ChemSusChem最新文献

Fe-based materials are widely recognized as highly promising electrocatalysts for the oxygen evolution reaction (OER) owing to their high cost-effectiveness and intrinsic activity. Nevertheless, their practical application is severely hindered by sluggish reconstruction kinetics toward forming the true active (oxy)hydroxide species, as well as significant structural degradation under high-current-density operation. Heteroatom doping or alloying represents an effective strategy to overcome these bottlenecks. Herein, we successfully synthesized Zn-incorporated FeB on nickel foam (ZnFeB/NF) via a facile electroless plating strategy. Comprehensive characterizations, including in situ Raman spectroscopy, reveal that Zn incorporation modulates the electronic structure and induces a high degree of amorphization. This not only significantly accelerates the dynamic surface reconstruction of the ZnFeB precatalyst but also confers robust resistance against deep anodic corrosion. Benefiting from the synergistic structural and electronic advantages, the reconstructed ZnFeB electrode exhibits outstanding OER performance, requiring a remarkably low overpotential of 320 mV to achieve an industrial current density of 1 A cm⁻², while maintaining continuous operation for 100 h without apparent degradation.

Lithium-metal batteries (LMBs) are promising candidates for next-generation high-energy-density energy storage systems, but their practical application is limited by unstable Li-metal interfaces and poor compatibility of conventional carbonate electrolytes with high-voltage cathodes. Here, we report a poly(vinylidene fluoride) (PVDF)-based suspension carbonate electrolyte as an effective electrolyte-modification strategy, which improves the electrochemical stability of LMBs by enabling more uniform Li deposition and better oxidative stability. Molecular dynamics simulations combined with spectroscopic analyses reveal that fluorine-rich PVDF particle/electrolyte interfaces locally regulate Li⁺ coordination by weakening solvent-dominated solvation and enhancing anion participation around PVDF particles, thereby increasing contact ion pairs and aggregates. This promotes the formation of a gradient interphase with a fluorinated/organic-rich outer region and an inorganic inner region, while the intrinsically higher oxidation resistance of PVDF helps suppress parasitic reactions under high-voltage conditions. As a result, the suspension electrolyte delivers a Li⁺ transference number of 0.611, an oxidative stability window up to 4.7 V, and stable Li plating/stripping for over 2500 h in symmetric cells, while also improving the cycling stability and rate capability of Li||LiFePO₄ and Li||NCM811 cells. This work provides a practical strategy for interfacial stabilization in carbonate electrolytes.

Amino acid-based surfactants combine renewable head groups with tunable amphiphilic functional groups and are therefore attractive candidates for the development of more sustainable surfactants. However, bio-based building blocks alone cannot guarantee sustainability. Moreover, it depends on the choice of synthetic route, waste generation, feedstock origin, catalyst, product performance, toxicity, and environmental fate. This perspective discusses borrowing hydrogen catalysis (BHC) as a central strategy toward N-alkylated and N,N-dialkylated amino acid-based surfactants, which are derived from alcohols and amines with water as the only formal by-product. To place BHC in context, complementary routes such as enzymatic N-acylation, pathway-engineered fermentation, and Diels–Alder/ring-opening strategies starting from renewable hydrophobes are highlighted. Finally, design criteria and future challenges for the translation of amino acid-based surfactants from promising lab studies toward scalable and sustainable platforms are proposed.

Bio-based antimicrobial materials are increasingly explored as sustainable alternatives for plant pathogen control. Here, we report a circular economy approach in which industrial kraft lignin was upcycled into cationic lignin (CL) and physically embedded within chitosan–genipin (CH–GPN) hydrogels to form CH–GPN–CL. These bioactive materials were evaluated for the in vitro inhibition of the plant pathogen Pseudomonas syringae pv. tomato DC3000. To enhance antimicrobial activity, kraft lignin was cationized with glycidyl trimethylammonium chloride (GTMAC) using different lignin/GTMAC mass ratios, producing CL samples with varying degrees of substitution (DS). Leaf infiltration-based phytotoxicity assays of CL using Nicotiana benthamiana showed no concentration- or DS-dependent phytotoxicity under buffered conditions, suggesting compatibility with infiltrated leaf tissue. Bacterial inhibition assays showed that GTMAC cationization strongly improved lignin antimicrobial activity. Based on strong activity and a lower lignin/GTMAC mass ratio, a representative CL sample was selected for incorporation into the hydrogel framework. The resulting CH–GPN–CL hydrogels retained gel-like behavior and porous morphology and showed enhanced in vitro antimicrobial activity compared to the control hydrogel without embedded CL. These findings highlight the potential of CH–GPN–CL hydrogels as sustainable bioactive materials for further plant protection evaluation.

Excessive CO₂ emission has led to environmental damage. Efficient CO₂ capture is a key strategy for mitigation. Given the low CO₂ concentration in air, appropriate adsorbent affinity is required. However, high affinity hinders regeneration, while low affinity reduces capacity. Therefore, maintaining adsorption enthalpy within an ideal range for efficient and reversible adsorption has long been a challenge. In this study, a silicon-rich porous aromatic framework, namely, PAF-141, was synthesized via a Scholl coupling reaction using octaphenyl-functionalized polyhedral oligomeric silsesquioxane and biphenyl as monomers. A fluorinated derivative, PAF-141-F, was subsequently obtained through hydrofluoric acid etching of silicon sites. Both materials exhibited high specific surface areas and good thermal stability. Under conditions of 273 K and 1 bar, the CO₂ adsorption capacities for PAF-141 and PAF-141-F were measured to be 42.10 and 39.38 cm³/g, respectively. Notably, PAF-141-F demonstrated superior pore affinity toward CO₂ at 298 K, with Q_st of 44.33 kJ/mol, which fell within an ideal range. This indicated its strong adsorption capacity and reversible adsorption-desorption performance. Furthermore, IAST calculations revealed that both materials possessed high selectivity for CO₂/N₂ separation, demonstrating their potential for efficient CO₂ capture.

The production of 5-hydroxymethylfurfural (HMF) presents the challenge of mitigating the undesired side reactions in its production via fructose dehydration to insoluble humins and rehydration products. For this, biphasic systems for in situ HMF extraction have proven effective. Here, a H₂O/cyclohexanone biphasic system showed a remarkable partition ratio of 2.91 compared to other biphasic systems to separate HMF as the reaction occurs. Sulphated zirconia, SO₄²⁻/ZrO₂, was used as acid catalyst, chosen among other heterogeneous catalysts through activity and recyclability screening over six cycles, with return to the initial activity upon regeneration. A phenomenological approach to kinetic model development was implemented, wherein a total of 12 reaction models were constructed to investigate the complexity of humin formation. Based on statistical discrimination criteria, a Langmuir–Hinshelwood–Hougen–Watson model with variable reaction orders for the production of humins was deemed the most plausible (RMSE = 0.1075), with activation energy for dehydration of fructose to HMF of 137.97 ± 6.40 kJ mol⁻¹, and reaction orders towards humin formation between 0.71 and 1.60. The calculation and comparison of green metrics show the promise of this biphasic system to conduct the reaction in the context of a process, although catalyst selectivity remains key to enhancing mass efficiency.

The biorenewable feedstock cardanol, a phenol compound substituted with an unsaturated C15 hydrocarbon chain, was selectively transformed into a cyclohexanone derivative through partial hydrogenation. Subsequent conversion via Baeyer-Villiger oxidation (BVO) gave a lactone product (pentadecylcaprolactone, PDCL), which is a mixture of two regioisomers. For the BVO, two variants that are based on either the direct use of a perbenzoic acid as reagent or alternatively the use of a readily available aldehyde in the presence of molecular oxygen as an attractive oxidation reagent have been studied and turned out to be feasible. In addition, suitable work-up has been demonstrated that furnished a sample of the cardanol-derived PDCL-type lactone in 84% isolated yield with 99% purity. Using metal-free polymerization techniques, a PDCL sample has then been readily converted into its homopolymer, which displays a low crystallinity, the latter due to moderate side-chain crystallization. Importantly, in a statistical copolymer with ε-caprolactone (CL), PDCL was shown to be a useful agent to modulate crystallinity, resulting in copolyesters with reduced or very minor crystallinity and accordingly low melting points. For such an effect, typically expensive and fossil-based monomers such as δ-valerolactone (VL) have to be used, highlighting the potential of PDCL for practical application.

Highly earth-abundant and simple calcium precatalysts are reported that address the long-standing challenge of broad scope in hydrophosphination catalysis. With more than 120 examples of hydrophosphination reactions, calcium catalysts are the broadest in scope, including traditional styrene substrates and activated alkenes (Michael acceptors), conjugated dienes, heterocumulenes, alkynes, unactivated alkenes, and even naturally occurring alkenes. Reactions are optimized to maximum conversion, and few examples have less than 90% conversion, making these the most active catalysts to date. Two features contribute to this exceptional scope and activity. The first feature is solvent. Reactions run in DMSO experience a step up in relative rate compared to those in lower-dielectric solvents. Second, more challenging substrates are readily accessed under photocatalytic conditions, a feature already established for calcium precatalysts. The simple precatalyst, Ca(HMDS)₂(THF)₂ (HMDS  =  ^-N(SiMe₃)₂, 1), works for all reactions described, and mechanistic evidence points to a nucleophilic attack for amenable substrates. This work highlights critical advances in hydrophosphination (solvent effects, s-block catalysts, and photocatalysis) to yield an abundant metal (calcium) in green solvent with low energy input to achieve hydrophosphination of the widest scope of substrates under operationally simple conditions.

As a sustainable direct wide bandgap semiconductor, ZnO nanowires have received an increasing interest in the past three decades to act as potential building blocks in a large number of functional devices. The chemical bath deposition (CBD) of ZnO nanowires, as a hydrothermal growth operating at low temperature and roughly ambient pressure, can easily be implemented and scaled up for industrial purposes, attracting most of the recent attention in the community. However, despite its relative simplicity, a thorough understanding of the different physicochemical processes at work has emerged as highly critical to ensure ZnO nanowires of high quality. The present review reports a detailed analysis of the most recent and well-established state-of-the-art and scientific challenges of the CBD of ZnO nanowires, including the nucleation and growth processes at work using diverse seed layers, chemicals, and reactors, via the spontaneous and selective area growth approaches. The description of the elongation process of ZnO nanowires through its theoretical modeling is also discussed in detail. Eventually, a special emphasis is placed on the compatibility of the CBD of ZnO nanowires with green chemistry in order to identify its assets and the different opportunities for improvement.

Herein, silver zirconate over graphene oxide (Ag₂ZrO₃@GO) nanocomposites were successfully synthesized via a facile co-precipitation route to develop a bifunctional material for sustainable energy conversion and storage. The interfacial coupling between Ag₂ZrO₃ (SZ) and graphene oxide (GO) facilitates efficient charge transport, suppresses charge carrier recombination, and enhances electrochemical activity, making the composite suitable for both photocatalytic hydrogen evolution and supercapacitor applications. The as-prepared SZ@GO was investigated for visible-light-driven photocatalytic hydrogen generation using EOSIN Y (EY) as a sensitizer, as well as for supercapacitor performance. Among the samples, 20% SZ@GO demonstrated superior photocatalytic activity, producing 4554.84 μmol g⁻¹ of hydrogen within 5 h under visible light irradiation. Electrochemical studies revealed that the 20% SZ@GO electrode exhibits a high specific capacitance of 266 F g⁻¹ at a scan rate of 5 mV s⁻¹. These findings highlight the potential of SZ@GO nanocomposites as efficient materials for both sustainable hydrogen production and high-performance energy storage devices, offering a promising avenue for integrated energy solutions.