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Abstract With a continually evolving society and increasing environmental energy concerns, green biomass materials are attracting considerable attention in the field of energy storage owing to their low cost, environmental friendliness, and excellent storage capacity. Biomass materials prepared by various methods have been used as electrodes in secondary batteries. In this review, we discuss the application scope of different types of biomass and biomass‐derived materials in zinc‐air, lithium‐ion, and lithium‐sulfur batteries. The application of biomass and biomass‐derived materials in batteries is gaining increasing attention and is expected to drive many exciting innovations in the field of sustainable energy storage technologies.

Abstract The electrification of the production of fine chemicals has received increased interest in combating petrochemical routes with a high carbon footprint. Oxidising biomass from waste streams with concomitant hydrogen production, such as the transformation of lignin to vanillin, would be a great asset. Here, we show the combination of activity screening using a scanning droplet cell on a thin‐film Ni−Fe library and performance testing in a flow‐through cell with pulse electrolysis. The identified optimal Ni−Fe material composition was prepared on Ni foam with a polymer/metal precursor spray method. Full factorial and Doehlert matrix designs were employed to better comprehend each parameter‘s effects on the complex system. The best conditions for the electrooxidation of Kraft lignin at room temperature were at E1st=1.36 V vs RHE, t1st=1 s for the first pulse and E2nd=1.60 V vs RHE and t2nd=15 s for the second pulse, leading to the significantly improved production of 2.15 μmols of vanillin at room temperature. Pulsed chronopotentiometry was demonstrated to be a cost‐effective and robust technique with a simple setup for the valorisation of Kraft lignin. Combined with a subsequent thermolysis step, 8.05 μmols of vanillin were obtained.

Abstract Multiphysics modeling enables probing of conditions inside a CO2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one‐dimensional model for a zero‐gap membrane electrode assembly (MEA) CO2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO3 concentration.

Abstract The green electricity‐driven electrocatalytic reduction of organic compounds in aqueous solution has merged as a sustainable and green platform for organic electrosynthesis, upcycling of chemical waste, and environmental remediation. Compared with the thermocatalytic hydrogenation process, the electrocatalytic reduction of organic compounds uses water as a proton source, which enables its operation at ambient conditions with simplified reaction schemes and significantly reduces operation cost and energy consumption. Most studies have demonstrated the development of electrocatalysts to boost the current efficiency, conversion, and product selectivity of the electrocatalytic reduction processes. Still, little attention has been paid to the mechanism (e. g., electron/proton transfer route) and related energetics behind the electrocatalytic reduction process. This Concept overviews the recent development of the electrocatalytic reduction systems for environmental remediation, pollutant upcycling, and valorization of biomass‐derived chemicals. This Concept highlights the underlying mechanisms and aims to provide instructive guidance on designing efficient and selective electrocatalytic systems.

Abstract The electrochemical characteristics and stability of hydrogel‐based environmentally friendly supercapacitors employing sodium acetate as salt have been investigated. To ensure the overall sustainability of the devices, chitosan (a biomaterial from renewable resources) and activated carbon (derived from coconut shells) have been used as a binder and filler within the electrodes, respectively. Cyclic voltammetry, galvanostatic charge/discharge, and impedance spectroscopy measurements have been performed to compare the electrochemical properties of the fabricated devices. Compared to reference electrolytes containing NaCl, the utilization of sodium acetate exhibited enhancements in energy performance and stability up to 50000 cycles. The most efficient device has been delivered approximately 10.6 Wh/kg of energy at a high‐power density of about 3940 W/kg. A comprehensive investigation of the electrochemical performances has been carried out, considering both faradaic and non‐faradaic processes as charge storage mechanisms within the devices. A model has been proposed to describe the storage mechanisms and to provide insights into the ageing phenomena observed during the cycling procedure.

Abstract The 1,5‐benzothiazepane structure is an important heterocyclic moiety present in a variety of commercial drugs and pharmaceuticals. This privileged scaffold exhibits a diversity of biological activities, including antimicrobial, antibacterial, anti‐epileptic, anti‐HIV, antidepressant, antithrombotic and anticancer properties. Its important pharmacological potential renders research into the development of new and efficient synthetic methods of high relevance. In the first part of this review, an overview of different synthetic approaches toward 1,5‐benzothiazepane and its derivatives is provided, ranging from established protocols to recent (enantioselective) methods that promote sustainability. In the second part, several structural characteristics influencing biological activity are briefly explored, providing a few insights into the structure‐activity relationships of these compounds.

Abstract A supercritical carbonation method for the preparation of lithium‐ion battery precursor (Ni0.6Co0.2Mn0.2CO3) is proposed. With appropriate selection of reaction temperature, pressure and pH, a desirable stoichiometry of transition metal ratio (6 : 2 : 2) can be achieved. The precursor synthesis time plays a significant role in the battery performance as the transition metal ion distributions become more uniform with increasing reaction time. This results in a more stable layered structure, lower cation mixing level, higher electrochemical reversibility, and lower impedance. The battery made of the precursor prepared under the best synthesis conditions can achieve a discharge capacity of 174.2 mAh g−1 in the first cycle and a capacity retention of 93.0 % after 50 cycles using a current density of 60 mA g−1. This study proves the feasibility of using supercritical carbon dioxide as the reagent for the coprecipitation of lithium‐ion battery precursor Ni0.6Co0.2Mn0.2CO3. Furthermore, this method can possibly be applied to the synthesis of other carbonate‐based materials.

Aqueous zinc-ion batteries (ZIBs) are gaining attraction for large-scale energy storage systems due to their high safety, significant capacity, cost-effectiveness, and environmental friendliness. On the other hand, the development of aqueous ZIBs is restricted by the limited practical application of zinc (Zn) because of the high reactivity of Zn in aqueous electrolytes, which results in the severe dendrite growth and parasitic side reactions such as hydrogen evolution reaction (HER). In this study, heteroatom-doped carbon porous surface modification by laser-assisted carbonization of copper (Cu) doped polyaniline (PANI) is designed and fabricated on top of the Zn metal anode (c-Cu-PANI/Zn). The c-Cu-PANI surface-modified Zn anodes exhibit high electrochemical stability and performance during the Zn plating-stripping cycles and suppress the dendrite formation. The symmetrical cell and half-cell with the c-Cu-PANI/Zn anodes exhibit stable cycles for 6000 h and 100% Coulombic efficiency for 2500 cycles, respectively. Moreover, the c-Cu-PANI/Zn║V 2 O 5 cell delivers a high specific capacity of 319 mAh g -1 at 0.2 A g -1 , which is significantly higher than that of the bare Zn║V 2 O 5 cell (240 mAh g -1 ). It is believed that applying c-Cu-PANI as a surface modification can enhance the stability and reversibility of the Zn anodes, therefore accelerating the commercialization of ZIBs., (© 2024 Wiley‐VCH GmbH.)

We report the use of carboxyl-functionalised alkylimidazolium salts as thermomorphic acid catalysts for the hydrolysis of cellulose and starch in water, free from organic solvents and auxiliary substances. The imidazolium salts are insoluble in water at room temperature and dissolve to form homogeneous solutions upon heating. Following catalysis at elevated temperatures the solution is cooled and the imidazolium salt precipitates from the aqueous layer to afford an aqueous glucose solution. This thermomorphic, temperature-switchable, process allows facile separation of the product and reuse of the catalyst while ensuring catalysis commensurate with homogeneous systems., (© 2024 Wiley‐VCH GmbH.)

Carbohydrates constitute the largest source of biomass on Earth, but their synthetic modification is challenging due to their high content in oxygen functionalities. The site- and stereoselective modification of native sugars is a definite goal of glycochemistry research. Recent efforts to bypass the need for protecting groups, leveraging selective activation through photochemical mechanisms for site-selective C-C bond formation from native sugars, are likely to largely impact all glycochemistry-related areas. Davis, Koh, and co-workers have recently presented their use of photocatalysis to develop a "cap and glycosylate" approach for the site- and stereoselective C-glycosylation of native sugars. A modernized direct radical functionalization of in situ formed thioglycoside using photocatalysis was used in the synthetic manipulation of unprotected carbohydrates. This allowed reaching complex saccharides, and post-translational modification of proteins., (© 2024 Wiley-VCH GmbH.)

This study focuses on the design, eco-friendly synthesis, and characterization of several novel three-legged triphenylamine derivatives. By performing Sonogashira couplings of functionalized aryl iodides with tris(4-ethynylphenyl)amine in glycerol, a readily available bio-derived solvent, we achieved the synthesis of target products in short times and high yields, up to 94 %, with consistently lower E-factors and reduced costs compared to standard conditions using toluene as the reaction medium. The target molecules possess a D-(π-A)₃ or D-(π-D)₃ structure, where an electron-donating core connects to three electron-donating (D) or electron-accepting (A) peripheral aromatic subunits through an acetylene spacer. Their main optical and electronic properties have been determined experimentally and by DFT simulations and suggest a possible implementation in energy conversion technologies such as luminescent solar concentrators (LSCs) and perovskite solar cells (PSCs)., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Extracting high-performance nanomaterials from waste presents a promising avenue for valorization. This study presents two methods for extracting cellulose nanofibrils (CNFs) from discarded textiles. Post-consumer cotton fabrics are chemically treated through either cationization with (2,3-epoxypropyl)trimethylammonium chloride or TEMPO/NaBr-catalyzed oxidation, followed by fibrillation to produce Cat-CNFs and TO-CNFs, respectively. Molecular models indicate variations in the effective volume of each grafted group, influencing the true densities of the functionalized fibers. Significant differences in the morphology of the CNFs arise from each functionalization route. Both CNF types exhibit high surface charge (>0.9 mmol g -1 ), small cross-sections (<10 nm), and high aspect ratios (>35). TO-CNFs have a higher surface charge, whereas Cat-CNFs exhibit a higher aspect ratio and greater colloidal stability across a broader pH range. Cat-CNFs exhibit cross-sections at the elementary fibril level, highlighting the steric impact of the grafted surface groups on fibrillation efficiency. Nanopapers from these CNFs demonstrate high optical transmittance and haze, whereas anisotropic foams show mechanical properties comparable to foams made from wood-based CNFs. This work highlights the potential of post-consumer cotton textiles as a CNF source and the impact of chemical treatment on the properties of the fibers, CNFs, and resulting lightweight materials., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

Waste, often overlooked, stands out as a prime source of valuable products, meeting the demand for natural resources. In the face of environmental challenges, this study explores the crucial role of waste-derived catalysts in sustainable practices, emphasizing the transformative potential of solid waste materials. Carbon-based catalysts sourced from agricultural, municipal, and industrial waste streams can be transformed into activated carbon, biochar, and hydrochar which are extensively used adsorbents. Furthermore, the paper also highlights the potential of transition metal-based catalysts derived from spent batteries, electronic waste, and industrial byproducts, showcasing their efficacy in environmental remediation processes. Calcium-based catalysts originating from food waste, including seashells, eggshells, bones, as well as industrial and construction waste also find an extensive application in biodiesel production, providing a comprehensive overview of their promising role in sustainable and eco-friendly practices. From mitigating pollutants to recovering valuable resources, waste-derived catalysts exhibit a versatile role in addressing waste management challenges and promoting resource sustainability. By transforming waste into valuable catalysts, this study champions a paradigm shift towards a more sustainable and resource-efficient future., (© 2024 Wiley-VCH GmbH.)

The cosmetic industry is now changing or rather having an ecological transition in which formulations such as creams, lotions, and powders for make-up, skin and hair care must not contain microplastics, now a taboo word in this field. Nowadays, many companies are intensifying their research and development (R&D) work to align with recent and future legislation that provides for their elimination to safeguard the ecosystem. The production of new eco-sustainable materials is currently a hot topic which finds its place in a market worth above 350 billion dollars which will reach more than 700 billion dollars in a very short time. This review offers an overview of the main advantages and adverse issues relating to the use of microplastics in cosmetics and of their impact, providing an insight into the properties of the polymeric materials that are currently exploited to improve the sensorial characteristics of cosmetic products. In addition, the various regulatory restrictions in the different geographical areas of the world are also described, which is matter for reflection on future direction. Finally, a prospective vision of possible solutions to replace microplastics with sustainable alternatives complete the picture of the next generation personal care products to support decision-making in the cosmetic marketplace., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

How to retrieve and reuse surfactants efficiently from surfactant-based microemulsions (MEs) has long been a problem, which is full of challenges and needs to be solved urgently. To this end, a pH-triggered precipitation-dissolution (PTPD) strategy is developed. The surfactant sodium 3-(laurylamino)propane-1-sulfonate (LMPS) transforms into an insoluble precipitate (the inner salt of LMPS, LMP) after reaction with HCl, by which the monophasic LMPS-based MEs demulsified entirely, giving a separable mixture of oil, water and LMP. LMP can be retrieved efficiently (~95.3 %) regardless of the ME type, and can then be conveniently restored to LMPS via reactions with NaOH. Conceptually, the retrieval of LMPS (~96.6 %), toxic benzo[a]pyrene (BaP, ~99.5 %) and a mixture of co-surfactant n-butanol and the oil phase n-heptane (~97.1 %) from the sufficiently emulsified soil eluents is achievable by respectively using the PTPD strategy and distillation, wherein the soil eluents were generated from the remediation of BaP-contaminated soil using an oil-in-water LMPS-based ME as washing agent. It reveals a promising future for the PTPD strategy in the post-processing of soil eluents containing toxic hydrophobic organic contaminants and excessive surfactants., (© 2024 Wiley-VCH GmbH.)

Humanity faces an unprecedented survival challenge: climate change, driven by the depletion of natural resources, excessive waste generation, and deforestation. Six out of nine planetary boundaries have been exceeded, signaling that Earth is far from a safe operating space for humanity. In this Viewpoint Article we explore three critical "atomic-molecular" challenges: Earth's limited atomic resources, its oxidative nature, and very rich chemistry. Addressing these requires a transformation in how we produce and consume, emphasizing sustainable practices aligned with the United Nations' 17 goals. The advancement of science and technology has extended human life expectancy and improved quality of life. However, to ensure a sustainable future, we must move towards less oxidative chemical processes, incorporate CH 4 -CO 2 redox chemistry into the circular economy, and transition from a linear, fossil fuel-dependent economy to a circular bioeconomy. Reforestation and the recovery of degraded lands are essential, alongside the shift towards green and sustainable chemistry. Earth's dynamic chemistry is governed by the principles of thermodynamics and kinetics, but science alone is insufficient. Achieving global sustainability requires coordinated economic, political, and social decisions that recognize Earth's limited resources and oxidative nature. Together, these efforts will position humanity to meet the challenges of climate change and secure a sustainable future., (© 2024 Wiley-VCH GmbH.)

Development of photovoltaic-electrochemical (PV-EC) systems for energy storage and industry decarbonization requires multidisciplinary collaborative efforts of different research groups from both photovoltaic and electrochemical research communities. Consequently, the evaluation of the solar-to-chemical or solar-to-fuel efficiency of a new electrolyzer (EC) as a part of a PV-EC system is a time-consuming task that is challenging in a routine optimization loop. To address this issue, a new rapid assessment method is proposed. This method employs power balance requirements to unfold the input EC characteristics into the parameter space of PV-EC systems. The system parameters, composed with the EC output characteristics, yield the solar-to-chemical efficiency attainable by the electrolyzer in combination with any PV device under any irradiance at any relative PV-to-EC scaling and any mode of power coupling. This comprehensive overview is achieved via a mathematically simple conversion of the EC characteristics in any spreadsheet software. The method, designed to streamline the development and minimize the efforts of both the photovoltaic and electrochemical communities, is demonstrated via the analysis of CO 2 -reduction electrolyzer characteristics and verified with dedicated PV-EC experiments., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

Given the importance of quinazolines and quinazolinethiones in therapeutic and Food and Drug Administration (FDA)-approved molecules, we thought interesting to consider their synthesis in green solvents. We have shown that obtain 4-(arylamino)quinazoline-2-(1H)-thiones and 4-(arylamino)pteridine-2-(1H)-thiones analogues was efficient in green solvents derived from biomass, especially eucalyptol. Although reaction times are somewhat long to achieve good yields, the products were obtained by simple filtration. This considerably limited the loss of atoms due to the use of large quantities of solvents for purification on silica gel columns, and makes our route a sustainable one., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

With the aim of transforming sewage sludge into a P-fertiliser material in a single combustion step, the chemical processes underlying sewage sludge combustion were analysed using powder X-ray diffraction (P-XRD), infrared spectroscopy (IR), thermogravimetric (TGA) as well as elemental analyses (EA). In addition to the combustion of sewage sludge on its own ("mono-combustion"), additions of different additives prior to the combustion step were also carried out. Based on the very positive effects of the additives sodium and potassium carbonate on the obtained ashes concerning their phosphate solubilities in neutral ammonium citrate (NAC) solution, sewage sludge combustions after additions of Na 2 CO 3 or K 2 CO 3 were investigated in detail. We found that these additions altered the main phosphate-containing product found in the ashes from whitlockite (Ca 9 (Mg,Fe)(PO 3 OH)(PO 4 ) 6 ), a hardly plant-accessible species, to other phosphate containing compounds such as buchwaldite (CaNaPO 4 ), which is known for a long time as a very good P-source for plants. Consecutive greenhouse experiments with maize (Zea mays L.) as test plant confirmed the results of the chemical analyses and demonstrated that Na- or K-ashes obtained from a "co-combustion" of sewage sludge mixed with alkali carbonates exhibit relative P-fertilising efficiencies of up to ~80 % in comparison to commercial superphosphate, making these materials promising surrogate phosphate mineral sources for agricultural production., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

The most influential technological innovations and societal progress lie at the intersection of scientific disciplines. Today, more than ever, biology assumes a more central and participatory role at this confluence. Within the context of this scientific inter-disciplinarity, the current effort was undertaken to explore the ecology of invasive tunicates, marine invertebrates increasingly considered a nuisance to the ecology of coastal ecosystems, yet potentially a resource for diverse applications in materials chemistry, construction, composites, and engineering. The intention of this perspective is to stimulate conversation and discussion with respect to benthic tunicates, a valuable yet underappreciated biological resource, which can be converted to cellulose nanocrystals, one of the most important bio-based materials sourced today. It will also attempt to consolidate current understandings of the ecology of tunicates and how potential material exploitation can be mutually compatible and compliant with efforts to protect coastal ecosystems and aquaculture which are currently inundated or threatened by invasive tunicates., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The transformation of CO 2 into chemical building blocks for various industries is considered a key technology in a net-zero energy future. To realize this, plasma discharges are one of the most promising approaches thanks to their electron-driven reactions and high operational flexibility. Most studies focused on room-temperature and vibrationally-excited discharges, however, lately, the importance of thermal reactions is considered. Therefore, we developed a temperature-dependent plasma-chemical reaction mechanism to investigate the temperature dependence of plasma-based CO 2 conversion. Here, we present the various effects of thermally-driven reactions on the CO 2 conversion as a function of the gas temperature and specific energy input. Our analysis pinpointed the key reactions controlling the plasma-based CO 2 conversion, shifting from an electron-driven to a thermal-driven regime. Additionally, we used the mechanism to verify the theoretical upper boundary of the process' energy efficiency, and discussed how our findings could lead to the further development and optimization of plasma discharges for efficient CO 2 conversion in the future., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

To access degradable polyolefin plastic, non-alternating copolymerization of ethylene (E) and carbon monoxide (CO) for producing polyethylene (PE) with in-chain ketones is particularly appealing; however, it still presents significant challenges such as molecular weight modulation (hydrogen response) and chain endgroup control (functional terminal). In this study, we achieved hydrogen-controlled E/CO non-alternating copolymerization using late transition metal catalysts. This process results in linear PEs containing the desired non-alternating in-chain keto groups (1.0-9.3 mol %) and with tunable molecular weights ranging from 43 to 195 kDa. In this reaction, H 2 serves as a chain transfer agent, modulating the polymer's molecular weight, forming unique aldehyde endgroups and eliminating usual olefinic endgroups; CO undergoes non-alternating insertion into the PE chain, resulting in a strictly non-alternating structure (>99 %) for the keto-PE. The dispersed incorporation of in-chain keto groups retains bulk properties of PE and makes PE susceptible to photodegradation, which produces significantly lower molecular weight polymers and oligomers with unambiguous vinyl and acetyl terminals., (© 2024 Wiley-VCH GmbH.)

The production of bacterial cellulose (BC) has indeed garnered global attention due to its versatile properties and applications. Despite potential benefits, the challenges like low productivity, high fermentation costs, and expensive culture media hinder its industrialization. Utilizing low-cost substrates, especially waste streams, can help address the challenges. In this study, waste feedstocks such as restaurant leftovers, oranges, and grapefruit from canteens and supermarkets were valorized for BC production by Komagataeibacter sucrofermentans. Orange juice is a fascinating substrate with a highest concentration of 20.6 g/L and productivity of 2.05 g/L/d. Using HS medium with supplementary ions, organic acids, ethanol, and various carbon sources is a strategic approach for enhancing BC production. The study reveals that the addition of organic acids or ethanol moderately increased BC production, while ions inhibit BC synthesis, highlighting the complex interplay between various cultivation medium components. Additionally, fermentation with K. sucrofermentans using single and mixed carbon sources was conducted to elucidate the potential metabolic mechanism of BC production. Through alkaline treatment and drying in a 30 °C incubator, we produced the highest quality BC with 92.09 % crystallinity. Overall, the study enhances BC production knowledge and provides green and sustainable strategies for fermentative BC production., (© 2024 Wiley-VCH GmbH.)

Organic synthesis has historically relied on solution-phase, polar transformations to forge new bonds. However, this paradigm is evolving, propelled by the rapid evolution of radical chemistry. Additionally, organic synthesis is witnessing a simultaneous resurgence in mechanochemistry, the formation of new bonds in the solid-state, further contributing to this shift in the status quo. The aforementioned advances in radical chemistry have predominantly occurred in the solution phase, while the majority of mechanochemical synthesis advances feature polar transformations. Herein, we discuss a rapidly advancing area of organic synthesis: mechanochemical radical reactions. Solid-state radical reactions offer improved green chemistry metrics, better reaction outcomes, and access to intermediates and products that are difficult or impossible to reach in solution. This review explores these reactions in the context of small molecule synthesis, from early findings to the current state-of-the-art, underscoring the pivotal role solid-state radical reactions are likely to play in advancing sustainable chemical synthesis., (© 2024 Wiley-VCH GmbH.)

Although the introduction of plastics has improved humanity's everyday life, the fast accumulation of plastic waste, including microplastics and nanoplastics, have created numerous problems with recent studies highlighting their involvement in various aspects of our lives. Upcycling of plastics, the conversion of plastic waste to high-added value chemicals, is a way to combat plastic waste that is receiving increased attention. Herein, we describe a novel aerobic photochemical process for the upcycling of real-life polystyrene-based plastics into benzoic acid. A new process employing a thioxanthone-derivative, in combination with N-bromosuccinimide, under ambient air and 390 nm irradiation is capable of upcycling real-life polystyrene-derived products in benzoic acid in yields varying from 24-54 %., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

We report the first metal- and catalyst-free protocol for the facile cross-coupling of aryl halides towards C-B, C-P and C-S bonds under solid-state ball milling conditions via UV light irradiation. The reactions can be performed in the absence of bulk solvents at room temperature in a mixer mill, yielding up to 99 % and being tolerant towards various functionalized aryl halides (X=I or Br). Furthermore, we developed a novel photoreactor design increasing the light intensity. With this we could demonstrate that our protocol surpasses classical solvent based as well as purely mechanochemical approaches in terms of green metrics and energy efficiency., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Plastics are an indispensable part of modern life. Due to the harmful environmental consequences of petroleum-based plastic usage, there is an urgent need to replace them with biodegradable bioplastics that meet the sustainability standards required for a low environmental footprint. Here, we use plant-derived proteins to produce bioplastics. Since most plant-derived proteins are not water-soluble, there has always been a need to use acidic or basic solutions or organic solvents with plasticizers and crosslinkers to produce bioplastic. Here, we present a counterintuitive approach for using water-insoluble plant-derived soy and pea proteins to manufacture large-scale bioplastics using only water as a solvent without common plasticizers or crosslinkers. We show that bioplastics can form via a self-assembly process initiated by a small molecular initiator while maintaining favourable mechanical properties. The lack of crosslinking and the protein nature of the bioplastic leads to a rapid biodegradation process under various conditions. Overall, the approach we present is highly attractive in terms of cost and time, and most importantly, it obeys all the relevant principles of green chemistry in bioplastics production., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

A sustainable and scalable protocol for synthesizing variously functionalized sulfonamides, from amines and sulfonyl chlorides, has been developed using environmentally responsible and reusable choline chloride (ChCl)-based deep eutectic solvents (DESs). In ChCl/glycerol (1 : 2 mol mol -1 ) and ChCl/urea (1 : 2 mol mol -1 ), these reactions yield up to 97 % under aerobic conditions at ambient temperature within 2-12 h. The practicality of the method is exemplified by the sustainable synthesis of an FFA4 agonist and a key building block en route to anti-Alzheimer drug BMS-299897. A subtle interplay of electronic effects and the solubility characteristics of the starting materials in the aforementioned DESs seem to be responsible for driving the reaction successfully over the hydrolysis of sulfonyl chlorides. The procedure's eco-friendliness is validated by quantitative metrics like the E-factor and the EcoScale, with products isolated by extraction or filtration after decantation., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Abstract Oxidised starch is currently produced from native starch using sodium hypochlorite as an oxidising agent. The use of hypochlorite has undesired side reactions and produces stoichiometric amounts of waste (salt), thus alternative oxidation methods are desired. In this study, the potential of two catalysed starch oxidation methods to reduce the environmental impact (EI) of oxidised starch production are assessed. We compared the EI of oxidation with molecular oxygen (heterogeneously catalysed) and hydrogen peroxide (homogeneously catalysed) to hypochlorite oxidation through life cycle assessment (LCA). The results confirm that hypochlorite oxidation is the main environmental hotspot in the current process of oxidised starch production, and that both hydroperoxide oxidation and molecular oxygen oxidation can significantly lower the EI of the process. The impact reduction is most significant in the categories of freshwater eutrophication (∼67 %), ozone depletion (∼66 %), climate change (35–60 %) and resource use (40 %–78 %) for peroxide and molecular oxygen oxidation, respectively.

Abstract Herein we report a conceptually new non‐decarboxylative electrolysis of carboxylic acids to obtain their corresponding anhydrides as highly valuable reagents in organic synthesis. All carbon atoms of the starting material are preserved in the product in an overall redox‐neutral reaction. In a broad substrate scope of carboxylic acids the anhydrides are generated with high selectivity, which demonstrates the versatility of the developed method. Beneficially, no dehydrating reagents are required in comparison to conventional methods and the synthesis is based on uncritical starting materials using graphite and stainless steel as very inexpensive and eco‐friendly electrode materials.

Abstract Recent decades have been marked by enormous progress in the field of synthesis and chemistry of 5‐(hydroxymethyl)furfural (HMF), an important platform chemical widely recognized as the “sleeping giant” of sustainable chemistry. This multifunctional furanic compound is viewed as a strong link for the transition from the current fossil‐based industry to a sustainable one. However, the low chemical stability of HMF significantly undermines its synthetic potential. A possible solution to this problem is synthetic diversification of HMF by modifying it into more stable multifunctional building blocks for further synthetic purposes.

Norbornadiene-based photoswitches have emerged as promising candidates for harnessing and storing solar energy, holding great promise as a viable solution to meet the growing energy demands. Despite their potential, the effectiveness of their direct photochemical conversion into the resulting quadricyclanes has room for improvement owing to (i) moderate quantum yields, (ii) poor overlap with the solar spectrum and (iii) photochemical back reactions. Herein, we present an approach to enhance the performance of such molecular solar thermal energy storage (MOST) systems through the triplet-sensitized conversion of aryl-substituted norbornadienes. Our study combines deep spectroscopic analyses, irradiation experiments, and quantum mechanical calculations to elucidate the energy transfer mechanism and inherent advantages of the resulting MOST systems. We demonstrate remarkable quantum yields using readily available sensitizers under both LED and solar light irradiation, significantly surpassing those achieved through direct excitation with photons of higher energy. In contrast to the conventional approach, light-induced back reactions of the high-energy products do not play any role, allowing quantitative switching within minutes. These results not only underscore the potential of triplet-sensitized MOST systems to leverage the high energy storage capabilities of multistate photoswitches but they might also stimulate the broader usage of sensitization strategies in photochemical energy conversion., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The field of carbocatalysis, often portrayed by paradigmatic graphitic carbonaceous structures, has become a booming topic tailored for multiple applications. To this end, a new metal-free carbocatalyst has been constructed from simple prebiotic monomers such as cyanamide and glyoxal. The resulting material shows an excellent performance as photocatalyst for H 2 production and CO 2 valorization, thus unveiling its real value to tackle sustainable goals. The unique oxygen-rich carbonaceous structure has been characterized in detail, which is consistent with a graphitic layered network. The described performance in two major societal concerns along with a facile preparation from C1/C2 platforms, makes this type of overlooked oxynitride carbocatalysts promising for real-life environmental endeavors., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The concepts of sustainability and sustainable chemistry have attracted increasing attention in recent years, being of great importance to the younger generation. In this Viewpoint Article, we share how early-career chemists can contribute to the sustainable transformation of their discipline. We identify ways in which they can engage to catalyse action for change. This article does not attempt to answer questions about the most promising or pressing areas driving research and chemical innovation in the context of sustainability. Instead, we want to inspire and engage early-career chemists in pursuing sustainable actions by showcasing opportunities in education, outreach and policymaking, research culture and publishing, while highlighting existing challenges and the complexity of the topic. We want to empower early-career chemists by providing resources and ideas for engagement for a sustainable future globally. While the article focuses on students and early-career chemists, it provides insights to further stimulate the engagement of scientists from diverse backgrounds., (© 2024 Wiley-VCH GmbH.)

Per- and polyfluoroalkyl substances (PFAS) are often considered the quintessential example of industrial chemical pollution - they are toxic and ubiquitous environmental contaminants that are extremely difficult to degrade. There has been a large research focus on the development of effective and renewable degradation technologies. In comparison to traditional pollutant degradation techniques, such as advanced oxidation processes and electrochemistry, degradation of PFAS using extracellular enzymes offers an eco-friendly solution as enzymes are biodegradable, recyclable and have low energy and chemical requirements. This review outlines the current understanding of extracellular enzymatic degradation of PFAS with a focus on reported results and proposed degradation mechanisms. More importantly, this review highlights limitations that hinder the application of enzymes for PFAS degradation and proposes critical future research that is needed to improve the applicability of this promising remediation strategy., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Driven by escalating environmental concerns, synthetic chemistry faces an urgent need for a green revolution. Green chemistry, with its focus on low environmental impacting chemicals and minimized waste production, emerges as a powerful tool in addressing this challenge. Metrics such as the E-factor guide the design of environmentally friendly strategies for chemical processes by quantifying the waste generated in obtaining target products, thus enabling interventions to minimize it. Phthalocyanines (Pcs), versatile molecules with exceptional physical and chemical properties, hold immense potential for technological applications. This review aims to bridge the gap between green chemistry and phthalocyanine synthesis by collecting the main examples of environmentally sustainable syntheses documented in the literature. The calculation of the E-factor of a selection of them provides insights on how crucial it is to evaluate a synthetic process in its entirety. This approach allows for a better evaluation of the actual sustainability of the phthalocyanine synthetic process and indicates possible strategies to improve it., (© 2024 Wiley-VCH GmbH.)

Biocatalysis has emerged in the last decade as a valuable and eco-friendly tool in chemical synthesis, allowing in several instances to reduce or eliminate the use of hazardous reagents, environmentally dangerous solvents and harsh reaction conditions. Enzymes are indeed able to catalyse chemical transformations on non-natural substrates under mild reaction conditions, still maintaining their high chemo-, regio-, and stereoselectivity. Enzyme immobilization, i. e. the grafting of enzymes on solid supports, can be viewed as an enabling technology, as it allows a better control of the reaction and the recycling of the biocatalyst, thus rendering economically viable the use of expensive enzymes also on a large scale. To pursue a sustainable approach, the supports for enzyme immobilization should be eco-friendly and possibly renewable. This review highlights the use of hydroxyapatite (HAP), an inorganic biomaterial able to confer strength and stiffness to the bone tissue in animals, as carrier for enzyme immobilization. HAP is a cheap, non-toxic and biocompatible material, with high surface area and protein affinity. Different enzyme classes, immobilization strategies, and the use of diverse HAP-based supports will be discussed, underlining the immobilization conditions and the properties of the obtained biocatalysts., (© 2024 Wiley-VCH GmbH.)

Carbon porous materials containing nitrogen functionalities and encapsulated iron-based active sites have been suggested as electrocatalysts for energy conversion, however their applications to the hydrogenation of organic substrates via electrocatalytic hydrogenation (ECH) remain unexplored. Herein, we report on a Fe@C:N material synthesized with an adapted annealing procedure and tested as electrocatalyst for the hydrogenation of benzaldehyde. Using different concentrations of the organic, and electrolysis coupled to gas chromatography experiments, we demonstrate that it is possible to use such architectures for the ECH of unsaturated organics. Potential control experiments show that ECH faradaic efficiencies >70 % are possible in acid electrolytes, while maintaining selectivity for the alcohol over the pinacol dimerization product. Estimates of product formation rates and turnover frequency (TOF) values suggest that these carbon-encapsulated architectures can achieve competitive performance in acid electrolytes relative to both base and precious metal electrodes., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The dissolution of elemental gold is a fundamental step in its recycling by hydrometallurgy but has a significant environmental impact due to the use of strong acids or highly toxic reagents. Herein, it is shown that mixtures of acetyl halides and hydrogen peroxide in alcohols promote the rapid room-temperature dissolution of gold by halogenation to form Au(III) metalates. After leaching, distillation of the alcohol and re-dissolution in dilute HCl, the gold was refined through its precipitation by a simple diamide ligand; this method was also applied to separate gold from a mixture of metals. The leaching process is rapid, avoids the use of highly toxic materials and corrosive acids, and can be integrated into selective separation processes, so has the potential to be used in the purification of gold from ores, spent catalysts, and electronic and nano-waste., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Semiochemicals can be used to manipulate insect behaviour for sustainable pest management strategies, but their high volatility is a major issue for their practical implementation. Inclusion of these molecules within porous materials is a potential solution to this issue, as it can allow for a slower and more controlled release. In this work, we demonstrate that a series of Zr(IV) and Al(III) metal-organic frameworks (MOFs) with channel-type pores enable controlled release of three semiochemicals over 100 days by pore size design, with the uptake and rate of release highly dependent on the pore size. Insight from grand canonical Monte Carlo simulations indicates that this is due to weaker MOF-guest interactions per guest molecule as the pore size increases. These MOFs are all stable post-release and can be reloaded to show near-identical re-release profiles. These results provide valuable insight on the diffusion behaviour of volatile guests in MOFs, and for the further development of porous materials for sustainable agriculture applications., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A major bottleneck limiting the commercialization of aqueous zinc ion batteries (AZIBs) is dendrite formation on the zinc (Zn) anode during the plating/stripping process, which leads to rapid deterioration in performance and, consequently to the device failure. In this regard, researchers are trying to design more stable anodes toward suppressing dendrite formation. One possible solution to tackle this problem and to extend the cycling life of AZIBs is to modify the zinc anode surface by coating carbonaceous materials, enabling more controlled charge flux and uniform ion distribution. This work reports sustainable and bio-derived polylactic acid (PLA) as a coating layer on the zinc anode. Carbonizing this polymer under ambient conditions using a high-power nanosecond laser forms a carbon-coated zinc foil, which was directly utilized as the anode in aqueous zinc ion batteries. The fabricated laser-processed PLA-derived carbon-coated zinc anode demonstrated an extended cycling life of almost 1600 hours, significantly outperforming the bare zinc anode. A full aqueous zinc ion battery assembled from as-modified anode and as-prepared V 2 O 5 nanofibers as cathode was able to deliver a specific capacity of 238 mAh g -1 at 1.0 A g -1 with a capacity retention of 70 % after 1000 cycles., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Abstract The synthesis of bio‐based and biodegradable plastics is a hot topic in research due to growing environmental problems caused by omnipresent plastics. As a result, polylactide, which has been known for years, has seen a tremendous increase in industrial production. Nevertheless, the manufacturing process using the toxic catalyst Sn(Oct)2 is very critical. As an alternative, five zinc acetate complexes have been synthesized with Schiff base‐like ligands that exhibit high activity in the ring‐opening polymerization of non‐purified lactide. The systems bear different side arms in the ligand scaffold. The influence of these substituents has been analyzed. For a detailed description of the catalytic activities, the rate constants kapp and kp were determined using in‐situ Raman spectroscopy at a temperature of 150 °C. The polymers produced have molar masses of up to 71 000 g mol−1 and are therefore suitable for a variety of applications. Toxicity measurements carried out for these complexes proved the nontoxicity of the systems.

The copper‐catalyzed Glaser coupling is conducted mechanochemically, with the milling balls and vessels being the catalyst. Thus, neither catalyst powders nor soluble catalyst salts are required. Substituting Cu0 milling tools by copper alloys not only increases the yield of the reaction, but also greatly reduces abrasion, and in turn increases catalyst long‐term stability and reusability. Tracking the reaction by Raman spectroscopy allows to identify the active intermediate directly on the milling ball surface and propose a reaction mechanism.

Chemistry, a vital tool for sustainable development, faces a challenge due to the lack of clear guidance on actionable steps, hindering the optimal adoption of sustainability practices across its diverse facets from discovery to implementation. This Scientific Perspective explores established frameworks and principles, proposing a conciliated set of triple E priorities anchored on Environmental, Economic, and Equity pillars for research and decision making. We outline associated metrics, crucial for quantifying impacts, classifying them according to their focus areas and scales tackled. Emphasizing catalysis as a key driver of sustainable synthesis of chemicals and materials, we exemplify how triple E priorities can practically guide the development and implementation of processes from renewables conversions to complex customized products. We summarize by proposing a roadmap for the community aimed at raising awareness, fostering academia-industry collaboration, and stimulating further advances in sustainable chemical technologies across their broad scope., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

5-(Hydroxymethyl)furfural (HMF) is a key platform chemical derived from renewable biomass sources, holding great potential as starting material for the synthesis of valuable compounds, thereby replacing petrochemical-derived counterparts. Among these valorised compounds, 2,5-furandicarboxylic acid (FDCA) has emerged as a versatile building block. Here we demonstrate the biocatalytic synthesis of FDCA from HMF via a one-pot three-step oxidative cascade performed via two operative steps under mild reaction conditions employing two unspecific peroxygenases (UPOs) using hydrogen peroxide as the only oxidant. The challenge of HMF oxidation by UPOs is the chemoselectivity of the first step, as one of the two possible oxidation products is only a poor substrate for further oxidation. The unspecific peroxygenase from Marasmius oreades (MorUPO) was found to oxidize 100 mM of HMF to 5-formyl-2-furoic acid (FFCA) with 95 % chemoselectivity. In the sequential one-pot cascade employing MorUPO (TON up to 13535) and the UPO from Agrocybe aegerita (AaeUPO, TON up to 7079), 100 mM of HMF were oxidized to FDCA reaching up to 99 % conversion and yielding 861 mg isolated pure crystalline FDCA, presenting the first example of a gram scale biocatalytic synthesis of FDCA involving UPOs., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Recycling of carbon fiber-reinforced polymer composites (CFRCs) based on thermosetting plastics is difficult. In the present study, high-performance CFRCs are fabricated through complexation of aromatic pinacol-cross-linked polyurethane (PU-AP) thermosets with carbon fiber (CF) cloths. PU-AP thermosets exhibit a breaking strength of 95.5 MPa and toughness of 473.6 MJ m -3 and contain abundant hydrogen-bonding groups, which can have strong adhesion with CFs. Because of the high interfacial adhesion between CF cloths and PU-AP thermosets and high toughness of PU-AP thermosets, CF/PU-AP composites possess a high tensile strength of >870 MPa. Upon heating in N,N-dimethylacetamide (DMAc) at 100 °C, the aromatic pinacols in the CF/PU-AP composites can be cleaved, generating non-destructive CF cloths and linear polymers that can be converted to high-performance elastomers. The elastomers are mechanically robust, healable, reprocessable, and damage-resistant with an extremely high tensile strength of 74.2 MPa and fracture energy of 149.6 kJ m -2 . As a result, dissociation of CF/PU-AP composites enables the recovery of reusable CF cloths and high-performance elastomers, thus realizing the upcycling of CF/PU-AP composites., (© 2024 Wiley-VCH GmbH.)

The development of mechanochemistry is considerably growing. Benign by design, this technology complies with several principles of green chemistry, contributing to the achievement of the United Nations Sustainable Development Goals (UN SDGs) and the European Green Deal objectives. Herein, we report the use of mechanochemical processes in batch to prepare kilogram-scale of the Active Pharmaceutical Ingredient (API): Ibuprofen-Nicotinamide (rac-IBP:NCT) co-crystal in an industrial eccentric vibration mill. This scenario shows a sustainable approach to the industrial up-scaling of pharmaceutical co-crystals by a solvent-free mechanochemical process in batch. The quantitative assessment of the greenness of the mechanochemical process against the Twelve Principles of Green Chemistry was performed using the DOZN 2.0 Green Chemistry Evaluator., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The interconversion of monoterpenes is facilitated by a complex network of carbocation rearrangement pathways. Controlling these isomerization pathways is challenging when using common Brønsted and Lewis acid catalysts, which often produce product mixtures that are difficult to separate. In contrast, natural monoterpene cyclases exhibit high control over the carbocation rearrangement reactions but are reliant on phosphorylated substrates. In this study, we present engineered squalene-hopene cyclases from Alicyclobacillus acidocaldarius (AacSHC) that catalyze the challenging isomerization of monoterpenes with unprecedented precision. Starting from a promiscuous isomerization of (+)-β-pinene, we first demonstrate noticeable shifts in the product distribution solely by introducing single point mutations. Furthermore, we showcase the tuneable cation steering by enhancing (+)-borneol selectivity from 1 % to >90 % (>99 % de) aided by iterative saturation mutagenesis. Our combined experimental and computational data suggest that the reorganization of key aromatic residues leads to the restructuring of the water network that facilitates the selective termination of the secondary isobornyl cation. This work expands our mechanistic understanding of carbocation rearrangements and sets the stage for target-oriented skeletal reorganization of broadly abundant terpenes., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Artificial leaves (a-leaves) can reduce carbon dioxide into syngas using solar power and could be combined with thermo- and biocatalytic technologies to decentralize the production of valuable products. By providing variable CO : H 2 ratios on demand, a-leaves could facilitate optimal combinations and control the distribution of products in most of these hybrid systems. However, the current design procedures of a-leaves concentrate on achieving high performance for a predetermined syngas composition. This study demonstrates that incorporating the electrolyte flow as a design variable enables flexible production without compromising performance. The concept was tested on an a-leaf using a commercial cell, a Cu 2 O:In x cathodic catalyst, and an inexpensive amorphous silicon thin-film photovoltaic module. Syngas with CO : H 2 ratio in the range of 1.8-2.3 could be attained with only 2 % deviation from the optimal cell voltage and controllable solely by catholyte flow. These features could be beneficial for downstream technologies such as Fischer-Tropsch synthesis and anaerobic fermentation., (© 2023 Wiley-VCH GmbH.)

Lignin, a major component of plant biomass, is a promising sustainable alternative carbon-based feedstock to petroleum as a source of valuable aromatic compounds such as vanillin. However, lignin upgrading reactions are poorly understood due to its complex and variable molecular structure. This work focuses on electrocatalytic lignin upgrading, which is efficient and sustainable at moderate temperatures and pressures and does not require stoichiometric reagents. We used a meta-analysis of published lignin conversion and product yield data to define the operating range, to select the catalyst, and then performed electrocatalytic experiments. We quantified the impact of temperature and electrical potential on the formation rate of valuable products (vanillic acid, acetovanillone, guaiacol, vanillin, and syringaldehyde). We found that increasing temperature increases their formation rate by an order of magnitude more than increasing electrical potential. For example, increasing temperature from 21 to 180 °C increases the vanillin formation rate by +16.5 mg⋅L -1 ⋅h -1 ±1.7 mg⋅L -1 ⋅h -1 , while increasing electrical potential from 0 to 2 V increases the vanillin formation rate by -0.6 mg⋅L -1 ⋅h -1 ±1.4 mg⋅L -1 ⋅h -1 ., (© 2023 Wiley-VCH GmbH.)