Pub Date : 2026-01-14DOI: 10.1016/j.jpcs.2026.113539
Xuelian Wang , Haoyu Wang , Xiaolei Wang , Bing Li
The solid-liquid phase transition has recently attracted increasing attention in the barocaloric field. In this work, binary fatty acids-impregnated diatomite (BFAD) composites are proposed. Binary fatty acids can achieve a phase-transition temperature around room temperature due to strong hydrogen-bond interactions. The diatomite carriers, which effectively encapsulate the fatty acids, prevent liquid leakage and enhance operational safety. The resultant composites exhibit a first-order reversible phase transition at 292 K with a low thermal hysteresis of 6 K under ambient pressure. With increasing pressure, the composites show a giant barocaloric effect, with an isothermal entropy change reaching 80 J kg−1 K−1 and a low thermal hysteresis of 4 K under 100 MPa. Simultaneously, the working temperature span is 3 K with a reversible entropy change of 10 J kg−1 K−1, resulting in a refrigerant capacity of 523 J kg−1. Raman analysis reveals that the phase transition of the fatty acids from an ordered structure (trans conformation) to a disordered structure (gauche conformation) contributes to the giant barocaloric performance. This work demonstrates that fatty-acid/diatomite composites have potential applications in the barocaloric field and could provide new material choices for designing barocaloric materials based on solid-liquid phase transition materials incorporated within a host matrix.
{"title":"Giant barocaloric effect of binary fatty acids-impregnated diatomite composites with low thermal hysteresis at room temperature","authors":"Xuelian Wang , Haoyu Wang , Xiaolei Wang , Bing Li","doi":"10.1016/j.jpcs.2026.113539","DOIUrl":"10.1016/j.jpcs.2026.113539","url":null,"abstract":"<div><div>The solid-liquid phase transition has recently attracted increasing attention in the barocaloric field. In this work, binary fatty acids-impregnated diatomite (BFAD) composites are proposed. Binary fatty acids can achieve a phase-transition temperature around room temperature due to strong hydrogen-bond interactions. The diatomite carriers, which effectively encapsulate the fatty acids, prevent liquid leakage and enhance operational safety. The resultant composites exhibit a first-order reversible phase transition at 292 K with a low thermal hysteresis of 6 K under ambient pressure. With increasing pressure, the composites show a giant barocaloric effect, with an isothermal entropy change reaching 80 J kg<sup>−1</sup> K<sup>−1</sup> and a low thermal hysteresis of 4 K under 100 MPa. Simultaneously, the working temperature span is 3 K with a reversible entropy change of 10 J kg<sup>−1</sup> K<sup>−1</sup>, resulting in a refrigerant capacity of 523 J kg<sup>−1</sup>. Raman analysis reveals that the phase transition of the fatty acids from an ordered structure (trans conformation) to a disordered structure (gauche conformation) contributes to the giant barocaloric performance. This work demonstrates that fatty-acid/diatomite composites have potential applications in the barocaloric field and could provide new material choices for designing barocaloric materials based on solid-liquid phase transition materials incorporated within a host matrix.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113539"},"PeriodicalIF":4.9,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-14DOI: 10.1016/j.jpcs.2026.113541
Summaira Khan , Mohammed T. Alotaibi , M.W. Iqbal , Fatemah Farraj Ayed Al-harbi , Manoj Kumar , Muhammad Arslan Sunny , Abhinav Kumar , Muhammad Ashraf , Nermin A , Ankit Dilipkumar Oza , Rashid Javed
Supercapacitors (SCs) have attracted significant interest as promising energy storage devices due to their ability to deliver both high power and high energy densities. Even though considerable efforts have been made, there is still a significant energy density gap between the batteries and SCs. Developing high-performance electrode materials is an essential challenge toward efficient and sustainable energy storage systems. This work addresses such a gap through the development of a CTF/CdZnTe@ReSe2 heterostructure that exhibits enhanced SCs performance. The fabricated composite exhibited a superior specific capacity (Qs) of 230 C/g at 2 A/g and energy density (Ed) of 85.43 Wh/kg relative to its single phases. Electrochemical impedance spectroscopy (EIS) revealed a lower charge transfer resistance (Rct), indicating faster ion transport and improved conductivity in the composite. Here we present a tunable CTF/CdZnTe@ReSe2 interface specifically designed to achieve efficient electron transfer. This represents a substantial improvement compared to the hybrid materials currently used for electrochemical sensing and energy storage applications. The strong electrochemical performance, along with structural integrity and stability, makes CTF/CdZnTe@ReSe2 a promising candidate for future industrial energy storage devices.
超级电容器（SCs）由于具有提供高功率和高能量密度的能力，作为一种有前途的能量存储设备，引起了人们的极大兴趣。尽管已经做出了相当大的努力，但电池和超级电池之间的能量密度差距仍然很大。开发高性能电极材料是实现高效、可持续能源存储系统的重要挑战。这项工作通过开发CTF/CdZnTe@ReSe2异质结构来解决这一差距，该异质结构表现出增强的SCs性能。制备的复合材料在2 a /g时的比容量（Qs）为230 C/g，能量密度（Ed）为85.43 Wh/kg。电化学阻抗谱（EIS）显示，复合材料的电荷转移电阻（Rct）较低，表明离子传输更快，电导率提高。在这里，我们提出了一个可调谐的CTF/CdZnTe@ReSe2接口，专门设计用于实现有效的电子转移。与目前用于电化学传感和储能应用的混合材料相比，这是一个实质性的改进。CTF/CdZnTe@ReSe2具有较强的电化学性能以及结构的完整性和稳定性，是未来工业储能器件的一个有希望的候选者。
{"title":"Tunable CTF/CdZnTe@ReSe2 interface for efficient electron transfer toward high-performance electrochemical sensors and energy storage devices","authors":"Summaira Khan , Mohammed T. Alotaibi , M.W. Iqbal , Fatemah Farraj Ayed Al-harbi , Manoj Kumar , Muhammad Arslan Sunny , Abhinav Kumar , Muhammad Ashraf , Nermin A , Ankit Dilipkumar Oza , Rashid Javed","doi":"10.1016/j.jpcs.2026.113541","DOIUrl":"10.1016/j.jpcs.2026.113541","url":null,"abstract":"<div><div>Supercapacitors (SCs) have attracted significant interest as promising energy storage devices due to their ability to deliver both high power and high energy densities. Even though considerable efforts have been made, there is still a significant energy density gap between the batteries and SCs. Developing high-performance electrode materials is an essential challenge toward efficient and sustainable energy storage systems. This work addresses such a gap through the development of a CTF/CdZnTe@ReSe<sub>2</sub> heterostructure that exhibits enhanced SCs performance. The fabricated composite exhibited a superior specific capacity (Qs) of 230 C/g at 2 A/g and energy density (E<sub>d</sub>) of 85.43 Wh/kg relative to its single phases. Electrochemical impedance spectroscopy (EIS) revealed a lower charge transfer resistance (Rct), indicating faster ion transport and improved conductivity in the composite. Here we present a tunable CTF/CdZnTe@ReSe<sub>2</sub> interface specifically designed to achieve efficient electron transfer. This represents a substantial improvement compared to the hybrid materials currently used for electrochemical sensing and energy storage applications. The strong electrochemical performance, along with structural integrity and stability, makes CTF/CdZnTe@ReSe<sub>2</sub> a promising candidate for future industrial energy storage devices.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113541"},"PeriodicalIF":4.9,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-13DOI: 10.1016/j.jpcs.2026.113534
Chandra M. Adhikari , Dinesh Thapa , Talon D. Alexander , Christopher K. Addaman , Shubo Han , Bishnu P. Bastakoti , Daniel E. Autrey , Svetlana Kilina , Binod K. Rai , Bhoj Gautam
Metal carbides, nitrides, or carbonitrides of early transition metals, better known as MXenes, possess notable structural, electrical, and magnetic properties. Analyzing electronic structures by calculating structural stability, band structure, density of states, Bader charge transfer, and work functions utilizing first principle calculations, we revealed that titanium nitride MXenes, namely TiN and TiN, have excess anionic electrons in their lattice voids, making them MXene electrides. Bulk TiN has competing antiferromagnetic (AFM) and ferromagnetic (FM) configurations with slightly more stable AFM configuration, while the TiN MXene is nonmagnetic. Although TiN favors AFM configuration with hexagonal crystal systems having point group symmetry, TiN does not support altermagnetism. The monolayer of the TiN MXene is a ferromagnetic electride. These unique properties of having non-nuclear interstitial anionic electrons in the electronic structure of titanium nitride MXene have not yet been reported in the literature. Density functional theory calculations show TiN is neither an electride, MXene, or magnetic.
{"title":"Confinement of quasi-atomic structures in Ti2N and Ti3N2 MXene electrides","authors":"Chandra M. Adhikari , Dinesh Thapa , Talon D. Alexander , Christopher K. Addaman , Shubo Han , Bishnu P. Bastakoti , Daniel E. Autrey , Svetlana Kilina , Binod K. Rai , Bhoj Gautam","doi":"10.1016/j.jpcs.2026.113534","DOIUrl":"10.1016/j.jpcs.2026.113534","url":null,"abstract":"<div><div>Metal carbides, nitrides, or carbonitrides of early transition metals, better known as MXenes, possess notable structural, electrical, and magnetic properties. Analyzing electronic structures by calculating structural stability, band structure, density of states, Bader charge transfer, and work functions utilizing first principle calculations, we revealed that titanium nitride MXenes, namely Ti<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>N and Ti<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, have excess anionic electrons in their lattice voids, making them MXene electrides. Bulk Ti<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> has competing antiferromagnetic (AFM) and ferromagnetic (FM) configurations with slightly more stable AFM configuration, while the Ti<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>N MXene is nonmagnetic. Although Ti<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> favors AFM configuration with hexagonal crystal systems having <span><math><mrow><mn>6</mn><mo>/</mo><mi>m</mi><mi>m</mi><mi>m</mi></mrow></math></span> point group symmetry, Ti<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> does not support altermagnetism. The monolayer of the Ti<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> MXene is a ferromagnetic electride. These unique properties of having non-nuclear interstitial anionic electrons in the electronic structure of titanium nitride MXene have not yet been reported in the literature. Density functional theory calculations show TiN is neither an electride, MXene, or magnetic.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113534"},"PeriodicalIF":4.9,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-13DOI: 10.1016/j.jpcs.2026.113537
Ankita Nayak, Sambit Jena, Priyadarshini Parida
<div><div>This work focuses on the thermoelectric behavior of CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>X<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> (X = S, Se, and Te) defect chalcopyrite compounds, carried out using density functional theory (DFT) within the generalized gradient approximation (GGA). The ab-initio structural analysis of these body-centered tetragonal compounds reveals a systematic increase in lattice parameters from CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> to CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Te<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>, along with the deviation from the ideal chalcopyrite structure. CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> exhibits the highest thermodynamic stability, having the lowest cohesive energy. The value of lowest defect formation energy of all the compounds confirmed that the formation of the defects can be done easily. The electronic properties show that all three systems are direct band gap semiconductors. The ductile nature of these compounds is obtained from the elastic behaviors, with CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> having the maximum stiffness. All the compounds are found to be thermally stable at elevated temperature (at 800K) through AIMD calculations. The electronic thermoelectric properties are calculated using the semi-classical Boltzmann transport theory. The thermoelectric parameters are calculated w.r.t. temperature, carrier concentration, and chemical potential, revealing enhanced performance under p-type doping. CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> and CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Se<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> show peak ZT values at high temperatures with a carrier concentration of 10<sup>18</sup> cm<sup>−3</sup>, while CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Te<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> peaks at 10<sup>20</sup> cm<sup>−3</sup>. Using the deformation potential theory and Slack method, the carrier relaxation time and the lattice thermal conductivity are determined, respectively. This study highlights the potential of CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>X<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> compounds as promising ther
{"title":"An ab-initio investigation of Cd-based defect chalcopyrite-type semiconductors: Promising candidates for sustainable energy goals","authors":"Ankita Nayak, Sambit Jena, Priyadarshini Parida","doi":"10.1016/j.jpcs.2026.113537","DOIUrl":"10.1016/j.jpcs.2026.113537","url":null,"abstract":"<div><div>This work focuses on the thermoelectric behavior of CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>X<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> (X = S, Se, and Te) defect chalcopyrite compounds, carried out using density functional theory (DFT) within the generalized gradient approximation (GGA). The ab-initio structural analysis of these body-centered tetragonal compounds reveals a systematic increase in lattice parameters from CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> to CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Te<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>, along with the deviation from the ideal chalcopyrite structure. CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> exhibits the highest thermodynamic stability, having the lowest cohesive energy. The value of lowest defect formation energy of all the compounds confirmed that the formation of the defects can be done easily. The electronic properties show that all three systems are direct band gap semiconductors. The ductile nature of these compounds is obtained from the elastic behaviors, with CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> having the maximum stiffness. All the compounds are found to be thermally stable at elevated temperature (at 800K) through AIMD calculations. The electronic thermoelectric properties are calculated using the semi-classical Boltzmann transport theory. The thermoelectric parameters are calculated w.r.t. temperature, carrier concentration, and chemical potential, revealing enhanced performance under p-type doping. CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> and CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Se<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> show peak ZT values at high temperatures with a carrier concentration of 10<sup>18</sup> cm<sup>−3</sup>, while CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>Te<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> peaks at 10<sup>20</sup> cm<sup>−3</sup>. Using the deformation potential theory and Slack method, the carrier relaxation time and the lattice thermal conductivity are determined, respectively. This study highlights the potential of CdGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>X<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> compounds as promising ther","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113537"},"PeriodicalIF":4.9,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing efficient photo-Fenton catalytic systems represents a promising strategy for degrading organic pollutants in wastewater. In this study, cobalt-loaded metakaolin-based geopolymer microspheres (Co-GM) were successfully prepared using suspension solidification and solution impregnation methods, and their performance in catalytic degradation of various pollutants was systematically evaluated. Experimental results demonstrated that in the Co-GM photo-Fenton system, the degradation rate of Rhodamine B (RhB) with an initial concentration of 20 mg/L reached 92 % within 30 min. The system also exhibited high degradation efficiency for various pollutants, such as ciprofloxacin and azo mixed dyes. Compared with other photo-Fenton catalysts, Co-GM has excellent performance in maintaining over 90 % degradation efficiency across a wide pH range (5–11). Free radical quenching experiments further confirmed that the primary active species involved in the catalytic process were ·OH, ·O2−, and h+, ·OH, ·O2− and h+ contribute 40 %, 60 % and 43 % respectively, with ·O2− being predominant. Moreover, Co-GM showed excellent reusability in cyclic degradation experiments. This study provides new insights into the development of cost-effective, pH-tolerant, and highly stable photo-Fenton catalysts.
{"title":"Degradation of dye by cobalt-loaded metakaolin geopolymer microspheres in broad-pH region","authors":"Qianru Zhao, Changwen Ma, Qiangwei Shi, Ruyan Li, Zhen Tian","doi":"10.1016/j.jpcs.2026.113538","DOIUrl":"10.1016/j.jpcs.2026.113538","url":null,"abstract":"<div><div>Developing efficient photo-Fenton catalytic systems represents a promising strategy for degrading organic pollutants in wastewater. In this study, cobalt-loaded metakaolin-based geopolymer microspheres (Co-GM) were successfully prepared using suspension solidification and solution impregnation methods, and their performance in catalytic degradation of various pollutants was systematically evaluated. Experimental results demonstrated that in the Co-GM photo-Fenton system, the degradation rate of Rhodamine B (RhB) with an initial concentration of 20 mg/L reached 92 % within 30 min. The system also exhibited high degradation efficiency for various pollutants, such as ciprofloxacin and azo mixed dyes. Compared with other photo-Fenton catalysts, Co-GM has excellent performance in maintaining over 90 % degradation efficiency across a wide pH range (5–11). Free radical quenching experiments further confirmed that the primary active species involved in the catalytic process were ·OH, ·O<sub>2</sub><sup>−</sup>, and h<sup>+</sup>, ·OH, ·O<sub>2</sub><sup>−</sup> and h<sup>+</sup> contribute 40 %, 60 % and 43 % respectively, with ·O<sub>2</sub><sup>−</sup> being predominant. Moreover, Co-GM showed excellent reusability in cyclic degradation experiments. This study provides new insights into the development of cost-effective, pH-tolerant, and highly stable photo-Fenton catalysts.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113538"},"PeriodicalIF":4.9,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-13DOI: 10.1016/j.jpcs.2026.113535
Jaysen Brian Susanto , Iman Santoso , Tzu-Jen Lin
Graphitic heptazine carbon nitride (g-h-C3N4) has garnered significant interest as a UV–visible light-driven photocatalyst due to its high thermal stability and semiconductor-like properties, making it a promising eco-friendly material for pollutant degradation. To enhance its photocatalytic performance, various strategies have been explored, including the introduction of dopants (or co-dopants) with non-metal elements such as oxygen (O), sulfur (S), and phosphorus (P). Thus, determining the electronic and optical properties, such as the Density of States (DOS) and Optical Conductivity (OPC), may provide more valuable insights. This study adopts the Trotter-Suzuki and Tight-Binding Time Propagation Method (TS-TBTPM) for real-space analysis of the pristine and non-metal doped g-h-C3N4 exceeding ∼1000000 atoms. Regarding our calculation results, the non-metal-doped g-h-C3N4 exhibits the emergence of additional VHS (Van Hove Singularities) as mid-gap states in the DOS, and a significant alteration of the OPC profile through red shifts. Additionally, the TS-TBTPM exhibits better resolution in the calculated DOS and OPC compared to the density functional theory (DFT) calculation. Moreover, our studies elucidate how the combined effects of multiple dopant types influence material properties, explaining the synergistic effects observed in experiments. Therefore, our findings confirm that non-metal dopants effectively tune the electronic and optical properties of g-h-C3N4, emphasizing the potential for future photocatalyst applications and optoelectronic material design.
{"title":"Using Trotter-Suzuki and Tight-Binding Time Propagation Method to calculate density of states and optical conductivity of non-metal doped graphitic heptazine carbon nitride","authors":"Jaysen Brian Susanto , Iman Santoso , Tzu-Jen Lin","doi":"10.1016/j.jpcs.2026.113535","DOIUrl":"10.1016/j.jpcs.2026.113535","url":null,"abstract":"<div><div>Graphitic heptazine carbon nitride (g-h-C<sub>3</sub>N<sub>4</sub>) has garnered significant interest as a UV–visible light-driven photocatalyst due to its high thermal stability and semiconductor-like properties, making it a promising eco-friendly material for pollutant degradation. To enhance its photocatalytic performance, various strategies have been explored, including the introduction of dopants (or co-dopants) with non-metal elements such as oxygen (O), sulfur (S), and phosphorus (P). Thus, determining the electronic and optical properties, such as the Density of States (DOS) and Optical Conductivity (OPC), may provide more valuable insights. This study adopts the Trotter-Suzuki and Tight-Binding Time Propagation Method (TS-TBTPM) for real-space analysis of the pristine and non-metal doped g-h-C<sub>3</sub>N<sub>4</sub> exceeding ∼1000000 atoms. Regarding our calculation results, the non-metal-doped g-h-C<sub>3</sub>N<sub>4</sub> exhibits the emergence of additional VHS (Van Hove Singularities) as mid-gap states in the DOS, and a significant alteration of the OPC profile through red shifts. Additionally, the TS-TBTPM exhibits better resolution in the calculated DOS and OPC compared to the density functional theory (DFT) calculation. Moreover, our studies elucidate how the combined effects of multiple dopant types influence material properties, explaining the synergistic effects observed in experiments. Therefore, our findings confirm that non-metal dopants effectively tune the electronic and optical properties of g-h-C<sub>3</sub>N<sub>4</sub>, emphasizing the potential for future photocatalyst applications and optoelectronic material design.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113535"},"PeriodicalIF":4.9,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-12DOI: 10.1016/j.jpcs.2026.113533
Hafiz Muhammad Naeem , Muhammad Adeel Tariq , Giedrius Stalnionis , Muhammad Abdul Basit , Loreta Tamašauskaitė-Tamašiūnaitė , Eugenijus Norkus , Ramūnas Levinas
Efficient and durable catalysts are essential for sustainable energy conversion via electrochemical water splitting. MoS2 is a promising candidate with abundant hydrogen adsorption sites, but its limited water dissociation kinetics hinder HER in alkaline media. Conversely, Co(OH)2 exhibits superior water dissociation performance, but lacks hydrogen adsorption activity. To address these limitations, we present a top-down electrochemical synthesis approach for a porous MoS2@Co(OH)2 hybrid structure, enabling synergistic performance for bifunctional water splitting. SEM reveals a sponge-like morphology that facilitates mass transport and electrolyte accessibility. Hydrogen evolution requires only an overpotential of 226 mV to reach 10 mA/cm2, due to the complementary roles of MoS2 in facilitating hydrogen adsorption/recombination and Co(OH)2 in accelerating water dissociation. XPS confirms Mo4+/Mo6+ and M-O-S species that can synergistically enhance adsorption-desorption. For OER, the hybrid catalyst reaches an overpotential of 341 mV at 10 mA/cm2, with excellent stability over 24 h. In overall water splitting, the Faradaic efficiencies were 94 % for H2 and 96 % for O2. The cell voltage of 1.86V for M0.6@C1 ||M1@C1 accentuates MoS2@Co(OH)2 as a promising bifunctional electrocatalyst. The design strategy presented herein unveils a broadly applicable approach for designing hybrid surface architectures via electrochemical top-down synthesis for advanced energy conversion systems.
{"title":"Engineering sponge-like MoS2@Co(OH)2 hybrid structures as efficient non-precious metal catalysts for overall alkaline water splitting","authors":"Hafiz Muhammad Naeem , Muhammad Adeel Tariq , Giedrius Stalnionis , Muhammad Abdul Basit , Loreta Tamašauskaitė-Tamašiūnaitė , Eugenijus Norkus , Ramūnas Levinas","doi":"10.1016/j.jpcs.2026.113533","DOIUrl":"10.1016/j.jpcs.2026.113533","url":null,"abstract":"<div><div>Efficient and durable catalysts are essential for sustainable energy conversion via electrochemical water splitting. MoS<sub>2</sub> is a promising candidate with abundant hydrogen adsorption sites, but its limited water dissociation kinetics hinder HER in alkaline media. Conversely, Co(OH)<sub>2</sub> exhibits superior water dissociation performance, but lacks hydrogen adsorption activity. To address these limitations, we present a top-down electrochemical synthesis approach for a porous MoS<sub>2</sub>@Co(OH)<sub>2</sub> hybrid structure, enabling synergistic performance for bifunctional water splitting. SEM reveals a sponge-like morphology that facilitates mass transport and electrolyte accessibility. Hydrogen evolution requires only an overpotential of 226 mV to reach 10 mA/cm<sup>2</sup>, due to the complementary roles of MoS<sub>2</sub> in facilitating hydrogen adsorption/recombination and Co(OH)<sub>2</sub> in accelerating water dissociation. XPS confirms Mo<sup>4+</sup>/Mo<sup>6+</sup> and M-O-S species that can synergistically enhance adsorption-desorption. For OER, the hybrid catalyst reaches an overpotential of 341 mV at 10 mA/cm<sup>2</sup>, with excellent stability over 24 h. In overall water splitting, the Faradaic efficiencies were 94 % for H<sub>2</sub> and 96 % for O<sub>2</sub>. The cell voltage of 1.86V for <span><span>M0.6@C1</span><svg><path></path></svg></span> ||M1@C1 accentuates MoS<sub>2</sub>@Co(OH)<sub>2</sub> as a promising bifunctional electrocatalyst. The design strategy presented herein unveils a broadly applicable approach for designing hybrid surface architectures via electrochemical top-down synthesis for advanced energy conversion systems.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113533"},"PeriodicalIF":4.9,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Halide perovskites have gained significant attention as multifunctional materials for next-generation solar energy and hydrogen production technologies. In this work, we explore a series of mixed halide RbSn-based perovskites derived from RbSnCl3 by partial substitution of Cl with Br and I (RbSnCl2X and RbSnClX2; X = Br, I), investigating their structural, electronic, optical, and photocatalytic properties using first-principles DFT calculations. All studied compounds are thermodynamically stable and exhibit direct band gaps, which decrease from 1.49 eV to 1.06 eV with increasing halide substitution, favoring visible-light absorption. Optical analyses reveal low reflectivity and strong absorption across the visible range. Based on the calculated band-edge alignment with respect to water redox potentials, the materials exhibit thermodynamic feasibility for photocatalytic water splitting. The calculated solar-to-hydrogen (STH) efficiencies reach up to 11,6 %, 12,7 %, 13,5 % and 15.7 % for RbSnCl2Br, RbSnClBr2, RbSnCl2I and RbSnClI2, respectively, suggesting that these compounds may serve as potential candidates for visible-light photovoltaic applications and photocatalytic hydrogen production. These findings highlight the promise of halogen-substituted Rb-based perovskites emerge as promising materials for integrated clean energy technologies.
卤化物钙钛矿作为下一代太阳能和制氢技术的多功能材料受到了广泛关注。在这项工作中，我们探索了一系列混合卤化物rbsn基钙钛矿，这些钙钛矿是通过Br和I部分取代Cl而得到的（RbSnCl2X和RbSnClX2； X = Br， I），利用第一性原理DFT计算研究了它们的结构、电子、光学和光催化性质。所有化合物热力学稳定，并表现出直接带隙，随着卤化物取代量的增加，带隙从1.49 eV减小到1.06 eV，有利于可见光吸收。光学分析显示低反射率和强吸收在可见光范围内。基于计算的水氧化还原电位的带边对准，材料表现出光催化水分解的热力学可行性。计算得到的RbSnCl2Br、RbSnClBr2、RbSnCl2I和RbSnClI2的太阳能制氢效率分别高达11.6%、12.7%、12.7%、13.5%和15.7%，这表明这些化合物可能是可见光光伏应用和光催化制氢的潜在候选化合物。这些发现突出了卤素取代铷基钙钛矿作为综合清洁能源技术的有前途的材料的前景。
{"title":"Lead-free RbSnCl3-Based halide perovskites for solar-to-hydrogen conversion: Insights from DFT calculations","authors":"Imane Laazizi , Boujemaa Jaber , Nejma Fazouan , Larbi Laanab","doi":"10.1016/j.jpcs.2026.113531","DOIUrl":"10.1016/j.jpcs.2026.113531","url":null,"abstract":"<div><div>Halide perovskites have gained significant attention as multifunctional materials for next-generation solar energy and hydrogen production technologies. In this work, we explore a series of mixed halide RbSn-based perovskites derived from RbSnCl<sub>3</sub> by partial substitution of Cl with Br and I (RbSnCl<sub>2</sub>X and RbSnClX<sub>2</sub>; X = Br, I), investigating their structural, electronic, optical, and photocatalytic properties using first-principles DFT calculations. All studied compounds are thermodynamically stable and exhibit direct band gaps, which decrease from 1.49 eV to 1.06 eV with increasing halide substitution, favoring visible-light absorption. Optical analyses reveal low reflectivity and strong absorption across the visible range. Based on the calculated band-edge alignment with respect to water redox potentials, the materials exhibit thermodynamic feasibility for photocatalytic water splitting. The calculated solar-to-hydrogen (STH) efficiencies reach up to 11,6 %, 12,7 %, 13,5 % and 15.7 % for RbSnCl<sub>2</sub>Br, RbSnClBr<sub>2</sub>, RbSnCl<sub>2</sub>I and RbSnClI<sub>2</sub>, respectively, suggesting that these compounds may serve as potential candidates for visible-light photovoltaic applications and photocatalytic hydrogen production. These findings highlight the promise of halogen-substituted Rb-based perovskites emerge as promising materials for integrated clean energy technologies.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113531"},"PeriodicalIF":4.9,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-10DOI: 10.1016/j.jpcs.2026.113518
Samriti Mehta , Rajni Thakur , Rohit Kumar , S. Sumanth Dongre , R. Shwetharani , Itika Kainthla
Transition metal dichalcogenides (TMDs) are attracting increasing attention as tunable materials with promising catalytic properties. This study presents Mo1-xWxSSe synthesized via the hydrothermal method as an electrocatalyst for the HER, demonstrating excellent activity in an acidic medium. Electrochemical measurements highlight that Mo50W50SSe displayed an onset potential of 12 mV and an overpotential of 228 mV at 10 mA cm−2. Additionally, Mo50W50SSe exhibits a high electrochemically active surface area of 458.64 cm2 and high double-layer capacitance (Cdl), along with low charge transfer resistance (RCT) compared to its counterparts. The enhanced performance of Mo50W50SSe arises from the synergistic Mo–W interaction, increase active sites, improve electron transfer, expose basal planes, and lower charge-transfer resistance. Furthermore, the catalyst exhibited good stability over 14 h. This work provides valuable insights into designing advanced TMD-based electrocatalysts for efficient and durable hydrogen generation and also aligns with SDG 7 (Affordable and clean energy) and SDG 13 (Climate action).
过渡金属二硫族化合物（TMDs）作为一种具有良好催化性能的可调材料越来越受到人们的关注。本研究采用水热法合成Mo1-xWxSSe作为HER的电催化剂，在酸性介质中表现出优异的活性。电化学测量表明，Mo50W50SSe在10 mA cm−2下的起始电位为12 mV，过电位为228 mV。此外，与同类材料相比，Mo50W50SSe具有458.64 cm2的高电化学活性表面积和高双层电容（Cdl），以及低电荷转移电阻（RCT）。Mo50W50SSe性能的增强是由于Mo-W相互作用的协同作用，增加了活性位点，改善了电子转移，暴露了基面，降低了电荷转移电阻。此外，该催化剂在14小时内表现出良好的稳定性。这项工作为设计先进的基于tmd的电催化剂提供了有价值的见解，这些电催化剂可用于高效和耐用的制氢，并符合可持续发展目标7（负担得起的清洁能源）和可持续发展目标13（气候行动）。
{"title":"Phase evolution and HER activity in MoWSSe multiphase transition metal dichalcogenides","authors":"Samriti Mehta , Rajni Thakur , Rohit Kumar , S. Sumanth Dongre , R. Shwetharani , Itika Kainthla","doi":"10.1016/j.jpcs.2026.113518","DOIUrl":"10.1016/j.jpcs.2026.113518","url":null,"abstract":"<div><div>Transition metal dichalcogenides (TMDs) are attracting increasing attention as tunable materials with promising catalytic properties. This study presents Mo<sub>1-x</sub>W<sub>x</sub>SSe synthesized via the hydrothermal method as an electrocatalyst for the HER, demonstrating excellent activity in an acidic medium. Electrochemical measurements highlight that Mo<sub>50</sub>W<sub>50</sub>SSe displayed an onset potential of 12 mV and an overpotential of 228 mV at 10 mA cm<sup>−2</sup>. Additionally, Mo<sub>50</sub>W<sub>50</sub>SSe exhibits a high electrochemically active surface area of 458.64 cm<sup>2</sup> and high double-layer capacitance (<em>C</em><sub><em>dl</em></sub>), along with low charge transfer resistance (<em>R</em><sub><em>CT</em></sub>) compared to its counterparts. The enhanced performance of Mo<sub>50</sub>W<sub>50</sub>SSe arises from the synergistic Mo–W interaction, increase active sites, improve electron transfer, expose basal planes, and lower charge-transfer resistance. Furthermore, the catalyst exhibited good stability over 14 h. This work provides valuable insights into designing advanced TMD-based electrocatalysts for efficient and durable hydrogen generation and also aligns with SDG 7 (Affordable and clean energy) and SDG 13 (Climate action).</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113518"},"PeriodicalIF":4.9,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-10DOI: 10.1016/j.jpcs.2026.113532
A. Erraji , R. Masrour , L. Xu , Rajwali Khan
The structural, electrochemical, thermodynamic, thermoelectric properties and optical properties of Li0.5Na0.5Mn2O4 have been investigated by first-principles calculations based on DFT. The calculated lattice constant for Li0.5Na0.5Mn2O4 is 9.83 μB. The volume of Na0.5Mn2O4 changes by 13 % with insertion/extraction of lithium. The voltage given by the battery is 2.12 V vs. Li+/Li at 0 K, the capacity is 141 mAh.g−1 and the energy density is 300 W kg−1. The sodium (Na+) doping suppresses the Jahn-Teller distortion induced by Mn3+ in LiMn2O4, which significantly improves capacity retention and cycle stability despite a slight decrease in maximum capacity. The Li0.5Na0.5Mn2O4 compound exhibits a direct band gap of 2.15 eV using GGA-PBE and 2.18 eV using the DFT + U method. This confirms that these compounds are thermodynamically stable. The volume of the Li0.5Na0.5Mn2O4 cell changed by 23 % as the temperature was increased from 0 K to 1000 K. The heat capacity of Li0.5Na0.5Mn2O4 is measured at 350 J/mol K. As a result, Li0.5Na0.5Mn2O4 has various properties that make it suitable to be used as a cathode material in Li-ion batteries. The static dielectric constant for Li0.5Na0.5Mn2O4 compound is 92.43. In addition, the compound shows excellent absorption, refractive index and extinction coefficient in the visible region.
采用基于DFT的第一性原理计算方法研究了Li0.5Na0.5Mn2O4的结构、电化学、热力学、热电性质和光学性质。计算得到Li0.5Na0.5Mn2O4的晶格常数为9.83 μB。随着锂离子的加入和萃取，Na0.5Mn2O4的体积变化了13%。电池给出的电压为2.12 V vs. Li+/Li在0 K时，容量为141 mAh。g−1，能量密度300w kg−1。钠（Na+）的掺杂抑制了Mn3+在LiMn2O4中引起的Jahn-Teller畸变，显著提高了LiMn2O4的容量保留率和循环稳定性，但最大容量略有下降。采用GGA-PBE法和DFT + U法，Li0.5Na0.5Mn2O4化合物的直接带隙分别为2.15 eV和2.18 eV。这证实了这些化合物是热力学稳定的。当温度从0 K升高到1000 K时，Li0.5Na0.5Mn2O4电池的体积变化了23%。在350 J/mol k下测得Li0.5Na0.5Mn2O4的热容量。结果表明，Li0.5Na0.5Mn2O4具有多种性能，适合作为锂离子电池的正极材料。Li0.5Na0.5Mn2O4化合物的静态介电常数为92.43。此外，该化合物在可见光区具有良好的吸收、折射率和消光系数。
{"title":"First-principles investigation of Na-doped LiMn2O4: Structural, electrochemical, thermodynamic, thermoelectric, and optical properties","authors":"A. Erraji , R. Masrour , L. Xu , Rajwali Khan","doi":"10.1016/j.jpcs.2026.113532","DOIUrl":"10.1016/j.jpcs.2026.113532","url":null,"abstract":"<div><div>The structural, electrochemical, thermodynamic, thermoelectric properties and optical properties of Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> have been investigated by first-principles calculations based on DFT. The calculated lattice constant for Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> is 9.83 μ<sub>B</sub>. The volume of Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> changes by 13 % with insertion/extraction of lithium. The voltage given by the battery is 2.12 V vs. Li<sup>+</sup>/Li at 0 K, the capacity is 141 mAh.g<sup>−1</sup> and the energy density is 300 W kg<sup>−1</sup>. The sodium (Na<sup>+</sup>) doping suppresses the Jahn-Teller distortion induced by Mn<sup>3+</sup> in LiMn<sub>2</sub>O<sub>4</sub>, which significantly improves capacity retention and cycle stability despite a slight decrease in maximum capacity. The Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> compound exhibits a direct band gap of 2.15 eV using GGA-PBE and 2.18 eV using the DFT + U method. This confirms that these compounds are thermodynamically stable. The volume of the Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> cell changed by 23 % as the temperature was increased from 0 K to 1000 K. The heat capacity of Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> is measured at 350 J/mol K. As a result, Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> has various properties that make it suitable to be used as a cathode material in Li-ion batteries. The static dielectric constant for Li<sub>0.5</sub>Na<sub>0.5</sub>Mn<sub>2</sub>O<sub>4</sub> compound is 92.43. In addition, the compound shows excellent absorption, refractive index and extinction coefficient in the visible region.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113532"},"PeriodicalIF":4.9,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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