Pub Date : 2026-03-20DOI: 10.1021/acs.jpcc.5c07242
Shivani Vinod, Tanu Choudhary, Raju K. Biswas
Engineering superlattices with enhanced intrinsic in-plane transport and high thermoelectric performance involves exploring new quantum phenomena that emerge from their individual sublayers and corresponding interfaces, which play crucial roles in modern semiconductor technology. Herein, we report a first-principles formalism along with Boltzmann transport theory to study the structural, mechanical, electronic, and thermoelectric properties of MSe (M = Ga, In) layer stacked on TlSe, forming MSe–TlSe superlattices. Lattice dynamics confirm that TlSe layers exclusively dominate the low-frequency region, inducing flat acoustic modes that are absent in pristine GaSe and InSe but intrinsic to TlSe, thereby enhancing phonon scattering and lowering lattice thermal conductivity (κl). Electronic structure analysis exhibits TlSe sublayer-induced valley degeneracy and strong unconventional band convergence originating from MSe sublayer in the conduction band regime, which enhances the density of states near the Fermi level and promotes favorable Seebeck coefficients as well as improved thermoelectric performance. Bonding and charge density analyses indicate that the MSe sublayer combined with TlSe introduces a conductive network that enhances carrier transport relative to pristine bulk systems. To address the inconsistencies present in the conventional DPT formalism, we incorporate the Fröhlich interaction, allowing for a more comprehensive and accurate assessment of carrier mobility. Quantitatively, GaSe–TlSe behaves as an n-type material with ZT values of 1.09 (electrons) and 0.79 (holes) at 600 K, while InSe–TlSe is p-type with superior ZT values of 2.45 (holes) and 0.74 (electrons) at 600 K. Overall, these results demonstrate how the TlSe layer suppresses phonon transport, while the MSe layer establishes a conductive network for efficient electronic transport, offering a rational pathway toward next-generation thermoelectric quantum materials.
{"title":"Interface-Mismatch-Induced High Thermoelectricity in MSe–TlSe Superlattices","authors":"Shivani Vinod, Tanu Choudhary, Raju K. Biswas","doi":"10.1021/acs.jpcc.5c07242","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07242","url":null,"abstract":"Engineering superlattices with enhanced intrinsic in-plane transport and high thermoelectric performance involves exploring new quantum phenomena that emerge from their individual sublayers and corresponding interfaces, which play crucial roles in modern semiconductor technology. Herein, we report a first-principles formalism along with Boltzmann transport theory to study the structural, mechanical, electronic, and thermoelectric properties of MSe (M = Ga, In) layer stacked on TlSe, forming MSe–TlSe superlattices. Lattice dynamics confirm that TlSe layers exclusively dominate the low-frequency region, inducing flat acoustic modes that are absent in pristine GaSe and InSe but intrinsic to TlSe, thereby enhancing phonon scattering and lowering lattice thermal conductivity (κ<sub>l</sub>). Electronic structure analysis exhibits TlSe sublayer-induced valley degeneracy and strong unconventional band convergence originating from MSe sublayer in the conduction band regime, which enhances the density of states near the Fermi level and promotes favorable Seebeck coefficients as well as improved thermoelectric performance. Bonding and charge density analyses indicate that the MSe sublayer combined with TlSe introduces a conductive network that enhances carrier transport relative to pristine bulk systems. To address the inconsistencies present in the conventional DPT formalism, we incorporate the Fröhlich interaction, allowing for a more comprehensive and accurate assessment of carrier mobility. Quantitatively, GaSe–TlSe behaves as an n-type material with ZT values of 1.09 (electrons) and 0.79 (holes) at 600 K, while InSe–TlSe is p-type with superior ZT values of 2.45 (holes) and 0.74 (electrons) at 600 K. Overall, these results demonstrate how the TlSe layer suppresses phonon transport, while the MSe layer establishes a conductive network for efficient electronic transport, offering a rational pathway toward next-generation thermoelectric quantum materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"14 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492813","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 : 2026-03-19DOI: 10.1021/acs.jpcc.6c00519
Sakthivel Sowndharya, Sankaran Meenakshi
To achieve superior photocatalytic activity, this research focused on incorporating a natural compound, such as an amino acid, into heterojunction photocatalysts. Amino-modified metal oxide compounds that achieve a high level of amino group coverage on their surfaces are utilized for various applications, including adsorption and chromatographic techniques. l-glutamic acid (L-GA) is an aliphatic branched-chain amino acid composed of a proton-acceptor amino group and a proton-donor carbonyl group that exists in a zwitterionic form. Refractory antibiotic pollutants pose a significant and hazardous threat to both the environment and human health. Ciprofloxacin (CIP) has one of the highest rates of antibiotic resistance and may have adverse environmental effects. This work describes the l-glutamic acid-assisted CuCO2O4/Bi2O3 (GCB) as a hybrid photocatalyst for CIP photodegradation. The photogenerated carriers are separated more quickly by the p–n junction, which also generates more active species to react with CIP. The optimum photocatalyst, GCB-0.5, exhibited excellent photocatalytic performance, achieving 97% degradation of CIP within 50 min under optimum conditions of an initial CIP concentration of 50 mg/L (pH 6) and a photocatalyst dosage of 50 mg. The reaction rate constant of GCB is 0.0666 min–1, which was 3.87, 2.86, and 2.4 times greater than the respective CuCo2O4, Bi2O3, and CuCo2O4/Bi2O3 photocatalysts.
{"title":"Mechanistic Insights into L-Glutamic Acid–Assisted CuCo2O4/Bi2O3 Hybrid Nanomaterial for Photodegradation of Fluoroquinolone Drug: Optimization of Operational Parameters and Byproducts Profiling","authors":"Sakthivel Sowndharya, Sankaran Meenakshi","doi":"10.1021/acs.jpcc.6c00519","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00519","url":null,"abstract":"To achieve superior photocatalytic activity, this research focused on incorporating a natural compound, such as an amino acid, into heterojunction photocatalysts. Amino-modified metal oxide compounds that achieve a high level of amino group coverage on their surfaces are utilized for various applications, including adsorption and chromatographic techniques. <span>l</span>-glutamic acid (L-GA) is an aliphatic branched-chain amino acid composed of a proton-acceptor amino group and a proton-donor carbonyl group that exists in a zwitterionic form. Refractory antibiotic pollutants pose a significant and hazardous threat to both the environment and human health. Ciprofloxacin (CIP) has one of the highest rates of antibiotic resistance and may have adverse environmental effects. This work describes the <span>l</span>-glutamic acid-assisted CuCO<sub>2</sub>O<sub>4</sub>/Bi<sub>2</sub>O<sub>3</sub> (GCB) as a hybrid photocatalyst for CIP photodegradation. The photogenerated carriers are separated more quickly by the p–n junction, which also generates more active species to react with CIP. The optimum photocatalyst, GCB-0.5, exhibited excellent photocatalytic performance, achieving 97% degradation of CIP within 50 min under optimum conditions of an initial CIP concentration of 50 mg/L (pH 6) and a photocatalyst dosage of 50 mg. The reaction rate constant of GCB is 0.0666 min<sup>–1</sup>, which was 3.87, 2.86, and 2.4 times greater than the respective CuCo<sub>2</sub>O<sub>4</sub>, Bi<sub>2</sub>O<sub>3</sub>, and CuCo<sub>2</sub>O<sub>4</sub>/Bi<sub>2</sub>O<sub>3</sub> photocatalysts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"419 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478505","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 : 2026-03-19DOI: 10.1021/acs.jpcc.5c08540
Hiroki Nagashima, Shu Iha
Efficient separation of hydrogen from mixed gas feeds remains a key challenge in hydrogen production. Here, nanoporous graphene (NPG) is investigated as a hydrogen-selective membrane using nonequilibrium molecular dynamics simulations that enforce steady-state flux via a constant axial driving force while allowing spontaneous membrane deformation. This approach captures realistic operating conditions often overlooked in idealized fixed-membrane studies. Binary mixtures of H2 with CO2, CO, CH4, O2, H2O, N2, and NH3 were examined across three nanopore geometries. The results demonstrate that membrane flexibility significantly influences separation performance: while dynamic pore expansion (parallel deflection) enhances permeance, it reduces selectivity relative to rigid models. We demonstrate that the hydraulic diameter governs the energy barrier for permeance: increasing pore area while disproportionately enlarging the perimeter reduces the hydraulic diameter, thereby increasing steric hindrance. Under these realistic conditions, NPG exhibits much higher permeance than polymer membranes. These findings highlight the importance of accounting for the dynamic coupling between permeation flux and membrane deformation for accurate performance prediction and suggest that mechanical strain is a potential strategy to balance the permeance–selectivity trade-off.
{"title":"Hydrogen Separation in Flexible Nanoporous Graphene under Steady-State Permeation: A Molecular Dynamics Study","authors":"Hiroki Nagashima, Shu Iha","doi":"10.1021/acs.jpcc.5c08540","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08540","url":null,"abstract":"Efficient separation of hydrogen from mixed gas feeds remains a key challenge in hydrogen production. Here, nanoporous graphene (NPG) is investigated as a hydrogen-selective membrane using nonequilibrium molecular dynamics simulations that enforce steady-state flux via a constant axial driving force while allowing spontaneous membrane deformation. This approach captures realistic operating conditions often overlooked in idealized fixed-membrane studies. Binary mixtures of H<sub>2</sub> with CO<sub>2</sub>, CO, CH<sub>4</sub>, O<sub>2</sub>, H<sub>2</sub>O, N<sub>2</sub>, and NH<sub>3</sub> were examined across three nanopore geometries. The results demonstrate that membrane flexibility significantly influences separation performance: while dynamic pore expansion (parallel deflection) enhances permeance, it reduces selectivity relative to rigid models. We demonstrate that the hydraulic diameter governs the energy barrier for permeance: increasing pore area while disproportionately enlarging the perimeter reduces the hydraulic diameter, thereby increasing steric hindrance. Under these realistic conditions, NPG exhibits much higher permeance than polymer membranes. These findings highlight the importance of accounting for the dynamic coupling between permeation flux and membrane deformation for accurate performance prediction and suggest that mechanical strain is a potential strategy to balance the permeance–selectivity trade-off.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147493022","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}
Understanding coherent ultrafast charge transfer in two-dimensional van der Waals heterostructures is essential for revealing nonequilibrium processes and advancing optoelectronic device engineering. Here, we employ terahertz emission spectroscopy to probe gate-tunable coherent charge transfer (CT) in graphene/MoS2 heterostructures. Our experimental and analytical results demonstrate that the gate voltage modulates coherent CT (i.e., direct CT) by tuning the heterostructure’s built-in electric field; a higher gate voltage diminishes this field, thereby suppressing the coherent CT component. In contrast, the incoherent CT (photothermionic emission) component exhibits the opposite trend. We attribute this to a gate-induced increase in hot carriers that can overcome the interfacial barrier, an effect that dominates the concurrent reduction in the built-in field. Our findings reveal the fundamental mechanisms of gate-controlled charge dynamics, providing deeper insight into carrier transport in van der Waals heterostructures and a guideline for device development.
{"title":"Gate-Tunable Coherent and Incoherent Charge Transfer Pathways in Graphene/MoS2 Heterostructures Revealed by Terahertz Emission Spectroscopy","authors":"Chen Wang, Yidan Zhang, Shujie Wang, Xian Lin, Peng Suo, Guohong Ma","doi":"10.1021/acs.jpcc.6c00646","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00646","url":null,"abstract":"Understanding coherent ultrafast charge transfer in two-dimensional van der Waals heterostructures is essential for revealing nonequilibrium processes and advancing optoelectronic device engineering. Here, we employ terahertz emission spectroscopy to probe gate-tunable coherent charge transfer (CT) in graphene/MoS<sub>2</sub> heterostructures. Our experimental and analytical results demonstrate that the gate voltage modulates coherent CT (i.e., direct CT) by tuning the heterostructure’s built-in electric field; a higher gate voltage diminishes this field, thereby suppressing the coherent CT component. In contrast, the incoherent CT (photothermionic emission) component exhibits the opposite trend. We attribute this to a gate-induced increase in hot carriers that can overcome the interfacial barrier, an effect that dominates the concurrent reduction in the built-in field. Our findings reveal the fundamental mechanisms of gate-controlled charge dynamics, providing deeper insight into carrier transport in van der Waals heterostructures and a guideline for device development.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492815","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 : 2026-03-19DOI: 10.1021/acs.jpcc.5c08514
Samya Suvra Datta, Surojit Pande
Surface-enhanced Raman scattering (SERS) is a sensitive spectroscopic method for enhancing Raman signals on roughened metal surfaces or nanostructures. Transition metal-based chalcogenide semiconductors are effective SERS substrates due to their low cost and various tunable properties; however, their enhancement factor (EF) is rather modest. To address this issue, semiconductor heterostructures can be used as SERS substrates due to their large-scale electron–hole pair separation, high interlayer interaction, and efficient photo-induced charge transfer (PICT). In this study, a ZnO/MoSx heterostructure is synthesized and employed as a SERS substrate for the detection of methylene blue (MB). To develop a ZnO/MoSx heterostructure, ZnO is first synthesized using seed-mediated electrodeposition, followed by calcination, and then MoSx is fabricated on ZnO via electrodeposition. The heterostructure ZnO/MoSx is able to detect MB at a lower concentration of 10–10 M with an apparent enhancement factor of 1.2 × 106. The substrate is also extremely stable and robust in nature. The photoluminescence peak intensity of ZnO decreases when MoSx is decorated on it, showing less electron–hole pair recombination in the ZnO/MoSx heterostructure. Thus, the improved SERS performance of the ZnO/MoSx substrate is attributed to the efficient electron–hole pair separation at the heterostructure interface, resulting in facile PICT between the substrate and the Raman analyte.
{"title":"ZnO/MoSx Heterostructure as a Noble Metal-Free SERS Substrate for the Detection of MB in Lower Concentration Levels","authors":"Samya Suvra Datta, Surojit Pande","doi":"10.1021/acs.jpcc.5c08514","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08514","url":null,"abstract":"Surface-enhanced Raman scattering (SERS) is a sensitive spectroscopic method for enhancing Raman signals on roughened metal surfaces or nanostructures. Transition metal-based chalcogenide semiconductors are effective SERS substrates due to their low cost and various tunable properties; however, their enhancement factor (EF) is rather modest. To address this issue, semiconductor heterostructures can be used as SERS substrates due to their large-scale electron–hole pair separation, high interlayer interaction, and efficient photo-induced charge transfer (PICT). In this study, a ZnO/MoS<sub><i>x</i></sub> heterostructure is synthesized and employed as a SERS substrate for the detection of methylene blue (MB). To develop a ZnO/MoS<sub><i>x</i></sub> heterostructure, ZnO is first synthesized using seed-mediated electrodeposition, followed by calcination, and then MoS<sub><i>x</i></sub> is fabricated on ZnO via electrodeposition. The heterostructure ZnO/MoS<sub><i>x</i></sub> is able to detect MB at a lower concentration of 10<sup>–10</sup> M with an apparent enhancement factor of 1.2 × 10<sup>6</sup>. The substrate is also extremely stable and robust in nature. The photoluminescence peak intensity of ZnO decreases when MoS<sub><i>x</i></sub> is decorated on it, showing less electron–hole pair recombination in the ZnO/MoS<sub><i>x</i></sub> heterostructure. Thus, the improved SERS performance of the ZnO/MoS<sub><i>x</i></sub> substrate is attributed to the efficient electron–hole pair separation at the heterostructure interface, resulting in facile PICT between the substrate and the Raman analyte.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"80 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479004","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}
Charged water microdroplets have been demonstrated to be microreactors capable of disintegrating hard minerals into nanoparticles (NPs) under ambient conditions. However, the high applied potentials required (∼4–4.5 kV) limit the energy efficiency and industrial applications of the phenomenon. Herein, we demonstrate that when aqueous solutions containing trace concentrations of salts (0.1 ppm) are electrosprayed, the threshold potential for quartz disintegration decreases by up to 85%, leading to the formation of 2–10 nm NPs at voltages as low as 1.5 kV. Systematic variation in salt concentration reveals that enhanced droplet conductivity, surface tension, interfacial charge polarization, and localized electric field amplification collectively facilitate efficient disintegration at lower voltages. The effect of ionic size was systematically investigated through different cations (H+ to Cs+) and anions (F– to I–), establishing that smaller ions promote stronger field localization and faster charge relaxation dynamics. COMSOL simulations elucidate how ionic additives modulate droplet deformation and cleavage of the mineral lattice. This salt-assisted electrospray route offers a green, energy-efficient, and scalable strategy for the ambient synthesis of mineral-derived nanomaterials.
{"title":"Salts Induce Enhanced Disintegration of Natural Minerals in Charged Water Microdroplets","authors":"Jamshiya Sulthana, Anubhav Mahapatra, Mridula Bhan, Depanjan Sarkar, Thalappil Pradeep","doi":"10.1021/acs.jpcc.6c00820","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00820","url":null,"abstract":"Charged water microdroplets have been demonstrated to be microreactors capable of disintegrating hard minerals into nanoparticles (NPs) under ambient conditions. However, the high applied potentials required (∼4–4.5 kV) limit the energy efficiency and industrial applications of the phenomenon. Herein, we demonstrate that when aqueous solutions containing trace concentrations of salts (0.1 ppm) are electrosprayed, the threshold potential for quartz disintegration decreases by up to 85%, leading to the formation of 2–10 nm NPs at voltages as low as 1.5 kV. Systematic variation in salt concentration reveals that enhanced droplet conductivity, surface tension, interfacial charge polarization, and localized electric field amplification collectively facilitate efficient disintegration at lower voltages. The effect of ionic size was systematically investigated through different cations (H<sup>+</sup> to Cs<sup>+</sup>) and anions (F<sup>–</sup> to I<sup>–</sup>), establishing that smaller ions promote stronger field localization and faster charge relaxation dynamics. COMSOL simulations elucidate how ionic additives modulate droplet deformation and cleavage of the mineral lattice. This salt-assisted electrospray route offers a green, energy-efficient, and scalable strategy for the ambient synthesis of mineral-derived nanomaterials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478564","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}
Sustainable recycling of lithium-ion battery (LIB) cathodes is essential for mitigating resource depletion and environmental pollution. However, the inherent trade-off between selectivity and efficiency remains a critical barrier limiting the performance of current recycling technologies. Herein, we demonstrate that the selectivity and efficiency of metal leaching from LiCoO2 cathodes in spent LIBs can be effectively mediated by the hydrogen bond donor (HBD) in sustainable low-melting mixture solvents. Employing phosphorous acid as the HBD in a betaine:phosphorous acid-based solvent system yields ultrahigh Li/Co selectivity during leaching from the LCO cathode. In contrast, high overall recovery efficiencies for both Li and Co are achieved when phosphoric acid serves as the HBD in a betaine:phosphoric acid-based solvent system.
{"title":"Hydrogen Bond Donor-Mediated Selectivity-to-Efficiency Trade-Off in Sustainable Recycling of Lithium-Ion Battery Cathodes","authors":"Xuemin Jing, Pengli Zhang, Ziyi Sun, Liyuan Liu, Wenbin Su, Guangxian Liu, Yu Chen","doi":"10.1021/acs.jpcc.6c00085","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00085","url":null,"abstract":"Sustainable recycling of lithium-ion battery (LIB) cathodes is essential for mitigating resource depletion and environmental pollution. However, the inherent trade-off between selectivity and efficiency remains a critical barrier limiting the performance of current recycling technologies. Herein, we demonstrate that the selectivity and efficiency of metal leaching from LiCoO<sub>2</sub> cathodes in spent LIBs can be effectively mediated by the hydrogen bond donor (HBD) in sustainable low-melting mixture solvents. Employing phosphorous acid as the HBD in a betaine:phosphorous acid-based solvent system yields ultrahigh Li/Co selectivity during leaching from the LCO cathode. In contrast, high overall recovery efficiencies for both Li and Co are achieved when phosphoric acid serves as the HBD in a betaine:phosphoric acid-based solvent system.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"34 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492814","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}
Clusterization-triggered emission (CTE) is a photophysical phenomenon where clusteroluminogens (CLgens) generate efficient luminescence through supramolecular self-assembly in the solid state. This phenomenon offers unique photophysical properties, distinguishing it from traditional chromophores. In the context of light-emitting devices, there is growing interest in single-component white-light (SCWL) emission, where a single material produces broad emission. However, SCWL emission based on CLgens has been rarely reported, particularly in single crystals, and fabricating SCWL emitters from small-molecule, nonconjugated luminogens remains a significant challenge. The underlying mechanism of CTE is still not fully understood, prompting investigations into small-molecule CLgens to explore their structure–property relationships. In this study, a novel organic salt, TET.Br4 (TET = N,N′-bis(2-aminoethyl)-1,3-propanediamine), is synthesized, consisting of saturated TET cations connected by a hydrogen-bonded network of bromine anions in the crystalline state. The photophysical properties of TET.Br4 are characterized through optical absorption, photoluminescence measurements, and density functional theory (DFT) calculations. The results demonstrate color-tunable CTE and near-white-light emission, highlighting the synergetic role of through-space conjugation, energy/charge transfer, and halogen atoms in the CTE mechanism. This study aims to unravel the mechanism of CTE in small-molecule CLgens and address the scarcity of reports on SCWL emission from nonconjugated luminogens, contributing to advancements in this field.
{"title":"Unveiling Clusterization-Triggered Emission Mechanism Through a Small-Molecule Clusteroluminogen with Color Tunable and White-Light Emission","authors":"Kawthar Abid, Sébastien Pillet, Amira Samet, Younes Abid","doi":"10.1021/acs.jpcc.5c08523","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08523","url":null,"abstract":"Clusterization-triggered emission (CTE) is a photophysical phenomenon where clusteroluminogens (CLgens) generate efficient luminescence through supramolecular self-assembly in the solid state. This phenomenon offers unique photophysical properties, distinguishing it from traditional chromophores. In the context of light-emitting devices, there is growing interest in single-component white-light (SCWL) emission, where a single material produces broad emission. However, SCWL emission based on CLgens has been rarely reported, particularly in single crystals, and fabricating SCWL emitters from small-molecule, nonconjugated luminogens remains a significant challenge. The underlying mechanism of CTE is still not fully understood, prompting investigations into small-molecule CLgens to explore their structure–property relationships. In this study, a novel organic salt, TET.Br<sub>4</sub> (TET = <i>N</i>,<i>N</i>′-bis(2-aminoethyl)-1,3-propanediamine), is synthesized, consisting of saturated TET cations connected by a hydrogen-bonded network of bromine anions in the crystalline state. The photophysical properties of TET.Br<sub>4</sub> are characterized through optical absorption, photoluminescence measurements, and density functional theory (DFT) calculations. The results demonstrate color-tunable CTE and near-white-light emission, highlighting the synergetic role of through-space conjugation, energy/charge transfer, and halogen atoms in the CTE mechanism. This study aims to unravel the mechanism of CTE in small-molecule CLgens and address the scarcity of reports on SCWL emission from nonconjugated luminogens, contributing to advancements in this field.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478195","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 : 2026-03-18DOI: 10.1021/acs.jpcc.5c08558
Kee Sung Han, Pasquale F. Pulvio
It is well known that the internal gradient (<i>g</i><sub>i</sub>) that exists within pores haunts the diffusion coefficient (<i>D</i>) as measured by the pulsed-field gradient (PFG) nuclear magnetic resonance (NMR). Several PFG-NMR methods developed to determine accurate <i>D</i> were not successful. Then, the steady-state diffusion coefficient (<i>D</i><sub>app,∞</sub>) for the cation [C<sub>4</sub>mim]<sup>+</sup> of [C<sub>4</sub>mim][Tf<sub>2</sub>N] [1-butyl-3-methylimidazolium][bis(trifluoromethylsulfonyl)imde] ionic liquid confined in ordered mesoporous carbon (OMC) was determined by comparing <i>D</i><sub>app,∞</sub> obtained from <sup>1</sup>H PFG-NMR performed with three different stimulated echo sequences: STE, alternating pulsed-field gradient (APFG), and magic pulsed-field gradient (MPFG) under the two external magnetic field strengths, <i>B</i><sub>0</sub> = 9.4 and 14.1 T. The measured <i>D</i><sub>app</sub>,<sub>∞</sub>, which is an order of magnitude smaller than <i>D</i> of bulk [C<sub>4</sub>mim][Tf<sub>2</sub>N], is in good agreement between APFG and MPFG in both <i>B</i><sub>0</sub> = 9.4 and 14.1 T. However, the strong <i>g</i><sub>i</sub> artifact, which caused apparent diffusion coefficient (<i>D</i><sub>app</sub>), depending strongly and weakly on <i>B</i><sub>0</sub> and temperature, respectively, in diffusion time-dependent <i>D</i><sub>app</sub>, <i>D</i><sub>app</sub>(Δ), obtained from a sequence with monopolar gradients (STE), was suppressed by using sequences employing bipolar gradients (APFG and MPFG) in the region of steady-state diffusion. However, the incompletely suppressed <i>g</i><sub>i</sub> artifact resulting in the different behaviors of the early part of <i>D</i><sub>app</sub>(Δ) between the sequences leads to α ≈ 0.6 and 0.9 in MPFG and APFG, respectively, in the relationship between mean-squared displacement and diffusion time: ⟨<i>z</i>(<i>t</i>)<sup>2</sup>⟩ = 2<i>Dt</i><sup>α</sup>, where α = 0.5 and 1 for one-dimensional single-file diffusion and 3D bulk diffusion, respectively. The above observations clearly show that the diffusion behavior of ions/molecules within the pores and pore structure, such as the surface-to-volume ratio <i></i><math display="inline"><mo stretchy="true">(</mo><mrow><msub><mi>D</mi><mi>app</mi></msub><mo stretchy="false">(</mo><mi mathvariant="normal">Δ</mi><mo stretchy="false">)</mo><mo>=</mo><msub><mi>D</mi><mn>0</mn></msub><mrow><mo stretchy="true">[</mo><mrow><mn>1</mn><mo>−</mo><mfrac><mn>4</mn><mrow><mn>9</mn><msqrt><mi>π</mi></msqrt></mrow></mfrac><mfrac><mi>S</mi><mi>V</mi></mfrac><msqrt><mrow><msub><mi>D</mi><mn>0</mn></msub><mi mathvariant="normal">Δ</mi></mrow></msqrt></mrow><mo stretchy="true">]</mo></mrow></mrow><mo stretchy="true">)</mo></math> and tortuosity (<i>T</i> ≡ <i>D</i><sub>0</sub>/<i>D</i><sub>app,∞</sub>), is possible to be misunderstood, especially in systems with a non-negligible <i>g</i><sub>i</sub>. This work demonstrates that it may be necess
{"title":"Challenges in Pulsed-Field Gradient Nuclear Magnetic Resonance on Magnetically Heterogeneous Interfaces: Sequence and Field-Dependent Apparent Diffusion Coefficients","authors":"Kee Sung Han, Pasquale F. Pulvio","doi":"10.1021/acs.jpcc.5c08558","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08558","url":null,"abstract":"It is well known that the internal gradient (<i>g</i><sub>i</sub>) that exists within pores haunts the diffusion coefficient (<i>D</i>) as measured by the pulsed-field gradient (PFG) nuclear magnetic resonance (NMR). Several PFG-NMR methods developed to determine accurate <i>D</i> were not successful. Then, the steady-state diffusion coefficient (<i>D</i><sub>app,∞</sub>) for the cation [C<sub>4</sub>mim]<sup>+</sup> of [C<sub>4</sub>mim][Tf<sub>2</sub>N] [1-butyl-3-methylimidazolium][bis(trifluoromethylsulfonyl)imde] ionic liquid confined in ordered mesoporous carbon (OMC) was determined by comparing <i>D</i><sub>app,∞</sub> obtained from <sup>1</sup>H PFG-NMR performed with three different stimulated echo sequences: STE, alternating pulsed-field gradient (APFG), and magic pulsed-field gradient (MPFG) under the two external magnetic field strengths, <i>B</i><sub>0</sub> = 9.4 and 14.1 T. The measured <i>D</i><sub>app</sub>,<sub>∞</sub>, which is an order of magnitude smaller than <i>D</i> of bulk [C<sub>4</sub>mim][Tf<sub>2</sub>N], is in good agreement between APFG and MPFG in both <i>B</i><sub>0</sub> = 9.4 and 14.1 T. However, the strong <i>g</i><sub>i</sub> artifact, which caused apparent diffusion coefficient (<i>D</i><sub>app</sub>), depending strongly and weakly on <i>B</i><sub>0</sub> and temperature, respectively, in diffusion time-dependent <i>D</i><sub>app</sub>, <i>D</i><sub>app</sub>(Δ), obtained from a sequence with monopolar gradients (STE), was suppressed by using sequences employing bipolar gradients (APFG and MPFG) in the region of steady-state diffusion. However, the incompletely suppressed <i>g</i><sub>i</sub> artifact resulting in the different behaviors of the early part of <i>D</i><sub>app</sub>(Δ) between the sequences leads to α ≈ 0.6 and 0.9 in MPFG and APFG, respectively, in the relationship between mean-squared displacement and diffusion time: ⟨<i>z</i>(<i>t</i>)<sup>2</sup>⟩ = 2<i>Dt</i><sup>α</sup>, where α = 0.5 and 1 for one-dimensional single-file diffusion and 3D bulk diffusion, respectively. The above observations clearly show that the diffusion behavior of ions/molecules within the pores and pore structure, such as the surface-to-volume ratio <i></i><math display=\"inline\"><mo stretchy=\"true\">(</mo><mrow><msub><mi>D</mi><mi>app</mi></msub><mo stretchy=\"false\">(</mo><mi mathvariant=\"normal\">Δ</mi><mo stretchy=\"false\">)</mo><mo>=</mo><msub><mi>D</mi><mn>0</mn></msub><mrow><mo stretchy=\"true\">[</mo><mrow><mn>1</mn><mo>−</mo><mfrac><mn>4</mn><mrow><mn>9</mn><msqrt><mi>π</mi></msqrt></mrow></mfrac><mfrac><mi>S</mi><mi>V</mi></mfrac><msqrt><mrow><msub><mi>D</mi><mn>0</mn></msub><mi mathvariant=\"normal\">Δ</mi></mrow></msqrt></mrow><mo stretchy=\"true\">]</mo></mrow></mrow><mo stretchy=\"true\">)</mo></math> and tortuosity (<i>T</i> ≡ <i>D</i><sub>0</sub>/<i>D</i><sub>app,∞</sub>), is possible to be misunderstood, especially in systems with a non-negligible <i>g</i><sub>i</sub>. This work demonstrates that it may be necess","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478196","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 : 2026-03-18DOI: 10.1021/acs.jpcc.5c08269
Muhammad Hammad Ali, Benjamin G. Janesko, MD Masud Rana, Umar Saleem, Naga Mani Gajula
Graphene quantum dots (GQDs) are emerging nanocarbon materials with tunable electronic structures and strong NIR emission, making them promising for bioimaging and optoelectronic applications. The chromophores responsible for GQDs’ NIR emission are often poorly characterized, limiting rational design and clinical applications. Extended π-conjugation, charge-transfer excitations, the presence of diradicaloids, stacking of multiple GQD layers, and blocking of nonradiative decay (as seen in nonaromatic fluorescence) may all contribute to GQDs’ NIR emission. Computation may help disentangle these contributions and aid development of NIR-emitting GQD nanostructures. However, predictive modeling of candidate GQD structures’ stability and NIR emission remains challenging. In this work, we develop a benchmark set of 16 well-defined GQD nanostructures known to emit in the NIR-I window, and we benchmark computational workflows for predicting these structures’ thermodynamic stability and NIR emission. Our workflows combine fast “pre-screening” of thermodynamic stability with symmetry-broken and symmetry-restricted time-dependent density functional theory (TD-DFT) predictions of absorption and emission, selected according to the open- or closed-shell nature of each nanostructure. We find that B3LYP provides acceptable agreement with experimental absorption, while CAM-B3LYP shows good agreement with experimental emission, and that a “synthetic feasibility” descriptor provides reasonable initial screening. We believe that this workflow provides the foundation for high-throughput computational studies accelerating development of NIR-emitting GQDs.
{"title":"Benchmarking a Computational Workflow Modeling Near-Infrared-Emitting Graphene Quantum Dots","authors":"Muhammad Hammad Ali, Benjamin G. Janesko, MD Masud Rana, Umar Saleem, Naga Mani Gajula","doi":"10.1021/acs.jpcc.5c08269","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08269","url":null,"abstract":"Graphene quantum dots (GQDs) are emerging nanocarbon materials with tunable electronic structures and strong NIR emission, making them promising for bioimaging and optoelectronic applications. The chromophores responsible for GQDs’ NIR emission are often poorly characterized, limiting rational design and clinical applications. Extended π-conjugation, charge-transfer excitations, the presence of diradicaloids, stacking of multiple GQD layers, and blocking of nonradiative decay (as seen in nonaromatic fluorescence) may all contribute to GQDs’ NIR emission. Computation may help disentangle these contributions and aid development of NIR-emitting GQD nanostructures. However, predictive modeling of candidate GQD structures’ stability and NIR emission remains challenging. In this work, we develop a benchmark set of 16 well-defined GQD nanostructures known to emit in the NIR-I window, and we benchmark computational workflows for predicting these structures’ thermodynamic stability and NIR emission. Our workflows combine fast “pre-screening” of thermodynamic stability with symmetry-broken and symmetry-restricted time-dependent density functional theory (TD-DFT) predictions of absorption and emission, selected according to the open- or closed-shell nature of each nanostructure. We find that B3LYP provides acceptable agreement with experimental absorption, while CAM-B3LYP shows good agreement with experimental emission, and that a “synthetic feasibility” descriptor provides reasonable initial screening. We believe that this workflow provides the foundation for high-throughput computational studies accelerating development of NIR-emitting GQDs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478506","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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