Pub Date : 2025-04-23DOI: 10.1021/acs.jpcc.4c07850
Anna Vidal-López, Judith Mahringer, Aleix Comas-Vives
CO2 activation is crucial to its upgrade to fuels and chemicals. In this work, we systematically studied CO2 cleavage on single-atom catalysts (SACs) based on metals M = (Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Au) supported on Mo2COx (6/9 O ML) and Ti2COx (7/9 O ML) MXenes via Density Functional Theory (DFT) calculations and Bader charge analysis to provide insights into the charge redistribution among the metal, MXene, interface, and CO2 during the process. CO2 activation involves a two-step mechanism, adsorbing at the M–MXene interface where it bends and acquires a highly anionic character and then breaks, forming CO* and O*. The energy barriers analyzed for the CO2 activation on M/Mo2COx and M/Ti2COx surfaces show that Cu, Ni, Rh, and Pt on Mo2COx and Cu, Ru, and Rh on Ti2COx presented the lowest energy barriers. Comparing the two MXenes, the electrophilic nature of Mo atoms facilitates CO2 cleavage, while the Ti atoms distribute charge differently, hindering the CO2 activation process. The energy barriers toward CO2 activation on M/Mo2COx and M/Ti2COx surfaces show that Cu, Ni, Rh, and Pt on Mo2COx and Cu, Ru, and Rh on Ti2COx presented the lowest energy barriers. Mo2COx systems presented geometrical structures of the transition states that were more product-like aligning with the Hammond’s principle, implying exoenergetic processes and lower energy barriers in contrast to Ti2COx. Moreover, the CO2 activation on M/2D-Mo2C follows a Brønsted–Evans–Polanyi (BEP) relationship while M/2D-Ti2C breaks it, a crucial factor to identify better catalytic materials. The ExtraTreesRegressor machine learning algorithm effectively predicts adsorption and transition-state energies using a small set of descriptors. The findings underscore the importance of transition metal electronic states, charge transfer, and support structure effects for SACs on MXenes, providing valuable insights for the design of catalytic materials. This detailed analysis provides a deeper understanding of the mechanistic aspects of CO2 activation, highlighting the role of single-atom metals and their interaction with metal-carbide surfaces.
{"title":"Key Descriptors of Single-Atom Catalysts Supported on MXenes (Mo2C, Ti2C) Determining CO2 Activation","authors":"Anna Vidal-López, Judith Mahringer, Aleix Comas-Vives","doi":"10.1021/acs.jpcc.4c07850","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07850","url":null,"abstract":"CO<sub>2</sub> activation is crucial to its upgrade to fuels and chemicals. In this work, we systematically studied CO<sub>2</sub> cleavage on single-atom catalysts (SACs) based on metals M = (Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Au) supported on Mo<sub>2</sub>CO<sub><i>x</i></sub> (6/9 O ML) and Ti<sub>2</sub>CO<sub><i>x</i></sub> (7/9 O ML) MXenes via Density Functional Theory (DFT) calculations and Bader charge analysis to provide insights into the charge redistribution among the metal, MXene, interface, and CO<sub>2</sub> during the process. CO<sub>2</sub> activation involves a two-step mechanism, adsorbing at the M–MXene interface where it bends and acquires a highly anionic character and then breaks, forming CO* and O*. The energy barriers analyzed for the CO<sub>2</sub> activation on M/Mo<sub>2</sub>CO<sub><i>x</i></sub> and M/Ti<sub>2</sub>CO<sub><i>x</i></sub> surfaces show that Cu, Ni, Rh, and Pt on Mo<sub>2</sub>CO<sub><i>x</i></sub> and Cu, Ru, and Rh on Ti<sub>2</sub>CO<sub><i>x</i></sub> presented the lowest energy barriers. Comparing the two MXenes, the electrophilic nature of Mo atoms facilitates CO<sub>2</sub> cleavage, while the Ti atoms distribute charge differently, hindering the CO<sub>2</sub> activation process. The energy barriers toward CO<sub>2</sub> activation on M/Mo<sub>2</sub>CO<sub><i>x</i></sub> and M/Ti<sub>2</sub>CO<sub><i>x</i></sub> surfaces show that Cu, Ni, Rh, and Pt on Mo<sub>2</sub>CO<sub><i>x</i></sub> and Cu, Ru, and Rh on Ti<sub>2</sub>CO<sub><i>x</i></sub> presented the lowest energy barriers. Mo<sub>2</sub>CO<sub><i>x</i></sub> systems presented geometrical structures of the transition states that were more product-like aligning with the Hammond’s principle, implying exoenergetic processes and lower energy barriers in contrast to Ti<sub>2</sub>CO<sub><i>x</i></sub>. Moreover, the CO<sub>2</sub> activation on M/2D-Mo<sub>2</sub>C follows a Brønsted–Evans–Polanyi (BEP) relationship while M/2D-Ti<sub>2</sub>C breaks it, a crucial factor to identify better catalytic materials. The ExtraTreesRegressor machine learning algorithm effectively predicts adsorption and transition-state energies using a small set of descriptors. The findings underscore the importance of transition metal electronic states, charge transfer, and support structure effects for SACs on MXenes, providing valuable insights for the design of catalytic materials. This detailed analysis provides a deeper understanding of the mechanistic aspects of CO<sub>2</sub> activation, highlighting the role of single-atom metals and their interaction with metal-carbide surfaces.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"52 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sergei Negria, Yinglong Jia, Noah A. Setterholm, Bhawna Barpuzary, John C. Chaput
Polymerases are among the most powerful tools in the molecular biology toolbox; however, access to large quantities of chemically modified nucleoside triphosphates for diverse applications remains hindered by the need for purification by high-performance liquid chromatography (HPLC). Here, we describe a scalable approach to modified nucleoside triphosphates that proceeds through a P(III)–P(V) mixed anhydride intermediate obtained from the coupling of a P(III) nucleoside phosphoramidite and a P(V) pyrene pyrophosphate reagent. The synthetic strategy allows the coupling, oxidation, and deprotection steps to proceed as stepwise transformations in a single one-pot reaction. The fully protected nucleoside triphosphates are purified by silica gel chromatography and converted to their desired compounds on scales exceeding those achievable by conventional strategies. The power of this approach is demonstrated through the synthesis of several natural and modified nucleoside triphosphates using protocols that are efficient and straightforward to perform.
{"title":"Scalable Multistep One-Pot Synthesis of Natural and Modified Nucleoside Triphosphates","authors":"Sergei Negria, Yinglong Jia, Noah A. Setterholm, Bhawna Barpuzary, John C. Chaput","doi":"10.1021/acs.joc.5c00268","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00268","url":null,"abstract":"Polymerases are among the most powerful tools in the molecular biology toolbox; however, access to large quantities of chemically modified nucleoside triphosphates for diverse applications remains hindered by the need for purification by high-performance liquid chromatography (HPLC). Here, we describe a scalable approach to modified nucleoside triphosphates that proceeds through a P(III)–P(V) mixed anhydride intermediate obtained from the coupling of a P(III) nucleoside phosphoramidite and a P(V) pyrene pyrophosphate reagent. The synthetic strategy allows the coupling, oxidation, and deprotection steps to proceed as stepwise transformations in a single one-pot reaction. The fully protected nucleoside triphosphates are purified by silica gel chromatography and converted to their desired compounds on scales exceeding those achievable by conventional strategies. The power of this approach is demonstrated through the synthesis of several natural and modified nucleoside triphosphates using protocols that are efficient and straightforward to perform.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.jpcc.5c00212
Aleksander Senderowski, Ana Andrea Méndez-Medrano, Isabelle Lampre, Hynd Remita, Dorota Rutkowska-Zbik
Platinum Chini clusters with a general formula [Pt3(CO)6]n2– are formed by stacked Pt3 units. They have fascinating electronic and optical properties that can be tuned with n. In the current manuscript, the electronic, photochemical, and charge transport properties of the platinum Chini clusters are studied with the density functional theory (PBE and CAM-B3LYP/6-31G(d,p)+LANL2DZ) as a function of their nuclearity number n. Our theoretical predictions are supported by experimental proof of concept, in which synthesized Chini clusters are deposited as cocatalysts on TiO2 for photocatalytic hydrogen generation. We demonstrate that smaller clusters (n = 4) are more effective than larger ones (n = 7–8), and that composites having lower Pt content perform better.
{"title":"Platinum Carbonyl Chini Clusters as Catalysts for Photocatalytic H2 Generation","authors":"Aleksander Senderowski, Ana Andrea Méndez-Medrano, Isabelle Lampre, Hynd Remita, Dorota Rutkowska-Zbik","doi":"10.1021/acs.jpcc.5c00212","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00212","url":null,"abstract":"Platinum Chini clusters with a general formula [Pt<sub>3</sub>(CO)<sub>6</sub>]<sub><i>n</i></sub><sup>2–</sup> are formed by stacked Pt<sub>3</sub> units. They have fascinating electronic and optical properties that can be tuned with <i>n</i>. In the current manuscript, the electronic, photochemical, and charge transport properties of the platinum Chini clusters are studied with the density functional theory (PBE and CAM-B3LYP/6-31G(d,p)+LANL2DZ) as a function of their nuclearity number <i>n</i>. Our theoretical predictions are supported by experimental proof of concept, in which synthesized Chini clusters are deposited as cocatalysts on TiO<sub>2</sub> for photocatalytic hydrogen generation. We demonstrate that smaller clusters (<i>n</i> = 4) are more effective than larger ones (<i>n</i> = 7–8), and that composites having lower Pt content perform better.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.jpcc.5c01741
Zhimeng Hao, Taifeng Liu
We investigated the formation of small-hole polarons in β-Ga2O3 from first-principles, accounting for their coupling to all phonon modes. Our results reveal that small-hole polarons can form at multiple oxygen sites, namely, OI, OII, and OIII, with the OII site being the most stable. The phonons involved in the coupling for polaron formation at these three oxygen sites exhibit minimal differences. However, at the OII site, the localized hole originates from entire highest valence band (EHVB), whereas at the OI and OIII sites, the localized hole state is a hybridization of the EHVB and lower-lying bands. This distinction results in the lower contribution of electronic weight of small hole polarons on the OII site, which leads the lowest formation energy for the polaron at this site. The hopping of small-hole polarons between OII sites occurs via an adiabatic process, with an activation energy of 0.37 eV. Additionally, we investigated electron polarons in β-Ga2O3 using the same approach but observed no evidence of polaronic states, either large or small. This study provides new insights into polaron physics in β-Ga2O3 and offers guidance for understanding and exploring polarons in related materials.
{"title":"Formation and Transport of Polarons in β-Ga2O3: an Ab Initio Study","authors":"Zhimeng Hao, Taifeng Liu","doi":"10.1021/acs.jpcc.5c01741","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01741","url":null,"abstract":"We investigated the formation of small-hole polarons in β-Ga<sub>2</sub>O<sub>3</sub> from first-principles, accounting for their coupling to all phonon modes. Our results reveal that small-hole polarons can form at multiple oxygen sites, namely, O<sub>I</sub>, O<sub>II</sub>, and O<sub>III</sub>, with the O<sub>II</sub> site being the most stable. The phonons involved in the coupling for polaron formation at these three oxygen sites exhibit minimal differences. However, at the O<sub>II</sub> site, the localized hole originates from entire highest valence band (EHVB), whereas at the O<sub>I</sub> and O<sub>III</sub> sites, the localized hole state is a hybridization of the EHVB and lower-lying bands. This distinction results in the lower contribution of electronic weight of small hole polarons on the O<sub>II</sub> site, which leads the lowest formation energy for the polaron at this site. The hopping of small-hole polarons between O<sub>II</sub> sites occurs via an adiabatic process, with an activation energy of 0.37 eV. Additionally, we investigated electron polarons in β-Ga<sub>2</sub>O<sub>3</sub> using the same approach but observed no evidence of polaronic states, either large or small. This study provides new insights into polaron physics in β-Ga<sub>2</sub>O<sub>3</sub> and offers guidance for understanding and exploring polarons in related materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sari Deketelaere, Emma Vandenheede, Nicola Piens, Lore Cools, Lieselotte Crul, Lotte Demeurisse, Karen Mollet, Christian V. Stevens, Matthias D’hooghe
3-Oxo-β-lactams are known to deliver different types of reaction products upon treatment with primary amines, predominantly governed by the nature of the C4 substituent. In this work, a C4 substituent-independent protocol for the conversion of 3-oxo-β-lactams to the corresponding 3-imino-β-lactams was developed. By using primary amine hydrochloric acid salts in combination with 2,4,6-collidine, or free primary amines in combination with acetic acid, the undesired ring opening of 4-aryl- and (S)-4-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)azetidine-2,3-diones toward ethanediamides and α-aminoamides, respectively, is avoided, enabling the smooth transformation of any 3-oxo-β-lactam into its imine counterpart. As demonstrated by the ensuing synthesis of 3-alkylamino-β-lactams, 3-imino-β-lactams serve as building blocks for the construction of functionalized 3-amino-β-lactams, with the latter being key motifs in drug discovery.
{"title":"Synthesis of 3-Amino-β-lactams through Selective Imination of 3-Oxo-β-lactams","authors":"Sari Deketelaere, Emma Vandenheede, Nicola Piens, Lore Cools, Lieselotte Crul, Lotte Demeurisse, Karen Mollet, Christian V. Stevens, Matthias D’hooghe","doi":"10.1021/acs.joc.5c00205","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00205","url":null,"abstract":"3-Oxo-β-lactams are known to deliver different types of reaction products upon treatment with primary amines, predominantly governed by the nature of the C4 substituent. In this work, a C4 substituent-independent protocol for the conversion of 3-oxo-β-lactams to the corresponding 3-imino-β-lactams was developed. By using primary amine hydrochloric acid salts in combination with 2,4,6-collidine, or free primary amines in combination with acetic acid, the undesired ring opening of 4-aryl- and (<i>S</i>)-4-((<i>S</i>)-2,2-dimethyl-1,3-dioxolan-4-yl)azetidine-2,3-diones toward ethanediamides and α-aminoamides, respectively, is avoided, enabling the smooth transformation of any 3-oxo-β-lactam into its imine counterpart. As demonstrated by the ensuing synthesis of 3-alkylamino-β-lactams, 3-imino-β-lactams serve as building blocks for the construction of functionalized 3-amino-β-lactams, with the latter being key motifs in drug discovery.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.jpcc.5c02065
Ali Ebrahimzadeh Pilehrood, Reza Moshrefi, Emmanuel Mena-Morcillo, Peter George Keech, Mehran Behazin, Samantha Michelle Gateman
Scanning electrochemical microscopy (SECM) is a powerful technique for analyzing the local electrochemical reactivity of surfaces. The effect of electrolyte concentration is often overlooked but can be a critical parameter to consider when exploring active substrates due to its influence on the corrosion reactions taking place. In this study, hexaammineruthenium(III) chloride was employed as a redox mediator (RM) to investigate the feedback (FB) response over a corroding Cu substrate under various concentrations of sodium chloride electrolyte. At high chloride concentrations (e.g., 600 mM), the FB response rapidly transitioned towards negative behavior due to the fast depletion of RM, which accelerated the substrate’s corrosion rate. The kinetic rate constant obtained using a finite element model for the RM’s reaction at the Cu surface over time revealed a gradual decrease in surface electroactivity due to the RM reaction with the metal. By diluting the chloride concentration (e.g., <10 mM), the open-circuit potential of Cu shifted to a more positive value than the RM’s redox potential, minimizing the oxidizing behavior of the RM towards Cu. As a result, reducing the electrolyte concentration prolonged positive FB behavior for a longer duration, enhancing the reliability of SECM imaging for corrosion studies.
{"title":"Influence of Electrolyte Concentration on the Scanning Electrochemical Microscopy Feedback Behavior of Copper","authors":"Ali Ebrahimzadeh Pilehrood, Reza Moshrefi, Emmanuel Mena-Morcillo, Peter George Keech, Mehran Behazin, Samantha Michelle Gateman","doi":"10.1021/acs.jpcc.5c02065","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02065","url":null,"abstract":"Scanning electrochemical microscopy (SECM) is a powerful technique for analyzing the local electrochemical reactivity of surfaces. The effect of electrolyte concentration is often overlooked but can be a critical parameter to consider when exploring active substrates due to its influence on the corrosion reactions taking place. In this study, hexaammineruthenium(III) chloride was employed as a redox mediator (RM) to investigate the feedback (FB) response over a corroding Cu substrate under various concentrations of sodium chloride electrolyte. At high chloride concentrations (e.g., 600 mM), the FB response rapidly transitioned towards negative behavior due to the fast depletion of RM, which accelerated the substrate’s corrosion rate. The kinetic rate constant obtained using a finite element model for the RM’s reaction at the Cu surface over time revealed a gradual decrease in surface electroactivity due to the RM reaction with the metal. By diluting the chloride concentration (e.g., <10 mM), the open-circuit potential of Cu shifted to a more positive value than the RM’s redox potential, minimizing the oxidizing behavior of the RM towards Cu. As a result, reducing the electrolyte concentration prolonged positive FB behavior for a longer duration, enhancing the reliability of SECM imaging for corrosion studies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"41 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chemical recycling methods for post-consumer textile waste are effective for sustainable textile waste management. However, recycling synthetic and blended (cotton and synthetic) textiles can contribute to the release of microplastic fibers (MPFs) into the environment. This study investigated MPF release across different stages of two chemical recycling approaches, acid and alkaline hydrolysis, of polyester/cotton-blended textiles. Recycling involves various stages, including dye removal, treatment stage, and product. In the treatment stage, acid hydrolysis breaks down cotton into cellulose, leaving the polyester (PET) intact, whereas alkaline hydrolysis degrades PET, allowing cotton recovery. Across all stages, dye removal generated the highest MPF count, averaging nearly 10,055 MPFs g–1 of textile waste. Statistical analysis confirmed that the recycling approach significantly affected MPF release (p < 0.05), whereas the fabric type did not (p > 0.05). Alkaline hydrolysis reduced MPF release during the treatment stage by 87.55% compared to acid hydrolysis, indicating that recovering cotton and chemically degrading PET can significantly minimize MPF emissions during recycling. Ridge regression analysis identified the reaction conditions as key factors in MPF fragmentation, with blend ratios influencing the number of released MPFs. Surface characterization revealed treatment-induced fiber alterations, raising concerns regarding MPF emissions throughout the process. These findings highlight the textile recycling industries can be a source of MPF release into the environment, but recovering PET through degradation or dissolution can help minimize this impact of the treatment stage.
{"title":"Textile Recycling’s Hidden Problem: Surface-Modified Fiber Fragments Emitted at Every Stage","authors":"Arun Chandra Manivannan, Logeshwaran Panneerselvan, Raji Kandaiah, Akila Ravindran, Gunasekhar Nachimuthu, Meredith Conaty, Thava Palanisami","doi":"10.1021/acs.est.5c01854","DOIUrl":"https://doi.org/10.1021/acs.est.5c01854","url":null,"abstract":"Chemical recycling methods for post-consumer textile waste are effective for sustainable textile waste management. However, recycling synthetic and blended (cotton and synthetic) textiles can contribute to the release of microplastic fibers (MPFs) into the environment. This study investigated MPF release across different stages of two chemical recycling approaches, acid and alkaline hydrolysis, of polyester/cotton-blended textiles. Recycling involves various stages, including dye removal, treatment stage, and product. In the treatment stage, acid hydrolysis breaks down cotton into cellulose, leaving the polyester (PET) intact, whereas alkaline hydrolysis degrades PET, allowing cotton recovery. Across all stages, dye removal generated the highest MPF count, averaging nearly 10,055 MPFs g<sup>–1</sup> of textile waste. Statistical analysis confirmed that the recycling approach significantly affected MPF release (<i>p</i> < 0.05), whereas the fabric type did not (<i>p</i> > 0.05). Alkaline hydrolysis reduced MPF release during the treatment stage by 87.55% compared to acid hydrolysis, indicating that recovering cotton and chemically degrading PET can significantly minimize MPF emissions during recycling. Ridge regression analysis identified the reaction conditions as key factors in MPF fragmentation, with blend ratios influencing the number of released MPFs. Surface characterization revealed treatment-induced fiber alterations, raising concerns regarding MPF emissions throughout the process. These findings highlight the textile recycling industries can be a source of MPF release into the environment, but recovering PET through degradation or dissolution can help minimize this impact of the treatment stage.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"3 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the left panel of Figure 3b, the HDPE NP distributions within macrophages (at −20° and 40°) have been corrected in the version shown below. Figure 3. Cellular association of PE-NPs with the macrophages. (b) Spatial distribution of HDPE NPs and their cellular accumulation determined by nano-CT. New videos for cells containing HDPE and LDPE NPs are provided as Supporting Information with this Addition/Correction. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.5c05027. Raw data of nano-CT imaging for HDPE accumulated in a single RAW 264.7 cell (MP4) Nano-CT imaging for HDPE accumulated in a single RAW 264.7 cell (MP4) Raw data of Nano-CT imaging for LDPE accumulated in a single RAW 264.7 cell (MP4) Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.
{"title":"Correction to “Protein Corona-Directed Cellular Recognition and Uptake of Polyethylene Nanoplastics by Macrophages”","authors":"Rui Cai, Didar Baimanov, Hao Yuan, Hongxin Xie, Shengtao Yu, Zehao Zhang, Jiacheng Yang, Feng Zhao, Yue You, Yong Guan, Pingping Zheng, Ming Xu, Mengying Qi, Zhiyong Zhang, Shengliang Zhong, Yu-Feng Li, Liming Wang","doi":"10.1021/acs.est.5c05027","DOIUrl":"https://doi.org/10.1021/acs.est.5c05027","url":null,"abstract":"In the left panel of Figure 3b, the HDPE NP distributions within macrophages (at −20° and 40°) have been corrected in the version shown below. Figure 3. Cellular association of PE-NPs with the macrophages. (b) Spatial distribution of HDPE NPs and their cellular accumulation determined by nano-CT. New videos for cells containing HDPE and LDPE NPs are provided as Supporting Information with this Addition/Correction. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.5c05027. Raw data of nano-CT imaging for HDPE accumulated in a single RAW 264.7 cell (MP4) Nano-CT imaging for HDPE accumulated in a single RAW 264.7 cell (MP4) Raw data of Nano-CT imaging for LDPE accumulated in a single RAW 264.7 cell (MP4) Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"6 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chengbo Ma, Jun Wang, Xiaomei Liu, Xiaoguang Duan, Junjie Qi, Shuai Li, Ning Li, Yang Li, Xiaobin Fan, Wenchao Peng
The Fenton reaction is usually limited by the sluggish regeneration of Fe(II). In this article, we developed a Fenton system that uses metal sulfides (MSx) and diluted Fe(III) to activate H2O2, and the enhanced mechanism of the Fe(III)/Fe(II) cycle in the presence of sulfides was investigated. The lattice sulfur of MSx can donate electrons to reduce Fe(III) into Fe(II) and is partially oxidized to SO42– during H2O2 activation. •OH and 1O2 are the primary reactive oxygen species for pollutant removal. Meanwhile, low-cost iron-based sulfide (FeSx) is selected for scale-up experiments in a fixed-bed reactor, which can maintain 100% atrazine degradation over 240 h. Additionally, the Fukui function is employed to analyze the selective degradation pathway of atrazine, and the biological toxicity of the organic intermediates is also assessed. The novel FeSx/Fe(III) system provides a potential alternative to the traditional Fenton reaction.
{"title":"Enhanced Fe(III)/Fe(II) Cycle by Lattice Sulfur for Continuous Fenton Reactions","authors":"Chengbo Ma, Jun Wang, Xiaomei Liu, Xiaoguang Duan, Junjie Qi, Shuai Li, Ning Li, Yang Li, Xiaobin Fan, Wenchao Peng","doi":"10.1021/acs.est.4c12824","DOIUrl":"https://doi.org/10.1021/acs.est.4c12824","url":null,"abstract":"The Fenton reaction is usually limited by the sluggish regeneration of Fe(II). In this article, we developed a Fenton system that uses metal sulfides (MS<sub><i>x</i></sub>) and diluted Fe(III) to activate H<sub>2</sub>O<sub>2</sub>, and the enhanced mechanism of the Fe(III)/Fe(II) cycle in the presence of sulfides was investigated. The lattice sulfur of MS<sub><i>x</i></sub> can donate electrons to reduce Fe(III) into Fe(II) and is partially oxidized to SO<sub>4</sub><sup>2–</sup> during H<sub>2</sub>O<sub>2</sub> activation. •OH and <sup>1</sup>O<sub>2</sub> are the primary reactive oxygen species for pollutant removal. Meanwhile, low-cost iron-based sulfide (FeS<sub><i>x</i></sub>) is selected for scale-up experiments in a fixed-bed reactor, which can maintain 100% atrazine degradation over 240 h. Additionally, the Fukui function is employed to analyze the selective degradation pathway of atrazine, and the biological toxicity of the organic intermediates is also assessed. The novel FeS<sub><i>x</i></sub>/Fe(III) system provides a potential alternative to the traditional Fenton reaction.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"7 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Modulating the carrier dynamics to achieve the effective separation of photoexcited carriers is crucial for enhancing photoelectric conversion efficiency and advancing high-performance optoelectronic devices. A prototype group-III monochalcogenide heterostructure, GaSe/GaTe, has been proposed to exhibit a superior light-harvesting capability and highly tunable charge separation characteristics via nonadiabatic molecular dynamics (NAMD) simulations. The significant influence of stacking patterns on carrier dynamics is revealed, with electron (hole) transfer occurring within 97 (40) to 390 (126) fs, while the carrier lifetime is dramatically prolonged from 12 to 213 ns, facilitating effective electron–hole (e-h) pair separation. Notably, the AA′ and A′A stacking configurations demonstrate remarkably extended carrier lifetimes of 213 and 161 ns, respectively, exceeding those observed in other 2D heterostructures. The weak nonadiabatic coupling and low-frequency phonon vibrational modes suppress e-h recombination, leading to a prolonged carrier lifetime. These findings offer atomic insights into stacking-dependent carrier dynamics, advancing 2D optoelectronic device design.
{"title":"Dramatically Prolonged Photoexcited Carrier Lifetimes in Group-III Monochalcogenide Heterostructures through Stacking Modulation","authors":"Zixiao Yan, Yifan Wu, TianQi Bao, Yunxiao Ban, Lichuan Zhang, Yangyang Wan, Shi-Qi Li, Yuee Xie, Yuanping Chen, Xiaohong Yan","doi":"10.1021/acs.jpclett.5c00700","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00700","url":null,"abstract":"Modulating the carrier dynamics to achieve the effective separation of photoexcited carriers is crucial for enhancing photoelectric conversion efficiency and advancing high-performance optoelectronic devices. A prototype group-III monochalcogenide heterostructure, GaSe/GaTe, has been proposed to exhibit a superior light-harvesting capability and highly tunable charge separation characteristics via nonadiabatic molecular dynamics (NAMD) simulations. The significant influence of stacking patterns on carrier dynamics is revealed, with electron (hole) transfer occurring within 97 (40) to 390 (126) fs, while the carrier lifetime is dramatically prolonged from 12 to 213 ns, facilitating effective electron–hole (e-h) pair separation. Notably, the AA′ and A′A stacking configurations demonstrate remarkably extended carrier lifetimes of 213 and 161 ns, respectively, exceeding those observed in other 2D heterostructures. The weak nonadiabatic coupling and low-frequency phonon vibrational modes suppress e-h recombination, leading to a prolonged carrier lifetime. These findings offer atomic insights into stacking-dependent carrier dynamics, advancing 2D optoelectronic device design.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"24 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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