ACS Sustainable Chemistry & Engineering最新文献

{"title":"Synergistic Enhancement of Light Harvesting and Interfacial Defect Reduction Using Metal–Organic Frameworks for Efficient and Stable Perovskite Solar Cells","authors":"Chenyu Zhao, Meihan Liu, Xiaoye Liu, Xinxuan Yang, Lin Fan, Maobin Wei, Huilian Liu, Xin Li, Tie Liu, Bin Li, Jinghai Yang, Fengyou Wang, Lili Yang","doi":"10.1021/acssuschemeng.5c00297","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00297","url":null,"abstract":"Perovskite solar cells (PSCs) employing a SnO₂ electron transport layer (ETL) have consistently broken efficiency records over the past decade by developing new active materials and optimizing device structures. As a key functional layer of PSCs, the SnO₂ ETL directly dictates the performance and stability of the entire device. However, the defect-induced recombination losses and the optical losses caused by suboptimal optical paths on the SnO₂/perovskite interface remain major barriers to PSCs performance improvement. Therefore, from the perspective of interfacial engineering, this study designs and synthesizes a metal–organic framework (MOF) material based on tin sulfate (SnSO₄) and 2-nitroterephthalic acid (NTA), namely, Sn-NTA, which combines the functions of regulating the incident optical path and passivating interface defects. The Sn-NTA nanocluster enhances light scattering at the SnO₂/perovskite interface, thus increasing perovskite light absorption. Moreover, the mesoporous MOF with carboxyl groups templates the crystallization of the perovskite and enables the formation of a radial MOF/perovskite junction, accelerating charge transfer. As a result, devices based on Sn-NTA show significantly improved photovoltaic properties, achieving a high power conversion efficiency of 24.04%. This work not only provides a new method for preparing multifunctional MOF materials but also inspires future researchers to focus on the collaborative design of interface optical structures and defect termination.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723597","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":"Evaluation of the Technical and Environmental Viability of a Bioethanol, Propene, and Green Ammonia Process for Acetonitrile Production through a Comprehensive Life Cycle Assessment","authors":"Izabela Silva Freitas, Aryane Maria de Oliveira Lima, Edson de Paiva Alves, Genes de Morais Souza, Luiz Antônio Magalhães Pontes","doi":"10.1021/acssuschemeng.4c09745","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09745","url":null,"abstract":"Acetonitrile (ACN) is a valuable product, serving as a feedstock in the petrochemical, pharmaceutical, and fine chemical industries. This study analyzes the environmental footprint of ACN production employing a life cycle assessment. A comparative assessment was conducted between the fossil-based process and a novel bioethanol and green ammonia approach. The ReCiPe Midpoint method was applied, utilizing Ecoinvent database in SIMAPRO. Dates to evaluate environmental impacts of adding bioethanol were obtained by using a pilot-scale reactor operating parallel to the main reactor in a Brazilian industrial unit. The scenario using bioethanol, propene, and petrochemical ammonia exhibited a noteworthy compensation for 96 kg of CO₂-equiv/t of ACN, when compared to scenario 1. Additionally, this scenario achieved a 14% reduction in fossil resource scarcity. The use of bioethanol and green ammonia can reduce environmental impacts by up to 5% in the six assessed categories. Specifically, while global warming potential and fossil resource scarcity have decreased, the introduction of bioethanol has increased human toxicity and ecotoxicity impacts in ACN production, primarily due to sugar cane cultivation. The study demonstrates that the proposed innovations offer a viable approach to mitigating the environmental effects of ACN production and maintaining process safety, also highlighting the increased impacts associated with bioethanol.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724003","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 Advanced Activated Biocarbon from Corn Distiller Soluble via Two-Step Carbonization: Investigating the Synergistic Effects of ZnO and K toward Enhanced CO2 Capture","authors":"Aneela Hayder, Saikat Kumar Kuila, Shahin Mazhkoo, Rafael M. Santos, Animesh Dutta","doi":"10.1021/acssuschemeng.4c10236","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10236","url":null,"abstract":"The excessive emissions of CO₂ into the atmosphere have a severe impact on the ecological environment. Activated carbon (AC) offers a promising strategy for cost-effective carbon dioxide (CO₂) emissions mitigation as a solid adsorbent. The chemical activation process, which involves direct mixing of an activating agent with biomass, is a common method to achieve a porous morphology and high surface area in AC. Herein, an advanced and highly microporous activated biocarbon was synthesized using a two-step carbonization process consisting of hydrothermal synthesis of the ZnO/C carbon precursor based on condensed corn distiller soluble (CDS) followed by potassium hydroxide (KOH) activation at 700 °C for 60 min. The results indicated that the synergistic use of ZnO and K plays a complementary role in structural development and functional enhancement. This synthesis strategy resulted in advanced activated biocarbon with a significantly higher surface area of 1744.6 m² g^–1, outperforming biocarbon activated with KOH alone. In this study, it was hypothesized that KOH would penetrate and activate the ZnO/C carbon precursor more effectively than the direct activation of CDS. The resulting advanced activated biocarbon materials were systematically investigated through comprehensive microstructural, physicochemical, interfacial, textural, and thermal analyses. Scanning electron microscopy (SEM) revealed a superior 3D hierarchical structure enriched with micropores, favorable mesopores, and interconnected macropores of synthesized biocarbon. Furthermore, CO₂ adsorption capacities were performed at various temperatures (273, 288, 298, and 308 K). The highest adsorption capacities, ranging from 3.70 to 6.30 mol kg^–1, were observed at 1 bar and 273 K for all advanced activated biocarbon samples. Notably, the combined catalytic and templating effects of ZnO and K resulted in a highly porous structure with a high surface area, abundant adsorption sites, and excellent selective CO₂ capture properties.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"188 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734117","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":"Y-Doped Na4Fe3(PO4)2(P2O7) as a High-Performance Cathode Material for Sodium-Ion Batteries","authors":"Yao Tan, Wenhao Ni, Jianwen Yang, Yanwei Li, Zhengwei Xie, Bin Huang","doi":"10.1021/acssuschemeng.4c10844","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10844","url":null,"abstract":"The Na₄Fe₃(PO₄)₂(P₂O₇) (NFPP) cathode material for sodium-ion batteries (SIBs) is modified through a facile yttrium (Y)-doping approach. The crystal structures, surface morphologies, and electrochemical performances of the pristine and Y-doped samples are comparatively investigated. The results indicate that the structure and morphology of the material are almost unchanged after Y doping. Doping with an appropriate amount of Y can enhance the electronic conductivity and electrochemical kinetics of the material, leading to superior electrochemical performance. Among the four samples prepared with different Y-doping levels, the optimum one exhibits the highest capacity of 115.8 mAh g^–1 (0.1C, 2–4 V, 1C = 129 mA g^–1), as well as outstanding cycling stability and rate capability (retaining a capacity of 87.8 mAh g^–1 after 3000 cycles at 20C, with a retention of 92.7%). Furthermore, scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements after cycling reveal that Y doping can stabilize the material structure, thereby further enhancing its lifespan during long-term cycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734118","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":"2,2,6,6-Tetramethyloxane as an Alternative Hindered Ether Solvent for Organic Synthesis","authors":"Suwiwat Sangon, Nontipa Supanchaiyamat, James Sherwood, Duncan J. Macquarrie, Andrew J. Hunt","doi":"10.1021/acssuschemeng.4c09195","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09195","url":null,"abstract":"A new hindered ether solvent, namely, 2,2,6,6-tetramethyloxane, has been successfully synthesized in excellent yields (90% from 2,6-dimethyl-2,6-heptanediol and 80% from 2,6-dimethyl-5-hepten-2-ol). The physical and solvation properties of 2,2,6,6-tetramethyloxane were evaluated, which indicated its potential to replace hydrocarbon solvents and also that it imparts strong hydrogen-bond-accepting ability. VEGA models (SARpy, KNN, ISS, and CAESAR), the lazy structure–activity relationship model (<i>Salmonella typhimurium</i>), and the Toxicity Estimation Software Tool indicated this solvent to be nonmutagenic. The application of 2,2,6,6-tetramethyloxane in model organic reactions including the Biginelli reaction, glucose conversion to 5-hydroxymethylfurfural, and the Sonogashira reaction, importantly, validates the nonpolar nature of this solvent and exhibits its potential as an alternative solvent to hazardous hydrocarbon solvents (including toluene).","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713652","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":"Organically Functionalized Mesoporous Silica Network for One-Pot Synthesis of 5-Hydroxymethylfurfural from Glucose in Water","authors":"Preeti Kang, Matej Gabrijelčič, Andraž Krajnc, Ilja Gasan Osojnik Črnivec, Blaž Likozar, Rakesh K Sharma","doi":"10.1021/acssuschemeng.4c09579","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09579","url":null,"abstract":"The conversion of lignocellulosic biomass to 5-hydroxymethylfurfural (HMF), a key renewable molecule and a potential alternative to petroleum-based chemicals, is of great research interest. In this study, we prepared a t-SiO₂@B@A catalyst consisting of a mesoporous silica support, where surface −OH groups were grafted with 3-(aminopropyl)triethoxysilane (APTES), followed by functionalization with 4-formylbenzoic acid. The synthesized t-SiO₂@B@A catalyst, bearing Brønsted basic (─C═N─) and acidic (−COOH) sites, exhibited bifunctional activity for the selective production of HMF from glucose in water. The structural and chemical properties of the t-SiO₂@B@A catalyst were determined using various characterization techniques, such as XRD, BET, FESEM, TGA, FTIR, TPD-NH₃/CO₂, and solid-state cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy, which confirmed the successful incorporation of organic moieties onto the silica support. The mesoporosity of the silica support was well maintained after surface modification, exhibiting a surface area of 266.4 m²/g, with a total acidity of 2.27 mmol/g and thermal stability up to 400 °C. The reaction system was optimized with various parameters, such as temperature, reaction time, catalyst amount, and solvents. Consequently, an HMF yield of 69.7% was achieved after 6 h at 120 °C over the t-SiO₂@B@A (0.5 w/v %) catalyst. Moreover, the catalyst showed good recyclability for eight test cycles without significant loss of catalytic activity. A kinetic model was developed to monitor the conversion of glucose and the temperature dependence of HMF production. Based on numerical modeling, the first step, isomerization of glucose to fructose, was found to be slower (rate constant: <i>k</i>_B1 = 0.348 min^–1) while the second step, dehydration of fructose to HMF is faster (rate constant: <i>k</i>_B1 = 0.348 min^–1). This study provides an efficient and environmentally benign method for the conversion of glucose to HMF, highlighting its potential for industrial applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723598","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":"Advancing Sustainable Ammonia Production via Solventless, Robust, and Thermally Conductive Absorbents","authors":"Tejas Nivarty, William C. Straub, Chinomso E. Onuoha, Michael Manno, Jeffrey H. Schott, Mahdi Malmali, Alon V. McCormick","doi":"10.1021/acssuschemeng.4c08837","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08837","url":null,"abstract":"Sorption-based low-pressure green ammonia synthesis using supported metal halide salts enables efficient interconversion between hydrogen and ammonia, allowing the high hydrogen density and well-established transportation network of ammonia to be used for green energy storage. Magnesium chloride supported on silica gel (MgCl₂/SiO₂) sorbent has been the subject of much investigation owing to its high capacity, selectivity, and reversibility at temperatures close to reactor conditions; however, MgCl₂/SiO₂ suffers from low thermal conductivity, which complicates absorber design at larger scales and prolongs absorption–desorption cycle times. We present a scalable, solventless method for supporting MgCl₂ on thermally conductive aluminum fibers (MgCl₂/Al)─a thermally conductive ammonia sorbent with a high working capacity of ∼220 mg_NH3/g_absorbent. Although the solventless synthesis causes variance in initial-cycle pressure drop and capacity, we show that this stabilizes after cycling. The high thermal conductivity of MgCl₂/Al allows for rapid absorption–desorption cycles, enabling easier scale-up. MgCl₂/Al also maintains its cyclic capacity up to at least 50 cycles.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"358 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723602","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":"Self-aggregation of the Interfacial Passivation Layer from Ionic Additive-Stabilized PbI2 Film for High-Performance Perovskite Solar Cells","authors":"Qin Cao, Yan Wang, Xuwu Xiang, Jiangsheng Yu, Jie Zhou","doi":"10.1021/acssuschemeng.5c00006","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00006","url":null,"abstract":"Lead halide perovskites (LHPs) face challenges in commercialization due to the instability of their thin films during the fabrication process. During the continuous spin-coating process of formamidinium/methylammonium (FA⁺/MA⁺) organic ammonium salts, the degradation and densification of the lead iodide (PbI₂) layer frequently result in incomplete conversion of the perovskite, which severely impacts the performance of perovskite solar cells. In this work, we introduced the organic ion compound tetrabutylammonium hexafluorophosphate (TBAPF6) into the PbI₂ precursor solution. TBAPF6 promotes the pre-expansion of the PbI₂ layer, resulting in a uniform nanoporous morphology on the surface of the PbI₂ film. The adsorption interaction between TBAPF6 and lead iodide stabilizes the morphology of the lead iodide film, thereby extending its storage time and further delaying the crystallization rate of the perovskite. The TBA⁺ cations can react with excess lead iodide to form two-dimensional perovskites, thereby enhancing the stability of the perovskite layers. Additionally, TBAPF6, as an ionic compound, can spontaneously diffuse into the buried interfaces of the perovskite to form an interfacial passivation layer. The power conversion efficiency of perovskite devices based on TBAPF6 was ultimately improved from 21.53% to 24.62%. Furthermore, these devices exhibit excellent environmental and operational stability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713688","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":"Fermentative Production of 2,4-Dihydroxybutyrate from Glucose via a Redox Balanced Route","authors":"Jia’nan Zhang, Yihan Wang, Dan Wang, Bo Yu","doi":"10.1021/acssuschemeng.5c00112","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00112","url":null,"abstract":"2,4-Dihydroxybutanoic acid (DHB) is a hydroxy fatty acid originating from butyric acid characterized by hydroxyl groups at the second and fourth carbon positions. Besides being initially synthesized as a precursor for methionine to improve animal nutrition, DHB is also acknowledged as a sustainable platform chemical to produce biobased products in the chemical and pharmaceutical industries with broad market potential. In this study, we illustrated a redox-balanced pathway for the <i>de novo</i> biosynthesis of DHB utilizing the native metabolic route of the <i>E. coli</i> strain, which highlights the advantage of the <span>l</span>-homoserine derived pathway for DHB biosynthesis. Subsequent improvements were achieved through systematic metabolic engineering strategies, including deletion of competing pathways, reinforcement of the biosynthetic pathway, and increasing the availability of precursors. The engineered strain achieved a production titer of 22.0 g/L DHB in a fed-batch bioreactor, the highest ever recorded yield of fermentative DHB production from glucose. This study demonstrated an effective <i>de novo</i> biosynthetic route for the sustainable production of DHB from abundant biomass.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723599","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":"Synthesis of Bis(dodecylammonium) Tetrachlorocuprate Using Ball Milling for Thermal Energy Storage","authors":"Rebeca Salgado-Pizarro, Jofre Mañosa, Camila Barreneche, Ana Inés Fernández","doi":"10.1021/acssuschemeng.4c08677","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08677","url":null,"abstract":"Layered hybrid halometallates are highlighted for their adaptable thermal, electrical, and optical properties by modifying the alkylammonium or metal constituents. However, the conventional synthesis procedures of these materials present some sustainability and scalability issues. To tackle these issues, mechanochemistry is a promising alternative synthesis which uses mechanical energy and can reduce the solvent content required. Mechanochemical synthesis has proven to be an effective synthesis route for various perovskite structures, but research on bis(alkylammonium) tetrahalometallates is limited. Here, we explore the feasibility of synthesizing bis(alkylammonium) tetrahalometallates through ball milling and reducing solvent usage. Crystal and molecular results confirmed the successful synthesis with minimal impurities, &lt;5 wt %. The bis(alkylammonium) tetrahalometallates obtained through ball milling presented comparable enthalpy and specific heat values to those obtained through traditional synthesis routes. Moreover, the ball milling synthesis consumed significantly less energy and solvent and led to higher reaction yield than the traditional synthesis methods, thereby enhancing the sustainability of the process. Overall, the results validate the synthesis through ball milling as a viable and environmentally efficient method for bis(alkylammonium) tetrahalometallates.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713691","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}