This study investigates the potential use of volcanic ash (VA) material from Mount Cameroon as an adsorbent for the removal of selenium (VI) from contaminated solutions. Selenium-sorbed materials were synthesized via a batch adsorption method, and the resulting samples were characterized using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray absorption spectroscopy (XAS). The results suggest that Se-sorbed VA material can adopt the local structure of CaSeO₃ and its chemical composition was associated with CaSeO₃, Na₂SeO₃, and Na₂SeO₄. The adsorption mechanisms were related to ion exchange, adsorption, and chemical reduction. Langmuir model was found to be suitable for the adsorption data indicating that the surface of VA adsorbent presents monolayer and homogeneous actives sites. XAS technique could be applied to track changes in oxidation state, resolve the adsorption mechanism, and identify the chemical species and local structure of the sorbed element in the adsorbent material.
{"title":"Selenium (VI) removal by volcanic ash material characterized by X-ray absorption spectroscopy","authors":"Gristianho Lontin Lontin , Bridinette Thiodjio Sendja , Carol Trudel Tchouank Tekou , Giuliana Aquilanti , Hubert Germain Ben-Bolie","doi":"10.1016/j.susc.2025.122856","DOIUrl":"10.1016/j.susc.2025.122856","url":null,"abstract":"<div><div>This study investigates the potential use of volcanic ash (VA) material from Mount Cameroon as an adsorbent for the removal of selenium (VI) from contaminated solutions. Selenium-sorbed materials were synthesized via a batch adsorption method, and the resulting samples were characterized using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray absorption spectroscopy (XAS). The results suggest that Se-sorbed VA material can adopt the local structure of CaSeO₃ and its chemical composition was associated with CaSeO₃, Na₂SeO₃, and Na₂SeO₄. The adsorption mechanisms were related to ion exchange, adsorption, and chemical reduction. Langmuir model was found to be suitable for the adsorption data indicating that the surface of VA adsorbent presents monolayer and homogeneous actives sites. XAS technique could be applied to track changes in oxidation state, resolve the adsorption mechanism, and identify the chemical species and local structure of the sorbed element in the adsorbent material.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122856"},"PeriodicalIF":1.8,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145220866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-02DOI: 10.1016/j.susc.2025.122859
Jinghao Wang , Guili Liu , Xiaotong Yang , Jianlin He , Guoying Zhang
The modulation mechanism of biaxial strain (-9 % to 9 %) on the structural stability, electronic properties, and optical properties of Janus monolayer MoTeSe is systematically investigated based on first-principles density functional theory calculations. The pristine monolayer exhibits a direct bandgap of 1.277 eV. Under biaxial tensile strain, the bandgap narrows significantly, decreasing from 1.277 eV to 0.021 eV, thereby enhancing carrier mobility. Notably, a semiconductor-to-metal transition occurs at 9 % tensile strain. Conversely, biaxial compressive strain induces a shift from a direct to an indirect bandgap. Optical analysis reveals that tensile strain causes a red shift in the absorption peaks and relocates energy loss to lower energies. In contrast, compressive strain induces a blue shift in absorption, substantially increasing the absorption coefficient (from 1.062 × 105cm-1 to 1.278 × 105cm-1) and light-harvesting capability. Additionally, compressive strain elevates the static dielectric constant, reaching 3.061 at -9 % strain. The study reveals the role of biaxial strain in modulating the optoelectronic properties of Janus MoTeSe. It provides a theoretical basis for the design of tunable optoelectronic devices based on strain engineering.
{"title":"Biaxial strain modulating optoelectronic responses in Janus MoTeSe monolayers","authors":"Jinghao Wang , Guili Liu , Xiaotong Yang , Jianlin He , Guoying Zhang","doi":"10.1016/j.susc.2025.122859","DOIUrl":"10.1016/j.susc.2025.122859","url":null,"abstract":"<div><div>The modulation mechanism of biaxial strain (-9 % to 9 %) on the structural stability, electronic properties, and optical properties of Janus monolayer MoTeSe is systematically investigated based on first-principles density functional theory calculations. The pristine monolayer exhibits a direct bandgap of 1.277 eV. Under biaxial tensile strain, the bandgap narrows significantly, decreasing from 1.277 eV to 0.021 eV, thereby enhancing carrier mobility. Notably, a semiconductor-to-metal transition occurs at 9 % tensile strain. Conversely, biaxial compressive strain induces a shift from a direct to an indirect bandgap. Optical analysis reveals that tensile strain causes a red shift in the absorption peaks and relocates energy loss to lower energies. In contrast, compressive strain induces a blue shift in absorption, substantially increasing the absorption coefficient (from 1.062 × 10<sup>5</sup>cm<sup>-1</sup> to 1.278 × 10<sup>5</sup>cm<sup>-1</sup>) and light-harvesting capability. Additionally, compressive strain elevates the static dielectric constant, reaching 3.061 at -9 % strain. The study reveals the role of biaxial strain in modulating the optoelectronic properties of Janus MoTeSe. It provides a theoretical basis for the design of tunable optoelectronic devices based on strain engineering.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"764 ","pages":"Article 122859"},"PeriodicalIF":1.8,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The adsorption of multiple hydrogen molecules on two different types of heptazine-based graphitic carbon nitride nanotubes (hg‒C3N4‒NTs), namely armchair (3,3) and zigzag (6,0) hg‒C3N4‒NTs, decorated with Al atom, was investigated using the periodic DFT method. The first hydrogen molecule adsorbed on all outer surfaces of Al-decorated hg‒C3N4‒NTs was found to be a dissociative H2 chemisorption and exhibited significantly stronger interaction than subsequent hydrogen molecules (the second to fourth). Notably, the first hydrogen molecule adsorbed on Al-decorated on armchair (3,3) and zigzag (6,0) hg‒C3N4‒NTs demonstrated high potential for hydrogen storage, with the strongest chemisorption observed on Al-decorated zigzag (6,0) hg‒C3N4‒NT, which exhibited an adsorption energy of -1.89 eV. Furthermore, the corresponding pristine armchair (3,3) and zigzag (6,0) hg‒C3N4‒NTs can serve as representative molecular models for the hg‒C3N4‒NTs.
{"title":"A DFT investigation of hydrogen adsorption onto the Al-decorated heptazine-based g-C3N4 nanotubes","authors":"Kanthira Kaewsud , Beate Paulus , Viwat Vchirawongkwin , Vithaya Ruangpornvisuti","doi":"10.1016/j.susc.2025.122858","DOIUrl":"10.1016/j.susc.2025.122858","url":null,"abstract":"<div><div>The adsorption of multiple hydrogen molecules on two different types of heptazine-based graphitic carbon nitride nanotubes (hg‒C<sub>3</sub>N<sub>4</sub>‒NTs), namely armchair (3,3) and zigzag (6,0) hg‒C<sub>3</sub>N<sub>4</sub>‒NTs, decorated with Al atom, was investigated using the periodic DFT method. The first hydrogen molecule adsorbed on all outer surfaces of Al-decorated hg‒C<sub>3</sub>N<sub>4</sub>‒NTs was found to be a dissociative H<sub>2</sub> chemisorption and exhibited significantly stronger interaction than subsequent hydrogen molecules (the second to fourth). Notably, the first hydrogen molecule adsorbed on Al-decorated on armchair (3,3) and zigzag (6,0) hg‒C<sub>3</sub>N<sub>4</sub>‒NTs demonstrated high potential for hydrogen storage, with the strongest chemisorption observed on Al-decorated zigzag (6,0) hg‒C<sub>3</sub>N<sub>4</sub>‒NT, which exhibited an adsorption energy of -1.89 eV. Furthermore, the corresponding pristine armchair (3,3) and zigzag (6,0) hg‒C<sub>3</sub>N<sub>4</sub>‒NTs can serve as representative molecular models for the hg‒C<sub>3</sub>N<sub>4</sub>‒NTs.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"764 ","pages":"Article 122858"},"PeriodicalIF":1.8,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145236390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01DOI: 10.1016/j.susc.2025.122857
Jamelah S. Al-Otaibi , Y. Sheena Mary , Martin Krátký , Jarmila Vinsova , Maria Cristina Gamberini
The search for effective molecular probes and drug candidates requires a clear understanding of their structural, spectroscopic, and biological behavior. In this work, we investigated 2-methylene-4-oxo-4-[(3,4,5-trichlorophenyl)amino]butanoic acid (MTB) through a combination of experimental and computational approaches. Surface-enhanced Raman scattering (SERS) was measured at different concentrations, while theoretical SERS simulations were performed with Ag6 clusters positioned at the most reactive sites of the molecule. Density functional theory (DFT) calculations, molecular docking, and molecular dynamics (MD) simulations were further employed to explore the electronic properties and binding interactions of MTB with the 4Z8D protein, both in its free form and when complexed with silver clusters. The results show that MTB binds strongly to Ag atoms through chemisorptions and adopts a tilted orientation that changes with concentration. Among the protein-ligand systems, the 4Z8D-MTB-Ag6-W1 complex was the most stable, stabilized by a combination of lipophilic, electrostatic, and hydrogen-bonding interactions. These findings highlight MTB as a promising bioactive-candidate whose performance is enhanced in the presence of silver clusters, offering useful insights for drug design and therapeutic development.
{"title":"SERS, docking and MD simulations of 2-methylene-4-oxo-4-[(3,4,5-trichlorophenyl)amino]butanoic acid (MTB): experimental and DFT modeling","authors":"Jamelah S. Al-Otaibi , Y. Sheena Mary , Martin Krátký , Jarmila Vinsova , Maria Cristina Gamberini","doi":"10.1016/j.susc.2025.122857","DOIUrl":"10.1016/j.susc.2025.122857","url":null,"abstract":"<div><div>The search for effective molecular probes and drug candidates requires a clear understanding of their structural, spectroscopic, and biological behavior. In this work, we investigated 2-methylene-4-oxo-4-[(3,4,5-trichlorophenyl)amino]butanoic acid (MTB) through a combination of experimental and computational approaches. Surface-enhanced Raman scattering (SERS) was measured at different concentrations, while theoretical SERS simulations were performed with Ag<sub>6</sub> clusters positioned at the most reactive sites of the molecule. Density functional theory (DFT) calculations, molecular docking, and molecular dynamics (MD) simulations were further employed to explore the electronic properties and binding interactions of MTB with the 4Z8D protein, both in its free form and when complexed with silver clusters. The results show that MTB binds strongly to Ag atoms through chemisorptions and adopts a tilted orientation that changes with concentration. Among the protein-ligand systems, the 4Z8D-MTB-Ag<sub>6</sub>-W1 complex was the most stable, stabilized by a combination of lipophilic, electrostatic, and hydrogen-bonding interactions. These findings highlight MTB as a promising bioactive-candidate whose performance is enhanced in the presence of silver clusters, offering useful insights for drug design and therapeutic development.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"764 ","pages":"Article 122857"},"PeriodicalIF":1.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-19DOI: 10.1016/j.susc.2025.122855
Athira P , Robert Güttel , Koustuv Ray
Conventionally, iron catalysts produce a variety of in-situ carbides, which are sometimes identified as the active phase in CO2 and CO hydrogenation, Reverse water gas shift (RWGS) and Fischer–Tropsch synthesis (FTS) reactions. However, the key questions arise towards the role of surface Fe and C atoms of iron carbides towards CO2 and CO activation. Spin-polarised Density Functional Theory (DFT) calculations performed on Fe metal and Fe-C-terminated surfaces of η-Fe2C, θ-Fe3C, and χ-Fe5C2 iron carbides reveal that, (i) surface carbon brings more stability to Fe-C-terminated surfaces compared to Fe-terminated iron carbides and metallic iron, (ii) Fe-terminated iron carbides and metallic iron are more conducive towards the exothermic CO2, CO adsorption than the Fe-C-terminated iron carbides. Moreover, electronic structure analysis unveils that Fe-C-terminated surfaces are comparatively less reactive due to the occurrence of the d-band center very far from the Fermi Level. Furthermore, moderately stable Fe(110) is found as the most preferred surface, favouring direct dissociation of both CO2 and CO kinetically and thermodynamically compared to all carbides considered. Overall, this study systematically analysed the role of surface energy, termination, surface Fe/C ratio, and surface C atom in iron carbides on the activation of CO2 and CO.
{"title":"Surface-dependent CO2 and CO activation on iron and iron carbides: Insights from density functional theory","authors":"Athira P , Robert Güttel , Koustuv Ray","doi":"10.1016/j.susc.2025.122855","DOIUrl":"10.1016/j.susc.2025.122855","url":null,"abstract":"<div><div>Conventionally, iron catalysts produce a variety of <em>in-situ</em> carbides, which are sometimes identified as the active phase in CO<sub>2</sub> and CO hydrogenation, Reverse water gas shift (RWGS) and Fischer–Tropsch synthesis (FTS) reactions. However, the key questions arise towards the role of surface Fe and C atoms of iron carbides towards CO<sub>2</sub> and CO activation. Spin-polarised Density Functional Theory (DFT) calculations performed on Fe metal and Fe-C-terminated surfaces of <em>η</em>-Fe<sub>2</sub>C, <em>θ</em>-Fe<sub>3</sub>C, and <em>χ</em>-Fe<sub>5</sub>C<sub>2</sub> iron carbides reveal that, (i) surface carbon brings more stability to Fe-C-terminated surfaces compared to Fe-terminated iron carbides and metallic iron, (ii) Fe-terminated iron carbides and metallic iron are more conducive towards the exothermic CO<sub>2</sub>, CO adsorption than the Fe-C-terminated iron carbides. Moreover, electronic structure analysis unveils that Fe-C-terminated surfaces are comparatively less reactive due to the occurrence of the d-band center very far from the Fermi Level. Furthermore, moderately stable Fe(110) is found as the most preferred surface, favouring direct dissociation of both CO<sub>2</sub> and CO kinetically and thermodynamically compared to all carbides considered. Overall, this study systematically analysed the role of surface energy, termination, surface Fe/C ratio, and surface C atom in iron carbides on the activation of CO<sub>2</sub> and CO.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122855"},"PeriodicalIF":1.8,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145159177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-19DOI: 10.1016/j.susc.2025.122854
Qi Liu, Xianquan Ao, Cuiqin Li, Dilan Cheng
Flotation is an indispensable approach for efficiently separating gangue minerals from phosphate rock, with significant implications for the development and utilization of mineral resources in a highly efficient and sustainable manner. The Al and Fe elements are incorporated as impurity defects within quartz crystals, which alter the physicochemical properties of quartz minerals and subsequently influence their flotation behavior. The present study investigated the impact of Al and Fe impurity defects on the crystal structure, electronic characteristics, and surface wettability of α-quartz through density function theory (DFT). The calculation results suggest that the α-quartz with impurity defects alter the structure crystal and electronic structure properties of α-quartz. The presence of impurity defect further raises the adsorption energy of the H2O molecule and decreases the interaction between the α-quartz (101) surface and the H2O molecule. In addition, the wettability of α-quartz (101) hydrated surface treated with Al3+ and Fe3+ and its adsorption effect on the H2O molecule or oleate ion (OL-) were studied by DFT and experimental. The findings testify that OL- can be adsorbed on α-quartz (101) hydrated surface via Al3+ and Fe3+, thereby enhancing the hydrophobicity of quartz surface and improving natural flotation recovery. The computational prediction was validated by experimental results. Consequently, the existence of Al and Fe impurities/cations can improve the surface wettability of α-quartz, which is conducive to enhancing the natural floatability and provides valuable guidance for the flotation process.
{"title":"Adsorption mechanism of H2O/oleate on α-quartz (101) surface with Al and Fe impurities/cations: DFT study and experimental verification","authors":"Qi Liu, Xianquan Ao, Cuiqin Li, Dilan Cheng","doi":"10.1016/j.susc.2025.122854","DOIUrl":"10.1016/j.susc.2025.122854","url":null,"abstract":"<div><div>Flotation is an indispensable approach for efficiently separating gangue minerals from phosphate rock, with significant implications for the development and utilization of mineral resources in a highly efficient and sustainable manner. The Al and Fe elements are incorporated as impurity defects within quartz crystals, which alter the physicochemical properties of quartz minerals and subsequently influence their flotation behavior. The present study investigated the impact of Al and Fe impurity defects on the crystal structure, electronic characteristics, and surface wettability of α-quartz through density function theory (DFT). The calculation results suggest that the α-quartz with impurity defects alter the structure crystal and electronic structure properties of α-quartz. The presence of impurity defect further raises the adsorption energy of the H<sub>2</sub>O molecule and decreases the interaction between the α-quartz (101) surface and the H<sub>2</sub>O molecule. In addition, the wettability of α-quartz (101) hydrated surface treated with Al<sup>3+</sup> and Fe<sup>3+</sup> and its adsorption effect on the H<sub>2</sub>O molecule or oleate ion (OL<sup>-</sup>) were studied by DFT and experimental. The findings testify that OL<sup>-</sup> can be adsorbed on α-quartz (101) hydrated surface via Al<sup>3+</sup> and Fe<sup>3+</sup>, thereby enhancing the hydrophobicity of quartz surface and improving natural flotation recovery. The computational prediction was validated by experimental results. Consequently, the existence of Al and Fe impurities/cations can improve the surface wettability of α-quartz, which is conducive to enhancing the natural floatability and provides valuable guidance for the flotation process.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122854"},"PeriodicalIF":1.8,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118878","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-17DOI: 10.1016/j.susc.2025.122853
Heloisa H.P. Silva , Matheus R.B. do Amaral , Angelo L. Gobbi , Carlos A.R. Costa , Edson R. Leite , Jefferson Bettini
In this work, the reproducibility of the magnetron sputtering technique was studied for more than three years using three sets of metallic glass samples grown by co-deposition of Zr and Cu. The reproducibility of metallic glasses or amorphous thin films is particularly critical due to their sensitivity to composition and structure. The analysis was made considering composition and deposition rate variation among the three sets and among the samples with different compositions of ZrxCu1-x and pure Zr and Cu. The composition was measured using Energy Dispersive Spectroscopy and Electron Energy Loss Spectroscopy, and the deposition rate was analyzed by Atomic Force Microscopy. The electron Pair Distribution Function was used to study the structural variation among the three sets and the samples in each set. Finally, the oxygen incorporation in the samples was investigated by electron Pair Distribution Function, Energy Loss Spectroscopy, and X-ray Photoelectron Spectroscopy to understand the oxygen profile incorporation. The analysis of the sets of samples indicated that reproducibility should be improved in the sputtering process of ZrCu alloys. Some improvements to increase the reproducibility of the sputtering technique were suggested.
{"title":"Reproducibility of magnetron-sputter co-deposited ZrCu metallic glasses","authors":"Heloisa H.P. Silva , Matheus R.B. do Amaral , Angelo L. Gobbi , Carlos A.R. Costa , Edson R. Leite , Jefferson Bettini","doi":"10.1016/j.susc.2025.122853","DOIUrl":"10.1016/j.susc.2025.122853","url":null,"abstract":"<div><div>In this work, the reproducibility of the magnetron sputtering technique was studied for more than three years using three sets of metallic glass samples grown by co-deposition of Zr and Cu. The reproducibility of metallic glasses or amorphous thin films is particularly critical due to their sensitivity to composition and structure. The analysis was made considering composition and deposition rate variation among the three sets and among the samples with different compositions of Zr<sub>x</sub>Cu<sub>1-x</sub> and pure Zr and Cu. The composition was measured using Energy Dispersive Spectroscopy and Electron Energy Loss Spectroscopy, and the deposition rate was analyzed by Atomic Force Microscopy. The electron Pair Distribution Function was used to study the structural variation among the three sets and the samples in each set. Finally, the oxygen incorporation in the samples was investigated by electron Pair Distribution Function, Energy Loss Spectroscopy, and X-ray Photoelectron Spectroscopy to understand the oxygen profile incorporation. The analysis of the sets of samples indicated that reproducibility should be improved in the sputtering process of ZrCu alloys. Some improvements to increase the reproducibility of the sputtering technique were suggested.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122853"},"PeriodicalIF":1.8,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-12DOI: 10.1016/j.susc.2025.122851
Zilian Tian, Lu Yang, Yanshuang Zhang, Yao Dong, Wei Zhao, Hang Yang
The threat posed by harmful gases such as sulfur dioxide (SO2) to the environment and human health is growing increasingly severe, making developing highly efficient gas-sensing materials a critical research focus. This study employs first-principles density functional theory (DFT) to systematically investigate the role of silicon (Si) doping in the SO2 adsorption process of single-layer WSe2. The computational results indicate that Si doping significantly enhances the adsorption capacity of WSe2 toward SO2, with the adsorption energy increasing from -1.364 eV in intrinsic WSe2 to -3.860 eV, suggesting that doping strengthens the interaction between the material and gas molecules. Further analysis shows that Si doping reduces the bandgap of WSe2 from 1.599 eV to 1.092 eV. Despite the narrowing of the bandgap, the material retains its semiconductor properties. Following the adsorption of SO2, a bandgap narrowing to 0.113 eV was observed, indicating an enhancement in the material’s sensitivity to gas response due to the synergistic effect of doping and gas adsorption. In the composite system with SO2 adsorption, an increase in the work function of the material from 5.09 eV to 5.21 eV was recorded, suggesting an enhancement in the interfacial electric field due to the synergistic effect of doping and gas adsorption, thereby optimising electron transfer and gas recognition capabilities. Differential charge density analysis revealed that Si doping and SO2 adsorption significantly induced interfacial charge transfer, improving gas recognition performance and electronic response. Optical performance analysis demonstrated that Si doping and SO2 adsorption jointly improve the material’s optical absorption properties. The intensity of the central absorption peak following the adsorption of SO2 by Si-doped WSe2 has been shown to increase to 14.39 × 104 cm−1, representing a 2.1 % increase compared with the intrinsic system. The findings of this study provide a theoretical foundation for the design of high-performance gas sensors and optoelectronic devices, thereby opening new avenues for the regulation of the optoelectronic properties of two-dimensional materials.
{"title":"SO2 adsorption properties of non-metal doped single-layer WSe2: A first-principles study","authors":"Zilian Tian, Lu Yang, Yanshuang Zhang, Yao Dong, Wei Zhao, Hang Yang","doi":"10.1016/j.susc.2025.122851","DOIUrl":"10.1016/j.susc.2025.122851","url":null,"abstract":"<div><div>The threat posed by harmful gases such as sulfur dioxide (SO<sub>2</sub>) to the environment and human health is growing increasingly severe, making developing highly efficient gas-sensing materials a critical research focus. This study employs first-principles density functional theory (DFT) to systematically investigate the role of silicon (Si) doping in the SO<sub>2</sub> adsorption process of single-layer WSe<sub>2</sub>. The computational results indicate that Si doping significantly enhances the adsorption capacity of WSe<sub>2</sub> toward SO<sub>2</sub>, with the adsorption energy increasing from -1.364 eV in intrinsic WSe<sub>2</sub> to -3.860 eV, suggesting that doping strengthens the interaction between the material and gas molecules. Further analysis shows that Si doping reduces the bandgap of WSe<sub>2</sub> from 1.599 eV to 1.092 eV. Despite the narrowing of the bandgap, the material retains its semiconductor properties. Following the adsorption of SO<sub>2</sub>, a bandgap narrowing to 0.113 eV was observed, indicating an enhancement in the material’s sensitivity to gas response due to the synergistic effect of doping and gas adsorption. In the composite system with SO<sub>2</sub> adsorption, an increase in the work function of the material from 5.09 eV to 5.21 eV was recorded, suggesting an enhancement in the interfacial electric field due to the synergistic effect of doping and gas adsorption, thereby optimising electron transfer and gas recognition capabilities. Differential charge density analysis revealed that Si doping and SO<sub>2</sub> adsorption significantly induced interfacial charge transfer, improving gas recognition performance and electronic response. Optical performance analysis demonstrated that Si doping and SO<sub>2</sub> adsorption jointly improve the material’s optical absorption properties. The intensity of the central absorption peak following the adsorption of SO<sub>2</sub> by Si-doped WSe<sub>2</sub> has been shown to increase to 14.39 × 10<sup>4</sup> cm<sup>−1</sup>, representing a 2.1 % increase compared with the intrinsic system. The findings of this study provide a theoretical foundation for the design of high-performance gas sensors and optoelectronic devices, thereby opening new avenues for the regulation of the optoelectronic properties of two-dimensional materials.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122851"},"PeriodicalIF":1.8,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145107224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Real-time monitoring of characteristic gases (CO, CO2, and C2H2) released during thermal runaway of lithium-ion batteries is crucial for battery safety. In this paper, the adsorption performance and gas-sensing mechanism of transition metal (Ag, Cu, Pt)-doped HfS2 monolayers for thermal runaway characteristic gases are systematically investigated based on density functional theory. By analyzing the parameters of adsorption energy, charge transfer, density of states and energy band structure, it is found that Cu-HfS2 exhibits optimal adsorption performance for CO with significant charge transfer. In addition, Ag-HfS2 and Pt-HfS2 also show strong chemisorption properties for CO and C2H2. The selective detection and rapid desorption of gases can be realized by modulating the working temperature. The results show that metal doping significantly improves the gas-sensing performance of HfS2, which provides a theoretical basis for the development of highly sensitive and selective lithium-ion battery thermal runaway gas sensors.
{"title":"DFT study of transition metal-doped HfS2 monolayers for detection of thermal runaway gases in lithium-ion batteries","authors":"Tianyan Jiang, Zhineng Zhou, Feifan Wu, Yuxin Liu, Shiqi Li, Shaolan Lei, Maoqiang Bi","doi":"10.1016/j.susc.2025.122852","DOIUrl":"10.1016/j.susc.2025.122852","url":null,"abstract":"<div><div>Real-time monitoring of characteristic gases (CO, CO<sub>2</sub>, and C<sub>2</sub>H<sub>2</sub>) released during thermal runaway of lithium-ion batteries is crucial for battery safety. In this paper, the adsorption performance and gas-sensing mechanism of transition metal (Ag, Cu, Pt)-doped HfS<sub>2</sub> monolayers for thermal runaway characteristic gases are systematically investigated based on density functional theory. By analyzing the parameters of adsorption energy, charge transfer, density of states and energy band structure, it is found that Cu-HfS<sub>2</sub> exhibits optimal adsorption performance for CO with significant charge transfer. In addition, Ag-HfS<sub>2</sub> and Pt-HfS<sub>2</sub> also show strong chemisorption properties for CO and C<sub>2</sub>H<sub>2</sub>. The selective detection and rapid desorption of gases can be realized by modulating the working temperature. The results show that metal doping significantly improves the gas-sensing performance of HfS<sub>2</sub>, which provides a theoretical basis for the development of highly sensitive and selective lithium-ion battery thermal runaway gas sensors.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122852"},"PeriodicalIF":1.8,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-09DOI: 10.1016/j.susc.2025.122850
Siyuan Lei , Yubing Yin , Linlin Xu , Ben Wang , Lele Wang , Changsong Zhou , Lushi Sun
Toluene and dichloromethane, as representative volatile organic compounds (VOCs) emissions from industrial exhaust gases, have attracted significant scientific attention. This study employs density functional theory (DFT) to investigate the adsorption mechanisms of toluene and dichloromethane on pristine anatase TiO₂(001) and its Ce-doped + CuO-doped surfaces. Results demonstrate that toluene undergoes stable chemisorption on the TiO₂(001) surface. Adsorption is significantly enhanced on both Ce/TiO₂(001) and CuO/TiO₂(001) modified surfaces, characterized by strong electron transfer and stable bonding. The toluene molecule undergoes unstable structural changes on the Ce/TiO2(001) substrate and eventually forms strong chemical bonds with the substrate atoms, indicating a strong adsorption capacity, with an adsorption energy of -190.578 kJ/mol. Dichloromethane also exhibits chemisorption, particularly on Ce/TiO₂(001) and oxygen-bridge CuO/TiO₂(001) surfaces, where it undergoes dechlorination to form Cl and chloromethyl radicals (CH₂Cl•). These radicals subsequently form stable chemical bonds with the surface. The high adsorption energy of dichloromethane on Ce/TiO₂(001) (-510.5 kJ/mol) confirms strong chemisorption. Dechlorination of dichloromethane, producing free Cl that establish stable chemical bonds with Ce atoms, is more advantageous both thermodynamically and kinetically. Subsequently, the CH₂Cl• undergoes an oxidation reaction, with a hydrogen atom being released.
{"title":"Density functional theory insights to VOCs adsorption mechanism on Ce/CuO modified TiO2(001) surface: A comparative study on toluene and dichloromethane","authors":"Siyuan Lei , Yubing Yin , Linlin Xu , Ben Wang , Lele Wang , Changsong Zhou , Lushi Sun","doi":"10.1016/j.susc.2025.122850","DOIUrl":"10.1016/j.susc.2025.122850","url":null,"abstract":"<div><div>Toluene and dichloromethane, as representative volatile organic compounds (VOCs) emissions from industrial exhaust gases, have attracted significant scientific attention. This study employs density functional theory (DFT) to investigate the adsorption mechanisms of toluene and dichloromethane on pristine anatase TiO₂(001) and its Ce-doped + CuO-doped surfaces. Results demonstrate that toluene undergoes stable chemisorption on the TiO₂(001) surface. Adsorption is significantly enhanced on both Ce/TiO₂(001) and CuO/TiO₂(001) modified surfaces, characterized by strong electron transfer and stable bonding. The toluene molecule undergoes unstable structural changes on the Ce/TiO<sub>2</sub>(001) substrate and eventually forms strong chemical bonds with the substrate atoms, indicating a strong adsorption capacity, with an adsorption energy of -190.578 kJ/mol. Dichloromethane also exhibits chemisorption, particularly on Ce/TiO₂(001) and oxygen-bridge CuO/TiO₂(001) surfaces, where it undergoes dechlorination to form Cl and chloromethyl radicals (CH₂Cl•). These radicals subsequently form stable chemical bonds with the surface. The high adsorption energy of dichloromethane on Ce/TiO₂(001) (-510.5 kJ/mol) confirms strong chemisorption. Dechlorination of dichloromethane, producing free Cl that establish stable chemical bonds with Ce atoms, is more advantageous both thermodynamically and kinetically. Subsequently, the CH₂Cl• undergoes an oxidation reaction, with a hydrogen atom being released.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"763 ","pages":"Article 122850"},"PeriodicalIF":1.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145107225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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