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.
{"title":"Thermodynamics of Transition Metal Electrodeposition in Concentrated Aqueous Electrolytes","authors":"Jing Liu,Thomas M. Webb,Juliana Ortiz-Castillo,Yunan Qin,Tao Gao","doi":"10.1021/acs.jpcc.5c06609","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06609","url":null,"abstract":"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.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"92 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098151","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.5c06987
Dong Youn Chung,Juliane Weber,Lawrence M. Anovitz,Barbara R. Evans,Ke Yuan,Sai Adapa,Matthew G. Boebinger,Michael A. McGuire,Raphaël P. Hermann,George Yumnam,Joanne E. Stubbs,Peter J. Eng,Peter J. Heaney,Andrew G. Stack
Brucite [Mg(OH)2] is a promising sorbent for carbon dioxide removal (CDR) due to its availability and low calcination temperatures. However, natural and synthetic brucites tend to contain metal impurities, such as iron or manganese, and how these impurities affect the interfacial chemical reactivity is uncertain. Here, the impact of low concentrations of iron and manganese impurities on the carbonation efficiency of Mg(OH)2 was examined. Mg(OH)2 with small amounts (1–5 mol %) of Fe and Mn was synthesized. The increasing substitution of Fe into Mg(OH)2 was accompanied by the oxidation of Fe. The phase transformation sequence during the carbonation was found to be brucite [Mg(OH)2] → amorphous magnesium carbonate (MgCO3·nH2O) → nesquehonite (MgCO3·3H2O), regardless of impurity concentration. Both the Fe- and Mn-doped Mg(OH)2 samples were more reactive than endmember Mg(OH)2, possibly due to their higher surface areas and lower stabilities. During carbonation, 3 mol % Fe- and Mn-doped Mg(OH)2 showed the highest reactivity. The variance in reactivity for Mn-doped Mg(OH)2 was less than that of Fe-doped Mg(OH)2. These results suggest that natural or industrial waste Mg(OH)2 with less than 5 mol % Fe and Mn impurities may be targeted as more effective CDR sorbents than endmember Mg(OH)2.
{"title":"The Effects of Iron and Manganese Doping on the Carbonation of Brucite [Mg(OH)2]","authors":"Dong Youn Chung,Juliane Weber,Lawrence M. Anovitz,Barbara R. Evans,Ke Yuan,Sai Adapa,Matthew G. Boebinger,Michael A. McGuire,Raphaël P. Hermann,George Yumnam,Joanne E. Stubbs,Peter J. Eng,Peter J. Heaney,Andrew G. Stack","doi":"10.1021/acs.jpcc.5c06987","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06987","url":null,"abstract":"Brucite [Mg(OH)2] is a promising sorbent for carbon dioxide removal (CDR) due to its availability and low calcination temperatures. However, natural and synthetic brucites tend to contain metal impurities, such as iron or manganese, and how these impurities affect the interfacial chemical reactivity is uncertain. Here, the impact of low concentrations of iron and manganese impurities on the carbonation efficiency of Mg(OH)2 was examined. Mg(OH)2 with small amounts (1–5 mol %) of Fe and Mn was synthesized. The increasing substitution of Fe into Mg(OH)2 was accompanied by the oxidation of Fe. The phase transformation sequence during the carbonation was found to be brucite [Mg(OH)2] → amorphous magnesium carbonate (MgCO3·nH2O) → nesquehonite (MgCO3·3H2O), regardless of impurity concentration. Both the Fe- and Mn-doped Mg(OH)2 samples were more reactive than endmember Mg(OH)2, possibly due to their higher surface areas and lower stabilities. During carbonation, 3 mol % Fe- and Mn-doped Mg(OH)2 showed the highest reactivity. The variance in reactivity for Mn-doped Mg(OH)2 was less than that of Fe-doped Mg(OH)2. These results suggest that natural or industrial waste Mg(OH)2 with less than 5 mol % Fe and Mn impurities may be targeted as more effective CDR sorbents than endmember Mg(OH)2.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"3 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098149","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 : 2026-02-01DOI: 10.1021/acs.jpcc.5c07706
Chiranjeevulu Kashi,Bhaskar Chilukuri,Ursula Mazur,K. W. Hipps
Metal porphyrins find wide use in catalysis, photoelectronics, sensing, and other applications. The application of covalently linked porphyrins is a new area that deserves attention. The driving forces are the desire for a high density of single metal ions on a surface, the potential to design in both electronic and steric intramolecular cooperativity, and chemical tunability. One method for creating surfaces with a high density of covalently linked porphyrins, self-assembly from fluid solution, is almost unexplored. In this study we give a detailed analysis of the self-assembled monolayer formed from an alkyne linked porphyrin dimer, 1,4-Bis{[5,10,15,20-tetra(n-hexyl)porphyrinato]zinc(II)}butadiyne, that forms well-ordered structures upon adsorption on highly oriented pyrolytic graphite (HOPG) from 1,2,4-trichlorobenzene. The adlayer is studied by scanning tunneling microscopy (STM) and by density functional theory (DFT). By combining experiment with computation, the detailed structure of the adlayer is determined. It is found that it has a higher density of single metal atoms (0.66 sites/nm2) than adlayers of well-known dimeric porphyrins or monomeric zinc octaethylporphyrin. DFT is key to understanding the alkane chain disposition and its possible role in cooperativity.
{"title":"A Self-Assembled Covalently Linked Porphyrin as a High-Density Reaction Center","authors":"Chiranjeevulu Kashi,Bhaskar Chilukuri,Ursula Mazur,K. W. Hipps","doi":"10.1021/acs.jpcc.5c07706","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07706","url":null,"abstract":"Metal porphyrins find wide use in catalysis, photoelectronics, sensing, and other applications. The application of covalently linked porphyrins is a new area that deserves attention. The driving forces are the desire for a high density of single metal ions on a surface, the potential to design in both electronic and steric intramolecular cooperativity, and chemical tunability. One method for creating surfaces with a high density of covalently linked porphyrins, self-assembly from fluid solution, is almost unexplored. In this study we give a detailed analysis of the self-assembled monolayer formed from an alkyne linked porphyrin dimer, 1,4-Bis{[5,10,15,20-tetra(n-hexyl)porphyrinato]zinc(II)}butadiyne, that forms well-ordered structures upon adsorption on highly oriented pyrolytic graphite (HOPG) from 1,2,4-trichlorobenzene. The adlayer is studied by scanning tunneling microscopy (STM) and by density functional theory (DFT). By combining experiment with computation, the detailed structure of the adlayer is determined. It is found that it has a higher density of single metal atoms (0.66 sites/nm2) than adlayers of well-known dimeric porphyrins or monomeric zinc octaethylporphyrin. DFT is key to understanding the alkane chain disposition and its possible role in cooperativity.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"105 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097807","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 : 2026-02-01DOI: 10.1021/acs.jpcc.5c07920
Silda Peters,Renjith S. Pillai,Tumpa Sadhukhan
The thermally responsive behavior of metal–organic frameworks offer a pathway to materials capable of adapting their internal architecture to external stimuli. In this study, we elucidate how fluorinated AlF5 pillars, together with linker-dependent internal motions, govern the distinctive thermoresponsive behavior of ALFFIVE-Ni frameworks. Using molecular simulations, we examine the temperature-induced structural evolution across three linkers of increasing rigidity and length and show that linker tilting, mediated through node–linker dynamics, drives the transformation from large-pore (lp) to narrow-pore (np) states. The magnitude and onset of this transition are finely tuned by linker chemistry, while all systems display pronounced negative thermal expansion arising from coordinated internal vibrations. Water interactions further modulate this response by stabilizing the framework under humid conditions and partially suppressing thermal contraction. By clarifying the microscopic mechanisms underlying flexibility in fluorinated MOFs, this work provides a foundation for designing thermally adaptive materials with tailored pore behavior, structural responsiveness, and application-specific performance.
{"title":"Unlocking Thermal Flexibility in Ni-Based Fluorinated Square-Pillared MOFs: Insights into Pore Transitions and Node-Linker Dynamics","authors":"Silda Peters,Renjith S. Pillai,Tumpa Sadhukhan","doi":"10.1021/acs.jpcc.5c07920","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07920","url":null,"abstract":"The thermally responsive behavior of metal–organic frameworks offer a pathway to materials capable of adapting their internal architecture to external stimuli. In this study, we elucidate how fluorinated AlF5 pillars, together with linker-dependent internal motions, govern the distinctive thermoresponsive behavior of ALFFIVE-Ni frameworks. Using molecular simulations, we examine the temperature-induced structural evolution across three linkers of increasing rigidity and length and show that linker tilting, mediated through node–linker dynamics, drives the transformation from large-pore (lp) to narrow-pore (np) states. The magnitude and onset of this transition are finely tuned by linker chemistry, while all systems display pronounced negative thermal expansion arising from coordinated internal vibrations. Water interactions further modulate this response by stabilizing the framework under humid conditions and partially suppressing thermal contraction. By clarifying the microscopic mechanisms underlying flexibility in fluorinated MOFs, this work provides a foundation for designing thermally adaptive materials with tailored pore behavior, structural responsiveness, and application-specific performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"10 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098153","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}
Far-red phosphors are critically important for advancing plant growth lighting. In this work, a novel far-red phosphor, KAlSi2O6:Cr3+, was synthesized and optimized. The material crystallizes in a tetragonal structure with space group I41/a. It exhibits two excitation bands at 428 nm (4A2 → 4T1) and 571 nm (4A2 → 4T2) and emits a dominant peak at 710 nm (R-line) with a weak shoulder at 730 nm (N2-line). XRD Rietveld refinement results reveal that the doped Cr3+ and Rb+ preferentially occupy K+ sites, while Ga3+ substitutes for Al3+ sites. Raman and XPS analyses show that these dopants induce lattice distortion, suppress high-frequency phonons, and slightly alter the electron cloud distribution of Cr3+ ions. Notably, Ga3+-Rb+ codoping shifts the main emission to 695 nm and markedly improves thermal stability (I423 K/I303 K increases from 46.01% to 66.52%). By leveraging the spectral overlap with phytochrome PFR absorption, pc-LED devices were fabricated. Pc-LEDs based on the Ga3+-doped or Ga3+–Rb+ codoped phosphors not only promote mint growth but also enable clear imaging in night-vision scenarios, demonstrating strong potential for dual-functional lighting.
{"title":"Tuning Far-Red Luminescence Properties of KAlSi2O6:Cr3+ Phosphors via Partial Cation Substitution","authors":"Panpan Li,Huanping Wang,Ruoshan Lei,Denghao Li,Youjie Hua,Shiqing Xu","doi":"10.1021/acs.jpcc.5c07727","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07727","url":null,"abstract":"Far-red phosphors are critically important for advancing plant growth lighting. In this work, a novel far-red phosphor, KAlSi2O6:Cr3+, was synthesized and optimized. The material crystallizes in a tetragonal structure with space group I41/a. It exhibits two excitation bands at 428 nm (4A2 → 4T1) and 571 nm (4A2 → 4T2) and emits a dominant peak at 710 nm (R-line) with a weak shoulder at 730 nm (N2-line). XRD Rietveld refinement results reveal that the doped Cr3+ and Rb+ preferentially occupy K+ sites, while Ga3+ substitutes for Al3+ sites. Raman and XPS analyses show that these dopants induce lattice distortion, suppress high-frequency phonons, and slightly alter the electron cloud distribution of Cr3+ ions. Notably, Ga3+-Rb+ codoping shifts the main emission to 695 nm and markedly improves thermal stability (I423 K/I303 K increases from 46.01% to 66.52%). By leveraging the spectral overlap with phytochrome PFR absorption, pc-LED devices were fabricated. Pc-LEDs based on the Ga3+-doped or Ga3+–Rb+ codoped phosphors not only promote mint growth but also enable clear imaging in night-vision scenarios, demonstrating strong potential for dual-functional lighting.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"292 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098155","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}
It is known that the UiO-66 metal–organic framework (MOF) undergoes dehydration of physisorbed water and dehydroxylation of the zirconium clusters from RT to ∼300 °C, while the porous structure remains intact. These two processes are typically studied by thermogravimetric analysis and its derivative method (TGA/DTG), as well as differential scanning calorimetry (DSC). Here, we probe the same phenomena using temperature-dependent complex impedance spectroscopy. Peaks observed in the AC conductivity and in the real and imaginary parts of the dielectric permittivity (σAC, ε′, and ε″) are due to thermally accelerated proton (Grotthuss) hopping competing with the loss of proton carriers during guest removal and dehydroxylation up to 350 °C. Meanwhile, peaks in the loss tangent (tan δ) and phase shift (Θ) identify the temperature at which dielectric-to-heat conversion is maximized. Additionally, peaks in the imaginary part of the impedance (−Z″) and in the real part of the electric modulus (M′) mark the temperature at which the material exhibits its highest insulating character. The MOFs examined include UiO-66 with the 1,4-benzenedicarboxylate linker and UiO-66-Py with the 2,5-pyridinedicarboxylate linker, the latter further modified through trifluoroacetic acid modulation, 1-bromopropane functionalization, and optional intermediate heat treatment. Impedance measurements under cooling reveal composition-dependent rehydroxylation behavior, with the conductivity recovery as early as at 250 °C in some Py-based derivatives vs flat response in pristine UiO-66. Overall, our work provides a comprehensive analysis of several complex electrical quantities and their physical interpretation, offering complementary insights into the dehydration, dehydroxylation, and rehydroxylation dynamics of UiO-66-based MOFs.
{"title":"Complex Impedance Formalism for Probing Dehydration, Dehydroxylation, and Rehydroxylation Dynamics of UiO-66-Based Metal–Organic Frameworks","authors":"Tosapol Maluangnont,Kanokwan Chaithaweep,Saichon Sriphan,Parinya Meejaiyen,Wipark Anutrasakda,Pawnprapa Pitakjakpipop,Naratip Vittayakorn","doi":"10.1021/acs.jpcc.5c08228","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08228","url":null,"abstract":"It is known that the UiO-66 metal–organic framework (MOF) undergoes dehydration of physisorbed water and dehydroxylation of the zirconium clusters from RT to ∼300 °C, while the porous structure remains intact. These two processes are typically studied by thermogravimetric analysis and its derivative method (TGA/DTG), as well as differential scanning calorimetry (DSC). Here, we probe the same phenomena using temperature-dependent complex impedance spectroscopy. Peaks observed in the AC conductivity and in the real and imaginary parts of the dielectric permittivity (σAC, ε′, and ε″) are due to thermally accelerated proton (Grotthuss) hopping competing with the loss of proton carriers during guest removal and dehydroxylation up to 350 °C. Meanwhile, peaks in the loss tangent (tan δ) and phase shift (Θ) identify the temperature at which dielectric-to-heat conversion is maximized. Additionally, peaks in the imaginary part of the impedance (−Z″) and in the real part of the electric modulus (M′) mark the temperature at which the material exhibits its highest insulating character. The MOFs examined include UiO-66 with the 1,4-benzenedicarboxylate linker and UiO-66-Py with the 2,5-pyridinedicarboxylate linker, the latter further modified through trifluoroacetic acid modulation, 1-bromopropane functionalization, and optional intermediate heat treatment. Impedance measurements under cooling reveal composition-dependent rehydroxylation behavior, with the conductivity recovery as early as at 250 °C in some Py-based derivatives vs flat response in pristine UiO-66. Overall, our work provides a comprehensive analysis of several complex electrical quantities and their physical interpretation, offering complementary insights into the dehydration, dehydroxylation, and rehydroxylation dynamics of UiO-66-based MOFs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"34 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098152","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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