Pub Date : 2026-04-01Epub Date: 2025-11-25DOI: 10.1016/j.chemphys.2025.113038
A. Bourfoune , L.B. Drissi
To address berberine’s low bioavailability and Dose-Limiting Toxicity, we loaded it onto a hexagonal -Gy (-graphyne) quantum dot, known as graphyne spoked wheel, and analyzed the complex via DFT calculations. Adsorption energy in the gas phase (–1.70 eV) confirms effective drug loading. Furthermore, thermodynamic values ( = –2.18 eV, = –1.36 eV) show exothermic, spontaneous binding under physiological conditions. Negative adsorption energy in water suggest stability during bloodstream circulation without premature release. Moreover, the increased dipole moments (up to 14.02 D) imply enhanced mobility and solubility, while FMO, DOS, and PDOS analyses reveal charge transfer from berberine to the dot. QTAIM, ELF and NCI analyses demonstrate noncovalent interactions that support controlled release. Functionalization with amine (NH) and carboxyl (COOH) groups adds pH sensitivity: significant binding at physiological pH, and shifts to 2.32 eV in acidic tumor environments, enabling targeted release. These results support functionalized -graphyne as a pH-responsive nanocarrier for precision cancer drug delivery.
{"title":"DFT study of functionalized γ-graphyne quantum dot as pH-sensitive nanocarrier for berberine anticancer drug","authors":"A. Bourfoune , L.B. Drissi","doi":"10.1016/j.chemphys.2025.113038","DOIUrl":"10.1016/j.chemphys.2025.113038","url":null,"abstract":"<div><div>To address berberine’s low bioavailability and Dose-Limiting Toxicity, we loaded it onto a hexagonal <span><math><mi>γ</mi></math></span>-Gy (<span><math><mi>γ</mi></math></span>-graphyne) quantum dot, known as graphyne spoked wheel, and analyzed the complex via DFT calculations. Adsorption energy in the gas phase (–1.70 eV) confirms effective drug loading. Furthermore, thermodynamic values (<span><math><mrow><mi>Δ</mi><mi>H</mi></mrow></math></span> = –2.18 eV, <span><math><mrow><mi>Δ</mi><mi>G</mi></mrow></math></span> = –1.36 eV) show exothermic, spontaneous binding under physiological conditions. Negative adsorption energy in water suggest stability during bloodstream circulation without premature release. Moreover, the increased dipole moments (up to 14.02 D) imply enhanced mobility and solubility, while FMO, DOS, and PDOS analyses reveal charge transfer from berberine to the dot. QTAIM, ELF and NCI analyses demonstrate noncovalent interactions that support controlled release. Functionalization with amine (NH<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>) and carboxyl (COOH) groups adds pH sensitivity: significant binding at physiological pH, and shifts to 2.32 eV in acidic tumor environments, enabling targeted release. These results support functionalized <span><math><mi>γ</mi></math></span>-graphyne as a pH-responsive nanocarrier for precision cancer drug delivery.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113038"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681697","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}
Phase transitions of the ionic liquid (IL) with a bulky cation were investigated at low temperature (LT) and high pressure (HP). The IL studied was trihexyl(tetradecyl)phosphonium hexafluorophosphate, [P666,14][PF6]. Upon cooling of 4.6 K/min, LT α phase was formed at 286 K. In the unit cell, void space was visualized. LT crystallization was influenced slightly by the cooling rate. Under HP, the crystal (α-phase) transformed into a flexible crystal (β phase) at 0.7 GPa by reducing void space. The HP α-β phase transition of [P666,14][PF6] was caused by compression of the void space within the unit cell. During the β phase with drastic volume contraction, the void fraction was almost constant. At 4.1 GPa, the flexible β phase transformed to a rigid ionic liquid crystal. Even at the maximum pressure of 7.2 GPa, a reversible volumetric phase transition was observed in the bulky [P666,14][PF6].
{"title":"Volumetric phase transitions in a bulky ionic liquid: trihexyl(tetradecyl)phosphonium hexafluorophosphate","authors":"Hiroshi Abe , Ryo Suzuki , Akihisa Aimi , Hiroaki Kishimura , Daisuke Okuyama , Hajime Sagayama","doi":"10.1016/j.chemphys.2025.113016","DOIUrl":"10.1016/j.chemphys.2025.113016","url":null,"abstract":"<div><div>Phase transitions of the ionic liquid (IL) with a bulky cation were investigated at low temperature (LT) and high pressure (HP). The IL studied was trihexyl(tetradecyl)phosphonium hexafluorophosphate, [P666,14][PF<sub>6</sub>]. Upon cooling of 4.6 K/min, LT α phase was formed at 286 K. In the unit cell, void space was visualized. LT crystallization was influenced slightly by the cooling rate. Under HP, the crystal (α-phase) transformed into a flexible crystal (β phase) at 0.7 GPa by reducing void space. The HP α-β phase transition of [P666,14][PF<sub>6</sub>] was caused by compression of the void space within the unit cell. During the β phase with drastic volume contraction, the void fraction was almost constant. At 4.1 GPa, the flexible β phase transformed to a rigid ionic liquid crystal. Even at the maximum pressure of 7.2 GPa, a reversible volumetric phase transition was observed in the bulky [P666,14][PF<sub>6</sub>].</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113016"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145555176","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}
Pub Date : 2026-04-01Epub Date: 2025-12-21DOI: 10.1016/j.chemphys.2025.113068
K.K. Purushothaman , B. Sethuraman , K. Karthikeyan , A. John Samuel , Sasikumar Moorthy , K. Jeyalakshmi
The development of high-power and high-energy supercapacitors (SCs) has long been pursued for use in transportation and energy storage systems. However, maintaining high rate performance, especially in integrated electrodes, is still challenging. In this work, we report a facile method to synthesize interconnected, flower-like and porous Co-doped NiO/MWCNT nanostructure. Benefiting from the synergistic effects of Co doping and MWCNT incorporation, the as-prepared electrode achieves a maximum specific capacitance of 1855 F g−1 at a current density of 1 A g−1 with the good cycling stability. Furthermore, the Dunn and Trasatti methods were employed to quantify the charge-storage contributions from surface-controlled and diffusion-controlled processes. An asymmetric supercapacitor (Co-doped NiO-MWCNT//rGO) achieves an energy density of 12.7 Wh kg−1 at a current density of 1 A g−1 and a maximum power density of 1246.5 W kg−1 at 5 A g−1.
大功率高能超级电容器（SCs）在交通运输和储能系统中的应用一直是人们追求的目标。然而，保持高速率性能，特别是集成电极，仍然具有挑战性。在这项工作中，我们报告了一种简单的方法来合成互连，花状和多孔共掺杂NiO/MWCNT纳米结构。得益于Co掺杂和MWCNT掺入的协同效应，所制备的电极在电流密度为1 a g−1时的最大比电容为1855 F g−1，并且具有良好的循环稳定性。此外，Dunn和Trasatti方法被用来量化表面控制和扩散控制过程的电荷存储贡献。非对称超级电容器（共掺杂NiO-MWCNT//rGO）在电流密度为1 a g−1时能量密度为12.7 Wh kg−1，在电流密度为5 a g−1时最大功率密度为1246.5 W kg−1。
{"title":"Cobalt doped NiO/MWCNT hybrid micro flowers for supercapacitor applications","authors":"K.K. Purushothaman , B. Sethuraman , K. Karthikeyan , A. John Samuel , Sasikumar Moorthy , K. Jeyalakshmi","doi":"10.1016/j.chemphys.2025.113068","DOIUrl":"10.1016/j.chemphys.2025.113068","url":null,"abstract":"<div><div>The development of high-power and high-energy supercapacitors (SCs) has long been pursued for use in transportation and energy storage systems. However, maintaining high rate performance, especially in integrated electrodes, is still challenging. In this work, we report a facile method to synthesize interconnected, flower-like and porous Co-doped NiO/MWCNT nanostructure. Benefiting from the synergistic effects of Co doping and MWCNT incorporation, the as-prepared electrode achieves a maximum specific capacitance of 1855 F g<sup>−1</sup> at a current density of 1 A g<sup>−1</sup> with the good cycling stability. Furthermore, the Dunn and Trasatti methods were employed to quantify the charge-storage contributions from surface-controlled and diffusion-controlled processes. An asymmetric supercapacitor (Co-doped NiO-MWCNT//rGO) achieves an energy density of 12.7 Wh kg<sup>−1</sup> at a current density of 1 A g<sup>−1</sup> and a maximum power density of 1246.5 W kg<sup>−1</sup> at 5 A g<sup>−1</sup>.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113068"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836593","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}
Pub Date : 2026-04-01Epub Date: 2025-12-05DOI: 10.1016/j.chemphys.2025.113054
Jiangyang Qin , Hong Zhang , Bo Ma , Xinlu Cheng
The interaction of defects in energetic materials(EMs) has been extensively investigated using continuum-scale simulations. However, such approaches inherently struggle to capture processes occurring at the atomic or molecular level. In this study, we offer an atomistic perspective to explore the potential mechanisms by which nanodefect distributions in RDX influence hotspot temperature under strong shock loading. Simulation results reveal that due to the effect of Mach Stem, a significant concentration of kinetic energy occurs in the downstream region within the double-defect model. In the triple-defect model, This kinetic energy concentration further amplifies the shock wave at the third defect, significantly increasing the local temperature and thereby accelerating the chemical reaction rate. This finding indicates that under strong shock loading, there are strong interactions between nanodefects within RDX, which can significantly affect hotspot temperatures. Specifically, the local temperature in the triple-defect model is 586.7 K higher than in the single-defect model.
{"title":"Interaction mechanism of RDX nanodefects under strong shock loading and the enhancement of hotspot temperature: A reactive atomistic perspective","authors":"Jiangyang Qin , Hong Zhang , Bo Ma , Xinlu Cheng","doi":"10.1016/j.chemphys.2025.113054","DOIUrl":"10.1016/j.chemphys.2025.113054","url":null,"abstract":"<div><div>The interaction of defects in energetic materials(EMs) has been extensively investigated using continuum-scale simulations. However, such approaches inherently struggle to capture processes occurring at the atomic or molecular level. In this study, we offer an atomistic perspective to explore the potential mechanisms by which nanodefect distributions in RDX influence hotspot temperature under strong shock loading. Simulation results reveal that due to the effect of Mach Stem, a significant concentration of kinetic energy occurs in the downstream region within the double-defect model. In the triple-defect model, This kinetic energy concentration further amplifies the shock wave at the third defect, significantly increasing the local temperature and thereby accelerating the chemical reaction rate. This finding indicates that under strong shock loading, there are strong interactions between nanodefects within RDX, which can significantly affect hotspot temperatures. Specifically, the local temperature in the triple-defect model is 586.7 K higher than in the single-defect model.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113054"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733044","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}
Pub Date : 2026-04-01Epub Date: 2025-11-23DOI: 10.1016/j.chemphys.2025.113037
Uzma Sattar , Zeeshan Ali , Godefroid Gahungu , Wenliang Li , Jingping Zhang
Electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) determine the efficiency of electrochemical water splitting. Therefore, we designed a series of multimetallic metal-organic frameworks (MOFs), NH2-BDC-TM3 and Br-BDC-TM3 (NH2-BDC = 2-aminoterephthalate, Br-BDC = 2,5-dibromoterephthalate), as bifunctional electrocatalysts for efficient HER and OER. This study computationally investigated the synergistic effect between metal atoms and substituent groups (NH2 and Br) within the main framework TM3-BDC. All three homonuclear (TM = Fe, Co, Ni) and three Fe-containing heteronuclear (TM3 = Fe2Co, Fe2Ni, FeCoNi) electrocatalysts designed for each (NH2 and Br) substituent group exhibit good stability. The minimum overpotential of NH2-BDC-Fe*CoNi (0.20 V) for OER, and HER (NH2-BDC-Fe2Ni, 0.02 V, O active site) represents that the NH2 substituent is most effective towards OER and HER activity among all the designed catalysts. Br-BDC-Fe*CoNi proved to be a highly efficient as a bifunctional electrocatalyst for OER and HER, with measured overpotentials of 0.45 and 0.18 V, respectively. Our investigation highlights the potential of an active class of MOF electrocatalysts for HER and OER.
{"title":"Enhancing HER and OER through the synergetic effect of metal and ligand in a metal-organic framework, a density functional theory study","authors":"Uzma Sattar , Zeeshan Ali , Godefroid Gahungu , Wenliang Li , Jingping Zhang","doi":"10.1016/j.chemphys.2025.113037","DOIUrl":"10.1016/j.chemphys.2025.113037","url":null,"abstract":"<div><div>Electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) determine the efficiency of electrochemical water splitting. Therefore, we designed a series of multimetallic metal-organic frameworks (MOFs), NH<sub>2</sub>-BDC-TM<sub>3</sub> and Br-BDC-TM<sub>3</sub> (NH<sub>2</sub>-BDC = 2-aminoterephthalate, Br-BDC = 2,5-dibromoterephthalate), as bifunctional electrocatalysts for efficient HER and OER. This study computationally investigated the synergistic effect between metal atoms and substituent groups (NH<sub>2</sub> and Br) within the main framework TM<sub>3</sub>-BDC. All three homonuclear (TM = Fe, Co, Ni) and three Fe-containing heteronuclear (TM<sub>3</sub> = Fe<sub>2</sub>Co, Fe<sub>2</sub>Ni, FeCoNi) electrocatalysts designed for each (NH<sub>2</sub> and Br) substituent group exhibit good stability. The minimum overpotential of NH<sub>2</sub>-BDC-Fe*CoNi (0.20 V) for OER, and HER (NH<sub>2</sub>-BDC-Fe<sub>2</sub>Ni, 0.02 V, O active site) represents that the <img>NH<sub>2</sub> substituent is most effective towards OER and HER activity among all the designed catalysts. Br-BDC-Fe*CoNi proved to be a highly efficient as a bifunctional electrocatalyst for OER and HER, with measured overpotentials of 0.45 and 0.18 V, respectively. Our investigation highlights the potential of an active class of MOF electrocatalysts for HER and OER.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113037"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681706","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}
Pub Date : 2026-04-01Epub Date: 2025-12-17DOI: 10.1016/j.chemphys.2025.113069
Anmei Wang , Xiaoyun Wang , Litian Wang
The decomposition mechanism of •OH/O3 with pentabromotoluene (PBT) and pentabromoethylbenzene (PBEB) is investigated using the density functional theory method. The reaction involves the •OH-addition, •OH-abstraction, O3-addition. The optimal initial pathways of PBT and PBEB initiated by •OH are PBT + •OH → IM1–5 + H2O and PBEB + •OH → IM2–7, respectively, with corresponding reaction energy barriers of 45.7 and 40.9 kJ/mol. The optimal initial pathways of PBT and PBEB initiated by O3 are PBT + O3 → TS1–6 (99.6 kJ/mol) → IM1–5 + H2O and PBEB + O3 → TS2–8 (97.6 kJ/mol) → IM2–8, respectively. The total kinetic rate constants for the reactions of •OH/O3 with PBT and PBEB at 298 K are 5.51 × 10−15, 6.63 × 10−14, 1.12 × 10−24, and 2.45 × 10−24 cm3 molecule−1 s−1, respectively. PBT and PBEB can degrade to small molecular products without acute and chronic toxicity during the degradation process.
{"title":"Oxidative degradation of pentabromotoluene and pentabromoethylbenzene in aqueous phase initiated by •OH/O3","authors":"Anmei Wang , Xiaoyun Wang , Litian Wang","doi":"10.1016/j.chemphys.2025.113069","DOIUrl":"10.1016/j.chemphys.2025.113069","url":null,"abstract":"<div><div>The decomposition mechanism of •OH/O<sub>3</sub> with pentabromotoluene (PBT) and pentabromoethylbenzene (PBEB) is investigated using the density functional theory method. The reaction involves the •OH-addition, •OH-abstraction, O<sub>3</sub>-addition. The optimal initial pathways of PBT and PBEB initiated by •OH are PBT + •OH → IM1–5 + H<sub>2</sub>O and PBEB + •OH → IM2–7, respectively, with corresponding reaction energy barriers of 45.7 and 40.9 kJ/mol. The optimal initial pathways of PBT and PBEB initiated by O<sub>3</sub> are PBT + O<sub>3</sub> → TS1–6 (99.6 kJ/mol) → IM1–5 + H<sub>2</sub>O and PBEB + O<sub>3</sub> → TS2–8 (97.6 kJ/mol) → IM2–8, respectively. The total kinetic rate constants for the reactions of •OH/O<sub>3</sub> with PBT and PBEB at 298 K are 5.51 × 10<sup>−15</sup>, 6.63 × 10<sup>−14</sup>, 1.12 × 10<sup>−24</sup>, and 2.45 × 10<sup>−24</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>, respectively. PBT and PBEB can degrade to small molecular products without acute and chronic toxicity during the degradation process.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113069"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836597","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}
Pub Date : 2026-04-01Epub Date: 2025-12-17DOI: 10.1016/j.chemphys.2025.113064
Ameneh Zarei, Alireza Fattahi
Ionic liquids (ILs) have become a significant area of interest across numerous industrial applications in contemporary settings. Ionic liquids possess distinctive features, including low melting points, low volatility, high electrical conductivity, remarkable chemical stability, and, importantly, low toxicity. These attributes render them particularly advantageous as solvents in green chemistry applications. This study focuses on designing and investigating ionic liquids comprising a cytosine-based cation paired with a range of carboxylate anions, known for their environmentally friendly properties. In developing these ionic liquids, various factors were assessed using quantum calculations, including the energy of the ion-pair arrangement, thermodynamic stability, and other electronic structure characteristics.
Furthermore, the analysis of bulk properties via molecular dynamics simulations addressed hydrogen bonds and the contributions of different interaction energies to the arrangement of ion pairs. Quantum calculations (thermochemical) indicate that all resulting ion pairs are energetically favorable, and hydrogen bonding plays a significant role in their arrangement. The binding energy for the most stable ion pairs (IPs) calculated using the quantum method is −91.41 kcal/mol, whereas the PBSA method, derived from molecular dynamics calculations, yields −82.02 kcal/mol, resulting in a 9.39 % difference. Additionally, the molecular dynamics approach identifies electrostatic interactions as the primary driver of ion-pair arrangement in the designed ILs.
{"title":"Design and computational analysis of cytosine-based ionic liquids for green chemistry applications","authors":"Ameneh Zarei, Alireza Fattahi","doi":"10.1016/j.chemphys.2025.113064","DOIUrl":"10.1016/j.chemphys.2025.113064","url":null,"abstract":"<div><div>Ionic liquids (ILs) have become a significant area of interest across numerous industrial applications in contemporary settings. Ionic liquids possess distinctive features, including low melting points, low volatility, high electrical conductivity, remarkable chemical stability, and, importantly, low toxicity. These attributes render them particularly advantageous as solvents in green chemistry applications. This study focuses on designing and investigating ionic liquids comprising a cytosine-based cation paired with a range of carboxylate anions, known for their environmentally friendly properties. In developing these ionic liquids, various factors were assessed using quantum calculations, including the energy of the ion-pair arrangement, thermodynamic stability, and other electronic structure characteristics.</div><div>Furthermore, the analysis of bulk properties via molecular dynamics simulations addressed hydrogen bonds and the contributions of different interaction energies to the arrangement of ion pairs. Quantum calculations (thermochemical) indicate that all resulting ion pairs are energetically favorable, and hydrogen bonding plays a significant role in their arrangement. The binding energy for the most stable ion pairs (IPs) calculated using the quantum method is −91.41 kcal/mol, whereas the PBSA method, derived from molecular dynamics calculations, yields −82.02 kcal/mol, resulting in a 9.39 % difference. Additionally, the molecular dynamics approach identifies electrostatic interactions as the primary driver of ion-pair arrangement in the designed ILs.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113064"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786515","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}
Pub Date : 2026-04-01Epub Date: 2025-12-14DOI: 10.1016/j.chemphys.2025.113061
Hamza Kellou , Salem Boudinar , Nassima Benbrahim , Eric Chainet
Chromium three oxide (Cr2O3) nanopowder (NPW) was synthesized by chemical method, using (NaBH4) as a reducing agent from chromium six oxide (CrO3) dissolved in water.
The obtained Cr2O3 NPWs were characterized by several techniques such as scanning electron microscopy (SEM) coupled energy dispersive spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–Visible spectrophotometer and Brunauer–Emmett–Teller (BET) analysis. The SEM observation of NPW, shows the formation of particles with nano-meter sizes about 25–175 nm. The FTIR shows two large band attributed to the CrO and CrO vibrations. The mesoporous Cr2O3 powder exhibited a specific surface area of 130 m2 g−1, as determined by BET analysis. UV–Vis spectrum of Cr2O3 NPs revels two strong bands (in solution) at 270 and 370 nm. For the solid UV–Vis, there are three peaks localized at 268, 397 and 603 nm which confirms the formation of Cr (III).
The electrochemical and photoelectrochemical performance of the synthesized NPW was evaluated by electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV), respectively. The powder presents a pseudo super-capacitor behavior. The stability, the electrochemical impedance, energy storage and semiconductor (SC) behavior of the NPW were also tested. Electrochemical impedance spectroscopy (EIS) analysis revealed a charge transfer resistance Rct of 7100, 4225 and 2970 Ω in the dark, under visible light and under UV irradiation, respectively, as shown in the Nyquist plot. The specific capacitance, calculated from cyclic voltammetry (CV) at a scan rate of 100 mV s−1, exhibited high stability, with a variation of only ∼83 nF after 1000 cycles. The highest areal specific capacitance equal 332 mF g−1 during the charging process and 388 mF g−1 during discharge at a current density of 160 mA g−1. The n-type semiconductor (SC) shows a good potential for energy storage and PEC applications.
The photocatalytic activity of Cr2O3 NPs was evaluated by degradation of methylene blue (MB) under UV and visible light irradiation, which lead to 98 and 93 % of BM degradation, respectively.
{"title":"Chromium three oxide nanoparticle electrodes for supercapacitor and photocatalytic applications","authors":"Hamza Kellou , Salem Boudinar , Nassima Benbrahim , Eric Chainet","doi":"10.1016/j.chemphys.2025.113061","DOIUrl":"10.1016/j.chemphys.2025.113061","url":null,"abstract":"<div><div>Chromium three oxide (Cr<sub>2</sub>O<sub>3</sub>) nanopowder (NPW) was synthesized by chemical method, using (NaBH<sub>4</sub>) as a reducing agent from chromium six oxide (CrO<sub>3</sub>) dissolved in water.</div><div>The obtained Cr<sub>2</sub>O<sub>3</sub> NPWs were characterized by several techniques such as scanning electron microscopy (SEM) coupled energy dispersive spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–Visible spectrophotometer and Brunauer–Emmett–Teller (BET) analysis. The SEM observation of NPW, shows the formation of particles with nano-meter sizes about 25–175 nm. The FTIR shows two large band attributed to the Cr<img>O and Cr<img>O vibrations. The mesoporous Cr<sub>2</sub>O<sub>3</sub> powder exhibited a specific surface area of 130 m<sup>2</sup> g<sup>−1</sup>, as determined by BET analysis. UV–Vis spectrum of Cr<sub>2</sub>O<sub>3</sub> NPs revels two strong bands (in solution) at 270 and 370 nm. For the solid UV–Vis, there are three peaks localized at 268, 397 and 603 nm which confirms the formation of Cr (III).</div><div>The electrochemical and photoelectrochemical performance of the synthesized NPW was evaluated by electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV), respectively. The powder presents a pseudo super-capacitor behavior. The stability, the electrochemical impedance, energy storage and semiconductor (SC) behavior of the NPW were also tested. Electrochemical impedance spectroscopy (EIS) analysis revealed a charge transfer resistance R<sub>ct</sub> of 7100, 4225 and 2970 Ω in the dark, under visible light and under UV irradiation, respectively, as shown in the Nyquist plot. The specific capacitance, calculated from cyclic voltammetry (CV) at a scan rate of 100 mV s<sup>−1</sup>, exhibited high stability, with a variation of only ∼83 nF after 1000 cycles. The highest areal specific capacitance equal 332 mF g<sup>−1</sup> during the charging process and 388 mF g<sup>−1</sup> during discharge at a current density of 160 mA g<sup>−1</sup>. The n-type semiconductor (SC) shows a good potential for energy storage and PEC applications.</div><div>The photocatalytic activity of Cr<sub>2</sub>O<sub>3</sub> NPs was evaluated by degradation of methylene blue (MB) under UV and visible light irradiation, which lead to 98 and 93 % of BM degradation, respectively.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113061"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786518","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}
Pub Date : 2026-04-01Epub Date: 2025-12-20DOI: 10.1016/j.chemphys.2025.113070
Asghar Hussain , Muhammad Khuram Shahzad , Muhammad Sagir , Adnan Khalil , Muhammad Bilal Tahir
The serious challenge of the modern era lies in identifying sustainable and cost-effective solutions for energy generation and utilization. Perovskite materials have emerged as a promising avenue to address these issues, offering efficient energy production at affordable costs. This study explores the properties of cubic inorganic perovskites Na2ScCuX6 (X = I, F) using Density Functional Theory (DFT). The investigations employ the ultrasoft pseudopotential plane wave (PW) method combined with the Perdew Burke Ernzerhof (PBE) exchange correlation functional within the Generalized Gradient Approximation (GGA) context. CASTEP code is utilized to analyze the structural, mechanical, electrical, and optical properties of these materials. The structural analysis exposes that these compounds crystallize in a cubic structure with a space group of 225 (Fmm). The formation energies of Na2ScCuF6, and Na2ScCuI6 are calculated to be −2.80 eV, and − 2.17 eV, respectively, while phonon dispersion calculations confirm their thermodynamic stability. The electronic band structure analysis indicates that both compounds exhibit indirect bandgaps, with values of 0.055 eV for Na2ScCuF6, and 1.528 eV for Na2ScCuI6, which means they behave like semiconductors. Mechanical properties, including Pugh's ratio (5.05, 3.47), Poisson's ratio (0.40, 0.37), and anisotropy factors (0.74, 1.74), further confirm the ductile nature of these perovskites. The thermodynamic features, including enthalpy, free energy, entropy, and heat capacity, were evaluated through phonon mode analysis. Based on their optical and thermodynamic performance, pure Na2ScCuF6 and Na2ScCuI6 compounds exhibit promising potential for use in optoelectronic and photovoltaic applications.
{"title":"Computational explorations of Lead-free double perovskite Na2ScCuX6 (X = F, I) compounds for optoelectronics applications","authors":"Asghar Hussain , Muhammad Khuram Shahzad , Muhammad Sagir , Adnan Khalil , Muhammad Bilal Tahir","doi":"10.1016/j.chemphys.2025.113070","DOIUrl":"10.1016/j.chemphys.2025.113070","url":null,"abstract":"<div><div>The serious challenge of the modern era lies in identifying sustainable and cost-effective solutions for energy generation and utilization. Perovskite materials have emerged as a promising avenue to address these issues, offering efficient energy production at affordable costs. This study explores the properties of cubic inorganic perovskites Na<sub>2</sub>ScCuX<sub>6</sub> (X = I, F) using Density Functional Theory (DFT). The investigations employ the ultrasoft pseudopotential plane wave (PW) method combined with the Perdew Burke Ernzerhof (PBE) exchange correlation functional within the Generalized Gradient Approximation (GGA) context. CASTEP code is utilized to analyze the structural, mechanical, electrical, and optical properties of these materials. The structural analysis exposes that these compounds crystallize in a cubic structure with a space group of 225 (Fm<span><math><mover><mn>3</mn><mo>¯</mo></mover></math></span>m). The formation energies of Na<sub>2</sub>ScCuF<sub>6</sub>, and Na<sub>2</sub>ScCuI<sub>6</sub> are calculated to be −2.80 eV, and − 2.17 eV, respectively, while phonon dispersion calculations confirm their thermodynamic stability. The electronic band structure analysis indicates that both compounds exhibit indirect bandgaps, with values of 0.055 eV for Na<sub>2</sub>ScCuF<sub>6</sub>, and 1.528 eV for Na<sub>2</sub>ScCuI<sub>6</sub>, which means they behave like semiconductors. Mechanical properties, including Pugh's ratio (5.05, 3.47), Poisson's ratio (0.40, 0.37), and anisotropy factors (0.74, 1.74), further confirm the ductile nature of these perovskites. The thermodynamic features, including enthalpy, free energy, entropy, and heat capacity, were evaluated through phonon mode analysis. Based on their optical and thermodynamic performance, pure Na<sub>2</sub>ScCuF<sub>6</sub> and Na<sub>2</sub>ScCuI<sub>6</sub> compounds exhibit promising potential for use in optoelectronic and photovoltaic applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113070"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836592","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}
We investigated the physical properties of K₂CaH₄ under 0–15 GPa using first-principles calculations. The lattice parameters are a = b = 4.4148 Å, c = 14.1434 Å, with formation enthalpy −0.4001 eV atom-1 and cohesive energy 2.85 eV atom-1. The elastic constants satisfy the mechanical-stability criteria. Electronic band gaps are wide, decreasing slightly with pressure (3.38 eV at 0 GPa to 3.23 eV at 15 GPa), identifying K₂CaH₄ as an insulator. Phonon dispersions show no imaginary modes up to 10 GPa and the onset of instability at 15 GPa. The Debye temperature rises from 388.04 K (0 GPa) to 419.88 K (10 GPa) and then drops to 352.59 K (15 GPa). Optically, the maximum absorption coefficient reaches 5.59 × 105 cm-1 at 35.58 eV, and peak reflectivity increases to 69%. Hydrogen-storage metrics are a gravimetric capacity of 2.86 wt% and a volumetric capacity of 48.17 gH₂L-1.
用第一性原理计算研究了K₂CaH₄在0-15 GPa条件下的物理性质。晶格参数为a = b = 4.4148 Å， c = 14.1434 Å，形成焓为−0.4001 eV原子-1，结合能为2.85 eV原子-1。弹性常数满足力学稳定性准则。电子带隙较宽，随压力的增大而减小（0 GPa时为3.38 eV， 15 GPa时为3.23 eV），表明K₂CaH₄为绝缘体。声子色散在10gpa以下无虚模，在15gpa时开始失稳。德拜温度从388.04 K （0 GPa）上升到419.88 K (10 GPa)，然后下降到352.59 K （15 GPa）。光学上，在35.58 eV下，最大吸收系数达到5.59 × 105 cm-1，峰值反射率增加到69%。储氢指标的重量容量为2.86 wt%，体积容量为48.17 gH₂L-1。
{"title":"Investigation on structural, mechanical, electronic, vibrational, thermophysical, optic, and hydrogen storage properties of K2CaH4 under pressures from 0 to 15 GPa","authors":"Çağatay Yamçıçıer , Cihan Kürkçü , Sümeyra Yamçıçıer","doi":"10.1016/j.chemphys.2025.113039","DOIUrl":"10.1016/j.chemphys.2025.113039","url":null,"abstract":"<div><div>We investigated the physical properties of K₂CaH₄ under 0–15 GPa using first-principles calculations. The lattice parameters are <em>a</em> = <em>b =</em> 4.4148 Å, <em>c</em> = 14.1434 Å, with formation enthalpy −0.4001 eV atom<sup>-1</sup> and cohesive energy 2.85 eV atom<sup>-1</sup>. The elastic constants satisfy the mechanical-stability criteria. Electronic band gaps are wide, decreasing slightly with pressure (3.38 eV at 0 GPa to 3.23 eV at 15 GPa), identifying K₂CaH₄ as an insulator. Phonon dispersions show no imaginary modes up to 10 GPa and the onset of instability at 15 GPa. The Debye temperature rises from 388.04 K (0 GPa) to 419.88 K (10 GPa) and then drops to 352.59 K (15 GPa). Optically, the maximum absorption coefficient reaches 5.59 × 10<sup>5</sup> cm<sup>-1</sup> at 35.58 eV, and peak reflectivity increases to 69%. Hydrogen-storage metrics are a gravimetric capacity of 2.86 wt% and a volumetric capacity of 48.17 gH₂L<sup>-1</sup>.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113039"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681696","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}
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