Green Chemistry最新文献

In this study, we report the development of an environmentally friendly artificial Vitreoscilla hemoglobin (VHb) for the synthesis of 3-amino-[1,2,4]-triazole and [4,3-a]pyridine. We employed a strategy that combines porphyrin substitution with axial ligand mutations to create a highly active VHb oxidase containing cobalt protoporphyrin IX (Co(ppIX)), while simultaneously introducing double mutations (H85Y, P54C). This artificial enzyme catalyzes the cyclization desulfurization reaction of the corresponding 2-hydrazinopyridine and isothiocyanate in PBS containing 10% DMSO (v/v) under aerobic conditions at room temperature. This method addresses the limitations of catalytic activity observed in natural hemoglobin and provides a novel pathway for the green synthesis of nitrogen-containing heterocycles. Furthermore, the porphyrin ligand substitution strategy broadens the application scope of artificial metalloenzymes in non-natural reactions.

The atom transfer radical addition (ATRA) of alkyl halides enables efficient simultaneous C–C and C–halogen bond formation in a single step. However, the development of mild, cost-effective ATRA protocols for the reaction of bicyclic alkenes with functionalized haloalkanes remains a significant challenge and underexplored. Herein, we report visible-light-mediated ATRA haloalkylation of bicyclic alkenes using functionalized haloalkanes. This catalytic system operates under mild and peroxide-free conditions, enabling the construction of haloalkylated bicyclic frameworks in a complete atom-economy across diverse substrates with generally good stereoselectivities. Scalability studies and downstream derivatizations of the products underscore the synthetic utility of the present haloalkylation protocol. Additionally, mechanistic studies including in-depth DFT calculations, have clarified the reaction pathway and origin of stereoselectivity.

This review provides a comprehensive overview of optimization strategies for the synthesis of poly(hydroxyurethane)s (PHUs) via the most common route: cyclic carbonate (CC) aminolysis with amines. PHUs represent a sustainable alternative to conventional polyurethanes, eliminating toxic isocyanates and allowing the use of bio-based monomers. Despite these advantages, their broader industrial adoption is limited by slow polymerization kinetics, modest molecular weights, side reactions, and scalability challenges. Key factors affecting the reaction are examined, including the structure and substituents of CCs and amines, reaction conditions (temperature, time, molar ratios), solvent selection, and the use of plasticizers to mitigate hydrogen bonding limitations. Special attention is given to catalytic approaches, including fundamental catalysts, ionic liquids, dual catalysis, and catalyst-free methods. Strategies to control regioselectivity, side reactions and the influence of solvent choice are also discussed. The potential of bio-based materials for sustainable PHU production is also highlighted. Finally, perspectives are provided on enhancing PHU reactivity and advancing industrial scalability.

Silicon monoxide (SiO) is one of the most widely applied silicon-based anode materials for commercial lithium-ion batteries. However, conventional high-temperature vacuum solid–phase synthesis suffers from low conversion efficiency (<80%) and sluggish reaction kinetics, leading to an unfavorable cost-to-performance ratio of SiO anodes. In this work, photovoltaic-cutting waste silicon powder was utilized as a sustainable alternative to conventional micron-sized silicon (8–10 μm) for the efficient synthesis of SiO. The ultrafine particle size (∼0.3 μm) and high chemical reactivity of the waste silicon powder markedly accelerated the solid–phase reaction, thereby enhancing both the reaction rate and conversion efficiency. The migration and transformation behaviors of metallic impurities within the waste silicon powder, as well as their effects on SiO conversion efficiency, were systematically elucidated. This synthesis strategy achieved a high SiO conversion rate exceeding 95% and delivered excellent cycling stability when applied to lithium-ion battery anodes. Moreover, the as-prepared anode, even without surface modification, maintained a reversible specific capacity above 580 mAh g⁻¹ after 200 cycles at 0.5 A g⁻¹. The successful implementation of this strategy not only enables the high-value utilization of photovoltaic waste silicon powder and the efficient synthesis of SiO, but also offers a feasible and sustainable pathway toward the low-cost, green, and scalable industrial production of SiO.

Lignocellulosic wastes are naturally abundant carbon resources but have been underutilized due to their complex structure and recalcitrant nature. They require energy- and water-intensive processes, such as thermal, chemical, and/or mechanical pretreatments, for their valorization. Here, we report a new function of raw tree waste for driving the solar-powered oxygen reduction reaction (ORR) and biocatalytic oxyfunctionalization of hydrocarbons. We reveal that various lignocellulosic wastes, such as fallen leaves, waste wood, and wastepaper, can produce hydrogen peroxide (H₂O₂) using only O₂, water, and light without any pretreatment. In particular, fallen leaves from Platanus trees exhibit high rates of ORR, which is ascribed to their superior photophysical properties, such as higher light extinction, longer charge relaxation lifetime, and lower electron transfer resistance. We treated the fallen leaves of Platanus with H₂O₂-dependent unspecific peroxygenase to produce optically pure alcohols and epoxides through the stereoselective hydroxylation and epoxidation of hydrocarbons. The waste-enzyme hybrid catalyst achieved record-high turnover frequency and total turnover number. This study establishes raw biomass wastes as green photocatalysts for sustainable photobiosynthesis, presenting a successful example of waste-to-wealth conversion.

Zinc oxide nanowires (ZnO NWs) are promising materials for applications in sensors, transistors, and energy harvesting devices, owing to their unique structural and electronic properties. Despite advances in synthesis techniques, their environmental impacts remain an important consideration for sustainable nanomaterial development. In this study, we introduce a novel hydrothermal synthesis route inspired by Fehling's reaction, enabling the growth of ZnO NWs at low temperature and atmospheric pressure using bio-based and low-cost reagents such as glucose. To assess the environmental footprint of this novel method, a comparative life cycle assessment (LCA) methodology was employed using the OpenLCA software. The new route was benchmarked against a conventional sol–gel/chemical bath deposition synthesis which yields NWs of similar morphology. Results show that the Fehling-inspired method significantly reduces environmental impacts—by one to two orders of magnitude—across key categories such as climate change, ozone depletion, and human toxicity. In both methods, the silicon wafer substrate, electricity use, and hazardous waste treatment emerged as the dominant contributors to overall impacts, while chemical inputs had relatively minor effects, reinforcing the green chemistry potential of the proposed process. Sensitivity analyses explored several strategies for further impact reduction, including testing the influence of substrate materials, energy optimization, and regionalization. This work underscores the value of LCA as a tool for early-stage process evaluation and highlights practical opportunities for improving the sustainability of nanomaterial synthesis.

Catalytic oxidation offers a promising green approach for converting polyethylene (PE) into valuable oxygenated products under mild conditions. However, its large-scale application is hindered by the high cost and limited activity of existing catalysts. Here, we report a noble-metal-free, carbon-modified TiO₂ (C/TiO₂) catalyst for efficient oxidative conversion of PE under mild conditions (150 °C, 1.5 MPa air). After 24 h of reaction, a 120 wt% product oil-to-feedstock mass ratio and 74% carbon molar conversion (based on product oil) were achieved. The product oil primarily consists of long-chain dicarboxylic acids, confirmed by Fourier transforms infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and high-resolution mass spectrometry (HRMS). Importantly, C/TiO₂ also effectively converts real post-consumer PE plastics containing pigments, yielding similar product profiles. Spectroscopic and microscopic analyses reveal that carbon deposition increases oxygen vacancies, enhancing catalytic activity. This work offers an economic strategy for sustainable plastic waste valorization via tunable catalyst surface engineering.

Sustainable mitigation of atmospheric CO₂ requires not only efficient capture technologies but also environmentally responsible production of the materials that enable them. Many capture systems rely on materials synthesized via energy-intensive, multi-step processes from non-renewable feedstocks. To create truly sustainable solutions, there is a critical need for green synthetic pathways that minimize the overall carbon footprint of capture technologies from cradle to grave. Here, we report a diphenoquinone-based CO₂ capture material synthesized from the lignin-derived monomer via an enzymatic coupling reaction, establishing a sustainable route under mild, aqueous conditions without complex purification. The reaction selectively forms a crystalline C4–C4′ linked diphenoquinone, confirmed by comprehensive spectroscopic analyses, and avoids the structural heterogeneity typical of lignin-derived products. The resulting molecule exhibits a positive redox potential and robust reversibility, enabling electrochemical CO₂ capture and release with a specific capacity of 1.9 mmol g⁻¹. While initial performance is limited by the physical stability of the reduced species, this work establishes a new paradigm for lignin valorization by transforming renewable phenolics into discrete, functional molecules for CO₂ capture, and offers a broadly applicable platform for green synthesis of bio-derived quinones, providing a foundation for sustainable technologies within a circular carbon economy.