A pair of Brønsted-Lewis acidic chlorozincate ionic liquids based on 2-alkyl-1,3-disulfoimidazolium cations (1a & 1b) was developed with complex anionic speciation [Zn2Cl6]2−/[ZnCl4]2−. These ionic liquids were further used as templates for fabricating ZnS quantum dots (QDs) via a grinding method. The ZnS QDs were characterized using various techniques. The use of ionic liquids (ILs) containing complex metal chloride anions resulted in small size and porous nature of the QDs. The presence of various types of defects was verified through XPS, EPR and photoluminescence spectroscopic analyses. These two QDs were used as reusable and recyclable catalysts for the degradation of a broad spectrum of pollutants such as crystal violet (CV), methylene blue (MB), malachite green (MG), morin hydrate, and oxytetracycline (OTC) under UV light irradiation. Free radical scavenging experiments showed that ˙OH and ˙O2− acted as primary reactive species during the degradation process. These QDs were further employed for iodine sorption experiments in water and hexane solutions. The XPS analysis revealed that the adsorption process occurred in molecular (I2) and polyiodide (I3−) forms. The recyclability study of the iodine sorption revealed that the QDs could retain 90.6% and 89.4% of their initial efficiency after the 5th cycle in water and hexane solution, respectively. No such reports regarding the use of Brønsted-Lewis acidic chlorozincate ionic liquids for the synthesis of mesoporous defective ZnS QDs has been published. Moreover, the utilization of the pristine ZnS QDs for iodine capture experiments is reported for the first time.
{"title":"Brønsted-Lewis acidic ionic liquid-derived ZnS quantum dots: synthesis, characterization, and multifunctional applications in pollutant degradation and iodine sorption","authors":"Debanga Bhusan Bora, Sukanya Das, Abhilekha Phukan, Sangeeta Kalita, Prapti Priyam Handique, Ruli Borah","doi":"10.1039/d5nr00043b","DOIUrl":"https://doi.org/10.1039/d5nr00043b","url":null,"abstract":"A pair of Brønsted-Lewis acidic chlorozincate ionic liquids based on 2-alkyl-1,3-disulfoimidazolium cations (<strong>1a</strong> & <strong>1b</strong>) was developed with complex anionic speciation [Zn<small><sub>2</sub></small>Cl<small><sub>6</sub></small>]<small><sup>2−</sup></small>/[ZnCl<small><sub>4</sub></small>]<small><sup>2−</sup></small>. These ionic liquids were further used as templates for fabricating ZnS quantum dots (QDs) <em>via</em> a grinding method. The ZnS QDs were characterized using various techniques. The use of ionic liquids (ILs) containing complex metal chloride anions resulted in small size and porous nature of the QDs. The presence of various types of defects was verified through XPS, EPR and photoluminescence spectroscopic analyses. These two QDs were used as reusable and recyclable catalysts for the degradation of a broad spectrum of pollutants such as crystal violet (CV), methylene blue (MB), malachite green (MG), morin hydrate, and oxytetracycline (OTC) under UV light irradiation. Free radical scavenging experiments showed that ˙OH and ˙O<small><sub>2</sub></small><small><sup>−</sup></small> acted as primary reactive species during the degradation process. These QDs were further employed for iodine sorption experiments in water and hexane solutions. The XPS analysis revealed that the adsorption process occurred in molecular (I<small><sub>2</sub></small>) and polyiodide (I<small><sub>3</sub></small><small><sup>−</sup></small>) forms. The recyclability study of the iodine sorption revealed that the QDs could retain 90.6% and 89.4% of their initial efficiency after the 5th cycle in water and hexane solution, respectively. No such reports regarding the use of Brønsted-Lewis acidic chlorozincate ionic liquids for the synthesis of mesoporous defective ZnS QDs has been published. Moreover, the utilization of the pristine ZnS QDs for iodine capture experiments is reported for the first time.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"64 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143790144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Baidyanath Roy, Tamal Dey, Shaona Bose, Somnath Mahato, Narayan Chandra Das, Samit K. Ray
Nanocrystal-sensitized solar cells have emerged as potential alternatives to traditional photovoltaic technology due to their unique light absorption and emission characteristics and size-dependent bandgap. In this work, we report the successful synthesis of cubic-phase CsPbI₃ and CsPbBr₃ nanocrystals for their use as photosensitizers in solar cells, referred to as perovskite nanocrystal-sensitized solar cells (PNCSSCs). Among the two systems, CsPbI₃ is found to be superior for PNCSSCs because of its high absorption efficiency, lower bandgap, and higher photoluminescence yield, as compared to CsPbBr₃. Our study examines the structural, compositional, optical, and electrical properties of these perovskite nanocrystals, focusing on their contributions to photoconversion efficiency. CsPbBr₃ nanocrystals exhibit a band gap of ~2.4 eV along with defect states-induced short carrier lifetime of around 18 ns. In contrast, CsPbI₃ demonstrates a band gap of ~1.8 eV closer to the peak of the solar spectrum with a much longer carrier lifetime of ~130 ns, which facilitates better separation and collection of photogenerated charge carriers. Consequently, CsPbI₃ nanocrystals-sensitized solar cells fabricated with mesoporous TiO2 reveal a photoconversion efficiency of ~ 12.5%, as compared to 3.8% for CsPbBr₃ nanocrystals solar cells. To the best of our knowledge, this is the highest reported photoconversion efficiency in solution-processed perovskite nanocrystal-sensitized solar cells.
{"title":"Superior Photoconversion Efficiency of Nanocrystal Sensitized Solar Cells Based on All-Inorganic CsPbX3 (X=Br, I) Perovskites","authors":"Baidyanath Roy, Tamal Dey, Shaona Bose, Somnath Mahato, Narayan Chandra Das, Samit K. Ray","doi":"10.1039/d4nr04752d","DOIUrl":"https://doi.org/10.1039/d4nr04752d","url":null,"abstract":"Nanocrystal-sensitized solar cells have emerged as potential alternatives to traditional photovoltaic technology due to their unique light absorption and emission characteristics and size-dependent bandgap. In this work, we report the successful synthesis of cubic-phase CsPbI₃ and CsPbBr₃ nanocrystals for their use as photosensitizers in solar cells, referred to as perovskite nanocrystal-sensitized solar cells (PNCSSCs). Among the two systems, CsPbI₃ is found to be superior for PNCSSCs because of its high absorption efficiency, lower bandgap, and higher photoluminescence yield, as compared to CsPbBr₃. Our study examines the structural, compositional, optical, and electrical properties of these perovskite nanocrystals, focusing on their contributions to photoconversion efficiency. CsPbBr₃ nanocrystals exhibit a band gap of ~2.4 eV along with defect states-induced short carrier lifetime of around 18 ns. In contrast, CsPbI₃ demonstrates a band gap of ~1.8 eV closer to the peak of the solar spectrum with a much longer carrier lifetime of ~130 ns, which facilitates better separation and collection of photogenerated charge carriers. Consequently, CsPbI₃ nanocrystals-sensitized solar cells fabricated with mesoporous TiO2 reveal a photoconversion efficiency of ~ 12.5%, as compared to 3.8% for CsPbBr₃ nanocrystals solar cells. To the best of our knowledge, this is the highest reported photoconversion efficiency in solution-processed perovskite nanocrystal-sensitized solar cells.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"29 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yajie Bai, Dongliang Shan, Huixian Li, Yuhao Ye, Suofu Wang, Tao Han, Wenhui Wang, Feng Li, Yunya Liu, Lei Shan, Mingsheng Long
Narrow bandgap two-dimensional (2D) semiconductors have garnered significant attention for their potential applications in next-generation optoelectronic devices. However, only a few previous studies have manipulated electronic polarizations such as ferroelectric polarization or spin polarization in conjunction with photodetectors. In this work, we designed Te ferroelectric field-effect transistors (Fe-FETs), which exhibit a clear counterclockwise hysteresis loop in transfer characteristic curves. The device achieves an ultrabroad band photoresponse from 637 nm to 10.6 μm, and high photoresponsivity (R) of 10.2 AW-1 under 1 V bias. Importantly, under a 637 nm laser, the device shows very fast speed with rise time (τr) of 3.86 μs and decay time (τd) of 6.28 μs. The proposed Te Fe-FET device provides a strategy for designing high-performance photodetectors with extensive applications.
{"title":"Broadband Photoresponse Based on Te/CuInP2S6 Ferroelectric Field-effect Transistor","authors":"Yajie Bai, Dongliang Shan, Huixian Li, Yuhao Ye, Suofu Wang, Tao Han, Wenhui Wang, Feng Li, Yunya Liu, Lei Shan, Mingsheng Long","doi":"10.1039/d5nr00514k","DOIUrl":"https://doi.org/10.1039/d5nr00514k","url":null,"abstract":"Narrow bandgap two-dimensional (2D) semiconductors have garnered significant attention for their potential applications in next-generation optoelectronic devices. However, only a few previous studies have manipulated electronic polarizations such as ferroelectric polarization or spin polarization in conjunction with photodetectors. In this work, we designed Te ferroelectric field-effect transistors (Fe-FETs), which exhibit a clear counterclockwise hysteresis loop in transfer characteristic curves. The device achieves an ultrabroad band photoresponse from 637 nm to 10.6 μm, and high photoresponsivity (R) of 10.2 AW-1 under 1 V bias. Importantly, under a 637 nm laser, the device shows very fast speed with rise time (τr) of 3.86 μs and decay time (τd) of 6.28 μs. The proposed Te Fe-FET device provides a strategy for designing high-performance photodetectors with extensive applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"4 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chudi Ni, Xiaoxia Chen, Yiwen Chen, Shiyu Li, Tao Zhou, Jing Yang, Meihuan Liu and Hui Su
Ultrafine ordered intermetallic nanoparticles are emerging as promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. However, they are difficult to obtain because high-temperature annealing inevitably leads to metal sintering, resulting in larger crystallites. Additionally, the resulting electronic effects are difficult to control, limiting both performance and stability improvements. Herein, we present an ultrafine ordered intermetallic platinum-cobalt alloy encaged in nitrogen-doped carbon (Pt3Co/NC) with a small particle size of 4.18 ± 1.00 nm and a high electrochemically active surface area (ECSA) of 73.16 m2 gPt−1. The contraction of the Pt–Pt pair induces strong electron coupling, resulting in electron transfer from Co to Pt. Using in situ spectroscopies, we revealed that incorporating the cost-effective transition metal Co into the Pt lattice induces Pt–Pt contraction and generates additional Pt d-band occupancy, which accelerates the protonation of *O to *OH, thereby significantly enhancing the kinetics of the four-electron ORR process. The meticulously designed catalyst achieves a superior half-wave potential of 0.89 V versus RHE and a remarkable mass activity of 0.79 A mgPt−1. More importantly, after 10 000 cycles, the particle size expansion is marginal (5.01 ± 0.92 nm), alongside slight reductions in mass activity (6%) and specific activity (2%), demonstrating excellent catalytic stability in an acidic medium.
{"title":"Ultrafine intermetallic platinum-cobalt with a contracted Pt–Pt pair for efficient acidic oxygen reduction reactions†","authors":"Chudi Ni, Xiaoxia Chen, Yiwen Chen, Shiyu Li, Tao Zhou, Jing Yang, Meihuan Liu and Hui Su","doi":"10.1039/D5NR00220F","DOIUrl":"10.1039/D5NR00220F","url":null,"abstract":"<p >Ultrafine ordered intermetallic nanoparticles are emerging as promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. However, they are difficult to obtain because high-temperature annealing inevitably leads to metal sintering, resulting in larger crystallites. Additionally, the resulting electronic effects are difficult to control, limiting both performance and stability improvements. Herein, we present an ultrafine ordered intermetallic platinum-cobalt alloy encaged in nitrogen-doped carbon (Pt<small><sub>3</sub></small>Co/NC) with a small particle size of 4.18 ± 1.00 nm and a high electrochemically active surface area (ECSA) of 73.16 m<small><sup>2</sup></small> g<small><sub>Pt</sub></small><small><sup>−1</sup></small>. The contraction of the Pt–Pt pair induces strong electron coupling, resulting in electron transfer from Co to Pt. Using <em>in situ</em> spectroscopies, we revealed that incorporating the cost-effective transition metal Co into the Pt lattice induces Pt–Pt contraction and generates additional Pt d-band occupancy, which accelerates the protonation of *O to *OH, thereby significantly enhancing the kinetics of the four-electron ORR process. The meticulously designed catalyst achieves a superior half-wave potential of 0.89 V <em>versus</em> RHE and a remarkable mass activity of 0.79 A mg<small><sub>Pt</sub></small><small><sup>−1</sup></small>. More importantly, after 10 000 cycles, the particle size expansion is marginal (5.01 ± 0.92 nm), alongside slight reductions in mass activity (6%) and specific activity (2%), demonstrating excellent catalytic stability in an acidic medium.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" 16","pages":" 10380-10388"},"PeriodicalIF":5.8,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The advent of nanotechnology has steered into a new era of medical advancements, with metal nanoparticles (MNPs) emerging as potent agents for precise regulation of the immune system. This review provides a comprehensive overview of the immunomodulatory roles of MNPs, including gold, silver, and metal oxide nanoparticles, in regulating innate and adaptive immunity. Additionally, we discuss the immunological effects of metal ions and metal complexes, offering a comparative analysis with nanoparticulate systems. We analyse cutting-edge strategies utilising MNPs to optimise vaccine efficacy, achieve targeted delivery to immune cells, and orchestrate inflammatory responses. Additionally, we discuss the therapeutic potential of MNPs in combating autoimmune diseases, cancers, and infectious agents, which is evaluated within the framework of precision medicine. Furthermore, we critically assess challenges such as biocompatibility, potential toxicity, and regulatory hurdles. Finally, we propose future directions for integrating MNPs with advanced delivery systems and other nanomaterials to propel the frontiers of immunotherapy. This review aims to provide a foundational understanding of MNP-mediated immunomodulation, inspiring further research and development in this burgeoning field.
{"title":"Immunomodulatory Effects of Metal Nanoparticles: Current Trends and Future Prospects","authors":"Puspendu Barik, Samiran Mondal","doi":"10.1039/d5nr01030f","DOIUrl":"https://doi.org/10.1039/d5nr01030f","url":null,"abstract":"The advent of nanotechnology has steered into a new era of medical advancements, with metal nanoparticles (MNPs) emerging as potent agents for precise regulation of the immune system. This review provides a comprehensive overview of the immunomodulatory roles of MNPs, including gold, silver, and metal oxide nanoparticles, in regulating innate and adaptive immunity. Additionally, we discuss the immunological effects of metal ions and metal complexes, offering a comparative analysis with nanoparticulate systems. We analyse cutting-edge strategies utilising MNPs to optimise vaccine efficacy, achieve targeted delivery to immune cells, and orchestrate inflammatory responses. Additionally, we discuss the therapeutic potential of MNPs in combating autoimmune diseases, cancers, and infectious agents, which is evaluated within the framework of precision medicine. Furthermore, we critically assess challenges such as biocompatibility, potential toxicity, and regulatory hurdles. Finally, we propose future directions for integrating MNPs with advanced delivery systems and other nanomaterials to propel the frontiers of immunotherapy. This review aims to provide a foundational understanding of MNP-mediated immunomodulation, inspiring further research and development in this burgeoning field.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"24 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shiwei Fu, Miao Zhang, Nicholas Calzadilla, Bowen Zhao, Xiao Zhang, Bowei Yang, Victoria A. A. McKenzie, Ajay Zheng, Qianqian Ni, Fuwu Zhang
Smart polymer prodrugs, created via responsive prodrug-initiated controlled polymerization of lactide, demonstrated extremely high drug loading, tuneale stimuli-triggered drug release, and significantly tumor growth inhibition and improved survival with minimal toxicity. This adaptable strategy can precisely tailor drugs' physicochemical properties for optimal therapeutic efficacy, demonstrating great promise for cancer treatment.
{"title":"Smart Polymer Prodrugs via Responsive Prodrug-Initiated Ring-Opening Polymerization of Lactide for Improved Drug Delivery","authors":"Shiwei Fu, Miao Zhang, Nicholas Calzadilla, Bowen Zhao, Xiao Zhang, Bowei Yang, Victoria A. A. McKenzie, Ajay Zheng, Qianqian Ni, Fuwu Zhang","doi":"10.1039/d5nr00780a","DOIUrl":"https://doi.org/10.1039/d5nr00780a","url":null,"abstract":"Smart polymer prodrugs, created via responsive prodrug-initiated controlled polymerization of lactide, demonstrated extremely high drug loading, tuneale stimuli-triggered drug release, and significantly tumor growth inhibition and improved survival with minimal toxicity. This adaptable strategy can precisely tailor drugs' physicochemical properties for optimal therapeutic efficacy, demonstrating great promise for cancer treatment.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"37 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lead-free Cs2BX6 (B = Zr4+, Sn4+, Te4+, Hf4+, Re4+, Os4+, Ir4+, Pt4+, and X = Cl–, Br–, I–) vacancy-ordered double perovskites have gained significant attention due to their high performance in solar cell devices. Besides mitigating toxicity concerns associated with the use of lead, the presence of formally tetravalent B site in Cs2BX6 has been demonstrated to improve the stability against air and moisture. Recently, experimental studies showed that high-entropy forms of the vacancy-ordered double perovskites can be synthesized and stabilized at room temperature, which opens new opportunities to design better solar cell absorbers. In this work, we employ high throughput density functional theory (DFT) calculations using the HSE06 hybrid functional to study 546 medium-to-high-entropy vacancy-ordered double perovskites. Our results show that Cs2{B1B22B3B4}1X6 and Cs2{B1B2B3B4}1{XX’}6 perovskites can break the existing linear scaling relationships between the bandgap and formation energy observed in the pure Cs2BX6 and Cs2B{XX’}6 perovskites, which enables the formation of compositions which simultaneously exhibit an optimal band gap of ~1.3 eV for single junction solar cell along with a low formation energy. Electronic structure analysis reveals that this can be attributed to the weak coupling between the BX6 octahedra in Cs2{B1B2B3B4}1X6 and Cs2{B1B2B3B4}1{XX’}6. Based on these findings, we identify analytical equations which can be used to efficiently predict the band gap and formation energy of high-entropy perovskites from their constituent pure perovskites. Our study offers simple and practical guidelines for the design and synthesis of novel high-entropy perovskites with improved photovoltaic performance.
{"title":"Pushing the Boundary of the Stability and Band Gap Pareto Front by Going Towards High-Entropy Perovskites","authors":"Zhendian Zhang, Victor Fung, Guoxiang Hu","doi":"10.1039/d4nr05013d","DOIUrl":"https://doi.org/10.1039/d4nr05013d","url":null,"abstract":"Lead-free Cs<small><sub>2</sub></small>BX<small><sub>6</sub></small> (B = Zr<small><sup>4+</sup></small>, Sn<small><sup>4+</sup></small>, Te<small><sup>4+</sup></small>, Hf<small><sup>4+</sup></small>, Re<small><sup>4+</sup></small>, Os<small><sup>4+</sup></small>, Ir<small><sup>4+</sup></small>, Pt<small><sup>4+</sup></small>, and X = Cl<small><sup>–</sup></small>, Br<small><sup>–</sup></small>, I<small><sup>–</sup></small>) vacancy-ordered double perovskites have gained significant attention due to their high performance in solar cell devices. Besides mitigating toxicity concerns associated with the use of lead, the presence of formally tetravalent B site in Cs<small><sub>2</sub></small>BX<small><sub>6</sub></small> has been demonstrated to improve the stability against air and moisture. Recently, experimental studies showed that high-entropy forms of the vacancy-ordered double perovskites can be synthesized and stabilized at room temperature, which opens new opportunities to design better solar cell absorbers. In this work, we employ high throughput density functional theory (DFT) calculations using the HSE06 hybrid functional to study 546 medium-to-high-entropy vacancy-ordered double perovskites. Our results show that Cs<small><sub>2</sub></small>{B<small><sub>1</sub></small>B2<small><sub>2</sub></small>B<small><sub>3</sub></small>B<small><sub>4</sub></small>}<small><sub>1</sub></small>X<small><sub>6</sub></small> and Cs<small><sub>2</sub></small>{B<small><sub>1</sub></small>B<small><sub>2</sub></small>B<small><sub>3</sub></small>B<small><sub>4</sub></small>}<small><sub>1</sub></small>{XX’}<small><sub>6</sub></small> perovskites can break the existing linear scaling relationships between the bandgap and formation energy observed in the pure Cs<small><sub>2</sub></small>BX<small><sub>6</sub></small> and Cs<small><sub>2</sub></small>B{XX’}<small><sub>6</sub></small> perovskites, which enables the formation of compositions which simultaneously exhibit an optimal band gap of ~1.3 eV for single junction solar cell along with a low formation energy. Electronic structure analysis reveals that this can be attributed to the weak coupling between the BX<small><sub>6</sub></small> octahedra in Cs<small><sub>2</sub></small>{B<small><sub>1</sub></small>B<small><sub>2</sub></small>B<small><sub>3</sub></small>B<small><sub>4</sub></small>}<small><sub>1</sub></small>X<small><sub>6</sub></small> and Cs<small><sub>2</sub></small>{B<small><sub>1</sub></small>B<small><sub>2</sub></small>B<small><sub>3</sub></small>B<small><sub>4</sub></small>}<small><sub>1</sub></small>{XX’}<small><sub>6</sub></small>. Based on these findings, we identify analytical equations which can be used to efficiently predict the band gap and formation energy of high-entropy perovskites from their constituent pure perovskites. Our study offers simple and practical guidelines for the design and synthesis of novel high-entropy perovskites with improved photovoltaic performance.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"34 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals known for their persistence in the environment due to their amphiphilic nature and the strength of carbon–fluorine bonds. While these properties lead to various industrial and commercial applications including firefighting foams and non-stick coatings, these same characteristics also result in significant environmental and health concerns. This study employs atomistic molecular dynamics (MD) simulations to achieve molecular level insights into PFAS self-assembly and adsorption dynamics, to inform PFAS water remediation. MD simulations of PFAS with different headgroup chemistries and chain lengths on a graphene sorbent surface under varied pH conditions were performed. These simulation results elucidated the impacts of headgroup, chain length, and pH on PFAS adsorption behavior. At neutral pH, PFAS headgroups are fully deprotonated, causing electrostatic repulsions that lead to micelle-like aggregate formation in solution, hindering adsorption. Conversely, at acidic pH, these repulsions are diminished due to protonated headgroups, resulting in higher adsorption percentage with large, stacked aggregates that fully adsorb onto the sorbent. Additionally, chain length notably influenced aggregation, with longer chains forming larger aggregates and achieving more stable adsorption compared to shorter chains. Furthermore, perfluoro-sulfonic acids (PFSAs) displayed stronger adsorption and greater aggregate order than perfluoro-carboxylic acids (PFCAs) in general. These findings underscore the complex interplay between PFAS structure and the dynamics of their adsorption behaviors, as well as the potential of pH as a tuning parameter to enhance PFAS adsorption stability and thereby improve PFAS removal efficiency.
{"title":"PFAS self-assembly and adsorption dynamics on graphene: molecular insights into chemical and environmental influences","authors":"Bradley G. Lamb, Boran Ma","doi":"10.1039/d4nr04995k","DOIUrl":"https://doi.org/10.1039/d4nr04995k","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals known for their persistence in the environment due to their amphiphilic nature and the strength of carbon–fluorine bonds. While these properties lead to various industrial and commercial applications including firefighting foams and non-stick coatings, these same characteristics also result in significant environmental and health concerns. This study employs atomistic molecular dynamics (MD) simulations to achieve molecular level insights into PFAS self-assembly and adsorption dynamics, to inform PFAS water remediation. MD simulations of PFAS with different headgroup chemistries and chain lengths on a graphene sorbent surface under varied pH conditions were performed. These simulation results elucidated the impacts of headgroup, chain length, and pH on PFAS adsorption behavior. At neutral pH, PFAS headgroups are fully deprotonated, causing electrostatic repulsions that lead to micelle-like aggregate formation in solution, hindering adsorption. Conversely, at acidic pH, these repulsions are diminished due to protonated headgroups, resulting in higher adsorption percentage with large, stacked aggregates that fully adsorb onto the sorbent. Additionally, chain length notably influenced aggregation, with longer chains forming larger aggregates and achieving more stable adsorption compared to shorter chains. Furthermore, perfluoro-sulfonic acids (PFSAs) displayed stronger adsorption and greater aggregate order than perfluoro-carboxylic acids (PFCAs) in general. These findings underscore the complex interplay between PFAS structure and the dynamics of their adsorption behaviors, as well as the potential of pH as a tuning parameter to enhance PFAS adsorption stability and thereby improve PFAS removal efficiency.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"20 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kang Wang, Lu Peng, Peng Jiang, Le Xu, Lianghui Li, Hongxia Wang, Xin Jin, Wenyu Wang, Tong Lin
Acoustoelectric transducers are often combined with an acoustic resonator to improve their acoustoelectric performance. Previous studies have mostly been based on Helmholtz resonators, which are bulky in size and have limited improvement in acoustoelectric performance. In this study, for the first time, a kazoo, a flat miniature musical instrument, was used as an acoustic resonator to improve the acoustoelectric performance of a nanofiber acoustoelectric transducer. When a polyvinylidene fluoride (PVDF) nanofiber membrane was incorporated into the kazoo as a sound vibration diaphragm, it improved the acoustoelectric output in the low-frequency sound range and allowed sound to be collected from the side of the entire device. The electrospun PVDF nanofiber membrane worked with the polymethylmethacrylate kazoo to increase the sound intensity by at least 15 decibels in the nanofiber region. Under 100 Hz, 115 dB input sound conditions, the device generated 196.0±8.6 V peak-to-peak voltage and 12.0±1.1 µA current outputs. The generated power was sufficient to power applications. By rethinking resonator design and exploiting the versatility of nanofibers, this work establishes a paradigm shift in acoustic energy harvesting, offering a scalable, high-efficiency alternative to conventional resonator-dependent systems.
声电传感器通常与声学谐振器相结合，以提高其声电性能。以往的研究大多基于亥姆霍兹谐振器，这种谐振器体积庞大，对声电性能的改善有限。在这项研究中，首次使用了一种扁平的微型乐器卡祖琴作为声共振，以改善纳米纤维声电换能器的声电性能。在卡祖琴中加入聚偏二氟乙烯（PVDF）纳米纤维膜作为声振膜片时，它改善了低频声音范围内的声电输出，并允许从整个装置的侧面收集声音。电纺 PVDF 纳米纤维膜与聚甲基丙烯酸甲酯卡祖配合使用，可将纳米纤维区域的声强提高至少 15 分贝。在 100 Hz、115 dB 输入声音条件下，该装置产生了 196.0±8.6 V 峰峰电压和 12.0±1.1 µA 电流输出。产生的功率足以为应用提供动力。通过重新思考谐振器的设计并利用纳米纤维的多功能性，这项研究成果实现了声能采集领域的范式转变，为依赖谐振器的传统系统提供了一种可扩展的高效替代方案。
{"title":"Enhancing Acoustoelectric Conversion of Nanofiber Transducer in Combination with Kazoo†","authors":"Kang Wang, Lu Peng, Peng Jiang, Le Xu, Lianghui Li, Hongxia Wang, Xin Jin, Wenyu Wang, Tong Lin","doi":"10.1039/d4nr05275g","DOIUrl":"https://doi.org/10.1039/d4nr05275g","url":null,"abstract":"Acoustoelectric transducers are often combined with an acoustic resonator to improve their acoustoelectric performance. Previous studies have mostly been based on Helmholtz resonators, which are bulky in size and have limited improvement in acoustoelectric performance. In this study, for the first time, a kazoo, a flat miniature musical instrument, was used as an acoustic resonator to improve the acoustoelectric performance of a nanofiber acoustoelectric transducer. When a polyvinylidene fluoride (PVDF) nanofiber membrane was incorporated into the kazoo as a sound vibration diaphragm, it improved the acoustoelectric output in the low-frequency sound range and allowed sound to be collected from the side of the entire device. The electrospun PVDF nanofiber membrane worked with the polymethylmethacrylate kazoo to increase the sound intensity by at least 15 decibels in the nanofiber region. Under 100 Hz, 115 dB input sound conditions, the device generated 196.0±8.6 V peak-to-peak voltage and 12.0±1.1 µA current outputs. The generated power was sufficient to power applications. By rethinking resonator design and exploiting the versatility of nanofibers, this work establishes a paradigm shift in acoustic energy harvesting, offering a scalable, high-efficiency alternative to conventional resonator-dependent systems.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"103 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Asamanjoy Bhunia, Anupam Jana, Arijit Maity, Ashadul Adalder, Sinthia Saha
The search for new robust and efficient heterogeneous photocatalysts for the reduction of CO2 through photocatalysis has emerged as a key focus in the realm of CO2 reduction research. However, there is a significant challenge in fabricating a photocatalyst with remarkable photoreduction activity. In context to this, accommodation of photocatalytic redox-active molecular metal complex into the stable MOF framework by replacing the existing linker through post synthetic exchange (PSE), also termed as solvent assisted ligand exchange (SALE), is a powerful tool for developing photocatalyst for CO2 reduction. Herein, we first time demonstrate the successful incorporation of a Ru(II) bis-terpyridine complex, [Ru(cptpy)2], into a stable ZrIV-based metal-organic framework (MOF) consisting of a naphthalene diimide (NDI) linker via SALE. The obtained MOF, Zr-NDI@Ru-tpy or Zr-NDI@Ru-tpy-m has been used for photocatalytic CO2 reduction under visible light. It shows an impressive CO production rate of 2449 μmol g–1 h–1 with a low hydrogen production rate of 101 μmol g–1 h–1, demonstrating a high selectivity of 97% for CO production. The turnover number (TON) for CO evolution by Zr-NDI@Ru-tpy is 123 in a 6 h photocatalytic run. Further, a plausible mechanism for CO2 conversion to CO has been proposed using photophysical and electrochemical investigation, along with in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. This study shows the insertion of a redox-active molecular catalyst into a MOF is a promising avenue to create efficient and stable photocatalysts that are also recyclable.
寻找通过光催化还原二氧化碳的新型强效异质光催化剂已成为二氧化碳还原研究领域的一个重点。然而，如何制造出具有显著光还原活性的光催化剂是一项重大挑战。为此，通过后合成交换（PSE），也称为溶剂辅助配体交换（SALE），将具有光催化氧化还原活性的分子金属复合物置换到稳定的 MOF 框架中，是开发用于还原二氧化碳的光催化剂的有力工具。在此，我们首次展示了通过 SALE 成功地将 Ru（II）双三吡啶配合物 [Ru(cptpy)2] 加入到由萘二亚胺（NDI）连接体组成的稳定的 ZrIV 基金属有机框架（MOF）中。获得的 MOF（Zr-NDI@Ru-tpy 或 Zr-NDI@Ru-tpy-m ）已被用于可见光下的光催化二氧化碳还原。它的 CO 生成率高达 2449 μmol g-1 h-1，而氢气生成率仅为 101 μmol g-1 h-1，显示出生成 CO 的高选择性（97%）。在 6 小时的光催化运行中，Zr-NDI@Ru-ttpy 的 CO 演化周转数（TON）为 123。此外，通过光物理和电化学研究以及原位漫反射红外傅立叶变换（DRIFT）光谱，提出了将 CO2 转化为 CO 的合理机制。这项研究表明，在 MOF 中加入氧化还原活性分子催化剂是一种很有前景的方法，可用于制造高效、稳定且可回收的光催化剂。
{"title":"Molecularly Engineered MOF Photocatalyst For CO Production from Visible Light-driven CO2 Reduction","authors":"Asamanjoy Bhunia, Anupam Jana, Arijit Maity, Ashadul Adalder, Sinthia Saha","doi":"10.1039/d5nr00077g","DOIUrl":"https://doi.org/10.1039/d5nr00077g","url":null,"abstract":"The search for new robust and efficient heterogeneous photocatalysts for the reduction of CO2 through photocatalysis has emerged as a key focus in the realm of CO2 reduction research. However, there is a significant challenge in fabricating a photocatalyst with remarkable photoreduction activity. In context to this, accommodation of photocatalytic redox-active molecular metal complex into the stable MOF framework by replacing the existing linker through post synthetic exchange (PSE), also termed as solvent assisted ligand exchange (SALE), is a powerful tool for developing photocatalyst for CO2 reduction. Herein, we first time demonstrate the successful incorporation of a Ru(II) bis-terpyridine complex, [Ru(cptpy)2], into a stable ZrIV-based metal-organic framework (MOF) consisting of a naphthalene diimide (NDI) linker via SALE. The obtained MOF, Zr-NDI@Ru-tpy or Zr-NDI@Ru-tpy-m has been used for photocatalytic CO2 reduction under visible light. It shows an impressive CO production rate of 2449 μmol g–1 h–1 with a low hydrogen production rate of 101 μmol g–1 h–1, demonstrating a high selectivity of 97% for CO production. The turnover number (TON) for CO evolution by Zr-NDI@Ru-tpy is 123 in a 6 h photocatalytic run. Further, a plausible mechanism for CO2 conversion to CO has been proposed using photophysical and electrochemical investigation, along with in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. This study shows the insertion of a redox-active molecular catalyst into a MOF is a promising avenue to create efficient and stable photocatalysts that are also recyclable.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"22 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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