and nitrogen-containing groups for binding. All nanoBC had a significantly higher binding affinity for As than bulk BC. These findings provide a deeper understanding of As-nanoBC binding mechanisms at the molecular level, facilitating more accurate prediction of As fate in biochar-amended soil and associated ecosystem risks.

Engineering Optimization of Producing High-Purity Dichlorosilane in a Fixed-Bed Reactor by Trichlorosilane Decomposition.

High-purity dichlorosilane (DCS) is an important raw material for thin film deposition in the semiconductor industry, such as epitaxial silicon, which is mainly produced by trichlorosilane (TCS) catalytic decomposition in a fixed-bed reactor. The productivity of DCS is strongly dependent on the controlling of the TCS decomposition reaction process, associated with the cost in practical application. In this study, we have performed computational fluid dynamics (CFD) simulation on the TCS decomposition reaction kinetics in a cylindrical fixed-bed reactor, in which the effects of catalyst bed height, feed temperature, and feed flow rate are stressed to predict the conversion rate of TCS and the generation rate of DCS. This indicates that the increase of bed height helps the reaction to proceed adequately, but too large a bed height does not improve the DCS generation rate. Meanwhile, the feed temperature and reactor temperature have important effects on the DCS generation rate. However, it is found that changing the feed flow rate and L/D ratio cannot effectively improve the DCS generation rate while the bed volume remains constant. Furthermore, we have designed a fixed-bed reactor to verify the simulation results, which are in good agreement with each other. These results are of significance for the practical industrial production of high-purity DCS in a fixed-bed reactor.

Analysis of emission of volatile organic compounds and thermal degradation in investment casting using fused deposition modeling (FDM) and three-dimensional printing (3DP) made of various thermoplastic polymers.

The study examined the degradation process of various types of polymers used to form models using the fused deposition modeling (FDM) and three-dimensional printing (3DP) methods and used in the investment casting method. Commercial filaments made of polylactide (PLA), acrylonitrile butadiene styrene terpolymer (ABS), high-impact polystyrene (HIPS), polyamide 12 (PA12), poly(methyl methacrylate) (PMMA), and polypropylene (PP) were used to produce gypsum molds. The assessment included organic volatile compounds (VOCs) released during mold heating and model degradation, which is characteristic of this technological process. The screening qualitative chromatographic analysis of decomposition products sampled from various points of the production hall made it possible to define potential threats related to the processing of selected polymers and the necessary preventive measures. Furthermore, passive diffusion-type samplers were used at the sampling stage of VOCs emitted to the gaseous phase to reduce nuisance and user interference. Studies have been completed to characterize the thermoplastic polymer degradation process. The coupled thermogravimetry (TGA) with analysis of gaseous products by infrared spectroscopy with Fourier transformation (FT-IR) has been used. The presented results are the first to compare and rate the use of this still-developing novel aspect of castings by the method of fused models.

An investigation on g-C3N4/ZnS/SnO2 ternary nanocomposites for electrochemical alkaline water splitting and photocatalytic methylene blue decomposition reactions

An investigation on g-C3N4/ZnS/SnO2 ternary nanocomposites for electrochemical alkaline water splitting and photocatalytic methylene blue decomposition reactions

Synthesis of copper-doped nanocrystalline tin stannate by thermal decomposition of a precursor

Zinc hydroxostannate ZnSn(OH)6, containing 5 mol.% Cu, was obtained from hydrochloric acid solutions of tin(IV), zinc and copper by adding sodium hydroxide to pH = 8–9. The thermolysis process of the obtained sample and the phase composition of the decomposition products were studied using thermal analysis, X-ray diffraction, and scanning electron microscopy. It was shown that the main stages of dehydration are completed at a temperature of about 350 °C and, as a result of thermolysis, an X-ray amorphous product is formed, from which a solid solution of copper in zinc stannate is obtained at an annealing temperature above 650 °C. At an annealing temperature of 800 °C, a mixture of nanocrystalline tin dioxide SnO2 with a cassiterite structure and copper-doped zinc orthostannate Zn2SnO4 with a spinel structure is formed. The room temperature sensors based on ZnSnO3 and carbon nanofibers as a conductive additive showed high response to NO2 (–6.1% to 2 ppm NO2).

A Comprehensive Study on the Parameters Affecting Magnesium Plating/Stripping Kinetics in Rechargeable Mg Batteries

AbstractMg metal anode‐based battery is a more sustainable, lower cost, and higher energy density alternative to Li‐ion. However, this battery chemistry also faces several challenges associated with the high charge density of Mg2+, including achieving high reversibility and low voltage hysteresis for Mg metal plating/stripping. While significant improvements are achieved in last decades, they involve rather complex electrolyte formulations and/or Mg salts difficult to produce, and the use of unpractical substrates such as platinum. Here, significant improvement in terms of Mg plating kinetics is achieved in electrolytes containing commercial magnesium bis(trifluoromethanesulfonyl)imide salt (Mg(TFSI)2) by using titanium substrate with similar crystal structure and lattice parameter as Mg leading to lower nucleation overpotential. Low salt concentration electrolyte and addition of dibutyl magnesium (Mg(butyl)2) also enable the formation of thinner interphase, richer in solvent based decomposition products, further improving Mg plating kinetics. This work highlights the complex role of Mg(butyl)2, often considered as a simple drying agent, and how it impacts ion solvation favoring the mobility of electroactive cationic species, paving the way toward better electrolyte design with improved cation transference number.

In-situ decomposition of citric acid for eliminating coking in steam reforming of acetic acid through enhanced gasification of coke precursors

H2O and CO2 are two important agents for gasification of precursors of coke in steam reforming (SR). Their in-situ formation from decomposition of reactant might facilitate removal of coke deposit from surface of catalyst. This was investigated in SR of acetic acid (HAc) mixed with presence of citric acid (CA) over Ni/SBA-15 catalyst, as CA could decompose to form simultaneously H2O and CO2 for potentially involving in gasification reactions. The results showed that CA presence could not enhance catalytic activity of Ni/SBA-15 but remarkably promoted the catalytic stability. This was due to effective suppression of coking by CA (42.3 % coke in SR of HAc versus ca. 10 % coke in co-reforming of HAc and CA and 6.7 % coke in SR of CA). The adsorbed *CO2 and *OH species produced in-situ by decomposition of CA effectively gasified the precursors of coke such as *CxHy and O-containing species like *CO and *C-O-C.

A red cell membrane-camouflaged nanoreactor for enhanced starvation/chemodynamic/ion interference therapy for breast cancer

In this study, a multifunctional Cu-doped CaO2 nanoreactor loaded with GOx and camouflaged with a folic acid-modified cell membranewas developed for breast cancer treatment. The as-developed composite nanoreactor showed a synergistic effect on calcium overload to damage mitochondria, thus killing tumor cells to achieve ion interference therapy (IIT). The loaded GOx could deplete glucose to “starve” tumor cells. The H2O2 released by CaO2 decomposition and enzyme catalytic reactions from GOx could not only be highly toxic in the tumor microenvironment but also enhance the efficiency of chemodynamic therapy (CDT) with Cu2+. The red blood cell membranes modified by folic acid achieved a combination of active targeting and passive targeting, thereby enhancing the targeting ability of the as-prepared multifunctional composite nanoreactor and prolonging its retention time at the tumor sites for more than 48 h.

Transitive path decompositions of Cartesian products of complete graphs

Transitive path decompositions of Cartesian products of complete graphs

Selective Conversion of Thermal Decomposition Products of Ammonium Perchlorate by Amorphous CoSnOx

The directional transformation of products in the multiphase decomposition process of ammonium perchlorate (AP) still faces significant challenges, one of which is the conversion of greenhouse gas N2O. Furthermore, additional elucidation of the structure and potential catalytic mechanisms of catalysts with high thermal stability is imperative for the aforementioned process. This study proposes a cobalt-based amorphous oxide with high thermal stability for catalysing the thermal decomposition of AP and achieving the transformation of catalytic products from N2O to NO (its derivatives). The results indicate that the type of catalytic decomposition products is related to the structural transformation of the catalyst, suggesting a synergistic oxidation mechanism by active oxygen and lattice oxygen. The peak decomposition temperature of AP has dropped to near the limit of 257.2 ° C, TG-IR test and MD simulation results indicate the selective generation of NO under the lattice oxygen mechanism. In addition, kinetic calculations elucidated the transition of catalysts from amorphous to crystalline state in catalysis. Finally, suggestions were made for the current characterization techniques of catalysts. This study offers a reference point for the catalyst design of AP decomposition-oriented products, which is beneficial for the transition to more environmentally-friendly products.

The microstructure evolution and mechanical properties of WC-cu-10Ni-5Mn-3Sn cemented carbides containing NbC prepared by pressureless melt infiltration

WC-based cemented carbides with different contents of NbC (0, 0.6, 0.8, 1.0, 1.2, and 1.4 wt%) are prepared via pressureless melt infiltration at 1200 °C for 1.5 h. Microstructure evolution regularity of WC-based cemented carbide is investigated to establish the effect of NbC addition and microstructure peculiarities on mechanical properties (flexural strength, hardness, and impact toughness) of final product. Experimental results reveal that NbC firstly dissolves in binder alloy during melt infiltration, which slows down dissolution-precipitation reaction of WC, thus refining WC grains. With the increase in NbC content, average WC grain size shows varying trend, achieving the minimum (3.779 μm) at NbC addition of 1 wt%. When NbC is added in smaller amounts, Nb is mainly distributed throughout binder alloy. With the increase in NbC content, Nb elements tend to form aggregates and attach to WC particle boundaries. Some WC and NbC also decompose under experimental conditions. At NbC addition greater than 1 wt%, decomposition products (Nb, W, and C) combine with other elements in binder phase to form new phases such as (Nb,W)C, Ni2W4C, Nb2C, and Nb4Ni2C. These phases further act as bridges for WC grain coarsening. Meanwhile, excessive NbC is detrimental to mechanical properties of the alloy. With the increase in NbC content, hardness and flexural strength of the alloy increase and then decrease, reaching the maximum values of 93.4 HRA and 1808.786 MPa, respectively, at 1 wt% NbC addition. In turn, impact toughness of the alloy shows consistently downward trend. Therefore, changes in mechanical properties of WC-based cemented carbides are mainly related to WC grain size, the appearance of new phases in binder phase, and their morphology.

Numerical investigation of turbulent mass transfer processes in turbulent fluidized bed by computational mass transfer

Turbulent fluidized bed possesses a distinct advantage over bubbling fluidized bed in high solids contact efficiency and thus exerts great potential in applications to many industrial processes. Simulation for fluidization of fluid catalytic cracking (FCC) particles and the catalytic reaction of ozone decomposition in turbulent fluidized bed is conducted using the Eulerian–Eulerian approach, where the recently developed two-equation turbulent (TET) model is introduced to describe the turbulent mass diffusion. The energy minimization multi-scale (EMMS) drag model and the kinetic theory of granular flow (KTGF) are adopted to describe gas–particles interaction and particle–particle interaction respectively. The TET model features the rigorous closure for the turbulent mass transfer equations and thus enables more reliable simulation. With this model, distributions of ozone concentration and gas–particles two-phase velocity as well as volume fraction are obtained and compared against experimental data. The average absolute relative deviation for the simulated ozone concentration is 9.67% which confirms the validity of the proposed model. Moreover, it is found that the transition velocity from bubbling fluidization to turbulent fluidization for FCC particles is about 0.5 m·s–1 which is consistent with experimental observation.

Synthesis of value-added uridine 5'-diphosphate-glucose from sucrose applying an engineered sucrose synthase counteracts the activity-stability trade-off

The one-step deconstruction of sucrose into uridine 5′-diphosphate-glucose (UDP-Glc), an important sugar donor for transglycosylation, employing sucrose synthase (Susy) is emerging as a valuable sucrose utilization process. The insufficient activity and stability of Susy limit the productivity of UDP-Glc from sucrose. Here, an engineered Susy (SusyM6) that counteracted the activity-stability trade-off was developed with the half-life time and activity being 43-fold and 1.4-fold of wild-type, respectively. Tighter hydrophobic patches and stabilization of the SSN2 domain contributed to greater activity and stability. The use of SusyM6 in UDP-Glc production resulted in a satisfactory space-time yield of 73 g/L/h within 1 h. The cascade of different biocatalysts with SusyM6, focusing on utilizing two products of sucrose decomposition, fructose and UDP-Glc, expanded sucrose utilization, efficiently promoting the UDP-Glc productivity and giving a cost-effective method for UDP-galactose (UDP-Gal) synthesis. This study demonstrated promising green pathways for producing multiple value-added products from sucrose using Susy.

Creating CoRu Dual Active Sites Codecorated Stable Porous Ceria Support for Enhanced Li-CO2 Batteries Cathodes.

Lithium-carbon dioxide (Li-CO2) battery represents a high-energy density energy storage with excellent real-time CO2 enrichment and conversion, but its practical utilization is hampered by the development of an excellent catalytic cathode. Here, the synergistic catalytic strategy of designing CoRu bimetallic active sites achieves the electrocatalytic conversion of CO2 and the efficient decomposition of the discharge products, which in turn realizes the smooth operation of the Li-CO2 battery. Moreover, obtained support based on metal-organic frameworks precursors facilitates the convenient diffusion and adsorption of CO2, resulting in higher reaction concentration and lower mass transfer resistance. Meanwhile, the optimization of the interfacial electronic structure and the effective transfer of electrons are achieved by virtue of the strong interaction of CoRu at the support interface. As a result, the Li-CO2 cell assembled based on bimetallic CoRu active sites achieved a discharge capacity of 19,111mAhg-1 and a steady-state discharge voltage of 2.58V as well as a cycle life of >175 cycles at a rate of 100mAg-1. Further experiments combined with density-functional theory calculations achieve a deeply view of the connection between cathode and electrochemical performance and pave a way for the subsequent development of advanced Li-CO2 catalytic cathodes.

Insight in sulfadiazine degradation by peroxymonosulfate activated by polydopamine-derived nitrogen-doped carbon supported CoFe2O4: Co leaching inhibition and degradation enhancement

Heterogeneous catalyst-mediated sulfate radical-based advanced oxidation processes (SR-AOPs) showed excellent performance during antibiotics degradation. Spinel was a promising catalyst for SR-AOPs, but the secondary contamination due to metal ions leaching needed to be addressed. And the destruction of catalyst structure could lead to the reduction of catalytic activity and the difficulty of recovery. Thus, a novel nitrogen-doped carbon (NC)-supported CoFe2O4 (CoFe2O4@NC) was synthesized as the activator of PMS for sulfadiazine (SDZ) degradation under low Co leaching conditions. The consequences indicated that the CoFe2O4@NC/PMS system exhibited higher PMS decomposition efficiency and reaction stoichiometry efficiency than the bare CoFe2O4/PMS systems (CoFe2O4-180 and CoFe2O4-800), which in turn demonstrated a better SDZ removal performance. Under the condition of CoFe2O4@NC dosage 0.1 g/L, PMS concentration 0.5 mM, solution pH 6.8 and temperature 25°C, SDZ (20 mg/L) was almost completely degraded within 60 min. XPS analysis showed that the NC not only protected and stabilized CoFe2O4, but also provided additional active sites for PMS activation. During SDZ degradation, SO4•−, HO•, •O2− and 1O2 were involved in the reaction, among which SO4• and HO• made the main contribution. Meanwhile, CoFe2O4@NC could be recovered by magnetic separation, and showed great stability (Co leaching 0.852 mg/L) and reusability. In the fifth cycle experiment, 85.02 % SDZ degradation was obtained. Based on the detected intermediates (12 intermediates were identified) and DFT calculations, possible degradation pathways for SDZ in CoFe2O4@NC/PMS were proposed. The condensed dual descriptor indicated that the N7, N11, and C15 atoms on SDZ molecule were the main sites of electrophilic attack, which was consistent with the detected intermediates. The degradation of SDZ involved hydroxylation of NH2, cleavage of S−N and extrusion of SO2. This study explored the improvements made in NC support material to catalytic performance and resistance to dissolution of spinel, providing new insights for subsequent researches.