Annu Balhara, Santosh K. Gupta, Partha Sarathi Ghosh, Malini Abraham, Mohit Tyagi, Ashok Kumar Yadav, Subrata Das, Kathi Sudarshan, P. S. Sarkar
Persistent luminescence (PersL) in inorganic phosphors offers great potential for anti-counterfeiting and optical storage, with optimization of PersL, multicolor tuning, and defect engineering. This study presents a Ca3Ga2Ge3O12:Pr3+ (CGGO:Pr) phosphor with long-lasting PersL and multicolor emissions. Aliovalent codoping with Er3+ and Yb3+ ions optimizes deep/shallow trap redistribution, controlling trap depths from 0.98 to optimal 0.73 eV through the creation of new shallow electron traps (YbCa•, ErCa•) alongside existing VO levels. The smart Pr3+/Er3+/Yb3+:CGGO phosphor exhibits three-dimensional visible emissions under 275 and 380 nm excitation, as well as upconversion emissions under 980 nm laser irradiation. Hybrid density functional calculations, thermoluminescence, and positron annihilation lifetime spectroscopy revealed the nature and density of different traps controlling the PersL. Together, a single system featuring multicolor luminescence has been developed, exhibiting improved PersL and regulated trap depths (≈0.73 eV) suitable for robust and multimodal anti-counterfeiting of documents, pharmaceuticals, and industrial products. Furthermore, the composite PMMA-CGGO:Pr phosphor films have shown remarkable capability for X-ray imaging, achieving a resolution of 4 lp/mm, which exceeds that of commercial Gd2O2S:Tb screens. These findings highlight the potential of this work for advanced anti-counterfeiting and X-ray imaging applications, offering enhanced PersL with controlled trap depths.
{"title":"Unleashing the Potential of Defect Engineered Persistent Pr3+-Activated Phosphors for Multi-Dimensional Anti-Counterfeiting and X-Ray Imaging Applications","authors":"Annu Balhara, Santosh K. Gupta, Partha Sarathi Ghosh, Malini Abraham, Mohit Tyagi, Ashok Kumar Yadav, Subrata Das, Kathi Sudarshan, P. S. Sarkar","doi":"10.1002/smll.202501752","DOIUrl":"https://doi.org/10.1002/smll.202501752","url":null,"abstract":"Persistent luminescence (PersL) in inorganic phosphors offers great potential for anti-counterfeiting and optical storage, with optimization of PersL, multicolor tuning, and defect engineering. This study presents a Ca<sub>3</sub>Ga<sub>2</sub>Ge<sub>3</sub>O<sub>12:</sub>Pr<sup>3+</sup> (CGGO:Pr) phosphor with long-lasting PersL and multicolor emissions. Aliovalent codoping with Er<sup>3+</sup> and Yb<sup>3+</sup> ions optimizes deep/shallow trap redistribution, controlling trap depths from 0.98 to optimal 0.73 eV through the creation of new shallow electron traps (Yb<sub>Ca</sub><sup>•</sup>, Er<sub>Ca</sub><sup>•</sup>) alongside existing V<sub>O</sub> levels. The smart Pr<sup>3+</sup>/Er<sup>3+</sup>/Yb<sup>3+</sup>:CGGO phosphor exhibits three-dimensional visible emissions under 275 and 380 nm excitation, as well as upconversion emissions under 980 nm laser irradiation. Hybrid density functional calculations, thermoluminescence, and positron annihilation lifetime spectroscopy revealed the nature and density of different traps controlling the PersL. Together, a single system featuring multicolor luminescence has been developed, exhibiting improved PersL and regulated trap depths (≈0.73 eV) suitable for robust and multimodal anti-counterfeiting of documents, pharmaceuticals, and industrial products. Furthermore, the composite PMMA-CGGO:Pr phosphor films have shown remarkable capability for X-ray imaging, achieving a resolution of 4 lp/mm, which exceeds that of commercial Gd<sub>2</sub>O<sub>2</sub>S:Tb screens. These findings highlight the potential of this work for advanced anti-counterfeiting and X-ray imaging applications, offering enhanced PersL with controlled trap depths.","PeriodicalId":228,"journal":{"name":"Small","volume":"32 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Viksit Kumar, Bharthkumar. H. Javaregowda, George Devasia, Aswini Narayanan, Sailaja Krishnamurty, Kothandam Krishnamoorthy, Sukumaran Santhosh Babu
Lithium-sulfur batteries (LSBs) hold incredible potential as next-generation energy storage systems. However, practical applications of LSBs are significantly hindered by several critical challenges. For the first time, scalable all-carbon porous 3D polymers (3DPs) that do not contain heteroatoms or functional groups and do not require post-functionalization are investigated as hosts in lithium–sulfur batteries, demonstrating enhanced cycling stability and overall battery performance. The pyrene-containing 3DP exhibits 75% capacity retention after 600 cycles at 1 C and 52% capacity retention after 1300 cycles at 0.2 C, better than phenyl comprising 3DP. Furthermore, even at higher sulfur loading (4.1 mg cm−2) with an electrolyte/sulfur ratio of 5 µL mg−1, pyrene 3DP displayed a high capacity of 600 mA h g−1 and stable performance over 250 cycles with negligible capacity fade. The defined pore structure of 3DPs prevents the migration of polysulfides through physical confinement and the large π-clouds of 3DPs interact with the negative charge-bearing polysulfides generated in charge–discharge cycles through anion-π interaction. In this way, The design ensures that the host 3DPs interact with neutral sulfur and anionic polysulfides, resulting in an excellent performance.
{"title":"Diamondoid All-Carbon Porous Aromatic Framework Host for Lithium–Sulfur Batteries","authors":"Viksit Kumar, Bharthkumar. H. Javaregowda, George Devasia, Aswini Narayanan, Sailaja Krishnamurty, Kothandam Krishnamoorthy, Sukumaran Santhosh Babu","doi":"10.1002/smll.202500388","DOIUrl":"https://doi.org/10.1002/smll.202500388","url":null,"abstract":"Lithium-sulfur batteries (LSBs) hold incredible potential as next-generation energy storage systems. However, practical applications of LSBs are significantly hindered by several critical challenges. For the first time, scalable all-carbon porous 3D polymers (3DPs) that do not contain heteroatoms or functional groups and do not require post-functionalization are investigated as hosts in lithium–sulfur batteries, demonstrating enhanced cycling stability and overall battery performance. The pyrene-containing 3DP exhibits 75% capacity retention after 600 cycles at 1 C and 52% capacity retention after 1300 cycles at 0.2 C, better than phenyl comprising 3DP. Furthermore, even at higher sulfur loading (4.1 mg cm<sup>−2</sup>) with an electrolyte/sulfur ratio of 5 µL mg<sup>−1</sup>, pyrene 3DP displayed a high capacity of 600 mA h g<sup>−1</sup> and stable performance over 250 cycles with negligible capacity fade. The defined pore structure of 3DPs prevents the migration of polysulfides through physical confinement and the large π-clouds of 3DPs interact with the negative charge-bearing polysulfides generated in charge–discharge cycles through anion-π interaction. In this way, The design ensures that the host 3DPs interact with neutral sulfur and anionic polysulfides, resulting in an excellent performance.","PeriodicalId":228,"journal":{"name":"Small","volume":"27 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biru Eshete Worku, Yang Lu, Mingzhi Song, Shumin Zheng, Bao Wang
Li-rich Mn-based cathode materials (LRMs) are the most promising cathodes for the next-generation Lithium-ion batteries due to their high energy density. However, LRMs encounter formidable challenges such as voltage/capacity decay, mediocre rate capability, low cyclability, and substantial capacity loss at low temperatures. These challenges stem from irreversible oxygen release and subsequent structural deterioration. As energy storage devices are required to operate across a wide temperature range, enhancing the electrochemical performance of LRMs at both room and low temperatures is crucial. Herein, an approach of Al and F co-doping on novel single-crystal Li1.2Mn0.54Ni0.13Co0.13O2 is proposed to promote oxygen redox reversibility and enhance structural stability. Investigations into the oxygen redox couple and manganese electronic structure demonstrate that the Al and F co-doped electrode (LRMAF) retains a higher amount of lattice oxygen (O2⁻) and a greater amount of Mn⁴⁺ after cycling. As a result, LRMAF exhibits a high energy density of 1185 Wh kg−1, an initial discharge capacity of 329 mAh g⁻¹ at 0.1C, achieves a rate performance of 155 mAh g⁻¹ at 5.0C and delivers 88% capacity retention after 100 cycles. Additionally, LRMAF exhibits excellent electrochemical performance at −20 °C. This enhancement is attributed to the novel single-crystal morphology combined with cation/anion co-doping.
{"title":"Cation/Anion Co-Doping Enhances Oxygen Redox Reversibility and Structural Stability in Single-Crystal Li-Rich Mn-Based Cathodes for Wide-Temperature Performance","authors":"Biru Eshete Worku, Yang Lu, Mingzhi Song, Shumin Zheng, Bao Wang","doi":"10.1002/smll.202501005","DOIUrl":"https://doi.org/10.1002/smll.202501005","url":null,"abstract":"Li-rich Mn-based cathode materials (LRMs) are the most promising cathodes for the next-generation Lithium-ion batteries due to their high energy density. However, LRMs encounter formidable challenges such as voltage/capacity decay, mediocre rate capability, low cyclability, and substantial capacity loss at low temperatures. These challenges stem from irreversible oxygen release and subsequent structural deterioration. As energy storage devices are required to operate across a wide temperature range, enhancing the electrochemical performance of LRMs at both room and low temperatures is crucial. Herein, an approach of Al and F co-doping on novel single-crystal Li<sub>1.2</sub>Mn<sub>0.54</sub>Ni<sub>0.13</sub>Co<sub>0.13</sub>O<sub>2</sub> is proposed to promote oxygen redox reversibility and enhance structural stability. Investigations into the oxygen redox couple and manganese electronic structure demonstrate that the Al and F co-doped electrode (LRMAF) retains a higher amount of lattice oxygen (O<sup>2</sup>⁻) and a greater amount of Mn⁴⁺ after cycling. As a result, LRMAF exhibits a high energy density of 1185 Wh kg<sup>−1</sup>, an initial discharge capacity of 329 mAh g⁻¹ at 0.1C, achieves a rate performance of 155 mAh g⁻¹ at 5.0C and delivers 88% capacity retention after 100 cycles. Additionally, LRMAF exhibits excellent electrochemical performance at −20 °C. This enhancement is attributed to the novel single-crystal morphology combined with cation/anion co-doping.","PeriodicalId":228,"journal":{"name":"Small","volume":"26 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ε-Iron carbide has garnered increasing interest for its superior magnetic characteristics and catalytic performance compared to other iron carbides. However, its metastable nature has posed significant challenges for synthesis, often requiring ultrahigh pressure, multistep processes, complex reaction condition control, and highly toxic reagents. Consequently, the properties of ε-iron carbide remain largely unexplored. A simplified synthesis method for ε-iron carbide can accelerate the exploration of new functionalities. In this study, a novel one-step selective synthesis method for ε-iron carbide nanoparticles under mild conditions via a wet-chemical approach is presented. In this method, Fe3(CO)12, cetyltrimethylammonium bromide (CTAB), and bis(pinacolato)diboron (B2pin2) are added to hexadecylamine and reacted at 220 °C—a simple process that eliminates the need for extreme pressures and toxic substances. Detailed investigations elucidate the crucial roles of CTAB and B2pin2 in facilitating the selective formation of ε-iron carbide. This accessible and efficient synthesis process for ε-iron carbide can further enable the discovery of unprecedented catalytic properties in the reductive amination of benzaldehyde, distinct from those of conventional iron nanoparticle catalysts. Density functional theory calculations reveal insights into the electronic states responsible for the distinct activity of the ε-iron carbide nanoparticles.
{"title":"One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts","authors":"Yuma Hirayama, Akira Miura, Motoaki Hirayama, Hiroyuki Nakamura, Koji Fujita, Hiroshi Kageyama, Sho Yamaguchi, Tomoo Mizugaki, Takato Mitsudome","doi":"10.1002/smll.202412217","DOIUrl":"https://doi.org/10.1002/smll.202412217","url":null,"abstract":"<i>ε</i>-Iron carbide has garnered increasing interest for its superior magnetic characteristics and catalytic performance compared to other iron carbides. However, its metastable nature has posed significant challenges for synthesis, often requiring ultrahigh pressure, multistep processes, complex reaction condition control, and highly toxic reagents. Consequently, the properties of <i>ε</i>-iron carbide remain largely unexplored. A simplified synthesis method for <i>ε</i>-iron carbide can accelerate the exploration of new functionalities. In this study, a novel one-step selective synthesis method for <i>ε</i>-iron carbide nanoparticles under mild conditions via a wet-chemical approach is presented. In this method, Fe<sub>3</sub>(CO)<sub>12</sub>, cetyltrimethylammonium bromide (CTAB), and bis(pinacolato)diboron (B<sub>2</sub>pin<sub>2</sub>) are added to hexadecylamine and reacted at 220 °C—a simple process that eliminates the need for extreme pressures and toxic substances. Detailed investigations elucidate the crucial roles of CTAB and B<sub>2</sub>pin<sub>2</sub> in facilitating the selective formation of <i>ε</i>-iron carbide. This accessible and efficient synthesis process for <i>ε</i>-iron carbide can further enable the discovery of unprecedented catalytic properties in the reductive amination of benzaldehyde, distinct from those of conventional iron nanoparticle catalysts. Density functional theory calculations reveal insights into the electronic states responsible for the distinct activity of the <i>ε</i>-iron carbide nanoparticles.","PeriodicalId":228,"journal":{"name":"Small","volume":"72 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sihwan Lee, Yong Eun Cho, Ho-Young Kim, Jeong-Yun Sun
Modulating the mechanical properties of soft materials with light is essential for achieving customizable functionalities. However, existing photo-responsive materials suffer from limited mechanical performance and a restricted tunable range. Here, a photo-tunable elastomer is developed by incorporating a urethane acrylate network with selenosulfide-based dynamic covalent crosslinkers, achieving high tensile strength exceeding 1.2 MPa in their stiff state and variable Young's modulus within a 0.8 MPa range. These crosslinkers undergo selenosulfide photo-metathesis, gradually breaking under ultraviolet light and reforming under visible light, enabling fine control over the modulus, strength, and stretchability of the elastomer. In terms of controllability, the design supports multiple tunable states, which allow for the use of intermediate mechanical properties. Moreover, by modeling the crosslinking density changes with reaction kinetics, modulus variation is predicted as a function of light exposure time. The light-induced modulation facilitates localized mechanical property adjustments, generating transformable multi-material structures and enhancing fracture resistance. Integrating these crosslinkers into different polymer networks provides a strategy for creating various photo-tunable elastomers and gels.
{"title":"Photo-Tunable Elastomers Enabling Reversible, Broad-Range Modulation of Mechanical Properties Via Dynamic Covalent Crosslinkers","authors":"Sihwan Lee, Yong Eun Cho, Ho-Young Kim, Jeong-Yun Sun","doi":"10.1002/smll.202412657","DOIUrl":"https://doi.org/10.1002/smll.202412657","url":null,"abstract":"Modulating the mechanical properties of soft materials with light is essential for achieving customizable functionalities. However, existing photo-responsive materials suffer from limited mechanical performance and a restricted tunable range. Here, a photo-tunable elastomer is developed by incorporating a urethane acrylate network with selenosulfide-based dynamic covalent crosslinkers, achieving high tensile strength exceeding 1.2 MPa in their stiff state and variable Young's modulus within a 0.8 MPa range. These crosslinkers undergo selenosulfide photo-metathesis, gradually breaking under ultraviolet light and reforming under visible light, enabling fine control over the modulus, strength, and stretchability of the elastomer. In terms of controllability, the design supports multiple tunable states, which allow for the use of intermediate mechanical properties. Moreover, by modeling the crosslinking density changes with reaction kinetics, modulus variation is predicted as a function of light exposure time. The light-induced modulation facilitates localized mechanical property adjustments, generating transformable multi-material structures and enhancing fracture resistance. Integrating these crosslinkers into different polymer networks provides a strategy for creating various photo-tunable elastomers and gels.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yushuang Lin, Yan Zhang, Zhao Dai, Xue Peng, Weihao Xue, Yongjun Zhang, Nan Li
Nanofiltration membranes hold great promise for ion separation but often suffer from a trade-off between selectivity and flux, limiting their use in precise separation processes. A key challenge is achieving precise control over pore orientation, as existing methods fail to provide real-time, quantitative insights for optimizing membrane structure and performance. To address this, an innovative in situ, real-time quantitative technique is developed that links pore alignment directly to separation efficiency. Using β-cyclodextrin as a model pore-forming compound, fluorescent labeling enables continuous monitoring of pore orientation and distribution during membrane fabrication. This method enables the capture of the complete distribution of pore orientation across the entire membrane surface, allowing for precise adjustments in membrane design. This approach provides the real-time quantification of pore alignment, facilitating the design of NF membranes with enhanced ion selectivity and permeability. The optimized membranes demonstrate exceptional Mg2+/Li+ separation efficiency, with a separation factor of 15.55 and permeance of 35.85 L m−2 h−1 bar−1, representing a significant step forward in high-performance nanofiltration membranes with broad applications in resource recovery, environmental remediation, and water treatment.
{"title":"In Situ Real-Time Quantitative Characterization of Nanofiltration Membrane Pore Orientation for Enhanced Ion Separation","authors":"Yushuang Lin, Yan Zhang, Zhao Dai, Xue Peng, Weihao Xue, Yongjun Zhang, Nan Li","doi":"10.1002/adma.202500447","DOIUrl":"https://doi.org/10.1002/adma.202500447","url":null,"abstract":"Nanofiltration membranes hold great promise for ion separation but often suffer from a trade-off between selectivity and flux, limiting their use in precise separation processes. A key challenge is achieving precise control over pore orientation, as existing methods fail to provide real-time, quantitative insights for optimizing membrane structure and performance. To address this, an innovative in situ, real-time quantitative technique is developed that links pore alignment directly to separation efficiency. Using β-cyclodextrin as a model pore-forming compound, fluorescent labeling enables continuous monitoring of pore orientation and distribution during membrane fabrication. This method enables the capture of the complete distribution of pore orientation across the entire membrane surface, allowing for precise adjustments in membrane design. This approach provides the real-time quantification of pore alignment, facilitating the design of NF membranes with enhanced ion selectivity and permeability. The optimized membranes demonstrate exceptional Mg<sup>2+</sup>/Li<sup>+</sup> separation efficiency, with a separation factor of 15.55 and permeance of 35.85 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>, representing a significant step forward in high-performance nanofiltration membranes with broad applications in resource recovery, environmental remediation, and water treatment.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"7 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-24DOI: 10.1016/j.mseb.2025.118305
Irlan S. Lima , Thawan G. Oliveira , Astrid Choquehuanca-Azaña , Sergio Espinoza-Torres , Enzo M. Otto , Mateus A. Batista , Giovane J. Oliveira , Mayara O. Silva , Ivan Verlangieri , Josué M. Gonçalves , Lúcio Angnes
A ternary metal-glycerolate combined with a low-cost platform electrode was demonstrated as an effective sensor for glucose analysis. The hybrid organic–inorganic NiFeCo-Glycerolate was fabricated by one-step solvothermal treatment. The proposed process produces microspheres with an average size of ∼1 µm that were extensively characterized by X-ray diffraction, FTIR, TGA, XPS, TEM, and SEM-EDS techniques. The combination of a scalable synthesis with a cost-effective conductive platform is an interesting strategy for the development of an enzyme-free glucose electrochemical sensor. Experiments employing chronoamperometry demonstrated a good linearity of response in the concentration range of 100 to 600 µmol L−1, with a detection and quantification limit of 6.20 and 20.5 µmol L−1, respectively. The developed sensor was utilized to quantify glucose in a synthetic urine sample, with a recovery rate of 105 ± 3 %, and a current retention of 94.8 % in an interval of time of 24 h. Thus, highlighting the potential of ternary metal-glycerolates allied to a low-cost platform in glucose sensing.
{"title":"Non-enzymatic detection of glucose using ternary NiFeCo-Glycerolate supported on graphite electrodes","authors":"Irlan S. Lima , Thawan G. Oliveira , Astrid Choquehuanca-Azaña , Sergio Espinoza-Torres , Enzo M. Otto , Mateus A. Batista , Giovane J. Oliveira , Mayara O. Silva , Ivan Verlangieri , Josué M. Gonçalves , Lúcio Angnes","doi":"10.1016/j.mseb.2025.118305","DOIUrl":"10.1016/j.mseb.2025.118305","url":null,"abstract":"<div><div>A ternary metal-glycerolate combined with a low-cost platform electrode was demonstrated as an effective sensor for glucose analysis. The hybrid organic–inorganic NiFeCo-Glycerolate was fabricated by one-step solvothermal treatment. The proposed process produces microspheres with an average size of ∼1 µm that were extensively characterized by X-ray diffraction, FTIR, TGA, XPS, TEM, and SEM-EDS techniques. The combination of a scalable synthesis with a cost-effective conductive platform is an interesting strategy for the development of an enzyme-free glucose electrochemical sensor. Experiments employing chronoamperometry demonstrated a good linearity of response in the concentration range of 100 to 600 µmol L<sup>−1</sup>, with a detection and quantification limit of 6.20 and 20.5 µmol L<sup>−1</sup>, respectively. The developed sensor was utilized to quantify glucose in a synthetic urine sample, with a recovery rate of 105 ± 3 %, and a current retention of 94.8 % in an interval of time of 24 h. Thus, highlighting the potential of ternary metal-glycerolates allied to a low-cost platform in glucose sensing.</div></div>","PeriodicalId":18233,"journal":{"name":"Materials Science and Engineering: B","volume":"319 ","pages":"Article 118305"},"PeriodicalIF":3.9,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864276","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}
Wei-Jiang Gan, Selvam Mathi, Jingting Li, Adewale K. Ipadeola, Jianqiu Deng, Aboubakr M Abdullah, M. Sadeeq Balogun, Zhongmin Wang
Strategic modulation of the electronic structure and surface chemistry of electrocatalysts is crucial for achieving highly efficient and cost-effective bifunctional catalysts for water splitting. This study demonstrates the strategic incorporation of redox-active elements (vanadium, V and iron, Fe) to optimize the catalytic interface of mixed-valence cobalt-based nanowires (Co5.47N and CoP), which enhances hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic abilities. Experimental and theoretical analyses reveal that dual-cation doping increases the surface area and optimizes the electronic structure, which promotes rapid water dissociation, favours hydrogen adsorption kinetics, and stabilizes oxygen intermediates. Consequently, V,Fe-Co5.47N and V,Fe-CoP nanowire electrocatalysts achieve low overpotentials of 55/251 and 63/265 mV for HER/OER at 10 mA cm-2 in 1 M KOH electrolyte, respectively, outperforming the pristine and single-cation-doped counterparts. The alkaline overall water splitting devices assembled based on these bifunctional catalysts require only 1.64 V and 1.66 V at 100 mA cm-2 and also demonstrates excellent durability. This work provides valuable insights into enhancing transition metal-based catalysts through redox-active element incorporation for efficient water splitting.
{"title":"Rational Design of Mixed-Valence Cobalt-Based Nanowires via Simultaneous Vanadium and Iron Modulations for Enhanced Alkaline Electrochemical Water Splitting","authors":"Wei-Jiang Gan, Selvam Mathi, Jingting Li, Adewale K. Ipadeola, Jianqiu Deng, Aboubakr M Abdullah, M. Sadeeq Balogun, Zhongmin Wang","doi":"10.1039/d5nr00801h","DOIUrl":"https://doi.org/10.1039/d5nr00801h","url":null,"abstract":"Strategic modulation of the electronic structure and surface chemistry of electrocatalysts is crucial for achieving highly efficient and cost-effective bifunctional catalysts for water splitting. This study demonstrates the strategic incorporation of redox-active elements (vanadium, V and iron, Fe) to optimize the catalytic interface of mixed-valence cobalt-based nanowires (Co<small><sub>5.47</sub></small>N and CoP), which enhances hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic abilities. Experimental and theoretical analyses reveal that dual-cation doping increases the surface area and optimizes the electronic structure, which promotes rapid water dissociation, favours hydrogen adsorption kinetics, and stabilizes oxygen intermediates. Consequently, V,Fe-Co<small><sub>5.47</sub></small>N and V,Fe-CoP nanowire electrocatalysts achieve low overpotentials of 55/251 and 63/265 mV for HER/OER at 10 mA cm<small><sup>-2</sup></small> in 1 M KOH electrolyte, respectively, outperforming the pristine and single-cation-doped counterparts. The alkaline overall water splitting devices assembled based on these bifunctional catalysts require only 1.64 V and 1.66 V at 100 mA cm<small><sup>-2</sup></small> and also demonstrates excellent durability. This work provides valuable insights into enhancing transition metal-based catalysts through redox-active element incorporation for efficient water splitting.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"78 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866367","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}
In response to the growing demand for novel catalyst designs for the selective growth of single-walled carbon nanotubes (SWCNTs), this study explores the use of ferrocenium (the oxidized state of ferrocene) as a new catalyst precursor for the first time. Utilizing the floating-catalyst chemical vapor deposition (FC-CVD) method, SWCNTs were synthesized and characterized through analytical transmission electron microscope selected area electron diffraction (TEM SAED) and optical techniques (Raman spectroscopy and UV-Vis-NIR absorption). The introduction of ferrocenium led to an enhancement in the metallicity of the nanotubes, raising the proportion of metallic SWCNTs to 43.1%, while also broadening the nanotube mean diameter from 1.84 nm to 2.10 nm. The key factor behind this improvement lies in the positive charge of Fe³⁺ in ferrocenium, which has been shown to stabilize metallic nanotube formation. These findings highlight the pivotal role of catalyst charge in controlling SWCNT chirality and electronic properties, paving the way for more precise control in nanotube synthesis for applications in nanoelectronics and materials science.
{"title":"The impact of ferrocenium as a catalyst on the chiral distribution of single-walled carbon nanotubes in floating-catalyst chemical vapor deposition synthesis","authors":"Anastasios Karakassides, Hirotaka Inoue, Peng Liu, Zhenyu Xu, Ghulam Yasin, Hua Jiang, Esko Kauppinen","doi":"10.1039/d5nr00297d","DOIUrl":"https://doi.org/10.1039/d5nr00297d","url":null,"abstract":"In response to the growing demand for novel catalyst designs for the selective growth of single-walled carbon nanotubes (SWCNTs), this study explores the use of ferrocenium (the oxidized state of ferrocene) as a new catalyst precursor for the first time. Utilizing the floating-catalyst chemical vapor deposition (FC-CVD) method, SWCNTs were synthesized and characterized through analytical transmission electron microscope selected area electron diffraction (TEM SAED) and optical techniques (Raman spectroscopy and UV-Vis-NIR absorption). The introduction of ferrocenium led to an enhancement in the metallicity of the nanotubes, raising the proportion of metallic SWCNTs to 43.1%, while also broadening the nanotube mean diameter from 1.84 nm to 2.10 nm. The key factor behind this improvement lies in the positive charge of Fe³⁺ in ferrocenium, which has been shown to stabilize metallic nanotube formation. These findings highlight the pivotal role of catalyst charge in controlling SWCNT chirality and electronic properties, paving the way for more precise control in nanotube synthesis for applications in nanoelectronics and materials science.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"13 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866371","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}
Minjun Kim, Jiyun Nam, Jiseok Kim, Hyunsik Hwang, Myungeun Seo, Hyunjoon Song
We report a new bottlebrush copolymer (BBCP) ligand design as robust patches for gold nanoparticles (Au NPs) to construct a rigid template guiding heterometal deposition on the surface. Given the spatial congestion of the side chains, BBCP rapidly forms dense and stationary patches on Au NPs and effectively blocks additional metal deposition. Reducing solvent quality varies the phase segregation of BBCP and subsequently restricts metal deposition to specific locations, fabricating diverse bimetallic heterostructures. The resulting morphology exhibits a unique orientation-dependent scattering property that thermodynamic configuration cannot achieve.
{"title":"Bottlebrush Polymer Patches Template Heterometal Growth on Gold Nanoparticle Surface","authors":"Minjun Kim, Jiyun Nam, Jiseok Kim, Hyunsik Hwang, Myungeun Seo, Hyunjoon Song","doi":"10.1039/d5nr01001b","DOIUrl":"https://doi.org/10.1039/d5nr01001b","url":null,"abstract":"We report a new bottlebrush copolymer (BBCP) ligand design as robust patches for gold nanoparticles (Au NPs) to construct a rigid template guiding heterometal deposition on the surface. Given the spatial congestion of the side chains, BBCP rapidly forms dense and stationary patches on Au NPs and effectively blocks additional metal deposition. Reducing solvent quality varies the phase segregation of BBCP and subsequently restricts metal deposition to specific locations, fabricating diverse bimetallic heterostructures. The resulting morphology exhibits a unique orientation-dependent scattering property that thermodynamic configuration cannot achieve.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"47 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866372","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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