ChemSusChem最新文献

Valorising crude glycerol, a major by-product of biodiesel production, is essential for advancing a circular chemical economy. Traditional methods of oxidising crude glycerol to produce value-added chemicals such as glycolic acid (GcA) and dihydroxyacetone (DHA) typically require noble metal catalysts and energy-intensive conditions. Herein, we present a catalyst-free, non-thermal plasma (NTP) process that operates in the liquid phase at ambient temperature and pressure. This novel approach enables the selective oxidation of glycerol into GcA and DHA without the need for added reagents or catalysts. With a deposited power of 9.6 W and short residence time, 100% selectivity towards GcA was achieved with 7% glycerol conversion. Extending the treatment time to 60 min increased glycerol conversion to 35%, with selectivities of 58% for GcA and 36% for DHA. These results highlight the potential of liquid-phase NTP as a sustainable and efficient method for upgrading crude glycerol under mild conditions.

Ammonia (NH₃), the world's second most produced chemical, is indispensable to modern society, with widespread applications in agriculture, chemical manufacturing, refrigeration, and energy storage. However, the conventional Haber–Bosch process for NH₃ synthesis is characterized by lengthy process flows, harsh operating conditions, and significant carbon emissions, rendering it increasingly misaligned with global carbon peaking and neutrality objectives. Consequently, there is an urgent need to develop new NH₃ synthesis technologies that are both energy-efficient and environmentally benign. This review specifically examines three promising gas–solid phase NH₃ synthesis routes driven by external fields: photocatalysis, plasma catalysis, and the emerging technique of alternating magnetic field (AMF) catalysis. We summarize recent progress in this area, discuss catalyst design strategies tailored to each approach, and identify persistent challenges at the level of catalytic materials, reaction mechanisms, and reactor engineering. Finally, we outline future research directions, emphasizing the importance of multi-scale collaborative design to advance toward the ultimate goal of green and low-carbon NH₃ production.

Organic cathode materials (OCMs), with their inherent structural diversity, elemental sustainability, and environmental compatibility, present a promising pathway to overcome the energy density and resource limitations of conventional inorganic cathodes. As such, they are regarded as highly promising candidates for next-generation rechargeable batteries. Nevertheless, the simultaneous achievement of high-energy density and robust stability in OCMs remains a significant challenge. High energy density depends on the high capacity and high voltage of the material, while robust stability relies on the low solubility of the material. In this review, we begin by systematically examining the fundamental causes of the low capacity, low voltage, and strong solubility in OCMs. On this basis, we summarize recent advances in enhancing the energy density of OCMs, including molecular-level material design, electrode-level engineering, and electrolyte-level optimization. Meanwhile, we offer forward-looking perspectives on the future development of organic electrodes for next-generation battery technologies.

An electrochemical platform enabling condition-dependent chemoselective reduction of alkynes was developed. Modulation of electrochemical parameters allowed selective formation of alkenes or alkanes via proton transfer or nickel hydride formation pathways, as supported by potentiodynamic analyses and detailed isotope-labeling studies. The reactions proceed under mild conditions without the use of molecular hydrogen, featuring broad scope and high functional-group tolerance, thus providing a practical and sustainable approach to chemoselective alkyne reduction.

Magnesium (Mg)-based implant materials exhibit unique biodegradable properties, but their excessively rapid corrosion leads to compromised mechanical performance, reduced biocompatibility, and insufficient capability to meet multifarious clinical demands. Herein, this work developed a multifunctional coating that both addresses corrosion protection and enables multifunctional applications. A facile Cu(II)-incorporated coating system through Schiff base covalently grafted UiO-66-NH₂ is constructed onto Mg surface for synergistic integration of corrosion control and biofunctionalization. The Cu(II) active sites contribute to biocatalytic reactions and antibacterial action, which can catalyze the decomposition of S-nitrosoglutathione (GSNO) to release NO (1.7 × 10⁻⁷ mol cm⁻² min⁻¹) for vasodilation, effectively decompose H₂O₂, and scavenge reactive oxygen species (ROS) to alleviate oxidative stress (catalytic decomposition and removal efficiency exceed 60%), as well as demonstrate superior antibacterial efficacy against both E. coli and S. aureus (over 99.9% inhibition rates). Moreover, the coating remarkably retards Mg corrosion and significantly improves cytocompatibility and hemocompatibility of Mg surface. Simultaneous control of Cu²⁺ and Mg²⁺ ions release on the surface microenvironment facilitates biochemical effect on osteoblast differentiation ability (gene expression of RUNX2 + 356% and OCN + 223%). This work opens up a feasible route of developing a multipurpose surface modification strategy incorporating metal active sites to Mg surface for customized functions.

The development of efficient and sustainable catalytic systems for plastic depolymerization is crucial for advancing a circular economy. Herein, we report the construction of boron-doped carbon nitride (B-CN) as a metal-free catalyst featuring frustrated Lewis pairs (FLPs) for the efficient glycolysis and methanolysis of polyethylene terephthalate (PET). The boron doping creates Lewis acid sites adjacent to intrinsic Lewis basic nitrogen sites, which synergistically activate the carbonyl group of PET and promote alcohol deprotonation. The optimized catalyst achieves over 90% yields of the BHET and DMT monomer and exhibits broad applicability to the depolymerization of various commercial PET wastes. The catalyst also exhibits exceptional catalytic stability, with no significant performance degradation over 10 consecutive cycles. This work pioneers a green and versatile FLPs-based metal free catalytic strategy for the chemical recycling of plastics.

Seawater electrolysis has emerged as a highly promising technology for sustainable hydrogen production, offering the dual advantages of utilizing abundant seawater resources and compatibility with offshore renewable energy systems. However, the practical implementation of this technology faces a critical challenge: the competing chlorine evolution reaction (CER) at the anode. This side reaction not only reduces the Faradaic efficiency for oxygen production but also induces severe catalyst corrosion through chloride-induced degradation pathways, ultimately compromising the durability and economic viability of electrolysis systems. To address these challenges, this review provides a comprehensive overview of recent advances in CER suppression strategies, systematically categorizing them into three interconnected approaches: enhancing catalyst selectivity through the construction of chloride-blocking layers and other selective adsorption strategies; improving intrinsic oxygen evolution reaction activity via electronic structure modulation, interface engineering, and other activation methods; and reinforcing catalyst stability using corrosion-resistant materials and related protective approaches. Furthermore, we examine electrolyte optimization and innovative electrolyzer designs that contribute to system-level CER mitigation. By synthesizing these developments, this review aims to establish fundamental principles and practical guidelines for designing highly efficient and durable seawater electrolysis systems, thereby accelerating the industrial implementation of this sustainable hydrogen production technology.

Reducing the environmental impact of the aviation sector is a pressing concern. The adoption of sustainable aviation fuel (SAF) to replace current fossil-based fuel is one of the most promising pathways for decarbonizing this sector. Currently, processes for producing iso- and n-alkanes—taking 50% of the composition of the jet fuel—are approved as alternatives to fossil-based procedures. However, to generate a fully sustainable blend, the production of cyclic hydrocarbons such as naphthenes and aromatics is also required. This perspective examines the potential of lignin from lignocellulosic biomass (LCB) as an alternative feedstock for producing naphthenes and aromatics through lignin hydrodeoxygenation (HDO). A mass-balancing exercise at European scale, based on harvestable woody biomass scenarios and recent product yields from state-of-the-art lignin-first biorefinery technology, demonstrates a balanced supply and demand toward a sustainable production of naphthenes and aromatics for SAF. The study reveals that developing feedstock-flexible LCB biorefining technologies—with promising perspective for the reductive catalytic fractionation case—will be critical to comply with European regulations and integrate into current industrial lignocellulosic biomass value-chains.

Lignin is an attractive feedstock for a wide variety of applications ranging from aromatic chemicals and transportation fuels to resins and coatings. Emerging biorefinery concepts, like the organosolv process, enable the separation of all the lignocellulose components, and moreover, produce lignins of high quality and purity susceptible to valorisation by depolymerisation. In this work, we focus on the depolymerisation of lignins obtained by γ-valerolactone (GVL) organosolv fractionation of four biomass feedstocks, eucalyptus, white birch, sugarcane bagasse and Scots pine. We demonstrate that lignins extracted with the GVL process are depolymerised using unsupported molybdenum-based catalysts under reductive conditions in supercritical ethanol. As a result, over 90% yields of low-molecular-weight lignin oils are obtained with minimal char formation, yields of the aromatic monomers being 7–16 wt%. Furthermore, the design of experiments method is used to analyse the effect of depolymerisation conditions, catalyst, hydrogen loading and temperature, on the yields and properties of the product fractions. Notably, we show that the properties of the lignin oils and monoaromatics can be tuned towards the targeted application by modifying the depolymerisation conditions.

In zero-gap saltwater electrolysis, ion transport is influenced by convective forces, but their effects have not been examined when using thin-film composite (TFC) membranes with advective flow through the membrane. In this study, we adapted a one-dimensional solution-friction transport model for a zero-gap electrolyzer to incorporate measured water flux across a TFC membrane. Open-circuit or electrolysis (20 mA cm^–2) experiments quantified ion transport with and without electrochemical reactions. Water velocity, estimated from volume changes in the anolyte and the catholyte, was used to infer convective contributions to ion transport. Ion-specific friction coefficients were determined using open-circuit data. Using the fitted friction factors and incorporating water flux, the modeled ion crossover concentration showed good agreement with electrolysis data, including changes caused by reversing the membrane orientation. Removing the convective flux from the model showed up to a 740% change in predicted ion crossover and worsened agreement with experimental data. The strong correlation between the fraction of charge carried by major salt ions and the measured water flux suggests that electroosmotic drag could be one of the main mechanisms responsible for the observed water flux. These results highlight the importance of incorporating solution convection when modeling ion behavior in zero-gap systems using TFC membranes.