ACS Sustainable Chemistry & Engineering最新文献

{"title":"Crafting an Exceptionally Redox-Active Organic Molecule Boasting Superior Electron Mobility for High-Performance Electrochemical Desalination","authors":"Yueheng Tao, Jing Jin, Yujie Cui, Houxiang Wang, Zhangjiashuo Qian, Minjie Shi","doi":"10.1021/acssuschemeng.4c06939","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06939","url":null,"abstract":"Access to freshwater is crucial for a sustainable environment and human ecosystems. Hybrid capacitive deionization (HCDI) based on attractive pseudocapacitive reactions is considered a promising environmentally friendly and energy-saving electrochemical desalination technology. However, the application of HCDI technology is still limited, mainly due to the unsatisfactory ion adsorption ability of the pseudocapacitive electrode. Herein, we unveil an innovative redox-active organic molecule (PATD) that showcases outstanding pseudocapacitive properties for electrochemical desalination. Notably, the integration of redox-active C═O and C═N groups in the PATD molecule promotes stable and efficient pseudocapacitive reactions. Additionally, the rigid molecular structure, combined with a minimal HOMO–LUMO energy gap, ensures exceptional redox characteristics and superior electron transfer capability of the PATD molecule, which are substantiated by experimental evidence and theoretical studies. As an electrode, the PATD molecule exhibits significant pseudocapacitive characteristics along with excellent long-term stability, retaining 89.0% of its capacitance after 5000 cycles in a NaCl aqueous solution. In practical applications, the developed HCDI device incorporating the PATD electrode demonstrates a remarkably high salt removal capacity of 56.9 mg g^–1, a swift average removal rate of 1.9 mg g^–1 min^–1, and consistent regeneration performance while attaining reliable energy recovery, which highlights its promising prospects for sustainable desalination technologies.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452076","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":"Unlocking the Potential of Dolomite for Developing More Sustainable Cementitious Materials through Partial Calcination","authors":"Yukun Qin, Xiong Qian, Yong Tao, Chuanlin Hu, Fazhou Wang","doi":"10.1021/acssuschemeng.4c06486","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06486","url":null,"abstract":"Waste dolomite powder, a widely available industrial byproduct, has recently gained attention as a potential supplementary cementitious material. However, its inert reactivity challenges its potential for substantial cement replacement. This study explores the effectiveness of partially calcined dolomite (PCD) integrated with calcined clay for a high cement substitution level. A novel partial calcination method is introduced to optimize the decomposition of MgCO₃ and CaCO₃ to produce a core–shell structure with a highly reactive external CaO/MgO layer and a dense internal core of CaCO₃ and MgO. This configuration significantly enhances the formation of calcium silicate hydrate gels and carboaluminate phases, improving the overall strength of the material by over 90% at both 7 and 28 days compared to the sample with uncalcined dolomite. Additionally, the formulation of the proposed materials reduces CO₂ emission by 43% and energy consumption by 47% without sacrificing compressive strength. This innovative calcination technique broadens the application of waste dolomite in the development of sustainable cementitious materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452077","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":"Toward Sustainable Adhesives with Biodegradability, Scalability, and Removability: Poly(butylene succinate)-Based Hot-Melt Adhesives","authors":"Kwang-Hyun Ryu, Ji-Hyun Cho, Tae-Hyung Lee, Hoon Kim, Gi-Yeon Han, Jong-Ho Back, Hyun-Joong Kim","doi":"10.1021/acssuschemeng.4c03234","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c03234","url":null,"abstract":"Previous studies aiming to achieve sustainability in adhesive materials, primarily focused on the integration of bioderived or biodegradable components. However, existing sustainable adhesives often prioritize permanent adhesion over removability, which limits their recyclability. Herein, we introduce an innovative approach for producing scalable, biodegradable, and removable hot-melt adhesives, offering sustainability. Polybutylene succinate (PBS) was selected as the base polymer because of its excellent melt processability, biodegradability, and commercial availability. To impart adhesiveness, three biomass-derived tackifiers were incorporated; basic rosin, disproportionated rosin, and rosin ester. The use of a twin-screw extruder enabled the efficient mixing of the base polymer and tackifiers for large-scale production at the kilogram scale. Our investigation revealed that basic rosin exhibited optimal compatibility and wettability, which were attributed to its high acid value. The high acid value promoted rapid crystallization and minimized crystal defects. A correlation between the crystallization behavior and adhesion strength was also established, identifying the optimal composition. The optimal composition yields a satisfactory adhesion strength (2.5 N/25 mm) that makes it suitable for removable or repositionable adhesives. Additionally, our optimized adhesive exhibited sufficient biodegradability and was completely decomposed by lipase within 21 d, which has not been observed in previous sustainable hot-melt adhesive studies. This study provides a practical pathway for enhancing adhesive sustainability with the potential for further advancements in tailoring the adhesion strength for diverse applications in future research.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452006","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":"Renewables-Based Routes to Paracetamol: A Green Chemistry Analysis","authors":"Jimin Park, Caria Evans, Jacob Maier, Marta Hatzell, Stefan France, Carsten Sievers, Andreas S. Bommarius","doi":"10.1021/acssuschemeng.4c05353","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05353","url":null,"abstract":"Three potential routes for paracetamol synthesis from renewable phenol feedstock were examined and compared to each other and existing industrial routes with respect to Green Chemistry metrics and industrial viability. The routes tested were the acetamidation of hydroquinone, the imination and reduction of benzoquinone, and the hydrogenation of 4-nitrophenol. The hydroquinone and benzoquinone routes suffered from poor conversion and selectivity. The 4-nitrophenol route achieved good conversion, yield, and Green Chemistry metrics and is the most industrially viable of the three routes. When compared to existing routes, the 4-nitrophenol route is comparable or superior in terms of reactor metrics, Green Chemistry considerations, and raw material costs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452007","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":"Visible Light Induced Synthesis of 2-Benzoxazolecarboxamides Promoted by a Conjugated Microporous Polymer","authors":"Yujie Zhang, Rui Wang, Cuifen Lu, Chao Ma, Feiyi Wang, Guichun Yang, Yuexing Zhang, Junqi Nie","doi":"10.1021/acssuschemeng.4c05275","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05275","url":null,"abstract":"A new and effective protocol driven by visible light has been introduced for the first time to synthesize 2-benzoxazolecarboxamides from benzoxazinones and amines in the presence of a conjugated microporous polymer, PATP. The reaction produced a variety of 2-benzoxazolecarboxamides in moderate to good yields while demonstrating excellent functional group tolerance under mild conditions. In comparison with transition metal complexes or organic dye molecules, PATP exhibited superior catalytic activity due to its extended π-conjugation system, porous structure, and electronic donor–acceptor (D-A) characteristics. Moreover, the polymer PATP showed consistent recyclability without any significant loss of photocatalytic efficiency after recovery.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452012","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":"Modulating Molecular Interactions in Bulk and Electrochemical Interfaces of Deep Eutectic Solvent-Based Tailored Electrolytes for Facilitating Reactive CO2 Capture","authors":"Cini M. Suresh, Mrityunjay K. Jha, Navneet, Hemant K. Kashyap, Pravin Popinand Ingole","doi":"10.1021/acssuschemeng.4c05394","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05394","url":null,"abstract":"The conventional CO₂ capture and utilization (CCU) uses aqueous amine solutions, but its environmental hostility and energy-intensive process to regenerate CO₂ are major hurdles toward sustainability. Alternatively, electrochemical reactive CO₂ capture (eRCC) that integrates CO₂ capture and its conversion has been considered a promising method for economical and sustainable CO₂ valorization. However, designing a suitable electrolyte system with tailored electrochemical interfaces for efficient eRCC is a major challenge. Herein, we report a tailored deep eutectic solvent (DES)-based electrolyte containing a superbase (DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene), an aprotic diluent (DMSO: dimethyl sulfoxide), and ethaline (Eth) for an efficient and low-cost eRCC. The tailored DES electrolyte depicts multifold improvement in eRCC performance compared to pristine Eth with good CO₂ capture capacity and a superior conversion rate (363.6 μmol cm^–2 h^–1) at elevated temperatures (i.e., 50 °C). The spectroscopic, electrochemical, and theoretical (AIMD) investigations suggest that the modulated molecular interactions between DES and CO₂ boost its capture and facilitate the release of captured CO₂ for subsequent reduction. Overall, the facile mass transport, higher concentration of CO₂ at the electrode surface, and greater stabilization of intermediates due to the formation of a compact electrical double layer in a tailored DES resulted in relatively high eRCC performance.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452074","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":"Singlet Oxygen-Mediated Regioselective Thiocyanation of Terminal Alkynes, Alkenes, Indoles, Pyrrole, Anilines, and Phenols","authors":"Mahima Gupta, Vaibhav Pramod Charpe, Kuo Chu Hwang","doi":"10.1021/acssuschemeng.4c05654","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05654","url":null,"abstract":"We have developed a singlet oxygen (¹O₂)-mediated regioselective thiocyanation of terminal alkynes, indoles, pyrrole, anilines, and phenols using ammonium thiocyanate (NH₄SCN) as an SCN source under visible light irradiation at room temperature. The oxidative thiocyanation of terminal alkynes forms α-keto thiocyanates, while indoles, pyrrole, anilines, and phenols regioselectively form the respective thiocyanate products. Herein, thiocyanate (SCN anion) undergoes single electron transfer (SET) by transferring an electron to singlet oxygen and forms an ^•SCN radical, which readily reacts with substrates to form thiocyanate products. Green chemistry metrics and Eco-scale evaluations signify that the current oxidative and regioselective thiocyanation protocol is an acceptable green organic synthesis process. Moreover, this method requires a simple reaction setup and uses inexpensive NH₄SCN as an SCN source, O₂ as an oxidant, and low-energy visible light. Thus, the current oxidative thiocyanation process is mild, green, highly efficient, eco-friendly, and environmentally feasible.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451654","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":"In-Situ Implanted Robust and Durable Cathode-Electrolyte Interphase for High-Performance Sodium-Based Dual-Ion Batteries","authors":"Yujia Wang, Qingjuan Ren, Qingqiang Kong, Liang He, Peng Zhang, Zhihong Xiao, Zhiqiang Shi","doi":"10.1021/acssuschemeng.4c04793","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04793","url":null,"abstract":"The practical applications of economically viable and environmentally friendly sodium-based dual-ion batteries (Na-DIBs) are currently restricted because of the short life spans of these systems. The development of a robust and durable cathode–electrolyte interphase (CEI) layer is expected to serve as an effective measure to enhance the cycling performances of Na-DIBs. Herein, a high charging voltage is employed during precycling to decompose sodium difluoro(oxalato)borate (NaDFOB) on an expanded mesocarbon microbead (HRO-MCMB) cathode surface, thereby promoting the formation of an inorganic-rich CEI layer. This CEI layer not only serves as a chemically stable and mechanically strong barrier but also effectively inhibits the volume expansion and exfoliation of the cathode graphite layer. Consequently, the HRO-MCMB cathode modified with 0.02 M NaDFOB exhibited a capacity retention of 97.0% after 1000 cycles at a current density of 1 C. The HRO-MCMB(+)||HC(−) (HC = hard carbon) full cell maintained a specific capacity of 110.9 mAh g^–1 after 300 cycles at 1 C. Furthermore, the Na-DIB full cell exhibited an impressive energy density of up to 422.6 Wh kg^–1, and its maximum power density reached 4682.9 W kg^–1. Overall, this study provides a novel strategy for the practical development of high-performance Na-DIBs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451660","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":"Interiorly Hydrophobic Modification of Electrodeposited Self-supported ZnAg Foam Electrodes for CO2 Electroreduction in a Microchannel Reactor","authors":"Zhihang Wei, Shenglin Yan, Jing Lin, Qing Hu, Yanran Cui, Qiong Wang, Zhenglong Li, Zhenmin Cheng","doi":"10.1021/acssuschemeng.4c07237","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07237","url":null,"abstract":"Electrodeposition is an effective approach to synthesize porous electrocatalysts; however, the impact of deposition conditions on the catalyst porosity and morphology has rarely been systematically studied. More importantly, the mass transport of CO₂ is poor because the electrodes are generally fully covered by aqueous electrolytes, leading to low current densities. Hydrophobic modification can generate gas–liquid–solid interfaces that facilitate CO₂ mass transport. However, the conventional superficially hydrophobic modification sacrifices the activity due to partially covered active sites, has difficulty in the uniform modification of internal pore surfaces due to large polymer size, and the surface hydrophobic sites are easily washed away. Here, we report a unique hydrogen bubble dynamic template electrodeposition method to synthesize interiorly hydrophobic ZnAg foam electrodes by physically trapping polytetrafluoroethylene (PTFE) during electrodeposition. Deposition conditions were found to influence the pore diameter and morphology. The pore diameter increases with the deposition current density and duration. The pore wall structure gradually transformed from nanodendrites at −0.5 A·cm^–2 into nanosheets at −1 A·cm^–2 or beyond. The resulting interiorly hydrophobic ZnAg(3A15s)-40 exhibits a maximum FE_CO of 97.6% and a significantly widened current density window of −5 to −50 mA·m^–2 with an FE_CO of more than 90.4% in a microchannel reactor, which is significantly higher than those of bare ZnAg(3A15s) (−5 to −30 mA·cm^–2 with an FE_CO more than 90.0%) and the Zn rod substrate (−5 mA·cm^–2 with an FE_CO of 64.0%). The in situ attenuated total reflection Fourier transformed infrared (ATR-FTIR) spectroscopy suggested the hydrophobic catalyst has enhanced CO₂ concentration near the inner surface, which promotes the activity of CO₂ reduction to CO.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449916","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":"Novel DABCO-Derived Ionic Liquids for Liquid Desiccant Air Conditioning","authors":"Wei-Chih Lee, Zih-Siang Hong, Yi-Hsiang Chen, Ai-Yu Liou, Po-Hsuan Hsieh, Chih-Hao Chen, Jiun-Jen Chen","doi":"10.1021/acssuschemeng.4c05343","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05343","url":null,"abstract":"Conventional air conditioners are inefficient, especially in hot and humid areas, to take water away from the moisture-rich air since this causes higher energy consumption. Liquid desiccant air-conditioning (LDAC) systems represent a promising alternative due to their effective temperature- and humidity-independent control with energy-saving potential. Ionic liquids (ILs) are considered desiccant substitutes for traditional halide salts with better performance and no metal corrosion. This study introduced the synthesis and structure characterization of novel ILs with cations based on 1,4-diazabicyclo[2.2.2]octane (DABCO) and anions derived from trialkylphosphate. The corrosion behavior of copper and aluminum in these IL solutions was studied with an electrochemical test. The resulting ionic liquids were strongly hygroscopic and antimicrobial while showing much lower corrosivity with no risk of crystallization. These advantages made DABCO-derived ILs the potential liquid desiccants of the next generation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449918","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}