Pub Date : 2025-01-17DOI: 10.1016/j.chemphys.2025.112609
Fenghua Zhu, Haowen Liu
CeO2 is a promising candidate as electrodes for aqueous battery systems, however, the bulk particles show rapid capacity fading. This work prepares CeO2 nanosheets via a rapid microwave heating route in 10 min. Benefitting from the unique two-dimensional structure and rich oxygen vacancies, the assembled CeO2 nanosheets electrode delivers a high initial discharge/charge capacity of 706.1/485.0 mAh g−1 at 120 mA/g, a good reversible capacity of 182.4 mAh g−1 remains after 400 cycles, superior rate capability (91.1 mAh g−1 at 480 mA/g), as well as a fast diffusion kinetics (7.8 × 10−12 cm2 S−1) for aqueous Zn-ion batteries (AZIBs). Capacitance fading issue has been greatly addressed compared to the reported bulk particles. Also, it exhibits a high specific capacitance of 436.8 F/g at 1 A/g, a long capacitance retention (98.9 % @ the 2nd cycle) after 5000 cycles at 2.0 A/g, a high energy density of 92.4 Wh kg−1 at a power density of 107 W kg−1 for supercapacitors (SCs).
{"title":"CeO2 nanosheets for high performance aqueous battery systems","authors":"Fenghua Zhu, Haowen Liu","doi":"10.1016/j.chemphys.2025.112609","DOIUrl":"10.1016/j.chemphys.2025.112609","url":null,"abstract":"<div><div>CeO<sub>2</sub> is a promising candidate as electrodes for aqueous battery systems, however, the bulk particles show rapid capacity fading. This work prepares CeO<sub>2</sub> nanosheets via a rapid microwave heating route in 10 min. Benefitting from the unique two-dimensional structure and rich oxygen vacancies, the assembled CeO<sub>2</sub> nanosheets electrode delivers a high initial discharge/charge capacity of 706.1/485.0 mAh g<sup>−1</sup> at 120 mA/g, a good reversible capacity of 182.4 mAh g<sup>−1</sup> remains after 400 cycles, superior rate capability (91.1 mAh g<sup>−1</sup> at 480 mA/g), as well as a fast diffusion kinetics (7.8 × 10<sup>−12</sup> cm<sup>2</sup> S<sup>−1</sup>) for aqueous Zn-ion batteries (AZIBs). Capacitance fading issue has been greatly addressed compared to the reported bulk particles. Also, it exhibits a high specific capacitance of 436.8 F/g at 1 A/g, a long capacitance retention (98.9 % @ the 2nd cycle) after 5000 cycles at 2.0 A/g, a high energy density of 92.4 Wh kg<sup>−1</sup> at a power density of 107 W kg<sup>−1</sup> for supercapacitors (SCs).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112609"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158613","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 : 2025-01-17DOI: 10.1016/j.chemphys.2025.112611
Xuelu Yang , Songsong Liu , Yang Gao , Lili Lin , Chuan-Kui Wang , Jianzhong Fan , Yuzhi Song
Multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters with high efficiency and narrowband emission characteristics have shown wide applications in organic light-emitting diodes. However, MR-TADF emitters usually exhibit slow reverse intersystem crossing (RISC) rates, the amount and species of efficient MR-TADF emitters are limited, corresponding structure–property relationship needs to be clarified. Herein, based on density functional theory, time-dependent density functional theory and SCS-ADC(2) method, five reported MR-TADF molecules (CzBO, CzBS, CzBSe, Cz-PTZ-BN and BN-Se) are adopted and their photophysical properties are studied by thermal vibration correlation function (TVCF) method, the heavy atom effect on increasing spin–orbit coupling (SOC) and thus accelerating RISC process is elucidated. Based on this strategy with π-conjugated extension of MR unit, four new molecules (wBN-O, wCz-PTZ-BN, wBN-Se and BN-O) are theoretically proposed and their full-width at half-maximum (FWHM) values and excited decay rates are calculated. Results indicate that all studied molecules possess small energy gaps (ΔEST) between S1 and T1, and they are corresponding well with experimental values. In addition, large SOC constants are determined for designed molecules, remarkable RISC processes are realized and TADF features can be expected. Moreover, the large planarity for studied molecules brings small FWHM value with decreased reorganization energies and restricted geometry changes between S1 and ground state (S0). However, the ΔEST values for large planarity molecules are increased and insufficient RISC processes are determined. Thus, the relationship between efficient RISC process with large SOC values and narrowband emission with small FWHM values should be carefully balanced by wise molecular design strategy. This work illustrates the key physical parameters in regulating FWHM values and TADF properties, which could pave the way for the development of efficient MR TADF molecules.
{"title":"The role of heavy atom effect in regulating multiple-resonance and thermally activated delayed fluorescence features: A theoretical perspective","authors":"Xuelu Yang , Songsong Liu , Yang Gao , Lili Lin , Chuan-Kui Wang , Jianzhong Fan , Yuzhi Song","doi":"10.1016/j.chemphys.2025.112611","DOIUrl":"10.1016/j.chemphys.2025.112611","url":null,"abstract":"<div><div>Multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters with high efficiency and narrowband emission characteristics have shown wide applications in organic light-emitting diodes. However, MR-TADF emitters usually exhibit slow reverse intersystem crossing (RISC) rates, the amount and species of efficient MR-TADF emitters are limited, corresponding structure–property relationship needs to be clarified. Herein, based on density functional theory, time-dependent density functional theory and SCS-ADC(2) method, five reported MR-TADF molecules (CzBO, CzBS, CzBSe, Cz-PTZ-BN and BN-Se) are adopted and their photophysical properties are studied by thermal vibration correlation function (TVCF) method, the heavy atom effect on increasing spin–orbit coupling (SOC) and thus accelerating RISC process is elucidated. Based on this strategy with π-conjugated extension of MR unit, four new molecules (wBN-O, wCz-PTZ-BN, wBN-Se and BN-O) are theoretically proposed and their full-width at half-maximum (FWHM) values and excited decay rates are calculated. Results indicate that all studied molecules possess small energy gaps (ΔE<sub>ST</sub>) between <em>S<sub>1</sub></em> and <em>T<sub>1</sub></em>, and they are corresponding well with experimental values. In addition, large SOC constants are determined for designed molecules, remarkable RISC processes are realized and TADF features can be expected. Moreover, the large planarity for studied molecules brings small FWHM value with decreased reorganization energies and restricted geometry changes between <em>S<sub>1</sub></em> and ground state (<em>S<sub>0</sub></em>). However, the ΔE<sub>ST</sub> values for large planarity molecules are increased and insufficient RISC processes are determined. Thus, the relationship between efficient RISC process with large SOC values and narrowband emission with small FWHM values should be carefully balanced by wise molecular design strategy. This work illustrates the key physical parameters in regulating FWHM values and TADF properties, which could pave the way for the development of efficient MR TADF molecules.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112611"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158616","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 : 2025-01-13DOI: 10.1016/j.chemphys.2025.112608
Shaimaa A.M. Abdelmohsen , Meznah M. Alanazi , Taghreed Muhammad Abdu Bahlool , Tamoor Ahmad
Nowadays, the impending depletion of fossil fuels and rising environmental concerns have increased research interest for energy storing devices. Supercapacitor are effective energy storage technologies because of their superior capacitive characteristics, cycling stability and high-power density. The current work is fabricated BaBiO3/rGO electrode to enhance the performance of supercapacitor. BaBiO3/rGO was fabricated through a hydrothermal approach for supercapacitor applications following number of analytical tools. The composite surface area and crystal structure, morphology was all ascertained by various characterizations. BaBiO3/rGO nanocomposite had remarkable characteristics, achieving a specific capacitance of 1209 F/g at 1 A/g. The material’s cycling stability was notably consistent with its initial capacitance even after 5000th cycles. The BaBiO3/rGO composite demonstrated enhanced and stable electrochemical performance for energy storing equipment’s.
{"title":"Synergistic integration of BaBiO3 and rGO nanocomposite electrode for enhancing energy storage performance","authors":"Shaimaa A.M. Abdelmohsen , Meznah M. Alanazi , Taghreed Muhammad Abdu Bahlool , Tamoor Ahmad","doi":"10.1016/j.chemphys.2025.112608","DOIUrl":"10.1016/j.chemphys.2025.112608","url":null,"abstract":"<div><div>Nowadays, the impending depletion of fossil fuels and rising environmental concerns have increased research interest for energy storing devices. Supercapacitor are effective energy storage technologies because of their superior capacitive characteristics, cycling stability and high-power density. The current work is fabricated BaBiO<sub>3</sub>/rGO electrode to enhance the performance of supercapacitor. BaBiO<sub>3</sub>/rGO was fabricated through a<!--> <!-->hydrothermal approach for supercapacitor applications following number of analytical tools. The composite surface area and crystal structure, morphology was all ascertained by various characterizations. BaBiO<sub>3</sub>/rGO nanocomposite had remarkable characteristics, achieving a specific capacitance of 1209 F/g at 1 A/g. The material’s cycling stability was notably consistent with its initial capacitance even after 5000<sup>th</sup> cycles. The BaBiO<sub>3</sub>/rGO composite demonstrated enhanced and stable electrochemical performance for energy storing equipment’s.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112608"},"PeriodicalIF":2.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158560","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 : 2025-01-13DOI: 10.1016/j.chemphys.2024.112598
Monica Gambhir , Sumana Devi , Vinod Prasad
The study examines the impact of microwave laser on the directional and thermal properties of a diatomic molecule adsorbed on a surface, focusing on its out-of-plane motion. The periodic laser interaction generates quasi-energy states, which are significantly influenced by surface-induced hindrance to rotational motion. This hindrance modifies the energy level spacing, facilitating selective transitions. The quasi-energy states are further analysed by varying key parameters, including the hindrance potential, laser frequency, and laser intensity. The directional properties, such as molecular alignment and orientation, strongly depend on these laser parameters. Additionally, thermodynamic characteristics, including specific heat, entropy, and internal energy, exhibit resonance-induced oscillations, particularly at low temperatures. These findings shed light on the complex interaction between laser and molecule, deepening our understanding of molecular behaviour in external fields. This research holds potential for applications in spectroscopy, quantum computing, and laser-based technologies.
{"title":"Microwave-assisted directional and thermal properties of surface-adsorbed diatomic molecule","authors":"Monica Gambhir , Sumana Devi , Vinod Prasad","doi":"10.1016/j.chemphys.2024.112598","DOIUrl":"10.1016/j.chemphys.2024.112598","url":null,"abstract":"<div><div>The study examines the impact of microwave laser on the directional and thermal properties of a diatomic molecule adsorbed on a surface, focusing on its out-of-plane motion. The periodic laser interaction generates quasi-energy states, which are significantly influenced by surface-induced hindrance to rotational motion. This hindrance modifies the energy level spacing, facilitating selective transitions. The quasi-energy states are further analysed by varying key parameters, including the hindrance potential, laser frequency, and laser intensity. The directional properties, such as molecular alignment and orientation, strongly depend on these laser parameters. Additionally, thermodynamic characteristics, including specific heat, entropy, and internal energy, exhibit resonance-induced oscillations, particularly at low temperatures. These findings shed light on the complex interaction between laser and molecule, deepening our understanding of molecular behaviour in external fields. This research holds potential for applications in spectroscopy, quantum computing, and laser-based technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112598"},"PeriodicalIF":2.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164918","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 : 2025-01-08DOI: 10.1016/j.chemphys.2025.112601
Kai Wang, Wenli Zou
Ab initio calculations on the low-lying states of BiX (X = Cl, Br, and I) below 45 000 cm−1 have been performed using the multi-reference configuration interaction and the equation-of-motion coupled-cluster methods with the spin–orbit coupling effects being included perturbatively and variationally, respectively. Totally ten states are found to be bound ones for each molecule, including the ground state , the first excited state , five higher-lying valence excited states (, , , , and ), and three Rydberg states (, , and ) originating from the Bi 7 occupation. The derived spectroscopic constants as well as the estimated radiative lifetimes are overall consistent with the available experimental values. Our results may enhance the understanding on the distribution of electronic states of BiX and provide theoretical references for future spectroscopic observations.
{"title":"Theoretical study of low-lying electronic states of BiCl, BiBr, and BiI","authors":"Kai Wang, Wenli Zou","doi":"10.1016/j.chemphys.2025.112601","DOIUrl":"10.1016/j.chemphys.2025.112601","url":null,"abstract":"<div><div><em>Ab initio</em> calculations on the low-lying <span><math><mi>Ω</mi></math></span> states of BiX (X = Cl, Br, and I) below 45<!--> <!-->000 cm<sup>−1</sup> have been performed using the multi-reference configuration interaction and the equation-of-motion coupled-cluster methods with the spin–orbit coupling effects being included perturbatively and variationally, respectively. Totally ten <span><math><mi>Ω</mi></math></span> states are found to be bound ones for each molecule, including the ground state <span><math><mrow><msub><mrow><mi>X</mi></mrow><mrow><mn>1</mn></mrow></msub><msup><mrow><mn>0</mn></mrow><mrow><mo>+</mo></mrow></msup></mrow></math></span>, the first excited state <span><math><mrow><msub><mrow><mi>X</mi></mrow><mrow><mn>2</mn></mrow></msub><mn>1</mn></mrow></math></span>, five higher-lying valence excited states (<span><math><mrow><mi>a</mi><mn>2</mn></mrow></math></span>, <span><math><mrow><msup><mrow><mi>A</mi></mrow><mrow><mo>′</mo></mrow></msup><msup><mrow><mn>0</mn></mrow><mrow><mo>−</mo></mrow></msup></mrow></math></span>, <span><math><mrow><mi>A</mi><msup><mrow><mn>0</mn></mrow><mrow><mo>+</mo></mrow></msup></mrow></math></span>, <span><math><mrow><msup><mrow><mi>A</mi></mrow><mrow><mo>′</mo><mo>′</mo></mrow></msup><mn>1</mn></mrow></math></span>, and <span><math><mrow><mi>B</mi><msup><mrow><mn>0</mn></mrow><mrow><mo>+</mo></mrow></msup></mrow></math></span>), and three Rydberg states (<span><math><mrow><msub><mrow><mi>C</mi></mrow><mrow><mn>1</mn></mrow></msub><msup><mrow><mn>0</mn></mrow><mrow><mo>−</mo></mrow></msup></mrow></math></span>, <span><math><mrow><msub><mrow><mi>C</mi></mrow><mrow><mn>2</mn></mrow></msub><msup><mrow><mn>0</mn></mrow><mrow><mo>+</mo></mrow></msup></mrow></math></span>, and <span><math><mrow><msub><mrow><mi>C</mi></mrow><mrow><mn>3</mn></mrow></msub><mn>1</mn></mrow></math></span>) originating from the Bi 7<span><math><mi>s</mi></math></span> occupation. The derived spectroscopic constants as well as the estimated radiative lifetimes are overall consistent with the available experimental values. Our results may enhance the understanding on the distribution of electronic states of BiX and provide theoretical references for future spectroscopic observations.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112601"},"PeriodicalIF":2.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164919","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 : 2025-01-08DOI: 10.1016/j.chemphys.2025.112607
Yang Zhu , Qian-Xu Wang , Wei-Cheng Sun , Fang Wang , Hui-Hui Hong , Bin Li , Feng-Lei Qi , Yu-Qing Wang , Yuan-Lai Xie , Chang-Qi Chen , Jin-Xia Liang
In the ultra-high vacuum environment of fusion devices, sorbent materials were required not only to remove H2, but also to capture impurity gases (i.e., H2O, CO2, O2, etc.). The adsorption of gases by sorbent materials was affected by a combination of surface adsorption and bulk diffusion. In this work, the first-principles method was employed to analyze the stability of interstitial sites for H and O atoms in Ti-Zr binary alloy sorbent. Diffusion pathways and barriers for H and O atoms among interstitial sites were calculated using the Climbing Image Nudged Elastic Band method (CI-NEB). The stability of interstitial sites occupied by solute atoms was found to affect the ease of diffusion of solute atoms between adjacent interstitial sites. The higher the stability of these interstitial sites, the more difficult it was for the atom to diffuse to other sites. However, solute atoms were more likely to diffuse from less stable interstitial sites to those with greater stability. The Tb tetrahedral interstitial site in Ti0.5Zr0.5 was most readily occupied by the H atom. The energy barrier for diffusion from the OC octahedral interstitial site to the Tb tetrahedral site was found to be the lowest, which was equal to 0.135 eV. The O atom was most likely to occupy the OC octahedral interstitial sites. When diffusing along the 2Ta3-3Ta3 path parallel to the C-axis, the lowest diffusion barrier for O atom was 5.425 eV. The next most favorable diffusion pathway was from the Ta tetrahedral interstitial site to the OC octahedral site, with a diffusion barrier of 5.435 eV. The main findings of the diffusion mechanism of H and O in the bulk structure of binary titanium-zirconium alloys revealed in this work are expected to provide a theoretical reference and potential feasibility analysis for the application of new titanium-zirconium-based sorbent materials.
{"title":"Diffusion mechanism of H and O at the interstitial sites of a Ti-Zr alloy sorbent: A first-principles investigation","authors":"Yang Zhu , Qian-Xu Wang , Wei-Cheng Sun , Fang Wang , Hui-Hui Hong , Bin Li , Feng-Lei Qi , Yu-Qing Wang , Yuan-Lai Xie , Chang-Qi Chen , Jin-Xia Liang","doi":"10.1016/j.chemphys.2025.112607","DOIUrl":"10.1016/j.chemphys.2025.112607","url":null,"abstract":"<div><div>In the ultra-high vacuum environment of fusion devices, sorbent materials were required not only to remove H<sub>2</sub>, but also to capture impurity gases (i.e., H<sub>2</sub>O, CO<sub>2</sub>, O<sub>2</sub>, etc.). The adsorption of gases by sorbent materials was affected by a combination of surface adsorption and bulk diffusion. In this work, the first-principles method was employed to analyze the stability of interstitial sites for H and O atoms in Ti-Zr binary alloy sorbent. Diffusion pathways and barriers for H and O atoms among interstitial sites were calculated using the Climbing Image Nudged Elastic Band method (CI-NEB). The stability of interstitial sites occupied by solute atoms was found to affect the ease of diffusion of solute atoms between adjacent interstitial sites. The higher the stability of these interstitial sites, the more difficult it was for the atom to diffuse to other sites. However, solute atoms were more likely to diffuse from less stable interstitial sites to those with greater stability. The Tb tetrahedral interstitial site in Ti<sub>0.5</sub>Zr<sub>0.5</sub> was most readily occupied by the H atom. The energy barrier for diffusion from the OC octahedral interstitial site to the Tb tetrahedral site was found to be the lowest, which was equal to 0.135 eV. The O atom was most likely to occupy the OC octahedral interstitial sites. When diffusing along the 2Ta3-3Ta3 path parallel to the C-axis, the lowest diffusion barrier for O atom was 5.425 eV. The next most favorable diffusion pathway was from the Ta tetrahedral interstitial site to the OC octahedral site, with a diffusion barrier of 5.435 eV. The main findings of the diffusion mechanism of H and O in the bulk structure of binary titanium-zirconium alloys revealed in this work are expected to provide a theoretical reference and potential feasibility analysis for the application of new titanium-zirconium-based sorbent materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112607"},"PeriodicalIF":2.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164917","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 : 2025-01-07DOI: 10.1016/j.chemphys.2025.112606
Yusong Pan , Shuhuan He , Linjie Ou , Shihui Zang , Run Huang
Photocatalytic technology is one of the most promising technologies for wastewater treatment. In this paper, Ag2S/Ag2CrO4 core–shell heterojunction were prepared using in-situ anion exchange method. The structure, morphology, and optical properties of the prepared samples were characterized by XRD, SEM, TEM, XPS, and DRS technologies. The photo-degradation results verified that the 2 %-Ag2S/Ag2CrO4 heterojunction exhibited excellent photocatalytic activity for degradation of organic dyes and antibiotics under visible light irradiation. The removal efficiency for RhB was 95 % in 15 min, which was obviously superior to that of pure Ag2CrO4 (∼73 %) and Ag2S (∼7%) photocatalysts. The enhanced photocatalytic performance of the Ag2S/Ag2CrO4 was mainly attributed to the Z-scheme core–shell heterojunction structure of the photocatalyst that facilitated excellent charge carriers separation and migration. Meanwhile, the results of trapping experiments for active species demonstrated that both the holes (h+) and superoxide radical (O2−) played an important role for degradation of organic pollutants.
{"title":"In-situ anion exchange preparation of Ag2S/Ag2CrO4 core–shell heterojunction with enhanced visible-light photocatalytic activity","authors":"Yusong Pan , Shuhuan He , Linjie Ou , Shihui Zang , Run Huang","doi":"10.1016/j.chemphys.2025.112606","DOIUrl":"10.1016/j.chemphys.2025.112606","url":null,"abstract":"<div><div>Photocatalytic technology is one of the most promising technologies for wastewater treatment. In this paper, Ag<sub>2</sub>S/Ag<sub>2</sub>CrO<sub>4</sub> core–shell heterojunction were prepared using <em>in-situ</em> anion exchange method. The structure, morphology, and optical properties of the prepared samples were characterized by XRD, SEM, TEM, XPS, and DRS technologies. The photo-degradation results verified that the 2 %-Ag<sub>2</sub>S/Ag<sub>2</sub>CrO<sub>4</sub> heterojunction exhibited excellent photocatalytic activity for degradation of organic dyes and antibiotics under visible light irradiation. The removal efficiency for RhB was 95 % in 15 min, which was obviously superior to that of pure Ag<sub>2</sub>CrO<sub>4</sub> (∼73 %) and Ag<sub>2</sub>S (∼7%) photocatalysts. The enhanced photocatalytic performance of the Ag<sub>2</sub>S/Ag<sub>2</sub>CrO<sub>4</sub> was mainly attributed to the Z-scheme core–shell heterojunction structure of the photocatalyst that facilitated excellent charge carriers separation and migration. Meanwhile, the results of trapping experiments for active species demonstrated that both the holes (h<sup>+</sup>) and superoxide radical (<img>O<sub>2</sub><sup>−</sup>) played an important role for degradation of organic pollutants.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112606"},"PeriodicalIF":2.0,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164920","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 : 2025-01-06DOI: 10.1016/j.chemphys.2024.112599
Boning Yan, Kang Xu, Ming Lei
This article takes the representative ternary and quaternary polycyclic aromatic amines (PAAs) isomers such as phenanthamine and pyreneamine as examples, and uses the Clar’s aromatic π-sextet rule combined with nucleus independent chemical shift (NICS) criteria and structural and electronic indices (such as HOMA, MCBO and MCI), to study their structure–reactivity relationship in electrochemical radical reactions based on the experimental results. By analyzing and discussing the changes in aromaticity and bond length of various ring systems in the structures of the substrates, radical intermediates, and products, as well as radical stability, we have gained a deeper understanding of the reaction mechanism and regioselectivity for construction of large π-conjugated frameworks of nitrogen fused helicenes and functional polymers through electrochemical tandem reactions of PAAs. In general, resonant structures containing more Clar’s aromatic π-sextet in the structure have higher stability, which determines the reaction pathway and types of the product. In this study, Clar’s rule, NICS criteria, HOMA, MCBO and MCI mutually supported and validated each other well, demonstrated that the combination of Clar’s rule and NICS criteria may be a beneficial tool for analyzing and predicting the reactivity of PAH derivatives and the structure of complex polycyclic aromatic products, moreover, expanding their application to non-planar heteroatom doped helicenes beyond PAH compounds.
{"title":"Insights into the electrochemical radical reaction of polycyclic aromatic amines from Clar’s aromatic π-sextet rule and NICS criteria","authors":"Boning Yan, Kang Xu, Ming Lei","doi":"10.1016/j.chemphys.2024.112599","DOIUrl":"10.1016/j.chemphys.2024.112599","url":null,"abstract":"<div><div>This article takes the representative ternary and quaternary polycyclic aromatic amines (PAAs) isomers such as phenanthamine and pyreneamine as examples, and uses the Clar’s aromatic π-sextet rule combined with nucleus independent chemical shift (NICS) criteria and structural and electronic indices (such as HOMA, MCBO and MCI), to study their structure–reactivity relationship in electrochemical radical reactions based on the experimental results. By analyzing and discussing the changes in aromaticity and bond length of various ring systems in the structures of the substrates, radical intermediates, and products, as well as radical stability, we have gained a deeper understanding of the reaction mechanism and regioselectivity for construction of large π-conjugated frameworks of nitrogen fused helicenes and functional polymers through electrochemical tandem reactions of PAAs. In general, resonant structures containing more Clar’s aromatic π-sextet in the structure have higher stability, which determines the reaction pathway and types of the product. In this study, Clar’s rule, NICS criteria, HOMA, MCBO and MCI mutually supported and validated each other well, demonstrated that the combination of Clar’s rule and NICS criteria may be a beneficial tool for analyzing and predicting the reactivity of PAH derivatives and the structure of complex polycyclic aromatic products, moreover, expanding their application to non-planar heteroatom doped helicenes beyond PAH compounds.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112599"},"PeriodicalIF":2.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164923","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 : 2025-01-06DOI: 10.1016/j.chemphys.2024.112597
Viviane S. Vaiss, Luciano T. Costa
The development of efficient technologies that allow the use of CO as a raw material for the synthesis of high value-added products is extremely important. Electrochemical methods are being considered promising. To assist in the planning of more efficient electrocatalysts, this work investigated, through DFT calculations, the structure and properties of pure MoS and doped with various elements. The results obtained indicate that doping with Nb or Ti elements provides a greater reduction in the work function of MoS. The lower the material’s work function, the higher the reaction current density and the better the material’s performance as an electrocatalyst. Furthermore, the formation energies of the COOH and CHO intermediates in MoS doped with Nb or Ti are more stable than those of the CO intermediate. The high stability of the binding energy of the CO* intermediate in relation to other intermediates represents a limitation for the catalytic efficiency.
{"title":"Theoretical Systematic investigation as a Strategic Tool for the design of more efficient pure and doped MoS2 catalysts for CO2 Electroreduction","authors":"Viviane S. Vaiss, Luciano T. Costa","doi":"10.1016/j.chemphys.2024.112597","DOIUrl":"10.1016/j.chemphys.2024.112597","url":null,"abstract":"<div><div>The development of efficient technologies that allow the use of CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> as a raw material for the synthesis of high value-added products is extremely important. Electrochemical methods are being considered promising. To assist in the planning of more efficient electrocatalysts, this work investigated, through DFT calculations, the structure and properties of pure MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and doped with various elements. The results obtained indicate that doping with Nb or Ti elements provides a greater reduction in the work function of MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>. The lower the material’s work function, the higher the reaction current density and the better the material’s performance as an electrocatalyst. Furthermore, the formation energies of the COOH<span><math><msup><mrow></mrow><mrow><mo>∗</mo></mrow></msup></math></span> and CHO<span><math><msup><mrow></mrow><mrow><mo>∗</mo></mrow></msup></math></span> intermediates in MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> doped with Nb or Ti are more stable than those of the CO<span><math><msup><mrow></mrow><mrow><mo>∗</mo></mrow></msup></math></span> intermediate. The high stability of the binding energy of the CO* intermediate in relation to other intermediates represents a limitation for the catalytic efficiency.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112597"},"PeriodicalIF":2.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164858","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 : 2025-01-06DOI: 10.1016/j.chemphys.2025.112604
Yiwei Feng , Yujie Yan , Hai Xie , Jinxiang Liu
We performed first-principles calculations and simulations to investigate the hydrogen storage properties of binary hydrates formed by H2 and CH4. The results showed that the optimum hydrogen storage capacity ranged from 3.43 wt% to 5.42 wt%, and the high storage capacity could be achieved by tuning cage occupation of CH4 in 512 or 51264 cages. Further, two binary hydrate structures (denoted as T1 and T2) were chosen to assess the effect of pressure and temperature on the hydrate stability. Simulation results showed that two hydrates were stable at the studied conditions (10–30 MPa, and 260–285 K). At high pressures (more than 20 MPa) T1 structure was stable, while at low pressures T2 structure was stable. More importantly, H2 + CH4 binary hydrates exhibit anomalous stability at about 275 K, which would be helpful for the application of hydrate-based hydrogen storage technology under mild conditions.
{"title":"Molecular Insight into hydrogen storage of H2 + CH4 sII hydrates","authors":"Yiwei Feng , Yujie Yan , Hai Xie , Jinxiang Liu","doi":"10.1016/j.chemphys.2025.112604","DOIUrl":"10.1016/j.chemphys.2025.112604","url":null,"abstract":"<div><div>We performed first-principles calculations and simulations to investigate the hydrogen storage properties of binary hydrates formed by H<sub>2</sub> and CH<sub>4</sub>. The results showed that the optimum hydrogen storage capacity ranged from 3.43 wt% to 5.42 wt%, and the high storage capacity could be achieved by tuning cage occupation of CH<sub>4</sub> in 5<sup>12</sup> or 5<sup>12</sup>6<sup>4</sup> cages. Further, two binary hydrate structures (denoted as <strong>T</strong>1 and <strong>T</strong>2) were chosen to assess the effect of pressure and temperature on the hydrate stability. Simulation results showed that two hydrates were stable at the studied conditions (10–30 MPa, and 260–285 K). At high pressures (more than 20 MPa) <strong>T</strong>1 structure was stable, while at low pressures <strong>T</strong>2 structure was stable. More importantly, H<sub>2</sub> + CH<sub>4</sub> binary hydrates exhibit anomalous stability at about 275 K, which would be helpful for the application of hydrate-based hydrogen storage technology under mild conditions.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112604"},"PeriodicalIF":2.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164922","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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