Journal of Electroanalytical Chemistry最新文献

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Surface structure optimization by selective dissolution to improve the oxygen reduction performance of SmMn2O5

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-28 DOI: 10.1016/j.jelechem.2025.119052

Shao-Hui Huang , Jie Wu , Jing Chi , Tai-Shen Yang , Jin-Chao Cao

Selective dissolution is an effective strategy to improve the catalytic performance. This method was used to regulate the surface structure of SmMn₂O₅ through HNO₃ acidification to promote its oxygen reduction reaction (ORR) performance. The relationship between the structures and ORR performances of SmMn₂O₅ acidified by different concentrations of HNO₃ (5-8 M) was investigated. HNO₃ can selectively dissolve part of Sm, which reduces Sm/Mn ratio, and increases Mn⁴⁺/Mn³⁺ and surface adsorbed oxygen/lattice oxygen ratios on the catalyst surface. Especially, the increase of Mn⁴⁺ content optimizes the adsorption of oxygen-containing intermediates on Mn³⁺ active sites and enhances the ORR activity. When treated with 7 M HNO₃ for 10 h, the acidified SmMn₂O₅ surface has suitable Mn⁴⁺/Mn³⁺ ratio, exhibiting excellent ORR performance. Compared with SmMn₂O₅, the half-wave potential of the acidified SmMn₂O₅ increases from 0.80 V to 0.83 V, and the diffusion-limited current density improves from 3.44 mA·cm⁻² to 4.76 mA·cm⁻². Additionally, the synergistic catalytic mechanism of Mn⁴⁺ with Mn³⁺ active sites was well discussed.

{"title":"Surface structure optimization by selective dissolution to improve the oxygen reduction performance of SmMn2O5","authors":"Shao-Hui Huang , Jie Wu , Jing Chi , Tai-Shen Yang , Jin-Chao Cao","doi":"10.1016/j.jelechem.2025.119052","DOIUrl":"10.1016/j.jelechem.2025.119052","url":null,"abstract":"<div><div>Selective dissolution is an effective strategy to improve the catalytic performance. This method was used to regulate the surface structure of SmMn<sub>2</sub>O<sub>5</sub> through HNO<sub>3</sub> acidification to promote its oxygen reduction reaction (ORR) performance. The relationship between the structures and ORR performances of SmMn<sub>2</sub>O<sub>5</sub> acidified by different concentrations of HNO<sub>3</sub> (5-8 M) was investigated. HNO<sub>3</sub> can selectively dissolve part of Sm, which reduces Sm/Mn ratio, and increases Mn<sup>4+</sup>/Mn<sup>3+</sup> and surface adsorbed oxygen/lattice oxygen ratios on the catalyst surface. Especially, the increase of Mn<sup>4+</sup> content optimizes the adsorption of oxygen-containing intermediates on Mn<sup>3+</sup> active sites and enhances the ORR activity. When treated with 7 M HNO<sub>3</sub> for 10 h, the acidified SmMn<sub>2</sub>O<sub>5</sub> surface has suitable Mn<sup>4+</sup>/Mn<sup>3+</sup> ratio, exhibiting excellent ORR performance. Compared with SmMn<sub>2</sub>O<sub>5</sub>, the half-wave potential of the acidified SmMn<sub>2</sub>O<sub>5</sub> increases from 0.80 V to 0.83 V, and the diffusion-limited current density improves from 3.44 mA·cm<sup>−2</sup> to 4.76 mA·cm<sup>−2</sup>. Additionally, the synergistic catalytic mechanism of Mn<sup>4+</sup> with Mn<sup>3+</sup> active sites was well discussed.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"984 ","pages":"Article 119052"},"PeriodicalIF":4.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effective electrocatalytic overall water splitting over a pearl chain-like NiCoP/CNT hybrid sponge electrode in basic solution

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-27 DOI: 10.1016/j.jelechem.2025.119034

Shuying Wang , Liuen Wang , Yang Lu , Yingjiu Zhang

The electrocatalytic splitting of water into H₂ and O₂ is a potential method for continuous and controllable production of clean energy. Herein, we developed a pearl chain-like nickel cobalt phosphide (NiCoP) nanoparticle-modified 3D CNT sponge electrode by a simple electrodeposition method. The NiCoP/CNT hybrid electrode was found to exhibit excellent electrocatalytic performance for HER and OER in the alkaline solution (1 M KOH). In particular, the NiCoP/CNT hybrid electrodes generated 10 and 100 mA cm⁻² cathodic currents at overpotentials of 73 mV, and 140 mV, respectively. Meanwhile, the NiCoP/CNT compounds generated anodic currents of 10 and 100 mA cm⁻² at overpotentials of 288 and 353 mV, respectively. More specifically, no significant degradation was observed after a 100 h stability test with connecting the NiCoP/CNTs (+) and NiCoP/CNTs (−) in two-electrode system for water splitting under KOH solution. This work demonstrated that bifunctional transition metal electrocatalyst would be a wonderful catalyst for overall water splitting in basic aqueous solution.

{"title":"Effective electrocatalytic overall water splitting over a pearl chain-like NiCoP/CNT hybrid sponge electrode in basic solution","authors":"Shuying Wang , Liuen Wang , Yang Lu , Yingjiu Zhang","doi":"10.1016/j.jelechem.2025.119034","DOIUrl":"10.1016/j.jelechem.2025.119034","url":null,"abstract":"<div><div>The electrocatalytic splitting of water into H<sub>2</sub> and O<sub>2</sub> is a potential method for continuous and controllable production of clean energy. Herein, we developed a pearl chain-like nickel cobalt phosphide (NiCoP) nanoparticle-modified 3D CNT sponge electrode by a simple electrodeposition method. The NiCoP/CNT hybrid electrode was found to exhibit excellent electrocatalytic performance for HER and OER in the alkaline solution (1 M KOH). In particular, the NiCoP/CNT hybrid electrodes generated 10 and 100 mA cm<sup>−2</sup> cathodic currents at overpotentials of 73 mV, and 140 mV, respectively. Meanwhile, the NiCoP/CNT compounds generated anodic currents of 10 and 100 mA cm<sup>−2</sup> at overpotentials of 288 and 353 mV, respectively. More specifically, no significant degradation was observed after a 100 h stability test with connecting the NiCoP/CNTs (+) and NiCoP/CNTs (−) in two-electrode system for water splitting under KOH solution. This work demonstrated that bifunctional transition metal electrocatalyst would be a wonderful catalyst for overall water splitting in basic aqueous solution.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"984 ","pages":"Article 119034"},"PeriodicalIF":4.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Comparative experimental and DFT study of the electrochemical oxidation of azo pyridone dyes 偶氮吡啶酮染料电化学氧化的实验和 DFT 比较研究

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-26 DOI: 10.1016/j.jelechem.2025.119043

Aleksandra Mašulović , Jelena Lađarević , Jelena Lović , Vesna Vitnik , Željko Vitnik , Milka Avramov Ivić , Dušan Mijin

This study examines electrooxidation behavior of three aryl azo pyridone using cyclic (CV) and square-wave voltammetry (SWV) on a glassy carbon electrode (GC) in Britton–Robinson (BR) aqueous buffer solutions and quantum-chemical calculations. Results indicate that the electrochemical activity is closely related to the presence of the hydrazone (–NH–N=) bridge of the dyes. The most stable protonated and deprotonated forms of dyes are identified by comparing experimental UV–Vis spectra with calculated spectra. Additionally, calculated ionization energies for both forms aligned with observed electrochemical activity, emphasizing the deprotonated anionic form as the most active. The proposed electrooxidation mechanism suggests that initial step involves dye deprotonation to achieve the most stable anionic form, followed by electron removal to generate a radical, and subsequent geometric adjustments to optimize electron density distribution and stability. The differences of the electrochemical behavior of dyes are discussed with consideration of underlying mechanism.

{"title":"Comparative experimental and DFT study of the electrochemical oxidation of azo pyridone dyes","authors":"Aleksandra Mašulović , Jelena Lađarević , Jelena Lović , Vesna Vitnik , Željko Vitnik , Milka Avramov Ivić , Dušan Mijin","doi":"10.1016/j.jelechem.2025.119043","DOIUrl":"10.1016/j.jelechem.2025.119043","url":null,"abstract":"<div><div>This study examines electrooxidation behavior of three aryl azo pyridone using cyclic (CV) and square-wave voltammetry (SWV) on a glassy carbon electrode (GC) in Britton–Robinson (BR) aqueous buffer solutions and quantum-chemical calculations. Results indicate that the electrochemical activity is closely related to the presence of the hydrazone (–NH–N=) bridge of the dyes. The most stable protonated and deprotonated forms of dyes are identified by comparing experimental UV–Vis spectra with calculated spectra. Additionally, calculated ionization energies for both forms aligned with observed electrochemical activity, emphasizing the deprotonated anionic form as the most active. The proposed electrooxidation mechanism suggests that initial step involves dye deprotonation to achieve the most stable anionic form, followed by electron removal to generate a radical, and subsequent geometric adjustments to optimize electron density distribution and stability. The differences of the electrochemical behavior of dyes are discussed with consideration of underlying mechanism.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"983 ","pages":"Article 119043"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143520514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Carbon-based thick films for electrochemical detection of neonicotinoid insecticides

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-26 DOI: 10.1016/j.jelechem.2025.119054

Barbara Repič , Gregor Marolt , Danjela Kuscer

Neonicotinoids (NNIs) are water-soluble, toxic, widespread-used systemic insecticides commonly found in the environment. Integrated electrochemical sensors enable the rapid on-site detection of NNIs in aqueous samples by analysing the reduction of the NNI's nitro functional group on the working electrode. We have investigated graphite (G), glassy carbon (GC) and carbon black (CB) thick films as working electrodes for the electrochemical detection of the NNI imidacloprid (IMD). Up to 35-μm-thick films of G, GC and CB on alumina were prepared by screen printing and subsequent firing at 850 °C in argon. G had the largest grain size, the roughest surface, and the lowest sheet resistance of 6.9 Ω/sq. GC and CB had a smoother surface, while their sheet resistances were up to 27 Ω/sq. All three films showed a reversible response to the Fe(CN)₆^3−/4− redox probe with G having the highest electrochemically active surface area and the highest heterogeneous electron transfer rate constant. In the IMD solution with neutral pH, G, GC and CB exhibited characteristic reduction peak at −1.1 V and a re-oxidation peak at +0.2 V. An additional adsorption cathodic peak was observed with CB, indicating a significantly higher affinity of CB for IMD adsorption. With LODs under 1 μM, the G, GC and CB pristine thick films exhibiting great potential for the sensitive detection of IMD.

{"title":"Carbon-based thick films for electrochemical detection of neonicotinoid insecticides","authors":"Barbara Repič , Gregor Marolt , Danjela Kuscer","doi":"10.1016/j.jelechem.2025.119054","DOIUrl":"10.1016/j.jelechem.2025.119054","url":null,"abstract":"<div><div>Neonicotinoids (NNIs) are water-soluble, toxic, widespread-used systemic insecticides commonly found in the environment. Integrated electrochemical sensors enable the rapid on-site detection of NNIs in aqueous samples by analysing the reduction of the NNI's nitro functional group on the working electrode. We have investigated graphite (G), glassy carbon (GC) and carbon black (CB) thick films as working electrodes for the electrochemical detection of the NNI imidacloprid (IMD). Up to 35-μm-thick films of G, GC and CB on alumina were prepared by screen printing and subsequent firing at 850 °C in argon. G had the largest grain size, the roughest surface, and the lowest sheet resistance of 6.9 Ω/sq. GC and CB had a smoother surface, while their sheet resistances were up to 27 Ω/sq. All three films showed a reversible response to the Fe(CN)<sub>6</sub><sup>3−/4−</sup> redox probe with G having the highest electrochemically active surface area and the highest heterogeneous electron transfer rate constant. In the IMD solution with neutral pH, G, GC and CB exhibited characteristic reduction peak at −1.1 V and a re-oxidation peak at +0.2 V. An additional adsorption cathodic peak was observed with CB, indicating a significantly higher affinity of CB for IMD adsorption. With LODs under 1 μM, the G, GC and CB pristine thick films exhibiting great potential for the sensitive detection of IMD.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"984 ","pages":"Article 119054"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

N, P co-doping Co9S8/NC for enhanced the Electrocatalytic water splitting in all-pH

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-25 DOI: 10.1016/j.jelechem.2025.119044

Qianqian Song , Yang Chen , Yongjian Xu , Yatao Yan , Qianhui Wu , Fang Guo , Ming Chen , Guowang Diao

Hydrogen energy represents a form of green energy, and the electrolysis of water for hydrogen production is recognized as an efficient method. Current research is primarily focused on the development of catalysts that are both efficient and stable, particularly those capable of functioning consistently across the entire pH spectrum. In this work, Co₉S₈/NC co doped with N and P was successfully synthesized through a series of sulfurization, calcination, and phosphating operations using dual ligand Co-ZIF as the precursor. By coating a carbon layer and co doping with nitrogen and phosphorus, the catalytic performance and stability of hydrogen evolution reaction (HER) were significantly improved over the entire pH range. At a fixed current density of 10 mA cm⁻², the overpotential of HER was measured at voltages of 136, 96, and 194 mV in three different pH solutions. Furthermore, the electrocatalyst exhibits remarkable electrochemical stability over extended periods. After 20 h or 2000 cycles of testing, the catalytic activity did not show a significant decrease across the entire pH range, but rather exhibited a relatively sustained constant.

{"title":"N, P co-doping Co9S8/NC for enhanced the Electrocatalytic water splitting in all-pH","authors":"Qianqian Song , Yang Chen , Yongjian Xu , Yatao Yan , Qianhui Wu , Fang Guo , Ming Chen , Guowang Diao","doi":"10.1016/j.jelechem.2025.119044","DOIUrl":"10.1016/j.jelechem.2025.119044","url":null,"abstract":"<div><div>Hydrogen energy represents a form of green energy, and the electrolysis of water for hydrogen production is recognized as an efficient method. Current research is primarily focused on the development of catalysts that are both efficient and stable, particularly those capable of functioning consistently across the entire pH spectrum. In this work, Co<sub>9</sub>S<sub>8</sub>/NC co doped with N and P was successfully synthesized through a series of sulfurization, calcination, and phosphating operations using dual ligand Co-ZIF as the precursor. By coating a carbon layer and co doping with nitrogen and phosphorus, the catalytic performance and stability of hydrogen evolution reaction (HER) were significantly improved over the entire pH range. At a fixed current density of 10 mA cm<sup>−2</sup>, the overpotential of HER was measured at voltages of 136, 96, and 194 mV in three different pH solutions. Furthermore, the electrocatalyst exhibits remarkable electrochemical stability over extended periods. After 20 h or 2000 cycles of testing, the catalytic activity did not show a significant decrease across the entire pH range, but rather exhibited a relatively sustained constant.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"984 ","pages":"Article 119044"},"PeriodicalIF":4.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Promoting air stability of Co-Li2O cathode additive via LiAlO2 coating for lithium-ion batteries

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-25 DOI: 10.1016/j.jelechem.2025.119042

Zhixin Yang , Qiyang Hu , Haiyan Yang , Xinhai Li , Zhixing Wang , Huajun Guo , Guochun Yan , Hui Duan , Jiexi Wang , Guangchao Li

The consumption of Li⁺ in anode or cathode side results in low coulombic efficiency and poor cycling stability. Prelithiation additive is considered as an effective way to offset the irreversible Li⁺ loss, especially the one with high irreversible specific capacity and suitable working voltage. Li₂O exhibits one of the most promising candidates, benefiting from its high theoretical specific capacity (1793 mAh g⁻¹) and adoptable working voltage. However, the sluggish Li⁺ deintercalation kinetics and inferior air stability restricts its further application. Herein, LiAlO₂ coated additives (Co-Li₂O@LAO) was prepared to alleviate the above inferior effects which Co element activated Li₂O and LiAlO₂ coating contributed to a stable interface. The as-prepared Co-Li₂O@ LAO additives showed a specific capacity as high as 813.0 mAh g⁻¹ and the initial coulombic efficiency was only 2.5 % in Li-half cells, well manifesting the prelithiation additives characteristics. Especially, the specific capacity of Co-Li₂O@ LiAlO₂ maintained at 746.4 mAh g⁻¹ even after being exposed into air for 24 h. As a comparison, the value of Co-Li₂O-24 sample was only 471.8 mAh g⁻¹. This work provides a new idea for air stable prelithiation additives preparation when it comes to the practical application.

{"title":"Promoting air stability of Co-Li2O cathode additive via LiAlO2 coating for lithium-ion batteries","authors":"Zhixin Yang , Qiyang Hu , Haiyan Yang , Xinhai Li , Zhixing Wang , Huajun Guo , Guochun Yan , Hui Duan , Jiexi Wang , Guangchao Li","doi":"10.1016/j.jelechem.2025.119042","DOIUrl":"10.1016/j.jelechem.2025.119042","url":null,"abstract":"<div><div>The consumption of Li<sup>+</sup> in anode or cathode side results in low coulombic efficiency and poor cycling stability. Prelithiation additive is considered as an effective way to offset the irreversible Li<sup>+</sup> loss, especially the one with high irreversible specific capacity and suitable working voltage. Li<sub>2</sub>O exhibits one of the most promising candidates, benefiting from its high theoretical specific capacity (1793 mAh g<sup>−1</sup>) and adoptable working voltage. However, the sluggish Li<sup>+</sup> deintercalation kinetics and inferior air stability restricts its further application. Herein, LiAlO<sub>2</sub> coated additives (Co-Li<sub>2</sub>O@LAO) was prepared to alleviate the above inferior effects which Co element activated Li<sub>2</sub>O and LiAlO<sub>2</sub> coating contributed to a stable interface. The as-prepared Co-Li<sub>2</sub>O@ LAO additives showed a specific capacity as high as 813.0 mAh g<sup>−1</sup> and the initial coulombic efficiency was only 2.5 % in Li-half cells, well manifesting the prelithiation additives characteristics. Especially, the specific capacity of Co-Li<sub>2</sub>O@ LiAlO<sub>2</sub> maintained at 746.4 mAh g<sup>−1</sup> even after being exposed into air for 24 h. As a comparison, the value of Co-Li<sub>2</sub>O-24 sample was only 471.8 mAh g<sup>−1</sup>. This work provides a new idea for air stable prelithiation additives preparation when it comes to the practical application.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"983 ","pages":"Article 119042"},"PeriodicalIF":4.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143520513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Understanding ion intercalation of LiMn2O4 in brine for electrochemical detection of Li+ 了解盐水中 LiMn2O4 的离子插层，用于电化学检测 Li+

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-22 DOI: 10.1016/j.jelechem.2025.119033

Hu Fu , Weigang Zhu , Wenhua Xu , Zhongwei Zhao

Lithium-ion detection is necessary for extraction of lithium. Electrochemical sensors based on spinel LiMn₂O₄/λ-MnO₂ are expected to enable low-cost detection of lithium ions. Many studies demonstrate preferential intercalation of lithium ions, but little research has been done on how the differences in intercalation between lithium and other ions arise. Here, the differences in intercalation were identified by electrochemical impedance spectroscopy. Lithium ions were preferentially intercalated into λ-MnO₂ because of low charge transfer impedance. The apparent diffusion coefficient of sodium or potassium ions was one order of magnitude lower than that of lithium ions, while that of magnesium or calcium ions was two orders of magnitude lower. Therefore, insignificant intercalation of sodium, magnesium, potassium, and calcium ions slowed down diffusion of lithium ions through the channel and obstructed lithium-ion intercalation. The concentration of lithium ions was detected in brine of Baqiancuo Salt Lake by stripping voltammetry using λ-MnO₂ and an average recovery of 95.0 % was achieved. This study gives insights into ion intercalation of LiMn₂O₄ in brine, which favors improvement of lithium-ion sensor based on LiMn₂O₄. In addition, the investigation facilitates understanding of the selectivity of similar materials (e.g., LiFePO₄ and Prussian blue analogous) in intercalation process.

{"title":"Understanding ion intercalation of LiMn2O4 in brine for electrochemical detection of Li+","authors":"Hu Fu , Weigang Zhu , Wenhua Xu , Zhongwei Zhao","doi":"10.1016/j.jelechem.2025.119033","DOIUrl":"10.1016/j.jelechem.2025.119033","url":null,"abstract":"<div><div>Lithium-ion detection is necessary for extraction of lithium. Electrochemical sensors based on spinel LiMn<sub>2</sub>O<sub>4</sub>/λ-MnO<sub>2</sub> are expected to enable low-cost detection of lithium ions. Many studies demonstrate preferential intercalation of lithium ions, but little research has been done on how the differences in intercalation between lithium and other ions arise. Here, the differences in intercalation were identified by electrochemical impedance spectroscopy. Lithium ions were preferentially intercalated into λ-MnO<sub>2</sub> because of low charge transfer impedance. The apparent diffusion coefficient of sodium or potassium ions was one order of magnitude lower than that of lithium ions, while that of magnesium or calcium ions was two orders of magnitude lower. Therefore, insignificant intercalation of sodium, magnesium, potassium, and calcium ions slowed down diffusion of lithium ions through the channel and obstructed lithium-ion intercalation. The concentration of lithium ions was detected in brine of Baqiancuo Salt Lake by stripping voltammetry using λ-MnO<sub>2</sub> and an average recovery of 95.0 % was achieved. This study gives insights into ion intercalation of LiMn<sub>2</sub>O<sub>4</sub> in brine, which favors improvement of lithium-ion sensor based on LiMn<sub>2</sub>O<sub>4</sub>. In addition, the investigation facilitates understanding of the selectivity of similar materials (e.g., LiFePO<sub>4</sub> and Prussian blue analogous) in intercalation process.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"983 ","pages":"Article 119033"},"PeriodicalIF":4.1,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Non-uniform nitrogen doped carbon nanosheet anchored platinum nanoparticles with high oxygen reduction reaction activity

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-21 DOI: 10.1016/j.jelechem.2025.119030

Jiaxing Chen , Jinghai Liu , Yanchao Zhu , Jiawei Shi , Weiwei Cai , Luhua Lu

High oxygen reduction reaction (ORR) activity and stability of cathode catalyst is one of key issues to obtain high performance proton-exchange membrane fuel cells. The most successful ORR catalysts are Pt/C based composites for their stable ORR activity in acidic electrolyte in practical application. Heteroatoms doped carbon materials especially nitrogen doped carbon supports for Pt are found to be highly effective in improving ORR activity of Pt/C based catalysts. However, research on distribution of doped nitrogen in carbon materials and its influence on ORR activity and stability is rare. In this work, we report a nitrogen doped carbon nanosheet (NC) with non-uniform distribution of doped nitrogen. Nitrogen enriched microporous regions are found to be favorable for selective anchoring Pt nanoparticles by the strong PtN interaction. The influence of non-uniform doped nitrogen on ORR activity and stability of Pt/NC catalysts via statistical analysis changes of Pt nanoparticles' size and their distribution before and after accelerated durability test (ADT) is carried out. It is found that NC with appropriate non-uniform doped nitrogen can well tune disperse anchoring of Pt nanoparticles and their size on NC surface and effectively improving and stabilizing activity of Pt in acidic electrolyte environment than commercial Pt/C catalyst.

{"title":"Non-uniform nitrogen doped carbon nanosheet anchored platinum nanoparticles with high oxygen reduction reaction activity","authors":"Jiaxing Chen , Jinghai Liu , Yanchao Zhu , Jiawei Shi , Weiwei Cai , Luhua Lu","doi":"10.1016/j.jelechem.2025.119030","DOIUrl":"10.1016/j.jelechem.2025.119030","url":null,"abstract":"<div><div>High oxygen reduction reaction (ORR) activity and stability of cathode catalyst is one of key issues to obtain high performance proton-exchange membrane fuel cells. The most successful ORR catalysts are Pt/C based composites for their stable ORR activity in acidic electrolyte in practical application. Heteroatoms doped carbon materials especially nitrogen doped carbon supports for Pt are found to be highly effective in improving ORR activity of Pt/C based catalysts. However, research on distribution of doped nitrogen in carbon materials and its influence on ORR activity and stability is rare. In this work, we report a nitrogen doped carbon nanosheet (NC) with non-uniform distribution of doped nitrogen. Nitrogen enriched microporous regions are found to be favorable for selective anchoring Pt nanoparticles by the strong Pt<img>N interaction. The influence of non-uniform doped nitrogen on ORR activity and stability of Pt/NC catalysts via statistical analysis changes of Pt nanoparticles' size and their distribution before and after accelerated durability test (ADT) is carried out. It is found that NC with appropriate non-uniform doped nitrogen can well tune disperse anchoring of Pt nanoparticles and their size on NC surface and effectively improving and stabilizing activity of Pt in acidic electrolyte environment than commercial Pt/C catalyst.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"984 ","pages":"Article 119030"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Gold and gold‑platinum clusters as nanocatalysts for conversion of hydrogen peroxide

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-21 DOI: 10.1016/j.jelechem.2025.119009

Konstanty Zdunek, Agnieszka Więckowska

The electrocatalytic properties of Au₂₄Pt(SR)₁₈ (shortly: Au₂₄Pt) clusters protected by n-butanethiol C₄H₉SH haven't been characterized in detail yet. The platinum atom, surrounded by delocalized electrons in the gold core Au₁₂Pt, exhibits different behaviour compared to atoms in pure platinum nanoparticles. In this study we confirm this phenomenon by demonstrating a strong electrocatalytic effect for the electrooxidation and electroreduction of hydrogen peroxide using a gold working electrode modified with a Nafion-suspended product containing Au₂₄Pt clusters (Nafion – perfluorosulfonic copolymer). The currents measured at constant potentials of ±0.5 V versus an Ag/AgCl reference electrode, and hydrogen peroxide molarities ranging from 1 to 10 mM, show a linear dependence with a high correlation coefficient of up to 0.999. Due to the durability of the modified electrodes in water-based solutions and the reproducibility of the results, this technique appears promising for detecting the hydrogen peroxide in biological samples without damaging the sample, provided it remains stable within the specified potential range.

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引用次数: 0

Double‑carbon protected pre-lithiated SiOx anode for lithium-ion storage with high initial Coulombic efficiency and long cycle life

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2025-02-21 DOI: 10.1016/j.jelechem.2025.119032

Minglu Liu , Min Zeng , Xiaocheng Li , Yao Liu , Fangfang Wang , Shengwen Zhong

Silicon monoxide (SiO_x) is the most prevalent high-capacity anode material because of their relatively low volume change and superior cycling performance in comparison to silicon (Si). Nevertheless, its low initial coulombic efficiency (ICE) acts as a hindrance to the advancement of anode materials for Li-ion batteries. This study proposes a novel strategy for achieving double‑carbon protected homogeneous pre-lithiation of Li-SiO_x/C/C microparticles, utilising in-situ solid phase prelithiation and secondary carbon coating. To enhance the ICE two pre‑lithium strategies were compared, one is in-situ pre‑lithium by direct contact of SiO_x with LiH (Li-SiO_x), and the other is in-situ pre‑lithium by mixing carbon-coated SiO_x with LiH (Li-SiO_x/C). We found that the presence of the carbon coating led to a mild prelithiation reaction between SiOx and LiH, which improved the homogeneity of the prelithiation and reduced the overgrowth of lithium silicate and crystalline Si. The double‑carbon coating improves the electrical conductivity and structural stability of SiO_x electrode. The Li-SiO_x/C/C prepared with up to 87.13 % ICE and excellent cycling stability. The Li-SiO_x/C/C material employed in the NMC811-Li-SiO_x/C/C full battery exhibits a capacity retention of 78.2 % after 100 cycles, in comparison to 70.13 % with the SiO_x/C material. The findings provide a practical solution to be applied in the commercial context of SiO_x-based anode materials.

{"title":"Double‑carbon protected pre-lithiated SiOx anode for lithium-ion storage with high initial Coulombic efficiency and long cycle life","authors":"Minglu Liu , Min Zeng , Xiaocheng Li , Yao Liu , Fangfang Wang , Shengwen Zhong","doi":"10.1016/j.jelechem.2025.119032","DOIUrl":"10.1016/j.jelechem.2025.119032","url":null,"abstract":"<div><div>Silicon monoxide (SiO<sub>x</sub>) is the most prevalent high-capacity anode material because of their relatively low volume change and superior cycling performance in comparison to silicon (Si). Nevertheless, its low initial coulombic efficiency (ICE) acts as a hindrance to the advancement of anode materials for Li-ion batteries. This study proposes a novel strategy for achieving double‑carbon protected homogeneous pre-lithiation of Li-SiO<sub>x</sub>/C/C microparticles, utilising in-situ solid phase prelithiation and secondary carbon coating. To enhance the ICE two pre‑lithium strategies were compared, one is in-situ pre‑lithium by direct contact of SiO<sub>x</sub> with LiH (Li-SiO<sub>x</sub>), and the other is in-situ pre‑lithium by mixing carbon-coated SiO<sub>x</sub> with LiH (Li-SiO<sub>x</sub>/C). We found that the presence of the carbon coating led to a mild prelithiation reaction between SiOx and LiH, which improved the homogeneity of the prelithiation and reduced the overgrowth of lithium silicate and crystalline Si. The double‑carbon coating improves the electrical conductivity and structural stability of SiO<sub>x</sub> electrode. The Li-SiO<sub>x</sub>/C/C prepared with up to 87.13 % ICE and excellent cycling stability. The Li-SiO<sub>x</sub>/C/C material employed in the NMC811-Li-SiO<sub>x</sub>/C/C full battery exhibits a capacity retention of 78.2 % after 100 cycles, in comparison to 70.13 % with the SiO<sub>x</sub>/C material. The findings provide a practical solution to be applied in the commercial context of SiO<sub>x</sub>-based anode materials.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"983 ","pages":"Article 119032"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

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