Pub Date : 2024-12-04DOI: 10.1016/j.synthmet.2024.117814
Jieming Dong , Junyao Li , Laidi Xu , Hongyu Zhang , Yong Kong , Guojun Zheng
Au nanoparticles (AuNPs)-poly(o-phenylenediamine) (PoPD) nanocomposite was facilely prepared by a one-step method and used as the built-in redox probe for the decoration of a glassy carbon electrode (GCE). As the template molecules, diethylstilbestrol (DES) was immobilized on the AuNPs-PoPD/GCE surface by using electropolymerized o-phenylenediamine (oPD) as the imprinting layer, which was then eluted from the imprinting layer with the mixture of ethanol and water (v/v, 50 %). The resultant molecularly imprinted PoPD/AuNPs-PoPD/GCE (MI-PoPD/AuNPs-PoPD/GCE) was used for the electrochemical detection of DES in a wide range from 0.1 to 10 μM, and the limit of detection (LOD) was 0.062 μM (S/N = 3). The parameters for DES detection were also optimized in this work. The molecularly imprinted DES sensor showed high stability, selectivity and reproducibility, and it was successfully used for the detection of DES in the milk samples.
{"title":"A molecularly imprinted electrochemical sensor based on Au nanoparticles-poly(o-phenylenediamine) for diethylstilbestrol detection","authors":"Jieming Dong , Junyao Li , Laidi Xu , Hongyu Zhang , Yong Kong , Guojun Zheng","doi":"10.1016/j.synthmet.2024.117814","DOIUrl":"10.1016/j.synthmet.2024.117814","url":null,"abstract":"<div><div>Au nanoparticles (AuNPs)-poly(o-phenylenediamine) (PoPD) nanocomposite was facilely prepared by a one-step method and used as the built-in redox probe for the decoration of a glassy carbon electrode (GCE). As the template molecules, diethylstilbestrol (DES) was immobilized on the AuNPs-PoPD/GCE surface by using electropolymerized <em>o</em>-phenylenediamine (oPD) as the imprinting layer, which was then eluted from the imprinting layer with the mixture of ethanol and water (v/v, 50 %). The resultant molecularly imprinted PoPD/AuNPs-PoPD/GCE (MI-PoPD/AuNPs-PoPD/GCE) was used for the electrochemical detection of DES in a wide range from 0.1 to 10 μM, and the limit of detection (LOD) was 0.062 μM (S/N = 3). The parameters for DES detection were also optimized in this work. The molecularly imprinted DES sensor showed high stability, selectivity and reproducibility, and it was successfully used for the detection of DES in the milk samples.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117814"},"PeriodicalIF":4.0,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173799","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}
Pub Date : 2024-12-03DOI: 10.1016/j.synthmet.2024.117811
O. Elouardi , J. Chenouf , S. Elhadfi , Y. Kensi , S.A.A. Abdelkader , B. Fakrach , A.H. Rahmani , H. Chadli , A. Rahmani
The instability of organic electronic devices under environmental conditions narrowly related to the unstable aggregate state of organic semiconductors is one key obstacle to practical application. Herein, we highlight a promising strategy to overcome these drawbacks consisting to make use of the hollow space within single-walled boron nitride nanotubes (SWBNNTs). As a prototypical system of organic π-conjugated molecules encapsulated in SWBNNTs, we investigate the energetic stability and Raman spectra of a series of oligothiophene molecules (nT) (n = 2, 4, and 6) inside SWBNNTs through a combination of molecular dynamics (MD), density functional theory (DFT), bond polarisability model (BPM), and spectral moments method (SMM). The structural stability of these nanohybrids are explored initially. The optimal SWBNNTs diameters in which the resulting nanohybrids are stable with either one molecule (nT@SWBNNTs) and two encapsulated molecular chains (nT-nT@SWBNNTs) are computed. Then, the computed Raman spectra of the oligothiophenes and SWBNNTs before and after filling are reported. The energetic stability and the possible appearance or not of charge transfer in such nanohybrids are investigated by attentive analysis of the nanoconfinement effect on Raman features of oligothiophenes and SWBNNTs. The present results provide benchmark theoretical data to efficiently probe the interactions subsisting in such nanohybrids based on SWBNNTs templates that can serve as a new stable component for organic electronic devices.
{"title":"Energetics and Raman spectroscopy of organic molecules encapsulated in single-walled boron nitride nanotubes: The example of π-conjugated oligothiophenes","authors":"O. Elouardi , J. Chenouf , S. Elhadfi , Y. Kensi , S.A.A. Abdelkader , B. Fakrach , A.H. Rahmani , H. Chadli , A. Rahmani","doi":"10.1016/j.synthmet.2024.117811","DOIUrl":"10.1016/j.synthmet.2024.117811","url":null,"abstract":"<div><div>The instability of organic electronic devices under environmental conditions narrowly related to the unstable aggregate state of organic semiconductors is one key obstacle to practical application. Herein, we highlight a promising strategy to overcome these drawbacks consisting to make use of the hollow space within single-walled boron nitride nanotubes (SWBNNTs). As a prototypical system of organic <em>π</em>-conjugated molecules encapsulated in SWBNNTs, we investigate the energetic stability and Raman spectra of a series of oligothiophene molecules (nT) (n = 2, 4, and 6) inside SWBNNTs through a combination of molecular dynamics (MD), density functional theory (DFT), bond polarisability model (BPM), and spectral moments method (SMM). The structural stability of these nanohybrids are explored initially. The optimal SWBNNTs diameters in which the resulting nanohybrids are stable with either one molecule (nT@SWBNNTs) and two encapsulated molecular chains (nT-nT@SWBNNTs) are computed. Then, the computed Raman spectra of the oligothiophenes and SWBNNTs before and after filling are reported. The energetic stability and the possible appearance or not of charge transfer in such nanohybrids are investigated by attentive analysis of the nanoconfinement effect on Raman features of oligothiophenes and SWBNNTs. The present results provide benchmark theoretical data to efficiently probe the interactions subsisting in such nanohybrids based on SWBNNTs templates that can serve as a new stable component for organic electronic devices.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117811"},"PeriodicalIF":4.0,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172396","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}
A novel composite anode material, CoxSy/G, has been developed through a novel hydrothermal synthesis method complemented by an innovative high-temperature vulcanization technique. This process facilitates the deposition of CoxSy nanoparticles, each less than 10 nm in size, onto a substrate of 3D rGO. This composite material combines the robust lithium storage capacity of CoxSy nanoparticles with the exceptional electrical conductivity and mechanical resilience of the 3D rGO framework, resulting in a significantly enhanced specific surface area and optimized mesoporous structure for CoxSy/G. Furthermore, it exhibits excellent electrochemical performance in lithium-ion batteries. Specifically, the CoxSy/G composites achieve a discharge capacity of 748.5 mA h g⁻¹ at 50 mA g⁻¹ , notably exceeding the 647 mA h g⁻¹ capacity demonstrated by pure CoxSy. Furthermore, these composites maintain an extraordinary cycle retention rate of 112.4 % after undergoing 500 charge-discharge cycles at a continuous rate of 0.5 A g⁻¹ . The reduced charge transfer resistance noted after cycling underscores the material’s enhanced performance attributes. This innovative creation of CoxSy/G composites offers critical insights and potential strategies for further development in the field of lithium-ion cobalt-sulfur electrodes.
{"title":"Ultra-small CoxSy nanoparticles adhered to 3D-reduced graphene oxide as attractive anodes for lithium-ion batteries","authors":"Baoyan Xing , Shang Jiang , Shuo Yu , Bingrong Dong , Yuqing Peng , Fangzhou Zhang , Caixia Huo , Aijun Li","doi":"10.1016/j.synthmet.2024.117813","DOIUrl":"10.1016/j.synthmet.2024.117813","url":null,"abstract":"<div><div>A novel composite anode material, Co<sub>x</sub>S<sub>y</sub>/G, has been developed through a novel hydrothermal synthesis method complemented by an innovative high-temperature vulcanization technique. This process facilitates the deposition of CoxSy nanoparticles, each less than 10 nm in size, onto a substrate of 3D rGO. This composite material combines the robust lithium storage capacity of CoxSy nanoparticles with the exceptional electrical conductivity and mechanical resilience of the 3D rGO framework, resulting in a significantly enhanced specific surface area and optimized mesoporous structure for CoxSy/G. Furthermore, it exhibits excellent electrochemical performance in lithium-ion batteries. Specifically, the CoxSy/G composites achieve a discharge capacity of 748.5 mA h g⁻¹ at 50 mA g⁻¹ , notably exceeding the 647 mA h g⁻¹ capacity demonstrated by pure CoxSy. Furthermore, these composites maintain an extraordinary cycle retention rate of 112.4 % after undergoing 500 charge-discharge cycles at a continuous rate of 0.5 A g⁻¹ . The reduced charge transfer resistance noted after cycling underscores the material’s enhanced performance attributes. This innovative creation of CoxSy/G composites offers critical insights and potential strategies for further development in the field of lithium-ion cobalt-sulfur electrodes.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117813"},"PeriodicalIF":4.0,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172392","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}
Pub Date : 2024-12-03DOI: 10.1016/j.synthmet.2024.117812
Si Zhang , Chuanbo Hu , Xianling Hei , Xin Zhang , Bo Lan , Huawei Yin , Chengli Tang , Jie Zhao , Tingzhen Li
Microbiologically influenced corrosion (MIC) can lead to structural weakening and shortened service life of carbon steel, resulting in serious economic losses and safety hazards. In particular, sulfate-reducing bacteria (SRB) produce hydrogen sulfide and sulfide during their growth and metabolism, which accelerates the corrosion of carbon steel. Thin films of poly(aniline-co-o-toluidine) (PA-co-POT) were electrodeposited on the surface of carbon steel using cyclic voltammetry in an electrolyte consisting of oxalic acid, aniline and o-toluidine monomers. The mechanical properties of the polymer films were analyzed by a micro-Vickers hardness tester. The corrosion resistance of the polymer films was evaluated by an electrochemical corrosion test and immersion test of the polymer films in a solution containing SRB and 3.5 % NaCl. The results showed that PA-co-POT films have superior SRB corrosion resistance than single polymer films. The corrosion rate of PA-co-POT film was 0.0171 mm/year, and the protection efficiency was 83 % after 14 days of immersion in solution. In addition, due to the antibacterial properties of the PA-co-POT film, the adhesion of bacteria on its surface is significantly reduced, and local corrosion is also effectively inhibited. This study demonstrates the potential of electropolymerized aniline derivative copolymer films in preventing MIC of carbon steel and provides valuable insights for the development of new corrosion protection materials.
{"title":"Evaluation of the antimicrobial corrosion properties of electropolymerized poly(aniline-co-o-toluidine) films on carbon steel surfaces","authors":"Si Zhang , Chuanbo Hu , Xianling Hei , Xin Zhang , Bo Lan , Huawei Yin , Chengli Tang , Jie Zhao , Tingzhen Li","doi":"10.1016/j.synthmet.2024.117812","DOIUrl":"10.1016/j.synthmet.2024.117812","url":null,"abstract":"<div><div>Microbiologically influenced corrosion (MIC) can lead to structural weakening and shortened service life of carbon steel, resulting in serious economic losses and safety hazards. In particular, sulfate-reducing bacteria (SRB) produce hydrogen sulfide and sulfide during their growth and metabolism, which accelerates the corrosion of carbon steel. Thin films of poly(aniline-co-<em>o</em>-toluidine) (PA-co-POT) were electrodeposited on the surface of carbon steel using cyclic voltammetry in an electrolyte consisting of oxalic acid, aniline and o-toluidine monomers. The mechanical properties of the polymer films were analyzed by a micro-Vickers hardness tester. The corrosion resistance of the polymer films was evaluated by an electrochemical corrosion test and immersion test of the polymer films in a solution containing SRB and 3.5 % NaCl. The results showed that PA-co-POT films have superior SRB corrosion resistance than single polymer films. The corrosion rate of PA-co-POT film was 0.0171 mm/year, and the protection efficiency was 83 % after 14 days of immersion in solution. In addition, due to the antibacterial properties of the PA-co-POT film, the adhesion of bacteria on its surface is significantly reduced, and local corrosion is also effectively inhibited. This study demonstrates the potential of electropolymerized aniline derivative copolymer films in preventing MIC of carbon steel and provides valuable insights for the development of new corrosion protection materials.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117812"},"PeriodicalIF":4.0,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173801","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}
Pub Date : 2024-12-02DOI: 10.1016/j.synthmet.2024.117799
Yasmin Wadzer, Ye Zar Ni Htwe, Hussin Mamat
Nanolubricants can give a solution to a variety of concerns with traditional lubricants. A good nanolubricant is expected to be stable without sedimentation for an extended period in order to provide good heat transfer and not degrade performance owing to nanolubricant instability. In this study, the stability of mono nanolubricants consists of graphene (Gr) and aluminium nitrite (AlN) in SUNISO 3GS compressor oil and PETRONAS SYNTIUM 500 15W-40 engine oil, in 0.05, 0.075 and 0.1 vol% concentration, without and with surfactant is investigated. The surfactants used in this study are CTAB and SPAN 80 for Gr and AlN, respectively. This study also investigates the difference of base fluid and how it affects the performance of the nanolubricants. Not only that, previous studies investigated the same type of nanoparticles however in this study, Gr and AlN are two different class of nanoparticles which are carbon and ceramic based nanoparticles, respectively. The stability of nanolubricants is investigated using visual observation method, thermal conductivity (TC) measurement and UV–vis spectrophotometer. Furthermore, rheological properties (viscosity, viscosity index and flash point) and tribological properties of nanolubricants are studied. The highest percentage difference for TC is 22.58 in comparison with pure compressor oil. Lastly, by using pin-on disc tribotester, it can be observed surfactant in nanolubricants reducing the specific wear rate (SWR) and the highest percentage difference is high as 76.37 % for nanolubricant. The final observation shows that GR (0.05)-CO(CT) and GR (0.05)-EO(CT) have the best performance among all nanolubricants.
{"title":"Stability and tribological performance of dispersed graphene (Gr) and aluminium nitride (AlN) nanoparticles in mineral oil","authors":"Yasmin Wadzer, Ye Zar Ni Htwe, Hussin Mamat","doi":"10.1016/j.synthmet.2024.117799","DOIUrl":"10.1016/j.synthmet.2024.117799","url":null,"abstract":"<div><div>Nanolubricants can give a solution to a variety of concerns with traditional lubricants. A good nanolubricant is expected to be stable without sedimentation for an extended period in order to provide good heat transfer and not degrade performance owing to nanolubricant instability. In this study, the stability of mono nanolubricants consists of graphene (Gr) and aluminium nitrite (AlN) in SUNISO 3GS compressor oil and PETRONAS SYNTIUM 500 15W-40 engine oil, in 0.05, 0.075 and 0.1 vol% concentration, without and with surfactant is investigated. The surfactants used in this study are CTAB and SPAN 80 for Gr and AlN, respectively. This study also investigates the difference of base fluid and how it affects the performance of the nanolubricants. Not only that, previous studies investigated the same type of nanoparticles however in this study, Gr and AlN are two different class of nanoparticles which are carbon and ceramic based nanoparticles, respectively. The stability of nanolubricants is investigated using visual observation method, thermal conductivity (TC) measurement and UV–vis spectrophotometer. Furthermore, rheological properties (viscosity, viscosity index and flash point) and tribological properties of nanolubricants are studied. The highest percentage difference for TC is 22.58 in comparison with pure compressor oil. Lastly, by using pin-on disc tribotester, it can be observed surfactant in nanolubricants reducing the specific wear rate (SWR) and the highest percentage difference is high as 76.37 % for nanolubricant. The final observation shows that GR (0.05)-CO(CT) and GR (0.05)-EO(CT) have the best performance among all nanolubricants.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117799"},"PeriodicalIF":4.0,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172391","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}
Pub Date : 2024-12-02DOI: 10.1016/j.synthmet.2024.117810
Jisoo Kim , Sehyeon Kim , Min-Jae Kim , Boseok Kang , Hoichang Yang
As an element of organic thin-film transistors, lightly doped conjugated polymers without high off-state electrical conductivities have received considerable attention. In this study, the impact of dopant loading in a benchmark semiconducting polymer, poly(3-hexyl thiophene) (P3HT), with controlled regioregularity was systemically investigated in view of structural evolution and change in optoelectronic properties, especially in relation to transistor performance. P3HTs doped with the p-type molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) exhibited distinct nanostructures as the molar dopant ratio (MDR, [F4TCNQ]/[hexylthiophene]) increased. The nucleation and crystal growth of 97 % regioregular P3HT were greatly enhanced by blending with F4TCNQ at low-level MDRs (≤ 0.015). At MDR = 0.015, the doped P3HT film exhibiting highly ordered conjugated nanodomains yielded a superior field-effect mobility of up to 0.10 cm2 V−1 s−1, considerably higher than the undoped P3HT (∼10−3 cm2 V−1 s−1). At relatively higher doping levels (MDR ≥ 0.05), the doped P3HT films showed large size aggregates with less long range order and resulted in poor transistor performances, while their electrical conductivities gradually increased as the MDR increased. Similarly, a regiorandom P3HT with 55 % regioregularity showed aggregated nanostructures as F4TCNQ was loaded, but their electrical properties were far inferior to regioregular P3HTs in the overall MDR ranges (0.005 – 0.5). Also, a diketopyrrolopyrrole-based p-type donor-acceptor copolymer was found to exhibit the µFET improvement upon light doping, like the µFET trends in rr-P3HT and rra-P3HT. These findings would provide valuable insights into the development of various electronic applications with doped conjugated polymers.
{"title":"Correlating the structural evolution and charge transport in lightly doped semiconducting polymers of controlled regioregularity","authors":"Jisoo Kim , Sehyeon Kim , Min-Jae Kim , Boseok Kang , Hoichang Yang","doi":"10.1016/j.synthmet.2024.117810","DOIUrl":"10.1016/j.synthmet.2024.117810","url":null,"abstract":"<div><div>As an element of organic thin-film transistors, lightly doped conjugated polymers without high off-state electrical conductivities have received considerable attention. In this study, the impact of dopant loading in a benchmark semiconducting polymer, poly(3-hexyl thiophene) (P3HT), with controlled regioregularity was systemically investigated in view of structural evolution and change in optoelectronic properties, especially in relation to transistor performance. P3HTs doped with the p-type molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F<sub>4</sub>TCNQ) exhibited distinct nanostructures as the molar dopant ratio (MDR, [F<sub>4</sub>TCNQ]/[hexylthiophene]) increased. The nucleation and crystal growth of 97 % regioregular P3HT were greatly enhanced by blending with F<sub>4</sub>TCNQ at low-level MDRs (≤ 0.015). At MDR = 0.015, the doped P3HT film exhibiting highly ordered conjugated nanodomains yielded a superior field-effect mobility of up to 0.10 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>, considerably higher than the undoped P3HT (∼10<sup>−3</sup> cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>). At relatively higher doping levels (MDR ≥ 0.05), the doped P3HT films showed large size aggregates with less long range order and resulted in poor transistor performances, while their electrical conductivities gradually increased as the MDR increased. Similarly, a regiorandom P3HT with 55 % regioregularity showed aggregated nanostructures as F<sub>4</sub>TCNQ was loaded, but their electrical properties were far inferior to regioregular P3HTs in the overall MDR ranges (0.005 – 0.5). Also, a diketopyrrolopyrrole-based p-type donor-acceptor copolymer was found to exhibit the <em>µ</em><sub>FET</sub> improvement upon light doping, like the <em>µ</em><sub>FET</sub> trends in rr-P3HT and rra-P3HT. These findings would provide valuable insights into the development of various electronic applications with doped conjugated polymers.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117810"},"PeriodicalIF":4.0,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173802","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}
Pub Date : 2024-11-29DOI: 10.1016/j.synthmet.2024.117802
Emerson C.G. Campos , Denis A. Turchetti , Raquel A. Domingues , Leni C. Akcelrud
Synthetic polymers containing lanthanide ions have emerged as materials with potential application in many areas, mainly due to the unique luminescent properties of these ions that complement those of their organic counterparts. The aim of this work is to strengthen the concept of chain rigidity in the emissive properties of this type of structures as previously proposed. For this purpose, the solvation effect on chain conformations was used as a probe, assuming that the higher the viscosity, the less mobile the chain will become. The higher rigidity as compared to the previous one was achieved by three ways: replacing the previous ter-pyridine sites by the less bulky di-pyridine ones; increasing the number of complexed lanthanide ions from 20 % to 80 % (molar basis) and inserting double bonds in place of single ones. The dual-emissive conjugated copolymer composed by fluorene-bipyridine units carrying complexed terbium ions, was synthesized and characterized by structural, thermal and photophysical measurements. The terbium emission occurs in dimethylsulfoxide (DMSO) and N,N–dimethylformamide (DMF) only, and its luminescence was not observed in other solvents tested. The photophysical measurements strongly suggest that the lanthanide luminescence is brought about by solvent effect in polymer’s main chain, minimizing non-radiative energy losses by restriction of intramolecular motion (RIM) due to properties of poor solvents and their high viscosity. These factors combined promoted aggregation-induced emission (AIE).
{"title":"Viscochromism in a dual emitter metallopolymer containing terbium ions","authors":"Emerson C.G. Campos , Denis A. Turchetti , Raquel A. Domingues , Leni C. Akcelrud","doi":"10.1016/j.synthmet.2024.117802","DOIUrl":"10.1016/j.synthmet.2024.117802","url":null,"abstract":"<div><div>Synthetic polymers containing lanthanide ions have emerged as materials with potential application in many areas, mainly due to the unique luminescent properties of these ions that complement those of their organic counterparts. The aim of this work is to strengthen the concept of chain rigidity in the emissive properties of this type of structures as previously proposed. For this purpose, the solvation effect on chain conformations was used as a probe, assuming that the higher the viscosity, the less mobile the chain will become. The higher rigidity as compared to the previous one was achieved by three ways: replacing the previous <em>ter</em>-pyridine sites by the less bulky <em>di</em>-pyridine ones; increasing the number of complexed lanthanide ions from 20 % to 80 % (molar basis) and inserting double bonds in place of single ones. The dual-emissive conjugated copolymer composed by fluorene-bipyridine units carrying complexed terbium ions, was synthesized and characterized by structural, thermal and photophysical measurements. The terbium emission occurs in dimethylsulfoxide (DMSO) and <em>N,N</em>–dimethylformamide (DMF) only, and its luminescence was not observed in other solvents tested. The photophysical measurements strongly suggest that the lanthanide luminescence is brought about by solvent effect in polymer’s main chain, minimizing non-radiative energy losses by restriction of intramolecular motion (RIM) due to properties of poor solvents and their high viscosity. These factors combined promoted aggregation-induced emission (AIE).</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117802"},"PeriodicalIF":4.0,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173800","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}
Pub Date : 2024-11-27DOI: 10.1016/j.synthmet.2024.117801
Vignesh Rajendran, K.R. Justin Thomas
Aggregation-induced emitters (AIEgens) have emerged as versatile materials capable of meeting the demands of diverse applications, including optoelectronic devices, bioimaging, chemical sensing, and addressing environmental and industrial challenges. Among the various molecules exhibiting aggregation-induced emission (AIE), tetraphenylethylene (TPE) has been extensively studied due to its robust AIE activity. Current research focuses on modifying TPE structures to fine-tune their optoelectronic properties for specific applications. Triphenyl acrylonitrile (TPAN), a derivative of TPE where one phenyl group is replaced with a cyano group, has garnered significant attention. The strong electron-withdrawing nature cyano group enhances electronic properties of the materials. Dipolar compounds based on TPAN exhibit notable intramolecular charge transfer, in addition to well-established AIE properties and mechanofluorochromism. This review highlights recent advancements in the design of AIEgens incorporating TPAN, including systems based on carbazole, pyrene, triphenylamine, and other heterocycles. Where available, comparisons are made between AIEgens derived from TPE and TPAN, providing insights into the advantages and unique characteristics of each system.
{"title":"Recent advances and importance of triphenyl acrylonitrile system as an aggregation-induced emitter","authors":"Vignesh Rajendran, K.R. Justin Thomas","doi":"10.1016/j.synthmet.2024.117801","DOIUrl":"10.1016/j.synthmet.2024.117801","url":null,"abstract":"<div><div>Aggregation-induced emitters (AIEgens) have emerged as versatile materials capable of meeting the demands of diverse applications, including optoelectronic devices, bioimaging, chemical sensing, and addressing environmental and industrial challenges. Among the various molecules exhibiting aggregation-induced emission (AIE), tetraphenylethylene (TPE) has been extensively studied due to its robust AIE activity. Current research focuses on modifying TPE structures to fine-tune their optoelectronic properties for specific applications. Triphenyl acrylonitrile (TPAN), a derivative of TPE where one phenyl group is replaced with a cyano group, has garnered significant attention. The strong electron-withdrawing nature cyano group enhances electronic properties of the materials. Dipolar compounds based on TPAN exhibit notable intramolecular charge transfer, in addition to well-established AIE properties and mechanofluorochromism. This review highlights recent advancements in the design of AIEgens incorporating TPAN, including systems based on carbazole, pyrene, triphenylamine, and other heterocycles. Where available, comparisons are made between AIEgens derived from TPE and TPAN, providing insights into the advantages and unique characteristics of each system.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117801"},"PeriodicalIF":4.0,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173550","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}
Pub Date : 2024-11-26DOI: 10.1016/j.synthmet.2024.117800
Kuladip G. Belekar , Sumita S. Patil , Shraddha B. Bhosale , Sambhaji S. Kumbhar , Ganesh D. Jadhav , Vinayak G. Parale , Chandrakant D. Lokhande , Hyung-Ho Park , Pranav K. Katkar , Umakant M. Patil
The rational design of electrode materials with structural flexibility and robust electroactive sites governed by the synergy of cations in bimetal compounds is obligatory to maximize the efficiency of energy storage devices. In light of this, amorphous nanoparticles of cobalt manganese phosphate thin film [CoxMn3-x(PO4)2·nH2O] electrodes (S-CMP series) with different compositions of Co and Mn cations are prepared via the successive ionic layer adsorption and reaction (SILAR) method in the present work. The cobalt manganese phosphate (CMP) nanoparticles thin films were directly used as binder-free active electrodes, and synergy between cations (Co:Mn) at optimal composition (∼0.75:0.25) provides a maximum specific capacitance of 743 F g−1 at 2.8 A g−1, with 90.6 % capacitance retention over 4000 cycles. Additionally, an asymmetric aqueous supercapacitor (AAS) and an asymmetric solid-state supercapacitor (ASSS) devices were evaluated in 1 M KOH and PVA-KOH as aqueous and gel electrolytes, respectively, using as-prepared CMP (S-CMP-4) as the cathode material and rGO as the anode material. High specific energies of 45.31 Wh kg−1 and 16.29 Wh kg−1 at specific powers of 0.79 kW kg−1 and 0.82 kW kg−1 are displayed by the AAS and ASSS devices, respectively. Based on the practical demonstration of an ASSS device to power 201 red LEDs, the cobalt manganese phosphate thin film cathodes seem to offer insights into commercialization. Overall, the remarkable electrochemical performances of both AAS and ASSS devices thus demonstrate that amorphous, nanoparticle-like cobalt manganese phosphate thin film prepared by SILAR are efficient binder-free cathodes for prospective applications in energy storage devices.
合理设计具有结构灵活性和由双金属化合物中阳离子协同作用控制的稳健电活性位点的电极材料是实现储能装置效率最大化的必要条件。鉴于此，本工作采用连续离子层吸附反应（SILAR）方法制备了不同Co和Mn阳离子组成的钴锰磷酸盐薄膜[CoxMn3-x(PO4)2·nH2O]电极（S-CMP系列）的非晶态纳米颗粒。磷酸钴锰（CMP）纳米颗粒薄膜直接用作无粘结剂的活性电极，在最佳组成（~ 0.75:0.25）下，阳离子（Co:Mn）之间的协同作用提供了743 F g−1和2.8 a g−1的最大比电容，在4000次循环中电容保持率为90.6 %。此外，以制备的CMP （S-CMP-4）为正极材料，还原氧化石墨烯（rGO）为负极材料，分别以1 M KOH和PVA-KOH为水溶液和凝胶电解质，对非对称水性超级电容器（AAS）和非对称固态超级电容器（ASSS）器件进行了评价。AAS和ASSS器件的比能分别为45.31 Wh kg−1和16.29 Wh kg−1，比功率分别为0.79 kW kg−1和0.82 kW kg−1。基于ASSS装置为201个红色led供电的实际演示，磷酸钴锰薄膜阴极似乎为商业化提供了见解。总的来说，AAS和ASSS器件的显著电化学性能表明，SILAR制备的非晶态纳米颗粒状磷酸钴锰薄膜是一种高效的无粘结剂阴极，有望应用于储能器件。
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Pub Date : 2024-11-24DOI: 10.1016/j.synthmet.2024.117797
Adrian Pizano, Raju Lampande, Robert Cawthorn, Noel C. Giebink
Rapid degradation of blue organic light-emitting diodes (OLEDs) is an ongoing challenge for the display and lighting industry. Bimolecular exciton annihilation reactions are one of the leading causes of molecular degradation in these devices, but are so far quantified mostly by fitting data to simplified rate equation models that crudely approximate the exciton and charge carrier densities in the recombination zone while neglecting the other layers in the device entirely. Here, we implement a rigorous drift-diffusion-based degradation model and compare its luminance fade and voltage rise to that of a corresponding rate-based model for a prototypical exciton-polaron-based degradation scenario. We find that the luminance fade predicted by the rate model yields functionally similar, but quantitatively different results than the drift-diffusion simulation, though reasonable agreement can be achieved by using effective values for the annihilation rate coefficient and hot polaron degradation probability. Importantly, the drift-diffusion model indicates that trap state defects formed in the emissive layer lead to only a minor increase in voltage, whereas those formed in the transport layers lead to a larger increase that is on par with experiment. These results suggest that OLED luminance loss and voltage rise largely originate from different sets of defect states formed in the emissive and transport layers, respectively, and that rate model degradation parameters fit from experiment should be viewed as effective values that do not directly correspond to the rate of the actual microscale processes occurring in the device.
{"title":"Drift-diffusion modeling of blue OLED degradation","authors":"Adrian Pizano, Raju Lampande, Robert Cawthorn, Noel C. Giebink","doi":"10.1016/j.synthmet.2024.117797","DOIUrl":"10.1016/j.synthmet.2024.117797","url":null,"abstract":"<div><div>Rapid degradation of blue organic light-emitting diodes (OLEDs) is an ongoing challenge for the display and lighting industry. Bimolecular exciton annihilation reactions are one of the leading causes of molecular degradation in these devices, but are so far quantified mostly by fitting data to simplified rate equation models that crudely approximate the exciton and charge carrier densities in the recombination zone while neglecting the other layers in the device entirely. Here, we implement a rigorous drift-diffusion-based degradation model and compare its luminance fade and voltage rise to that of a corresponding rate-based model for a prototypical exciton-polaron-based degradation scenario. We find that the luminance fade predicted by the rate model yields functionally similar, but quantitatively different results than the drift-diffusion simulation, though reasonable agreement can be achieved by using effective values for the annihilation rate coefficient and hot polaron degradation probability. Importantly, the drift-diffusion model indicates that trap state defects formed in the emissive layer lead to only a minor increase in voltage, whereas those formed in the transport layers lead to a larger increase that is on par with experiment. These results suggest that OLED luminance loss and voltage rise largely originate from different sets of defect states formed in the emissive and transport layers, respectively, and that rate model degradation parameters fit from experiment should be viewed as effective values that do not directly correspond to the rate of the actual microscale processes occurring in the device.</div></div>","PeriodicalId":22245,"journal":{"name":"Synthetic Metals","volume":"311 ","pages":"Article 117797"},"PeriodicalIF":4.0,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173549","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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