Pub Date : 2024-11-13DOI: 10.1021/acs.jpcc.4c04815
Mihaela Iuliana Avadanei, Radu Ionut Tigoianu, Mirela-Fernanda Zaltariov, Mihaela Balan-Porcarasu, Mihaela Silion, Ovidiu Gabriel Avadanei
The investigations reported in this work concern the capabilities of the 3-carboxy-salicylidene unit in three dicompartmental Schiff bases with a flexible spacer bearing silane or siloxane units to efficiently coordinate rare earth and transition-metal ions as well as the efficiency to act as antenna or organometallic antenna for Ln(III) sensitization. The Ln(III) complexation studies of the H4L1, H4L2, and H4L3 ligands were performed by spectrophotometric titration. The selectivity toward seven Ln(III) ions and the trend of the stability constants are analyzed in connection with the structure of the ligands. In order to find the energetic factors that impact the efficiency of Ln(III) sensitization, the corresponding Gd(III) complexes were prepared and were in-depth analyzed from the point of view of the photophysical properties. The investigations were carried out using time-resolved emission and transient absorption spectroscopy. Phosphorescence data prove the unhindered path of the ligands to the triplet state and the probability to transfer the excitation energy to the Ln(III) ion. Applicability of two selected Gd(III) complexes in detection and recognition of transition and heavy metal ions has been studied with a double purpose: to evaluate their sensitivity and recognition ability so that they could be applied in pollutants detection and to estimate the capability of the M(II)-Schiff base unit as an organometallic antenna for Visible emission sensitization. The Gd(III) complex with a long π-conjugation showed multiple fluorescence responses to various kinds of 3d ions, which gave it pattern recognition ability. The discrimination power was finally analyzed by a principal component analysis.
{"title":"Photophysics of 3-Carboxy-Salicylideneaniline in Rare Earth Metal Complexes with Silicon-Containing Schiff Base Ligands","authors":"Mihaela Iuliana Avadanei, Radu Ionut Tigoianu, Mirela-Fernanda Zaltariov, Mihaela Balan-Porcarasu, Mihaela Silion, Ovidiu Gabriel Avadanei","doi":"10.1021/acs.jpcc.4c04815","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04815","url":null,"abstract":"The investigations reported in this work concern the capabilities of the 3-carboxy-salicylidene unit in three dicompartmental Schiff bases with a flexible spacer bearing silane or siloxane units to efficiently coordinate rare earth and transition-metal ions as well as the efficiency to act as antenna or organometallic antenna for Ln(III) sensitization. The Ln(III) complexation studies of the H<sub>4</sub><b>L1</b>, H<sub>4</sub><b>L2</b>, and H<sub>4</sub><b>L3</b> ligands were performed by spectrophotometric titration. The selectivity toward seven Ln(III) ions and the trend of the stability constants are analyzed in connection with the structure of the ligands. In order to find the energetic factors that impact the efficiency of Ln(III) sensitization, the corresponding Gd(III) complexes were prepared and were in-depth analyzed from the point of view of the photophysical properties. The investigations were carried out using time-resolved emission and transient absorption spectroscopy. Phosphorescence data prove the unhindered path of the ligands to the triplet state and the probability to transfer the excitation energy to the Ln(III) ion. Applicability of two selected Gd(III) complexes in detection and recognition of transition and heavy metal ions has been studied with a double purpose: to evaluate their sensitivity and recognition ability so that they could be applied in pollutants detection and to estimate the capability of the M(II)-Schiff base unit as an organometallic antenna for Visible emission sensitization. The Gd(III) complex with a long π-conjugation showed multiple fluorescence responses to various kinds of 3d ions, which gave it pattern recognition ability. The discrimination power was finally analyzed by a principal component analysis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"12 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601523","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c03861
Alem Teklu, Noah Kern, Narayanan Kuthirummal, Joe Tidwell, Maxwell Rabe, Yu Gong, Wenkai Zhang, Luis Balicas
Nanoindentation was used to measure the nanomechanical properties of four two-dimensional transition metal dichalcogenides (TMDs), namely molybdenum disulfide (MoS2), rhenium disulfide (ReS2), rhenium diselenide (ReSe2), and tungsten diselenide (WSe2), with very high tensile strengths comparable to graphene. These materials have potential applications for new electronic device applications, but their nanomechanical properties have not yet been well studied. For this purpose, an atomic force microscope (AFM) capable of measuring the elastic moduli of these two-dimensional nanomaterials through nanoindentation was used to generate force–distance curves for analysis. In this work, we developed a new Python code to analyze these force–distance curves, resulting in more accurate values of the reduced Young’s modulus and stiffness of each of these nanomaterials as compared to existing data analysis software such as AtomicJ and MountainsSPIP. The values obtained using our code for reduced Young’s modulus of MoS2, ReS2, ReSe2, and WSe2 were 140, 79, 37, and 38 GPa, respectively, with percent differences as summarized in Table 3. Among the samples, MoS2 has the highest values for its reduced Young’s modulus and stiffness followed by, in order, ReS2, WSe2, and ReSe2. Our results were in better agreement with theoretical calculations in the literature than those obtained by the other two pieces of data analysis software.
{"title":"Experimental Analysis of the Elastic Moduli of Atomically Thin Transition Metal Dichalcogenides","authors":"Alem Teklu, Noah Kern, Narayanan Kuthirummal, Joe Tidwell, Maxwell Rabe, Yu Gong, Wenkai Zhang, Luis Balicas","doi":"10.1021/acs.jpcc.4c03861","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03861","url":null,"abstract":"Nanoindentation was used to measure the nanomechanical properties of four two-dimensional transition metal dichalcogenides (TMDs), namely molybdenum disulfide (MoS<sub>2</sub>), rhenium disulfide (ReS<sub>2</sub>), rhenium diselenide (ReSe<sub>2</sub>), and tungsten diselenide (WSe<sub>2</sub>), with very high tensile strengths comparable to graphene. These materials have potential applications for new electronic device applications, but their nanomechanical properties have not yet been well studied. For this purpose, an atomic force microscope (AFM) capable of measuring the elastic moduli of these two-dimensional nanomaterials through nanoindentation was used to generate force–distance curves for analysis. In this work, we developed a new Python code to analyze these force–distance curves, resulting in more accurate values of the reduced Young’s modulus and stiffness of each of these nanomaterials as compared to existing data analysis software such as AtomicJ and MountainsSPIP. The values obtained using our code for reduced Young’s modulus of MoS<sub>2</sub>, ReS<sub>2</sub>, ReSe<sub>2</sub>, and WSe<sub>2</sub> were 140, 79, 37, and 38 GPa, respectively, with percent differences as summarized in Table 3. Among the samples, MoS<sub>2</sub> has the highest values for its reduced Young’s modulus and stiffness followed by, in order, ReS<sub>2</sub>, WSe<sub>2</sub>, and ReSe<sub>2</sub>. Our results were in better agreement with theoretical calculations in the literature than those obtained by the other two pieces of data analysis software.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609806","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c04986
Shuaib A. Balogun, Mark. D. Losego
This study investigates the use of TiCl4 vapor phase infiltration (VPI) to cleave ester groups in the main chain of a polymer and drive depolymerization and film etching. Prior investigations have demonstrated that the infiltration of TiCl4 into PMMA results in dealkylation of its ester bond, cleaving its side groups. This study investigates the VPI of TiCl4 into poly(lactic acid), which is a prototypical polymer with an ester group in its main chain. Utilizing in situ quartz crystal microbalance (QCM) measurements and spectroscopic ellipsometry, PLA is observed to depolymerize readily at 135 °C with extended TiCl4 precursor exposure, resulting in significant thickness and mass reduction, whereas at 90 °C, depolymerization is significantly slower and etching is negligible. Utilizing Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and a residual gas analyzer (RGA), dealkylation is shown to be the primary depolymerization mechanism. FTIR and XPS analyses reveal the consumption of carbonyl and methoxy groups and the emergence of hydroxyl, chlorine, and titanium moieties. In situ RGA measurements provide further insights into the byproducts formed during the TiCl4 and water exposure steps, indicating that the depolymerized components undergo further breakdown into other substances. Residuals left after 135 °C TiCl4 VPI are easily removed with a 0.1 M HCl aqueous solution. These findings highlight the expanding functionality of VPI, revealing its capability as both an additive and subtractive process and suggesting its broader applications.
{"title":"Depolymerization and Etching of Poly(lactic acid) via TiCl4 Vapor Phase Infiltration","authors":"Shuaib A. Balogun, Mark. D. Losego","doi":"10.1021/acs.jpcc.4c04986","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04986","url":null,"abstract":"This study investigates the use of TiCl<sub>4</sub> vapor phase infiltration (VPI) to cleave ester groups in the main chain of a polymer and drive depolymerization and film etching. Prior investigations have demonstrated that the infiltration of TiCl<sub>4</sub> into PMMA results in dealkylation of its ester bond, cleaving its side groups. This study investigates the VPI of TiCl<sub>4</sub> into poly(lactic acid), which is a prototypical polymer with an ester group in its main chain. Utilizing <i>in situ</i> quartz crystal microbalance (QCM) measurements and spectroscopic ellipsometry, PLA is observed to depolymerize readily at 135 °C with extended TiCl<sub>4</sub> precursor exposure, resulting in significant thickness and mass reduction, whereas at 90 °C, depolymerization is significantly slower and etching is negligible. Utilizing Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and a residual gas analyzer (RGA), dealkylation is shown to be the primary depolymerization mechanism. FTIR and XPS analyses reveal the consumption of carbonyl and methoxy groups and the emergence of hydroxyl, chlorine, and titanium moieties. <i>In situ</i> RGA measurements provide further insights into the byproducts formed during the TiCl<sub>4</sub> and water exposure steps, indicating that the depolymerized components undergo further breakdown into other substances. Residuals left after 135 °C TiCl<sub>4</sub> VPI are easily removed with a 0.1 M HCl aqueous solution. These findings highlight the expanding functionality of VPI, revealing its capability as both an additive and subtractive process and suggesting its broader applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"72 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601509","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c05848
Yuchuan Xu, Yi Zhao, WanZhen Liang
Electronic circular dichroism (ECD) spectroscopy is the preferred tool for studying organic chiral supramolecules. However, it is a great challenge to experimentally clarify the contributions to ECD spectra from molecular vibrational motions and the intermolecular interactions, key factors for an efficient system architecture design of chemical sensors, catalysts, or optoelectronics. Focusing on this issue, here, we perform theoretical studies on the vibrationally resolved absorption and ECD spectra of two one-dimensional bay-substituted chiral perylene diimides (PDIs) by employing the non-Markovian stochastic Schrödinger equation (NMSSE) with respect to the model Hamiltonian in the diabatic representation, which includes the intramolecular localized excited states (LEs), intermolecular change-transfer excited states (CTEs), and the vibronic couplings (VC) as well. Our calculated results exhibit that the theoretical spectra, with the inclusion of the VC effect, agree better with the experimental ones than those without this effect and that the difference between the traditional absorption spectra of the two bay-substituted PDIs is much less obvious than that in their ECD spectra, verifying that ECD spectroscopy is sensitive to the absolute configuration and conformation of chiral supramolecules. We further make a comparison among the pure electronic spectra of aggregates with different aggregate sizes calculated by the time-dependent density functional theory and the mixed exciton model with and without decoupling the LE and CTE states. It is shown that the hybridization between LE and CTE states results in the emergence of new peaks or troughs in the high-energy band and a significant deviation between the calculated ECD spectrum and that predicted by the exciton chirality rule. It is further shown that the ECD spectra of oligomers exhibit an odd–even alternation pattern with changes in aggregate size.
{"title":"Electronic Absorption and Circular Dichroism Spectra of One-Dimensional Bay-Substituted Chiral PDIs: Effects of Intermolecular Interactions, Vibronic Coupling, and Aggregate Size","authors":"Yuchuan Xu, Yi Zhao, WanZhen Liang","doi":"10.1021/acs.jpcc.4c05848","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05848","url":null,"abstract":"Electronic circular dichroism (ECD) spectroscopy is the preferred tool for studying organic chiral supramolecules. However, it is a great challenge to experimentally clarify the contributions to ECD spectra from molecular vibrational motions and the intermolecular interactions, key factors for an efficient system architecture design of chemical sensors, catalysts, or optoelectronics. Focusing on this issue, here, we perform theoretical studies on the vibrationally resolved absorption and ECD spectra of two one-dimensional bay-substituted chiral perylene diimides (PDIs) by employing the non-Markovian stochastic Schrödinger equation (NMSSE) with respect to the model Hamiltonian in the diabatic representation, which includes the intramolecular localized excited states (LEs), intermolecular change-transfer excited states (CTEs), and the vibronic couplings (VC) as well. Our calculated results exhibit that the theoretical spectra, with the inclusion of the VC effect, agree better with the experimental ones than those without this effect and that the difference between the traditional absorption spectra of the two bay-substituted PDIs is much less obvious than that in their ECD spectra, verifying that ECD spectroscopy is sensitive to the absolute configuration and conformation of chiral supramolecules. We further make a comparison among the pure electronic spectra of aggregates with different aggregate sizes calculated by the time-dependent density functional theory and the mixed exciton model with and without decoupling the LE and CTE states. It is shown that the hybridization between LE and CTE states results in the emergence of new peaks or troughs in the high-energy band and a significant deviation between the calculated ECD spectrum and that predicted by the exciton chirality rule. It is further shown that the ECD spectra of oligomers exhibit an odd–even alternation pattern with changes in aggregate size.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601511","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}
Polymeric carbon nitrides have gained significant interest in photocatalysis owing to their tunable electronic and structural diversity. However, traditional polymeric carbon nitrides, regardless of their structural motifs, have shown limited or no effectiveness in producing H2O2 through photocatalysis. This study introduces a controllable carbonization technique assisted by post molten salt treatment, as demonstrated across three structurally distinct polymeric carbon nitrides: melon and two ionic variants. Through the molten salt treatment, the photoactivities for H2O2 synthesis were significantly enhanced on all three carbon nitride variants. The enhanced activity is attributed to the precise control of the carbonization process, resulting in the formation of a composite material comprising carbon and carbon nitride. The formation of this composite material not only improves charge separation but also imparts hydrophobic properties to the material, thereby preventing the decomposition of H2O2 synthesized under photocatalytic conditions.
{"title":"Enhanced Photocatalytic Hydrogen Peroxide Synthesis Performance of Polymeric Carbon Nitrides with a Controllable Carbonization Strategy","authors":"Ziqi Wang, Runjie Zhao, Xinyu Chen, Jiahui Xie, Qihua Yang, Xiaobo Li","doi":"10.1021/acs.jpcc.4c06330","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06330","url":null,"abstract":"Polymeric carbon nitrides have gained significant interest in photocatalysis owing to their tunable electronic and structural diversity. However, traditional polymeric carbon nitrides, regardless of their structural motifs, have shown limited or no effectiveness in producing H<sub>2</sub>O<sub>2</sub> through photocatalysis. This study introduces a controllable carbonization technique assisted by post molten salt treatment, as demonstrated across three structurally distinct polymeric carbon nitrides: melon and two ionic variants. Through the molten salt treatment, the photoactivities for H<sub>2</sub>O<sub>2</sub> synthesis were significantly enhanced on all three carbon nitride variants. The enhanced activity is attributed to the precise control of the carbonization process, resulting in the formation of a composite material comprising carbon and carbon nitride. The formation of this composite material not only improves charge separation but also imparts hydrophobic properties to the material, thereby preventing the decomposition of H<sub>2</sub>O<sub>2</sub> synthesized under photocatalytic conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601512","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c04696
Priscila Hasse Palharim, Xianwei Wang, Emmanuel Varesio, Thomas Bürgi, Antonio Carlos Silva Costa Teixeira
Photocatalysts made of WO3 coupled with AgCl have demonstrated enhanced photocatalytic activity for degrading organic contaminants. While various studies have focused on the degradation of organic molecules and the formation of intermediate species during photocatalysis, the catalytic interface during illumination has received less attention. Attenuated total reflection infrared spectroscopy (ATR-IR) is ideal for studying solid–liquid interfaces and has shown potential for studying catalytic reactions. In this study, the application of in situ ATR-IR for the degradation of the model contaminant acetaminophen using pure WO3 and WO3–AgCl with and without a surface-directing agent (citric acid) was explored. ATR-IR experiments in batch and continuous flow modes were conducted to characterize the interface and its adsorbates during illumination. Liquid chromatography–high-resolution mass spectrometry (LC-HRMS) was used to further explore the reaction intermediates and to support the ATR-IR data. ACT dimers, ACT trimers, dimers of ACT and p-benzoquinone, and p-benzoquinone were identified as degradation products. NH3-TPD was employed to investigate the surface acidity and its role in the photocatalytic process, revealing that the combination of AgCl with WO3 reduced the number of weak and moderate acidic sites, while the addition of citric acid promoted the formation of strong acidic sites in the photocatalyst, which significantly impacted the degradation efficiency. Some limitations of the ATR-IR technique were highlighted; nevertheless, it remains a powerful tool for probing solid–liquid interfaces during photocatalytic degradation.
{"title":"In Situ ATR-IR Spectroscopy for the Degradation of Acetaminophen on WO3–AgCl Photocatalysts","authors":"Priscila Hasse Palharim, Xianwei Wang, Emmanuel Varesio, Thomas Bürgi, Antonio Carlos Silva Costa Teixeira","doi":"10.1021/acs.jpcc.4c04696","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04696","url":null,"abstract":"Photocatalysts made of WO<sub>3</sub> coupled with AgCl have demonstrated enhanced photocatalytic activity for degrading organic contaminants. While various studies have focused on the degradation of organic molecules and the formation of intermediate species during photocatalysis, the catalytic interface during illumination has received less attention. Attenuated total reflection infrared spectroscopy (ATR-IR) is ideal for studying solid–liquid interfaces and has shown potential for studying catalytic reactions. In this study, the application of in situ ATR-IR for the degradation of the model contaminant acetaminophen using pure WO<sub>3</sub> and WO<sub>3</sub>–AgCl with and without a surface-directing agent (citric acid) was explored. ATR-IR experiments in batch and continuous flow modes were conducted to characterize the interface and its adsorbates during illumination. Liquid chromatography–high-resolution mass spectrometry (LC-HRMS) was used to further explore the reaction intermediates and to support the ATR-IR data. ACT dimers, ACT trimers, dimers of ACT and <i>p-</i>benzoquinone, and <i>p-</i>benzoquinone were identified as degradation products. NH<sub>3</sub>-TPD was employed to investigate the surface acidity and its role in the photocatalytic process, revealing that the combination of AgCl with WO<sub>3</sub> reduced the number of weak and moderate acidic sites, while the addition of citric acid promoted the formation of strong acidic sites in the photocatalyst, which significantly impacted the degradation efficiency. Some limitations of the ATR-IR technique were highlighted; nevertheless, it remains a powerful tool for probing solid–liquid interfaces during photocatalytic degradation.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609807","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c05672
Javier D. Fuhr, J. Esteban Gayone, Hugo Ascolani
In this work, we report the growth of a mixed Bi1–x Sbx single layer on the Ag(111) surface with various stoichiometries. The atomic geometry has been thoroughly investigated by low-energy electron diffraction, scanning tunneling microscopy, and X-ray photoelectron spectroscopy experiments, as well as calculations based on density functional theory. We first determined that the Sb/Ag(111) system for coverages below 2/3 monolayer behaves similarly to the Bi/Ag(111) system, with a dealloying transition to a rectangular (3 × √3) phase when the Sb coverage exceeds 1/3 monolayer. We found two alternative preparation strategies to obtain a mixed Bi1–x Sbx layer: sequential deposition and simultaneous deposition of Bi and Sb. In the first case, one of the elements is deposited on a completely covered surface alloy of the other element. The obtained phase corresponds to a single mixed BiSb layer free of Ag atoms, forming a rectangular (3 × √3) structure. The simultaneous deposition strategy yields the same structure but offers the significant advantage of enabling controlled variation of the stoichiometry. The obtained mixed Bi–Sb phase has a lateral atomic arrangement very similar to the one in the nonalloyed phase observed for Sb on Ag(111), with Sb and Bi atoms distributed disorderly, and presents a significant vertical corrugation, promising considerable Rashba effects.
{"title":"Single-Layer of Bi1–xSbx Grown on Ag(111)","authors":"Javier D. Fuhr, J. Esteban Gayone, Hugo Ascolani","doi":"10.1021/acs.jpcc.4c05672","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05672","url":null,"abstract":"In this work, we report the growth of a mixed Bi<sub>1–<i>x</i></sub> Sb<sub><i>x</i></sub> single layer on the Ag(111) surface with various stoichiometries. The atomic geometry has been thoroughly investigated by low-energy electron diffraction, scanning tunneling microscopy, and X-ray photoelectron spectroscopy experiments, as well as calculations based on density functional theory. We first determined that the Sb/Ag(111) system for coverages below 2/3 monolayer behaves similarly to the Bi/Ag(111) system, with a dealloying transition to a rectangular (3 × √3) phase when the Sb coverage exceeds 1/3 monolayer. We found two alternative preparation strategies to obtain a mixed Bi<sub>1–<i>x</i></sub> Sb<sub><i>x</i></sub> layer: sequential deposition and simultaneous deposition of Bi and Sb. In the first case, one of the elements is deposited on a completely covered surface alloy of the other element. The obtained phase corresponds to a single mixed BiSb layer free of Ag atoms, forming a rectangular (3 × √3) structure. The simultaneous deposition strategy yields the same structure but offers the significant advantage of enabling controlled variation of the stoichiometry. The obtained mixed Bi–Sb phase has a lateral atomic arrangement very similar to the one in the nonalloyed phase observed for Sb on Ag(111), with Sb and Bi atoms distributed disorderly, and presents a significant vertical corrugation, promising considerable Rashba effects.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"6 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609809","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c06806
Vishnu Priya H. Radhakantha, Shristi Pradhan, Aninda Jiban Bhattacharyya
Rechargeable aluminum-ion batteries (AIBs) are promising alternatives to lithium-based batteries due to their competitive energy densities. Aqueous AIBs enable the use of electrode materials with open-framework structures and large interlayer spacings, which facilitate aluminum ion insertion and extraction. Herein, we explore ammonium vanadate (NH4V4O10; NVO) with a high interlayer spacing of ∼9.4 Å as a potential positive electrode for AIBs. The material demonstrates an initial high discharge capacity of 210 mA h g–1 in 1 M AlCl3 electrolyte but degrades due to structural distortion from the strain induced by the intercalating [Al(H2O)6]3+ cation. The effects of ammonium salt additives (NH4X: X = Cl, F, CH3CO2, HCO2) on the electrochemical performance are investigated, with a detailed focus on NH4Cl, demonstrating notable improvements in structural stability over 1 M AlCl3. Ex situ XRD, Fourier transform infrared, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectrometry analyses reveal partial stabilization of the NVO structure and enhanced cyclability over a few tens of cycles. Solvent composition adjustments with 1 M AlCl3 as the salt showed similar trends. This work, in addition to identifying optimal Al3+ intercalating hosts, emphasizes the critical role of electrolytes in advancing aqueous AIB technologies.
可充电铝离子电池（AIBs）因其具有竞争力的能量密度而有望成为锂电池的替代品。水性 AIB 可以使用具有开放式框架结构和大层间距的电极材料，这有利于铝离子的插入和萃取。在此，我们探讨了具有 9.4 Å 高层间距的钒酸铵（NH4V4O10；NVO）作为 AIBs 潜在正极的可能性。该材料在 1 M AlCl3 电解液中显示出 210 mA h g-1 的初始高放电容量，但由于插层[Al(H2O)6]3+ 阳离子引起的应变导致结构畸变而退化。研究了铵盐添加剂（NH4X：X = Cl、F、CH3CO2、HCO2）对电化学性能的影响，重点是 NH4Cl，结果表明其结构稳定性明显优于 1 M AlCl3。原位 XRD、傅立叶变换红外光谱、X 射线光电子能谱和电感耦合等离子体-光发射光谱分析表明，NVO 结构在几十次循环后部分稳定，循环能力增强。以 1 M AlCl3 为盐的溶剂成分调整也显示出类似的趋势。这项工作除了确定最佳的 Al3+ 插层宿主外，还强调了电解质在推进水性 AIB 技术中的关键作用。
{"title":"Exploring Aluminum-Ion (Al3+) Insertion in Ammonium Vanadium Bronze (NH4V4O10) for Aqueous Aluminum-Ion Rechargeable Batteries","authors":"Vishnu Priya H. Radhakantha, Shristi Pradhan, Aninda Jiban Bhattacharyya","doi":"10.1021/acs.jpcc.4c06806","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06806","url":null,"abstract":"Rechargeable aluminum-ion batteries (AIBs) are promising alternatives to lithium-based batteries due to their competitive energy densities. Aqueous AIBs enable the use of electrode materials with open-framework structures and large interlayer spacings, which facilitate aluminum ion insertion and extraction. Herein, we explore ammonium vanadate (NH<sub>4</sub>V<sub>4</sub>O<sub>10</sub>; NVO) with a high interlayer spacing of ∼9.4 Å as a potential positive electrode for AIBs. The material demonstrates an initial high discharge capacity of 210 mA h g<sup>–1</sup> in 1 M AlCl<sub>3</sub> electrolyte but degrades due to structural distortion from the strain induced by the intercalating [Al(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> cation. The effects of ammonium salt additives (NH<sub>4</sub>X: X = Cl, F, CH<sub>3</sub>CO<sub>2</sub>, HCO<sub>2</sub>) on the electrochemical performance are investigated, with a detailed focus on NH<sub>4</sub>Cl, demonstrating notable improvements in structural stability over 1 M AlCl<sub>3</sub>. Ex situ XRD, Fourier transform infrared, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectrometry analyses reveal partial stabilization of the NVO structure and enhanced cyclability over a few tens of cycles. Solvent composition adjustments with 1 M AlCl<sub>3</sub> as the salt showed similar trends. This work, in addition to identifying optimal Al<sup>3+</sup> intercalating hosts, emphasizes the critical role of electrolytes in advancing aqueous AIB technologies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609812","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c03516
Ardavan Farahvash, Mayank Agrawal, Adam P. Willard, Andrew A. Peterson
The adsorption and desorption of reactants and products from a solid surface are essential for achieving sustained surface chemical reactions. At a liquid–solid interface, these processes can involve the collective reorganization of interfacial solvent molecules in order to accommodate the adsorbing or desorbing species. Identifying the role of solvent in adsorption and desorption is important for advancing our understanding of surface chemical rates and mechanisms and enabling the rational design and optimization of surface chemical systems. In this manuscript, we use all-atom molecular dynamics simulation and transition path sampling to identify water’s role in the desorption of CO from a Pt(100) surface in contact with liquid water. We demonstrate that the solvation of CO, as quantified by the water coordination number, is an essential component of the desorption reaction coordinate. We use meta dynamics to compute the desorption free energy surface and conclude based on its features that desorption proceeds via a two-step mechanism whereby the final detachment of CO from the surface is preceded by the formation of a nascent solvation shell.
反应物和产物在固体表面的吸附和解吸对实现持续的表面化学反应至关重要。在液固界面上，这些过程可能涉及界面溶剂分子的集体重组，以适应吸附或解吸物种。确定溶剂在吸附和解吸过程中的作用对于加深我们对表面化学反应速率和机理的理解以及合理设计和优化表面化学体系非常重要。在本手稿中，我们利用全原子分子动力学模拟和过渡路径采样来确定水在 CO 从与液态水接触的 Pt（100）表面解吸过程中的作用。我们证明，以水配位数量化的 CO 溶解是解吸反应坐标的重要组成部分。我们利用元动力学计算了解吸自由能表面，并根据其特征得出结论：解吸是通过两步机制进行的，即在 CO 最终脱离表面之前，先形成一个新生的溶解壳。
{"title":"The Influence of Solvent on Surface Adsorption and Desorption","authors":"Ardavan Farahvash, Mayank Agrawal, Adam P. Willard, Andrew A. Peterson","doi":"10.1021/acs.jpcc.4c03516","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03516","url":null,"abstract":"The adsorption and desorption of reactants and products from a solid surface are essential for achieving sustained surface chemical reactions. At a liquid–solid interface, these processes can involve the collective reorganization of interfacial solvent molecules in order to accommodate the adsorbing or desorbing species. Identifying the role of solvent in adsorption and desorption is important for advancing our understanding of surface chemical rates and mechanisms and enabling the rational design and optimization of surface chemical systems. In this manuscript, we use all-atom molecular dynamics simulation and transition path sampling to identify water’s role in the desorption of CO from a Pt(100) surface in contact with liquid water. We demonstrate that the solvation of CO, as quantified by the water coordination number, is an essential component of the desorption reaction coordinate. We use meta dynamics to compute the desorption free energy surface and conclude based on its features that desorption proceeds via a two-step mechanism whereby the final detachment of CO from the surface is preceded by the formation of a nascent solvation shell.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"95 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601478","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 : 2024-11-13DOI: 10.1021/acs.jpcc.4c06269
Tasnim Ahmed Mahi, Imran Hossain Sabuj, Quazi Shafayat Hossain, Sadiq Shahriyar Nishat, Shirin Akter Jahan, Mohammed Nazrul Islam Khan, Umme Sarmeen Akhtar, Muhammad Shahriar Bashar, Dipa Islam, Md. Zakir Sultan, Sharmin Jahan, Khandker Saadat Hossain, Imtiaz Ahmed
The presence of strong anharmonicity poses significant challenges in modeling the lattice dynamics of tetragonal (I4/mmm) and cubic (Fm3̅m) phases of halide double perovskite Cs2NaBiCl6. Moreover, a direct electronic transition with a reduced band gap of ∼3 eV can be optoelectronically more attractive than the usual indirect wide band gap (∼3.8 eV) of cubic Cs2NaBiCl6. Here, we established the dynamical stability of the cubic Cs2NaBiCl6 (>110 K) using the cubic and quartic anharmonic phonon renormalization technique in favor of the tetragonal to cubic phase transition near ∼110 K. The tetragonal I4/m phase turned out to be dynamically stable in Cs2NaBiCl6 at T = 0 K. We report a direct band gap of ∼3 eV in cubic Cs2NaBiCl6 by incorporating the long-range van der Waals and relativistic spin–orbit coupling corrections to different sophisticated and accurate exchange-correlation approximations in density functional theory (DFT). The diffuse reflectance spectroscopy of hydrothermally synthesized cubic Cs2NaBiCl6 provided experimental evidence of this direct transition. The experimentally observed Raman modes are identified in the reliable DFT simulations. The room temperature photoluminescence emission of cubic Cs2NaBiCl6 was observed near ∼574 nm. The cubic Cs2NaBiCl6 displayed ∼100% photocatalytic degradation of rhodamine B dye under 50 min of optical irradiation. Overall, this work may have provided a comprehensive DFT-experimental understanding of the functional properties of Cs2NaBiCl6 relevant to dynamic stability and optoelectronic applications.
{"title":"First-Principles Modeling of Lattice Dynamics and Direct Electronic Transition in Halide Double Perovskite Cs2NaBiCl6","authors":"Tasnim Ahmed Mahi, Imran Hossain Sabuj, Quazi Shafayat Hossain, Sadiq Shahriyar Nishat, Shirin Akter Jahan, Mohammed Nazrul Islam Khan, Umme Sarmeen Akhtar, Muhammad Shahriar Bashar, Dipa Islam, Md. Zakir Sultan, Sharmin Jahan, Khandker Saadat Hossain, Imtiaz Ahmed","doi":"10.1021/acs.jpcc.4c06269","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06269","url":null,"abstract":"The presence of strong anharmonicity poses significant challenges in modeling the lattice dynamics of tetragonal (<i>I</i>4/<i>mmm</i>) and cubic (<i>Fm</i>3̅<i>m</i>) phases of halide double perovskite Cs<sub>2</sub>NaBiCl<sub>6</sub>. Moreover, a direct electronic transition with a reduced band gap of ∼3 eV can be optoelectronically more attractive than the usual indirect wide band gap (∼3.8 eV) of cubic Cs<sub>2</sub>NaBiCl<sub>6</sub>. Here, we established the dynamical stability of the cubic Cs<sub>2</sub>NaBiCl<sub>6</sub> (>110 K) using the cubic and quartic anharmonic phonon renormalization technique in favor of the tetragonal to cubic phase transition near ∼110 K. The tetragonal <i>I</i>4/<i>m</i> phase turned out to be dynamically stable in Cs<sub>2</sub>NaBiCl<sub>6</sub> at <i>T</i> = 0 K. We report a direct band gap of ∼3 eV in cubic Cs<sub>2</sub>NaBiCl<sub>6</sub> by incorporating the long-range van der Waals and relativistic spin–orbit coupling corrections to different sophisticated and accurate exchange-correlation approximations in density functional theory (DFT). The diffuse reflectance spectroscopy of hydrothermally synthesized cubic Cs<sub>2</sub>NaBiCl<sub>6</sub> provided experimental evidence of this direct transition. The experimentally observed Raman modes are identified in the reliable DFT simulations. The room temperature photoluminescence emission of cubic Cs<sub>2</sub>NaBiCl<sub>6</sub> was observed near ∼574 nm. The cubic Cs<sub>2</sub>NaBiCl<sub>6</sub> displayed ∼100% photocatalytic degradation of rhodamine B dye under 50 min of optical irradiation. Overall, this work may have provided a comprehensive DFT-experimental understanding of the functional properties of Cs<sub>2</sub>NaBiCl<sub>6</sub> relevant to dynamic stability and optoelectronic applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"80 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601510","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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