Frontiers of Chemical Science and Engineering最新文献

High-entropy alloys are described as materials that have equiatomic and multi-element compositions. Their unique atomic structure may provide alternative electrocatalysts for water electrolysis over traditional and expensive noble metal-based catalysts, delivering superior catalytic activity and stability. Among various high-entropy alloys synthesis methods, electrodeposition stands out as a versatile and cost-effective approach due to its mild conditions and precise control over composition and deposition properties. This review focuses on noble metalfree high-entropy alloys prepared by electrodeposition, with applications in water electrolysis. The impacts of alloying elements and electrodeposition parameters on the morphology, composition, and electrochemical performance of the resulting coatings for hydrogen evolution reaction and oxygen evolution reaction are also examined. The roles of key alloying elements are discussed, including their individual contributions during the electrodeposition process, interactions within the bath, and effects on the final coating. The review also discusses critical deposition parameters such as bath chemistry, pH value, current density, temperature, and bath agitation, and their influences on properties and electrochemical activity of electrodeposited coatings. Finally, future research directions and recommendations in several key areas are outlined to address important knowledge gaps for further advancing the optimization and application of electrode-posited high-entropy alloys as effective electrocatalysts for water electrolysis.

The co-reaction of methanol with C₅–C₁₆ n-alkanes was investigated over microsphere catalysts with varying surface acidity and ZSM-5 as the active components. The results indicate that, as the carbon number of alkanes increases, the formation of C₁–C₄ alkanes decreases while the production of C₂–C₄ alkenes increases on the catalyst with weak outer surface acidity. This suggests that side reactions such as alkene aromatization and hydrogen transfer are suppressed. Conversely, on the catalyst with strong outer surface acidity, further reaction of olefins significantly increases, leading to a gradual decrease in light olefin yield and a corresponding increase in benzene, toluene, xylene, and heavy aromatics. Additionally, it is observed that long-chain n-alkanes (the kinetic diameter of n-hexadecane exceeds the pore size of ZSM-5 zeolite, the active component in the microspherical catalyst) cannot enter the internal pores of ZSM-5, resulting in primary cracking due to the acidic sites on the outer surface. However, long-chain n-alkanes can adjust their molecular orientation on pure ZSM-5 zeolites and enter the pore structure, leading to alkane cracking influenced by both internal and external surface acidity. These findings provide valuable guidance for the design of industrial catalysts, particularly in terms of pore size and acidity.

Plasma catalysis technology is emerging as a promising approach for addressing energy and environmental challenges in sustainability. This review provides an overview of plasma technology and summarizes recent advances in plasma catalysis from both experimental and theoretical perspectives. Current laboratory-scale studies have demonstrated the versatility of plasma catalysis in various processes, including carbon conversion, hydrogen production, and the removal of volatile organic compounds. The inherently complex environment of plasma catalysis requires in situ characterization and theoretical modeling to elucidate the underlying reaction mechanisms, which in turn guide the rational design of efficient catalysts and optimized reactor configurations. These advances are vital for enhancing the economic feasibility and accelerating the commercialization of this technology. Nevertheless, the scale-up and practical deployment of plasma-catalytic systems from laboratory to industrial scales remain challenging. In this review, we critically examine the current state of plasma catalysis research and its applications across a wide range of reactions. Particular attention is given to in situ mechanistic studies, reactor design, catalyst development, process scale-up, and theoretical modeling. Finally, we provide a forward-looking perspective on the opportunities and future directions to address existing challenges and harness the potential of plasma catalysis toward sustainable development.

In the past decades, the advancement of sensor technology has enabled the development and application of reliable process analytical technology in pharmaceutical manufacturing for process monitoring and control. Soft sensors as mathematical models are often coupled with process analytical technology tools to monitor critical quality attributes such as concentrations and particle sizes. Crystallinity and polymorphism changes are prevalent phenomena in pharmaceutical manufacturing. These changes may impact drug manufacturability, drug quality, and patients’ safety. Therefore, assessment of impact of crystallinity and polymorphism change has been one critical aspect of pharmaceutical chemistry, manufacturing, and control review and inspection. Chemistry, manufacturing, and control risk assessment has been largely qualitative in nature and has heavily relied on past knowledge and experience. The potential use of soft sensors to monitor such changes and establish a science supported risk-based control strategy is not widely discussed. In this work, by applying soft sensor models to key unit operations, we presented case studies to discuss the capability and potential of soft sensors in predicting critical quality attributes for key pharmaceutical unit operations, including crystallinity and polymorphism changes in selected drugs with moderate to high solid-state risk levels in drug product manufacturing. Population balance models, semi-empirical models, and statistical correlations are applied to wet granulator, fluidized bed dryer, mill, and tablet press to enable soft sensing. Sensitivity analysis using the established models is conducted to quantitatively assess the impacts of process inputs onto different outputs to support a risk-based control strategy with regulatory insights. Knowledge, experience, and discussion in these aspects can contribute to the future development of advanced technologies and the implementation of modeling tools toward advanced manufacturing.

Medium- and low-temperature thermochemical energy storage materials are vulnerable to deliquescence, agglomeration, and structural fracturing under hyperhumid conditions, yet the fundamental origins of excess environmental moisture within reactors remain insufficiently characterized. This study systematically elucidates water vapor transport mechanisms between air and physical adsorption materials in thermochemical reactors, with emphasis on transient humidity transfer phenomena during incomplete charging and discharging cycles. Moisture saturation was defined as the key parameter for standardized humidity analysis. Results indicate that uncontrolled saturation arises from thermally driven vapor depression, in which water vapor desorbed from materials or transported by inlet air undergoes progressive condensation during downstream migration. Moisture saturation dynamics were governed by coupled effects of inlet air temperature, flow velocity, and relative humidity. Reverse charging was shown to effectively reduce maximum moisture saturation in cases where materials remained incompletely hydrated after prior discharging. Optimization of inlet air conditions through controlled transitions from low-temperature, high-velocity states to a predesigned charging protocol achieved a 45.7% reduction in maximum moisture saturation (from 1.38 to 0.75). In addition, preheating prior to discharging significantly suppressed reactor moisture saturation, thereby mitigating material failure risks.

Perturbed-chain statistical associating fluid theory has emerged as a powerful thermodynamic framework for predicting drug-polymer miscibility and stability in amorphous solid dispersions. This review provides a comprehensive overview of the theoretical foundations of perturbed-chain statistical associating fluid theory, including its forma, the meanings of key parameters in physics, and common strategies for parameterization. Its applications to solid–liquid and liquid–liquid equilibrium calculations are highlighted, particularly in the construction of phase diagrams and the prediction of phase separation phenomena such as amorphous-amorphous and liquid–liquid phase separation. The utility of perturbed-chain statistical associating fluid theory in amorphous solid dispersions is illustrated through its roles in solubility prediction, stability assessment, drug release mechanism analysis, and rational formulation and process design. In addition, perturbed-chain statistical associating fluid theory is critically compared with alternative predictive methods, including solubility parameter theory, Flory–Huggins models, molecular simulation approaches, and machine learning. Finally, this review outlines the key challenges and future directions for integrating perturbed-chain statistical associating fluid theory with data-driven and multi-scale modeling approaches to advance model-informed amorphous solid dispersion design.

The electrocatalytic co-reduction of carbon dioxide (CO₂) and nitrate (NO₃⁻) to urea represents a sustainable alternative to energy-intensive industrial synthesis processes. Herein, we report copper-doped cerium oxide nanorods (Cu-CeO₂) as an efficient catalyst for this reaction, achieving a urea yield of 358.5 mg·h⁻¹·g⁻¹ at −0.7 V vs. reversible hydrogen electrode with 21.1% Faradaic efficiency. In situ Fourier transform infrared spectroscopy analysis reveals that during electrocatalytic urea synthesis, CO₂ activation at the catalyst surface generates carbonyl-containing intermediates (*CO), which couple with nitrogenous species (NH_x) derived from NO₃⁻ reduction. The key coupling reaction intermediate *NHCO was detected, and the *NHCO intermediate played a crucial role in promoting C–N bond formation. The stability of this intermediate directly facilitated the successful formation of urea. These findings elucidate the reaction pathway mediated by the Cu-CeO₂ catalyst, establishing a theoretical foundation for subsequent catalyst design optimization.

BiVO₄, with its moderate band gap (∼2.4 eV) and visible light absorption properties, is considered a promising photoanode material. However, its photoelectrochemical performance is hindered by intrinsic defects such as poor charge carrier transport and rapid electron-hole recombination, resulting in a significant gap between its practical and theoretical photocurrent densities. In this work, we present a simple surface reconstruction method by adding citric acid to Na₂SO₄ electrolyte. Citric acid’s multidentate structure strongly chelates the metal-sites on the BiVO₄ surface, triggering lattice reconstruction through intense interactions. This surface modification not only prolongs hole lifetime but also acts as an interface modifier, leaving a carboxyl-rich, superhydrophilic interface on the BiVO₄ surface after the reaction (contact angle ≈ 0°). The multi-dimensional optimization synergistically improves BiVO₄’s photoelectrochemical performance, achieving an excellent photocurrent density of 6.8 mA·cm⁻² under AM 1.5G irradiation. Importantly, our findings reveal a three-pronged synergy achieved with inexpensive citric acid: structural reconfiguration, electronic tuning, and extreme wettability, which offered a streamlined route for solar fuel production without solid co-catalysts.

The rapid advancement of flexible electronics creates an urgent demand for high-performance printed electronic materials. MXene-based inks have been widely studied and used for screen-printing electronics, while they usually suffer from poor screen-printability and inadequate mechanical properties of the printed coatings. Therefore, we incorporate 2,2,6,6-tetramethylpiperidinooxy oxidized cellulose nanofibers into MXene ink to regulate its rheology and enhance printability on both porous A4 paper and compact polyethylene terephthalate substrates. The introduction of cellulose enables precise control over the rheology and microstructure of the resultant MXene coatings. Critically, the strong interfacial hydrogen bonding and physical entanglement between cellulose and MXene contribute to the substantial enhancements of the mechanical properties and structural stability of the resultant composite coatings, where a remarkable 9.04-fold increase of hardness and a 1.74-fold increase of Young’s modulus are achieved. The interfacial binding strength between the coating and substrate is also well enhanced with the anchoring of cellulose. This work thereby presents a promising strategy for the design and fabrication of flexible screen-printed electronics.