Pub Date : 2024-07-03DOI: 10.3390/electrochem5030017
Md Shafiul Islam, Alan J. Branigan, Dexian Ye, M. Collinson
This work describes the fabrication and characterization of a new high surface area nanocomposite electrode containing reduced graphene oxide (rGO) and titanium nitride (TiN) for electrochemical applications. This approach involves electrochemically depositing rGO on a high surface area TiN nanorod array electrode to form a new nanocomposite electrode. The TiN nanorod array was first formed by the glancing angle deposition technique in a DC (Direct Current) sputtering system. GO flakes of ~1.5 μm in diameter, as confirmed by Dynamic Light Scattering (DLS), were electrodeposited on the nanostructured TiN electrode via the application of a fixed potential for one hour. The surface morphology of the as-prepared rGO/TiN electrode was evaluated by scanning electron microscopy (SEM) and the presence of rGO on TiN was confirmed by Raman Microscopy. The CV shows an increase in the capacitive current at rGO/TiN as compared to TiN. The rGO decorated TiN electrode was then used for analyzing the electrocatalytic oxidation of ascorbic acid and dopamine, and the reduction of nitrate by CV and linear sweep voltammetry (LSV), respectively. CV or LSV show that the electrochemical kinetics of these three analytes are significantly faster on rGO/TiN than TiN itself. Overall, the rGO/TiN electrode showed better electrochemical behavior for biomolecules like ascorbic acid and dopamine as well as another target analyte, nitrate ions, compared to TiN by itself.
这项工作描述了一种新型高比表面积纳米复合电极的制造和表征，这种电极包含用于电化学应用的还原氧化石墨烯（rGO）和氮化钛（TiN）。这种方法是在高比表面积的 TiN 纳米棒阵列电极上电化学沉积 rGO，形成新的纳米复合电极。TiN 纳米棒阵列首先是在直流（DC）溅射系统中通过闪烁角沉积技术形成的。经动态光散射（DLS）确认，直径约为 1.5 μm 的 GO 片通过施加一小时的固定电位电沉积在纳米结构的 TiN 电极上。扫描电子显微镜（SEM）评估了制备的 rGO/TiN 电极的表面形态，拉曼显微镜证实了 rGO 在 TiN 上的存在。CV 显示，与 TiN 相比，rGO/TiN 的电容电流有所增加。然后，rGO 装饰的 TiN 电极被用于分析抗坏血酸和多巴胺的电催化氧化，以及硝酸盐的电催化还原，分析方法分别是 CV 和线性扫描伏安法（LSV）。CV 或 LSV 显示，这三种分析物在 rGO/TiN 上的电化学动力学速度明显快于 TiN 本身。总体而言，与 TiN 本身相比，rGO/TiN 电极对抗坏血酸和多巴胺等生物大分子以及另一种目标分析物硝酸根离子显示出更好的电化学行为。
{"title":"Reduced Graphene Oxide Decorated Titanium Nitride Nanorod Array Electrodes for Electrochemical Applications","authors":"Md Shafiul Islam, Alan J. Branigan, Dexian Ye, M. Collinson","doi":"10.3390/electrochem5030017","DOIUrl":"https://doi.org/10.3390/electrochem5030017","url":null,"abstract":"This work describes the fabrication and characterization of a new high surface area nanocomposite electrode containing reduced graphene oxide (rGO) and titanium nitride (TiN) for electrochemical applications. This approach involves electrochemically depositing rGO on a high surface area TiN nanorod array electrode to form a new nanocomposite electrode. The TiN nanorod array was first formed by the glancing angle deposition technique in a DC (Direct Current) sputtering system. GO flakes of ~1.5 μm in diameter, as confirmed by Dynamic Light Scattering (DLS), were electrodeposited on the nanostructured TiN electrode via the application of a fixed potential for one hour. The surface morphology of the as-prepared rGO/TiN electrode was evaluated by scanning electron microscopy (SEM) and the presence of rGO on TiN was confirmed by Raman Microscopy. The CV shows an increase in the capacitive current at rGO/TiN as compared to TiN. The rGO decorated TiN electrode was then used for analyzing the electrocatalytic oxidation of ascorbic acid and dopamine, and the reduction of nitrate by CV and linear sweep voltammetry (LSV), respectively. CV or LSV show that the electrochemical kinetics of these three analytes are significantly faster on rGO/TiN than TiN itself. Overall, the rGO/TiN electrode showed better electrochemical behavior for biomolecules like ascorbic acid and dopamine as well as another target analyte, nitrate ions, compared to TiN by itself.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141683804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-05DOI: 10.3390/electrochem5020014
D. Conti, Claudia Urru, Giovanna Bruni, Pietro Galinetto, B. Albini, V. Berbenni, D. Capsoni
In the present study, LiFePO4/CNF self-standing cathodes for LIBs are synthesized by electrospinning. A lower active material amount (12.3 and 34.5 wt%) is used, compared to the conventional tape-casted cathodes (70–85 wt%). The characterization techniques (XRPD, SEM, TEM, EDS, Raman spectroscopy, and thermogravimetry) confirm that the olivine-type structure of LiFePO4 is maintained in the binder-free electrodes, and the active material is homogeneously dispersed into and within the carbon nanofibers. The electrochemical investigation demonstrates that higher Li+ diffusion coefficients (1.36 × 10−11 cm2/s) and improved reversibility are reached for free-standing electrodes, compared to the LiFePO4 tape-casted cathode (80 wt% of active material) appositely prepared for comparison. The 34.5 wt% LiFePO4 self-standing cathode displays a lower capacity fading, good reversibility and stability, enhanced capacity values at C-rates higher than 5C, and a good lifespan when cycled 1000 cycles at 1C and further cycled up to 20C, compared to the tape-casted counterpart. Notably, the improved electrochemical performances are obtained by only the 34.5 wt% of active material. The results evidence the relevant role of the CNF matrix suitable to host LiFePO4, to promote electrolyte permeation and contact with the active material, and to increase the electronic conductivity.
{"title":"High C-Rate Performant Electrospun LiFePO4/Carbon Nanofiber Self-Standing Cathodes for Lithium-Ion Batteries","authors":"D. Conti, Claudia Urru, Giovanna Bruni, Pietro Galinetto, B. Albini, V. Berbenni, D. Capsoni","doi":"10.3390/electrochem5020014","DOIUrl":"https://doi.org/10.3390/electrochem5020014","url":null,"abstract":"In the present study, LiFePO4/CNF self-standing cathodes for LIBs are synthesized by electrospinning. A lower active material amount (12.3 and 34.5 wt%) is used, compared to the conventional tape-casted cathodes (70–85 wt%). The characterization techniques (XRPD, SEM, TEM, EDS, Raman spectroscopy, and thermogravimetry) confirm that the olivine-type structure of LiFePO4 is maintained in the binder-free electrodes, and the active material is homogeneously dispersed into and within the carbon nanofibers. The electrochemical investigation demonstrates that higher Li+ diffusion coefficients (1.36 × 10−11 cm2/s) and improved reversibility are reached for free-standing electrodes, compared to the LiFePO4 tape-casted cathode (80 wt% of active material) appositely prepared for comparison. The 34.5 wt% LiFePO4 self-standing cathode displays a lower capacity fading, good reversibility and stability, enhanced capacity values at C-rates higher than 5C, and a good lifespan when cycled 1000 cycles at 1C and further cycled up to 20C, compared to the tape-casted counterpart. Notably, the improved electrochemical performances are obtained by only the 34.5 wt% of active material. The results evidence the relevant role of the CNF matrix suitable to host LiFePO4, to promote electrolyte permeation and contact with the active material, and to increase the electronic conductivity.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141382590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study reports on the use of supercritical CO2 (scCO2) for the metallization of ultrahigh-molecular-weight polyethylene (UHMW-PE) filaments, which are used as functional components in weavable devices. UHMW-PE is well known for its chemical and impact resistance, making it suitable for use in bulletproof clothing and shields. However, its chemical resistance poses a challenge for metallization. By utilizing scCO2 as the solvent in the catalyzation process, a uniform and defect-free layer of Ni-P is successfully deposited on the UHMW-PE filaments. The deposition rate of Ni-P is enhanced at higher temperatures during the scCO2 catalyzation. Importantly, the durability of the Ni-P-metalized UHMW-PE filaments is improved when the scCO2 catalyzation is carried out at 120 °C, as evidenced by minimal changes in electrical resistivity after a rolling test.
{"title":"Supercritical CO2-Assisted Electroless Plating of Ultrahigh-Molecular-Weight Polyethylene Filaments for Weavable Device Application","authors":"Hikaru Kondo, Tomoyuki Kurioka, Wan-Ting Chiu, Chun-Yi Chen, Jhen-Yang Wu, Tso-Fu Mark Chang, Machiko Yamaguchi, Hiromichi Kurosu, Masato Sone","doi":"10.3390/electrochem5020013","DOIUrl":"https://doi.org/10.3390/electrochem5020013","url":null,"abstract":"This study reports on the use of supercritical CO2 (scCO2) for the metallization of ultrahigh-molecular-weight polyethylene (UHMW-PE) filaments, which are used as functional components in weavable devices. UHMW-PE is well known for its chemical and impact resistance, making it suitable for use in bulletproof clothing and shields. However, its chemical resistance poses a challenge for metallization. By utilizing scCO2 as the solvent in the catalyzation process, a uniform and defect-free layer of Ni-P is successfully deposited on the UHMW-PE filaments. The deposition rate of Ni-P is enhanced at higher temperatures during the scCO2 catalyzation. Importantly, the durability of the Ni-P-metalized UHMW-PE filaments is improved when the scCO2 catalyzation is carried out at 120 °C, as evidenced by minimal changes in electrical resistivity after a rolling test.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141270621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-05-21DOI: 10.3390/electrochem5020012
Antonio Ruiz-Gonzalez
Food quality assessment is becoming a global priority due to population growth and the rise of ionic pollutants derived from anthropogenic sources. However, the current methods used to quantify toxic ions are expensive and their operation is complex. Consequently, there is a need for affordable and accessible methods for the accurate determination of ion concentrations in food. Electrochemical sensors based on potentiometry represent a promising approach in this field, with the potential to overcome limitations of the currently available systems. This review summarizes the current advances in the electrochemical quantification of heavy metals and toxic anions in the food industry using potentiometric sensors. The healthcare impact of common heavy metal contaminants (Cd2+, Hg2+, Pb2+, As3+) and anions (ClO4−, F−, HPO4−, SO42−, NO3−, NO2−) is discussed, alongside current regulations, and gold standard methods for analysis. Sensor performances are compared to current benchmarks in terms of selectivity and the limit of detection. Given the complexity of food samples, the percentage recovery values (%) and the methodologies employed for ion extraction are also described. Finally, a summary of the challenges and future directions of the field is provided. An overview of technologies that can overcome the limitations of current electrochemical sensors is shown, including new extraction methods for ions in food.
{"title":"Ion-Selective Electrodes in the Food Industry: Development Trends in the Potentiometric Determination of Ionic Pollutants","authors":"Antonio Ruiz-Gonzalez","doi":"10.3390/electrochem5020012","DOIUrl":"https://doi.org/10.3390/electrochem5020012","url":null,"abstract":"Food quality assessment is becoming a global priority due to population growth and the rise of ionic pollutants derived from anthropogenic sources. However, the current methods used to quantify toxic ions are expensive and their operation is complex. Consequently, there is a need for affordable and accessible methods for the accurate determination of ion concentrations in food. Electrochemical sensors based on potentiometry represent a promising approach in this field, with the potential to overcome limitations of the currently available systems. This review summarizes the current advances in the electrochemical quantification of heavy metals and toxic anions in the food industry using potentiometric sensors. The healthcare impact of common heavy metal contaminants (Cd2+, Hg2+, Pb2+, As3+) and anions (ClO4−, F−, HPO4−, SO42−, NO3−, NO2−) is discussed, alongside current regulations, and gold standard methods for analysis. Sensor performances are compared to current benchmarks in terms of selectivity and the limit of detection. Given the complexity of food samples, the percentage recovery values (%) and the methodologies employed for ion extraction are also described. Finally, a summary of the challenges and future directions of the field is provided. An overview of technologies that can overcome the limitations of current electrochemical sensors is shown, including new extraction methods for ions in food.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141113647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-04DOI: 10.3390/electrochem5010007
E. Evshchik, S. Borisevich, M. G. Ilyina, E. Khamitov, Alexander V. Chernyak, T. A. Pugacheva, Valery G. Kolmakov, O. V. Bushkova, Yuri A. Dobrovolsky
Determining the oxidation potential (OP) of lithium-ion battery (LIB) electrolytes using theoretical methods will significantly speed up and simplify the process of creating a new generation high-voltage battery. The algorithm for calculating OP should be not only accurate but also fast. Our work proposes theoretical principles for evaluating the OP of LIB electrolytes by considering LiDFOB solutions with different salt concentrations in EC/DMC solvent mixtures. The advantage of the new algorithm compared to previous versions of the theoretical determination of the oxidation potential of electrolyte solutions used in lithium-ion batteries for calculations of statistically significant complexes, the structure of which was determined by the molecular dynamics method. This approach significantly reduces the number of atomic–molecular systems whose geometric parameters need to be optimized using quantum chemical methods. Due to this, it is possible to increase the speed of calculations and reduce the power requirements of the computer performing the calculations. The theoretical calculations included a set of approaches based on the methods of classical molecular mechanics and quantum chemistry. To select statistically significant complexes that can make a significant contribution to the stability of the electrochemical system, a thorough analysis of molecular dynamics simulation trajectories was performed. Their geometric parameters (including oxidized forms) were optimized by QM methods. As a result, oxidation potentials were assessed, and their dependence on salt concentration was described. Here, we once again emphasize that it is difficult to obtain, by calculation methods, the absolute OP values that would be equal (or close) to the OP values estimated by experimental methods. Nevertheless, a trend can be identified. The results of theoretical calculations are in full agreement with the experimental ones.
利用理论方法确定锂离子电池（LIB）电解质的氧化电位（OP）将大大加快和简化新一代高压电池的制造过程。计算 OP 的算法不仅要准确，而且要快速。我们的研究通过考虑 EC/DMC 溶剂混合物中不同盐浓度的 LiDFOB 溶液，提出了评估 LIB 电解质 OP 的理论原则。与以前版本的锂离子电池所用电解质溶液氧化电位理论测定相比，新算法的优势在于计算统计意义上的复合物，其结构由分子动力学方法确定。这种方法大大减少了需要使用量子化学方法优化几何参数的原子-分子系统的数量。因此，可以提高计算速度，降低对进行计算的计算机的功率要求。理论计算包括一套基于经典分子力学和量子化学方法的方法。为了选择在统计意义上对电化学系统的稳定性有重大贡献的复合物，对分子动力学模拟轨迹进行了全面分析。它们的几何参数（包括氧化形式）是通过质量管理方法进行优化的。因此，对氧化电位进行了评估，并描述了氧化电位与盐浓度的关系。在此，我们再次强调，很难通过计算方法获得与实验方法估算的 OP 值相等（或接近）的绝对 OP 值。尽管如此，我们还是可以发现一种趋势。理论计算的结果与实验结果完全一致。
{"title":"Determining the Oxidation Stability of Electrolytes for Lithium-Ion Batteries Using Quantum Chemistry and Molecular Dynamics","authors":"E. Evshchik, S. Borisevich, M. G. Ilyina, E. Khamitov, Alexander V. Chernyak, T. A. Pugacheva, Valery G. Kolmakov, O. V. Bushkova, Yuri A. Dobrovolsky","doi":"10.3390/electrochem5010007","DOIUrl":"https://doi.org/10.3390/electrochem5010007","url":null,"abstract":"Determining the oxidation potential (OP) of lithium-ion battery (LIB) electrolytes using theoretical methods will significantly speed up and simplify the process of creating a new generation high-voltage battery. The algorithm for calculating OP should be not only accurate but also fast. Our work proposes theoretical principles for evaluating the OP of LIB electrolytes by considering LiDFOB solutions with different salt concentrations in EC/DMC solvent mixtures. The advantage of the new algorithm compared to previous versions of the theoretical determination of the oxidation potential of electrolyte solutions used in lithium-ion batteries for calculations of statistically significant complexes, the structure of which was determined by the molecular dynamics method. This approach significantly reduces the number of atomic–molecular systems whose geometric parameters need to be optimized using quantum chemical methods. Due to this, it is possible to increase the speed of calculations and reduce the power requirements of the computer performing the calculations. The theoretical calculations included a set of approaches based on the methods of classical molecular mechanics and quantum chemistry. To select statistically significant complexes that can make a significant contribution to the stability of the electrochemical system, a thorough analysis of molecular dynamics simulation trajectories was performed. Their geometric parameters (including oxidized forms) were optimized by QM methods. As a result, oxidation potentials were assessed, and their dependence on salt concentration was described. Here, we once again emphasize that it is difficult to obtain, by calculation methods, the absolute OP values that would be equal (or close) to the OP values estimated by experimental methods. Nevertheless, a trend can be identified. The results of theoretical calculations are in full agreement with the experimental ones.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140080195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-20DOI: 10.3390/electrochem5010006
A. Achoh, Denis Bondarev, E. Nosova, S. Melnikov
This study focuses on the modification of ion-exchange membranes by incorporating a phosphorylated dendrimer into sulfonated polytetrafluoroethylene membranes to enhance the specific selectivity between mono-/divalent ions, using the Ca2+/Na+ pair as an example. This research employs mechanical, physicochemical, and electrochemical analyses to explore the effects of P-H20 incorporation on membrane properties. Bulk modification significantly increases membrane selectivity towards calcium ions (the specific permselectivity coefficient rises from 1.5 to 7.2), while maintaining the same level of the limiting current density. Other findings indicate that bulk modification significantly changes the transport-channel structure of the membrane and alters the mechanism of over-limiting mass transfer. The over-limiting current for the pristine membrane is mainly due to non-equilibrium electroconvection, while modified membranes actively participate in the water-splitting reaction, leading to the suppression of the electroconvection. Despite this drawback, the decrease of the over-limiting potential drop results in a decrease in specific energy consumption from 0.11 to 0.07 kWh/mol. In the underlimiting current mode, the specific energy consumption for all studied membranes remains within the same limits of 0.02–0.03 kWh/mol.
{"title":"The Effect of Bulk Modification of the MF-4SK Membrane with Phosphorylated Hyper-Branched Dendrimer Bolthorn H20 on the Mechanisms of Electroconvection/Dissociation of Water and Specific Selectivity to Divalent Ions","authors":"A. Achoh, Denis Bondarev, E. Nosova, S. Melnikov","doi":"10.3390/electrochem5010006","DOIUrl":"https://doi.org/10.3390/electrochem5010006","url":null,"abstract":"This study focuses on the modification of ion-exchange membranes by incorporating a phosphorylated dendrimer into sulfonated polytetrafluoroethylene membranes to enhance the specific selectivity between mono-/divalent ions, using the Ca2+/Na+ pair as an example. This research employs mechanical, physicochemical, and electrochemical analyses to explore the effects of P-H20 incorporation on membrane properties. Bulk modification significantly increases membrane selectivity towards calcium ions (the specific permselectivity coefficient rises from 1.5 to 7.2), while maintaining the same level of the limiting current density. Other findings indicate that bulk modification significantly changes the transport-channel structure of the membrane and alters the mechanism of over-limiting mass transfer. The over-limiting current for the pristine membrane is mainly due to non-equilibrium electroconvection, while modified membranes actively participate in the water-splitting reaction, leading to the suppression of the electroconvection. Despite this drawback, the decrease of the over-limiting potential drop results in a decrease in specific energy consumption from 0.11 to 0.07 kWh/mol. In the underlimiting current mode, the specific energy consumption for all studied membranes remains within the same limits of 0.02–0.03 kWh/mol.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140448928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-31DOI: 10.3390/electrochem5010004
Zaheer Masood, Haji Muhammad, Iftikhar Ahmed Tahiri
Understanding electrochemical reactions at the surface of electrodes requires the accurate calculation of key parameters—the transfer coefficient (α), diffusion coefficient (D0), and heterogeneous electron transfer rate constant (k0). The choice of method to calculate these parameters requires careful consideration based on the nature of the electrochemical reaction. In this study, we conducted the cyclic voltammetry of paracetamol to calculate the values of these parameters using different methods and present a comparative analysis. Our results demonstrate that the Ep − Ep/2 equation for α and the modified Randles–Ševčík equation for D0 is particularly effective for the calculations of these two parameters. The Kochi and Gileadi methods are reliable alternatives for the calculation of k0. Nicholson and Shain’s method using the equation k0 = Ψ(πnD0Fν/RT)1/2 gives the overestimated values of k0. However, the value of k0 calculated using the plot of ν−1/2 versus Ψ (from the Nicholson and Shain equation, where ν is scan rate) agrees well with the values calculated from the Kochi and Gilaedi methods. This study not only identifies optimal methodologies for quasi-reversible reactions but also contributes to a deeper understanding of electrochemical reactions involving complex electron transfer and coupled chemical reactions, which can be broadly applicable in various electrochemical studies.
{"title":"Comparison of Different Electrochemical Methodologies for Electrode Reactions: A Case Study of Paracetamol","authors":"Zaheer Masood, Haji Muhammad, Iftikhar Ahmed Tahiri","doi":"10.3390/electrochem5010004","DOIUrl":"https://doi.org/10.3390/electrochem5010004","url":null,"abstract":"Understanding electrochemical reactions at the surface of electrodes requires the accurate calculation of key parameters—the transfer coefficient (α), diffusion coefficient (D0), and heterogeneous electron transfer rate constant (k0). The choice of method to calculate these parameters requires careful consideration based on the nature of the electrochemical reaction. In this study, we conducted the cyclic voltammetry of paracetamol to calculate the values of these parameters using different methods and present a comparative analysis. Our results demonstrate that the Ep − Ep/2 equation for α and the modified Randles–Ševčík equation for D0 is particularly effective for the calculations of these two parameters. The Kochi and Gileadi methods are reliable alternatives for the calculation of k0. Nicholson and Shain’s method using the equation k0 = Ψ(πnD0Fν/RT)1/2 gives the overestimated values of k0. However, the value of k0 calculated using the plot of ν−1/2 versus Ψ (from the Nicholson and Shain equation, where ν is scan rate) agrees well with the values calculated from the Kochi and Gilaedi methods. This study not only identifies optimal methodologies for quasi-reversible reactions but also contributes to a deeper understanding of electrochemical reactions involving complex electron transfer and coupled chemical reactions, which can be broadly applicable in various electrochemical studies.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140478160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-23DOI: 10.3390/electrochem5010003
Tijana Mutić, D. Stanković, D. Manojlović, Djordje Petrić, Ferenc Pastor, V. Avdin, M. Ognjanović, V. Stanković
In this work, we successfully prepared a modified cobalt oxide (Co3O4) carbon paste electrode to detect Levofloxacin (LEV). By synthesizing Co3O4 nanoparticles through the chemical coprecipitation method, the electrochemical properties of the electrode and LEV were thoroughly investigated using CV, SWV, and EIS, while material properties were scrutinized using ICP-OES, TEM, SEM, and XRD. The results showed that the prepared electrode displayed a better electrocatalytic response than the bare carbon paste electrode. After optimizing SWV, the electrode exhibited a wide linear working range from 1 to 85 μM at pH 5 of BRBS as the supporting electrolyte. The selectivity of the proposed method was satisfactory, with good repeatability and reproducibility, strongly suggesting a potential application for determining LEV in real samples, particularly in pharmaceutical formulations. The practicality of the approach was demonstrated through good recoveries, and the morphology of the materials was found to be closely related to other parameters, indicating that the developed method can provide a cost-effective, rapid, selective, and sensitive means for LEV monitoring. Overall, this project has made significant progress towards developing a reliable method for detecting LEV and has opened up new opportunities for future research in this field.
在这项研究中，我们成功制备了一种检测左氧氟沙星（LEV）的改性氧化钴（Co3O4）碳浆电极。通过化学共沉淀法合成了 Co3O4 纳米粒子，使用 CV、SWV 和 EIS 对电极和 LEV 的电化学性质进行了深入研究，并使用 ICP-OES、TEM、SEM 和 XRD 对材料性质进行了仔细研究。结果表明，制备的电极比裸碳浆电极显示出更好的电催化反应。对 SWV 进行优化后，在以 BRBS 为支撑电解质的 pH 值为 5 时，电极显示出 1 至 85 μM 的宽线性工作范围。该方法的选择性令人满意，具有良好的重复性和再现性，有力地证明了其在实际样品，尤其是药物制剂中测定 LEV 的潜在应用价值。良好的回收率证明了该方法的实用性，同时发现材料的形态与其他参数密切相关，这表明所开发的方法可以为 LEV 监测提供一种经济、快速、选择性强且灵敏的手段。总之，该项目在开发可靠的 LEV 检测方法方面取得了重大进展，并为该领域的未来研究开辟了新的机遇。
{"title":"Micromolar Levofloxacin Sensor by Incorporating Highly Crystalline Co3O4 into a Carbon Paste Electrode Structure","authors":"Tijana Mutić, D. Stanković, D. Manojlović, Djordje Petrić, Ferenc Pastor, V. Avdin, M. Ognjanović, V. Stanković","doi":"10.3390/electrochem5010003","DOIUrl":"https://doi.org/10.3390/electrochem5010003","url":null,"abstract":"In this work, we successfully prepared a modified cobalt oxide (Co3O4) carbon paste electrode to detect Levofloxacin (LEV). By synthesizing Co3O4 nanoparticles through the chemical coprecipitation method, the electrochemical properties of the electrode and LEV were thoroughly investigated using CV, SWV, and EIS, while material properties were scrutinized using ICP-OES, TEM, SEM, and XRD. The results showed that the prepared electrode displayed a better electrocatalytic response than the bare carbon paste electrode. After optimizing SWV, the electrode exhibited a wide linear working range from 1 to 85 μM at pH 5 of BRBS as the supporting electrolyte. The selectivity of the proposed method was satisfactory, with good repeatability and reproducibility, strongly suggesting a potential application for determining LEV in real samples, particularly in pharmaceutical formulations. The practicality of the approach was demonstrated through good recoveries, and the morphology of the materials was found to be closely related to other parameters, indicating that the developed method can provide a cost-effective, rapid, selective, and sensitive means for LEV monitoring. Overall, this project has made significant progress towards developing a reliable method for detecting LEV and has opened up new opportunities for future research in this field.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139603746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-04DOI: 10.3390/electrochem5010002
Adam Cherni, K. Halouani
At present, direct carbon fuel cells constitute an emerging energy technology that electrochemically converts solid carbon to electricity with high efficiency. The recent trend of DCFCs fueled with biochar from biomass carbonization as green fuel has reinforced the environmental benefits of DCFCs as a clean and sustainable technology. However, there remain new challenges related to some complex unknown kinetic parameters, X=(αa,αc,σg,i0,a,i0,c,ilO2,ilCO2,c,ilCO2,a,ilCO), of the electrochemical conversion of biochar in DCFCs and there is a need for intelligent techniques for prediction and optimization, refering to the available experimental data. The differential evolution (DE) algorithm, which ranked as one of the top performers in optimization competitions with competitive accuracy and convergence speed, was used here for providing the optimized values of these parameters by minimizing the root mean squared errors (RMSE). The proposed technique was then applied to DCFCs fueled by activated pure carbon (APC) using CO2 and CO/CO2 electrochemical models with RMSE around 10−2 and 10−3, respectively. Then, the CO/CO2 model was applied to a DCFC fueled with almond shell biochar (ASB), which displayed a slight increase in RMSE (of the order of 10−2) due to the complex porous structure of ASB and the content of additional chemical elements that affect the electrochemistry of the DCFC and are not considered in the model.
{"title":"Artificial Intelligence for Electrochemical Prediction and Optimization of Direct Carbon Fuel Cells Fueled with Biochar","authors":"Adam Cherni, K. Halouani","doi":"10.3390/electrochem5010002","DOIUrl":"https://doi.org/10.3390/electrochem5010002","url":null,"abstract":"At present, direct carbon fuel cells constitute an emerging energy technology that electrochemically converts solid carbon to electricity with high efficiency. The recent trend of DCFCs fueled with biochar from biomass carbonization as green fuel has reinforced the environmental benefits of DCFCs as a clean and sustainable technology. However, there remain new challenges related to some complex unknown kinetic parameters, X=(αa,αc,σg,i0,a,i0,c,ilO2,ilCO2,c,ilCO2,a,ilCO), of the electrochemical conversion of biochar in DCFCs and there is a need for intelligent techniques for prediction and optimization, refering to the available experimental data. The differential evolution (DE) algorithm, which ranked as one of the top performers in optimization competitions with competitive accuracy and convergence speed, was used here for providing the optimized values of these parameters by minimizing the root mean squared errors (RMSE). The proposed technique was then applied to DCFCs fueled by activated pure carbon (APC) using CO2 and CO/CO2 electrochemical models with RMSE around 10−2 and 10−3, respectively. Then, the CO/CO2 model was applied to a DCFC fueled with almond shell biochar (ASB), which displayed a slight increase in RMSE (of the order of 10−2) due to the complex porous structure of ASB and the content of additional chemical elements that affect the electrochemistry of the DCFC and are not considered in the model.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139384272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-21DOI: 10.3390/electrochem5010001
I. Christakis, Elena Sarri, O. Tsakiridis, Ilias Stavrakas
Nowadays, the study of air quality has become an increasingly prominent field of research, particularly in large urban centers, given its significant impact on human health. In many countries, government departments and research centers use official high-cost scientific instruments to monitor air quality in their regions. Meanwhile, concerned citizens interested in studying the air quality of their local areas often employ low-cost air quality sensors for monitoring purposes. The optimization and evaluation of low-cost sensors have been a field of research by many research groups. This paper presents an extensive study to identify the safe percentage change limits that low-cost electrochemical air quality sensors can have, in order to optimize their measurements. For this work, three low-cost air quality monitoring stations were used, which include an electrochemical sensor for nitrogen dioxide (NO2) (Alphasense NO2-B43F) and an electrochemical sensor for ozone (O3) (Alphasense OX-B431). The aim of this work is to explore the variance of the aforementioned sensors and how this variability can be used to optimize the measurements of low-cost electrochemical sensors, closer to real ones. The analysis is conducted by employing diagrams, boxplot and violin curves of the groups of sensors used, with satisfactory results.
{"title":"Identification of the Safe Variation Limits for the Optimization of the Measurements in Low-Cost Electrochemical Air Quality Sensors","authors":"I. Christakis, Elena Sarri, O. Tsakiridis, Ilias Stavrakas","doi":"10.3390/electrochem5010001","DOIUrl":"https://doi.org/10.3390/electrochem5010001","url":null,"abstract":"Nowadays, the study of air quality has become an increasingly prominent field of research, particularly in large urban centers, given its significant impact on human health. In many countries, government departments and research centers use official high-cost scientific instruments to monitor air quality in their regions. Meanwhile, concerned citizens interested in studying the air quality of their local areas often employ low-cost air quality sensors for monitoring purposes. The optimization and evaluation of low-cost sensors have been a field of research by many research groups. This paper presents an extensive study to identify the safe percentage change limits that low-cost electrochemical air quality sensors can have, in order to optimize their measurements. For this work, three low-cost air quality monitoring stations were used, which include an electrochemical sensor for nitrogen dioxide (NO2) (Alphasense NO2-B43F) and an electrochemical sensor for ozone (O3) (Alphasense OX-B431). The aim of this work is to explore the variance of the aforementioned sensors and how this variability can be used to optimize the measurements of low-cost electrochemical sensors, closer to real ones. The analysis is conducted by employing diagrams, boxplot and violin curves of the groups of sensors used, with satisfactory results.","PeriodicalId":11612,"journal":{"name":"Electrochem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138947985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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