Reaction Environment Research Articles

Ab initio investigation of hot electron transfer in CO2 plasmonic photocatalysis in the presence of hydroxyl adsorbate.

Photoreduction of carbon dioxide (CO2) on plasmonic structures is of great interest in photocatalysis to aid selectivity. While species commonly found in reaction environments and associated intermediates can steer the reaction down different pathways by altering the potential energy landscape of the system, they are often not addressed when designing efficient plasmonic catalysts. Here, we perform an atomistic study of the effect of the hydroxyl group (OH) on CO2 activation and hot electron generation and transfer using first-principles calculations. We show that the presence of OH is essential in breaking the linear symmetry of CO2, which leads to a charge redistribution and a decrease in the OCO angle to 134°, thereby activating CO2. Analysis of the partial density of states (pDOS) demonstrates that the OH group mediates the orbital hybridization between Au and CO2 resulting in more accessible states, thus facilitating charge transfer. By employing time-dependent density functional theory (TDDFT), we quantify the fraction of hot electrons directly generated into hybridized molecular states at resonance, demonstrating a broader energy distribution and an 11% increase in charge-transfer in the presence of OH groups. We further show that the spectral overlap between excitation energy and plasmon resonance plays a critical role in efficiently modulating electron transfer processes. These findings contribute to the mechanistic understanding of plasmon-mediated reactions and demonstrate the importance of co-adsorbed species in tailoring the electron transfer processes, opening new avenues for enhancing selectivity.

Tailoring Microenvironments and In Situ Transformations of Cu Catalysts for Selective and Stable Electrosynthesis of Multicarbon Products

AbstractElectrochemical CO2 reduction is of tremendous interest for storing chemical energy from renewable sources while reducing CO2 emissions. While copper is one of the most effective catalysts, it suffers from low selectivity and limited long‐term durability. Here, these limitations are overcome by engineering Nafion coatings on CuO nanoparticle‐based catalysts supported on glassy carbon. By tuning the Nafion thickness and internal structure, it is shown that both the selectivity to multicarbon (C2+) products and long‐term stability can be dramatically enhanced. Optimized catalyst layers reach Faradaic efficiencies for C2+ products of 86% during long‐term testing for 200 h, with no evidence for performance degradation. Indeed, the C2+ Faradaic efficiency increases during testing, which is attributed to favorable in situ electrochemical fragmentation of catalytic nanoparticles. Finally, the optimized Nafion/Cu catalytic coatings are utilized to create scalable membrane electrode assemblies for CO2 electrolysis, yielding significantly enhanced C2H4 selectivity (≈58%) and activity at technologically‐relevant currents of 1–2 A. These results highlight the potential for creating multi‐functional Nafion coatings on CO2 reduction catalysts to favorably tune the reaction environment, while also promoting in situ transformations to active and selective nanoscale structures and morphologies, not just on model surfaces but also in state‐of‐the‐art gas diffusion electrodes.

Deciphering the Role of Nickel in Electrochemical Organic Oxidation Reactions

AbstractOrganic oxidation reactions (OORs) powered by renewable energy sources are gaining importance as a favorable alternative to oxygen evolution reaction, with the promise of reducing the cell potential and enhancing the overall viability of the water electrolysis. This comprehensive review delves into the electrochemical oxidation of diverse organic compounds, including alcohols, aldehydes, amines, and urea, as well as biomass‐derived renewable feedstocks such as hydroxymethylfurfural and glycerol. The key focus centers on the role of nickel (Ni)‐based catalysts for these OORs. The unique redox activity and chemical nature of Ni have been proven instrumental for the sustainable and cost‐effective oxidation of various organic molecules more efficiently and selectively. This review article discusses how strategic choices, such as the selection of foreign metals, intercalating species, vacancies, defects, and a secondary element (e.g. chalcogens and non‐metals), contribute to tuning the electrochemical performances of a Ni‐based (pre)catalyst for OORs. Moreover, this review provides insights into the active species in various reaction environments and further explores reaction mechanisms, to apparent phase changes of the catalyst with the most relevant examples. Finally, the review not only elucidates the limitations of the current approaches but also outlines potential avenues for future advancements in OOR.

Fe3O4@SiO2@CSH+VO3− as a novel recyclable heterogeneous catalyst with core–shell structure for oxidation of sulfides

Iron nanoparticles, with low toxicity and many active sites, are among the materials that not only reduce waste along with green chemistry but also increase the separation power and recover the catalyst from the reaction environment. In this study, first, the surface of iron nanoparticles was silanized, and in the next step, the complex of chitosan HCl.VO3 was placed on the surface of Fe3O4 (Fe3O4@SiO2@CSH+VO3−). This nanocatalyst is a novel, recoverable, and potent nanocatalyst with high selectivity for the oxidation of sulfides to sulfoxides. Various physicochemical techniques such as IR, XRD, TGA, SEM, EDX, mapping, TEM, and VSM were used to affirm the well synthesis of the catalyst. Oxidation of sulfides in the presence of hydrogen peroxide as a green oxidant and in ethanol was catalyzed by the Fe3O4@SiO2@CSH+VO3−. All sulfoxides were achieved with high efficiency and in a short time. The notable privileges of this method include facile and economic catalyst synthesis, proper catalyst durability, great performance, simple catalyst isolation, good recovery capability, at least up to 5 times without an index drop in catalytic power.

Water-promoted selective hydrogenation of cinnamaldehyde over hydrotalcite-derived Co catalysts

Non-noble metal-catalyzed selective CO hydrogenation of α,β-unsaturated aldehydes to corresponding alcohols is chemically atom economic and practically feasible. This work reports hydrotalcite-derived Co-based catalysts for catalyzing aqueous phase selective hydrogenation reaction of cinnamaldehyde to cinnamyl alcohol. The structure characterizations demonstrate the phase transition from hydrotalcite to co-existed CoOx and metallic Co0 in the optimal Co2Al-H2-400 catalyst. It exhibits superior catalytic activity and selectivity relative to other as-obtained Co catalysts, because of the synergy effect of Co2+ sites to promote the adsorptive activation of CO group and small-size Co0 sites to facilitate the activating dissociation of hydrogen. Furthermore, the catalytic role of water has also been explored. Adopting water as pure solvent and partially adding water into organic solvent can both effectively enhance the activity and selectivity. Such reaction environment may induce creation of more intermolecular hydrogen bonds for promoting the hydrogen transfer and thus boosting the hydrogenation reaction.

Finding Natural, Dense, and Stable Frustrated Lewis Pairs on Wurtzite Crystal Surfaces for Small‐Molecule Activation

The surface frustrated Lewis pairs (SFLPs) open up new opportunities for substituting noble metals in the activation and conversion of stable molecules. However, the applications of SFLPs on a larger scale are impeded by the complex construction process, low surface density, and sensitivity to the reaction environment. Herein, wurtzite‐structured crystals such as GaN, ZnO, and AlP are found for developing natural, dense, and stable SFLPs. It is revealed that the SFLPs can naturally exist on the (100) and (110) surfaces of wurtzite‐structured crystals. All the surface cations and anions serve as the Lewis acid and Lewis base in SFLPs, respectively, contributing to the surface density of SFLPs as high as 7.26 × 1014 cm‐2. Ab initio molecular dynamics simulations indicate that the SFLPs can keep stable under high temperatures and the reaction atmospheres of CO and H2O. Moreover, outstanding performance for activating the given small molecules is achieved on these natural SFLPs, which originates from the optimal orbital overlap between SFLPs and small molecules. Overall, these findings not only provide a simple method to obtain dense and stable SFLPs but also unfold the nature of SFLPs toward the facile activation of small molecules.

A DNA circuit that records molecular events.

Characterizing the relative onset time, strength, and duration of molecular signals is critical for understanding the operation of signal transduction and genetic regulatory networks. However, detecting multiple such molecules as they are produced and then quickly consumed is challenging. A MER can encode information about transient molecular events as stable DNA sequences and are amenable to downstream sequencing or other analysis. Here, we report the development of a de novo molecular event recorder that processes information using a strand displacement reaction network and encodes the information using the primer exchange reaction, which can be decoded and quantified by DNA sequencing. The event recorder was able to classify the order at which different molecular signals appeared in time with 88% accuracy, the concentrations with 100% accuracy, and the duration with 75% accuracy. This simultaneous and highly programmable multiparameter recording could enable the large-scale deciphering of molecular events such as within dynamic reaction environments, living cells, or tissues.

Finding Natural, Dense, and Stable Frustrated Lewis Pairs on Wurtzite Crystal Surfacesfor Small-Molecule Activation.

The surface frustrated Lewis pairs (SFLPs) open up new opportunities for substituting noble metals in the activation and conversion of stable molecules. However, the applications of SFLPs on a larger scale are impeded by the complex construction process, low surface density, and sensitivity to the reaction environment. Herein, wurtzite-structured crystals such as GaN, ZnO, and AlP are found for developing natural, dense, and stable SFLPs. It is revealed that the SFLPs can naturally exist on the (100) and (110) surfaces of wurtzite-structured crystals. All the surface cations and anions serve as the Lewis acid and Lewis base in SFLPs, respectively, contributing to the surface density of SFLPs as high as 7.26 × 1014 cm-2. Ab initio molecular dynamics simulations indicate that the SFLPs can keep stable under high temperatures and the reaction atmospheres of CO and H2O. Moreover, outstanding performance for activating the given small molecules is achieved on these natural SFLPs, which originates from the optimal orbital overlap between SFLPs and small molecules. Overall, these findings not only provide a simple method to obtain dense and stable SFLPs but also unfold the nature of SFLPs toward the facile activation of small molecules.

Efficacy of active and passive modified atmosphere packaging on quality preservation and storage life of pomegranate fruit and arils: A review

Pomegranate has nutritional value and health benefits due to its bioactive compounds and antioxidant properties. Fruit consumption is strongly recommended due to its high content of vitamins, fiber, minerals, and polyphenols. Supplying ready-to-eat pomegranate can be a beneficial technique to increase consumption with regard to its nutritional properties. However, maintaining nutritional quality and preventing microbial spoilage is a major challenge. Fruit quality is lost with visible symptoms such as weight loss, shriveling, husk scald, chilling injury, fungal rot, aril color degradation, and off-flavor during long-term storage. Therefore, it is very important to use appropriate strategies to maintain pomegranate whole fruit and aril quality. Gases around the product create a suitable environment for oxidative reactions and aerobic microorganism growth. Therefore, changing the atmosphere around the product can help maintain its quality. One of the effective methods to increase the postharvest life of products is to use modified atmosphere packaging (MAP), which reduces microbial spoilage and chilling injury, preserves the quality, and extends the shelf life by reducing the respiration rate. Modified atmosphere packaging, which uses natural atmospheric components (O2, CO2 and N2), has been widely accepted due to the lack of toxic residues on the product. This review discusses on recent research in terms of MAP application on quality properties and postharvest life of pomegranate fruit and arils during storage.

Rational Design of Local Reaction Environment for Electrocatalytic Conversion of CO2 into Multicarbon Products

The electrocatalytic conversion of CO2 into multi‐carbon (C2+) products provides an attractive route for storing intermittent renewable electricity as fuels and feedstocks with high energy densities. Although substantial progress has been made in selective electrosynthesis of C2+ products via engineering the catalyst, rational design of the local reaction environment in the vicinity of catalyst surface also acts as an effective approach for further enhancing the performance. Here, we discuss recent advances and pertinent challenges in the modulation of local reaction environment, encompassing local pH, the choice of the species and concentrations of cations and anions as well as local reactant/intermediate concentrations, for achieving high C2+ selectivity. In addition, mechanistic understanding in the effects of the local reaction environment is also discussed. Particularly, the important progress extracted from in situ and operando spectroscopy techniques provides insights into how local reaction environment affects C‐C coupling and key intermediates formation that lead to reaction pathways toward a desired C2+ product. The possible future direction in understanding and engineering the local reaction environment is also provided.

Physics of pressurized hydrogen spontaneous ignition in pipes containing bends of different angles

In the context of hydrogen-based energy storage systems, the safeguarding against spontaneous ignition during high-pressure hydrogen release is of paramount importance. This study delves into the thermal safety and management technologies pertinent to such systems by numerically investigating the effects of pipeline geometry on the risk of spontaneous ignition. Employing Large Eddy Simulation (LES) coupled with detailed chemical kinetics and a linear eddy model, the research assesses the impact of different pipe angles and burst pressures on ignition behavior. The simulations are validated against experimental data, ensuring the veracity of the findings. The results demonstrate a significant interplay between the ignition propensity and both the geometrical configuration of the pipeline and the pressure of hydrogen release. Notably, the emergence and interaction of transverse waves in pipe bends are revealed to amplify mixing processes, generating vortices that elevate the temperature and promote a conducive environment for chemical reactions leading to stable flame propagation. The ignition is shown to occur predominantly near the stoichiometric mixture ratio, suggesting a narrow ignition region. These insights are vital for enhancing the safety protocols and thermal management strategies of hydrogen-based energy storage systems, paving the way for safer and more efficient energy solutions.

Local oxygen transport resistance in polymer electrolyte fuel cells: origin, dependencies and mitigation

Next-generation polymer electrolyte fuel cells (PEFCs) require an integral design of the porous structure of electrodes at different scales to improve performance and enlarge durability while reducing cost. One of today’s biggest challenges is the stable, high-performance operation at low Pt loading due to the detrimental effect of the local oxygen transport resistance caused by ionomer around catalyst sites. Hindered local oxygen transport arises from sluggish kinetics at the local reaction environment, that comprises adsorption at (wet) ionomer and Pt interfaces, and diffusivity of gas species in ionomer and water. Diverse factors affect oxygen transport, including operating conditions (relative humidity, temperature, and pressure), ionomer content and morphology, ionomer heterogeneity, porosity of carbon support, catalyst dispersity, and flooding. To attain performance and durability targets, it is essential to maximize the oxygen utilization of the catalyst layer by implementing enhanced membrane electrode assembly architectures. This involves employing advanced catalyst layer preparation techniques, including electrospraying, to generate optimized highly porous morphologies. Furthermore, achieving these targets necessitates the development of new materials with tailored properties, such as high permeability and porous ionomers, among other innovative strategies.

Chemical diversity in angiosperms - monoterpene synthases control complex reactions that provide the precursors for ecologically and commercially important monoterpenoids.

Monoterpene synthases (MTSs) catalyze the first committed step in the biosynthesis of monoterpenoids, a class of specialized metabolites with particularly high chemical diversity in angiosperms. In addition to accomplishing a rate enhancement, these enzymes manage the formation and turnover of highly reactive carbocation intermediates formed from a prenyl diphosphate substrate. At each step along the reaction path, a cationic intermediate can be subject to cyclization, migration of a proton, hydride, or alkyl group, or quenching to terminate the sequence. However, enzymatic control of ligand folding, stabilization of specific intermediates, and defined quenching chemistry can maintain the specificity for forming a signature product. This review article will discuss our current understanding of how angiosperm MTSs control the reaction environment. Such knowledge allows inferences about the origin and regulation of chemical diversity, which is pertinent for appreciating the role of monoterpenoids in plant ecology but also for aiding commercial efforts that harness the accumulation of these specialized metabolites for the food, cosmetic, and pharmaceutical industries.

In-situ texturing hollow carbon host anchored with Fe single atoms accelerating solid-phase redox for Li-Se batteries

Se-based cathodes have caught tremendous attention owing to their comparable volumetric capacity and better electronic conductivity to S cathodes. However, its low utilization ratio and sluggish redox kinetics due to the high reaction barrier of solid-phase transformation from Se to Li2Se limit its practical application. Herein, an in-situ texturing hollow carbon host by gas–solid interface reaction anchored with Fe single-atomic catalyst is designed and prepared for advanced Li-Se batteries. This Se host presents high pore volume of 1.49 cm3 g−1, Fe single atom content of 1.53 wt%, and its specific structure protects single-atomic catalyst from the destructive reaction environment, thus balancing catalytic activity and durability. After Se loading by reduction of H2SeO3, this homogenous Se-based cathode delivers a superior rate capacity of 431.3 mA h g−1 at 4C, and great discharge capacity of 301.8 mA h g−1 after 1000 cycles at 10C, with high Li-ion diffusion coefficient and capacitance-contributed ratio. The distribution of relaxation times analysis verifies solid-phase transformation mechanism of this cathode and density functional theory calculations confirm the adsorption and bidirectionally catalysis effect of Fe single-atomic catalyst. This work provides a new strategy to prepare high-efficient Se cathode associated with non-noble metal single atoms for high-performance Li-Se batteries.

High-precision charge analysis in a catalytic nanoparticle by electron holography.

The charge state of supported metal catalysts is the key to understanding the elementary processes involved in catalytic reactions. However, high-precision charge analysis of the metal catalysts at the atomic level is experimentally challenging. To address this critical challenge, high-sensitivity electron holography has recently been successfully applied for precisely measuring the elementary charges on individual platinum nanoparticles supported on a titanium dioxide surface. In this review, we introduce the latest advancements of high-precision charge analysis and discuss mechanisms of charge transfer at the metal-support interface. The development of charge measurements is entering a new era, and charge analyses under conditions closer to practical working environments, such as real-time, real-space, and reactive gas environments, are expected to be realized in near future.

Catalytic Ammonia Formation in a Microreaction Chamber with Electrically Intensified Arc Plasma

Ammonia (NH3) production is of global concern for today’s food supply security and as future energy vector. Plasma technology can add to supply‐chain resilience of fertilizer production and improve the environmental profile using renewable energy; allowing distributed NH3 production. With the objective to provide process intensification of small‐capacity reactors for local supply, a novel micropyramid‐disk plasma reactor operated in micro‐arc mode was developed. NH3 was synthesized from N2, nitrogen, and H2, hydrogen over Ru/MCM‐41 catalyst at atmospheric pressure. The microplasma brings plasma and catalyst surface close together and intensifies the electric field. The arc plasma elevates temperature, ‘nonthermal’, releasing high‐energy free electrons, known to be effective in converting low‐reactive molecules. The study demonstrates that microplasma, with reduced electrode‐to‐electrode dimensions and a microstructured reaction environment, enhances the performance of the NH3 synthesis and opens novel process windows. This is detailed on the impact of feed ratio (N2/H2), applied voltage, frequency, electrode gap, and the flow distribution by which the gas is fed in. Optical emission spectroscopy (OES) was used to identify vibrationally and other excited species generated by the microplasma and confirms the catalyst is in symbiosis with the radicals.

Carbon vacancies and hydrogen bonds in graphitic carbon nitride: Enhanced charge transfer and photocatalytic hydrogen evolution

Accelerating the separation and transfer of photogenerated electron to the active site is an effective strategy for enhancing the photocatalytic hydrogen evolution. However, it is generally limited by the scarcity of active sites, as well as the sluggish photogenerated electron transfer kinetics. Herein, a g-C3N4 catalyst with controllable carbon vacancy and hydrogen bond was prepared using a hot–cold cycles heat treatment. It is demonstrated that after hot–cold cycles, abundant carbon vacancies were introduced into the catalyst and hydrogen bonds were broken. The abundant carbon vacancies not only provide additional electron-active sites, affords more opportunities for photogenerated electron to transfer to the active site, but also optimize the reaction environment for photogenerated electrons by regulating the hydrogen adsorption kinetics of the photocatalyst. Additionally, the broken hydrogen bonds promotes electron transfer to the active site. The combined action of the two effectively enhances the separation and transfer of photogenerated electron to the optimal active site, ultimately leading to a significant increase in photocatalytic hydrogen evolution. Consequently, the g-C3N4 resulting from the fourth cycles (CN-4) demonstrates a substantial improvement in the performance of photocatalytic hydrogen evolution under visible light irradiation (1.69 mmol·g−1·h−1), which is 4.05 times higher than initial g-C3N4. This work may provide new insights into the defect and hydrogen bond regulation design of g-C3N4.

Inhibition of NF-κB-Mediated Proinflammatory Transcription by Ru(II) Complexes of Anti-Angiogenic Ligands in Triple-Negative Breast Cancer.

Nuclear factor kappa beta (NF-κB) plays a pivotal role in breast cancer, particularly triple-negative breast cancer, by promoting inflammation, proliferation, epithelial-mesenchymal transition, metastasis, and drug resistance. Upregulation of NF-κB boosts vascular endothelial growth factor (VEGF) expression, assisting angiogenesis. The Ru(II) complexes of methyl- and dimethylpyrazolyl-benzimidazole N,N donors inhibit phosphorylation of ser536 in p65 and translocation of the NF-κB heterodimer (p50/p65) to the nucleus, disabling transcription to upregulate inflammatory signaling. The methyl- and dimethylpyrazolyl-benzimidazole inhibit VEGFR2 phosphorylation at Y1175, disrupting downstream signaling through PLC-γ and ERK1/2, ultimately suppressing Ca(II)-signaling. Partial release of the antiangiogenic ligand in a reactive oxygen species-rich environment is possible as per our observation to inhibit both NF-κB and VEGFR2 by the complexes. The complexes are nontoxic to zebrafish embryos up to 50 μM, but the ligands show strong in vivo antiangiogenic activity at 3 μM during embryonic growth in Tg(fli1:GFP) zebrafish but no visible effect on the adult phase.

Size reduction and water dispersibility improvement of hexagonal boron nitride particles by femtosecond laser irradiation in water

Controlling the size and surface state of inorganic particles, which strongly influence their dispersibility in solvents, is important for diverse applications. Intense femtosecond laser pulses can induce plasma formation in material–dispersed solvents and interact with both materials and solvents. In this study, femtosecond laser pulses are employed to modify hexagonal boron nitride (hBN) particles dispersed in water, with the aim of evaluating the effects of the femtosecond laser process on the size reduction and surface modification of hBN particles. Shadowgraph imaging reveals the formation of the reactive environment in hBN–dispersed water, resulting from the ionization of water molecules which leads to the generation of OH radicals. Evaluation of the hBN particle sizes suggests an overall reduction from 160 to 110 nm after 60 min of irradiation and the generation of nanodots between 5 and 10 nm in size. In addition, it is confirmed that the number of particles with higher zeta potentials increases after the samples are laser-irradiated, suggesting a change in the surface state. Consequently, the duration of hBN particle dispersion in water is significantly increased, with an improvement of at least one order of magnitude, for the laser-irradiated samples. This study presents a demonstration of the formation of a reaction field that affects hBN particles in size and dispersibility in water.

Electron‐Donating Cu Atoms Induced High Proton Supply and Anti‐Poisoning Ruthenium Clusters for Superior Direct Seawater Hydrogen Production

AbstractDirect seawater hydrogen production via electrolysis would be a transformative technology for large‐scale pathways for future sustainable energy systems. However, prohibiting the formation of insoluble hydroxides and promoting proton supply at the electrode‐seawater interface are extremely desirable but remain challenging. Herein, inspired by the dual‐metal pair sites in natural enzyme, the de novo design of an efficient, robust, and precise electron‐donating Cu‐modulated ruthenium clusters on porous carbon matrix (Cu@Runc‐C) is reported as a high proton supply and anti‐poisoning cathode material for superior direct seawater hydrogen production. Benefitting from the unique Cu@Runc pair sites, the cathode exhibits particularly high hydrogen evolution activities with ultralow overpotentials to reach a high current density of 300 mA cm−2 in both alkaline (115 mV) and seawater (459 mV) electrolytes, and notably, the cathode can maintain superior long‐lasting stability in seawater electrolysis. The mechanism exploration demonstrates that the ruthenium cathode with Cu@Runc pair sites exhibits low oxophilic and fast proton‐transferring local reaction environments to prohibit the formation of insoluble precipitates and provide efficient proton supply within the electrode‐seawater interface. It is expected that the proposed bioinspired regulation strategy offers a new pathway for constructing efficient, robust, and selective cathode materials for scalable seawater hydrogen production.