Tiara-like metal nanoclusters (TNCs) composed of group 10 transition metals and thiolates can easily change their number of polymerization and include various molecules and metal ions as guests within their ring structures. Therefore, they are expected to be applied in sensing, storage, and catalyst materials based on the selective inclusion of molecules. However, there are very few reports regarding the principles of selective inclusion for guest molecules/ions in TNCs. In this study, we focused on the nickel (Ni) hexanuclear TNC, Ni6(PET)12 (PET = 2-phenylethanethiolate), to clarify the kinds of the metal ions that can be included in TNCs. As a result, we found that gold (Au) ion can be selectively included in Ni6(PET)12 among various metal ions to form a stable structure. From the various experiments and density functional theory calculations, we concluded that the main reasons for this are that [Ni6(PET)12]0 has (1) a pore large enough to include Au ion and (2) Ni and Au favor the formation of bonding orbitals based on charge transfer interactions. These insights are expected to lead to a better understanding of host–guest interactions in TNCs and provide clear design guidelines for forming various inclusion structures in the future.
{"title":"Inclusion of Gold Ion in Tiara-Like Nickel Hexanuclear Nanoclusters","authors":"Kana Takemae, Shiho Tomihari, Takumi Naitou, Makito Takagi, Tomomi Shimazaki, Tokuhisa Kawawaki, Masanori Tachikawa, Yuichi Negishi","doi":"10.1039/d4nr04579c","DOIUrl":"https://doi.org/10.1039/d4nr04579c","url":null,"abstract":"Tiara-like metal nanoclusters (TNCs) composed of group 10 transition metals and thiolates can easily change their number of polymerization and include various molecules and metal ions as guests within their ring structures. Therefore, they are expected to be applied in sensing, storage, and catalyst materials based on the selective inclusion of molecules. However, there are very few reports regarding the principles of selective inclusion for guest molecules/ions in TNCs. In this study, we focused on the nickel (Ni) hexanuclear TNC, Ni6(PET)12 (PET = 2-phenylethanethiolate), to clarify the kinds of the metal ions that can be included in TNCs. As a result, we found that gold (Au) ion can be selectively included in Ni6(PET)12 among various metal ions to form a stable structure. From the various experiments and density functional theory calculations, we concluded that the main reasons for this are that [Ni6(PET)12]0 has (1) a pore large enough to include Au ion and (2) Ni and Au favor the formation of bonding orbitals based on charge transfer interactions. These insights are expected to lead to a better understanding of host–guest interactions in TNCs and provide clear design guidelines for forming various inclusion structures in the future.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"42 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929134","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}
Rechargeable alkaline zinc batteries are emerging as promising candidates for next-generation energy storage systems, owing to their affordability, eco-friendliness and high energy density. However, their widespread application is hindered by stability challenges, particularly in alkaline environments, due to cathode corrosion and deformation, as well as dendrite formation and unwanted side reactions at the Zn anode. To address these issues, we successfully developed a 3D nickel micromesh-supported NiCoP (3D NM@NiCoP) electrode. This unique structure integrates an ultrathin (4μm), flexible and conductive nickel micromesh (NM) with a high-capacity bimetallic phosphide, NiCoP, fabricated through a combination of photolithography, chemical etching, and electro-deposition processes. The resulting electrode achieves an impressive capacitance of 26.1 μAh cm-2 at a current density of 4 mA cm-2 in a 2 M KOH electrolyte. As assembled with superhydrophilic Zn@Al2O3@TiO2 anode, the device (3D NM@NiCoP//Zn@Al2O3@TiO2) exhibits outstanding stability, remaining 91% of its initial capacity after 11000 cycles at 3 mA cm-2 in a 2 M KOH electrolyte. This novel configuration, with the potential for scalable fabrication, provides valuable insights into the development of high-capacity and durable electrodes for alkaline zinc batteries.
{"title":"Ultralight Flexible 3D Nickel Micromesh Decorated with NiCoP for High Stability Alkaline Zinc Batteries","authors":"Zana Karim Abdul, Zeqi Nie, Yapeng Zhang, XiuXue Liu, Xiaohu Wang, Gilbert Niwamanya, Donghai Wei, Wen Zhang, Guanhua Zhang","doi":"10.1039/d4nr04021j","DOIUrl":"https://doi.org/10.1039/d4nr04021j","url":null,"abstract":"Rechargeable alkaline zinc batteries are emerging as promising candidates for next-generation energy storage systems, owing to their affordability, eco-friendliness and high energy density. However, their widespread application is hindered by stability challenges, particularly in alkaline environments, due to cathode corrosion and deformation, as well as dendrite formation and unwanted side reactions at the Zn anode. To address these issues, we successfully developed a 3D nickel micromesh-supported NiCoP (3D NM@NiCoP) electrode. This unique structure integrates an ultrathin (4μm), flexible and conductive nickel micromesh (NM) with a high-capacity bimetallic phosphide, NiCoP, fabricated through a combination of photolithography, chemical etching, and electro-deposition processes. The resulting electrode achieves an impressive capacitance of 26.1 μAh cm<small><sup>-2</sup></small> at a current density of 4 mA cm<small><sup>-2</sup></small> in a 2 M KOH electrolyte. As assembled with superhydrophilic Zn@Al<small><sub>2</sub></small>O<small><sub>3</sub></small>@TiO<small><sub>2 </sub></small>anode, the device (3D NM@NiCoP//Zn@Al<small><sub>2</sub></small>O<small><sub>3</sub></small>@TiO<small><sub>2</sub></small>) exhibits outstanding stability, remaining 91% of its initial capacity after 11000 cycles at 3 mA cm<small><sup>-2 </sup></small> in a 2 M KOH electrolyte. This novel configuration, with the potential for scalable fabrication, provides valuable insights into the development of high-capacity and durable electrodes for alkaline zinc batteries.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"5 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929136","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}
Ivo Tanghe, Chao-Yang Lin, Isabella Wagner, Servet Ataberk Cayan, Margarita Samoli, Zeger Hens, Justin Hodgkiss, Kai Chen, Pieter Geiregat
Many applications of nanocrystals rely on their use in light detection and emission. In recent years, nanocrystals with more relaxed carrier confinement, including so-called 'bulk' and 2D implementations, have made their stake. In such systems, the charge carriers generated after (photo-)excitation are spread over a semi-continuous density of states, behavior controlled by the carrier temperature T. Current established methods to measure this dynamically changing temperature include transient absorption and luminescence spectroscopy, yet they very often fail to agree on the exact temperature leading to contradicting reports. Here, we show through a combined side-by-side experimental and theoretical study on state-of-art II-VI and perovskite nanocrystals under weak confinement that only transient PL can yield unambiguously the correct T. In particular, temperatures extracted from TA are heavily affected by the effective masses of the electron and hole bands involved leading to overestimations. Our results pave a way to a more robust extraction of carrier temperature and will help to consolidate ensuing structure-property relations derived from it.
{"title":"On the Determination of the Carrier Temperature in Weakly Confined Semiconductor Nanocrystals Using Time-Resolved Optical Spectroscopy","authors":"Ivo Tanghe, Chao-Yang Lin, Isabella Wagner, Servet Ataberk Cayan, Margarita Samoli, Zeger Hens, Justin Hodgkiss, Kai Chen, Pieter Geiregat","doi":"10.1039/d4nr04208e","DOIUrl":"https://doi.org/10.1039/d4nr04208e","url":null,"abstract":"Many applications of nanocrystals rely on their use in light detection and emission. In recent years, nanocrystals with more relaxed carrier confinement, including so-called 'bulk' and 2D implementations, have made their stake. In such systems, the charge carriers generated after (photo-)excitation are spread over a semi-continuous density of states, behavior controlled by the carrier temperature T. Current established methods to measure this dynamically changing temperature include transient absorption and luminescence spectroscopy, yet they very often fail to agree on the exact temperature leading to contradicting reports. Here, we show through a combined side-by-side experimental and theoretical study on state-of-art II-VI and perovskite nanocrystals under weak confinement that only transient PL can yield unambiguously the correct T. In particular, temperatures extracted from TA are heavily affected by the effective masses of the electron and hole bands involved leading to overestimations. Our results pave a way to a more robust extraction of carrier temperature and will help to consolidate ensuing structure-property relations derived from it.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"48 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929132","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}
Andrey Shibaev, Rui Carvalho, Senentxu Lanceros-Mendez, Pedro Martins, Paula Rodriguez-Lejarraga, Viktor I. Petrenko, Joachim Kohlbrecher
Poly(vinylidene fluoride) (PVDF) holds strong technological relevance due to its thermal stability, chemical, mechanical and radiation resistance, transparency, biocompatibility, and ease of processing. Several of those applications are related to its high electroactivity, for which the β-phase of the polymer is its most renowned protagonist. It is in this context there is extensive research on the crystallization of PVDF in the β-phase, both when processed from the melt and from solution. Several decades of research revealed that the electroactive β-PVDF can be nucleated by introducing nanofillers within the polymer matrix, based on electrostatic interactions between polymer chains and fillers. However, one question persists. Beyond these electrostatic interactions, on what mechanism does the nucleation of the β-phase in composites depend? This works demonstrates, through the use of small-angle neutron scattering measurements, that the answer is related with the type of fillers’ agglomeration.
{"title":"Insights into the Electroactive Impact of Magnetic Nanostructures in PVDF Composites via Small-Angle Neutron Scattering","authors":"Andrey Shibaev, Rui Carvalho, Senentxu Lanceros-Mendez, Pedro Martins, Paula Rodriguez-Lejarraga, Viktor I. Petrenko, Joachim Kohlbrecher","doi":"10.1039/d4nr03759f","DOIUrl":"https://doi.org/10.1039/d4nr03759f","url":null,"abstract":"Poly(vinylidene fluoride) (PVDF) holds strong technological relevance due to its thermal stability, chemical, mechanical and radiation resistance, transparency, biocompatibility, and ease of processing. Several of those applications are related to its high electroactivity, for which the β-phase of the polymer is its most renowned protagonist. It is in this context there is extensive research on the crystallization of PVDF in the β-phase, both when processed from the melt and from solution. Several decades of research revealed that the electroactive β-PVDF can be nucleated by introducing nanofillers within the polymer matrix, based on electrostatic interactions between polymer chains and fillers. However, one question persists. Beyond these electrostatic interactions, on what mechanism does the nucleation of the β-phase in composites depend? This works demonstrates, through the use of small-angle neutron scattering measurements, that the answer is related with the type of fillers’ agglomeration.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"44 3 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929133","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}
Based on the ab initio molecular dynamics (AIMD), the temperature and velocity statistics of diatomic semiconductors are proposed to be classified by atomic species. The phase differences resulting from the lattice vibrations of different atoms indicate the existence of anharmonicity at finite atomic temperatures. To explore the electronic properties further, the effect of temperature on electrostatic potential field vibrations in semiconductors is studied, and the definition of electrostatic potential oscillation (EPO) at finite atomic temperature is introduced. It is confirmed that EPO in semiconductors is caused by lattice vibrations at finite temperatures. As the temperature rises, both the intensity of EPO and the rate of EPO change in heavy and light atoms increase, which affects electron thermal transport. To characterize the uncertainties in atomic lattice vibrations and EPO, the entropies of atomic EPO, atomic velocity of EPO (VEPO), atomic temperature, and atomic velocity are defined, and the results are consistent with the principle of entropy increase. This study not only aids in understanding the fundamental physical picture of electronic properties in semiconductors at finite temperatures but also provides a method for describing their uncertainties. The new theoretical concepts and statistical methods presented here can advance the understanding of electron thermal transport problems in semiconductor devices.
{"title":"The effect originated from atomic vibration on thermal transport in diatomic semiconductors via ab initio molecular dynamics","authors":"Dian Huang, Guihua Tang, Zhibin Gao, Shengying Yue","doi":"10.1039/d4nr05240d","DOIUrl":"https://doi.org/10.1039/d4nr05240d","url":null,"abstract":"Based on the ab initio molecular dynamics (AIMD), the temperature and velocity statistics of diatomic semiconductors are proposed to be classified by atomic species. The phase differences resulting from the lattice vibrations of different atoms indicate the existence of anharmonicity at finite atomic temperatures. To explore the electronic properties further, the effect of temperature on electrostatic potential field vibrations in semiconductors is studied, and the definition of electrostatic potential oscillation (EPO) at finite atomic temperature is introduced. It is confirmed that EPO in semiconductors is caused by lattice vibrations at finite temperatures. As the temperature rises, both the intensity of EPO and the rate of EPO change in heavy and light atoms increase, which affects electron thermal transport. To characterize the uncertainties in atomic lattice vibrations and EPO, the entropies of atomic EPO, atomic velocity of EPO (VEPO), atomic temperature, and atomic velocity are defined, and the results are consistent with the principle of entropy increase. This study not only aids in understanding the fundamental physical picture of electronic properties in semiconductors at finite temperatures but also provides a method for describing their uncertainties. The new theoretical concepts and statistical methods presented here can advance the understanding of electron thermal transport problems in semiconductor devices.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"12 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929135","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}
Nanoporous organic polymers (NPOPs) have emerged as versatile materials with robust thermal stability, large surface area (up to 2500 m²/g), and customizable porosity, making them ideal candidates for advanced hydrogen (H2) storage applications. This review provides a comprehensive analysis of various NPOPs, including covalent organic frameworks (COFs), hypercrosslinked polymers (HCLPs), conjugated microporous polymers (CMPs), and porous aromatic frameworks (POAFs). Notably, these materials demonstrate superior H2 storage capacities, achieving up to 10 wt% at cryogenic temperatures, which is essential for applying H2 as a clean energy carrier. The review also highlights recent advancements, such as integrating metal-organic frameworks (MOFs) into NPOPs, further enhancing storage capacities by up to 30%. Their multifaceted properties underpin various applications, from fuel storage and gas separation to water treatment and optical devices. This review explores the significance and versatility of NPOPs in H2 storage due to their unique properties and enhanced storage capacities. Additionally, recent advancements in utilizing NPOPs for H2 storage are highlighted with a detailed discussion of emerging trends and the synthesis of innovative NPOPs. The review concludes with a discussion of the advantages, applications, challenges, research, and future directions for research in this area.
{"title":"Recent Advances in Nanoporous Organic Polymers (NPOPs) for Hydrogen Storage Applications","authors":"Shagufta Jabin, Sadiqa Abbas, Priti Gupta, Sapana Jadoun, Anupama Rajput, Prachika Rajput","doi":"10.1039/d4nr03623a","DOIUrl":"https://doi.org/10.1039/d4nr03623a","url":null,"abstract":"Nanoporous organic polymers (NPOPs) have emerged as versatile materials with robust thermal stability, large surface area (up to 2500 m²/g), and customizable porosity, making them ideal candidates for advanced hydrogen (H2) storage applications. This review provides a comprehensive analysis of various NPOPs, including covalent organic frameworks (COFs), hypercrosslinked polymers (HCLPs), conjugated microporous polymers (CMPs), and porous aromatic frameworks (POAFs). Notably, these materials demonstrate superior H2 storage capacities, achieving up to 10 wt% at cryogenic temperatures, which is essential for applying H2 as a clean energy carrier. The review also highlights recent advancements, such as integrating metal-organic frameworks (MOFs) into NPOPs, further enhancing storage capacities by up to 30%. Their multifaceted properties underpin various applications, from fuel storage and gas separation to water treatment and optical devices. This review explores the significance and versatility of NPOPs in H2 storage due to their unique properties and enhanced storage capacities. Additionally, recent advancements in utilizing NPOPs for H2 storage are highlighted with a detailed discussion of emerging trends and the synthesis of innovative NPOPs. The review concludes with a discussion of the advantages, applications, challenges, research, and future directions for research in this area.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"17 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917395","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}
Claudio Maria Pecoraro, Hanna Sopha, Siming Wu, Hyesung Kim, Yue Wang, Jan Macak, Monica Santamaria, Patrik Schmuki
The photocatalytic degradation of unwanted organic species has been investigated for decades using modified and non-modified titania nanostructures. In the present study, we investigate the co-catalytic effect of single atoms (SAs) of Pt and Pt nanoparticles on titania substrates on the degradation of the two typical photodegradation model pollutants: Acid Orange 7 (AO7) and Rhodamine B (RhB). For this, we use highly defined sputter deposited anatase layers and load them with Pt SAs at different loading densities or alternatively with Pt nanoparticles. We find that the Pt SAs have strong accelerating effects (already for a low loading density of ∼105 SAs μm−2) on the photodegradation of AO7, whereas Pt nanoparticles do hardly have an effect on the decay kinetics. The main beneficial effect of SA Pt is facilitated superoxide formation, which for SAs is significantly enhanced. Overall, the work demonstrates that Pt SA co-catalysts can have a beneficial effect not only for the well-studied use of H2 generation, but also in the photocatalytic degradation of pollutants—this is particularly the case if the degradation is dominated by a conduction band electron transfer to dissolved O2 in the solution.
{"title":"Platinum single atoms on titania aid dye photodegradation whereas platinum nanoparticles do not","authors":"Claudio Maria Pecoraro, Hanna Sopha, Siming Wu, Hyesung Kim, Yue Wang, Jan Macak, Monica Santamaria, Patrik Schmuki","doi":"10.1039/d4nr02450h","DOIUrl":"https://doi.org/10.1039/d4nr02450h","url":null,"abstract":"The photocatalytic degradation of unwanted organic species has been investigated for decades using modified and non-modified titania nanostructures. In the present study, we investigate the co-catalytic effect of single atoms (SAs) of Pt and Pt nanoparticles on titania substrates on the degradation of the two typical photodegradation model pollutants: Acid Orange 7 (AO7) and Rhodamine B (RhB). For this, we use highly defined sputter deposited anatase layers and load them with Pt SAs at different loading densities or alternatively with Pt nanoparticles. We find that the Pt SAs have strong accelerating effects (already for a low loading density of ∼10<small><sup>5</sup></small> SAs μm<small><sup>−2</sup></small>) on the photodegradation of AO7, whereas Pt nanoparticles do hardly have an effect on the decay kinetics. The main beneficial effect of SA Pt is facilitated superoxide formation, which for SAs is significantly enhanced. Overall, the work demonstrates that Pt SA co-catalysts can have a beneficial effect not only for the well-studied use of H<small><sub>2</sub></small> generation, but also in the photocatalytic degradation of pollutants—this is particularly the case if the degradation is dominated by a conduction band electron transfer to dissolved O<small><sub>2</sub></small> in the solution.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"1 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917397","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}
Asmi Aris, Wulan Tri Wahyuni, Budi Riza Putra, Angga Hermawan, Ferry Anggoro Ardy Nugroho, Zhi Wei Seh, Munawar Khalil
This study reports on the development of a highly sensitive non-enzymatic electrochemical sensor based on two-dimensional Ti3C2Tx/MWCNT-OH nanocomposite for the detection of the paraoxon-based pesticide. The synergistic effect between the Ti3C2Tx nanosheet and the functionalized multi-walled carbon nanotubes enhanced the sensor’s conductivity and catalytic activity. The nanocomposite demonstrated superior electrochemical and electroanalytical performance compared to the pristine Ti3C2Tx and MWCNT-OH in detecting paraoxon-ethyl in fruit samples (green and red grapes) with a linear response range from 0.1 to 100 μM, a low limit of detection (LOD) of 10 nM, limit of quantitation (LOQ) of 70 nM, and sensitivity of 0.957 µA μM-1 cm-2 at pH 8. Furthermore, the sensors maintained excellent selectivity and effectiveness in detecting paraoxon-ethyl even in the presence of various interferents, including diazinon, carbaryl, Fe2+, NO2−, NO3−, ascorbic acid, and glucose. The facile fabrication and enhanced sensing capabilities of the Ti3C2Tx/MWCNT-OH nanocomposite position it as a reliable, cost-effective, and sustainable alternative to conventional detection systems for monitoring pesticide residues in agricultural products.
{"title":"Ultrasensitive non-enzymatic electrochemical detection of paraoxon-ethyl in fruit samples using a 2D Ti3C2Tx/MWCNT-OH","authors":"Asmi Aris, Wulan Tri Wahyuni, Budi Riza Putra, Angga Hermawan, Ferry Anggoro Ardy Nugroho, Zhi Wei Seh, Munawar Khalil","doi":"10.1039/d4nr04060k","DOIUrl":"https://doi.org/10.1039/d4nr04060k","url":null,"abstract":"This study reports on the development of a highly sensitive non-enzymatic electrochemical sensor based on two-dimensional Ti<small><sub>3</sub></small>C<small><sub>2</sub></small>T<small><sub>x</sub></small>/MWCNT-OH nanocomposite for the detection of the paraoxon-based pesticide. The synergistic effect between the Ti<small><sub>3</sub></small>C<small><sub>2</sub></small>T<small><sub>x</sub></small> nanosheet and the functionalized multi-walled carbon nanotubes enhanced the sensor’s conductivity and catalytic activity. The nanocomposite demonstrated superior electrochemical and electroanalytical performance compared to the pristine Ti<small><sub>3</sub></small>C<small><sub>2</sub></small>T<small><sub>x</sub></small> and MWCNT-OH in detecting paraoxon-ethyl in fruit samples (green and red grapes) with a linear response range from 0.1 to 100 μM, a low limit of detection (LOD) of 10 nM, limit of quantitation (LOQ) of 70 nM, and sensitivity of 0.957 µA μM<small><sup>-1</sup></small> cm<small><sup>-2</sup></small> at pH 8. Furthermore, the sensors maintained excellent selectivity and effectiveness in detecting paraoxon-ethyl even in the presence of various interferents, including diazinon, carbaryl, Fe<small><sup>2+</sup></small>, NO<small><sup>2−</sup></small>, NO<small><sup>3−</sup></small>, ascorbic acid, and glucose. The facile fabrication and enhanced sensing capabilities of the Ti<small><sub>3</sub></small>C<small><sub>2</sub></small>T<small><sub>x</sub></small>/MWCNT-OH nanocomposite position it as a reliable, cost-effective, and sustainable alternative to conventional detection systems for monitoring pesticide residues in agricultural products.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"34 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917475","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}
Xing Liu, Hejin Yan, Zheng Shu, Xiangyue Cui, Yongqing Cai
Two-dimensional organic-inorganic perovskites have garnered extensive interest due to their unique structure and optoelectronic performance. However, their loose structures complicate mechanism illustration and tend to cause uncertainty and diversity of experimental and calculated results. This can generally be rooted in the dynamically swinging spacer molecules through two mechanisms: one is intrinsic geometric steric effect, and the other is related to electronic effect via orbital overlapping and electronic screening. Here, we intentionally design three types of spacer molecules, phenyl methyl ammonium (PMA), thiophene methyl ammonium (THMA), and furan methyl ammonium (FUMA) which adopt different aromatic units. We examine the influence of different aromatic spacers on the structural properties of the inorganic layer of the perovskite based on first-principles calculation and find that a marginal change in the aromatic ending group in the spacer ligand would trigger significant changes in octahedral in inorganic layer. We predict that the use of THMA and FUMA can improve the stability and increase the size of crystal domains due to enhanced binding between the organic and inorganic layers. Compared to prototype phenyl-based perovskite (PMA)2PbI4, thiophene-based perovskite (THMA)2PbI4 has states closer to the band edge, thus boosting carrier transport across inorganic and organic layers. Compared with perovskite using PMA as a spacer cation, the THMA-based perovskite has a higher dielectric constant and a smaller exciton binding energy, suggesting THMA more suitable as an organic spacer and a good passivation agent in 3D perovskites. The difference in screening ability of the molecules induces varying interlayer excitonic binding energy. Our work provides theoretical ground for the engineering of spacer molecules toward high-efficiency light conversion of mixed perovskites.
{"title":"Theoretical Insights into Spacer Molecule Design to Tune Stability, Dielectric, and Exciton Properties in 2D Perovskites","authors":"Xing Liu, Hejin Yan, Zheng Shu, Xiangyue Cui, Yongqing Cai","doi":"10.1039/d4nr04406a","DOIUrl":"https://doi.org/10.1039/d4nr04406a","url":null,"abstract":"Two-dimensional organic-inorganic perovskites have garnered extensive interest due to their unique structure and optoelectronic performance. However, their loose structures complicate mechanism illustration and tend to cause uncertainty and diversity of experimental and calculated results. This can generally be rooted in the dynamically swinging spacer molecules through two mechanisms: one is intrinsic geometric steric effect, and the other is related to electronic effect via orbital overlapping and electronic screening. Here, we intentionally design three types of spacer molecules, phenyl methyl ammonium (PMA), thiophene methyl ammonium (THMA), and furan methyl ammonium (FUMA) which adopt different aromatic units. We examine the influence of different aromatic spacers on the structural properties of the inorganic layer of the perovskite based on first-principles calculation and find that a marginal change in the aromatic ending group in the spacer ligand would trigger significant changes in octahedral in inorganic layer. We predict that the use of THMA and FUMA can improve the stability and increase the size of crystal domains due to enhanced binding between the organic and inorganic layers. Compared to prototype phenyl-based perovskite (PMA)2PbI4, thiophene-based perovskite (THMA)2PbI4 has states closer to the band edge, thus boosting carrier transport across inorganic and organic layers. Compared with perovskite using PMA as a spacer cation, the THMA-based perovskite has a higher dielectric constant and a smaller exciton binding energy, suggesting THMA more suitable as an organic spacer and a good passivation agent in 3D perovskites. The difference in screening ability of the molecules induces varying interlayer excitonic binding energy. Our work provides theoretical ground for the engineering of spacer molecules toward high-efficiency light conversion of mixed perovskites.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"92 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917855","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}
Jie Sun, Heng Yuan, Yuqing yang, zhibo cui, yuting xu, yan xu, Yulan Fu, Zhen Chai
Low-frequency noise in detection systems significantly affects the performance of ultrasensitive and ultracompact spin-exchange relaxation-free atomic magnetometers. High frequency modulation detection helps effectively suppress the 1/f noise and enhance the signal-to-noise ratio, but conventional modulators are bulky and restrict the development of integrated atomic magnetometer modulation-detection systems. Resonant metasurface-based thin-film lithium-niobate (TFLN) active optics can modulate free-space light within a compact configuration. In this study, we demonstrate a TFLN metasurface platform that leverages guided mode resonance for efficient phase modulation, achieving a modulation amplitude of 0.063 rad at a frequency of 100 kHz. We exploit the resonance in the TFLN waveguide and obtain a high-quality factor of 166 at a resonant wavelength of 795.8 nm. Using the fabricated modulator, we achieve an optical rotation angle measurement sensitivity of 4×10-7 rad/Hz1/2 with the modulation. Compared to conventional bulky modulators, the modulator fabricated in this study realizes a more than 90% reduction in volume. This study provides a feasible approach for developing miniaturized integrated atomic magnetometers to achieve improved sensitivity through optical modulation techniques.
{"title":"Atomic spin precession electro-optic modulation detection based on guided mode resonant lithium niobate metasurfaces","authors":"Jie Sun, Heng Yuan, Yuqing yang, zhibo cui, yuting xu, yan xu, Yulan Fu, Zhen Chai","doi":"10.1039/d4nr04794j","DOIUrl":"https://doi.org/10.1039/d4nr04794j","url":null,"abstract":"Low-frequency noise in detection systems significantly affects the performance of ultrasensitive and ultracompact spin-exchange relaxation-free atomic magnetometers. High frequency modulation detection helps effectively suppress the 1/f noise and enhance the signal-to-noise ratio, but conventional modulators are bulky and restrict the development of integrated atomic magnetometer modulation-detection systems. Resonant metasurface-based thin-film lithium-niobate (TFLN) active optics can modulate free-space light within a compact configuration. In this study, we demonstrate a TFLN metasurface platform that leverages guided mode resonance for efficient phase modulation, achieving a modulation amplitude of 0.063 rad at a frequency of 100 kHz. We exploit the resonance in the TFLN waveguide and obtain a high-quality factor of 166 at a resonant wavelength of 795.8 nm. Using the fabricated modulator, we achieve an optical rotation angle measurement sensitivity of 4×10-7 rad/Hz1/2 with the modulation. Compared to conventional bulky modulators, the modulator fabricated in this study realizes a more than 90% reduction in volume. This study provides a feasible approach for developing miniaturized integrated atomic magnetometers to achieve improved sensitivity through optical modulation techniques.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"4 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917398","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：