Sultan Akhtar, Fatimah Zuhair, Muhammad Nawaz and Firdos Alam Khan
The synthesis of gold nanoparticles (AuNPs) via green methods is advantageous due to their economic viability, reduced environmental pollution, and safety towards human health. According to our best knowledge, there is limited documented research on synthesizing AuNPs using gum Arabic (GA) and cinnamon (CNM) and studying their anticancer activities against colorectal cancer cells. This study presents a simple approach to synthesizing AuNPs using GA and CNM, characterized by advanced analytical techniques, including UV-Vis and FTIR spectroscopies, SEM, EDS, TEM, SAED, Zeta sizer, and Zeta potential. The absorption spectra displayed characteristic bands between 520–530 nm, confirming the successful synthesis of AuNPs. TEM analysis revealed that AuNPs@GA exhibited a spherical shape, while AuNPs@CNM displayed diverse morphologies (e.g., spherical, hexagonal, and diamond shapes) with average sizes of approximately 12 nm and 17 nm, respectively. SEM/EDS data confirmed the presence of AuNPs alongside organic compounds such as carbon, oxygen, and phosphorus. The cytotoxic effects of these AuNPs were evaluated on colorectal cancer cells (HCT-116) and healthy cells (HEK-293) using an MTT assay. Notably, AuNPs@GA resulted in a 43.61% loss in cell viability at the dose of 5 μg mL−1, while AuNPs@CNM led to an impressive 80.33% loss. The calculated IC50 values were 9.14 μg mL−1 for AuNPs@GA and 11.76 μg mL−1 for AuNPs@CNM, highlighting the potential of these AuNPs as effective agents in colon cancer treatment. This study not only addresses the lack of research on GA and CNM in NP synthesis but also demonstrates their promising anticancer properties, paving the way for further exploration in cancer therapeutics.
{"title":"Green synthesis, characterization, morphological diversity, and colorectal cancer cytotoxicity of gold nanoparticles†","authors":"Sultan Akhtar, Fatimah Zuhair, Muhammad Nawaz and Firdos Alam Khan","doi":"10.1039/D4RA06340F","DOIUrl":"https://doi.org/10.1039/D4RA06340F","url":null,"abstract":"<p >The synthesis of gold nanoparticles (AuNPs) <em>via</em> green methods is advantageous due to their economic viability, reduced environmental pollution, and safety towards human health. According to our best knowledge, there is limited documented research on synthesizing AuNPs using gum Arabic (GA) and cinnamon (CNM) and studying their anticancer activities against colorectal cancer cells. This study presents a simple approach to synthesizing AuNPs using GA and CNM, characterized by advanced analytical techniques, including UV-Vis and FTIR spectroscopies, SEM, EDS, TEM, SAED, Zeta sizer, and Zeta potential. The absorption spectra displayed characteristic bands between 520–530 nm, confirming the successful synthesis of AuNPs. TEM analysis revealed that AuNPs@GA exhibited a spherical shape, while AuNPs@CNM displayed diverse morphologies (<em>e.g.</em>, spherical, hexagonal, and diamond shapes) with average sizes of approximately 12 nm and 17 nm, respectively. SEM/EDS data confirmed the presence of AuNPs alongside organic compounds such as carbon, oxygen, and phosphorus. The cytotoxic effects of these AuNPs were evaluated on colorectal cancer cells (HCT-116) and healthy cells (HEK-293) using an MTT assay. Notably, AuNPs@GA resulted in a 43.61% loss in cell viability at the dose of 5 μg mL<small><sup>−1</sup></small>, while AuNPs@CNM led to an impressive 80.33% loss. The calculated IC<small><sub>50</sub></small> values were 9.14 μg mL<small><sup>−1</sup></small> for AuNPs@GA and 11.76 μg mL<small><sup>−1</sup></small> for AuNPs@CNM, highlighting the potential of these AuNPs as effective agents in colon cancer treatment. This study not only addresses the lack of research on GA and CNM in NP synthesis but also demonstrates their promising anticancer properties, paving the way for further exploration in cancer therapeutics.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36576-36592"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06340f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lithium–sulfur batteries (LSBs) with metal lithium as the anode and elemental sulfur as the cathode active materials have attracted extensive attention due to their high theoretical specific capacity (1675 mA h g−1), high theoretical energy density (2600 W h kg−1), low cost, and environmental friendliness. However, the discharge intermediate lithium polysulfide undergoes a shuttle side reaction between the two electrodes, resulting in low utilization of the active substances. This limits the capacity and cycle life of LSBs and further delays their commercial development. However, the number of active sites and electron transport capacity of such catalysts still do not meet the practical development needs of lithium–sulfur batteries. In view of these issues, this paper focuses on a zinc–cobalt compound catalyst, modifying it through heteroatom doping, bimetallic synergistic effect and heterogeneous structure design to enhance the performance of LSBs as a separator modification material. A carbon shell-supported boron-doped ZnS/CoS2 heterojunction catalytic material (B–ZnS/CoS2@CS) was prepared, and its performance in lithium–sulfur batteries was evaluated. A carbon substrate (CS) was prepared by pyrolysis of sodium citrate, and the boron-doped ZnS/CoS2 heterojunction catalyst was formed on the CS using a one-step solvothermal method. The unique heterogeneous interface provides numerous active sites for the adsorption and catalysis of polysulfides. The uniformly doped, electron-deficient boron further enhances the Lewis acidity of the ZnS/CoS2 heterojunction, while also regulating electron transport. The B–ZnS/CoS2@CS catalyst effectively inhibits the diffusion of LiPS anions by utilizing additional lone-pair electrons. The lithium–sulfur battery using the catalyst-modified separator achieves a high specific capacity of 1241 mA h g−1 at a current density of 0.2C and retains a specific capacity of 384.2 mA h g−1 at 6.0C. In summary, B–ZnS/CoS2@CS heterojunction catalysts were prepared through boron doping modification. They can promote the conversion of polysulfides and effectively inhibit the shuttle effect. The findings provide valuable insights for the future modification and preparation of lithium–sulfur battery catalysts.
以金属锂为正极、元素硫为负极活性材料的锂硫电池(LSBs)因其理论比容量高(1675 mA h g-1)、理论能量密度高(2600 W h kg-1)、成本低和环境友好而受到广泛关注。然而,放电中间体多硫化锂会在两个电极之间发生穿梭副反应,导致活性物质利用率低。这限制了 LSB 的容量和循环寿命,进一步推迟了其商业开发。然而,此类催化剂的活性位点数量和电子传输能力仍无法满足锂硫电池的实际开发需求。针对这些问题,本文以锌钴化合物催化剂为研究对象,通过杂原子掺杂、双金属协同效应和异质结构设计等方法对其进行改性,以提高锂硫电池作为隔膜改性材料的性能。制备了一种碳壳支撑的掺硼 ZnS/CoS2 异质结催化材料(B-ZnS/CoS2@CS),并对其在锂硫电池中的性能进行了评估。通过热解柠檬酸钠制备了碳基底(CS),并采用一步溶热法在 CS 上形成了掺硼的 ZnS/CoS2 异质结催化剂。独特的异质界面为多硫化物的吸附和催化提供了大量活性位点。均匀掺杂的缺电子硼进一步增强了 ZnS/CoS2 异质结的路易斯酸性,同时也调节了电子传输。B-ZnS/CoS2@CS 催化剂通过利用额外的孤对电子,有效抑制了锂硫电池阴离子的扩散。使用催化剂改性隔膜的锂硫电池在 0.2C 电流密度下实现了 1241 mA h g-1 的高比容量,并在 6.0C 时保持了 384.2 mA h g-1 的比容量。总之,通过硼掺杂改性制备了 B-ZnS/CoS2@CS 异质结催化剂。它们能促进多硫化物的转化并有效抑制穿梭效应。这些发现为今后锂硫电池催化剂的改性和制备提供了宝贵的启示。
{"title":"Preparation of a lithium–sulfur battery diaphragm catalyst and its battery performance","authors":"Jiayi Ren and Qihao Zhao","doi":"10.1039/D4RA06366J","DOIUrl":"https://doi.org/10.1039/D4RA06366J","url":null,"abstract":"<p >Lithium–sulfur batteries (LSBs) with metal lithium as the anode and elemental sulfur as the cathode active materials have attracted extensive attention due to their high theoretical specific capacity (1675 mA h g<small><sup>−1</sup></small>), high theoretical energy density (2600 W h kg<small><sup>−1</sup></small>), low cost, and environmental friendliness. However, the discharge intermediate lithium polysulfide undergoes a shuttle side reaction between the two electrodes, resulting in low utilization of the active substances. This limits the capacity and cycle life of LSBs and further delays their commercial development. However, the number of active sites and electron transport capacity of such catalysts still do not meet the practical development needs of lithium–sulfur batteries. In view of these issues, this paper focuses on a zinc–cobalt compound catalyst, modifying it through heteroatom doping, bimetallic synergistic effect and heterogeneous structure design to enhance the performance of LSBs as a separator modification material. A carbon shell-supported boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalytic material (B–ZnS/CoS<small><sub>2</sub></small>@CS) was prepared, and its performance in lithium–sulfur batteries was evaluated. A carbon substrate (CS) was prepared by pyrolysis of sodium citrate, and the boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalyst was formed on the CS using a one-step solvothermal method. The unique heterogeneous interface provides numerous active sites for the adsorption and catalysis of polysulfides. The uniformly doped, electron-deficient boron further enhances the Lewis acidity of the ZnS/CoS<small><sub>2</sub></small> heterojunction, while also regulating electron transport. The B–ZnS/CoS<small><sub>2</sub></small>@CS catalyst effectively inhibits the diffusion of LiPS anions by utilizing additional lone-pair electrons. The lithium–sulfur battery using the catalyst-modified separator achieves a high specific capacity of 1241 mA h g<small><sup>−1</sup></small> at a current density of 0.2C and retains a specific capacity of 384.2 mA h g<small><sup>−1</sup></small> at 6.0C. In summary, B–ZnS/CoS<small><sub>2</sub></small>@CS heterojunction catalysts were prepared through boron doping modification. They can promote the conversion of polysulfides and effectively inhibit the shuttle effect. The findings provide valuable insights for the future modification and preparation of lithium–sulfur battery catalysts.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36471-36487"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06366j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zafar Ali Shah, Khalid Khan, Tanzeel Shah, Nasir Ahmad and Asad Khan
Fungal metabolites are known for their broad therapeutic effects. In this context, the fungal strain of Aspergillus ficuum (FCBP-DNA-1266) was examined for its secondary metabolites and in vivo activities. This led to the isolation of naphtho-gamma-pyrone (aurasperone B) and a sterol (ergosterol), characterized using advanced spectroscopic techniques such as 1H NMR and 13C NMR. The isolated metabolites were evaluated for their in vivo anti-inflammatory and analgesic activities utilizing an animal model. The study showed that both metabolites have significant pharmacological effects (P ≤ 0.05) in a dose-dependent manner. In addition, in silico analysis was employed to aid the in vivo anti-inflammatory activity and the molecular docking results were in agreement with the experimental findings. For the first time, we present the pharmacological activities and 2D NMR of aurasperone B, which will shed light on the bioactive potential of secondary metabolites of Aspergillus ficuum.
{"title":"Isolation, characterization and pharmacological investigations of secondary metabolites from Aspergillus ficuum via experimental and computational techniques†","authors":"Zafar Ali Shah, Khalid Khan, Tanzeel Shah, Nasir Ahmad and Asad Khan","doi":"10.1039/D4RA03674C","DOIUrl":"https://doi.org/10.1039/D4RA03674C","url":null,"abstract":"<p >Fungal metabolites are known for their broad therapeutic effects. In this context, the fungal strain of <em>Aspergillus ficuum</em> (FCBP-DNA-1266) was examined for its secondary metabolites and <em>in vivo</em> activities. This led to the isolation of naphtho-gamma-pyrone (aurasperone B) and a sterol (ergosterol), characterized using advanced spectroscopic techniques such as <small><sup>1</sup></small>H NMR and <small><sup>13</sup></small>C NMR. The isolated metabolites were evaluated for their <em>in vivo</em> anti-inflammatory and analgesic activities utilizing an animal model. The study showed that both metabolites have significant pharmacological effects (<em>P</em> ≤ 0.05) in a dose-dependent manner. In addition, <em>in silico</em> analysis was employed to aid the <em>in vivo</em> anti-inflammatory activity and the molecular docking results were in agreement with the experimental findings. For the first time, we present the pharmacological activities and 2D NMR of aurasperone B, which will shed light on the bioactive potential of secondary metabolites of <em>Aspergillus ficuum</em>.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36527-36537"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra03674c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Issues such as the polysulfide shuttle effect and sulfur loss challenge the development of high-energy-density lithium–sulfur batteries. To address these limitations, a tailored approach is introduced using nickel phosphide carbon composite nanofibers (NixP/C) with controlled surface oxidation layers. These nanofibers feature a hierarchical structure that leverages the benefits of nickel phosphide nanoparticles and a carbonaceous matrix to enable efficient sulfur encapsulation and suppress polysulfide diffusion. Comprehensive characterization and electrochemical testing reveal that NixP/C, when employed as interlayers in a cell with a bio-waste-derived carbon-based sulfur cathode, significantly enhance electrochemical performance by increasing charge–discharge capacities and reducing charge-transfer resistance. Post-mortem analyses further show effective polysulfide trapping and conversion on the cathode side, preventing their shuttle to the anode, which results in a remarkable cycle stability of up to 200 cycles at 2C with a high discharge capacity of about 800 mA h g−1. These findings confirm the potential of NixP/C to improve lithium–sulfur battery technologies and demonstrate their applicability in diverse lithium–sulfur cell configurations.
多硫穿梭效应和硫损失等问题给高能量密度锂硫电池的开发带来了挑战。为了解决这些局限性,我们引入了一种定制方法,即使用具有可控表面氧化层的磷化镍碳复合纳米纤维(NixP/C)。这些纳米纤维具有分层结构,充分利用了磷化镍纳米颗粒和碳基质的优点,从而实现了高效的硫封装并抑制了多硫化物的扩散。综合表征和电化学测试表明,NixP/C 作为夹层应用于带有生物废料碳基硫阴极的电池中时,通过提高充放电容量和降低电荷转移电阻,显著提高了电化学性能。死后分析进一步表明,多硫化物在阴极一侧得到了有效的捕获和转化,阻止了它们向阳极的穿梭,从而实现了在 2C 下长达 200 个循环的显著循环稳定性,以及约 800 mA h g-1 的高放电容量。这些发现证实了 NixP/C 在改进锂硫电池技术方面的潜力,并证明了其在各种锂硫电池配置中的适用性。
{"title":"Polysulfide-mediating properties of nickel phosphide carbon composite nanofibers as free-standing interlayers for lithium–sulfur batteries†","authors":"Ayaulym Belgibayeva, Gulderaiym Turarova, Akmaral Dangaliyeva, Fail Sultanov, Arailym Nurpeissova, Aliya Mukanova and Zhumabay Bakenov","doi":"10.1039/D4RA07285E","DOIUrl":"https://doi.org/10.1039/D4RA07285E","url":null,"abstract":"<p >Issues such as the polysulfide shuttle effect and sulfur loss challenge the development of high-energy-density lithium–sulfur batteries. To address these limitations, a tailored approach is introduced using nickel phosphide carbon composite nanofibers (Ni<small><sub><em>x</em></sub></small>P/C) with controlled surface oxidation layers. These nanofibers feature a hierarchical structure that leverages the benefits of nickel phosphide nanoparticles and a carbonaceous matrix to enable efficient sulfur encapsulation and suppress polysulfide diffusion. Comprehensive characterization and electrochemical testing reveal that Ni<small><sub><em>x</em></sub></small>P/C, when employed as interlayers in a cell with a bio-waste-derived carbon-based sulfur cathode, significantly enhance electrochemical performance by increasing charge–discharge capacities and reducing charge-transfer resistance. Post-mortem analyses further show effective polysulfide trapping and conversion on the cathode side, preventing their shuttle to the anode, which results in a remarkable cycle stability of up to 200 cycles at 2C with a high discharge capacity of about 800 mA h g<small><sup>−1</sup></small>. These findings confirm the potential of Ni<small><sub><em>x</em></sub></small>P/C to improve lithium–sulfur battery technologies and demonstrate their applicability in diverse lithium–sulfur cell configurations.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36593-36601"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra07285e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Shamim Al Mamun, Yasuyuki Sainoo, Tsuyoshi Takaoka, Atsushi Ando and Tadahiro Komeda
We report the characteristic behaviors of the hysteresis observed in the transfer characteristics of back-gated field-effect transistors with an exfoliated MoS2 channel under various conditions. We find that the hysteresis is strongly enhanced by temperature, environmental gas, or light irradiation. Our measurements reveal the characteristic hysteresis behaviors in a 1 atm oxygen environment, which we explain as an oxygen molecule facilitated charge acceptor on the MoS2 surface. The decrease in the current value in the ON state of the device may indicate that oxygen molecules are more effective charge acceptors than nitrogen molecules. We conclude that intrinsic defects in MoS2, such as S vacancies, which result in effective adsorbate trapping, play an important role in the hysteresis behavior, in addition to oxygen and nitrogen adsorbates on the passivated device surface. The availability of thermally or photo-generated minority carriers (holes) in MoS2 is increased by both light and temperature. This leads to subsequent processes of positive charge trapping, which intensify the hysteresis.
{"title":"Hysteresis in the transfer characteristics of MoS2 field effect transistors: gas, temperature and photo-irradiation effect†","authors":"Muhammad Shamim Al Mamun, Yasuyuki Sainoo, Tsuyoshi Takaoka, Atsushi Ando and Tadahiro Komeda","doi":"10.1039/D4RA04820B","DOIUrl":"https://doi.org/10.1039/D4RA04820B","url":null,"abstract":"<p >We report the characteristic behaviors of the hysteresis observed in the transfer characteristics of back-gated field-effect transistors with an exfoliated MoS<small><sub>2</sub></small> channel under various conditions. We find that the hysteresis is strongly enhanced by temperature, environmental gas, or light irradiation. Our measurements reveal the characteristic hysteresis behaviors in a 1 atm oxygen environment, which we explain as an oxygen molecule facilitated charge acceptor on the MoS<small><sub>2</sub></small> surface. The decrease in the current value in the ON state of the device may indicate that oxygen molecules are more effective charge acceptors than nitrogen molecules. We conclude that intrinsic defects in MoS<small><sub>2</sub></small>, such as S vacancies, which result in effective adsorbate trapping, play an important role in the hysteresis behavior, in addition to oxygen and nitrogen adsorbates on the passivated device surface. The availability of thermally or photo-generated minority carriers (holes) in MoS<small><sub>2</sub></small> is increased by both light and temperature. This leads to subsequent processes of positive charge trapping, which intensify the hysteresis.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36517-36526"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04820b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Tariq Aziz, Waqas Amber Gill, Muhammad Kaleem Khosa, Saba Jamil and Muhammad Ramzan Saeed Ashraf Janjua
Understanding the adsorption behavior of molecular hydrogen (H2) on solid surfaces is essential for a variety of technological applications, including hydrogen storage and catalysis. We examined the adsorption of H2 (∼2800 configurations) molecules on the surface of fullerene (C60) using a combined approach of density functional theory (DFT) and molecular dynamics (MD) simulations with an improved Lennard-Jones (ILJ) potential force field. First, we determined the adsorption energies and geometries of H2 on the C60 surface using DFT calculations. Calculations of the electronic structure help elucidate underlying mechanisms administrating the adsorption process by revealing how H2 molecules interact with the C60 surface. In addition, molecular dynamics simulations were performed to examine the dynamic behavior of H2 molecules on the C60 surface. We accurately depicted the intermolecular interactions between H2 and C60, as well as the collective behavior of adsorbed H2 molecules, using an ILJ potential force field. Our findings indicate that H2 molecules exhibit robust physisorption on the C60 surface, forming stable adsorption structures with favorable adsorption energies. Calculated adsorption energies and binding sites are useful for designing efficient hydrogen storage materials and comprehending the nature of hydrogen's interactions with carbon-based nanostructures. This research provides a comprehensive understanding of H2 adsorption on the C60 surface by combining the theoretical framework of DFT calculations with the dynamical perspective of MD simulations. The outcomes of the present research provide new insights into the fields of hydrogen storage and carbon-based nanomaterials, facilitating the development of efficient hydrogen storage systems and advancing the use of molecular hydrogen in a variety of applications.
{"title":"Adsorption of molecular hydrogen (H2) on a fullerene (C60) surface: insights from density functional theory and molecular dynamics simulation","authors":"Muhammad Tariq Aziz, Waqas Amber Gill, Muhammad Kaleem Khosa, Saba Jamil and Muhammad Ramzan Saeed Ashraf Janjua","doi":"10.1039/D4RA06171C","DOIUrl":"https://doi.org/10.1039/D4RA06171C","url":null,"abstract":"<p >Understanding the adsorption behavior of molecular hydrogen (H<small><sub>2</sub></small>) on solid surfaces is essential for a variety of technological applications, including hydrogen storage and catalysis. We examined the adsorption of H<small><sub>2</sub></small> (∼2800 configurations) molecules on the surface of fullerene (C<small><sub>60</sub></small>) using a combined approach of density functional theory (DFT) and molecular dynamics (MD) simulations with an improved Lennard-Jones (ILJ) potential force field. First, we determined the adsorption energies and geometries of H<small><sub>2</sub></small> on the C<small><sub>60</sub></small> surface using DFT calculations. Calculations of the electronic structure help elucidate underlying mechanisms administrating the adsorption process by revealing how H<small><sub>2</sub></small> molecules interact with the C<small><sub>60</sub></small> surface. In addition, molecular dynamics simulations were performed to examine the dynamic behavior of H<small><sub>2</sub></small> molecules on the C<small><sub>60</sub></small> surface. We accurately depicted the intermolecular interactions between H<small><sub>2</sub></small> and C<small><sub>60</sub></small>, as well as the collective behavior of adsorbed H<small><sub>2</sub></small> molecules, using an ILJ potential force field. Our findings indicate that H<small><sub>2</sub></small> molecules exhibit robust physisorption on the C<small><sub>60</sub></small> surface, forming stable adsorption structures with favorable adsorption energies. Calculated adsorption energies and binding sites are useful for designing efficient hydrogen storage materials and comprehending the nature of hydrogen's interactions with carbon-based nanostructures. This research provides a comprehensive understanding of H<small><sub>2</sub></small> adsorption on the C<small><sub>60</sub></small> surface by combining the theoretical framework of DFT calculations with the dynamical perspective of MD simulations. The outcomes of the present research provide new insights into the fields of hydrogen storage and carbon-based nanomaterials, facilitating the development of efficient hydrogen storage systems and advancing the use of molecular hydrogen in a variety of applications.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36546-36556"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06171c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuankun Liu, Xiaotian Guo, Liyuan Zhao, Wenqi Duan, Yeqian Huang and Xiaojuan Wang
Modified magnetic chitosan nanoparticles (EMMCS-G), used as a Fenton-like catalyst, were successfully prepared and modified with glutaraldehyde and ethylenediamine. EMMCS-G has strong magnetization, good reusability, stability, environmental friendliness, and high efficiency. In the Fenton-like system, the synergistic effect of adsorption and advanced oxidation significantly enhances the removal effect of tetracycline (TC). The optimal concentration of persulfate was found to be 20 mmol L−1, and at a pH of 3, the removal efficiency of TC reached 95.6% after 6 hours. The oxidation system demonstrated excellent pH adaptability, achieving a TC removal rate of 94% within 6 hours across a pH range of 3 to 8. Hydroxyl (˙OH) and sulfate (SO4−˙ ) radicals were present in the reaction system, with ˙OH playing an important role in the oxidation process of TC. The attack sites of tetracycline were identified using density functional theory (DFT), and five degradation pathways for TC were proposed based on LS-MS experiments. Finally, quantitative structure–activity relationship (QSAR) analysis was employed to assess the toxicity of the intermediates. Overall, toxicity gradually decreased, indicating that the Fenton reaction system effectively reduced the toxicity and mutagenicity of TC. This study suggests EMMCS-G as a potential catalyst for enhanced Fenton-like degradation with excellent efficiency observed for the degradation of tetracycline for environmental remediation.
{"title":"Synergistic removal mechanism of tetracycline by ethylenediamine modified magnetic chitosan based Fenton-like catalyst†","authors":"Yuankun Liu, Xiaotian Guo, Liyuan Zhao, Wenqi Duan, Yeqian Huang and Xiaojuan Wang","doi":"10.1039/D4RA04059G","DOIUrl":"https://doi.org/10.1039/D4RA04059G","url":null,"abstract":"<p >Modified magnetic chitosan nanoparticles (EMMCS-G), used as a Fenton-like catalyst, were successfully prepared and modified with glutaraldehyde and ethylenediamine. EMMCS-G has strong magnetization, good reusability, stability, environmental friendliness, and high efficiency. In the Fenton-like system, the synergistic effect of adsorption and advanced oxidation significantly enhances the removal effect of tetracycline (TC). The optimal concentration of persulfate was found to be 20 mmol L<small><sup>−1</sup></small>, and at a pH of 3, the removal efficiency of TC reached 95.6% after 6 hours. The oxidation system demonstrated excellent pH adaptability, achieving a TC removal rate of 94% within 6 hours across a pH range of 3 to 8. Hydroxyl (˙OH) and sulfate (SO<small><sub>4</sub></small><small><sup>−</sup></small>˙ ) radicals were present in the reaction system, with ˙OH playing an important role in the oxidation process of TC. The attack sites of tetracycline were identified using density functional theory (DFT), and five degradation pathways for TC were proposed based on LS-MS experiments. Finally, quantitative structure–activity relationship (QSAR) analysis was employed to assess the toxicity of the intermediates. Overall, toxicity gradually decreased, indicating that the Fenton reaction system effectively reduced the toxicity and mutagenicity of TC. This study suggests EMMCS-G as a potential catalyst for enhanced Fenton-like degradation with excellent efficiency observed for the degradation of tetracycline for environmental remediation.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36507-36516"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04059g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yingqian Li, Yali Liu, Di Hao, Liang Xu and Ping Liu
In this study, we report a novel and efficient method for the regioselective bromination of pyrrolo[1,2-a]quinoxalines using tetrabutylammonium tribromide (TBATB). This method exploits the mild nature of TBATB to obtain highly selective C3-brominated or C1, C3-dibrominated products in good yields. Notably, the reaction has a broad substrate applicability, and the C3-brominated product can be synthesized on a gram scale and can be further converted into structurally diverse pyrrolo[1,2-a]quinoxaline derivatives.
{"title":"Regioselective bromination of pyrrolo[1,2-a]quinoxalines†","authors":"Yingqian Li, Yali Liu, Di Hao, Liang Xu and Ping Liu","doi":"10.1039/D4RA07358D","DOIUrl":"https://doi.org/10.1039/D4RA07358D","url":null,"abstract":"<p >In this study, we report a novel and efficient method for the regioselective bromination of pyrrolo[1,2-<em>a</em>]quinoxalines using tetrabutylammonium tribromide (TBATB). This method exploits the mild nature of TBATB to obtain highly selective C3-brominated or C1, C3-dibrominated products in good yields. Notably, the reaction has a broad substrate applicability, and the C3-brominated product can be synthesized on a gram scale and can be further converted into structurally diverse pyrrolo[1,2-<em>a</em>]quinoxaline derivatives.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36488-36496"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra07358d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nafisa Tabassum, Raamisa Anjum, Papia Haque, Md. Sahadat Hossain, Mashrafi Bin Mobarak, Md. Saiful Quddus, Fariha Chowdhury, Lutfor Rahman, Dipa Islam, Samina Ahmed and Monika Mahmud
The deployment of magnetically responsive and polymeric materials to remove dyes that are hazardous in aquatic environments has profoundly revolutionized environmental sustainability. This study focuses on removing the hazardous cationic Malachite Green (MG) dye from solutions, employing a novel magnetic composite film as an adsorbent, designated as Ag0.2Co0.8 Fe2O4 (ACFCeP). The composite was synthesized via solvent casting, incorporating Ag0.2Co0.8 Fe2O4 nanoparticles and CeO2 into a cellulose acetate/polyvinylpyrrolidone (CA/PVP) polymer matrix. The Ag0.2Co0.8Fe2O4 nanoparticles were synthesized by a co-precipitation method. Comprehensive characterization of the synthesized composite was conducted using techniques, such as Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), and vibrating sample magnetometer (VSM). The Ag-doped cobalt ferrite component retained a strong hysteresis loop within the final composite, even when blended with the CA/PVP polymer, preserving the robust magnetic properties that facilitate the easy removal of the composite post-treatment without secondary pollution. Additionally, the mesoporous structure of the composite effectively aids in the adsorption mechanism. The isothermal study shows that both linear Langmuir isotherm and Freundlich isotherm are well fitted with R2 values of 0.99 and 0.97, respectively. The linear Langmuir maximum adsorption capacity, qmax, is 45.66 mg g−1 at pH 7. The kinetic studies of the composite resemble the pseudo-second-order kinetic model, reaching adsorption equilibrium within 70 min for a 100 ppm MG dye concentration. The composite film exhibits excellent reusability, maintaining high removal efficiency over three cycles. Overall, the ACFCeP composite film showcases excellent dye removal capabilities, a fast adsorption rate, and satisfactory magnetic properties and offers a sustainable solution for environmental pollution, thus contributing to ecosystem preservation through efficient recycling and reuse in dye adsorption applications.
{"title":"Ag–Co ferrite-based magnetic polymeric composite film: a breakthrough in cationic dye remediation for sustainable environment†","authors":"Nafisa Tabassum, Raamisa Anjum, Papia Haque, Md. Sahadat Hossain, Mashrafi Bin Mobarak, Md. Saiful Quddus, Fariha Chowdhury, Lutfor Rahman, Dipa Islam, Samina Ahmed and Monika Mahmud","doi":"10.1039/D4RA06315E","DOIUrl":"https://doi.org/10.1039/D4RA06315E","url":null,"abstract":"<p >The deployment of magnetically responsive and polymeric materials to remove dyes that are hazardous in aquatic environments has profoundly revolutionized environmental sustainability. This study focuses on removing the hazardous cationic Malachite Green (MG) dye from solutions, employing a novel magnetic composite film as an adsorbent, designated as Ag<small><sub>0.2</sub></small>Co<small><sub>0.8</sub></small> Fe<small><sub>2</sub></small>O<small><sub>4</sub></small> (ACFCeP). The composite was synthesized <em>via</em> solvent casting, incorporating Ag<small><sub>0.2</sub></small>Co<small><sub>0.8</sub></small> Fe<small><sub>2</sub></small>O<small><sub>4</sub></small> nanoparticles and CeO<small><sub>2</sub></small> into a cellulose acetate/polyvinylpyrrolidone (CA/PVP) polymer matrix. The Ag<small><sub>0.2</sub></small>Co<small><sub>0.8</sub></small>Fe<small><sub>2</sub></small>O<small><sub>4</sub></small> nanoparticles were synthesized by a co-precipitation method. Comprehensive characterization of the synthesized composite was conducted using techniques, such as Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), and vibrating sample magnetometer (VSM). The Ag-doped cobalt ferrite component retained a strong hysteresis loop within the final composite, even when blended with the CA/PVP polymer, preserving the robust magnetic properties that facilitate the easy removal of the composite post-treatment without secondary pollution. Additionally, the mesoporous structure of the composite effectively aids in the adsorption mechanism. The isothermal study shows that both linear Langmuir isotherm and Freundlich isotherm are well fitted with <em>R</em><small><sup>2</sup></small> values of 0.99 and 0.97, respectively. The linear Langmuir maximum adsorption capacity, <em>q</em><small><sub>max</sub></small>, is 45.66 mg g<small><sup>−1</sup></small> at pH 7. The kinetic studies of the composite resemble the pseudo-second-order kinetic model, reaching adsorption equilibrium within 70 min for a 100 ppm MG dye concentration. The composite film exhibits excellent reusability, maintaining high removal efficiency over three cycles. Overall, the ACFCeP composite film showcases excellent dye removal capabilities, a fast adsorption rate, and satisfactory magnetic properties and offers a sustainable solution for environmental pollution, thus contributing to ecosystem preservation through efficient recycling and reuse in dye adsorption applications.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36557-36575"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06315e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142636614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrolyzing CO2 into ethylene (C2H4) is a promising strategy for CO2 utilization and carbon neutrality since C2H4 is an important industrial feedstock. However, selectively converting CO2 into C2H4via the CO2 electro-reduction reaction (CO2 ERR) is still a great challenge. Herein, Cu–Cu2O nanoparticles anchored on reduced graphene oxide nanosheets (Cu–Cu2O/rGO) were prepared from copper hydroxide nanostrands (CHNs) and graphene oxide (GO) nanosheets via in situ electrochemical reduction. Cu–Cu2O nanoparticles with diameter less than 10 nm were formed on the surface of rGO nanosheets. After assembling the Cu–Cu2O/rGO catalyst into a flow cell, it demonstrated high Faraday efficiencies (FEs) of 55.4%, 37.6%, and 6.7% for C2H4, C2H6, and H2, respectively, and a total 93% FE for C2 at −1.3 V vs. the standard hydrogen electrode (SHE). Moreover, its FE was 68.2% for C2H4, 10.2% for C2H6, and 20.5% for H2 at −1.4 (vs. SHE). Besides, no liquid carbon product was detected. This high selectivity is attributed to the synergistic effect arising from the small diameter of Cu–Cu2O NPs with the combination of Cu0–Cu+ and rGO nanosheets, which promotes the activation of CO2 molecules, facilitates C–C coupling, and enhances stability. This may provide a facile way for designing an efficient catalyst for selectively electrolyzing CO2 into valuable C2 chemicals.
{"title":"Selectively electrolyzing CO2 to ethylene by a Cu–Cu2O/rGO catalyst derived from copper hydroxide nanostrands/graphene oxide nanosheets†","authors":"Chenxiang Peng, Bing Yao, Lei Wang and Xinyi Wan","doi":"10.1039/D4RA07259F","DOIUrl":"https://doi.org/10.1039/D4RA07259F","url":null,"abstract":"<p >Electrolyzing CO<small><sub>2</sub></small> into ethylene (C<small><sub>2</sub></small>H<small><sub>4</sub></small>) is a promising strategy for CO<small><sub>2</sub></small> utilization and carbon neutrality since C<small><sub>2</sub></small>H<small><sub>4</sub></small> is an important industrial feedstock. However, selectively converting CO<small><sub>2</sub></small> into C<small><sub>2</sub></small>H<small><sub>4</sub></small> <em>via</em> the CO<small><sub>2</sub></small> electro-reduction reaction (CO<small><sub>2</sub></small> ERR) is still a great challenge. Herein, Cu–Cu<small><sub>2</sub></small>O nanoparticles anchored on reduced graphene oxide nanosheets (Cu–Cu<small><sub>2</sub></small>O/rGO) were prepared from copper hydroxide nanostrands (CHNs) and graphene oxide (GO) nanosheets <em>via in situ</em> electrochemical reduction. Cu–Cu<small><sub>2</sub></small>O nanoparticles with diameter less than 10 nm were formed on the surface of rGO nanosheets. After assembling the Cu–Cu<small><sub>2</sub></small>O/rGO catalyst into a flow cell, it demonstrated high Faraday efficiencies (FEs) of 55.4%, 37.6%, and 6.7% for C<small><sub>2</sub></small>H<small><sub>4</sub></small>, C<small><sub>2</sub></small>H<small><sub>6</sub></small>, and H<small><sub>2</sub></small>, respectively, and a total 93% FE for C<small><sub>2</sub></small> at −1.3 V <em>vs.</em> the standard hydrogen electrode (SHE). Moreover, its FE was 68.2% for C<small><sub>2</sub></small>H<small><sub>4</sub></small>, 10.2% for C<small><sub>2</sub></small>H<small><sub>6</sub></small>, and 20.5% for H<small><sub>2</sub></small> at −1.4 (<em>vs.</em> SHE). Besides, no liquid carbon product was detected. This high selectivity is attributed to the synergistic effect arising from the small diameter of Cu–Cu<small><sub>2</sub></small>O NPs with the combination of Cu<small><sup>0</sup></small>–Cu<small><sup>+</sup></small> and rGO nanosheets, which promotes the activation of CO<small><sub>2</sub></small> molecules, facilitates C–C coupling, and enhances stability. This may provide a facile way for designing an efficient catalyst for selectively electrolyzing CO<small><sub>2</sub></small> into valuable C<small><sub>2</sub></small> chemicals.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36602-36609"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra07259f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}