ACS Sustainable Chemistry & Engineering最新文献

{"title":"Sustainable Fe–Cr–Ni Stainless Steels via Hydrogen Reduction of Blended Oxides","authors":"Maryam Al-Buainain, David C. Dunand","doi":"10.1021/acssuschemeng.5c02264","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c02264","url":null,"abstract":"Hydrogen reduction of iron oxide is a promising solid-state, moderate-temperature steelmaking approach with no direct CO₂ emission. However, alloy steels require alloying elements such as Cr, whose oxides are too thermodynamically stable to be reduced by hydrogen when they are in pure form. Blends of Fe₂O₃, NiO, and Cr₂O₃ particles are shown here, using <i>in situ</i> X-ray diffraction and <i>ex situ</i> metallography, to undergo a sequential hydrogen reduction up to 1300 °C, for two Fe–Cr–Ni alloys with low-Ni (Fe-18Cr-8Ni, wt %) and high Ni (Fe-18Cr-35Ni) content, corresponding to two major stainless steels (304 and 330, respectively). Sintering during hydrogen reduction entraps small amounts of Cr₂O₃ particles (&lt;1.1 vol %) while also leaving residual porosity, which can be eliminated in a subsequent step via remelting or forging. The forging case demonstrates a fully solid-state path, from ore to part, with the following benefits: (i) no melting or solidification, (ii) low energy footprint, (iii) low CO₂ footprint, and (iv) high material utilization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acetaldehyde Production via Photocatalytic Heterolytic Dehydrogenation of Ethanol Accelerated by Tuning Lewis Acid–Base Pairs over CsGeX33 (X = Cl, Br, I) Halide Perovskites","authors":"Yan Jie Li, Shuang Chao Tang, Ting Zhao, Jie Tian, Tao He, Yanjie Wang, Zhuoyu Ji, Yu Li, Yitao Dai, Wan In Lee, Detlef W. Bahnemann, Jia Hong Pan","doi":"10.1021/acssuschemeng.5c00309","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00309","url":null,"abstract":"Photocatalytic hydrogen (H₂) production from ethanol offers the dual advantages of low energy consumption and the cogeneration of high-value chemicals. However, challenges remain in enhancing product selectivity and elucidating the precise reaction pathway. In this study, lead-free halide perovskites CsGeX₃ (X = Cl, Br, I) were synthesized and utilized for the simultaneous generation of H₂ and acetaldehyde via photocatalytic ethanol oxidation under UV and visible light irradiation. Among them, CsGeI₃ is reported for the first time as a highly effective photocatalyst, exhibiting the highest activity for both the hydrogen evolution reaction (HER) and the ethanol oxidation reaction (EOR). Under UV light irradiation for 3 h, CsGeI₃ achieves H₂ and acetaldehyde yields of 97.74 and 92.08 μmol g^– 1, respectively, with an apparent quantum yield (AQY) of 2.31% for H₂. Optical characterization and density functional theory (DFT) calculations revealed that the Lewis acid–base properties of CsGeI₃ are mainly governed by the halogen component, enabling the selective activation and cleavage of the α-C–H and O–H bonds in ethanol, promoting heterolytic reactions that enhance the formation of both H₂ and acetaldehyde. This study provides new insights into the application of lead-free halide perovskites in tunable solar fuel generation and selective value-added chemical synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbon Footprint and Decarbonization Potential of Battery-Grade Synthetic Graphite","authors":"Fang Wang, Shaojun Zhang, Min Liu, Yiling Xiong, Daniel De Castro Gomez, Xin He, Mohammed A. Almoniee, Omar Hurtado Perez, Ziyu Liu, Xuexing Pan, Guangliang Lin, Ye Wu","doi":"10.1021/acssuschemeng.5c00921","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00921","url":null,"abstract":"Natural graphite was listed as a critical mineral due to the demand surge for battery anodes. However, synthetic graphite (SG) dominates the battery anode market because of its superior product performance. The lack of clarity regarding SG production and its carbon footprint (CF) poses challenges to the implementation of battery CF regulations. Here, the process-resolved inventories of 12 operational and 22 upcoming SG plants in China were examined, representing major capacities of global battery-grade SG. We reveal that the average plant-specific CF is 9.0 tonne CO₂ per tonne of SG (tCO₂/t), with a wide range of 6.8 ∼ 12.9 tCO₂/t, due to variances in feedstocks and energy efficiency. Reinforced premium SG that undergoes additional carbonization processes and uses oil-based needle coke as the main feedstock exhibits a higher CF of 11.2 tCO₂/t. We further project that the utilization of renewable electricity and green hydrogen in SG production could effectively reduce the CF by 41% to 70%, presenting substantial decarbonization potential for battery anode materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-Function Monoliths Prepared by Supercritical CO2 Foaming to Control Aedes aegypti","authors":"Glaucia Burin, Vinícius Pires, Elaine C.M. Cabral-Albuquerque, Silvio A.B. Vieira de Melo, Gabriel B. Faierstein, Rosângela M.R. Barbosa, José Miranda, Fabio R. Formiga, Hermínio C. de Sousa, Mara E.M. Braga","doi":"10.1021/acssuschemeng.5c01126","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c01126","url":null,"abstract":"<i>Aedes aegypti</i>, a vector of dengue, yellow fever, chikungunya, and Zika, is a major public health threat in Brazil and tropical countries; now, it is also in Europe. Tea tree oil (TTO) and curcuminoids (Cur) have shown larvicidal and repellent effects against <i>A. aegypti</i>. This study developed porous poly(ε-caprolactone) (PCL) monoliths with Pluronic F-68 (Plu) using the supercritical CO₂ foaming method (SFM) for controlled TTO and Cur release. SFM conditions and monolith compositions were varied to modify monolith properties. Bioactive agents’ release was tested in water and air (gravimetric and wind tunnel) with volatiles persisting for over 15 days. Larvicidal and repellent tests were performed on <i>A. aegypti</i> colonies. This study prospects the TTO- and TTO-Cur-loaded PCL:Plu monoliths as emerging and sustainable biomaterials for mosquito control, acting as both larvicidal and insect repellents.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165452","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Role of Systems Engineering in Energy Transition – A Framework to Analyze Green Methanol Synthesis in Texas","authors":"Abdullah Al-Aboosi, Debalina Sengupta, Mahmoud El-Halwagi, Fadhil Al-Aboosi, Wei Zhan","doi":"10.1021/acssuschemeng.5c00577","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00577","url":null,"abstract":"The new era of energy transition is significantly impacted by technological and economic advances in process technology. It is driven by the need to use renewable energy resources, reducing carbon dioxide, and other greenhouse gas emissions. Electrification has a major role to play in the energy transition, and it can contribute to renewables integration in the current energy mix while also minimizing nonpoint and distributed emissions. However, for hard-to-decarbonize sectors such as refining and chemical manufacturing processes, a dual challenge exists to simultaneously electrify and reduce emissions while supplying the continuous energy required for industrial processes, thereby highlighting the need for wider systems analysis and integration with process technology. The main objective of this work was to design a novel framework for producing green methanol while integrating renewable energy sources into the energy mix. The framework is tested for the viability of a green methanol facility in Texas. Three coastal counties in Texas with five greenhouse gas-emitting facilities were chosen for the case study. Scenarios included incorporating solar photovoltaics (PV) with battery storage, supplementing on-grid and off-grid energy production for electricity generation. Hydrogen required in the methanol production process is supplied through green hydrogen production process, through desalination of seawater, and an integrated system of nanofiltration (NF), reverse osmosis (RO), and membrane brine concentration (MBC) (to avoid coastal brine discharge) is considered. An electrolyzer for producing hydrogen and an electric boiler for providing the required heat to the process are included. The carbon capture unit is designed to accommodate carbon emitted from industrial facilities and power plants at the chosen site. A comprehensive techno-economic analysis (TEA) shows that the production cost for green methanol using the on-grid system is lower than the off-grid system due to cost of batteries. However, life cycle assessment (LCA) demonstrates that adopting an off-grid system produces nearly zero carbon emissions. The internal rate of return (IRR) for the largest methanol production facility in the on-grid case is 32%, while the off-grid case with battery integration is 24%. A sensitivity analysis shows a reduction in production costs through multiple timeline scenarios from 2025 to 2050.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Dynamics Insights of CO2 Capture through Phosphonium-Based Deep Eutectic Solvents for Direct Air Capture","authors":"Rajib Nandi, Nabendu Paul, Tamal Banerjee","doi":"10.1021/acssuschemeng.4c10594","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10594","url":null,"abstract":"Negative emission technologies (NETs) have emerged as a mandatory step to achieve the respective sustainable goals of this generation, and direct air capture (DAC) is the newest addition to this class. Conventional amine- and alkaline-based solvents commonly used for DAC pose various operating disadvantages, and for that reason, deep eutectic solvents (DESs) are seen as a promising sustainable alternative solvent for this purpose. In this study, three DESs based on different compositions of tetrabutylphosphonium bromide (TBPBr) and triethylene glycol (TEG) are computationally studied with the help of molecular dynamics (MD) and density functional theory (DFT). The systems were analyzed based on intermolecular interactions such as radial distribution function, combined distribution function, hydrogen bonds, interaction energy, and diffusion behaviors. The results indicated the ability of the long-chained phosphonium cations to facilitate CO₂ molecules in a cage-like structure, whereas TEG molecules proved to be the deciding factor due to their higher polarity. DES2, with a 1:2 molar ratio of TBPBr:TEG showed better structural distribution and affinity toward CO₂ overall, which was confirmed with DFT studies. Finally, DES2 was studied under atmospheric conditions (400 ppm of CO₂) to confirm the possibility of this solvent being used as a DAC solvent. This showed very promising selectivity for CO₂ molecules over nitrogen and oxygen molecules.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dialdehyde Polysaccharides as Templates for Green Synthesis of Polypyrrole-Based Materials without Oxidative Polymerization","authors":"Jan Vícha, Lukáš Münster, Filip Latečka, Martina Martínková, Zdenka Víchová, Ondřej Vašíček, Petr Humpolíček","doi":"10.1021/acssuschemeng.5c02711","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c02711","url":null,"abstract":"Polypyrrole (PPy) is one of the most promising conductive polymers, with potential applications in energy storage, flexible electronics, and biomedicine. Broader use of PPy-based materials is, however, limited by harmful reactants used in their preparation and by the absence of strong interactions between relatively chemically inert PPy and the used matrices. Here, an innovative and green method is introduced based on a spontaneous condensation reaction between dialdehyde polysaccharides (DAPs) and pyrrole. The unique structure of DAPs spontaneously facilitates the chaining of pyrrole cycles into PPy copolymers without any added oxidizing agent or catalysts. This presents a new approach for preparing PPy-based materials with low cytotoxicity and strong antioxidative, anti-inflammatory, and immunomodulatory effects, ideal for biomedical applications. Moreover, this method can be combined with traditional oxidative polymerization to prepare covalently linked PPy composites with greatly improved resistance toward wear and loss of conductivity.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of a Green and Rapid Emulsive Liquid–Liquid Microextraction Method for Organophosphate Insecticides","authors":"Yulin Wang, Xiaoning Wei, Yajie Yue, Qingrong Peng, Xianzhao Zhang, Agnieszka Brandt-Talbot, Jiajun Han, Xu Jing","doi":"10.1021/acssuschemeng.5c04394","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c04394","url":null,"abstract":"This study presents a rapid method for detecting organophosphate insecticide residues using emulsive liquid–liquid microextraction combined with ultraviolet spectrophotometry (ELLME-UV). By employing the conductor-like screening model for real solvents to predict the chemical potentials of 17 extractants, oleic acid was identified as the optimal extractant owing to its high binding affinity, eliminating the need for trial-and-error selection. In the ELLME-UV process, an oil-in-water emulsion was formed by combining oleic acid with an aqueous alkaline solution, followed by sample addition, allowing rapid extraction within 1 min. Then, citric acid was added to induce rapid demulsification and separate oleic acid from the sample within 10 s, eliminating the need for a time-consuming centrifugation step. Under alkaline conditions, p-nitrophenol, prepared from parathion-methyl, exhibited a strong UV signal, and it was efficiently transferred to the separated oleic acid phase, enabling its detection in a 96-well plate within 1 min. Using pH adjustment, oleic acid was successfully used as an extractant, achieving emulsification and demulsification in the sample. By integrating extraction and derivatization into a single step, the proposed method simplifies sample pretreatment and detection, increasing the overall efficiency. The ELLME-UV method was successfully applied to various matrices, and recoveries ranged from 85.3 to 102.9%, with relative standard deviations of 0.6–4.5%, demonstrating its accuracy and reproducibility. These results highlight the potential of the proposed method as a rapid, simple, and environmentally sustainable solution for detecting organophosphate insecticide residues. This study highlights the environmentally friendly properties of oleic acid, which has historically been difficult to emulsify.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Recycling of PET-PE Multilayer Packaging Materials Based on Enzymatic Depolymerization of PET","authors":"Daan M. van Vliet, Jurgen J. Mateman, Rick H.A.M. van de Vondervoort, Antoine P. H. A. Moers, Lucas Collazo, Ana Mencher, Marc W. T. Werten, Shanmugam Thiyagarajan, Arno Cordes, Christian Sonnendecker, Eggo U. Thoden van Velzen, Rosa Doménech-Mata, Juan Antonio Tamayo-Ramos, Mattijs K. Julsing, Tom A. Ewing","doi":"10.1021/acssuschemeng.4c09388","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09388","url":null,"abstract":"The transition to a sustainable, circular economy requires more plastic waste to be recycled into high-quality recycled plastics. However, it is challenging to recycle mixed waste fractions or common multilayer materials by using current mechanical recycling technology. Enzymatic hydrolysis potentially offers a solution because of its mild conditions and selectivity. In this study, we show that polyester hydrolases can be applied to recycle PET-PE multilayer packaging waste without costly amorphization pretreatment. Polyester hydrolases were produced by recombinant <i>Pichia pastoris</i> yeast and used to efficiently depolymerize the PET layer of PET-PE multilayer trays. High yields were obtained at laboratory scale with unpurified enzyme and high PET-PE loading (10–20% w/w PET-PE, ≥94% PET depolymerization, and ≥80% terephthalic acid recovery). The enzymatic reaction was scaled up to 4.5 kg of PET-PE production waste. After depolymerization (≥95% PET depolymerized), terephthalic acid was isolated and repolymerized into rPET. The remaining PE layer was recovered, treated with an alkaline cleaning step to remove residual PET contamination, and successfully reprocessed into rPE films with similar properties to virgin low-density PE. This study demonstrates the applicability of enzymatic hydrolysis for the recycling of PET-PE multilayer materials and highlights its general potential for the recycling of polyesters in mixed post-consumer waste.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"71 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupling Mechanochemistry with Advanced Oxidation and Chelation for Sustainable Recovery of Spent Ternary Lithium-Ion Batteries","authors":"Jun-Sik Sin, Qian Xu, Hao Deng, Jianjian Tang, Zhilin Liang, Longsheng Wu, Jingping Hu, Huijie Hou, Jiakuan Yang","doi":"10.1021/acssuschemeng.5c02538","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c02538","url":null,"abstract":"The surge in spent lithium-ion batteries poses significant environmental risks, yet conventional recycling methods suffer from high energy consumption, equipment corrosion, and secondary pollution. Here, we develop a sustainable approach integrating mechanochemistry with advanced oxidation for recovering valuable metals from spent ternary lithium-ion batteries. Under optimized conditions, exceptional leaching efficiencies of 98.89%, 98.90%, 97.42%, and 98.99% were achieved for Li, Ni, Co, and Mn, respectively. The free radical capture experiments demonstrated that the mechanochemical process activates ammonium persulfate, generating hydroxyl and sulfate radicals, which was further confirmed through selective radical quenching experiments. The synergistic effect of these radicals induces the collapse of the layered structure of cathode material, as evidenced by X-ray diffraction analysis. X-ray photoelectron spectroscopy demonstrated that citric acid facilitates the reduction of high-valence metal ions to their soluble states while maintaining an acidic environment conducive to metal leaching. This innovative approach eliminates the conventional separate leaching step by employing a wet ball-milling process where citric acid simultaneously chelates and reduces metal ions, resulting in a significantly homogeneous precursor that directly enhances the final calcination product. The regenerated ternary cathode material exhibited excellent electrochemical performance with a discharge capacity of 125 mAh·g^–1 and 94.64% capacity retention after 100 cycles. Life cycle assessment indicated significantly reduced environmental impact compared to traditional hydrometallurgical processes. This study provides new insights into the mechanistic role of free radicals in solid-phase mechanochemical systems and establishes a sustainable strategy for battery recycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"244 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}