ACS Sustainable Chemistry & Engineering最新文献

{"title":"A Green, Additive-Free FeCl2-Catalyzed Microwave Platform for Acylsulfonamide Synthesis from Sodium Sulfinates and Dioxazolones in Ethanol","authors":"Long Yin Lam,Sinyu Ke,King Hong Chan,Cong Ma","doi":"10.1021/acssuschemeng.6c06920","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c06920","url":null,"abstract":"Abstract Acylsulfonamides are valuable carboxylic acid bioisosteres in medicinal chemistry and well applied in the pharmaceutical industry, but their preparation commonly relies on activated acyl/sulfonyl chlorides, sulfonyl azides, carbon monoxide surrogates, or stoichiometric activating reagents. Here, we report an additive-free, ligand-free, FeCl2-catalyzed microwave protocol for the synthesis of acylsulfonamides directly from bench-stable sodium organosulfinates and dioxazolones in ethanol. The method represents a distinct nitrene-transfer/S–N coupling platform that avoids precious metals, external oxidants or reductants, hazardous chlorinated reagents, and problematic polar aprotic solvents. Under microwave irradiation, diverse aryl, heteroaryl, and alkyl sulfinates are converted to acylsulfonamides within 5–15 min using only 2.5 mol % FeCl2. Most products are isolated by simple filtration, minimizing purification solvent demand and avoiding column chromatography. The utility of the protocol is demonstrated by gram-scale synthesis of the anticancer agent tasisulam and late-stage modification of pharmaceutically relevant molecules. Green chemistry metrics, including atom economy, reaction mass efficiency, optimum efficiency, and process mass intensity, reveal substantial advantages over our previously reported photocatalytic route and representative literature methods, particularly in additive economy, reaction time, scalability, and waste minimization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"237 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209586","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":"Leveraging Automation and Machine Learning To Bridge the Sustainability Data Gap","authors":"Eric T. Sletten,Lenz Fiedler,Pooja Dwivedi,Ilia Dorokhov,Peter H. Seeberger,Theodore Tyrikos-Ergas","doi":"10.1021/acssuschemeng.6c02432","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c02432","url":null,"abstract":"Abstract Materials with minimal environmental impact are urgently needed if we want to meet climate goals. The chemical industry, responsible for approximately 5% of global greenhouse gas emissions, is a critical sector for reducing or eliminating human-caused carbon dioxide. Designing inherently sustainable products and processes, emphasizing renewable feedstocks, greener solvents, and energy-efficient methods are at the core of “sustainable chemistry”. However, robust metrics and comprehensive chemical data are needed to measure the progress toward sustainability. Life cycle sustainability assessment is a key framework for fully quantifying potential sustainability impact but has several limitations that need to be overcome including a disconnect between the data demands of AI for predictive sustainability metrics and the data that exist. Advanced data-driven methods, coupled with standardized data workflows, can help bridge these gaps. Integrating ML with automated experimentation enables closed-loop optimization, embedding sustainability directly into chemical process design while acquiring high fidelity data, which can be later used.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209543","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":"CO2-Product-Driven Integrated Carbon Capture and Utilization to Produce Cyclic Carbonates","authors":"Alejandro Belinchón,Pablo Navarro,Pedro Carvalho,José Palomar","doi":"10.1021/acssuschemeng.6c08760","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08760","url":null,"abstract":"There is an urgent need to develop energy-efficient solutions for CO2 capture and utilization, because current integrated processes remain limited by the compatibility of the capture and conversion stages. This work proposes a novel product-driven carbon capture and utilization concept, in which the CO2-derived cyclic carbonate product is sequentially employed as a physical CO2 absorbent and subsequently as the reaction medium for its own synthesis, eliminating the intermediate solvent regeneration step. Density, viscosity, and CO2 solubility were experimentally determined for four cyclic carbonates, while cycloaddition reactions were performed under representative integrated process conditions using the ionic liquid [bmim]I as a catalyst. The complete process for natural gas purification was evaluated through conductor-like screening model (COSMO)-based/Aspen process simulation and life cycle assessment. Experimental and computational results demonstrate that propylene, butylene, and hexylene carbonates provide competitive CO2 absorption performance, extending the applicability of the proposed concept to other CO2-derived cyclic carbonates. More importantly, the direct use of the CO2-rich cyclic carbonate stream as the reaction medium was experimentally validated without significant thermodynamic or kinetic limitations despite the high product concentration. The proposed concept achieves a competitive energy demand and CO2-related emissions while avoiding deep vacuum operation and intermediate solvent regeneration.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151967","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":"Upgradation of n-Butanol to Jet-Fuel-Grade Butyl-butyrate and Hydrogen Catalyzed by Pincer-Ruthenium Complexes","authors":"Pran Gobinda Nandi,Vikas,Sunil Dhole,Akshai Kumar","doi":"10.1021/acssuschemeng.6c09214","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c09214","url":null,"abstract":"The production of jet-fuel-grade butyl-butyrate from butanol has been investigated using a series of NNN pincer-Ru catalysts. Notably, a majority of the considered pincer-Ru complexes, excluding the Ru precursors, demonstrated good activity toward the upgradation of n-butanol to butyl-butyrate. In particular, in the presence of 10 mol % of KOtBu at 160 °C, the complex [(MeBim2NNN)RuCl2(PPh3)2]Cl (1 mol %) based on the 2,6-bis(benzimidazole-2-yl)pyridine ligand demonstrated very high activity, giving up to 90% yield of butyl-butyrate starting from n-butanol after 72 h of reaction. The reaction proceeded with favorable green metrics (97.3% atom economy, 87.6% atom efficiency, 100% carbon efficiency, and 87% reaction mass efficiency). On the other hand, the complex ((p-OMe-C6H4)2NNN)RuCl2PPh3 based on the bis(imino)pyridine ligand exhibited the lowest activity and gave 40% yield of butyl-butyrate. Mechanistic studies reveal that the catalytic transformation of n-butanol to butyl-butyrate has a first-order dependence of the initial rate on the concentration of [(MeBim2NNN)RuCl2(PPh3)2]Cl, while a second-order dependence on the concentration of n-butanol is observed. The catalytically active species is homogeneous with a well-defined molecular nature; a few of these molecular species, including the resting-state (MeBim2NNN)RuHCl (experimentally trapped as its PPh3 adduct), have been identified by HRMS and NMR analysis. While the observed KIEs of 1.1 and 2.4 in experiments with C4H9OD and C4D9OD, respectively, are suggestive of the involvement of a rate-determining C–H bond activation, the corresponding activation Gibbs free energy is experimentally determined to be 25.3 kcal/mol by Eyring plot analysis. DFT studies further fortify the experimental observations while suggesting that the rate-determining step (RDS) involves the β-hydride elimination from hemiacetal coordinated pincer-Ru species with a barrier of 25.2 kcal/mol leading to the extrusion of butyl-butyrate along with the formation of the resting-state (RS) species (MeBim2NNN)RuHCl. In stark contrast, the catalysis with ((p-OMe-C6H4)2NNN)RuCl2PPh3, which is the least active among the considered catalysts, is kinetically unfavorable (ΔG160‡ = 34.6 kcal/mol). This study not only provides a convenient high-yield synthetic protocol to jet-fuel-grade butyl-butyrate via pincer-Ru-catalyzed dehydrogenative coupling of n-butanol but also provides key mechanistic insights that could leverage the global efforts in designing effective dehydrogenative esterification catalysts for the upgradation of alcohols.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"238 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151977","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":"Alloying-Induced Asymmetrical Pd Sites Enabling Efficient and Durable Formic Acid Dehydrogenation","authors":"Zhengxu Yan,Xujia Cao,Shuai Zhu,Yunyun Gui,Yuan Lin,Linghao Yu,Lijun Liu","doi":"10.1021/acssuschemeng.6c09715","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c09715","url":null,"abstract":"Abstract Developing Pd-based catalysts for formic acid (HCOOH) dehydrogenation is of great significance to the advancement of renewable hydrogen utilization. However, traditional Pd surfaces typically display symmetrical electronic and geometrical configurations that suffer from both selectivity issues and CO poisoning phenomena, deteriorating their long-term HCOOH dehydrogenation performance. In this study, we report a bismuth–palladium (BiPd) alloy catalyst with asymmetric electronic and geometric Pd sites that achieved an exceptional H2-evolving turnover frequency (5893.7 h–1) of HCOOH dehydrogenation while maintaining over 96% catalytic activities spanning consecutive 15-round experiments. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and synchrotron X-ray absorption spectroscopy (XAS) characterizations verified the successful construction of BiPd alloys and that Bi components desymmetrized the electronic configuration of Pd sites toward the thermodynamically favored HCOOH dehydrogenation pathway for H2 evolution. On the other hand, in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) and kinetic isotope effect experiments combined with density functional theory (DFT) calculations collectively demonstrated that Bi also diluted Pd ensembles, and the resulting asymmetric Pd architectures reduced the diversity of *CO adsorption configurations on the surface of BiPd alloys, effectively mitigating CO poisoning. This work underscores the critical role of alloying engineering in designing Pd-based catalysts for practically implementing sustainable hydrogen release from liquid organic hydrogen carriers.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209183","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":"Interfacial Strong Metal-Support Interaction over Ni/CeO2 for Hydrodeoxygenation of Guaiacol to Phenols","authors":"Bingbing Qiu,Xingkai Zhai,Weiyao Cao,Huaqiang Chu","doi":"10.1021/acssuschemeng.6c08806","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08806","url":null,"abstract":"Abstract The hydrodeoxygenation (HDO) of guaiacol demonstrates significant potential for the efficient conversion of biomass into biofuels and fine chemicals. In this work, a Ni/CeO2 catalyst was synthesized via a combined hydrothermal and pyrolysis method; the catalytic performance of the material was evaluated, with a water-glycerol mixture employed as the in situ hydrogen donor. Under the optimal conditions of 280 °C and 6 h, the guaiacol conversion reached 56.71%, and the catalyst maintained a conversion rate close to 50% after four consecutive uses, showing excellent reusability. Combined with product distribution and characterization results, the HDO reaction pathways and mechanisms of guaiacol over Ni/CeO2 were proposed. Metallic Ni active sites, oxygen vacancies, and surface acid sites exerted a synergistic effect to modulate the cleavage of C–O bonds and product selectivity. This study provides a feasible strategy for the selective conversion of guaiacol into high-value phenols.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209184","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":"Facile Fabrication of Sustainable Chitosan Bioplastics Integrating High Strength, Water Resistance, and Closed-Loop Recyclability","authors":"Mingshuai Guo,Zitong Wang,Jialong Zhao,Zhiping Mao,Bijia Wang,Liduo Rong,Xueling Feng","doi":"10.1021/acssuschemeng.6c07668","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c07668","url":null,"abstract":"The growing environmental concern over petroleum-based plastics has intensified the demand for sustainable alternatives with high performance and reliable processability. Bio-based plastics have attracted considerable attention as sustainable alternatives to petroleum-derived plastics. However, despite their environmental advantages, their development and application are severely constrained by the necessity for tedious chemical modification and complex processing. Herein, we propose a covalent adaptable network strategy to transform chitosan (CS) into a thermally processable bioplastic through simple and efficient dynamic covalent enamine cross-linking. The enamine bonds enable network rearrangement upon heating, imparting hot-press processability, thermal repairability, and closed-loop recyclability to the material. The resulting bioplastic exhibits a high flexural strength of 189.8 MPa, excellent moisture and solvent resistance, favorable recyclability, high thermal stability, a low thermal expansion coefficient of 1.05 ppm k−1, superior quantitative green chemistry metrics, and rapid soil-burial disintegration. With these advantageous features, the developed bioplastic represents a promising sustainable substitute for conventional petroleum-based plastics.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151973","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":"Critically Assessing Environmental and Resource Competitiveness for Layered Oxide Sodium-Ion Batteries against Lithium-Ion Batteries","authors":"Quanwei Chen,Junjie Chen,Xin Lai,Fu Liu,Zhicheng Zhu,Wentian Zhang,Fang Zhao,Ning Li,Yunfeng Huang,Xiaolong Song,Xuebing Han,Yuejiu Zheng","doi":"10.1021/acssuschemeng.6c03683","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c03683","url":null,"abstract":"Abstract Sodium-ion batteries (SIBs) have garnered widespread attention as a highly promising alternative technology to lithium-ion batteries (LIBs). Based on life cycle assessment and supply risk evaluation methods, this study establishes an evaluation framework to compare the resource–environment impacts of two SIBs and four LIBs. Results indicate that layered oxide SIBs reduce toxicity and human health impacts by more than 50% compared to LiCoxNiyMn1–x–yO2 (NCM) batteries, primarily due to their avoidance of copper and cobalt. Among LIBs, LiFePO4 (LFP) exhibits the lowest greenhouse gas emissions, endpoint environmental impacts, and supply risks. The environmental burden of NCM batteries alleviates with increasing nickel content, but emissions from cathode materials remain above 37% of the total. Due to the geographical concentration and geopolitical instability of lithium, cobalt, and nickel in LIBs, their supply risk (208–815 × 107) is higher than that of SIBs (18–26 × 107). Competitiveness evaluation indicates that layered oxide SIBs exhibit superior sustainability (0.393–0.489) compared to high-nickel NCM (0.959). Moreover, optimizing production layout can reduce the carbon footprint by 15%, and increasing energy density can lower environmental burden and resource demand by 66%. This study provides a quantitative decision-making basis for battery technology selection, supply chain risk management, and global low-carbon layouts, holding significant importance for advancing the energy transition.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209182","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":"Fluorite-Dominated High-Entropy Composite Oxide for Chemical Looping Steam Reforming of Biomass Tar","authors":"Ditao Pu,Peng Wang,Qiang Hu,Yang Yang,Haiping Yang,Hao Jiang,Jiageng Xia,Tania Farias,Hanping Chen","doi":"10.1021/acssuschemeng.6c07953","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c07953","url":null,"abstract":"High-entropy oxides (HEOs) have recently been proposed as promising catalysts for tar cracking, a major challenge in biomass gasification. However, their catalytic performance and reaction mechanisms remain insufficiently understood. In this work, fluorite-dominated high entropy composite oxides (HECOs) with different fuel-to-oxidizer oxygen-equivalent ratios (F/O) were synthesized by the glycine-nitrate process (GNP). The as-prepared HECOs (Fe0.2Co0.2Ni0.2Mg0.2Ce0.2)O2–δ were applied as oxygen carriers (OCs) for the chemical looping steam reforming of toluene (CL-SRT), a model compound of biomass tar. Results showed that the synthesized HEOs presented abundant surface porosity and uniform elemental distribution. The higher F/O ratio and temperature improved the CL-SRT performance, while the S/C ratio effectively tuned product composition. Under the conditions of 800 °C and S/C of 2.4, the OC of F/O = 2.0 achieved the optimal reforming performance, with a syngas yield and purity of 4.01 L/g and 86.30%, respectively. The longtime life cycle performance test showed that the toluene conversion stayed at about 97.36% and syngas purity remained near 86%, with only slight carbon deposition observed. The structural characterization suggested that the dynamic exsolution of FeNi alloy may generate additional active sites for toluene conversion, contributing to the enhanced reforming performance. These results highlight fluorite-dominated HECOs as viable oxygen carriers for efficient biomass tar reforming and H2-rich syngas production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151966","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 and Stable Fractionation of Pennisetum × sinese by Three-Stage Countercurrent Recycling of a Fermentation Compatible Deep Eutectic Solvent","authors":"Changliu He,Chengye Li,Yuan Fang,Xi Zhao,Tianwei Tan,Huimin Yun,Xu Zhang","doi":"10.1021/acssuschemeng.6c09016","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c09016","url":null,"abstract":"Efficient fractionation of lignocellulosic biomass is essential for maximizing carbon utilization and enabling integrated biorefinery processes. We developed a three-stage countercurrent recycling process using a fermentation compatible deep eutectic solvent (DES) for Pennisetum × sinese. In this process, regenerated DES contacted the partially fractionated solids in the final stage, while the lignin-rich DES stream was used for the initial treatment of fresh biomass. This countercurrent arrangement improved the use of the remaining solvent capacity. Lignin and hemicellulose removals remained at approximately 90 and 95%, respectively, over 12 recycling cycles. The glucose yield remained at 34.28–37.26 g per 100 g of dry biomass, with fluctuations between cycles being smaller than those observed in conventional batch cycles. In addition, 10–14 g of low-molecular-weight lignin was recovered per 100 g of dry biomass, with limited structural variation during recycling. The DES recovered remained suitable for microbial fermentation and showed high glycerol utilization, demonstrating its potential for further biological conversion. Overall, the three-stage countercurrent recycling process provides a practical strategy for extending DES reuse and integrating biomass fractionation, fermentable-sugar production, lignin recovery, and further valorization of the solvent within a lignocellulosic biorefinery.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"238 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151969","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}