ACS Sustainable Chemistry & Engineering最新文献

The hydrogenation of CO₂ to methanol serves as a practical approach extensively applied in achieving carbon cycling utilization and reducing carbon emissions. Nevertheless, the rational design of Cu-based catalysts with satisfactory catalytic performance and corresponding structure–activity relationship understanding still remains a challenging goal. Inspired by the characteristics of both hydrotalcite structures and active Cu species for CO₂ hydrogenation, a series of hydrotalcite-derived Cu nanocatalysts with highly dispersed Cu nanoclusters and tunable electronic and geometric structures are obtained via simply controlling structural topological transformation process temperature, verified by a comprehensive study including Bader charge analyses, TG-MS, HAADF-STEM, in situ CO–DRIFTS, and XAFS experiments. The optimized catalyst demonstrates an exceptional normalized CO₂ reaction rate of 30.6 mmol·g_cat^–1·h^–1 and a methanol selectivity of 92%, yielding an excellent methanol space-time yield (∼0.9 g·g_cat^–1·h^–1) and a stability of 100 h under mild conditions (220 °C, 3 MPa). This is approximately twice that of the control catalyst and ranks among the top outcomes reported so far for Cu-based systems. Operando FTIR, structure–activity relationship, and DFT studies elucidate that the active Cu species at the Cu–ZnO interface function as intrinsic active centers, accelerating the formation of key intermediates (HCOO* and H₃CO*), leading to a lower activation-energy barrier. Therefore, this work presents an effective strategy for fabricating Cu nanocatalysts featuring a precisely controllable Cu–ZnO interface via a facile LDH topological transformation, offering a promising application path in the large-scale synthesis of methanol from CO₂ hydrogenation.

The transition toward sustainable plastics calls for biodegradable polymers with enhanced performance and scalable processing routes. Plant-derived nanofibers are promising reinforcements, yet their adoption is hindered by energy-intensive isolation, incompatibility with hydrophobic matrices, and aggregation during drying. Here, we report a dual-function reactive extrusion strategy that combines nanofibrillation and surface modification in a single step. Lignocellulosic fibers are prefunctionalized with maleic anhydride to introduce carboxyl groups while retaining native lignin, and in-situ transesterification during melt compounding generates well-dispersed cellulose nanofibrils covalently bonded to PBAT. This integrated approach removes the need for costly nanocellulose isolation and drying while simultaneously ensuring compatibility and mechanical integrity through both chemical bonding and the hydrophobic contribution of lignin. The resulting composite films exhibit a 30% increase in stiffness while maintaining superior tensile strength and strain at failure, along with a 42% and 56% reduction in water vapor and oxygen permeability, respectively, compared to neat polymers. Additionally, the preserved lignin imparts over 90% antibacterial activity, enabling improved fruit preservation, while many film trials confirmed effective soil moisture retention and good biodegradability. Overall, this work establishes a scalable, industry-ready route to transform raw biomass into multifunctional nanofillers, providing a green pathway toward high-performance composite films for packaging and agricultural applications.

Washing and thermal treatment are among the most promising technologies for managing municipal solid waste incineration fly ash (FA). However, the fate of residual ash after treatment remains uncertain and requires further investigation to achieve full resource utilization. In this study, the feasibility of using raw fly ash (RFA), washed fly ash (WFA), and thermally activated fly ash (TFA) as partial replacements for cement in composite cementitious materials was investigated. The macroscopic properties, strength development, environmental safety, and hydration mechanisms of FA-based composites were systematically examined. After the removal of hazardous substances, the physicochemical properties of WFA and TFA became closer to those of ordinary Portland cement (OPC). The mechanical performance of the composites followed the order TFA > WFA > RFA. At a 30% replacement level, the compressive strength of TFA reached 64.2 MPa, slightly higher than that of pure OPC and 103% greater than that of RFA. The corresponding carbon emission calibrated by strength is 29.5% lower than that of pure OPC, reaching 672.5 kgCO₂e/t. In terms of environmental performance, heavy-metal leaching from all FA-based composites met the relevant standards, and the chloride immobilization efficiency exceeded 90%. The crystalline phases of hydration products included ettringite (AFt), calcium silicate hydrate [C-(A)-S-H], and Friedel’s salt. During hydration, the formation of portlandite, precipitation of AFt, and deposition of C-(A)-S-H led to an interlaced microstructure in the TFA-derived composites, effectively refining the microstructure and thereby enhancing the macroscopic performance. These findings provide a reference pathway for the utilization of FA and contribute to the sustainable management of FA.

This study reports the development of a dual self-healing, antibacterial, and pH-responsive wood coating using intelligent microcapsule technology. Microcapsules were synthesized with UV wood wax oil (UVW) as the core and hydroxypropyl methylcellulose/TiO₂-modified chitosan as the shell, achieving 78.2% encapsulation efficiency. The microcapsules released contents most effectively in a pH 9 water, sustaining release for 1000 h following Fickian diffusion. The coating with 10.0% microcapsules reached a healing efficiency of 83.3% after 8 days at room temperature, while 2.0% microcapsule coatings achieved 42.9% healing under 10 min UV exposure. The 2.0% coating also demonstrated antibacterial activity against Escherichia coli (E. coli) at 75.82%. In addition, it showed minimal yellowing, gloss loss, and color change under cold liquid exposure. The coating exhibited strong mechanical performance, with a load-bearing capacity of 129.363 N, adhesion strength of 8.985 MPa, and maximum elongation at break of 8.87%. These results support the potential of this multifunctional coating for advanced wood surface protection.

Lignin biorefining technologies support the circular bioeconomy by transforming biogenic carbon within lignin into value-added aromatic compounds. While valorizing renewable feedstocks aligns with green chemistry principles, the inherent “greenness” of biorefining technologies is often overlooked. Thus, the goal of this perspective is to critically benchmark prominent lignin biorefining technologies, including organosolv, reductive catalytic fractionation (RCF), pyrolysis, and oxidation, by evaluating process performance and greenness using mass-based green chemistry metrics. Using aromatic monomer yields as a product benchmark, we compare the relative energy and material footprints of competing biorefining technologies to deconstruct lignin into small aromatics. Among biorefining technologies, the material footprints of liquid-phase processes are exacerbated by high solvent consumption, highlighting the need for integrated solvent recycling steps. Conventional thermal processes, such as pyrolysis, mitigate solvent consumption and can operate with relatively short process times, thus demonstrating lower material footprints and favorable energy economies compared to emerging technologies. Promoting solvent recycling alongside separation steps designed for material efficiency will further reduce the resource demands of lignin biorefining. Overall, we present insights into competing trade-offs between process productivity and the sustainability of biorefining technologies and identify challenges impeding sustainable biorefining through a quantitative, mass-based assessment.

Porous physical adsorbents with low cost hold great promise for direct air capture (DAC) of CO₂, offering a solution to the prohibitive costs of current technologies. However, traditional microporous adsorbents face severe diffusion limitations and sluggish adsorption kinetics under trace CO₂ conditions due to their narrow pore architectures. Here, we present a protozeolite-assisted kinetic regulation strategy to synthesize monolithic mordenite (MOR) zeolites with honeycomb-like, hierarchical micro-meso-macroporous networks. The hierarchical structure provides rapid mass transfer channels, while the binder-free monolithic architecture avoids pore occlusion and ensures efficient diffusion. Benefiting from enhanced site accessibility and optimized diffusion pathways, the honeycomb-like MOR exhibits a CO₂ breakthrough adsorption capacity of 1.15 mmol g^–1 at 400 ppm, significantly surpassing the breakthrough performance of conventional zeolitic materials. Combined Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations elucidate the hierarchical pore-driven enhancement of CO₂ diffusion coefficients (D_s) and establish the structure-diffusion-adsorption interplay. This work provides critical insights into the role of pore architecture in trace CO₂ capture and delivers guidelines for designing the next generation of high-capacity DAC adsorbents that align with the principles of green chemistry and sustainable engineering.

Grasslands represent one of the world’s largest yet most underexploited renewable biomass resources. Here, we present a techno-economic framework for transforming grass silage into edible protein and microbial lipids through mechanochemical and biocatalytic processing. Two biorefinery configurations were evaluated using stochastic and spatial modeling: a baseline system producing protein and biogas (Scenario 1) and an integrated design incorporating lipid fermentation (Scenario 2). Both achieve strong economic performance at industrial scale, with median net present values (NPVs) of £528 million and £1.21 billion, respectively, and protein production costs of £2.97–3.40 kg^–1─comparable to plant-derived alternatives. Sensitivity analysis reveals that protein extraction efficiency and product price dominate profitability, while scale and coproduct valorisation drive the largest gains in expected NPV. Spatial simulations show that sourcing 33,333 t y^–1 of wet silage (25% DM) is logistically feasible across UK grasslands at delivered costs of £51–58 t^–1, enabling decentralised, regionally integrated deployment. Together, these results establish grass-based biorefineries as a scalable and economically credible route to sustainable protein production, bridging agricultural residues and food technology. The study provides quantitative guidance on how process yield, market development, and spatial logistics can be co-optimized to accelerate the emergence of a circular, pasture-driven bioeconomy.

The treatment of fluoride-contaminated drinking water remains a critical environmental challenge. In capacitive deionization (CDI) systems, the strong binding affinity of certain electrode materials toward fluoride ions (F^–) often compromises the electrochemical reversibility and limits the regeneration capacity. In this study, superlong lanthanum metal–organic framework (La-BDC) nanowire was synthesized successfully by temperature-modulating crystal nucleation and growth, with a higher specific surface area (293.2 m² g^–1) and an average diameter of ∼20 nm for La-BDC-140 (heated at 140 °C for 20 h). More importantly, La-BDC-140 exhibits exceptional fluoride removal performance in CDI, achieving 28.7 mg g^–1 in 50 mL of 10 mg L^–1 NaF solution at 1.4 V, significantly higher than values reported in previous studies. In addition, the synergistic effect of alkaline electrolytes and reverse voltage can effectively facilitate the desorption process; hydroxide ions (OH^–) compete with F^– for binding to the La³⁺ center, thereby destabilizing the stable La–F bond. Meanwhile, the electrostatic force enhances the migration of fluoride ions away from the electrode surface. This significantly improves the electrodesorption efficiency of electrode materials with high affinity for fluoride ions, achieving a single-cycle desorption rate of approximately 95%. After 20 electrodesorption cycles in alkaline solution, the fluoride removal efficiency was maintained at over 80%, successfully addressing the regeneration challenge commonly associated with high-affinity adsorbents in CDI systems. This work provides a highly efficient and regenerable La-MOF-based electrode for CDI defluoridation, offering a novel approach for the electrodesorption regeneration of electrode materials exhibiting strong binding affinity toward F^–.

Dry reforming of methane (DRM) converts the greenhouse gases CH₄ and CO₂ into syngas for downstream Fischer–Tropsch synthesis. However, Ni catalysts deactivate rapidly by coking and sintering at high temperatures. Here we report a Ni₃Zn/MgAl₂O₄ catalyst that achieves exceptional stability by integrating dynamic carbon migration with dual-site electronic modulation. At 650 °C, the catalyst sustains stable operation for 90 h, delivering nearly double CH₄ and CO₂ conversions, while the carbon deposition rate was reduced to 1/28 of that on the Ni/MgAl₂O₄ catalyst. Combined experimental and theoretical studies reveal that Zn incorporation redistributes charge to generate polarized Ni^δ--Zn^δ+ sites, which weaken CO binding and promote cooperative CH₄ and CO₂ activation. Simultaneously, CH₄-derived carbon migrates into the Ni₃Zn lattice, reversibly forming a carbide phase (Ni₃ZnC_0.7) that prevents surface carbon accumulation. This synergy between electronic modulation and dynamic carbon accommodation provides a robust strategy for designing durable, coke-resistant Ni-based catalysts for DRM and related high-temperature reactions.

Lignocellulosic biomass films are promising green alternatives to petroleum-derived packaging. However, their high hydrophilicity and poor barrier properties remain critical challenges for commercialization. To address these critical challenges, herein, we propose a skin-mimetic surface engineering strategy to synergistically enhance the hydrophobicity and gas barrier properties of regenerated whole-component bamboo biomass films while feasibly regulating their biodegradability. Specifically, we constructed the skin-mimetic surface via an in situ ring-opening polymerization of epoxidized soybean oil (ESO), which was adsorbed onto the regenerated biomass film through soaking in an ESO solution. This skin-mimetic architecture endows the films with exceptional hydrophobicity, as reflected by a water contact angle of 115° and an 89% reduction in water absorption compared with that of the control sample. Furthermore, the skin-mimetic bamboo films exhibited enhanced barrier properties, showing 37–97% reductions in both oxygen transmission rate (OTR) and water vapor transmission rate (WVTR). The optimal barrier performance was observed at an epidermal thickness of 15 μm, with a WVTR of 63.4 g/m²·24 h and an OTR of 0.32 cm³/(m²·24 h·0.1 MPa). Besides, the epidermal layers allowed the modulation of the biodegradation rate under soil burial, with the film stability ranging from 10 to 150 days depending on the epidermal thickness. This work provides an efficient method to develop a high-performance, biodegradable bamboo-based packaging material.