Pub Date : 2026-02-03DOI: 10.1021/acs.jpcc.5c07286
Pei-Chen Tsai, Manivannan Madhu, Wei-Lung Tseng
This study unveils how heteroatom incorporation and the structural geometry of dopant precursors tune the fluorescence and room-temperature phosphorescence (RTP) of carbonized polymer dots (CPDs). Citric acid was selected as the carbon source, while cysteine, homocysteine, cysteamine, N-acetylcysteine, and thiomalic acid served as structurally related dopant precursors. Although CA–HCys–CPDs, synthesized from hydrothermal treatment of citric acid and homocysteine, did not exhibit the highest total emission quantum yield, they possessed a comparable phosphorescence quantum yield and longer phosphorescence lifetimes and showed persistent afterglow. The enhanced performance arises from the additional methylene in homocysteine, which increases chain spacing and promotes a confined-domain cross-link-enhanced emission effect, as well as from the formation of itaconic anhydride–related compounds, which generate fluorescence and phosphorescence through cluster-triggered emission. Additionally, X-ray photoelectron spectroscopy confirms the indispensable role of nitrogen in enabling the RTP of the CPDs. Time-dependent dialysis experiments demonstrate that high-molecular-weight polymeric luminophores and polymer-integrated carbon dots dominate the phosphorescence of the CPDs. Importantly, the combination of reversed-phase high-performance liquid chromatography coupled with electrospray ionization mass spectrometry and time-dependent density functional theory simulations identified two itaconic anhydride–derived molecules as core luminophores governing both fluorescence and phosphorescence. These findings offer new guidelines for the rational design of CPDs with enhanced and tunable phosphorescent properties.
{"title":"Rational Dopant Design Uncovers Precursor–Structure Rules for Room-Temperature Phosphorescence in Carbonized Polymer Dots","authors":"Pei-Chen Tsai, Manivannan Madhu, Wei-Lung Tseng","doi":"10.1021/acs.jpcc.5c07286","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07286","url":null,"abstract":"This study unveils how heteroatom incorporation and the structural geometry of dopant precursors tune the fluorescence and room-temperature phosphorescence (RTP) of carbonized polymer dots (CPDs). Citric acid was selected as the carbon source, while cysteine, homocysteine, cysteamine, <i>N</i>-acetylcysteine, and thiomalic acid served as structurally related dopant precursors. Although CA–HCys–CPDs, synthesized from hydrothermal treatment of citric acid and homocysteine, did not exhibit the highest total emission quantum yield, they possessed a comparable phosphorescence quantum yield and longer phosphorescence lifetimes and showed persistent afterglow. The enhanced performance arises from the additional methylene in homocysteine, which increases chain spacing and promotes a confined-domain cross-link-enhanced emission effect, as well as from the formation of itaconic anhydride–related compounds, which generate fluorescence and phosphorescence through cluster-triggered emission. Additionally, X-ray photoelectron spectroscopy confirms the indispensable role of nitrogen in enabling the RTP of the CPDs. Time-dependent dialysis experiments demonstrate that high-molecular-weight polymeric luminophores and polymer-integrated carbon dots dominate the phosphorescence of the CPDs. Importantly, the combination of reversed-phase high-performance liquid chromatography coupled with electrospray ionization mass spectrometry and time-dependent density functional theory simulations identified two itaconic anhydride–derived molecules as core luminophores governing both fluorescence and phosphorescence. These findings offer new guidelines for the rational design of CPDs with enhanced and tunable phosphorescent properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"89 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122427","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c07558
Jing Wan, Yi Xiao, Chao Ran, Rongqin Xu, Kunya Yang, Xingyi Tan, Li Huang
As silicon-based field-effect transistors (FETs) approach their physical scaling limits, 2D semiconductors have emerged as promising alternative channel materials. This study employs an ab initio quantum transport method to simulate double-gate monolayer ScSI FETs with sub-5 nm gate length (Lg). Our findings demonstrate that ScSI devices with 5 nm Lg and underlaps (UL) of 0–3 nm, as well as 3 nm Lg with UL of 1–3 nm, satisfy the stringent 2028 high-performance targets of the International Technology Roadmap for Semiconductor (ITRS 2013) in terms of on-state current (Ion), power dissipation (PDP), and delay time (τ). Moreover, devices with 5 nm Lg (UL of 1–3 nm) and 3 nm Lg (UL of 2–3 nm) meet the low-power-dissipation requirements on Ion, τ, and PDP. Additionally, when incorporating negative capacitance technology, devices with 1 nm Lg and 2 or 3 nm UL also meet the high-performance ITRS requirements. These findings suggest that monolayer ScSI is a highly promising channel material for pushing Moore’s law scaling to sub-1 nm gate lengths.
{"title":"Monolayer ScSI: An Excellent Performance Material for Sub-5 nm Transistors","authors":"Jing Wan, Yi Xiao, Chao Ran, Rongqin Xu, Kunya Yang, Xingyi Tan, Li Huang","doi":"10.1021/acs.jpcc.5c07558","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07558","url":null,"abstract":"As silicon-based field-effect transistors (FETs) approach their physical scaling limits, 2D semiconductors have emerged as promising alternative channel materials. This study employs an <i>ab initio</i> quantum transport method to simulate double-gate monolayer ScSI FETs with sub-5 nm gate length (<i>L</i><sub>g</sub>). Our findings demonstrate that ScSI devices with 5 nm <i>L</i><sub>g</sub> and underlaps (<i>U</i><sub>L</sub>) of 0–3 nm, as well as 3 nm <i>L</i><sub>g</sub> with <i>U</i><sub>L</sub> of 1–3 nm, satisfy the stringent 2028 high-performance targets of the International Technology Roadmap for Semiconductor (ITRS 2013) in terms of on-state current (<i>I</i><sub>on</sub>), power dissipation (PDP), and delay time (τ). Moreover, devices with 5 nm <i>L</i><sub>g</sub> (<i>U</i><sub>L</sub> of 1–3 nm) and 3 nm <i>L</i><sub>g</sub> (<i>U</i><sub>L</sub> of 2–3 nm) meet the low-power-dissipation requirements on <i>I</i><sub>on</sub>, τ, and PDP. Additionally, when incorporating negative capacitance technology, devices with 1 nm <i>L</i><sub>g</sub> and 2 or 3 nm <i>U</i><sub>L</sub> also meet the high-performance ITRS requirements. These findings suggest that monolayer ScSI is a highly promising channel material for pushing Moore’s law scaling to sub-1 nm gate lengths.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"51 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122537","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c05802
Roberto Prado-Rivera, Daniela Radu, Vincent H. Crespi, Yuanxi Wang
Despite the rapid pace of computationally and experimentally discovering new two-dimensional layered materials, a general criterion for a given compound to prefer a layered structure over a nonlayered one remains unclear. Articulating such criteria would allow one to identify materials at the verge of an interdimensional structural phase transition between a 2D layered phase and a 3D bulk one, with potential applications in phase change memory devices. Here, we identify a general stabilization effect driven by vibrational entropy that can favor 2D layered structures over 3D bulk structures at higher temperatures, which can manifest in ordered vacancy compounds where phase competition is tight. We demonstrate this vibrational-entropy stabilization effect for three prototypical ordered vacancy chalcogenides, ZnIn2S4, In2S3, and Cu3VSe4, either by vacancy rearrangement or by cleaving through existing vacancies. The relative vibrational entropy advantage of the 2D layered phase originates mainly from softened out-of-plane dilation phonon modes.
{"title":"Vibrational Entropic Stabilization of Layered Chalcogenides: From Ordered Vacancy Compounds to Two-Dimensional Layers","authors":"Roberto Prado-Rivera, Daniela Radu, Vincent H. Crespi, Yuanxi Wang","doi":"10.1021/acs.jpcc.5c05802","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05802","url":null,"abstract":"Despite the rapid pace of computationally and experimentally discovering new two-dimensional layered materials, a general criterion for a given compound to prefer a layered structure over a nonlayered one remains unclear. Articulating such criteria would allow one to identify materials at the verge of an interdimensional structural phase transition between a 2D layered phase and a 3D bulk one, with potential applications in phase change memory devices. Here, we identify a general stabilization effect driven by vibrational entropy that can favor 2D layered structures over 3D bulk structures at higher temperatures, which can manifest in ordered vacancy compounds where phase competition is tight. We demonstrate this vibrational-entropy stabilization effect for three prototypical ordered vacancy chalcogenides, ZnIn<sub>2</sub>S<sub>4</sub>, In<sub>2</sub>S<sub>3</sub>, and Cu<sub>3</sub>VSe<sub>4</sub>, either by vacancy rearrangement or by cleaving through existing vacancies. The relative vibrational entropy advantage of the 2D layered phase originates mainly from softened out-of-plane dilation phonon modes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"2 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122425","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c07899
Rui Yu, Junwei Sun, Dominik Legut, Ruifeng Zhang
To enable efficient and cost-effective hydrogen production from water splitting, transition-metal clusters (TMCs) loaded on various functionalized Ti2CT2 MXenes (TMCs/Ti2CT2) are systematically investigated as potential electrocatalysts for the hydrogen evolution reaction (HER) using first-principles calculations. The results indicate that 24 optimal combinations of functional groups and TMCs (e.g., Te–Co, Te–Rh, and Se–Ir) are screened from 223 candidates, which exhibit favorable stability and even lower |ΔGH| than that of the noble-metal Pt benchmark (ΔGH = −0.09 eV). Crucially, the enhanced activity originates from the electronegativity match between functional groups and TMCs, which induces uniform valence states across the cluster sites and thereby optimizes the hydrogen binding strength. Furthermore, a machine-learning framework with high predictive accuracy (R2 = 0.89) is established to enable the rapid screening of TMCs/Ti2CT2 and reveal the correlation between their structural properties and HER catalytic activity. These findings not only provide promising HER electrocatalyst candidates but also elucidate the electronic origins of catalytic activity, offering a rational design strategy for TMCs/Ti2CT2.
{"title":"Rational Design of Cluster-Modified MXene for Electrocatalytic High-Efficiency Hydrogen Evolution Reaction","authors":"Rui Yu, Junwei Sun, Dominik Legut, Ruifeng Zhang","doi":"10.1021/acs.jpcc.5c07899","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07899","url":null,"abstract":"To enable efficient and cost-effective hydrogen production from water splitting, transition-metal clusters (TMCs) loaded on various functionalized Ti<sub>2</sub>CT<sub>2</sub> MXenes (TMCs/Ti<sub>2</sub>CT<sub>2</sub>) are systematically investigated as potential electrocatalysts for the hydrogen evolution reaction (HER) using first-principles calculations. The results indicate that 24 optimal combinations of functional groups and TMCs (e.g., Te–Co, Te–Rh, and Se–Ir) are screened from 223 candidates, which exhibit favorable stability and even lower |Δ<i>G</i><sub>H</sub>| than that of the noble-metal Pt benchmark (Δ<i>G</i><sub>H</sub> = −0.09 eV). Crucially, the enhanced activity originates from the electronegativity match between functional groups and TMCs, which induces uniform valence states across the cluster sites and thereby optimizes the hydrogen binding strength. Furthermore, a machine-learning framework with high predictive accuracy (<i>R</i><sup>2</sup> = 0.89) is established to enable the rapid screening of TMCs/Ti<sub>2</sub>CT<sub>2</sub> and reveal the correlation between their structural properties and HER catalytic activity. These findings not only provide promising HER electrocatalyst candidates but also elucidate the electronic origins of catalytic activity, offering a rational design strategy for TMCs/Ti<sub>2</sub>CT<sub>2</sub>.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"177 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122538","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c07153
Longlong Xiong, Gang Meng, Dongzheng Yang, Bin Jiang
Inelastic scattering processes of NO and CO from metal surfaces have served as benchmarks in revealing vibrational energy transfer dynamics at gas–surface interfaces. While the quasi-classical trajectory (QCT) method has been widely employed for modeling such processes because of its superior efficiency, considering the discrete nature of vibrational transitions, its accuracy has seldom been verified against the accurate quantum dynamical (QD) method. This is mainly due to the difficulty of high-dimensional state-to-state QD scattering calculations for heavy molecules on the surfaces. In this work, we report the first six-dimensional state-to-state quantum dynamics of NO and CO from a rigid Au(111) surface, allowing us to compare them with corresponding QCT dynamics in the same conditions based on first-principles neural network-fit potential energy surfaces. It is found that for rare vibrational transition events, QCT substantially underestimates vibrationally inelastic scattering probabilities. While for processes with more apparent vibrational inelasticity, for example, NO (vi = 3 → vf ≠ 3), QCT and QD results align with each other reasonably well. In addition, both methods predict similar rotational state distributions with consistent energy-dependent patterns. This validates the appropriateness of QCT in describing translational-to-rotational energy transfer. These findings highlight the necessity of using the QD method for accurately predicting low-probability vibrationally inelastic scattering channels. Meanwhile, they also suggest the validity of QCT for studying highly vibrationally and rotationally inelastic molecule–surface state-to-state scattering processes, where high-dimensional QD simulations remain intractable.
{"title":"Six-Dimensional State-to-State Scattering of CO and NO from Au(111): A Comparison of Quantum and Quasi-Classical Dynamics","authors":"Longlong Xiong, Gang Meng, Dongzheng Yang, Bin Jiang","doi":"10.1021/acs.jpcc.5c07153","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07153","url":null,"abstract":"Inelastic scattering processes of NO and CO from metal surfaces have served as benchmarks in revealing vibrational energy transfer dynamics at gas–surface interfaces. While the quasi-classical trajectory (QCT) method has been widely employed for modeling such processes because of its superior efficiency, considering the discrete nature of vibrational transitions, its accuracy has seldom been verified against the accurate quantum dynamical (QD) method. This is mainly due to the difficulty of high-dimensional state-to-state QD scattering calculations for heavy molecules on the surfaces. In this work, we report the first six-dimensional state-to-state quantum dynamics of NO and CO from a rigid Au(111) surface, allowing us to compare them with corresponding QCT dynamics in the same conditions based on first-principles neural network-fit potential energy surfaces. It is found that for rare vibrational transition events, QCT substantially underestimates vibrationally inelastic scattering probabilities. While for processes with more apparent vibrational inelasticity, for example, NO (<i>v</i><sub><i>i</i></sub> = 3 → <i>v</i><sub><i>f</i></sub> ≠ 3), QCT and QD results align with each other reasonably well. In addition, both methods predict similar rotational state distributions with consistent energy-dependent patterns. This validates the appropriateness of QCT in describing translational-to-rotational energy transfer. These findings highlight the necessity of using the QD method for accurately predicting low-probability vibrationally inelastic scattering channels. Meanwhile, they also suggest the validity of QCT for studying highly vibrationally and rotationally inelastic molecule–surface state-to-state scattering processes, where high-dimensional QD simulations remain intractable.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"51 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122426","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c07994
Vera M. Metalnikova, Dmitry A. Svintsitskiy, Svetlana V. Cherepanova, Andrei I. Boronin
Mixed oxides AgFeO2 (delafossite) and AgMnO2 (crednerite) were prepared during hydrothermal synthesis. The catalytic properties were investigated in the low-temperature CO oxidation reaction, depending on the pretreatment temperature in CO + O2. Correlations were established between the catalytic activity of mixed oxides, structural features, thermal stability, and silver surface state. Oxide AgMnO2 was characterized by enhanced reactivity toward CO (below 100 °C) and enhanced oxygen mobility in comparison with AgFeO2. In situ XRD and ex situ XPS revealed the relationship between the high catalytic CO oxidation activity of AgMnO2 and the presence of active oxygen forms related to the Ag2+ surface species, which were not found on the AgFeO2 surface. High catalytic activity on the surface of the AgMnO2 particles is considered to involve a redox cycle with the participation of Ag2+, Ag1+, and Ag0 silver states, while the reduced catalytic activity of AgFeO2 is caused by the reaction occurring at the interface between the Ag1+Ox/Ag0 particles and the delafossite surface, excluding the involvement of Ag2+-type species in the redox cycle.
{"title":"Understanding the Room-Temperature Catalytic Activity of Silver-Containing Mixed Oxides: The Role of Ag2+ Surface Species","authors":"Vera M. Metalnikova, Dmitry A. Svintsitskiy, Svetlana V. Cherepanova, Andrei I. Boronin","doi":"10.1021/acs.jpcc.5c07994","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07994","url":null,"abstract":"Mixed oxides AgFeO<sub>2</sub> (delafossite) and AgMnO<sub>2</sub> (crednerite) were prepared during hydrothermal synthesis. The catalytic properties were investigated in the low-temperature CO oxidation reaction, depending on the pretreatment temperature in CO + O<sub>2</sub>. Correlations were established between the catalytic activity of mixed oxides, structural features, thermal stability, and silver surface state. Oxide AgMnO<sub>2</sub> was characterized by enhanced reactivity toward CO (below 100 °C) and enhanced oxygen mobility in comparison with AgFeO<sub>2</sub>. <i>In situ</i> XRD and <i>ex situ</i> XPS revealed the relationship between the high catalytic CO oxidation activity of AgMnO<sub>2</sub> and the presence of active oxygen forms related to the Ag<sup>2+</sup> surface species, which were not found on the AgFeO<sub>2</sub> surface. High catalytic activity on the surface of the AgMnO<sub>2</sub> particles is considered to involve a redox cycle with the participation of Ag<sup>2+</sup>, Ag<sup>1+</sup>, and Ag<sup>0</sup> silver states, while the reduced catalytic activity of AgFeO<sub>2</sub> is caused by the reaction occurring at the interface between the Ag<sup>1+</sup>O<sub><i>x</i></sub>/Ag<sup>0</sup> particles and the delafossite surface, excluding the involvement of Ag<sup>2+</sup>-type species in the redox cycle.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122432","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 : 2026-02-03DOI: 10.1021/acs.jpcc.5c07317
Teng-Ze Zhang, Jin-Tao Ye, You-Qi Zhou, Li-Ping Wang, Liang-Feng Huang
The attractive application of two-dimensional (2D) materials as nanoscale corrosion-resistant coatings for metals in realistic environments is being challenged by ubiquitous galvanic corrosion, for which the key electromotive mechanism still lacks reliable clarification. In this work, four representative heterostructures based on the two most robust 2D coatings (graphene and hexagonal boron nitride) and two prototypical metal substrates (Cu and Ni) are comparatively studied by first-principles calculations. The obtained work functions are combined with available experimental results to confirm that the previously supposed electromotive force based on the static electronic-potential difference cannot rationalize the expected metal → coating electron transfer. Alternatively, the cathodic oxygen-reduction reactions (ORRs) on coating/metal surfaces, as well as the hydrogen-evolution reactions (HERs) in certain acidic conditions, are found able to provide a reasonable dynamic electromotive force to drive the electronic depletion on metals. The yielded corrosion potentials accurately unify the measured values in various neutral and acidic solutions, and the stability of O2 adsorption (i.e., the starting step of ORR) closely explains the experimental corrosion current density. The joint electronic-structure and electrochemical mechanisms underlying the surface-reactivity trends are revealed by both quantitatively portraying the free-energy profiles (plus kinetic corrections) for the cathodic reactions and systematically analyzing the multibody couplings between metal surfaces, 2D coatings, and adsorbates. The dynamic electromotive mechanism discovered here precisely confirms the realistic electrochemical reactions on coating/metal surfaces and the associated interfacial electron-transfer behaviors and can motivate more effective corrosion-control strategies.
{"title":"Dynamic Electromotive Mechanism for the Galvanic Corrosion of 2D Coatings on Metals","authors":"Teng-Ze Zhang, Jin-Tao Ye, You-Qi Zhou, Li-Ping Wang, Liang-Feng Huang","doi":"10.1021/acs.jpcc.5c07317","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07317","url":null,"abstract":"The attractive application of two-dimensional (2D) materials as nanoscale corrosion-resistant coatings for metals in realistic environments is being challenged by ubiquitous galvanic corrosion, for which the key electromotive mechanism still lacks reliable clarification. In this work, four representative heterostructures based on the two most robust 2D coatings (graphene and hexagonal boron nitride) and two prototypical metal substrates (Cu and Ni) are comparatively studied by first-principles calculations. The obtained work functions are combined with available experimental results to confirm that the previously supposed electromotive force based on the static electronic-potential difference cannot rationalize the expected metal → coating electron transfer. Alternatively, the cathodic oxygen-reduction reactions (ORRs) on coating/metal surfaces, as well as the hydrogen-evolution reactions (HERs) in certain acidic conditions, are found able to provide a reasonable dynamic electromotive force to drive the electronic depletion on metals. The yielded corrosion potentials accurately unify the measured values in various neutral and acidic solutions, and the stability of O<sub>2</sub> adsorption (i.e., the starting step of ORR) closely explains the experimental corrosion current density. The joint electronic-structure and electrochemical mechanisms underlying the surface-reactivity trends are revealed by both quantitatively portraying the free-energy profiles (plus kinetic corrections) for the cathodic reactions and systematically analyzing the multibody couplings between metal surfaces, 2D coatings, and adsorbates. The dynamic electromotive mechanism discovered here precisely confirms the realistic electrochemical reactions on coating/metal surfaces and the associated interfacial electron-transfer behaviors and can motivate more effective corrosion-control strategies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122536","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 : 2026-02-03DOI: 10.1021/acs.jpcc.6c00408
Sophia Trejo, Juliana J. Antonio, Elfi Kraka, Haoyuan Chen
The stability of metal–organic frameworks (MOFs) is crucial for their industrial applications, with metal–linker coordination bonds often being the weakest structural points. Here, we assessed the strength of these bonds in representative MOF series (UiO-66, MOF-5, and ZIFs) using local vibrational mode theory, which converts delocalized normal modes to local vibrational modes and associated local mode force constants, reflecting bond strength. Good agreement between the bond strengths obtained from local force constants and the corresponding experimental stability data was obtained, which in some cases was not reflected by the electron density at the bond critical points. The effects of linker functionalization were also analyzed, in which ortho-NH2 substitutions on the linkers were found to weaken the adjacent coordination bonds via intramolecular hydrogen bonding. These findings establish a readily computable quantum-mechanical metric for evaluating bond strengths in MOFs, paving the way for accurate evaluation and prediction of MOF stability.
{"title":"Assessing the Stability of Metal–Organic Frameworks with Local Vibrational Mode Theory","authors":"Sophia Trejo, Juliana J. Antonio, Elfi Kraka, Haoyuan Chen","doi":"10.1021/acs.jpcc.6c00408","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00408","url":null,"abstract":"The stability of metal–organic frameworks (MOFs) is crucial for their industrial applications, with metal–linker coordination bonds often being the weakest structural points. Here, we assessed the strength of these bonds in representative MOF series (UiO-66, MOF-5, and ZIFs) using local vibrational mode theory, which converts delocalized normal modes to local vibrational modes and associated local mode force constants, reflecting bond strength. Good agreement between the bond strengths obtained from local force constants and the corresponding experimental stability data was obtained, which in some cases was not reflected by the electron density at the bond critical points. The effects of linker functionalization were also analyzed, in which <i>ortho</i>-NH<sub>2</sub> substitutions on the linkers were found to weaken the adjacent coordination bonds via intramolecular hydrogen bonding. These findings establish a readily computable quantum-mechanical metric for evaluating bond strengths in MOFs, paving the way for accurate evaluation and prediction of MOF stability.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"66 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122270","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}
Flexible, versatile sensors prepared using simple, harsh chemical-free techniques are required for sensing hazardous molecules at low concentrations. In this work, we demonstrate a chemical-free, femtosecond laser-based synthesis procedure to achieve spherical Ti3C2 MXene nanoparticles via the technique of liquid-assisted laser ablation (LAL) while using a Bessel beam profile. The as-prepared MXene nanoparticles and their Au-decorated hybrids were deposited onto flexible filter paper substrates and evaluated as surface-enhanced Raman scattering (SERS) sensors for the trace-level detection of ammonium nitrate (AN), picric acid (PA), and Nile Blue (NB). The structural and compositional analyses (XRD, XPS, and TEM) confirmed near-complete etching of Al from Ti3AlC2 and successful incorporation of Au. The standalone MXene substrates provided a significant chemical enhancement [enhancement factor (EF)] of 103, enabling nanomolar detection of analytes without any noble metals. MXene/Au hybrids exhibited synergistic chemical and electromagnetic enhancements, achieving EF values of up to 105 for NB. These results highlight the potential of femtosecond laser-ablated MXene nanoparticles in filter paper as sustainable, flexible, and cost-effective SERS platforms for environmental and security sensing.
{"title":"Chemical-Free MXene Nanoparticles Synthesized Using Femtosecond Bessel Beam for Flexible SERS Sensors","authors":"Amrit Kumar,Supriya Pradhan,Niharika Pradhan,Venugopal Rao Soma","doi":"10.1021/acs.jpcc.5c07669","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07669","url":null,"abstract":"Flexible, versatile sensors prepared using simple, harsh chemical-free techniques are required for sensing hazardous molecules at low concentrations. In this work, we demonstrate a chemical-free, femtosecond laser-based synthesis procedure to achieve spherical Ti3C2 MXene nanoparticles via the technique of liquid-assisted laser ablation (LAL) while using a Bessel beam profile. The as-prepared MXene nanoparticles and their Au-decorated hybrids were deposited onto flexible filter paper substrates and evaluated as surface-enhanced Raman scattering (SERS) sensors for the trace-level detection of ammonium nitrate (AN), picric acid (PA), and Nile Blue (NB). The structural and compositional analyses (XRD, XPS, and TEM) confirmed near-complete etching of Al from Ti3AlC2 and successful incorporation of Au. The standalone MXene substrates provided a significant chemical enhancement [enhancement factor (EF)] of 103, enabling nanomolar detection of analytes without any noble metals. MXene/Au hybrids exhibited synergistic chemical and electromagnetic enhancements, achieving EF values of up to 105 for NB. These results highlight the potential of femtosecond laser-ablated MXene nanoparticles in filter paper as sustainable, flexible, and cost-effective SERS platforms for environmental and security sensing.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098147","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 : 2026-02-02DOI: 10.1021/acs.jpcc.5c07925
Samiksha Mukesh Jain,Samrat Das Adhikari,Camilo A. Mesa,Hind Benzidi,José Manuel González-Acosta,Andrés F. Gualdrón-Reyes,Núria López,Sixto Giménez,Iván Mora-Seró
Photocatalytic hydrogen (H2) production with 2D Ruddlesden–Popper tin-iodide perovskites has recently emerged as a promising route toward sustainable solar-to-fuel conversion. However, a major limitation of these systems lies in their rapid degradation caused by tin and iodide oxidation. In the present study, we report the synthesis of 4-fluorophenethylammonium tin-iodide (4FPSI) perovskite microcrystals in a mixture of hydroiodic acid (HI) and H2O, which exhibit remarkable long-term photostability and sustained photocatalytic H2 production via HI splitting. Intermittent light irradiation was shown to further boost H2 production by promoting efficient charge separation and suppressing the accumulation of trapped charge carriers that drive recombination. Notably, reused and aged materials showed enhanced photocatalytic performance, which theoretical simulations attributed to surface reconstruction that exposes additional tin catalytic active sites. The samples that underwent degradation after multiple photocatalytic tests could be recovered through a simple chemical treatment and restore the H2 production capability. Together, these findings highlight tin-iodide perovskites as highly promising photocatalysts for solar H2 production, combining durability, recyclability, and facile recovery strategies to simultaneously advance all key performance metrics.
{"title":"Efficient and Stable Hydrogen Evolution from HI Splitting Using a Robust 2D Tin-Iodide Perovskite","authors":"Samiksha Mukesh Jain,Samrat Das Adhikari,Camilo A. Mesa,Hind Benzidi,José Manuel González-Acosta,Andrés F. Gualdrón-Reyes,Núria López,Sixto Giménez,Iván Mora-Seró","doi":"10.1021/acs.jpcc.5c07925","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07925","url":null,"abstract":"Photocatalytic hydrogen (H2) production with 2D Ruddlesden–Popper tin-iodide perovskites has recently emerged as a promising route toward sustainable solar-to-fuel conversion. However, a major limitation of these systems lies in their rapid degradation caused by tin and iodide oxidation. In the present study, we report the synthesis of 4-fluorophenethylammonium tin-iodide (4FPSI) perovskite microcrystals in a mixture of hydroiodic acid (HI) and H2O, which exhibit remarkable long-term photostability and sustained photocatalytic H2 production via HI splitting. Intermittent light irradiation was shown to further boost H2 production by promoting efficient charge separation and suppressing the accumulation of trapped charge carriers that drive recombination. Notably, reused and aged materials showed enhanced photocatalytic performance, which theoretical simulations attributed to surface reconstruction that exposes additional tin catalytic active sites. The samples that underwent degradation after multiple photocatalytic tests could be recovered through a simple chemical treatment and restore the H2 production capability. Together, these findings highlight tin-iodide perovskites as highly promising photocatalysts for solar H2 production, combining durability, recyclability, and facile recovery strategies to simultaneously advance all key performance metrics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"67 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098148","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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