Chemical Engineering Research Articles

Defect engineering on metal-organic frameworks for enhanced photocatalytic reduction of Cr(VI)

Cr(VI) stands as a profoundly toxic chemical and photocatalysis technology has shown promising potential in photocatalytic reduction of Cr(VI) to Cr(III), where the reduced Cr(III) is less toxic and can be further precipitated in a wide pH range. Metal-organic frameworks (MOFs), as emerging class of porous coordination polymers, is expected to be ideal platform for photocatalysis. In this study, defect engineering on MOFs was applied to promote photoreduction of Cr(VI). The obtained oxygen vacancy-containing MIL-125-NH2 samples showed modified electron structure, adjusted surface and porous properties, and enriched active sites. Among these oxygen vacancy-containing MIL-125-NH2 samples, the 300-M (MIL-125-NH2 heated at 300 °C for 2 h under N2 atmosphere) displayed the most remarkable performance in terms of photocatalytic Cr(VI) reduction. The pronounced efficacy of 300-M is evident from the achieved removal rate of Cr (VI), reaching an impressive 98 % in just 20 mins (19.6 mgCr(VI) g−1cata min−1), in stark contrast to MIL-125-NH2, which exhibited a modest removal rate of 53 %. Remarkably, the k-value for 300-M is 5.1 times that of MIL-125-NH2, further underscoring the superior efficiency of 300-M. The photoreduction mechanism of 300-M was further substantiated through a battery of advanced characterization techniques including transient photocurrent, electrochemical impedance spectroscopy, fluorescence spectroscopy, the Mott-Schottky analysis, and electron spin resonance. Those results disclosed that oxygen vacancies and mesopores introduced via controlled heat treatment play a pivotal role in facilitating the photoreduction of Cr(VI) within the MIL-125-NH2 structure. More advanced characterizations for the structures of photocatalysts and the photocatalytic mechanisms including charge transfer path need further studied. The systematic exploration of temperature-dependent effects on material properties opens avenues for future research in designing efficient and versatile MOF-based photocatalysts for environmental remediation applications.

A Review on Pulsed Laser Preparation of Quantum Dots in Colloids for the Optimization of Perovskite Solar Cells: Advantages, Challenges, and Prospects.

In recent years, academic research on perovskite solar cells (PSCs) has attracted remarkable attention, and one of the most crucial issues is promoting the power conversion efficiency (PCE) and operational stability of PSCs. Generally, modification of the electron or hole transport layers between the perovskite layers and electrodes via surface engineering is considered an effective strategy because the inherent structural defects between charge carrier transport layers and perovskite layers can be reshaped and modified by adopting the functional nanomaterials, and thus the charge recombination rate can be naturally decreased. At present, large amounts of available nanomaterials for surface modification of the perovskite films are extensively investigated, mainly including nanocrystals, nanorods, nanoarrays, and even colloidal quantum dots (QDs). In particular, as unique size-dependent nanomaterials, the diverse quantum properties of colloidal QDs are different from other nanomaterials, such as their quantum confinement effects, quantum-tunable effects, and quantum surface effects, which display great potential in promoting the PCE and operational stability of PSCs as the charge carriers in perovskite layers can be effectively tuned by these quantum effects. However, preparing QDs with a neat and desirable size remains a technical difficulty, even though the present chemical engineering is highly advanced. Fortunately, the rapid advances in laser technology have provided new insight into the precise preparation of QDs. In this review, we introduce a new approach for preparing the QDs, namely pulsed laser irradiation in colloids (PLIC), and briefly highlight the innovative works on PLIC-prepared QDs for the optimization of PSCs. This review not only highlights the advantages of PLIC for QD preparation but also critically points out the challenges and prospects of QD-based PSCs.

The importance of both catalyst and process design in unlocking sustainable carbon feedstocks through syngas

As part of its move towards net zero, the chemical industry, over time, will transition away from fossil-based chemical feedstocks towards more sustainable, ‘green’ carbon—biomass, recycled waste and captured carbon dioxide. One gateway to transforming these feedstocks into the vital chemicals and fuels society relies on is via synthesis gas or ‘syngas’—a gaseous mixture of chemical building blocks (H 2 , CO and CO 2 ). While today the majority of syngas is produced via steam reforming of natural gas, commercially available technologies are enabling syngas production and transformation from sustainable feedstocks. The optimization of sustainable syngas technologies would not be possible without the integrated development of both catalyst and process technology and the associated skills in chemistry and chemical engineering. This paper covers three example technologies that are unlocking the role of syngas as a gateway to sustainable fuels and chemicals and highlights the innovative developments in catalyst and process design that have enabled their optimization and commercialization. This article is part of the discussion meeting issue ‘Green carbon for the chemical industry of the future’.

A Cognitive Load Approach to Molecular Geometries: Augmented Reality Technology and Visuospatial Abilities in Chemistry

Within chemistry education, methods for effectively teaching students the three-dimensional spatial arrangements of matter at the molecular level remains a topical issue. As a form of geometric problem solving, it requires learners to apply mental rotation abilities as an evolved visuospatial skill to obtain subject-specific content knowledge. Recent research into the use of Cognitive Load Theory (CLT) as a framework for instructional design in conjunction with augmented reality (AR) technology as a learning tool has begun to show promise in reducing unnecessary cognitive activity to improve learning. Yet, broader conclusions remain inconclusive, especially within the context of a learner’s mental rotation abilities. This study investigated the relationship between these factors by collecting data using a 2 × 3 experimental design that divided a sample of Year 10 students (n = 42) into two groups. The intervention group (n = 24) used mobile devices utilising AR technology with instructional 3D molecular geometry content featuring design principles based on CLT to encourage hand movements to rotate three-dimensional molecular structures. The non-AR-based control group (n = 18) was taught using traditional methods. Analysis of the data revealed participants using AR technology that featured CLT design principles experienced less cognitive load and improved achievement in post-testing compared to those taught using traditional methods, suggesting under certain conditions, the use of hand movement applied to AR design material improves learning.

Study of the magnetic and structural properties of BaFe12 – xCuxO19 ferrites obtained by hydrothermal synthesis

Hexagonal ferrites of M-type (in particular, BaFe12O19) are magnetic materials with functional characteristics affected both by chemical composition and technology of their synthesis. We present the results of studying the magnetic and structural properties of BaFe12 – xCuxO19 hexaferrites (x = 0, 0.1, 0.2, 0.3, 0.4) obtained by hydrothermal synthesis with partial substitution of copper for iron. The composition of the synthesized samples was analyzed using X-ray diffraction, and the magnetic characteristics were measured using a vibration magnetometer. It has been revealed that the coercivity of the ferrite powders depends non-monotonically on the copper concentration and reaches the maximum (5629 Oe) and minimum (4698 Oe) values at x = 0 and x = 0.2. The presence of copper reduces the coercive force, but at the same time the values remain rather high compared to the results of similar studies. The saturation magnetization of the obtained ferrites gradually decreases (from 65.88 to 60.75 A · m2/kg at x = 0 and x = 0.4, respectively) with increasing. The distribution of Cu over ferrite sublattices was studied using Mössbauer spectroscopy. It is shown that in the hexaferrite structure, copper ions preferentially occupy 12k and 4f1 sites. Hence, a decrease in the saturation magnetization with increasing x is most likely attributed to the presence of side non-magnetic phases observed on X-ray diffraction patterns. It is also revealed that during synthesis, copper participates in the formation of low-melting phases on the surface of hexaferrite grains which promotes agglomeration of the particles. Thus, the resulting powders can potentially be sintered at lower temperatures and, therefore, without a significant increase in the size of crystallites. Herewith, the coercivity retains its original high values. The results obtained can be used in developing ferrite permanent magnets with improved characteristics.

Impact of yeast extract and basal salts medium on 1,4-dioxane biodegradation rates and the microorganisms involved in carbon uptake from 1,4-dioxane

Conventional physical and chemical treatment technologies for 1,4-dioxane can be ineffective and consequently attention has focused on bioremediation. Towards this, the current research investigated the impact of basal salts medium (BSM) and yeast extract on 1,4-dioxane biodegradation rates in microcosms with different soil or sediment (agricultural soil, wetland sediment, sediment from an impacted site). Phylotypes responsible for carbon uptake from 1,4-dioxane were determined using stable isotope probing (SIP), both with and without BSM and yeast extract. Further, putative functional genes were investigated using 1) soluble di-iron monooxygenase (SDIMO) based amplicon sequencing, 2) qPCR targeting propane monooxygenase (large subunit, prmA) and 3) a predictive approach (PICRUSt2). The addition of BSM and yeast extract significantly enhanced 1,4-dioxane removal rates the agricultural soil and impacted site sediment microcosms. The phylotypes associated with carbon uptake varied across treatments and inocula. Gemmatimonas was important in the heavy SIP fractions of the wetland sediment microcosms. Unclassified Solirubacteraceae, Solirubrobacter, Pseudonocardia and RB4 were dominant in the heavy SIP fractions of the agricultural soil microcosms. The heavy SIP fractions of the impacted site microcosms were dominated by only two phylotypes, unclassified Burkholderiaceae and oc3299. SDIMO based amplicon sequencing detected three genes previously associated with 1,4-dioxane. The predicted functional gene analysis suggested the importance of propane monooxygenases associated with Solirubrobacter and Pseudonocardia. Overall, more microorganisms were involved in carbon uptake from 1,4-dioxane in both the wetland and agricultural soil microcosms compared to the impacted site sediment microcosms. Many of these microorganisms have not previously been associated with 1,4-dioxane removal.

Evaluation of heat transfer for unsteady thin film flow of mono and hybrid nanomaterials with five different shape features

Recent advancement in nanotechnology brings the idea of hybrid nanomaterials which offer distinguish applications in thermal reservoirs, cooling systems, energy applications, chemical engineering, vehicle engines etc. The understating of shape features for hybrid nanomaterials is quite essential as such consequences highly influenced various thermal properties like viscosity, thermal conductivity, optical properties, stability etc. The objective of current work is to examine heat transfer analysis due to thin film unsteady flow of hybrid nanofluid. The properties of hybrid nanofluid are justified for entertaining the copper (Cu), aluminium oxide (Al2O3) nanoparticles with water (H2O) base fluid. Additionally, applications of viscous dissipation, heat source and nonlinear radiated effects are attributed to current flow problem. The thermal properties of nanoparticles are examined in presence of five shape features consisting of blades, platelets, cylinders, bricks and spheres. Numerical simulations of problem are performed via Runge-Kutta-Fehlberg method. Comparative heat transfer is performed for mono nanofluid (Cu/H2O) and hybrid nanofluid (Cu−Al2O3)//H2O. It has been observed that heat transfer enhancement is more stable for cylindrical particles as compared to spherical nanoparticles. The skin friction enhances due to Hartmann number for both mono nanofluid (MNF) and hybrid nanofluid (HNF). Current results claim applications in coating thin films, lubrication systems, improving the thermal efficiency in thermal and industrial systems, heat exchangers, cooling systems etc.

Convective diffusive thermal flow over an inclined surface with viscous dissipation and aligned magnetic field applications

This investigation incorporating the fluctuation in heat and mass transfer associated to the mixed convection magnetized flow of viscous fluid due to inclined surface with porous media. The contribution of Soret effects and viscous dissipation appliances is addressed. Furthermore, the heat transfer improvement is also assessed by thermal radiation, heat source and joule heating effects. The chemical reaction enrollment is also studied for concentration phenomenon. The convection of problem into non-dimensional framework is based on implication of new variables. The perturbation technique is followed to tracking the analytical outcomes. Physical visualization and interpretation of results under the influence of perturbed parameters have been studied. It is observed that heat and mass transfer enhances due to Soret number. Presence of chemical reaction leads to decrement of concentration profile. Claimed results presents applications in heat and mass transfer processes, chemical reaction, manufacturing systems, chemical engineering, extrusion processes etc.

Continuous process design of the microwave chemical recycling of waste plastics using microwave-absorbing heating elements

Conventional pyrolysis methods to chemically recycle plastic waste require significant energy input owing to inefficient energy transfer from the heat sources to plastics and the generation of excess CO2. Accordingly, there is an urgent need to develop alternative methods for the chemical recycling of waste plastics to limit global warming. In this study, the use of microwaves (MWs) as an efficient energy source for pyrolysis and chemical recycling. However, because plastic is transparent to MW energy, a method that utilizes carbon materials as MW-absorbing heating elements (MWAHEs) was developed. This method directly converted high-density polyethylene (HDPE) into light chemicals in up to 94% yield with 45% ethylene selectivity. A two-stage pyrolysis system incorporating MWAHE-assisted MW pyrolysis was also developed to produce light chemicals in 95% yield with 49% ethylene selectivity. From a chemical engineering perspective, this two-step pyrolysis system is an efficient and feasible method for producing valuable light olefins. This study also demonstrates that MWAHE assisted MW pyrolysis is effective for the chemical recycling of plastic waste. This study offers potential solutions for the environmental problems posed by plastic waste by developing efficient and scalable methods for its chemical recycling.

Estimation of isoniazid by digital image colorimetry: an integration of green chemistry and smartphone technology

BackgroundThis study proposes a simple digital image colorimetric method using a smartphone for the quantitative analysis of isoniazid in pharmaceutical medications. The analytical methodology employed in this study involved the utilization of the reaction between isoniazid and FC reagent under alkaline conditions. The chemical reaction led to the creation of a complex with a blue-gray color, exhibiting a peak absorption at a wavelength of 760 nm. An Android application was employed to perform a smartphone-based determination based on separating the captured color into different color channels such as red, blue, green, etc. The experimental procedure involved the utilization of three smartphones for the determination, which was subsequently followed by a comparative analysis of the results obtained from these devices using spectrophotometric measurements.ResultsThe B channel had the highest level of optimization in terms of analytical parameters. The limits of detection (LOD) were 0.586, 2.478, and 1.396 µg/ml for S1, S2, and S3, respectively, and for the spectrophotometer, it was found to be 0.416 µg/ml. Similarly, LOQs were determined as 1.673, 7.511, 4.232, and 1.302 µg/ml. A %RSD of 1.3 for precision and an LOD of 0.013 g dm−3 were obtained for the spectroscopic method. The % recovery in the accuracy study was found to be 99.69, 101.804, 109.28, and 100.13 for S1, S2, S3, and spectrophotometer, respectively.ConclusionThe colorimetric results from smartphone application are similar to those from spectrophotometric analyses.

Self-growth of dense Ag nanoislands on Ag-59.3at%V alloy films as sensitive SERS substrates

High-performance and high-stability surface enhanced Raman scattering (SERS) substrates are urgently needed in the detection field, chemical engineering, etc. Ag nanoislands/Ag-V alloy films on polyimide (PI) have been designed and fabricated as high-sensitivity SERS substrates. The dependence of surface morphology, roughness, water contact angle, and contents of islands and films on SERS performance are systematically discussed. In addition, covering the surface of the annealed alloy films with a 12 nm Ag layer could improve the SERS performance of the alloy films by coupling enhancement of the electric field. The Ag layer/Ag nanoisland/Ag-V alloy films SERS substrates are capable of detecting rhodamine 6 G (R6G) solution at a consistency of 5 × 10−13 mol/L. The low-cost, mass-producible Ag nanoisland/film prepared in this paper can be used as stable and sensitive SERS substrates.

An Opportunity for Synergizing Desalination by Membrane Distillation Assisted Reverse-Electrodialysis for Water/Energy Recovery.

Industry, agriculture, and a growing population all have a major impact on the scarcity of clean-water. Desalinating or purifying contaminated water for human use is crucial. The combination of thermal membrane systems can outperform conventional desalination with the help of synergistic management of the water-energy nexus. High energy requirement for desalination is a key challenge for desalination cost and its commercial feasibility. The solution to these problems requires the intermarriage of multidisciplinary approaches such as electrochemistry, chemical, environmental, polymer, and materials science and engineering. The most feasible method for producing high-quality freshwater with a reduced carbon footprint is demanding incorporation of industrial low-grade heat with membrane distillation (MD). More precisely, by using a reverse electrodialysis (RED) setup that is integrated with MD, salinity gradient energy (SGE) may be extracted from highly salinized MD retentate. Integrating MD-RED can significantly increase energy productivity without raising costs. This review provides a comprehensive summary of the prospects, unresolved issues, and developments in this cutting-edge field. In addition, we summarize the distinct physicochemical characteristics of the membranes employed in MD and RED, together with the approaches for integrating them to facilitate effective water recovery and energy conversion from salt gradients and freshwater.

Electronics and Optoelectronics Based on Tellurium.

As a true 1Dsystem, group-VIA tellurium (Te) is composed of van der Waals bonded molecular chains within a triangular crystal lattice. This unique crystal structure endows Te with many intriguing properties, including electronic, optoelectronic, thermoelectric, piezoelectric, chirality, and topological properties. In addition, the bandgap of Te exhibits thickness dependence, ranging from 0.31eV in bulk to 1.04eV in the monolayer limit. These diverse properties make Te suitable for a wide range of applications, addressing both established and emerging challenges. This review begins with an elaboration of the crystal structures and fundamental properties of Te, followed by a detailed discussion of its various synthesis methods, which primarily include solution phase, and chemical and physical vapor deposition technologies. These methods form the foundation for designing Te-centered devices. Then the device applications enabled by Te nanostructures are introduced, with an emphasis on electronics, optoelectronics, sensors, and large-scale circuits. Additionally, performance optimization strategies are discussed for Te-based field-effect transistors. Finally, insights into future research directions and the challenges that lie ahead in this field are shared.

Inside Cover Picture

The picture in the background is the old chemistry building of Soochow University, the symbols of S are: 1. for the research field of Prof. Wang Shunyi's group at Soochow University: Organic Sulfur Chemistry; 2. for Soochow University; 3. for Suzhou; 4. for Singapore. We would like to take this opportunity to celebrate the 110th anniversary of the founding of Chemistry and Chemical Engineering in Soochow University, as well as the 30th anniversary of the Suzhou‐Singapore Industrial Park. The cover image portrays the reductive coupling reaction of xanthate esters with sulfur‐containing and selenium‐containing compounds (thio(seleno)sulfonates and disulfides(selenides)) under the nickel‐catalyzed condition. It provides a mild and effective method for the synthesis of unsymmetric sulfides and selenides. More details are discussed in the article by Wang et al. on pages 2453—2458.image

Mapping Full Conformational Transition Dynamics of Intrinsically Disordered Proteins Using a Single-Molecule Nanocircuit.

Intrinsically disordered proteins (IDPs) are emerging therapeutic targets for human diseases. However, probing their transient conformations remains challenging because of conformational heterogeneity. To address this problem, we developed a biosensor using a point-functionalized silicon nanowire (SiNW) that allows for real-time sampling of single-molecule dynamics. A single IDP, N-terminal transactivation domain of tumor suppressor protein p53 (p53TAD1), was covalently conjugated to the SiNW through chemical engineering, and its conformational transition dynamics was characterized as current fluctuations. Furthermore, when a globular protein ligand in solution bound to the targeted p53TAD1, protein-protein interactions could be unambiguously distinguished from large-amplitude current signals. These proof-of-concept experiments enable semiquantitative, realistic characterization of the structural properties of IDPs and constitute the basis for developing a valuable tool for protein profiling and drug discovery in the future.

Enhancing durability of superhydrophobic surfaces via nanoparticle-induced bipolar interface effects and micro-nano composite structures: A femtosecond laser and chemical modification approach

Superhydrophobic coatings are vital in energy, aerospace, and chemical engineering, while their complex preparation and limited durability hinder widespread application. Therefore, inspired by the unique structures of hydrophobic cotton surfaces and mosquito eyes in nature, a durable aluminum alloy superhydrophobic surface is developed using a combination of femtosecond laser and chemical modification methods. Initially, porous microneedle micro-nanostructures are ablated on the surface of the aluminum alloy via femtosecond laser technology. Then, epoxy resin modified with γ-aminopropyl triethoxysilane (KH550) forms a covalently bonded intermediate layer. Finally, biphasic silicon dioxide (BP-SiO2) nanoparticles modified by hexadecyltrimethoxysilane (HDTMS) are used to construct the top hydrophobic layer. The covalent interface interactions between the aluminum alloy substrate and the intermediate layer, as well as between the intermediate layer and the top layer, significantly enhance the durability of the superhydrophobic surface. The prepared F-M@KH-EP/BP-SiO2 coating exhibits outstanding superhydrophobic properties, with a water contact angle (CA) as high as 168.56° and a sliding angle (SA) as low as 1.52° More encouragingly, the composite coating maintains its excellent water resistance even when subjected to harsh mechanical durability damage, including sandpaper wear, tape stripping tests, water drop and sand impact tests. Moreover, the prepared coatings maintain distinguished non-wettability in harsh operating conditions such as corrosive liquid environments, ultraviolet radiation, ultrasonic vibration, etc. Additionally, the coating demonstrates remarkable self-cleaning properties. Superhydrophobic surface durability is significantly enhanced by combining nanoparticle-induced bipolar interface effect and micro-nano structures. These findings provide theoretical reference for the design and application of durable superhydrophobic coatings.

Optimization of a novel hydrogen production process integrating biomass and sorption-enhanced reforming for reduced CO2 emissions

Recently, there has been a growing demand for clean and sustainable energy sources to bridge the energy gap. Hydrogen has emerged as an attractive and environmentally friendly energy carrier due to its potential for high energy efficiency and minimal pollution generation, making it a promising alternative to fossil fuels. This study proposes and investigates a novel coupled process that utilizes chemical looping technologies for hydrogen production, simultaneously utilizing natural gas and biomass as feedstocks. The primary objective of this research is to develop a process model that maximizes hydrogen production while minimizing carbon dioxide emissions. Aspen Plus version 10 was employed to simulate and analyze the proposed process configuration to achieve this. One of the proposed process's key advantages is its competitiveness compared to conventional steam methane reforming (SMR) processes, which are widely used in industry. The novel process offers significant benefits, such as enhanced hydrogen purity and reduced CO2 content in the product gas. The simulation results obtained from Aspen Plus reveal the successful production of highly pure hydrogen with a molar ratio of H2/CO equal to 268 and syngas with a molar ratio of H2/CO approximately equal to 1. Additionally, the process demonstrates the capability to produce highly high-purity hydrogen with a molar ratio of H2/CO equal to 155,000 in three-section reactors.

Construction of homologous branched oligomer megamolecules based on linker-directed protein assembly.

Utilizing the building blocks of recombinant proteins and synthetic linkers, we have obtained two distinct octameric megamolecules with diverse branched structures. This approach combines principles from both click chemistry and protein engineering technology, enabling the integration of functional domains within highly ordered protein assemblies for biomedical applications.

The effect of Al and Zr content on corrosion of AlNiCoCuZr high-entropy alloys in a 5 wt% NaCl solution

High-entropy alloys are attractive structural materials for the design of apparatus for various chemical technologies due to their relative ease of production, corrosion resistance and high values of mechanical properties (hardness, strength). In the present work, the influence of aluminum and zirconium content on the corrosion resistance of Al(20−35)-Ni(5−15)-Co(15−30)-Cu(20−35)-Zr(5−40) high-entropy alloys was studied experimentally for the first time. Corrosion tests were performed in a 5 wt% NaCl aqueous solution during 1500 h at 298 K. It is established that the electronegative metals included in the alloy - Al and Zr are passivation components and with increasing their content in AlNiCoCuZr composition the corrosion rate in the studied conditions is decreased. It is shown that degradation of alloys occurs mainly as a result of nickel and cobalt hydroxide formation, the solubility of which is several orders of magnitude higher than that of aluminum hydroxide and zirconium hydroxide.

Extra trees regression assisted 1D monolith reactor simulations based on microkinetic analysis and rate transformation

The incorporation of microkinetic method for surface reaction calculation is a key development direction in monolith reactor simulations, albeit posing significant computational stability and efficiency challenges. A data-driven multi-scale simulation framework is proposed to bridge the gap between macroscopic numerical model and microscopic reaction solvers. After the generating of precomputed microkinetic dataset, we utilize a tailor-designed preprocessing transformation, AD_log10, to effectively manage the common challenges of large variances and reversed directions in microkinetic rate data. A suite of machine learning regression models is developed as reaction rate solver integrated into the 1D two-phase monolith model. We employ NH3 selective catalytic oxidation on Cu(100) and Cu(111) as probe systems to validate our framework’s efficacy. In the context of on-board simulations under operating conditions, the Extra Trees Regression (with best regression performance) based model exhibits commendable accuracy and efficiency, successfully addressing complex processes previously unmanageable with interpolation-based models. This innovative approach paves the way for advanced monolith reactor modeling and sheds light on multi-scale simulation methodologies in chemical reaction engineering.