Complex Reaction Research Articles

Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li-CO2 Batteries.

Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li-CO2 batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO2 activation. In this study, the local spin states are regulated by incorporating Ni into Co3O4 and its impact on activity in Li-CO2 batteries is explored. The results show that Ni atoms with high spin states in Ni0.1Co2.9O4 facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni0.1Co2.9O4 shows superior catalytic performance with an overpotential of 0.72V and an energy efficiency of ≈70% after 500h. This work provides insights into the relationship between spin states and CO2 reactions, highlighting a promising avenue for developing high-performance metal-CO2 batteries.

Highly Active and Stable Cu-Cd Bimetallic Oxides for Enhanced Electrochemical CO2 Reduction.

Electrochemical reduction of carbon dioxide (CO2) can produce value-added chemicals such as carbon monoxide (CO) and multicarbon(C2+). However, the complex reaction pathways of CO2electro-reduction reaction (CO2RR) greatly limit the product selectivity and conversion efficiency. Herein, the Cu-Cd bimetallic oxides catalyst was designed and applied for the CO2RR. The optimized 4.73%Cd-CuO exhibits remarkable electrocatalytic CO2RR activity for selective CO production in H-cell using 0.5 M 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6)/MeCN as electrolyte. The Faradaic efficiency of CO (FE(CO)) can be maintained above 90% over a wide potential range of -2.0 to -2.4 V vs. Ag/Ag+. Particularly, the catalyst achieves an impressive FE(CO) of 96.3% with a current density of 60.7 mA cm-2at -2.2 V vs. Ag/Ag+. Furthermore, scaling up the 4.73%Cd-CuO catalyst into a flow cell can reach 56.64% FE of C2+products (ethylene, ethanol and n-propanol) with a current density as high as 600 mA cm-2steadily.The excellent CO2RR performance of the as-synthesized 4.73%Cd-CuOcan be mainly attributed to the introduction of CdO to improve the ability of CuO to activate CO2, the electronic interactions between Cu and Cd can boostactivation and conversionkey intermediates of CO2RR and ensure the continuous stability of4.73%Cd-CuOin electrolysis process.

Thought Experiments in Design Ethics

How is the designer to approach questions of responsibility, obligation, or right and wrong in relation to their role in creating, sustaining and altering the complex worlds which we inhabit together? Every design decision stands as the first teetering domino at the head of an infinitely complex fractal chain reaction of consequences, the full repercussions of which are ultimately unforeseeable. The moment of ethical crisis – being faced with a range of possible options and lacking a fully adequate knowledge of which path is best to choose – is an unavoidable component of the design process. Ethical theories, principles, codes and rules always lag one step behind the frontier of the new, the territory in which design operates. Recognising that ethical crisis is an integral reality of the design process, how can designers be best supported and equipped for this challenge? This paper explores one path towards this aim, presenting the case for the use of philosophical thought experiments as appropriate and useful devices for developing capacities for ethical thinking and for nurturing a transformed ethical mindset within practising designers. Thought experiments do not directly guide or provide knowledge or answers as to the ‘right’ thing to do in any given situation. Rather, the argument is presented here that thought experiments can stimulate productive conditions in which designers can learn not to ‘know ethics’ but to ‘think ethics’. By playing these mind games, the designer can exercise and strengthen their mental capacities for responding to ethical encounters within the complexity of real-world design practice.

Safety of Crovalimab Versus Eculizumab in Patients With Paroxysmal Nocturnal Haemoglobinuria (PNH): Pooled Results From the Phase 3 COMMODORE Studies.

To evaluate the tolerability of crovalimab versus eculizumab in C5 inhibitor (C5i)-naive and -experienced patients with PNH from COMMODORE 2, 3 and 1 (NCT04434092, NCT04654468 and NCT04432584). Pooled safety data were assessed in the total crovalimab and eculizumab populations and by C5i-naive versus C5i-switched status in patients receiving crovalimab. Analyses include 6.5 months of additional follow-up from the COMMODORE 2 and 1 primary analyses. COMMODORE safety data (crovalimab, 393 patients [naive, 192 patients; switched, 201 patients]; eculizumab, 111 patients) were analysed. The total patient years (PY) were 503.9 and 51.1 in the total crovalimab and eculizumab populations, respectively, with 471 and 581 adverse events (AEs) per 100 PY. Serious infection rates were 8.9 and 13.7 AEs per 100 PY, respectively; no meningococcal infections were reported. Fatal AEs occurred in eight (2%) patients receiving crovalimab (naive, six patients; switched, two patients) and one (1%) receiving eculizumab, all treatment unrelated. In C5i-switched patients, 39 (19%) had transient immune complex reactions (risk when switching between C5i and crovalimab); the majority were Grades 1-2 arthralgia and rash, and 16 (8%) had Grade 3 events. Crovalimab's safety profile was consistent with eculizumab's and was generally comparable between C5i-naive and C5i-switched patients.

Aromatics Alkylated with Olefins Utilizing Zeolites as Heterogeneous Catalysts: A Review

The alkylation reaction of aromatic compounds gains considerable attention because of its wide application in bulk and fine chemical production. Aromatics alkylated with olefins is a well-known process, particularly for linear alkylbenzene, phenyloctanes, and heptyltoluene production. As octane boosters and precursors for various petrochemical and bulk chemical products, a wide range of alkylated compounds are in high demand. Numerous unique structures have been proposed in addition to the usual zeolites (Y and beta) utilized in alkylation procedures. The inevitable deactivation of industrial catalysts over time on stream, which is followed by a decrease in catalytic activity and product selectivity, is one of their disadvantages. Therefore, careful consideration of catalyst deactivation regarding the setup and functioning of the process of catalysis is necessary. Although a lot of work has been carried out to date to prevent coke and increase catalyst lifespan, deactivation of the catalyst is still unavoidable. Coke deposition can lead to catalyst deactivation in industrial catalytic processes by obstructing pores and/or covering acid sites. It is very desirable to regenerate inactive catalysts in order to remove the coke and restore catalytic activity at the same time. Depending on the kind of catalyst, the deactivation processes, and the regeneration settings, each regeneration approach has pros and cons. In this comprehensive study, the focus was on discussing the reaction mechanism of 1-octene isomerization and toluene alkylation as an example of isomerization and alkylation reactions that occur simultaneously, shedding light in detail on the catalysts used for this type of complex reaction, taking into account the challenges facing the catalyst deactivation and reactivation procedures.

In situ Monitoring of Photocatalysis on Polymeric Carbon Nitride Thin Films.

Polymeric carbon nitride has attracted significant interest in heterogeneous photocatalysis due to its activity under visible-light irradiation. Herein, we report on using carbon nitride-coated NMR tubes for in situ studies of photocatalytic reaction mechanisms. In a first step, we exploited carbon nitride-coated crimp vials as batch photoreactors for visible photocatalytic fluorinations of unactivated C(sp3)-H bonds, with moderate to excellent yields and reusability over multiple cycles. Eventually, carbon nitride-coated NMR tubes were used as a photoreactor by coupling them with optical fiber irradiation directly inside the spectrometer. This enabled us to follow the reaction with in situ NMR spectroscopy identifying reactive intermediates otherwise elusive in conventional analyses. The method provides advantages for the study of photocatalytic mechanisms of complex reactions and substantially reduces the need of comparative tests for depicting reaction intermediates and conversion pathways.

Development of Software for Hydrometallurgical Calculation of Metal Extraction

Hydrometallurgy plays a critical role in the metallurgical industry by providing an efficient method for extracting metals from ores and secondary materials using aqueous solutions. This approach is particularly advantageous for processing low-grade and complex ores, as well as secondary resources that cannot be effectively processed by traditional pyrometallurgical methods. The objective of this study is to develop specialized software to automate and optimize the calculations necessary for metal extraction in hydrometallurgical processes. The software integrates a complete computational framework for automating the various stages of the hydrometallurgical process, including ore composition initialization, total element mass calculations, and the determination of metal concentrations in both metal products (matte) and by-products (slag). The methodology involves the design and implementation of a web-based application using Django for the user interface and MySQL for robust data storage. The computational module, written in Python, automates the mathematical operations required to simulate complex chemical reactions and metal extraction processes. This module supports real-time processing and ensures accurate calculations for each stage of metal extraction, including leaching, extraction, re-extraction, sorption, and electrolysis. The software also features detailed tables and dynamic graphs that allow users to analyze the distribution of valuable metals and assess the influence of key operational parameters on extraction efficiency. The results show that the developed software successfully manages large datasets, enhances the precision of hydrometallurgical calculations, and minimizes the risk of human error. The implementation of the software leads to significant improvements in the economic efficiency of production by optimizing metal recovery rates and reducing operational costs. Additionally, it supports comprehensive process control by providing actionable insights into each stage of extraction, thus improving the quality of the final metal product. Overall, the software represents a significant technological advancement in the field, offering a scalable solution for industries aiming to streamline hydrometallurgical processes.

Major-auxiliary cooperative metal pairs in MOFs enable cascade oxidation of KA oil to ε-caprolactone

Direct oxidation of KA oil (the mixture of cyclohexanone and cyclohexanol) toward ε-caprolactone is in high demand yet hard to implement in need of juggling the activation of both methyne C-H bond of cyclohexanol and α-C-C bond of cyclohexanone. Here we demonstrate that in situ formed Cu1+δ-Oδ-• active site, which originates from relay reaction at Ni(II) and Cu(I) pairs in a metal-organic framework (known as NiCu-MOF-74) with O2 and benzaldehyde (PhCHO), efficiently oxidizes KA oil toward ɛ-caprolactone along with good stability. Mechanism investigation discloses that the auxiliary Ni(II) site first adsorbs O2 for abstracting formyl hydrogen in PhCHO followed by transfer of PhCO· to react with another O2 over the major Cu(I) site, leading to formation of Cu1+δ-Oδ-• and PhCOOH. This major-auxiliary cooperative strategy will be particularly suitable for multivariate MOFs as next generation catalysts towards complex reactions.

Catalytic Cracking of Liquefied Petroleum Gas (LPG) to Light Olefins Using Zeolite-based Materials: Recent Advances, Trends, Challenges and Future Perspectives.

The catalytic cracking of liquefied petroleum gas (LPG) has attracted significant attention due to its importance in producing valuable feedstocks for the petrochemical industry. This review provides an overview of recent developments in zeolite-based catalyst technology for converting LPG into light olefins. Catalytic cracking utilizes zeolite-based catalysts usually associated with stability challenges, such as coking and sintering. The discussion focused on the underlying mechanisms that govern the catalytic cracking process and provided insights into the complex reaction pathways involved. A comprehensive analysis of various strategies employed for improving the effectiveness of zeolite catalysts has been discussed in this review. These strategies encompass using transition metals to modify catalyst properties, treatments involving phosphorous modification, alkaline earth metals, and alkali metals to alter the acidity level of the zeolites. The elucidation of the impact of silica-to-alumina ratios in zeolites and the development of hierarchical zeolite-based catalysts through top-down and bottom-up methodologies are also discussed.

Application of graph neural network in computational heterogeneous catalysis.

Heterogeneous catalysis, as a key technology in modern chemical industries, plays a vital role in social progress and economic development. However, its complex reaction process poses challenges to theoretical research. Graph neural networks (GNNs) are gradually becoming a key tool in this field as they can intrinsically learn atomic representation and consider connection relationship, making them naturally applicable to atomic and molecular systems. This article introduces the basic principles, current network architectures, and datasets of GNNs and reviews the application of GNN in heterogeneous catalysis from accelerating the materials screening and exploring the potential energy surface. In the end, we summarize the main challenges and potential application prospects of GNNs in future research endeavors.

Visualizing the Structure and Dynamics of Transition Metal-Based Electrocatalysts Using Synchrotron X-Ray Absorption Spectroscopy.

As the global energy structure evolves and clean energy technologies advance, electrocatalysis has become a focal point as a critical conversion pathway in the new energy sector. Transitional metal electrocatalysts (TMEs) with their distinctive electronic structures and redox properties show great potential in electrocatalytic reactions. However, complex reaction mechanisms and kinetic limitations hinder the improvement of energy conversion efficiency, highlighting the necessity for comprehensive studies on structure and performance of electrocatalysts. X-ray Absorption Fine Structure (XAFS) spectra stand out as a robust tool for examining the electrocatalyst's structures and performance due to its atomic selectivity and sensitivity to local environments. This review delves into the application of XAFS technology in characterizing TMEs, providing in-depth analyses of X-ray Absorption Near-Edge Structure (XANES) spectra, and Extended XAFS (EXAFS) spectra in both R-space and k-space. These analyses reveal intrinsic structural information, electronic interactions, catalyst stability, and aggregation morphology. Furthermore, the paper examines advancements in in-situ XAFS techniques for real-time monitoring of active site changes, capturing critical intermediate and transitional states, and elucidating the evolution of active species during electrocatalytic reactions. These insights deepen our understanding on structure-activity relationship of electrocatalysts and offer valuable guidance for designing and developing highly active and stable electrocatalysts.

Influence of (ultra-)processing methods on aquatic proteins and product quality.

Aquatic products are a high-quality source of protein for humans, and the changes in protein during aquatic product processing are crucial for nutritional value, product performance, and consumer health. With the advancement of science and technology, aquatic product processing methods have become increasingly diverse. In addition to traditional methods such as thermal processing (steaming, roasting, and frying) and pickling, emerging non-thermal processing technologies, such as high pressure, ultrasound, and irradiation, are also being applied. During (ultra-)processing, aquatic products undergo complex biochemical reactions, among which protein oxidation significantly affects the quality of aquatic products. Protein oxidation can alter the molecular structure of proteins, thereby changing their functional properties and ultimately impacting product quality. This paper primarily explored the effects of protein changes under different processing methods on aquatic product quality and human health, as well as techniques for controlling protein oxidation. It aims to provide a theoretical basis for selecting appropriate processing methods, improving aquatic product quality, and controlling protein oxidation in aquatic products, and to offer scientific guidance for practical production.

Synthesis of a Pd2L4 Hydrazone Molecular Cage Through Multiple Reaction Pathways

Molecular cages are preorganized molecules with a central cavity, typically formed through the reaction of their building blocks through chemical bonds. This requires, in most cases, forming and breaking reversible bonds during the cage formation reaction pathway for error correction to drive the reaction to the cage product. In this work, we focus on both Pd–ligand and hydrazone bonds implemented in the structure of a Pd2L4 hydrazone molecular cage. As the cage contains two different types of reversible bonds, we envisaged a cage formation comparative study by performing the synthesis of the cage through three different reaction pathways involving the formation of Pd–ligand bonds, hydrazone bonds, or a combination of both. The three reaction pathways produce the cage with yields ranging from 73% to 79%. Despite the complexity of the reaction, the cage is formed in a high yield, even for the reaction pathway that involves the formation of 16 bonds. This research paves the way for more sophisticated cage designs through complex reaction pathways.

Modulating N−H Bond Cleavage in Catalytic Ammonia Oxidation Reaction

AbstractThe ammonia oxidation reaction (AOR) exhibits significant potential for environmental remediation and energy utilization. Nevertheless, the complex reaction mechanism of the AOR poses numerous challenges to its application. To overcome these challenges and realize an efficient AOR process, a thorough understanding of every elementary reaction step, especially the cleavage of N−H bonds, is crucial. This review delves into the influence of N−H bond cleavage on the rate and selectivity of AOR, and summarizes the latest advancements in promoting this crucial step. Furthermore, we discuss the challenges faced by N−H bond cleavage and provide insights into the design of efficient catalytic AOR systems.

Electric Field-Induced Sequential Prototropic Tautomerism in Enzyme-like Nanopocket Created by Single Molecular Break Junction.

Mastering the control of external stimuli-induced chemical transformations with detailed insights into the mechanistic pathway is the key for developing efficient synthetic strategies and designing functional molecular systems. Enzymes, the most potent biological catalysts, efficiently utilize their built-in electric field to catalyze and control complex chemical reactions within the active site. Herein, we have demonstrated the interfacial electric field-induced prototropic tautomerization reaction in acylhydrazone entities by creating an enzymatic-like nanopocket within the atomically sharp gold electrodes using a mechanically controlled break junction (MCBJ) technique. In addition to that, the molecular system used here contains two coupled acylhydrazone reaction centers, hence demonstrating a cooperative stepwise electric field-induced reaction realized at the single molecular level. Furthermore, the mechanistic studies revealed a proton relay-assisted tautomerization showing the importance of external factors such as solvent in such electric field-driven reactions. Finally, single-molecule charge transport and energetics calculations of different molecular species at various applied electric fields using a polarizable continuum solvent model confirm and support our experimental findings. Thus, this study demonstrates that mimicking an enzymatic pocket using a single molecular junction's interfacial electric field as a trigger for chemical reactions can open new avenues to the field of synthetic chemistry.

Whole UVCB Tests Can Yield Biotic and Abiotic Degradation Kinetics of Known and Unknown Constituents for an Enhanced UVCB Degradation Profile

The green transition and move towards safe and sustainable-by-design chemicals entail the need for new methods to study the biodegradability of UVCBs (substances of Unknown or Variable composition, Complex reaction products and Biological materials). Standard simulation biodegradation tests have been developed for single substances and are generally not applicable for UVCBs. The aims of this study were (1) to combine a whole UVCB biodegradation test with a sensitive constituent specific analytical technique, (2) to measure biotic and abiotic degradation of known and unknown UVCB constituents and (3) to determine the impact of a WWTP discharge on the constituent specific biodegradation in stream water. Lavender oil and black pepper oil are of significance in the perfume and cosmetics industries and served as model UVCBs. Stream water sampled upstream and downstream of a wastewater treatment plant (WWTP) discharge point was used as inoculum (i.e., naturally and wastewater adapted bacterial consortia). Tests were conducted in gastight headspace vials and automated Arrow Solid Phase Microextraction GC-MS-scan was applied on unopened vials. Peak area ratios between biotic test systems and abiotic controls were used to determine primary biodegradation kinetics, and freshly spiked analytical references to separate biotic from abiotic degradation. Biodegradation half-times were below 20 days for all known (8-12) and unknown constituents (>78) in the essential oils. Dual column GC-MS analysis produced a level 2 identification of 16 unknown lavender constituents. Biodegradation kinetics were similar in inoculum taken before and after the WWTP outlet, confirming that native stream microorganisms were competent degraders.

Mixed-mode oscillations and chaos in a complex chemical reaction network involving heterogeneous catalysis.

The nonlinear dynamical behavior in a complex isothermal reaction network involving heterogeneous catalysis is studied. The method first determines the multiple steady states in the reaction network. This is followed by an analysis of bifurcation continuations to identify several kinds of bifurcations, including limit point, Bogdanov-Takens, generalized Hopf, period doubling, and generalized period doubling. Numerical simulations are performed around the period doubling and generalized period doubling bifurcations. Rich nonlinear behaviors are observed, including simple sustained oscillations, mixed-mode oscillations, non-mixed-mode chaotic oscillations, and mixed-mode chaotic oscillations. Concentration-time plots, 2D phase portraits, Poincaré maps, maximum Lyapunov exponents, frequency spectra, and cascade of bifurcations are reported. Period-doubling and period-adding routes leading to chaos are observed. Maximum Lyapunov exponents are positive for all the chaotic cases, but they are also positive for some non-chaotic orbits. This result diminishes the reliability of using maximum Lyapunov exponents as a tool for determining chaos in the network under study.

“Neither Side Really Knows… What an Abortion Is Like”: A Qualitative Analysis of Medical Students’ Experiences With Second-Trimester Procedural Abortions

ObjectivesMedical students value abortion education; however, there has been little study regarding participation in second-trimester procedures, which are less common yet receive significant societal attention. We aimed to explore medical students’ perceptions of participation in second-trimester procedural abortions to optimize this educational experience. Study DesignWe conducted qualitative semi-structured interviews with third- and fourth-year medical students who voluntarily participated in second-trimester dilation and evacuation cases. We coded interviews inductively and performed thematic content analysis until thematic saturation was reached. ParticipantsWe interviewed 25 medical students, including 16 third-year and nine fourth-year students. Most participants were female (64%) and white (58%) and had no prior abortion care experience (80%). ResultsFour major themes emerged: 1) students felt unprepared for second-trimester procedural abortions and were unable to find adequate educational resources for preparation; 2) students experienced complex emotional reactions to the procedures, often finding the experience more challenging than expected; 3) students observed implicit expectations and biases in the learning environment; and 4) students highly valued their involvement in abortion procedures, noting that participation was important for their future practice and allowed acquisition of essential clinical skills. ConclusionsMedical students value the educational opportunity to participate in second-trimester procedural abortions; however, most feel unprepared for the technical and emotional aspects, despite utilizing available educational resources. To maximize educational experience and psychological safety, educators should develop specialized training resources. This could strengthen physician knowledge and comfort with abortion care in the future, ultimately improving patient care.

Exploring interactive effects of environmental and microbial factors on food waste anaerobic digestion performance: Interpretable machine learning models

Biogas yield in anaerobic digestion (AD) involves continuous and complex biological reactions. The traditional linear models failed to quantitatively assess the interactive effects of these factors on AD performance. To further explore the internal relationship between target variables and AD performance, this study developed four machine learning models to predict biogas yield and consider the interaction among various factors. Results indicated that the highest prediction accuracy of AD performance was achieved by adding bacterial genera dataset with environmental factors. Random forest model exhibited the highest accuracy, with the testing coefficient of determination equal to 0.9879. Among two types of input features, the bacterial genera accounted for 89.9 % of the impact on biogas yield, followed by environmental factors. The results revealed Keratinibaculum and Acetomicrobium as critical bacteria. The volatile fatty acid controlled below 2000 mg/L and the improved stirring system in AD process were recommended to achieve maximum biogas yield.

Thiol‐Ene Coupling Reaction for Functionalization of Non‐Activated Alkenes: An Experimental Study on the Chemistry of the Methyl Oleate Amination

AbstractThis work investigates the functionalization of molecules with non‐activated internal double bonds via thiol‐ene coupling (TEC) reaction. A comprehensive study of the reaction between cysteamine hydrochloride (CAHC) and methyl oleate (MO) was carried out. A series of reactions were conducted under different operating conditions in order to assess their effect on conversion and selectivity. Different conditions were considered like the type of atmospheres and solvents, a portionwise addition of CAHC, reagents concentrations, and excess of CAHC. Maximum conversion and selectivity were reached under inert atmosphere, diluted conditions, ethanol as solvent, and the addition of CAHC at the beginning of the reaction with a molar ratio of CAHC/MO of 3/1. This provides an approach for analyzing more complex reaction systems.