ChemSusChem最新文献

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.

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.

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.

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.

Lignin (L)-stabilized emulsions have gained interest as sustainable systems. Despite their advantages, the interaction of lignin derivatives with oil and water in emulsion systems remains unclear. In this work, we verified a hypothesis that different modification strategies would generate lignin derivatives with different emulsifying performances, even if lignin is anionically charged to a similar degree. To verify this hypothesis, we generated sulfoethylated lignin (SL) and carboxyethylated lignin (CL) softwood kraft lignin (L) as functional emulsifiers for soybean water emulsion systems. It was observed that lignin derivatives with a more negative zeta potential (ζ-potential) and smaller oil particles resulted in more stable emulsions at alkaline pH due to enhanced electrostatic repulsion. Due to well-dispersed oil droplets and a strong electrostatic system, the viscosity of emulsions was lower at alkaline conditions. It was also noted that SL and CL generated Pickering emulsions via depositing on oil droplets and developing steric hindrance with oil droplet sizes of 436 and 452 nm at acidic pH. However, such systems had shorter lifespans under acidic environments, indirectly implying that steric hindrance was insufficient to generate emulsions with long-term stability. These findings verified the involvement of different mechanisms for stabilizing oil emulsions at various pH levels.

The properties of sulfur host materials are critical for mitigating the lithium polysulfide (LiPS) shuttle effect and prolonging the Li–S battery lifetime. Herein, we have developed a unique polyvinyl chloride (PVC)-derived polymeric host material (named as XC); results show that XC host is capable of achieving strong chemical/physical confinement to the encapsulated sulfur and lithium polysulfide (LiPS) intermediates, thus significantly reducing the shuttling effect and improving the battery cycle life to above 500 cycles with only 9.3% capacity loss (74.4% after 1000 cycles). While with increased S loading of 6.2 mg-S/cm² and electrolyte-to-sulfur ratio of 6 μL/mg-S, the XC/S28 composite comprising 20% XC and 80% S maintains 67.5% of its capacity at the 200^th cycle. Apart from the chemical immobilization of short-chain S_x (x = 2−4) in micropores or organic skeletons, the use of XC as a polymeric encapsulant still maintains the solid–liquid–solid conversion in highly solvating electrolytes, guaranteeing high discharge voltage and energy while significantly extending cycle life.

The development of low-cost, earth-abundant electrocatalysts is essential for advancing hydrogen-based energy technologies, yet conventional water splitting remains constrained by the sluggish oxygen evolution reaction (OER). Substituting OER with the urea oxidation reaction (UOR) offers a more favorable alternative, reducing the reaction potential while simultaneously addressing wastewater remediation. Herein, we develop a heterostructured electrocatalyst of amorphous FeOOH quantum dots (QDs) uniformly anchored on NiMn layered double hydroxide (LDH) nanosheets grown on nickel foam (NF). The ultrathin conductive NiMn-LDH scaffold offers high surface accessibility and tunable redox activity, while the FeOOH QDs introduce abundant active centers that accelerate charge transfer and optimize OH⁻ and urea adsorption. As a result, FeOOH QDs/NiMn-LDH/NF requires only a low overpotential of 1.42 V to reach 50 mA cm⁻² for OER and 1.33 V for UOR, with small Tafel slopes of 31 and 29 mV dec⁻¹ and exhibits outstanding long-term durability of 50 h. Moreover, the heterostructured electrocatalyst shows competent activity for the hydrogen evolution reaction (η₁₀ = 125 mV) and delivers an average Faradaic efficiency of ≈95.7% during electrolysis, confirming highly selective charge-to-hydrogen conversion. This enables efficient urea-assisted overall water electrolysis at only 1.44 V. This work underscores the synergistic integration of LDH nanosheets with amorphous QDs as a versatile and scalable strategy to engineer next-generation bifunctional electrocatalysts for energy-efficient hydrogen production coupled with wastewater treatment.

This work focuses on improving the sustainability of electrolytes for sodium-ion capacitors (SICs). Through the combination of a low-fluorinated salt, namely sodium difluoro(oxalato)borate (NaDFOB), and the bio-based solvent γ-Valerolactone (GVL), a new electrolyte formulation (1 mol L⁻¹ NaDFOB in GVL) is being studied for application in SICs. Remarkably, the performance of the SIC full-cells is very comparable to the most commonly used formulation of sodium hexafluorophosphate in ethylene carbonate:propylene carbonate (1 mol L⁻¹ NaPF₆ in EC:PC). Furthermore, presodiation strategies were compared for the novel electrolyte system. The in situ oxidation of a sacrificial salt (sodium squarate, Na₂C₄O₄) incorporated into the positive electrode yielded comparable results to the ex situ electrochemical approach. X-ray photoelectron spectroscopy studies revealed that depending on the presodiation strategy, the solid-electrolyte-interphase composition varies significantly.