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}
Pub Date : 2026-02-02DOI: 10.1021/acs.jpcc.5c07731
Diego Hunt,Victor Oestreicher,Valeria Ferrari
In this work, we present a microscopic analysis of the magnetic properties of the α-CoII layered hydroxide (LHs) family. Using first-principles molecular dynamics complemented by DFT+U calculations and Monte Carlo simulations, we provide a detailed magnetic characterization of the previously reported hybrid α-CoII LHs ( Chem. Eur. J. 2021, 27, 921−927). By parametrizing Heisenberg-type Hamiltonians, we demonstrate that interlayer magnetic interactions are significantly weaker than intralayer ones and even smaller than the thermal energies involved in typical experiments. This indicates that the magnetic behavior of these systems is primarily governed by intralayer interactions, effectively rendering them two-dimensional magnets. Monte Carlo simulations allow us to estimate the relevant macroscopic magnetic variables, yielding excellent agreement with our previously reported experimental data. Extending the analysis to different coordination ligands, we find that variations in the magnetic properties of α-CoII LHs are mainly driven by local distortions in the tetrahedral Co(II) environment, which directly modulate the superexchange interaction between tetrahedral and octahedral Co(II) ions. For the hybrid α-CoII LHs, these distortions are closely linked to the specific orientation of the organic molecules within the interlayer region, suggesting that a controlled molecular arrangement can be exploited as a form of molecular engineering to tailor the magnetic response of LHs. Our findings support the formulation of a simplified model that captures the essential magnetic physics of these compounds, based on the modulation of intralayer exchange interactions. These insights pave the way toward the design of layered materials with tunable magnetic properties and underscores their potential as adaptable platforms for future spintronics applications.
{"title":"α-Cobalt Hydroxides as 2D Magnets: Tuning Magnetism through Exchange Interactions","authors":"Diego Hunt,Victor Oestreicher,Valeria Ferrari","doi":"10.1021/acs.jpcc.5c07731","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07731","url":null,"abstract":"In this work, we present a microscopic analysis of the magnetic properties of the α-CoII layered hydroxide (LHs) family. Using first-principles molecular dynamics complemented by DFT+U calculations and Monte Carlo simulations, we provide a detailed magnetic characterization of the previously reported hybrid α-CoII LHs ( Chem. Eur. J. 2021, 27, 921−927). By parametrizing Heisenberg-type Hamiltonians, we demonstrate that interlayer magnetic interactions are significantly weaker than intralayer ones and even smaller than the thermal energies involved in typical experiments. This indicates that the magnetic behavior of these systems is primarily governed by intralayer interactions, effectively rendering them two-dimensional magnets. Monte Carlo simulations allow us to estimate the relevant macroscopic magnetic variables, yielding excellent agreement with our previously reported experimental data. Extending the analysis to different coordination ligands, we find that variations in the magnetic properties of α-CoII LHs are mainly driven by local distortions in the tetrahedral Co(II) environment, which directly modulate the superexchange interaction between tetrahedral and octahedral Co(II) ions. For the hybrid α-CoII LHs, these distortions are closely linked to the specific orientation of the organic molecules within the interlayer region, suggesting that a controlled molecular arrangement can be exploited as a form of molecular engineering to tailor the magnetic response of LHs. Our findings support the formulation of a simplified model that captures the essential magnetic physics of these compounds, based on the modulation of intralayer exchange interactions. These insights pave the way toward the design of layered materials with tunable magnetic properties and underscores their potential as adaptable platforms for future spintronics applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098146","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}
The self-assembly of nucleotides into sophisticated biomolecular architectures offers a powerful platform for developing advanced functional materials. Herein, we exploit the innate chirality and metal-coordination capability of nucleotides to fabricate biomolecular coordination polymers with circularly polarized luminescence (CPL). By integrating nucleotides (AMP, GMP, UMP, CMP) with lanthanide-based deep eutectic solvents (DESs) that serve as both a reactive medium and a source of red and green emission, we successfully constructed nucleotide-lanthanide coordination polymers. These biomolecular complexes not only exhibited characteristic lanthanide emissions but also demonstrated significant CPL activity. Remarkably, a white-light-emitting coordination polymer with white circularly polarized luminescence (W-CPL) was achieved by incorporating blue-emitting carbon dots into the AMP-coordinated system, forming a solvent-free supramolecular assembly. Furthermore, a prototype light-emitting diode (LED) device was fabricated by coating these nucleotide-based complexes onto a UV chip, successfully generating electrically driven polarized visible light. This work underscores the immense potential of nucleotide biomolecules as versatile scaffolds for crafting next-generation polarized optical materials and devices.
{"title":"Nucleotide-Based White Circularly Polarized Luminescence Materials in Lanthanide Deep Eutectic Solvents","authors":"Xuetao Yan,Lifei Chen,Yuze Ren,Kaixuan Cui,Tianliang Li,Lixing Lin,Zeyu Li,Yingying Chen,Zhenzhen Li,Lingyan Feng","doi":"10.1021/acs.jpcc.5c08455","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08455","url":null,"abstract":"The self-assembly of nucleotides into sophisticated biomolecular architectures offers a powerful platform for developing advanced functional materials. Herein, we exploit the innate chirality and metal-coordination capability of nucleotides to fabricate biomolecular coordination polymers with circularly polarized luminescence (CPL). By integrating nucleotides (AMP, GMP, UMP, CMP) with lanthanide-based deep eutectic solvents (DESs) that serve as both a reactive medium and a source of red and green emission, we successfully constructed nucleotide-lanthanide coordination polymers. These biomolecular complexes not only exhibited characteristic lanthanide emissions but also demonstrated significant CPL activity. Remarkably, a white-light-emitting coordination polymer with white circularly polarized luminescence (W-CPL) was achieved by incorporating blue-emitting carbon dots into the AMP-coordinated system, forming a solvent-free supramolecular assembly. Furthermore, a prototype light-emitting diode (LED) device was fabricated by coating these nucleotide-based complexes onto a UV chip, successfully generating electrically driven polarized visible light. This work underscores the immense potential of nucleotide biomolecules as versatile scaffolds for crafting next-generation polarized optical materials and devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097878","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.6c00288
Christian S. Erickson,Matthew J. Crane,Tyler J. Milstein,Daniel R. Gamelin
{"title":"Correction to “Photoluminescence Saturation in Quantum-Cutting Yb3+-Doped CsPb(Cl1–xBrx)3 Perovskite Nanocrystals: Implications for Solar Downconversion”","authors":"Christian S. Erickson,Matthew J. Crane,Tyler J. Milstein,Daniel R. Gamelin","doi":"10.1021/acs.jpcc.6c00288","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00288","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"23 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098144","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.5c07878
Matthew B. Leonard,Jason K. Navin,Md Raian Yousuf,Ashish Tripathi,Ayman M. Karim,John R. Morris,Thomas P. Pearl,Christopher J. Karwacki
To develop enhanced catalytically active materials for use in protection against toxic chemical exposures, such as chemical warfare agents (CWAs), there needs to be a fundamental understanding of the driving factors for agent decomposition. Within this study, we used in situ infrared absorbance spectroscopy to investigate the role of sample pretreatment in modifying the surfaces of TiO2 and 1% Pt/TiO2 and the subsequent decomposition of the nerve agent simulant diisopropyl methylphosphonate (DIMP). Surface and subsurface defects were generated in both TiO2 and 1% Pt/TiO2 when pretreated in a reducing environment. These defects served as sites for the decomposition of DIMP into acetone, mesityl oxide, and isopropyl alcohol (IPA). Due to the increased defect density on the surface resulting from a strong metal–surface interaction, reduced 1% Pt/TiO2 showed increased DIMP decomposition compared to that of reduced TiO2. Pretreatment of the materials in an oxidizing environment resulted in both TiO2 and 1% Pt/TiO2 having a lower defect density compared with the reduced samples. However, for the oxidized 1% Pt/TiO2, surface-accessible active oxygen species were produced, leading to a more selective degradation of DIMP. This study provides an understanding of the impact of different pretreatments of titania, with and without surface-supported Pt, on DIMP decomposition. This includes capturing the roles defects or active oxygen species formed during pretreatment play in DIMP surface reactivity. These insights will assist in the development of next-generation CWA protection or decontamination materials.
{"title":"Adsorption and Decomposition of Sarin Simulant DIMP on Reduced and Oxidized TiO2 and Pt/TiO2","authors":"Matthew B. Leonard,Jason K. Navin,Md Raian Yousuf,Ashish Tripathi,Ayman M. Karim,John R. Morris,Thomas P. Pearl,Christopher J. Karwacki","doi":"10.1021/acs.jpcc.5c07878","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07878","url":null,"abstract":"To develop enhanced catalytically active materials for use in protection against toxic chemical exposures, such as chemical warfare agents (CWAs), there needs to be a fundamental understanding of the driving factors for agent decomposition. Within this study, we used in situ infrared absorbance spectroscopy to investigate the role of sample pretreatment in modifying the surfaces of TiO2 and 1% Pt/TiO2 and the subsequent decomposition of the nerve agent simulant diisopropyl methylphosphonate (DIMP). Surface and subsurface defects were generated in both TiO2 and 1% Pt/TiO2 when pretreated in a reducing environment. These defects served as sites for the decomposition of DIMP into acetone, mesityl oxide, and isopropyl alcohol (IPA). Due to the increased defect density on the surface resulting from a strong metal–surface interaction, reduced 1% Pt/TiO2 showed increased DIMP decomposition compared to that of reduced TiO2. Pretreatment of the materials in an oxidizing environment resulted in both TiO2 and 1% Pt/TiO2 having a lower defect density compared with the reduced samples. However, for the oxidized 1% Pt/TiO2, surface-accessible active oxygen species were produced, leading to a more selective degradation of DIMP. This study provides an understanding of the impact of different pretreatments of titania, with and without surface-supported Pt, on DIMP decomposition. This includes capturing the roles defects or active oxygen species formed during pretreatment play in DIMP surface reactivity. These insights will assist in the development of next-generation CWA protection or decontamination materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"89 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098145","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.5c06609
Jing Liu,Thomas M. Webb,Juliana Ortiz-Castillo,Yunan Qin,Tao Gao
Electrodeposition of transition metals (TMs) is important for energy storage and sustainable metal production (such as ironmaking). Although M2+/M redoxes, including Fe2+/Fe, have been investigated in concentrated aqueous electrolytes, thermodynamic measurements and modeling of the equilibrium M2+/M potential considering metal–chloride complexation in highly concentrated electrolytes remain elusive. For the first time, we systematically examine how a concentrated electrolyte affects the thermodynamics of TM electrodeposition by combining experimental, theoretical, and computational methods. Our study revealed that the electrodeposition potentials (Eeq) of a wide range of TMs (Fe, Cr, Co, Ni, Zn) are strongly dependent on the electrolyte concentration. The classical thermodynamic model, the Nernst equation, cannot quantify such concentration dependence due to its neglect of metal–anion complexation, a unique structural feature of concentrated aqueous electrolytes of TM ions due to their strong cation–anion interaction. By examining the energy landscape of the electrodeposition reaction together with the metal–ligand complexation equilibria, we develop a thermodynamic model that predicts the equilibrium electrodeposition potential in concentrated electrolytes. The model is general in structure and can be applied to other aqueous Mn+/M systems when speciation and activity data are available. The model is used for predicting the electrodeposition potential of selected TMs in both supported and unsupported electrolytes, and the prediction agrees very well with experiments. A unified thermodynamic framework for metal deposition is proposed by generalizing our model, which reduces to previously proposed models under limiting conditions and covers electrodeposition from a dilute electrolyte to a molten salt electrolyte. The fundamental and practical implications of the results are discussed, shedding light on future electrolyte engineering for a wide range of electrode reactions and engineering applications.
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