Stage Of Reaction Research Articles

Comparative study on oxidation reaction characteristics of different forms of hydroxyl‑containing coal molecules

Hydroxyl groups in coal contain a variety of forms. It is very important to study the reaction characteristics of different forms of hydroxyl‑containing coal molecules for revealing the mechanism of coal spontaneous combustion and the development of inhibitor. Therefore, this study focuses on the influence and reaction mechanism of the molecular oxidation reaction stage of different forms of hydroxyl‑containing coal by molecular dynamics, quantum chemistry and FTIR. The results show that there are two paths in the reaction of different hydroxyl structure: dehydrogenation and hydroxyl addition. The consumption rate of polyhydroxyl coal molecules (88 %) is higher than that of monohydroxyl (18 %), and the consumption rate of 2-methylphenol (58 %) is higher than that of other positions. The reaction of monohydroxyl coal is mainly influenced by aliphatic hydrocarbon, and the reaction of polyhydroxyl coal is mainly influenced by hydroxyl group. Quantum chemical calculation shows that the reactivity difference of different forms of hydroxy‑containing coal molecules is due to the active sites. Furthermore, the free energy barrier of hydroxyl addition reaction is 73–89 KJ /mol and the heat release is 52–56 KJ /mol, which can increase the trend of benzene ring-opening reaction.

Synergetic effects during co-pyrolysis of waste textiles and Ca/Fe-rich industrial sewage sludge: Reaction kinetics and product distribution

Co-pyrolysis is a promising technology for industrial organic waste to utilize their unique resource and energy properties for efficient conversion into valuable products. This study was the first time to characterize the co-pyrolysis of waste textiles with Ca-rich industrial sludge and Fe-rich industrial sludge on a laboratory-scale fixed bed. The properties, mechanisms, gas, oil and carbon production were investigated as a function of temperature and mixing type. Co-pyrolysis increased the total weight loss from 50.05 % to 69.81 % for Ca-rich industrial sludge mixed with 50 % waste textiles and from 49.13 % to 70.01 % for Fe-rich industrial sludge mixed with 50 % waste textiles. The activation energy of co-pyrolysis was approximately 50 % lower compared to the pyrolysis of waste textiles alone. The optimal reaction model for the different reaction stages for all samples was three diffusion (D3). Co-pyrolysis resulted in lower CO and CO2 emission temperatures of about 25–110 °C and produced more short-chain organic compounds (C < 10). Co-pyrolysis produced more aldehydes and ketones organics. Moreover, co-pyrolysis char exhibited an elevated level of fatty alkyl side chains and bridge branching, as well as higher degrees of aromatization and stability. This study offers valuable insights into the potential application of pyrolysis for the management of Ca/Fe-rich industrial sludge and waste textiles, thereby serving as a basis for future utilization endeavors.

Effect of copper content on the pyrolysis process of organic components in waste printed circuit boards: Based on experimental and quantum chemical DFT simulations

In recent years, scientists have become increasingly concerned in recycling electronic trash, particularly waste printed circuit boards (WPCBs). Previous research has indicated that the presence of Cu impacts the pyrolysis of WPCBs. However, there may be errors in the experimental results, as printed circuit boards (PCBs) with copper and those without copper are produced differently. For this experiment, we blended copper powder with PCB nonmetallic resin powder in various ratios to create the samples. The apparent kinetics and pyrolysis properties of four resin powders with varying copper concentrations were compared using nonisothermal thermogravimetric analysis (TG) and thermal pyrolysis-gas chromatography mass spectrometry (Py-GC/MS). From the perspective of kinetics, the apparent activation energy of the resin powder in the pyrolysis reaction shows a rise (0.1＜α＜0.2)-stable (0.2＜α＜0.4)-accelerated increase (0.4＜α＜0.8)- decrease (0.8＜α＜0.9) process. After adding copper powder, the apparent activation energy changes more obviously when (0.2＜α＜0.4). In the early stage of the pyrolysis reaction (0.1＜α＜0.6), the apparent activation energy is reduced, but when α=0.8, it is much higher than that of the resin sample without copper. Additionally, it is discovered using thermogravimetric analysis and Py-GC/MS that copper shortens the temperature range of the primary pyrolysis reaction and prevents the creation of compounds containing bromine. This inhibition will raise the temperature at which compounds containing bromine first form, and it will keep rising as the copper level rises. The majority of the circuit board molecules have lower bond energies when copper is present, according to calculations performed using the gaussian09 software, which promotes the pyrolysis reaction.

Synergistic Effect of In2O3/NC-Co3O4 Interface on Enhancing the Redox Conversion of Polysulfides for High-Performance Li-S Cathode Materials at Low Temperatures.

Lithium-sulfur (Li-S) batteries are considered as a promising energy storage technology due to their high energy density; however, the shuttling effect and sluggish redox kinetics of lithium polysulfides (LiPSs) severely deteriorate the electrochemical performance of Li-S batteries. Herein, we report a novel configuration wherein In2O3 and Co3O4 are incorporated into N-doped porous carbon as a sulfur host material (In2O3@NC-Co3O4) using metal-organic framework-based materials to synergistically tune the catalytic abilities of different metal oxides for different reaction stages of LiPSs, achieving a rapid redox conversion of LiPSs. In particular, the introduction of N-doped carbon improved the electron transport of the materials. The polar interface of In2O3 and Co3O4 anchors both long- and short-chain LiPSs and catalyzes long-chain and short-chain LiPSs, respectively, even at low temperatures. Consequently, the Li-S battery with In2O3@NC-Co3O4 cathode materials delivered an excellent discharge capacity of 1042.4 mAh g-1 at 1 C and a high capacity retention of 85.1% after 500 cycles. Impressively, the In2O3@NC-Co3O4 cathode displays superior performances at high current density and low temperature due to the enhanced redox kinetics, delivering 756 mAh g-1 at 2 C (room temperature) and 755 mAh g-1 at 0.1 C (-20 °C).

Experimental and numerical investigation of chemical-loop steam methane reforming on monolithic BaCoO3/CeO2 oxygen

Chemical looping steam methane reforming (CL-SMR) is a promising approach to co-production of syngas and hydrogen. As the CL-SMR process relies on the redox reaction of the oxygen carriers, the reactivity of oxygen carriers is crucial in the performance of CL-SMR. In this study, a monolithic BaCoO3/CeO2 oxygen carrier was synthesized, and the reaction performance was evaluated in CL-SMR. The kinetic parameters were determined based on Sestak-Berggren model, an unsteady-state CFD model was established to predict the dynamic reaction processes in three reaction stages of CL-SMR. The result suggests that the flow rate of inlet gas in reaction stages could affect the mass transfer during gas-solid reactions, and then change the evolution and distribution of reaction rate in monolithic oxygen carrier. Increasing the flow rate could improve the uniformity of reaction rate distribution and decrease the time consumption for cyclic process, but decreased the concentration of gas productions and increased the burden of gas product separation at the same time. Among three reaction stages, the conversion of oxygen carrier was accelerated with the increase of temperature, and the varied half-life time of conversions suggested that the reactivity in RS stage is intense and the reactivity in AC stage is mild.

Nonsterile Process for Biohydrogen Production: Recent Updates, Challenges, and Opportunities.

Hydrogen (H2), a clean and versatile energy carrier, has recently gained significant attention as a potential solution for reducing carbon emissions and promoting sustainable energy systems. The yield and efficiency of the biological H2 production process primarily depend on sterilization conditions. Various strategies, such as heat inactivation and membrane-based sterilization, have been used to achieve desirable yields via microbial fermentation. Almost every failed biotransformation process is linked to nonsterile conditions at any reaction stage. Therefore, the production of renewable biofuels as alternatives to fossil fuels is more attractive. Pure sugars have been widely documented as a costly feedstock for H2 production under sterile conditions. Biotransformation under nonsterile conditions is more desirable for stable and sustainable operation. Low-cost feeds, such as biowaste, are considered suitable alternatives, but they require appropriate sterilization to overcome the limitations of inherited or contaminating microbes during H2 production. This article describes the status of microbial fermentative processes for H2 production under nonsterile conditions and discusses strategies to improve such processes for sustainable, cleaner production.

The gut microbiota patterns of patients with COVID-19: protocol for a case-control study

BackgroundSARS-CoV-2 caused an outbreak in late December 2019. It has been suggested that gut microbiota dysbiosis influences the severity, mortality, and quality of life of patients with COVID-19. So, identifying the gut microbiota pattern could be helpful to determine the prognosis of the disease, and maybe determine some potential treatment approaches. Our aim will be to compare gut microbiota patterns between patients with severe or non-severe COVID-19, and healthy controls.MethodsWe will include 183 samples: 122 samples from COVID-19 patients, including 61 severe patients and 61 non-severe patients, and 61 samples from healthy controls. Total bacterial DNA will be extracted from samples and 16 S rRNA gene will be amplified through two polymerase chain reaction (PCR) stages. Fecal samples will be analyzed using a targeted metabolomics technique. The differences in each RNA or DNA expression between patients with severe COVID-19, patients with non-severe COVID-19, and controls will be compared. Also, we will assess the relationships between each DNA or RNA and the risk of COVID-19 severity, sort of clinical manifestations, and comorbidities. Concurrent medication data will be collected and patients will also be grouped based on their drug history.ResultsWe hypothesize that the gut microbiota composition will be affected by the COVID-19 severity and there might be differences in terms of sex and age.ConclusionsThe results of our study could be the backbone for further trials which might lead to the development of prognostic factors and treatment options. Further studies can also consider the limitations of the study like potential confounders and selection and recall biases.

Bimetal Cu/Ni-BTC@SiO2 metal-organic framework as high performance photocatalyst for degradation of azo dyes under visible light irradiation

There has been significant attention on the efficient degradation of pollutants in wastewater using metal-organic frameworks (MOFs) photocatalytic methods over the past decade. Herein, we examined the elimination of two different types of water-contaminating dyes, specifically cationic dye methylene blue (MB) and anionic dye methyl orange (MO), through the application of bimetal Cu/Ni-BTC@SiO2 MOF as high performance photocatalyst. The bimetal Cu/Ni-BTC@SiO2 photocatalyst was synthesized and characterized by XRD, FTIR, SEM, TEM, TGA, BET, DRS, and VSM techniques. The examination of the impact of different operational factors on the elimination of pollutants involved a comprehensive analysis of variables including the photocatalyst type, initial pollutant concentration, quantity of photocatalyst, and pH levels. The highest removal efficiency for MO and MB dyes by the photocatalyst was found to be 98 and 71%, respectively, within 60 min. In the fifth reaction stage, degradation efficiency for MO and MB was 76 and 56% respectively. Kinetic investigations demonstrated that, in the context of the uptake of MB and MO dyes, the interparticle diffusion, and pseudo-second-order models emerged as possessing the most robust correlation coefficients with the experimental data, registering values of 0.988 and 0.961, respectively. The examination of isotherms reveals that the isotherm models proposed by BET, and Anderson (V) demonstrate the highest level of conformity with the empirical data for the decomposition of MB and MO dyes, correspondingly. The TOC levels decreased significantly from 51 to 14 and 47 to 3 mg/L for MB and MO dyes, indicating the effective mineralization process using Cu/Ni-BTC@SiO2.

Efficient Catalyst-Free One-Pot Synthesis of Polysaccharide-Polypeptide Hydrogels in Aqueous Solution.

The preparation of polysaccharide-peptide hydrogels usually involves multiple synthetic steps, thus reducing the effectiveness and practicality of these approaches. Inspired by recent discoveries in aqueous N-carboxyanhydride (NCA) ring-opening polymerization (ROP) and ring-opening polymerization-induced nanogelation, we present an aqueous one-pot strategy to prepare polysaccharide-polypeptide hydrogels. In this study, water-soluble polysaccharide carboxymethyl chitosan is used as the macromolecular initiator to prepare polysaccharide-polypeptide copolymers through the aqueous ROP of NCA. The catalyst-free approach afforded hydrogels with properties that could be controlled by adjusting the type and amount of NCA used, with the elastic modulus ranging from 50 Pa to 18000 Pa. The hydrogen bond-cross-linked hydrogel exhibited self-healing and injectable properties. Morphology characterization revealed that micelles were formed in the early stage of reaction, suggesting that the polymerization follows an aqueous ring-opening polymerization-induced self-assembly (ROPISA) mechanism and that aggregation of micelles during the reaction caused the gelation. Moreover, the hydrogels displayed high swelling ratios (>95% water content), and hemolysis and cytotoxicity experiments demonstrated that the hydrogels had excellent biocompatibility, indicating their potential in medical applications.

Evaluation of anisole hydrodeoxygenation reaction pathways over a Ni/Al2O3 catalyst

Anisole is a model molecule for studying hydrodeoxygenation (HDO) of lignin-derived oxygenates. Here we elucidate its HDO pathway over 10 % Ni/Al2O3 catalyst. Adsorption experiments showed that anisole is adsorbed on the acidic sites of the Al2O3. Anisole adsorption at 200–300 °C is reactive in nature, and results in its demethylation. The catalyst was tested at 100–300 °C, 5–40 bar H2 pressure. Conversion of 78 % was obtained at 5 bar and 300 °C, restricted by hydrogenation-dehydrogenation equilibrium. HDO mainly starts through the ring-hydrogenation pathway. This is followed by demethoxylation beyond 180 °C. At 5–12 bar, cyclohexane dehydrogenates to benzene. This was confirmed by conducting an HDO experiment with methoxycyclohexane. At lower pressure deoxygenation is favored; and demethylation is accompanied with methylation of the aromatic ring, for temperature >260 °C. Investigation of the initial reaction stages showed that anisole HDO on Ni/Al2O3 catalyst proceeds via two independent pathways i.e., reactive adsorption/(de)methylation and aromatic ring hydrogenation.

Regulating Sulfur Redox Kinetics by Coupling Photocatalysis for High‐Performance Photo‐Assisted Lithium‐Sulfur Batteries

AbstractChallenges such as shuttle effect have hindered the commercialization of lithium‐sulfur batteries (LSBs), despite their potential as high‐energy‐density storage devices. To address these issues, we explore the integration of solar energy into LSBs, creating a photo‐assisted lithium‐sulfur battery (PA‐LSB). The PA‐LSB provides a novel and sustainable solution by coupling the photocatalytic effect to accelerate sulfur redox reactions. Herein, a perovskite quantum dot‐loaded MOF material serves as a cathode for the PA‐LSB, creating built‐in electric fields at the micro‐interface to extend the lifetime of photo‐generated charge carriers. The band structure of the composite material aligns well with the electrochemical reaction potential of lithium‐sulfur, enabling precise regulation of polysulfides in the cathode of the PA‐LSB system. This is attributed to the selective catalysis of the liquid‐solid reaction stage in the lithium‐sulfur electrochemical process by photocatalysis. These contribute to the outstanding performance of PA‐LSBs, particularly demonstrating a remarkably high reversible capacity of 679 mAh g−1 at 5 C, maintaining stable cycling for 1500 cycles with the capacity decay rate of 0.022 % per cycle. Additionally, the photo‐charging capability of the PA‐LSB holds the potential to compensate for non‐electric energy losses during the energy storage process, contributing to the development of lossless energy storage devices.

Regulating the Ion Transport in the Layered V2O5 Electrochromic Films with Tunable Interlayer Spacing

AbstractUnveiling the ion transport mechanism to design and explore efficient and stable ion transport pathways for high‐performance transition metal oxide (TMO)−based electrochromic materials is highly desired yet challenging. Herein, this study has demonstrated that the interlayer spacing of layered vanadium penoxide (V2O5) films can be tuned by inserting different amounts of lithium−ion (Li+) within host V2O5 material, as well as adjusting ion transport behavior and electrochromic performance. These results show that V2O5 with a small amount of ion insertion delivers a stable ion transport process and electrochromic properties. Increasing the amount of inserted Li+ will enlarge the interlayer spacing, which provides abundant active sites and efficient ion transport channels, and thus reversible and rich color variation of yellow−green−blue−olive green−orange is realized. Nevertheless, an excess of ion insertion results in the crystal structure collapse and cyclic stability degradation. These findings give a rationale for the evolution of electrochromic properties during different electrochemical reaction stages. This work provides considerable insight into the ion transport behavior within the layered V2O5 films, which gives fundamental theoretical guidance for developing and designing superior layered TMO electrochromic materials.

Regulating Sulfur Redox Kinetics by Coupling Photocatalysis for High-Performance Photo-Assisted Lithium-Sulfur Batteries.

Challenges such as shuttle effect have hindered the commercialization of lithium-sulfur batteries (LSBs), despite their potential as high-energy-density storage devices. To address these issues, we explore the integration of solar energy into LSBs, creating a photo-assisted lithium-sulfur battery (PA-LSB). The PA-LSB provides a novel and sustainable solution by coupling the photocatalytic effect to accelerate sulfur redox reactions. Herein, a perovskite quantum dot-loaded MOF material serves as a cathode for the PA-LSB, creating built-in electric fields at the micro-interface to extend the lifetime of photo-generated charge carriers. The band structure of the composite material aligns well with the electrochemical reaction potential of lithium-sulfur, enabling precise regulation of polysulfides in the cathode of the PA-LSB system. This is attributed to the selective catalysis of the liquid-solid reaction stage in the lithium-sulfur electrochemical process by photocatalysis. These contribute to the outstanding performance of PA-LSBs, particularly demonstrating a remarkably high reversible capacity of 679 mAh g-1 at 5 C, maintaining stable cycling for 1500 cycles with the capacity decay rate of 0.022 % per cycle. Additionally, the photo-charging capability of the PA-LSB holds the potential to compensate for non-electric energy losses during the energy storage process, contributing to the development of lossless energy storage devices.

The role of water vapour on CO2 mobility on calcite surface during carbonation process for calcium looping: A DFT study

The presence of water vapour has been proven to stimulate carbonation for the calcium looping process, while its effect mechanism during the slow reaction stage still lacks insight understanding at the atomic level, where H2O molecules may interact with the product layer to affect the transportation of CO2. This study tried to reveal the role of water vapour on CO2 mobility on the calcite surface through density functional theoretical (DFT) calculation. H2O molecule has higher adherence to calcite surface than CO2, and it can react with CO3 to generate HCO3− and OH− ions. Then, the formed OH− ion above the surface layer can adsorb CO2. Moreover, H2O can also react with O2− defect to form OH− ions, and the OH ion at the deeper position can still adsorb CO2 through a two-step process with remarkable energy barriers. However, the formation of HCO3− can degrade the energy barriers to CO2 release from the calcite surface, owning to the weaker CO bond. Two directions of CO2 movement between anions were involved in this investigation, including crossing through the surface layer to the second layer and the movement inside the surface layer, where the higher mobility of CO2 from HCO3− to O2− ion occurs in both movement directions. For the case inside the surface layer, the movement from O2− ion to HCO3− has a higher energy barrier, indicating that the stimulation by H2O is a one-way effect, and the enhancement by H2O for CO2 mobility is caused by the reaction with CO32− other than O2− ion.

The structural basis for 2′−5′/3′−5′-cGAMP synthesis by cGAS

cGAS activates innate immune responses against cytosolic double-stranded DNA. Here, by determining crystal structures of cGAS at various reaction stages, we report a unifying catalytic mechanism. apo-cGAS assumes an array of inactive conformations and binds NTPs nonproductively. Dimerization-coupled double-stranded DNA-binding then affixes the active site into a rigid lock for productive metal•substrate binding. A web-like network of protein•NTP, intra-NTP, and inter-NTP interactions ensures the stepwise synthesis of 2′−5′/3′−5′-linked cGAMP while discriminating against noncognate NTPs and off-pathway intermediates. One divalent metal is sufficient for productive substrate binding, and capturing the second divalent metal is tightly coupled to nucleotide and linkage specificities, a process which manganese is preferred over magnesium by 100-fold. Additionally, we elucidate how mouse cGAS achieves more stringent NTP and linkage specificities than human cGAS. Together, our results reveal that an adaptable, yet precise lock-and-key-like mechanism underpins cGAS catalysis.

The effect of PEG-content and molecular weight of PEG-PPG-PEG block copolymers on the structure and performance of polyphenylsulfone ultra- and nanofiltration membranes

Thin-film composite (TFC) membranes obtained by forming a selective polyamide (PA) layer on a surface of a porous membrane-substrate via interfacial polymerization (IP) technique are the most effective membranes for nanofiltration (NF). The idea of this study is that addition of polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) block copolymers to the polyphenylsulfone (PPSU) casting solution tunes the pore structure (pore size and porosity), water contact angle and topology of the selective layer of ultrafiltration (UF) membranes. This influences the formation of PA layer via IP since membrane-substrate significantly effects the first stage of IP reaction. For the first time the effect of PEG-PPG-PEG copolymer molecular weight, content of PEG blocks and copolymer concentration in the PPSU casting solution on the structure, hydrophilicity and performance of ultrafiltration and TFC NF membranes was revealed. It was found that increase in PEG block content and PEG-PPG-PEG molecular weight led to the increase in pore size, porosity and hydrophilicity of selective layer of ultrafiltration membranes which results in the formation of thinner and more uniform PA layer with higher cross-linking degree of NF membranes via IP. It was revealed that NF membrane flux increased with the rise in the content of PEG units from 10 to 80 wt% and increase in molecular weight of PEG-PPG-PEG block copolymer. Modification of PPSU membrane-substrate yielded the increase in selectivity of the corresponding TFC NF membranes due to the formation of more uniform and denser defect-free PA layer attributed to the rise in hydrophilicity of membrane-substrate. It was found that membrane-substrate modification by PEG-PPG-PEG results in the enhancement of antifouling performance toward bovine serum albumin (flux recovery ratio is 99–100 %) and long-term stability during 48 h operation compared to the reference membrane. Modification of PPSU membrane-substrate by F38 PEG-PPG-PEG block copolymer (Mn = 5000 g mol−1, PEG block content of 80 wt%) was found to yield the TFC NF membranes with the best combination of permeation, separation and antifouling performance and long-term stability.

Enhancing crystal integrity and structural rigidity of CsPbBr3 nanoplatelets to achieve a narrow color-saturated blue emission

Quantum-confined CsPbBr3 perovskites are promising blue emitters for ultra-high-definition displays, but their soft lattice caused by highly ionic nature has a limited stability. Here, we endow CsPbBr3 nanoplatelets (NPLs) with atomic crystal-like structural rigidity through proper surface engineering, by using strongly bound N-dodecylbenzene sulfonic acid (DBSA). A stable, rigid crystal structure, as well as uniform, orderly-arranged surface of these NPLs is achieved by optimizing intermediate reaction stage, by switching from molecular clusters to mono-octahedra, while interaction with DBSA resulted in formation of a CsxO monolayer shell capping the NPL surface. As a result, both structural and optical stability of the CsPbBr3 NPLs is enhanced by strong covalent bonding of DBSA, which inhibits undesired phase transitions and decomposition of the perovskite phase potentially caused by ligand desorption. Moreover, rather small amount of DBSA ligands at the NPL surface results in a short inter-NPL spacing in their closely-packed films, which facilitates efficient charge injection and transport. Blue photoluminescence of the produced CsPbBr3 NPLs is bright (nearly unity emission quantum yield) and peaks at 457 nm with an extremely narrow bandwidth of 3.7 nm at 80 K, while the bandwidth of the electroluminescence (peaked at 460 nm) also reaches a record-narrow value of 15 nm at room temperature. This value corresponds to the CIE coordinates of (0.141, 0.062), which meets Rec. 2020 standards for ultra-high-definition displays.

Changes in the state of matter of KCIO4 to improve thermal and combustion properties of Al/MoO3 nanothermite

To improve the thermal and combustion properties of nanothermites, a design theory of changing the state of matter and structural state of the reactants during reaction was proposed. The Al/MoO3/KClO4 (Kp) nanothermite was prepared and the Al/MoO3 nanothermite was used as a control. SEM and XRD were used to characterize the nanothermites; DSC was used to test thermal properties; and constant volume and open combustion tests were performed to examine their combustion performance. Phase and morphology characterization of the combustion products were performed to reveal the mechanism of the aluminothermic reaction. The results show that the Al/MoO3/Kp nanothermite exhibited excellent thermal properties, with a total heat release of 1976 J·g− 1, increasing by approximately 33% of 1486 J·g− 1 of the Al/MoO3 nanothermite, and activation energy of 269.66 kJ·mol− 1, which demonstrated higher stability than the Al/MoO3 nanothermite (205.64 kJ·mol− 1). During the combustion test, the peak pressure of the Al/MoO3/Kp nanothermite was 0.751 MPa, and the average pressure rise rate was 25.03 MPa·s− 1, much higher than 0.188 MPa and 6.27 MPa·s− 1 of the Al/MoO3 nanothermite. The combustion products of Al/MoO3 nanothermite were Al2O3, MoO, and Mo, indicating insufficient combustion and incomplete reaction, whereas, the combustion products of Al/MoO3/Kp nanothermite were Al2O3, MoO, and KCl, indicating complete reaction. Their “coral-like” morphology was the effect of reactants solidifying after melting during the combustion process. The characterization of reactants and pressure test during combustion reveals the three stages of aluminothermic reaction in thermites. The excellent thermal and combustion performance of Al/MoO3/Kp nanothermite is attributed to the melt and decomposition of Kp into O2 in the third stage. This study provides new ideas and guidance for the design of high-performance nanothermites.

Demineralization effects on physicochemical and combustion characteristics of biomass: Insights into distributed kinetics, flue gas evolution, and slag formation

Biomass as the only carbon-bearing renewable energy has enormous potential to challenge the established energy structure dominated by fossil resources, and incineration technology is one of the most direct and efficient pathways for utilizing biomass resources, unfortunately enduring the inevitable sintering and slagging problems owing to the excessive alkali metals. Herein, we comparatively investigated the effects of five leaching solvents (water, acetic acid, wood vinegar, hydrochloric acid, and oxalic acid) on the physicochemical properties and ash-removal capabilities of wheat straw (WS) and rice husk (RH), with a view to achieving better performance in the subsequent combustion characteristics, kinetic examination, flue gas, and slag evolution. Results indicated with ionization ability increased (water < acetic acid < hydrochloric acid), the WS exhibited a strong demineralization performance (maximum 61.1%), further leading to a steep weight loss in its combustion characteristic curve at approximately 350 °C and a delayed peak temperature after the removal of alkali metal. Multiple distributed activation energy model and sensitivity analysis revealed that leaching pretreatment enhanced the activation energy (189–191.8 kJ mol−1) and optimized energy distribution at the preliminary stage of the combustion reaction. In addition, the absence of alkali metals suppressed the catalytic oxidation reaction in the flue gas, remarkably limiting the formation of CO2 but facilitating the release of CO and CH4. Meanwhile, a considerable optimal in biomass ash slagging, in which the initial temperature of the liquid phase slag for WS ash increased to 991 °C. Notably, HCl showed the strongest demineralization performance among the five leaching solvents during pretreatment, but the high-temperature slag content was still higher than that of acetic acid. Therefore, slagging performance is not only associated with the demineralization ability of leaching solvents, but also with ash composition.

Design of earth-abundant Ni3ZnC0.7@Ni@C catalyst for selective butadiene hydrogenation

The pursuit of developing catalysts from earth-abundant materials to supplant those based on precious metals is of paramount importance in selective hydrogenations. While nickel-based systems have shown promise in the selective hydrogenation of butadiene, their practical applications are hampered by severe deactivation issues due to coke deposition and excessive hydrogenation. Here, a novel catalyst, Ni3ZnC0.7@Ni@C, is ingeniously engineered through the controlled oxidation of Ni3ZnC0.7@C. This catalyst is characterized by small Ni0 ensembles elegantly embellishing the Ni3ZnC0.7 nanoparticles, all encased within porous carbon shells. The evolutions of this catalyst, in terms of composition and structure during the oxidation process, is meticulously observed and characterized using a spectrum of advanced techniques. The Ni3ZnC0.7@Ni@C catalyst exhibits outstanding activity and stability in the hydrogenation of butadiene, surpassing other Ni-based systems, including its precursor Ni3ZnC0.7@C and other previously documented catalysts such as Ni3InC0.5 and the Ni3In alloy. A pivotal finding of this research is the self-limiting behavior of coke deposition in the initial reaction stages. This intriguing phenomenon not only curbs further deactivation but also significantly enhances butene production, maintaining operational stability for an impressive duration of 80 hours. This discovery underscores the advantageous role of in situ generated ‘soft’ cokes in augmenting the selectivity and stability of the catalyst, which is particularly enlightening for other catalytic processes that are similarly afflicted by coking issues, thereby opening avenues for further in-depth investigations in this field.