ChemSusChem最新文献

The Cover Feature illustrates a charged composite anode with both graphite (Gr) and silicon (Si) active materials. The transfer lithiation from Gr to Si, driven by their potential differences, can lead to overlithiation of Si, thus material stress and degradation, even when Si is used in lower ratios. More information can be found in the Research Article by J. Kasnatscheew and co-workers (DOI: 10.1002/cssc.202401290).

The Cover Feature shows laccases as biocatalysts with high potential in lignocellulose biorefineries. Protein engineering has enhanced their efficiency for valorizing lignin monomers into value-added biologically active molecules. This biocatalytic process is solvent-free, achieves faster reaction times, uses lower amounts of enzyme, and delivers excellent yields (up to 100 %). The work advances lignin combinatory chemistry knowledge and marks a step forward in producing sustainable and eco-friendly natural dimeric compounds for medicinal chemistry and polymer synthesis. More information can be found in the Research Article by M. P. Robalo, M. R. Ventura, L. O. Martins and co-workers (DOI: 10.1002/cssc.202401386). Cover design: Joel Arruda (ITQB-NOVA Science Communication Office).

The Cover Feature illustrates how the incorporation of Pd single-atom sites within a Pd₁/α-MoC catalyst alters the pathway of selective hydrogenation of furfural. Specifically, it facilitates the reaction under milder conditions and enhances its efficiency. The desert, rough road and bicycle symbolize the high reaction temperatures and low efficiency associated with the α-MoC catalyst. Conversely, the lush plant, highway and vehicle represent the mild conditions and high efficiency achieved with the Pd₁/α-MoC catalyst. Additionally, the models of the catalysts indicate that the Pd single atom effectively activates hydrogen molecules and selectively targets the C=O structure of furfural, enabling the reaction to proceed rapidly through a direct hydrogenation pathway, rather than via the MPV route. More information can be found in the Research Article by Q. Zhang, L. Yan and co-workers.

The increasing challenge of plastic pollution, coupled with the depletion of fossil resources, necessitates innovative solutions for the sustainable management of end-of-life plastics. This issue is particularly pressing for polyoxymethylene (POM), a widely used engineering thermoplastic known for its exceptional mechanical properties and durability, which degrades slowly and releases harmful formaldehyde (HCHO). In this study, we present a straightforward method to convert POM waste into formic acid (FA) using hydrogen peroxide (H2O2) as the oxidant. While H2O2 is recognized as a selective and mild oxidation agent, its potential for upcycling plastics into valuable chemicals has been largely uncharted. Our approach utilizes microporous aluminosilicate zeolite H-Beta, known for its Brønsted acidity, to effectively catalyze both the depolymerization of POM into HCHO and its subsequent oxidation to FA. A significant aspect of this method is the incorporation of 1,1,1,3,3,3-hexafluoroisopropanol, which enhances depolymerization through strong hydrogen bonding interactions. This catalytic system efficiently transforms a variety of post-consumer POM waste into FA while also facilitating the Baeyer-Villiger-type oxidation of various carbonyl compounds, achieving high yields in both processes. Overall, these findings advance the conversion of plastic waste into value-added chemicals via H2O2-mediated reactions, enhancing sustainable waste management and supporting circular economy principles.

Redox-mediated electrodialysis (redox-ED) enhances the economic and energy feasibility of conventional electrodialysis by substituting water splitting and costly metal-basedelectrodes with reversible redox reactions and porous carbon electrodes. Despite growing interest, the development of scale-up strategies for redox-ED remains limited, delaying its industrial implementation. This study proposes a scale-up strategy by examining the impact of stacking electrodes and channels on the desalination performance of the system, aiming to enable economically viable desalination. The results show that electrode and channel stacking (up to three stacks) significantly enhances desalination performance, resulting in a 6.8-fold increase in the salt removal rate, and a 30% improvement in productivity. These enhancements can be attributed to synergistic effects of electrode and channel stacking, which improve the redox reaction rate by increasing the surface area and enhancing the system capacity by increasing the volumetric flow rate. Technoeconomic analysis underscores the economic viability of the scale-up strategy proposed in this study, showing 18% and 32% reductions in capital and operating costs, respectively, compared with multiple unit cell systems. Overall, incorporating multiple stacks of electrodes and channels offers an effective strategy for scaling up redox-ED systems with high economic viability, thereby providing a pathway for their industrial utilization.

Glycerol electrooxidation is a promising alternative to the oxygen evolution reaction in carbon dioxide electroreduction processes. It has the potential to both reduce the overall cell voltage and enable the commercialization of anodic oxidation products. Gold is a material that exhibits a high performance for glycerol oxidation but has a high manufacturing cost. In this work we have synthesized a gold indium alloy that exhibits enhanced electrocatalytically properties, as evidenced by a reduction in the glycerol oxidation onset potential by 210 mV while reducing the electrode cost by 28%. This electrocatalyst has been evaluated in a flow cell configuration coupled with the cathodic reduction of carbon dioxide, and high faradaic efficiencies up to 90% have been achieved for both the anodic and cathodic products.

Herein, we report a paired electrosynthesis of ethylene glycol from formaldehyde and methanol facilitated by TEMPO. The use of TEMPO accentuates formaldehyde production at the anode, providing additional formaldehyde for pinacol coupling at the cathode. The reaction is performed in water/methanol solution in a simple undivided cell using sulfuric acid treated graphite electrodes with industrially feasible current densities between 300 to 350 mA cm-2. Other components of the reaction are sodium chloride which is used as a supporting electrolyte and tributylmethylammonium chloride which raises the current efficiency. With a slight modification in the reaction temperature and current density, the outcome can be tuned from high current efficiency towards higher chemical yields. The conditions of the batch reaction were successfully transferred to a continuous flow-cell arrangement. Mechanistic studies indicate the involvement of hydroxymethyl radicals in the electrolysis.

Catalytic synthesis of alkane-based lubricant base oils from biomass and plastic waste offers low-carbon and sustainable pathways toward carbon neutrality. In this review, recent advancements in catalytic strategies for the conversion of lipids, lignocellulosic biomass-derived molecules, and polyolefin plastic wastes into hydrocarbon-based lubricant base oils are highlighted. For the bio-lubricant production, catalytic routes involve C-C coupling reactions, followed by hydrodeoxygenation (HDO) or hydrogenation reactions to produce hydrocarbons. For the lubricant production from polyolefin plastic wastes, catalytic strategies include pyrolysis followed by hydroconversion or direct hydrogenolysis. Various strategies along with their respective catalysts, are exemplified. The performance and mechanisms of catalysts for each reaction are systematically summarized. Additionally, the structure-property relationships of lubricant molecules are comprehensively discussed to gain the guidance for the design of superior lubricant architectures. Technoeconomic analysis and life cycle assessment are also addressed to evaluate commercial viability and environmental impact. Finally, perspectives on future developments in this field are offered. It is anticipated that this review will inspire innovations in catalytic process development and rational catalyst design for the conversion of biomass and plastic waste into high-performance lubricant base oils to establish a low-carbon economy.

Hydrogen production from seawater electrolysis holds significant promise for future energy crisis. However, various ions in the seawater disrupt the electrolysis process, impelling the discovery of efficient oxygen evolution reaction (OER) catalysts coupling with organic small molecules to accelerate the hydrogen generation efficiency. Herein, an easy method is presented for loading Fe electrodepositon layer (EL) onto carbonized wood (CW) via a straightforward electrodeposition process. Fe-EL enriches the active sites on the hierarchical pores natural carbon materials, resulting in exceptional hydrogen evolution reaction (HER) performance. In KOH and artificial seawater, Fe-CW demonstrates overpotentials of merely 38 and 94 mV at 10 mA cm^-2, accompanied with excellent stability. For the anodic counterpart, OER is replaced with the 5-hydroxyfurfural oxidation reaction (HMFOR) using Fe/NiB/CF catalyst. It achieves an oxidation potential of 1.46 V to attain 100 mA cm^-2 for HMFOR and convertes 5-hydroxyfurfural to 2,5-furandicarboxylic acid with a remarkable conversion rate of approximately 100%. When coupled HER with HMFOR in the seawater, the Fe-CW‖Fe/NiB/CF cell achieves 100 mA cm^-2 at an ultralow voltage of 1.47 V. This approach not only addresses the challenges posed by seawater electrolysis but also paves ways for the industrial application of biomass-coupled hydrogen production.

While the world remains dependent on fossil fuels in nearly every aspect of life, unused biomass is piling up as waste, despite its significant potential for valuable applications - a critical missed opportunity for sustainable innovation. Phase change materials (PCMs) have emerged as a pivotal technology in the urgent transition toward carbon neutrality, especially considering that heating and cooling consume nearly half of global energy expenditure. This comprehensive review advances the scientific understanding of sustainability and circularity in PCM fabrication by providing a strategic framework for developing composites from renewable resources. This framework involves the introduction of a novel classification system (Types 0-3) for biomass-derived PCMs based on their levels of modification, enabling a comparison of material sources, performance metrics, and environmental impacts. By showing recent innovative developments in PCM shape stabilization, thermal conductivity enhancement, and leakage protection, it critically highlights the opportunities to replace conventional materials with innovative biomass-derived alternatives, such as biomass-derived carbons and polymers. Furthermore, the study integrates tools aligned with the Principles of Green Chemistry to aid the fabrication of truly sustainable materials, helping to guide researchers through material selection, process optimization, and the comprehensive evaluation of the environmental impact associated with their use and disposal.