The 50 most-cited articles in Industrial & Engineering Chemistry Research, 2024

Bionic electronic skin, with its integrated biological functions, is capable of sensing and responding to external stimuli, potentially surpassing the ideal flexibility of natural skin in certain aspects. Most current preparation strategies employ the “bottom-up” approach, using various monomers or polymer materials to construct artificial networks through physical or chemical cross-linking, leading to issues of complexity and limited performance. In this work, we adopted a “top-down” strategy, in which the collagen fiber network of natural aluminum-tanned sheepskin was utilized as a scaffold to load monomers itaconic acid (IA) and hydroxyethyl acrylate (HEA). The subsequent in situ polymerization of IA and HEA led to the formation of poly(itaconic acid- co -hydroxyethyl acrylate) (P(IA-HEA)) and its filling among sheepskin collagen fiber skeleton, which results in the successful fabrication of a high-strength bionic electronic skin based on natural sheepskin (LIHEZ). The advantage of this approach is that it can retain the structure and properties of natural sheepskin and give the…

High Resolution Image Download MS PowerPoint Slide Poly(ethylene terephthalate) (PET) is the most widely produced thermoplastic used in many applications, such as drink bottles, packaging, and textiles. Chemical depolymerization represents a way to recycle PET that is robust to the low purity and quality of some waste PET sources. This work investigates process modeling of the three primary routes to depolymerize PET: methanolysis, glycolysis, and hydrolysis. We combine industrial patent literature and process design knowledge to simulate complete depolymerization processes and demonstrate how different configurations and process variables impact the process. We find glycolysis to be the simplest and least energy-intensive process when purification is simple, methanolysis to be attractive when purification is more challenging, and hydrolysis to be fundamentally the most complex and energy-intensive process. We reasonably expect a PET depolymerization process to be able to convert PET into monomers with an energy demand between 6000 and 10,000 kJ/kg of PET.

Poly(ethylene terephthalate) (PET) is the most widely produced thermoplastic and is used in drink bottles, packaging, and textiles. Chemical depolymerization represents a way to recycle PET that is robust to the low purity and quality of some waste PET sources. This work investigates the three primary routes to depolymerize PET into feedstocks used to produce the PET polymer: methanolysis, glycolysis, and hydrolysis. This work is unique in providing a thorough review of the depolymerization thermodynamics, chemistry, purification strategies, and design of PET depolymerization processes from an industrial perspective. This work provides detailed descriptions of different variants of PET depolymerization processes. We summarize available data necessary to design a PET depolymerization process and indicate where gaps in data exist. We demonstrate the importance of separation and purification sections of the process, which are rarely addressed in academic literature. We also demonstrate different designs and strategies that industrial technologies employ to address challenges.

Cu/ZnO/Al 2 O 3 catalysts are widely used in methanol synthesis due to their low cost and high catalytic activity. The structural and surface characteristics of Cu are crucial to the formation of the active sites for methanol production. In this study, a series of methods for the synthesis of Cu/ZnO/Al 2 O 3 are employed to modulate the catalyst structure and catalytic efficiency for the hydrogenation of CO 2 to methanol. A correlation of catalytic activity with the Cu 0 surface area and Cu particle sizes has been established. The Cu/ZnO/Al 2 O 3 catalyst derived from hydrotalcite-like precursor (CZA-LDH) exhibits the maximum Cu 0 specific surface area, the smallest Cu particle size, and high dispersion of elements, yielding the largest methanol production rate, which is comparable to the commercial Cu catalyst. Stability testing shows that the CZA-LDH catalyst can retain ∼94% of the initial activity. The in situ Fourier transform infrared spectroscopy analysis indicates that HCOO*, CH 3 O* intermediates, and product CH 3 OH are generated on the catalyst surface, and the reaction…

The Dubinin–Radushkevich (DR) isotherm is a well-established model for describing adsorption equilibria in vapor–solid systems. Its adaptation for liquid–solid systems, especially in water contaminant adsorption research, has led to several modified forms. In this study, we refer to the original formulation as the traditional DR equation, which incorporates a term representing saturation concentration. A simplified variant eliminates the need for this term, enhancing practicality. Additionally, three other variants address dimensional inconsistencies identified in a previous DR adaptation. This study evaluates the performance of the traditional DR equation and these four variants in characterizing the adsorption of antibiotic contaminants─specifically tetracycline, sulfamethoxazole, and ciprofloxacin─from aqueous solutions using published data. Notable differences emerge in the fit of each equation to the data and in the estimation of key parameters such as maximum adsorption capacity and characteristic energy of adsorption. To address these discrepancies, we introduce the…

emissions in the chemical sector is associated with the production and use of heat for material synthesis, which conventionally was generated through the combustion of fossil fuels. To address this grand challenge, Joule heating has emerged as an alternative heating method that greatly increases process efficiency, reducing both energy consumption and greenhouse gas emissions. In this Review, we discuss the key concepts that govern these Joule heating processes including material selection and reactor design, as well as the current state-of-the-art in the literature for employing these processes to synthesize commodity chemicals along with advanced materials such as graphene, metal species, and metal carbides. Finally, we provide a perspective on future research avenues within this field, which can facilitate the widespread adoption of Joule heating for decarbonizing industrial processes.

High Resolution Image Download MS PowerPoint Slide This study compares the performance of amine-functionalized γ-alumina sorbents in the form of 3 mm γ-alumina pellets and of a γ-alumina wash-coated monolith for CO 2 capture for direct air capture (DAC). Breakthrough experiments were conducted on the two contactors to analyze the adsorption kinetics and performance for different gas feeds. A constant pattern analysis revealed dominant mass transfer resistances in the gas film and in the pores, with axial dispersion also observed, particularly at higher concentrations. A 1D, physical model was used to fit the experiments and thus to estimate mass transfer and axial dispersion coefficients, which appear to be consistent with the hypotheses derived from constant pattern analysis. A dual kinetic model to describe mass transfer was found to better describe the tail behavior in the monolith, whereas a pseudo-first-order model was sufficient to describe breakthroughs on packed beds. A substantial two-order magnitude decrease in mass transfer coefficients was noted when reducing the feed…

The methanolysis of polyethylene terephthalate (PET) can address the environmental pollution and resource waste caused by waste PET, and the obtained monomer dimethyl terephthalate (DMT) is easy to separate and purify. However, conventional methanolysis of PET usually uses metal-containing catalysts, resulting in metal residues in the degradation products, which affects subsequent high-value utilization. Meantime, the reaction conditions of high temperature and high pressure promotes the occurrence of side reactions and reduces the yield of the main products. Herein, the nonmetallic deep eutectic solvent (DES) 1,5-diazabicyclo [4.3.0]-5-nonene (DBN)/Phenol was employed as a catalyst for PET methanolysis. 100% PET conversion and 95.3% DMT yield were obtained at 130 °C for 1 h. The possible reaction mechanism was investigated by combining NMR, FT-IR, GPC analysis, and DFT calculations. DBN and phenol were connected through N–H–O hydrogen bonding, where the hydrogen atom interacted with the carbonyl oxygen of PET and the oxygen atom activated the hydroxyl group of methanol.…

High Resolution Image Download MS PowerPoint Slide In recent years, there has been a surge of interest in transforming biomass into fuel, driven by its potential as the only realistic renewable carbon resource. Several conversion methods have been explored to achieve this, including gasification for producing synthesis gas, fast pyrolysis or hydrothermal liquefaction for obtaining bio-oils, and hydrolysis for generating aqueous sugars. Bio-oils offer environmental benefits due to their lower CO 2 emissions, but their direct use as fuels is hindered by limitations such as thermal instability, high viscosity and acidity, and low calorific value. Consequently, advancements in treatment methods are necessary before bio-oils can be used as direct fuels. This review focuses on the catalytic hydrotreatment of bio-oils, which has been shown to be an effective approach for the removal of heteroatoms at moderate temperatures (between 300 and 450 °C) but at high pressures (up to 20 MPa). Oxygenated compounds are transformed into H 2 O, and N and S are transformed into NH 3 and H 2 S,…

With the rapid progress in micro/nanofluidics, understanding the fundamental mechanisms of ionic transport, fluid behavior, and microsystem dynamics is more crucial than ever. Given the substantial expenses associated with manufacturing such systems, computational simulations offer a cost-effective avenue for advancing this industry sector while minimizing financial burdens. In this context, the current study explores the impact of electrolyte characteristics by numerically analyzing electroosmotic flow (EOF) in a conical nanochannel featuring charged slippery surfaces coated with a polyelectrolyte layer. Two types of electrolytic fluids, namely, water (representing a Newtonian fluid) and blood plasma (representing a non-Newtonian fluid), were investigated. The behavior of non-Newtonian electrolytes was modeled using the Bingham–Papanastasiou model. The governing equations of this nonlinear model, namely, the Poisson–Nernst–Planck and Navier–Stokes equations, were solved using the finite element method. Various parameters including slip length, surface charge density, soft layer…

Cross-linked polyethylene is one of the most widely used thermosetting plastics. Due to its low cost, lightweight, and exceptional insulation properties against electricity and heat, it is frequently used as an insulation material for wires and cables. This polymer attracted interest in several different applications, including building services, piping systems, hydronic radiant heating, cooling systems, etc. However, because XLPE is a thermosetting plastic with limited fluidity and poor moldability, recycling this cross-linked form of polyethylene is extremely important. Due to irreversible covalent cross-linking, recycling XLPE is a very challenging task, and it can contribute to serious environmental issues, including soil and air pollution because most of this industrial waste is buried in landfills or removed by incineration. Therefore, recycling this kind of material with a cross-linked network structure is highly problematic. Therefore, we need an energy-efficient, cost-effective, and eco-friendly recycling process to safeguard our ecosystem. In this article, we are…

A MXene/poly(dimethyl diallyl ammonium chloride) (PDDA)/Fe 3 O 4 (MPF) hybrid with exceptional oxidation resistance was synthesized via electrostatic self-assembly. Subsequently, a magnetic field was utilized to construct the parallel-aligned MPF within the waterborne epoxy coating (WEC). This parallel-aligned hybrid could significantly hinder the penetration of the corrosive ions. The electrochemical impedance spectroscopy (EIS) results revealed that the WEC containing parallel-aligned MPF (VMPF/WEC) exhibited the highest low-frequency impedance modulus (| Z 0.01 Hz |) among all coatings, which was 3 orders of magnitude higher than that of WEC in the initial stage of corrosion. After 42 days of the corrosion, the | Z 0.01 Hz | of VMPF/WEC surpassed that of WEC by more than 2 orders of magnitude, thereby indicating the exceptional long-term corrosion resistance of VMPF/WEC. This work proposed novel ideas for constructing high-performance anticorrosion WECs.

LiMn x Fe 1– x PO 4 is the most promising olivine-type cathode material following LiFePO 4 in terms of development potential. However, several technological challenges remain in its widespread application, particularly in terms of its low electronic conductivity, slow Li + diffusion rate, and undetermined optimal Mn/Fe ratio. To date, enormous efforts have been devoted to addressing the intrinsic defects of LiMn x Fe 1– x PO 4 to facilitate its electrochemical kinetics, and some companies have launched first-generation LiMn x Fe 1– x PO 4 . In this review, the structural characteristics, lithium storage mechanism, and synthesis methods of LiMn x Fe 1– x PO 4 are first introduced. Wherein, a particular emphasis is placed on the rational design of precursors with tunable composition and tailored architecture, encompassing the Mn–Fe binary precursors and Mn–Fe–P ternary precursors. Then, up-to-date optimization strategies for improving the electrochemical performance of LiMn x Fe 1– x PO 4, such as Mn/Fe ratio optimizing, conductive material compositing, element doping, and morphology…

High Resolution Image Download MS PowerPoint Slide Deep eutectic solvents (DESs) have gained significant attention as green solvents for liquid–liquid extraction applications. Predictive thermodynamic models can identify suitable DESs for a specific separation problem. To this end, we conducted a comprehensive evaluation of the conductor-like screening model for real solvents (COSMO-RS) to predict liquid–liquid equilibrium (LLE) in systems containing DESs. The TZVP and TZVPD-FINE parameter sets of COSMO-RS were considered, and the salts were modeled as associated or fully dissociated ions. The results showed that COSMO-RS predicted LLE in all systems with an average root mean square deviations (RMSDs) below 10% and represented lower average RMSD in systems with nonsalt DESs than salt-based DESs. COSMO-RS predictions using the TZVPD-FINE parameter set were slightly better than the TZVP parameter set. Nevertheless, the COSMO-RS predictions of the solute distribution between the phases were not accurate enough compared to experimental data using either of the parameter sets. COSMO-RS…

Equilibrium and breakthrough studies of H 2 O adsorption and the competition of CO 2 /H 2 O on a physisorbent metal–organic framework (MOF) CALF-20, commercialized for CO 2 capture from cement plants, are reported. Volumetric measurements and thermogravimetry were used to measure the water isotherm at various temperatures and relative humidity (RH) values. A cubic-Langmuir model was used to describe the water isotherms at different temperatures. Both adsorption and desorption dynamic column breakthrough experiments were performed at different RH values to examine different transitions in the isotherm. To quantify the competitive adsorption of CO 2 and H 2 O, both thermogravimetric analysis and dynamic column breakthrough techniques were required. A wide range of relative humidity (RH) values were considered, i.e., 10–90% RH. CALF-20 showed that high CO 2 loadings for RH were smaller than 47%, showing its exceptional capacity to be deployed for CO 2 capture from industrial flue gas. Beyond 70% RH, water was strongly adsorbed, resulting in a significant loss of CO 2 capacity. In the…

Traditional epoxy resins (EPR), represented by bisphenol A type, have high chemical bond energy, low polarity, and stable chemical properties. The topological structure after curing makes EPR impossible for convenient recycling through heating or dissolution like thermoplastics. This results in traditional EPR having no advantage of efficient recycling, both in molecular structure and the combination morphology of polymer chains. However, introducing degradable or dynamically cross-linked structures into epoxy resins to modify their molecular structures will bring good special responsiveness, with the expectation to achieve efficient recycling while maintaining their original performance. This paper reviews the research progress of EPR with degradable or dynamically cross-linkable structures such as ester, acetal, and similar structures, Schiff bases, disulfide bonds, and Diels–Alder addition structures. This highlights the impact of these structures themselves on EPR recycling. We discussed the potential of these structures’ research findings in small-molecule organic chemistry for…

High Resolution Image Download MS PowerPoint Slide This paper investigates the production of biocrude via hydrothermal liquefaction (HTL) of sewage sludge. Results on the effect of the separation protocol of the oily/aqueous phases highlighted the superior performance of inertial separation over liquid–liquid extraction, with a biocrude yield of 43% attained at a HTL temperature of 350 °C. Experimental results revealed that processing time exerts a nonmonotonic effect on the biocrude yield with maximum yields of 35 and 43% after 30 and 10 min processing times at 300 and 350 °C, respectively. The best results in terms of energy recovery (about 59%) and reduced content of S in the biocrude (about 1%) are obtained at 350 °C. A minimum yield of water-soluble compounds (29%) is achieved at 10 min of processing time at 350 °C, whereas the maximum yield (49%) is attained after 30 min of processing time at the same temperature. From both NMR and LC-MS analyses, the biocrude obtained proved to be a complex mixture mainly constituted by aliphatic compounds, with small amounts of aromatic…

Fluidized beds heated via fossil fuel combustion have been widely used in industry for various applications. Heating these fluidized beds with clean electricity is emerging as a promising solution to reduce greenhouse gas emissions, improve overall energy efficiency, and for some applications, improve product quality. This review covers the development status of electrically heated fluidized beds (EHFBs) with a variety of heating principles, including Joule heating, induction heating, electromagnetic irradiation, sonication, plasma heating and gas preheating. An analysis of the advantages and disadvantages of these heating principles is presented, along with their suitability for different applications. Current and potential industrial applications using EHFBs for highly diversified processes, from material processing and biomass gasification to space exploration, are highlighted. Each application presents its own unique opportunities and challenges. The selection of a method to deliver electrical heat depends on the specific purpose of each application, materials involved, and the…

High Resolution Image Download MS PowerPoint Slide The problem of microplastics (MPs) in the environment has been an emerging concern to the world in recent times. This is because the migration of MPs in the environment has been identified as deleterious culprits of the entire ecosystem and by extension may cause a decrease in life expectancy and quality of life in humans, fauna, and flora. This threat is seriously militating against the continuous existence and well-being of the entire ecosystem. Therefore, this research attempts to provide a solution to this global problem through the application of amino-functionalized zeolite series/phosphoric acid-coffee waste biochar (AFZ) for the removal of polystyrene MPs in solutions, drinking water, and wastewater. Findings from this research showed that AFZ removed 4.78 to 4.85 mg g –1 of polystyrene MPs from solutions at 20 to 50 °C, respectively. This was achieved by a combination of chemisorption and physisorption mechanisms via hydrophobic interactions between the π-electrons of the sp 2 carbon orbital and π–π aromatic moieties of AFZ…

CO 2 capture and conversion have garnered worldwide attention in view of the objective of sustainable development and carbon neutrality. Recently, ionic liquid-functionalized metal–organic frameworks (MOFs) or covalent–organic frameworks (COFs) (MOFs/COFs) offer a rising platform for the effective CO 2 separation from specific gas mixture and CO 2 conversion into value-added chemicals. Benefiting from the synergistic effect offered by ILs and MOFs/COFs, IL-MOFs/COFs exhibit better exceptional adsorption/catalytic performance than pristine MOFs/COFs or ILs. Herein, the review intends to establish a primary database for the recently emerging IL-MOFs/COFs in CO 2 capture and conversion, covering the functionalization strategies, interaction between ILs and MOFs/COFs, and the representative applications, aiding in the rational design and optimization of novel IL-MOFs/COFs with exceptional properties for real-world application. Along this line, CO 2 capture from different systems (CO 2 /N 2, CO 2 /CH 4, and CO 2 /C 2 H 2 ) and further conversion into multiproducts (cyclic carbonate,…

Green tea’s main polyphenol, epigallocatechin-gallate (EgCg), garners attention for diverse health-promoting properties. Due to the limited bioavailability of EgCg, drug formulation methodologies are imperative. Herein, cyclodextrins (CDs) were employed as hosts to create the host–guest complexes. The establishment of these complexes is contingent upon the dimensions of the host cavity and the orchestration of noncovalent interactions between the constituents. Among the natural CDs, namely, α-, β-, and γ-CD, γ-CD was determined to be the optimal host for EgCg based on cavity size. To improve the stability of inclusion complexes (ICs), various derivatized forms of γ-cyclodextrin were investigated. Among these, hydroxypropyl-γ-CD (HP-γ-CD) demonstrated the highest affinity for EgCg. HP-γ-CD is synthesized by substituting hydrogen atoms in the hydroxyl groups of γ-CD with hydroxypropyl groups at five positions. Molecular dynamics simulations on the microsecond time scale were performed to analyze the internal motion of EgCg and the rotational tumbling of the complexes. The binding…

This review explores the application of machine learning in predicting and optimizing the key physicochemical properties of deep eutectic solvents, including CO 2 solubility, density, electrical conductivity, heat capacity, melting temperature, surface tension, and viscosity. By leveraging machine learning, researchers aim to enhance the understanding and customization of deep eutectic solvents, a critical step in expanding their use across various industrial and research domains. The integration of machine learning represents a significant advancement in tailoring deep eutectic solvents for specific applications, marking progress toward the development of greener and more efficient processes. As machine learning continues to unlock the full potential of deep eutectic solvents, it is expected to play an increasingly pivotal role in revolutionizing sustainable chemistry and driving innovations in environmental technology.

Electrochemical nitrate reduction reaction (NO 3 – RR) to ammonia is a promising route to eliminate one of the major pollutants in surface water and groundwater. When powered by renewable electricity, electrolysis provides a sustainable method to generate ammonia from nitrate ions, facilitating the transition from a linear to a circular economy. Optimizing the physical and chemical properties of electrolysis cells is crucial to making this process economically viable for widespread implementation. Here, we explore how the choice of current density, conductivity, pH, interelectrode distance, membrane, catalyst, and buffer solution affect nitrate removal performance and efficiency. We developed a modeling framework to investigate the cell characteristics and fluid dynamics during electrochemical NO 3 – RR using both laminar and bubbly flows. To obtain more precise results, we employed the bubbly flow model (i.e., multiphase fluid) to take into account how gas production near the electrode surface affects liquid velocity, pH distribution, and, ultimately, potential losses. We exploit…

High Resolution Image Download MS PowerPoint Slide This study assessed seven cases of distinct raw material compositions with the aid of process simulation using Aspen Plus V12.1, focusing on reducing carbon dioxide (CO 2 ) emissions and energy demands from clinker production. Material and energy flows for the raw meal mixes were simulated in a natural gas-fueled plant. The results indicated up to 45.5% energy and 35.1% CO 2 reduction using alternative clinkers compared to ordinary Portland cement (OPC) clinker. Calcium silicate cement (CSC) clinker had the lowest energy consumption and CO 2 emissions, resulting from raw meal limestone reduction and a lower sintering temperature. Partially replacing OPC clinker with a supplementary cementitious material (SCM) from CO 2 mineralization reduced CO 2 emissions by ∼45% compared to OPC. Location-dependent CO 2 emission analysis revealed that Brazil yielded the least emissions compared to the United States and China. These findings underscore the imperative for cement industries to adopt alternative clinkers, coupled with SCMs, as…

High Resolution Image Download MS PowerPoint Slide Residual emissions from post-combustion CO 2 capture plants must be reduced to zero or recaptured from the atmosphere to be compatible with long-term climate change goals. For amine-based CO 2 capture, increasing CO 2 capture fractions requires maintaining sufficient driving force of absorption at the top of the absorber column by reducing lean solvent loadings. To produce low lean loadings without excessively increasing the specific thermal energy input, increased operational pressures are required in the CO 2 stripper, inevitably leading to higher temperatures, which may increase the specific thermal degradation rate of the solvent. Concurrently, for solvents that react rapidly with dissolved O 2, increased residence time in the absorber due to the increased packing heights also associated with high capture fractions may increase the specific oxidative degradation rate as the direct contact with O 2 in the flue gas is extended. Through process modeling and the application of a newly developed monoethanolamine (MEA) degradation…

Li(Fe 0.6 Mn 0.4 ) 1– x Ti x PO 4 /C cathode materials, with x values of 0, 0.01, 0.02, 0.03, and 0.04, were fabricated through a dual-stage synthesis process, incorporating both coprecipitation and high-temperature solid-phase techniques. The composition, microstructure, and surface morphology of these materials were thoroughly characterized using a suite of analytical techniques. These analyses confirmed the successful doping of Ti ions into the olivine lattice, resulting in a decrease in unit cell volume and the formation of an amorphous carbon layer on the particles’ surfaces, which also improved particle dispersion. The electrochemical performance of the Li(Fe 0.6 Mn 0.4 ) 1– x Ti x PO 4 /C samples was assessed using techniques including constant current charge–discharge testing, cyclic voltammetry, and electrochemical impedance spectroscopy. The findings showed that Ti-doping markedly diminishes potential polarization in these materials and the strong Ti–O coordination suppresses the Jahn–Teller effect of Mn 3+, effectively enhancing the stability and lithium-ion diffusion…

High Resolution Image Download MS PowerPoint Slide This study presents a comprehensive comparison between the packed bed and monolith contactor configurations for direct air capture (DAC) via process modeling of a temperature-vacuum swing adsorption (TVSA) process. We investigate various design parameters to optimize performance across different contactor geometries, including pellet size, monolith wall thickness, active sorbent content in monoliths, and packed bed structure configurations, considering both a traditional long column (PB 40 ) and multiple shorter columns configured in parallel (PB 5 ). Our parametric analysis assesses specific exergy consumption, sorbent, and volume requirements across different operating conditions of a five-step TVSA cycle. For minimizing sorbent requirements, PB 5 and monoliths with over 80% sorbent loading were the best-performing contactor designs with overlapping performance in the low-exergy region. Beyond this region, PB 5 faced limitations in reducing sorbent requirements further and was constrained by a maximum velocity at which it is…

Ammonia is considered an excellent hydrogen storage medium, and its synthesis and utilization have received increasing attention. Here the recent advances and challenges in ammonia synthesis and utilization are reviewed and summarized. For the synthesis of ammonia, we describe the different methods, i.e., the Haber–Bosch method, the electrocatalytic method, the photocatalytic method, the plasma-assisted method, and the chemical looping method, and discuss their synthesis mechanisms. For the utilization of ammonia, we summarize ammonia as an excellent hydrogen carrier that produces CO x -free hydrogen and is a zero-carbon energy source that can be used directly as a fuel. Moreover, the structure–performance relationships of catalysts in ammonia decomposition and hydrogen purification process have been explored in this section. Hopefully, this review will provide a detailed paradigm for ammonia synthesis and utilization and inspire the practical application of ammonia as energy.

Hybrid modeling has gained substantial recognition due to its capacity to seamlessly integrate machine learning methodologies while preserving the fundamental physical principles inherent in a model. Although these hybrid models have predominantly been applied to temporal processes governed by ordinary differential equations, the intricacies of various real-world systems, characterized by a diverse array of physical processes, extend far beyond this domain. This study extensively investigates the application of hybrid modeling techniques within the context of a complex biological system regulated by the reaction–diffusion equation, a specific type of partial differential equation. The primary objective is to tackle the challenges associated with latent chemical mechanisms that are concealed from direct observation. The proposed approach introduces a hybrid modeling framework that synergizes neural networks with mathematical methods to estimate parameters exhibiting spatiotemporal variations within a category of problems involving dynamic boundaries. Model training is executed…

High Resolution Image Download MS PowerPoint Slide This work explores the impact of solute conformers on the conductor-like screening model for real solvents (COSMO-RS) solubility predictions of vanillin and ethyl vanillin in water, short alcohols, and their mixed solvents. Two major conformers of these solutes and changes with solvent polarity were experimentally established by Raman spectroscopy and further confirmed by density functional theory calculations. The COSMO-RS predictions using the individual conformers show a poor description of the solubilities. Estimation with the COSMO-RS default conformer distribution gave better predictions and an intermediate behavior between the predictions obtained using each individual conformer. To further improve the description of the solubilities, the weight of each conformer was fitted to the experimental solid–liquid equilibrium data of the solute in a pure solvent at different temperatures. Better solubility predictions in ternary systems describing solubility maxima were found, suggesting a semipredictive approach to COSMO-RS. This…

Among all of the lithium-bearing minerals, spodumene possesses the highest theoretical lithium abundance. Since the 1990s, Australia, with the world’s largest spodumene (LiAl(SiO 3 ) 2 ) reserves, has been producing lithium as a mineral concentrate rather than a refined product. Nevertheless, the country is now moving forward to fortify its processing facilities, aligning with the vision for greener energy. This review provides a comprehensive outlook on the current status of spodumene reserves and their processing facilities along with potential expansion in the future. Spodumene processing requires several metallurgical processes ranging from salt roasting to acid leaching. However, the conventional industrial practices for Li-extraction from ores result in excessive pressure on resources, energy, and waste management. Considering these factors as an indicator of a circular economy, the process of lithium extraction should be simplified. In such a context, different practices for Li-extraction from spodumene are exemplified by recent technological advancements. Afterward,…

Complex coacervation, a specific type of associative phase separation that happens when oppositely charged macro-ions (or polyelectrolytes) are mixed, is the formation of a dense macro-ion-rich phase (the coacervate) in equilibrium with a dilute macro-ion-poor phase (the continuous phase or supernatant). Since Bungenberg de Jong and colleagues’ ground-breaking work on the gelatin–acacia gum complex coacervation in the 1920s and 1940s, coacervates have drawn increasing research attention because they are essential to a wide range of established and developing technologies. Charge complexation in solution may play a role in this association. Unfortunately, misconceptions about the theoretical foundations of complex coacervation are common, and conceptual errors have persisted in the literature. This Review is an attempt to provide a concise and comprehensive overview of the main research streams pursued in this field regarding the parameters influencing the formation of complex coacervates, encompassing various technological aspects enabling the investigation of complex coacervates in…

High Resolution Image Download MS PowerPoint Slide The scaling up of fluidized beds has been purposefully pursued for more than 100 years. Yet, over that time, scale-up tools have not significantly changed. Data analysis is typically a standard analysis of variances statistical exercise, perhaps reinforced with a design of experimental procedure. Flowsheeting and equipment design are based on institutional knowledge, albeit graphical user interface-based process flow models make that job more manageable. Advanced models such as computational fluid dynamics are used but often as a supplement and not a primary driver. As a result, the scale-up process for a fluidized bed can take more than 10 years. Fluidized beds remain at the forefront of the present time-critical sustainability challenges, e.g., carbon capture by particulate sorbents, methane-to-hydrogen, plastic-to-chemicals, etc. In view of the exigency toward net zero, today’s scale-up efforts need to be accelerated, leveraging the advanced new tools that have become readily available. The problem is that such tools are often…

Tetracycline (TC), a widely prescribed antibiotic to treat bacterial infections in humans and animals, poses a substantial threat to the environment due to its extensive use. To address this issue, a TiO 2 -based photocatalyst was employed for the effective sonophotocatalytic degradation of TC. The ultrasound-driven TiO 2 synthesis induced oxygen vacancies and Ti 3+ species, enhancing the sonophotocatalytic efficiency. The formation of Ti 3+ and oxygen vacancies was confirmed by using various analytical techniques. The synthesized TiO 2 with ultrasound (TiO 2 US) demonstrates remarkable TC degradation under halogen lamp irradiation, achieving an efficiency of ∼96%, 1.56 times higher than that of TiO 2 synthesized without ultrasound (TiO 2 WUS). Under diffuse sunlight, TiO 2 US and TiO 2 WUS exhibit degradation efficiencies of 95 and 79%, respectively. Notably, TiO 2 US effectively degraded the hospital effluent, achieving 83% degradation efficiency. This nanophotocatalyst displays appreciable reusability and stability, offering a promising solution for efficiently degrading…

In this paper, the thermodynamic properties of binary mixtures of the surfactants hexadecyltrimethylammonium bromide (HA)–sodium deoxycholate (DC) and dodecyltrimethylammonium bromide (DA)–sodium deoxycholate (DC) in an aqueous NaCl solution (0.3 mol kg –1 ) in the temperature interval T = 273.1–323.1 K are examined. In binary mixed micelles such as HA–DC and DA–DC, there are synergistic interactions between structurally different micellar building units. The dependence of the molar excess Gibbs free energy of the formation of the binary mixed micellar pseudophase on the micellar molar fractions of the surfactants ( g E = f ( x i )) is a symmetric function (a first-order Margules function) where the molar excess entropy is not zero, i.e., the strict theory of regular mixtures does not apply. If the phenomenon of enthalpy–entropy compensation is valid for each partial thermodynamic process during the formation of a binary mixed micellar pseudophase (at a constant temperature) and there is an interval of surfactant mole fraction from the initial binary mixture, where each ratio…

The optimization of the membrane electrode assembly (MEA) is crucial for enhancing the performance of proton exchange membrane water electrolysis. Nevertheless, achieving global optimization of all manufacturing parameters of the MEA poses challenges due to their high-dimensional complexity and limited experimental data. In this study, machine learning (ML) techniques were introduced to tackle this intricate engineering challenge. 58 MEAs were fabricated and tested to construct a comprehensive database enriched with features and ample data. This was achieved through a data expansion method that involves altering the operating temperature of the electrolyzer. The XGBoost was employed to perform regression predictions on high-dimensional variables, achieving a remarkable coefficient of determination ( R 2 ) value of 0.99926. The SHAP (SHapley Additive exPlanations) method and the genetic algorithm were applied for model interpretation and global optimization, respectively. By utilizing the insights provided by the SHAP method, we could narrow the decision variable dimensionality down…

Given the global greenhouse effect caused by excessive CO 2 emissions and fossil energy exploitation, cleaner energy sources are crucial for modern developments. Lignin present in biomass is being considered to replace petroleum due to its abundance and reproducibility. Although the depolymerization of lignin to produce high-value chemicals has gained attention, it encounters significant challenges. Lignin possesses a high molecular weight, and the structural changes during separation often diminish its potential for producing value-added chemicals. This study reviews the recent research on lignin depolymerization using three traditional methods, including hydrolysis, pyrolysis, and hydrogenolysis. First, the lignin hydrolysis is presented, where its properties and mechanisms under various conditions are detailed. Subsequently, the pyrolysis mechanism, products, and pyrolysis methods (catalytic pyrolysis, microwave pyrolysis, molten salt pyrolysis) are discussed in detail. In addition, this study provides a comprehensive summary of hydrogenolysis in terms of both solvent selection…

A new naphthalimide core containing molecular probe has been designed and synthesized. The photophysical properties of the probe in solvents of different polarities showed solvatochromic behavior. Probe displayed a weak aggregation-induced emission in THF–water (fw; 80%–90%) with a blue shift. Studies under a wide pH range (HEPES buffer) displayed significant fluorescence quenching under acidic medium. Probe showed “Off–On” behavior under acid and alkaline conditions. Probe upon interaction with different classes of ions and nitroaromatic compounds (NACs) displayed remarkable fluorescence quenching (switched-Off) with picric acid ( PA ) selectively in aqueous-THF (9:1, v/v) solution. Similarly, upon interaction with different biomolecules and anions, a probable complex of probe with picric acid ( 5.PA ) showed enhanced emission with uric acid ( UA ) selectively. Interestingly, the quenched emission of 5.PA was rejuvenated upon interaction with UA and the OH – ion. Job’s plot analysis revealed a 1:2 binding stoichiometry between probe and PA with a binding constant of 2.26 × 10 8 M…

High Resolution Image Download MS PowerPoint Slide Molecular design is a critical aspect of various scientific and industrial fields, where the properties of molecules hold significant importance. In this study, a 3-fold methodology design is presented that leverages the power of generative artificial intelligence (AI), predictive modeling, and reinforcement learning to create tailored molecules with desired properties. This model synergistically combines deep learning techniques with Self-Referencing Embedded Strings (SELFIES) molecular representation to build a generative model that generates valid molecules and a graphical neural network model that accurately forecasts molecular properties. The Variational Autoencoder (VAE) coupled with reinforcement learning helps refine molecule generation based on targeted attributes. Data from an experimental study involving surfactants were used to test the framework. A validation of the structural integrity of the molecules generated was conducted, and Tanimoto similarities were used to quantify the similarity and diversity between the…

Carbon capture, utilization, and storage (CCUS) technology plays a crucial role in the pursuit of carbon neutrality. To reduce the cost of carbon neutrality, it is necessary to optimally design the supply chain of CCUS, which leads to mega scale problems for vast countries such as China. In this paper, a novel three-module framework including source-sink matching, meshing, and pipeline transportation network allocating, which has the advantage of plant-level decision and trunk transportation while keeping the size of the model solvable, is proposed. In addition, a database including major CO 2 emission sources in thermal power, cement, and iron-steel sectors as well as major CO 2 storage sinks in China is set up. By comparison of scenarios with and without offshore storage, offshore storage is found to be superior in those southern coastal provinces. With a transportation distance not exceeding 250 km, around 4.2 Gt of CO 2 can be captured and stored. Simultaneously, establishing sensible CCUS deployment objectives is crucial. As the planned deployment capacity rises from 601.8 to…

The rapid assembly of ternary heterostructures with robust solar light absorption and high redox potential of photogenerated charged species is a pragmatic approach for achieving photocatalytic activation of tenacious atmospheric molecules. In the current study, a novel CeVO 4 /Bi/Bi 2 MoO 6 ternary heterostructure was fabricated by in situ deposition of CeVO 4 over one-pot-synthesized Bi/Bi 2 MoO 6 binary composite. The effect of the salt precursor and reaction duration on the morphology and crystal structure of Bi/Bi 2 MoO 6 was studied in detail. The initial formation of Bi 2 MoO 6 nanoplates and their subsequent disintegration to nanorods upon prolonged reaction time was observed due to concurrent leaching and reduction of Bi 3+ ions to plasmonic Bi 0 metal. The salt precursors also crucially influenced the reaction kinetics for the formation of Bi/Bi 2 MoO 6 heterostructures. The CeVO 4 /Bi/Bi 2 MoO 6 ternary heterostructure demonstrated a uniform deposition of CeVO 4 nanoparticles (10–20 nm) over Bi 2 MoO 6 nanorods that are embedded with ultrasmall Bi 0 nanodots (2–5 nm). The…

This work addresses the problem of leveraging first-principles knowledge with data-driven techniques in the Physics-Informed/Inspired Neural Network (PINN) framework to handle plant–model mismatch. To this end, a PINN is developed utilizing the first-principles model of the system and plant data and demonstrated to handle plant–model mismatch. The PINN is compared with another dynamic modeling technique, a Recurrent Neural Network (RNN), and for the illustrative simulation example, is shown to improve the predictive capabilities of the model compared to the other techniques. In particular, purely data-driven approaches often encounter challenges when applied to complex systems. This can lead to compromised predictive performance in situations where the model fails to capture the actual relationships among system variables. In contrast, the PINN respects the physical characteristics of the problem, while yielding a good dynamic model, based on process data. These results indicate the benefit of utilizing hybrid modeling techniques and their potential application to more complex…

High Resolution Image Download MS PowerPoint Slide Ultrasonication has emerged as a promising and effective technique for generating nanoscale oil-in-water (O/W) emulsions, offering enhanced physical stability and superior encapsulation activity for various bioactive molecules. Despite its numerous advantages, the impact of the chemical effects of ultrasonic cavitation on the chemical (oxidative) stability of O/W emulsions has not been thoroughly investigated. This study focuses on addressing this gap and comprehending the mechanism of lipid oxidation during the ultrasonic emulsification process. To assess the extent of degradation, the peroxide value (PV) was determined under different ultrasonic conditions (power and time) and monitored throughout the storage to elucidate the kinetics involved. The results indicated that ultrasonication induced lipid oxidation in the emulsions by generating free radicals, leading to a significant increase in PV during storage, particularly under intense sonication conditions. Further investigations explored effective strategies to inhibit lipid…

Photocatalysis for environmental cleanup applications has seen an enormous increase in interest recently. This study aimed to examine the in situ photoactivity of the photocatalyst BiOI/g-C 3 N 4 /Bi 2 WO 6 /Biochar for the photocatalytic decomposition of the target pollutant methylene blue (MB). During photocatalysis, biochar is utilized as a support material by using light harvesting and electron-conductive qualities to hinder the quick recombination of e – /h + pairs. The BiOI/g-C 3 N 4 /Bi 2 WO 6 /Biochar composite showed improved photoactivity and stability after adding biochar. For MB degradation, the attained rate constant K was found to be 0.04102 > 0.02446 > 0.01818 > 0.0119 > 0.00933 > 0.00705 min –1 for g-C 3 N 4 /Bi 2 WO 6 /BIOI/Biochar > g-C 3 N 4 /Bi 2 WO 6 /BIOI > g-C 3 N 4 /Bi 2 WO 6 > BiOI > Bi 2 WO 6 > g-C 3 N 4, respectively. The degradation efficiencies of BiOI/g-C 3 N 4 /Bi 2 WO 6 /Biochar photocatalysts for MB were 97.56% within 70 min. Scavenger and electron spin resonance (ESR) studies further demonstrated that h +, • O 2 –, and • OH are significant reactive…

High Resolution Image Download MS PowerPoint Slide Dilute concentration (∼400 ppm) and humidity are two important factors in the direct air capture (DAC) of CO 2 by supported sorbents. In this work, a minimal DAC CO 2 adsorption-kinetics model was formulated for supported amine sorbents under dry and humid conditions. Our model fits well with a recent DAC experiment with supported amine sorbent in both dry and humid conditions. Temperature and flow rate effects on breakthrough curves were quantitatively captured, and increasing temperature led to faster CO 2 adsorption kinetics. Moisture was shown to broaden the breakthrough curve with slower CO 2 adsorption kinetics but significantly improve the uptake capacity. The present minimal model provides a versatile platform for kinetic modeling of the DAC of CO 2 on supported amine and other chemisorption systems.

Thermoplastic polyamide elastomers (TPAEs) have emerged as important elastomer materials with significant practical applications, because of their outstanding mechanical properties, good thermal stability, and broad operating temperature window. However, the traditional raw precursors of TPAEs are mainly from fossil materials, which greatly limit their sustainability. To solve this problem, the preparation and application of biobased TPAEs (BTPAEs) have aroused much interest, and a series of achievements have been achieved in the past decades. In this Review, the research progress of BTPAEs is systematically summarized, in which the raw materials, synthesis, properties, and applications of BTPAEs are introduced. In addition, opportunities and challenges for achieving high-performance BTPAEs are presented. This Review is expected to stimulate more unprecedented achievements derived from BTPAEs, thus further promoting their future practical applications.

Nickel-based catalysts exhibit high activity in dry reforming of methane (DRM); however, Ni-based catalysts are susceptible to sintering and coke deposition, resulting in deactivation. In the present work, a Ni–Mg–Al catalyst was prepared by reverse microemulsion synthesis and used for DRM. The catalyst calcination conditions were controlled to study how the surface properties of the catalysts impact coke deposition and CO 2 activation. The coke deposition species on the Ni–Mg–Al catalyst calcined at 700 °C were amorphous carbon, and those on the Ni–Mg–Al catalyst calcined at 900 °C were filamentous carbon. The strong metal–support interaction enhanced at 900 °C did not prevent the formation of coke. The basic sites play an important role in coke deposition in the DRM reaction. The relationship between basic sites and CO 2 activation was investigated by CO 2 -TPD and DRIFTS. Bidentate carbonates and monodentate carbonates led to the deposition of different coke types. The catalyst possesses more weak and medium basic sites, which reduces the formation of filamentous carbon.

In the past decade, traditional fuel vehicles have gradually been replaced by electric vehicles (EVs) to help reduce the consumption of fossil fuels and the emissions of greenhouse gases, and lithium iron phosphate (LFP) batteries stand as one of the promising batteries to power such EVs, because of their cost-effectiveness and high energy density. However, with the increasing number of EVs each year and the end-of-life of LFP batteries, proper recycling of such spent LFP (SLFP) batteries has become an unavoidable challenge. As such, the development of a green, efficient, and low-cost method to recycle SLFP batteries is of crucial importance, which will benefit the industries for manufacturing LFP batteries and EVs. To this end, we provide a review to focus on understanding the current development of recycling SLFP batteries and summarizing the current research status and technological challenges existing in recycling SLFP batteries. Specifically, we provide detailed elucidations regarding the environmental risks of such SLFP batteries, common techniques deployed for separating…

Intelligent microfluidics in nanoparticle synthesis embodies a comprehensive synergistic approach that merges numerical modeling, artificial intelligence, and experimental analysis, striving for controllability over an energy-efficient microfluidic device designed for nanoparticle synthesis with desired physical properties. This study delves into a microfluidic mass transfer system, employing an innovative methodology that combines data-driven modeling, machine learning-based comparative multiobjective optimization, and experimental analysis to model a micromixing system. A surrogate data-driven model is employed to the microfluidic mass transfer system, considering four critical geometrical parameters and inlet Reynolds as design variables. The model provides insights into mixer’s functionality. It is observed that at lower Reynolds numbers, increasing NoT increases the mixing efficiency by more than 20%. Moreover, altering SND i value leads to a significant 80% reduction in pressure drop. Identifying the optimal system from numerous design parameters is challenging but…