Pub Date : 2026-01-30DOI: 10.1021/acs.jpcc.5c08632
Maohua Quan, Yuting Qiu, Zhou Yang
In Raman spectroscopy, the optimal signal is obtained when the sample is irradiated by a laser at normal incidence. Ensuring both signal stability and high sensitivity for capturing analyte molecules on nonflat or tilted substrates remains difficult, especially in the process of rapid testing. Here, 3D hemispherical polydimethylsiloxane (PDMS) substrate with bioinspired compound-eye structure was fabricated by utilizing the liquid–liquid interface self-assembly and transfer technique. Using Au monolayer films decorated PDMS substrate as a surface-enhanced Raman scattering (SERS) substrate. The rotational symmetry of the bioinspired SERS substrate architecture enables stable SERS performance even under substrate tilting from 0 to 75°, demonstrating excellent suitability for field-based detection applications. The hemispherical SERS substrate demonstrated a minimum detectable urea concentration of 10–5 M, which is significantly lower than the minimum urea level (10–3 M) in the tear fluid of the body.
{"title":"Stable Light-Trapping SERS Substrates with Bioinspired Arrays for Biochemical Sensing","authors":"Maohua Quan, Yuting Qiu, Zhou Yang","doi":"10.1021/acs.jpcc.5c08632","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08632","url":null,"abstract":"In Raman spectroscopy, the optimal signal is obtained when the sample is irradiated by a laser at normal incidence. Ensuring both signal stability and high sensitivity for capturing analyte molecules on nonflat or tilted substrates remains difficult, especially in the process of rapid testing. Here, 3D hemispherical polydimethylsiloxane (PDMS) substrate with bioinspired compound-eye structure was fabricated by utilizing the liquid–liquid interface self-assembly and transfer technique. Using Au monolayer films decorated PDMS substrate as a surface-enhanced Raman scattering (SERS) substrate. The rotational symmetry of the bioinspired SERS substrate architecture enables stable SERS performance even under substrate tilting from 0 to 75°, demonstrating excellent suitability for field-based detection applications. The hemispherical SERS substrate demonstrated a minimum detectable urea concentration of 10<sup>–5</sup> M, which is significantly lower than the minimum urea level (10<sup>–3</sup> M) in the tear fluid of the body.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"284 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-29DOI: 10.1021/acs.jpcc.5c07253
J. Hingies Monisha, Vasumathi Velachi, Prabal K. Maiti
Ensuring the stability of the AuNP-gene complex until it reaches the target sites is a crucial factor for the success of gene therapy. Although different AuNP sizes and AuNP-to-DNA ratios are investigated for specific therapeutic needs, their role in the stability and packaging of AuNP-DNA complex remains unclear. In this study, we employ all-atom molecular dynamics simulations to investigate the influence of cationic ligand-functionalized AuNP (CAuNP) size and CAuNP-to-DNA ratio on DNA wrapping and binding affinity. The obtained results show that a single DNA interacting with smaller CAuNPs exhibits greater bending and wrapping due to their higher curvature. However, when two DNAs bind to smaller CAuNPs, electrostatic repulsion prevents the effective wrapping, which leads the DNAs to twist from their original orientation. Such behavior is not observed with larger CAuNPs since their increased size may mitigate repulsive forces. Further, the analysis on axial bending angle reveals that smaller AuNPs induce sharper DNA bending and larger AuNPs promote smoother bending. In addition, the potential of mean force (PMF) analysis confirms a stronger DNA binding affinity for larger AuNPs, with affinity decreasing when two DNAs attach to a single CAuNP. Our results from the DNA loading capacity calculations provide insights into the maximum number of DNA molecules that can be loaded onto CAuNPs of a given size. These findings offer key insights into optimizing the size of AuNP and DNA-to-AuNP ratios for the development of efficient gene delivery systems.
{"title":"Effect of Gold Nanoparticle Size and DNA Concentration on DNA-Nanoparticles Complexation: A Molecular Dynamics Study","authors":"J. Hingies Monisha, Vasumathi Velachi, Prabal K. Maiti","doi":"10.1021/acs.jpcc.5c07253","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07253","url":null,"abstract":"Ensuring the stability of the AuNP-gene complex until it reaches the target sites is a crucial factor for the success of gene therapy. Although different AuNP sizes and AuNP-to-DNA ratios are investigated for specific therapeutic needs, their role in the stability and packaging of AuNP-DNA complex remains unclear. In this study, we employ all-atom molecular dynamics simulations to investigate the influence of cationic ligand-functionalized AuNP (CAuNP) size and CAuNP-to-DNA ratio on DNA wrapping and binding affinity. The obtained results show that a single DNA interacting with smaller CAuNPs exhibits greater bending and wrapping due to their higher curvature. However, when two DNAs bind to smaller CAuNPs, electrostatic repulsion prevents the effective wrapping, which leads the DNAs to twist from their original orientation. Such behavior is not observed with larger CAuNPs since their increased size may mitigate repulsive forces. Further, the analysis on axial bending angle reveals that smaller AuNPs induce sharper DNA bending and larger AuNPs promote smoother bending. In addition, the potential of mean force (PMF) analysis confirms a stronger DNA binding affinity for larger AuNPs, with affinity decreasing when two DNAs attach to a single CAuNP. Our results from the DNA loading capacity calculations provide insights into the maximum number of DNA molecules that can be loaded onto CAuNPs of a given size. These findings offer key insights into optimizing the size of AuNP and DNA-to-AuNP ratios for the development of efficient gene delivery systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"85 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c04627
Jing Xu, Wanlin Guo, Yufeng Guo
Developing catalysts based on graphene heterostructures is an attractive aspect for advancing the application of graphene. Our extensive first-principles calculations and ab initio molecular dynamics simulations reveal that the catalytic capability of graphene/Cu heterostructures for the electrochemical oxygen evolution reaction (OER) can be activated and significantly enhanced by the synergistic effect of introducing Stone–Wales (SW) defects into graphene and applying biaxial compressive strains to the heterostructures. The overpotential of the SW-defected graphene/Cu heterostructure for the OER decreases to 0.39 V under a biaxial compressive strain of −3%, which is lower than most theoretical overpotentials obtained when using graphene heterostructures as catalysts. The alteration and improvement in the catalytic capability of SW-defected graphene/Cu heterostructures under compressive strains are mainly attributed to the facilitated desorption of intermediates on graphene, the decreased reaction activation energy, and the charge transfer from the SW defect sites to the Cu substrates.
{"title":"Catalytic Capability of Graphene/Cu Heterostructures for Oxygen Evolution Reaction Activated by the Synergistic Effect of Defects and Strain","authors":"Jing Xu, Wanlin Guo, Yufeng Guo","doi":"10.1021/acs.jpcc.5c04627","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04627","url":null,"abstract":"Developing catalysts based on graphene heterostructures is an attractive aspect for advancing the application of graphene. Our extensive first-principles calculations and <i>ab initio</i> molecular dynamics simulations reveal that the catalytic capability of graphene/Cu heterostructures for the electrochemical oxygen evolution reaction (OER) can be activated and significantly enhanced by the synergistic effect of introducing Stone–Wales (SW) defects into graphene and applying biaxial compressive strains to the heterostructures. The overpotential of the SW-defected graphene/Cu heterostructure for the OER decreases to 0.39 V under a biaxial compressive strain of −3%, which is lower than most theoretical overpotentials obtained when using graphene heterostructures as catalysts. The alteration and improvement in the catalytic capability of SW-defected graphene/Cu heterostructures under compressive strains are mainly attributed to the facilitated desorption of intermediates on graphene, the decreased reaction activation energy, and the charge transfer from the SW defect sites to the Cu substrates.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c08205
Shu-Hui Guan, Yi-Wen Wei, Cheng Shang, Zhi-Pan Liu
Scandia (Sc) and yttria (Y) codoped zirconia (ScYSZ) emerged as a promising candidate for high-performance solid electrolyte materials utilized in intermediate-temperature solid oxide fuel cells (IT-SOFCs). While it exhibits a record-high ionic conductivity (∼0.10 S/cm at 800 °C), the physical origin of the superior performance remains poorly understood, limiting the further optimization and the application in IT-SOFC. Here, we construct the Sc–Y–Zr–O global neural network potential and explore systematically the thermodynamic landscape of ScYSZ across 65 different compositions (6.7–14.3 mol % dopants). From millions of candidate structures, we identify a thermodynamically stable cubic phase region at Sc/Y < 1 with Y2O3 ≥ 8 mol %. Large-scale molecular dynamics simulations further show that ScYSZ at Sc2O3 = 3 mol % and Y2O3 = 8 mol % yields an exceptional ionic conductivity of 0.13 S/cm at 800 °C, surpassing conventional 8 mol % Y-stabilized zirconia (YSZ) by an order of magnitude. Our analysis reveals that the presence of Sc not only increases the Ov concentration by allowing ⟨111⟩ Ov–Ov pairs but also reduces the oxygen migration barriers markedly. Our results not only pinpoint the optimal ScYSZ composition for IT-SOFC applications theoretically but also establish a general framework for the rational design of advanced solid electrolyte materials.
{"title":"Scandia as the Oxygen Vacancy Stabilizer to Boost the Ionic Conductivity of Sc–Y-Codoped Zirconia","authors":"Shu-Hui Guan, Yi-Wen Wei, Cheng Shang, Zhi-Pan Liu","doi":"10.1021/acs.jpcc.5c08205","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08205","url":null,"abstract":"Scandia (Sc) and yttria (Y) codoped zirconia (ScYSZ) emerged as a promising candidate for high-performance solid electrolyte materials utilized in intermediate-temperature solid oxide fuel cells (IT-SOFCs). While it exhibits a record-high ionic conductivity (∼0.10 S/cm at 800 °C), the physical origin of the superior performance remains poorly understood, limiting the further optimization and the application in IT-SOFC. Here, we construct the Sc–Y–Zr–O global neural network potential and explore systematically the thermodynamic landscape of ScYSZ across 65 different compositions (6.7–14.3 mol % dopants). From millions of candidate structures, we identify a thermodynamically stable cubic phase region at Sc/Y < 1 with Y<sub>2</sub>O<sub>3</sub> ≥ 8 mol %. Large-scale molecular dynamics simulations further show that ScYSZ at Sc<sub>2</sub>O<sub>3</sub> = 3 mol % and Y<sub>2</sub>O<sub>3</sub> = 8 mol % yields an exceptional ionic conductivity of 0.13 S/cm at 800 °C, surpassing conventional 8 mol % Y-stabilized zirconia (YSZ) by an order of magnitude. Our analysis reveals that the presence of Sc not only increases the O<sub>v</sub> concentration by allowing ⟨111⟩ O<sub>v</sub>–O<sub>v</sub> pairs but also reduces the oxygen migration barriers markedly. Our results not only pinpoint the optimal ScYSZ composition for IT-SOFC applications theoretically but also establish a general framework for the rational design of advanced solid electrolyte materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"56 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c08343
Yitao He, Jiří Červenka
Electrochemistry lies at the heart of modern energy technologies, yet connecting atomic-level insights to macroscopic performance remains an enduring challenge. Quantum-based simulations, such as density functional theory, have illuminated many fundamental processes, but their reach is limited by the complexity of real electrochemical environments. Bridging these scales requires a new conceptual framework that can expose the hidden connections between theory and experiment. Here, we argue that the thoughtful integration of artificial intelligence (AI) can transform electrochemical research by unifying theory, experiment, and data-driven inference. AI-assisted frameworks can accelerate convergence between computation and experiment, revealing hidden physical relationships and enabling closed-loop discovery. Realizing this vision will require developing transparent, interpretable AI models that earn the same scientific trust as human reasoning, unlocking deeper understanding and innovation across the electrochemical sciences.
{"title":"How Artificial Intelligence Can Advance Electrochemical Science and Identify Water Molecule Orientation on Platinum Electrodes","authors":"Yitao He, Jiří Červenka","doi":"10.1021/acs.jpcc.5c08343","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08343","url":null,"abstract":"Electrochemistry lies at the heart of modern energy technologies, yet connecting atomic-level insights to macroscopic performance remains an enduring challenge. Quantum-based simulations, such as density functional theory, have illuminated many fundamental processes, but their reach is limited by the complexity of real electrochemical environments. Bridging these scales requires a new conceptual framework that can expose the hidden connections between theory and experiment. Here, we argue that the thoughtful integration of artificial intelligence (AI) can transform electrochemical research by unifying theory, experiment, and data-driven inference. AI-assisted frameworks can accelerate convergence between computation and experiment, revealing hidden physical relationships and enabling closed-loop discovery. Realizing this vision will require developing transparent, interpretable AI models that earn the same scientific trust as human reasoning, unlocking deeper understanding and innovation across the electrochemical sciences.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c08141
Rens Cuijpers, Wietse F. M. van Geel, Dorothée S. Mader, K. Danique Grevink, Matthijs van Velzen, Martin Lutz, Stefan C. J. Meskers
Materials consisting of organic dye molecules play an important role as pigments, as active layer in organic light emitting diodes or solar cells, and as bistable medium in optical transistors and switches. Yet there is currently no working protocol to accurately predict one of the most basic optical properties of these solids: their reflection spectrum. Here we develop a method to calculate the reflection spectrum of crystals of dye molecules based on the crystal structure and optical absorption of the dye in solution. We treat the interaction between light and matter in the crystals as strong. Electromagnetic four-potentials are gauged consistently, and their boundary conditions at the reflecting interface are derived. Finally, we include both excitonic and charge transfer interactions between molecules in the crystals. We test our approach on a large data set of reflection spectra and crystal structures including several industrial pigments.
{"title":"Optical Reflection of Crystals of Dye Molecules and Strong Coupling between Light and Matter","authors":"Rens Cuijpers, Wietse F. M. van Geel, Dorothée S. Mader, K. Danique Grevink, Matthijs van Velzen, Martin Lutz, Stefan C. J. Meskers","doi":"10.1021/acs.jpcc.5c08141","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08141","url":null,"abstract":"Materials consisting of organic dye molecules play an important role as pigments, as active layer in organic light emitting diodes or solar cells, and as bistable medium in optical transistors and switches. Yet there is currently no working protocol to accurately predict one of the most basic optical properties of these solids: their reflection spectrum. Here we develop a method to calculate the reflection spectrum of crystals of dye molecules based on the crystal structure and optical absorption of the dye in solution. We treat the interaction between light and matter in the crystals as strong. Electromagnetic four-potentials are gauged consistently, and their boundary conditions at the reflecting interface are derived. Finally, we include both excitonic and charge transfer interactions between molecules in the crystals. We test our approach on a large data set of reflection spectra and crystal structures including several industrial pigments.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"55 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056959","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c06506
Rashid Rafeek V Valappil, Sayan Maity, Ashwini Anshu, Lavanya M. Ramaniah, Varadharajan Srinivasan
Varying the rate at which pressure is applied to a crystal is known to yield different pressure-induced polymorphic structures in experiments. In this work, we investigate the effect of pressure increase rate on pressure-induced polymerization in crystalline acrylamide, using room temperature constant pressure ab initio molecular dynamics simulations. Simulations performed with two different compression rates revealed very different structural evolutions of the system at lower pressures. Fast (nonequilibrated) pressure increase yields disordered (polymer) structures with unanticipated linkages for pressures up to 67 GPa. On the other hand, slow (quasi-static) pressure increase gives no new structures until 64 GPa. At pressures greater than 67 GPa, both pathways converge toward an ordered 3-dimensional polymer through a hierarchical mechanism involving 1-dimensional polymeric intermediates. The structural and electronic details of the mechanisms leading to polymerization are discussed.
{"title":"Compression Rate Dependence and Hierarchical Mechanism in the Pressure-Induced Polymerization of Acrylamide: Insights from Ab Initio Molecular Dynamics","authors":"Rashid Rafeek V Valappil, Sayan Maity, Ashwini Anshu, Lavanya M. Ramaniah, Varadharajan Srinivasan","doi":"10.1021/acs.jpcc.5c06506","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06506","url":null,"abstract":"Varying the rate at which pressure is applied to a crystal is known to yield different pressure-induced polymorphic structures in experiments. In this work, we investigate the effect of pressure increase rate on pressure-induced polymerization in crystalline acrylamide, using room temperature constant pressure <i>ab initio</i> molecular dynamics simulations. Simulations performed with two different compression rates revealed very different structural evolutions of the system at lower pressures. Fast (nonequilibrated) pressure increase yields disordered (polymer) structures with unanticipated linkages for pressures up to 67 GPa. On the other hand, slow (quasi-static) pressure increase gives no new structures until 64 GPa. At pressures greater than 67 GPa, both pathways converge toward an ordered 3-dimensional polymer through a hierarchical mechanism involving 1-dimensional polymeric intermediates. The structural and electronic details of the mechanisms leading to polymerization are discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c07043
Andreas Ziegler, Chiara I. Wagner, Hao Chen, Matthias A. Blatnik, Alexander Wolfram, Anne Brandmeier, Zdeněk Jakub, Michele Riva, Jiri Pavelec, Michael Schmid, Ulrike Diebold, Bernd Meyer, Margareta Wagner
Research on sustainable energy has intensified to reduce greenhouse gas emissions, especially CO2. One promising strategy is the catalytic reduction of CO2 to methanol, and indium oxide (In2O3) has emerged as a highly efficient catalyst, with high turnover rates and selectivity. This work investigates methanol, the end product of CO2 reduction, and its interaction with the In2O3(111) surface. Utilizing an ultrahigh vacuum (UHV) environment, this study combines temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), noncontact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The coverages investigated range from 1 to 12 methanol molecules per unit cell. The results are compared to water adsorption on In2O3(111), as the chemical behavior of both molecules is similar in many respects. At low coverage, the adsorption patterns and interactions with the In2O3(111) surface mirror those seen with water, including dissociative and molecular adsorption. The first three methanol molecules dissociate at specific sites within the surface unit cell, while molecular adsorption becomes favored for subsequent molecules at temperatures below 300 K. At the highest coverage (before multilayer adsorption) methanol and water exhibit distinct structures due to their differing hydrogen bonding capabilities.
{"title":"Revealing the Intricate Structure of Surface Phases of Methanol on In2O3(111)","authors":"Andreas Ziegler, Chiara I. Wagner, Hao Chen, Matthias A. Blatnik, Alexander Wolfram, Anne Brandmeier, Zdeněk Jakub, Michele Riva, Jiri Pavelec, Michael Schmid, Ulrike Diebold, Bernd Meyer, Margareta Wagner","doi":"10.1021/acs.jpcc.5c07043","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07043","url":null,"abstract":"Research on sustainable energy has intensified to reduce greenhouse gas emissions, especially CO<sub>2</sub>. One promising strategy is the catalytic reduction of CO<sub>2</sub> to methanol, and indium oxide (In<sub>2</sub>O<sub>3</sub>) has emerged as a highly efficient catalyst, with high turnover rates and selectivity. This work investigates methanol, the end product of CO<sub>2</sub> reduction, and its interaction with the In<sub>2</sub>O<sub>3</sub>(111) surface. Utilizing an ultrahigh vacuum (UHV) environment, this study combines temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), noncontact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The coverages investigated range from 1 to 12 methanol molecules per unit cell. The results are compared to water adsorption on In<sub>2</sub>O<sub>3</sub>(111), as the chemical behavior of both molecules is similar in many respects. At low coverage, the adsorption patterns and interactions with the In<sub>2</sub>O<sub>3</sub>(111) surface mirror those seen with water, including dissociative and molecular adsorption. The first three methanol molecules dissociate at specific sites within the surface unit cell, while molecular adsorption becomes favored for subsequent molecules at temperatures below 300 K. At the highest coverage (before multilayer adsorption) methanol and water exhibit distinct structures due to their differing hydrogen bonding capabilities.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"80 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.jpcc.5c07216
Lu Yang, Huabing Shu, Jian Zhang, Jianping Li, Gang Zhang, Kai Ren
Low interfacial thermal conductance often emerges as a primary barrier to effective heat management in advanced nanodevices. This study examines how topological defects affect the interfacial thermal conductance of graphene/SiC lateral heterostructure, utilizing nonequilibrium molecular dynamics simulations. The significant lattice mismatch between graphene and SiC results in a pristine interface that experiences severe strain and structural distortion, ultimately reducing the level of phonon transmission. By introduction of 5|8|5 topological defects, the interfacial deformation is effectively alleviated, thereby improving phonon coupling across the boundary. The results reveal an unconventional increase in interfacial thermal conductance, with the maximal value achieved when three defects are incorporated, representing a 61% improvement compared with the pristine interface. However, an excessive number of defects can lead to a reduction in the thermal conductivity. These findings demonstrate that controlled defect engineering offers a tunable pathway to optimize interfacial heat transport in 2D heterostructures, providing valuable insights for thermal management in nanoscale devices.
{"title":"Manipulation of Abnormal Thermal Conductance at the Graphene/SiC Interface through Topological Defects","authors":"Lu Yang, Huabing Shu, Jian Zhang, Jianping Li, Gang Zhang, Kai Ren","doi":"10.1021/acs.jpcc.5c07216","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07216","url":null,"abstract":"Low interfacial thermal conductance often emerges as a primary barrier to effective heat management in advanced nanodevices. This study examines how topological defects affect the interfacial thermal conductance of graphene/SiC lateral heterostructure, utilizing nonequilibrium molecular dynamics simulations. The significant lattice mismatch between graphene and SiC results in a pristine interface that experiences severe strain and structural distortion, ultimately reducing the level of phonon transmission. By introduction of 5|8|5 topological defects, the interfacial deformation is effectively alleviated, thereby improving phonon coupling across the boundary. The results reveal an unconventional increase in interfacial thermal conductance, with the maximal value achieved when three defects are incorporated, representing a 61% improvement compared with the pristine interface. However, an excessive number of defects can lead to a reduction in the thermal conductivity. These findings demonstrate that controlled defect engineering offers a tunable pathway to optimize interfacial heat transport in 2D heterostructures, providing valuable insights for thermal management in nanoscale devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056958","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}
Mayer bond order (MBO) allows partitioning of total charge in a given system into overlap population components which can be interpreted as charges shared among atoms and retained by them through atomic orbitals. In this work, we formulate a spatial distribution of these partitioned components, rendering a breakup of the total charge density into individual densities of charges shared between all the available pairs of atoms, as well as charges exclusively retained by each of the atoms themselves. The spatial density of the interatomic MBOs in particular facilitates an unbiased physical description of electrons shared between two atoms, thus essentially constituting a plottable representation of a covalent bond, obtained without inducing any explicit localization of electrons between atoms, which otherwise is an inherent source of bias. We demonstrate the proposed formulation in the basis of Wannierized atomic orbitals constructed from first principles, in a few representative varieties of systems with varying degrees of interatomic hybridization, including scenarios of multicentered bonds in molecules, to metavalent bonding in periodic systems introduced and debated in the past few years. Pertinently, in GeTe, we find two electrons (2e) contributed by collinear p orbitals in each of the three Ge–Te–Ge(Te–Ge–Te) segments passing through Te(Ge), constituting a compact distribution of 2e over the 3 atom segments (3c), along with the relatively inert s electrons maintaining a spherical shape, to facilitate near completion of subshell filling of both the atoms, thus supporting the prevalence of 3c-2e metavalent bonding in the class of narrow band gap rock-salt structures.
梅尔键序（MBO）允许将给定体系中的总电荷划分为重叠居群分量，这些重叠居群分量可以解释为原子之间共享并通过原子轨道保留的电荷。在这项工作中，我们制定了这些分区组件的空间分布，将总电荷密度分解为所有可用原子对之间共享的单个电荷密度，以及每个原子本身独家保留的电荷。原子间mbo的空间密度特别有助于对两个原子之间共享的电子进行无偏物理描述，从而基本上构成了共价键的可绘图表示，而不会引起原子之间电子的任何显式定位，否则这是固有的偏倚来源。我们在从第一性原理构建的万尼化原子轨道的基础上，在几个具有不同程度的原子间杂化的具有代表性的系统中论证了所提出的公式，包括分子中多中心键的情况，以及在过去几年引入和争论的周期系统中的元价键。相应地，在GeTe中，我们发现在通过Te（Ge）的三个Ge - Te - Ge（Te - Ge - Te）段中，每一个都有两个共线p轨道贡献的电子（2e），构成了3个原子段（3c）上2e的紧凑分布，以及相对惰性的s电子保持球形，以促进两个原子的亚壳填充接近完成，从而支持3c-2e元价键在窄带隙岩盐结构类中普遍存在。
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