Pub Date : 2025-03-06DOI: 10.1021/acs.jpcc.4c07101
B. Almohammed, D. Barba, E. Haddad, R. Nechache, F. Rosei, F. Vetrone
Erbium and erbium oxide nanoparticles (Er-NPs) have been synthesized in deionized (DI) water using the green and environmentally friendly technique of pulsed laser ablation in liquid (PLAL), with laser fluence ranging from 2.5 to 20.9 J/cm2. Owing to the careful examination of the nanoparticle morphology, crystal structure, and chemical composition, the occurrence of various growth regimes is evidenced. The size of the Er-NPs is found to increase with the laser fluence, and the formed nanoparticles are surrounded by a thin hydroxide layer of a few nanometers thickness, originating from water and chemical residues. The activation of 4f–4f optical transitions associated with trivalent Er3+ ions is promoted by the formation of erbium oxide. The Er-NPs having diameters lower than 100 nm are made of Er2O3, whereas Er-NPs of larger dimensions are made of an oxidized erbium oxide matrix containing a large amount of excess Er, the concentration of which increases gradually inside the Er-NPs. The formation of this graded Er/Er2O3 core–shell structure gives rise to a decrease in the Er visible photoluminescence emission. These findings shed light on the influence of the PLAL laser fluence on both the geometry and the composition of Er-NPs, as well as its consequence on their photoemission capacity, making them relevant for easy implementation with tunable properties in advanced photonics devices.
{"title":"Luminescent Erbium-Based Nanoparticles Synthesized by Pulsed Laser Ablation in Liquid","authors":"B. Almohammed, D. Barba, E. Haddad, R. Nechache, F. Rosei, F. Vetrone","doi":"10.1021/acs.jpcc.4c07101","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07101","url":null,"abstract":"Erbium and erbium oxide nanoparticles (Er-NPs) have been synthesized in deionized (DI) water using the green and environmentally friendly technique of pulsed laser ablation in liquid (PLAL), with laser fluence ranging from 2.5 to 20.9 J/cm<sup>2</sup>. Owing to the careful examination of the nanoparticle morphology, crystal structure, and chemical composition, the occurrence of various growth regimes is evidenced. The size of the Er-NPs is found to increase with the laser fluence, and the formed nanoparticles are surrounded by a thin hydroxide layer of a few nanometers thickness, originating from water and chemical residues. The activation of 4f–4f optical transitions associated with trivalent Er<sup>3+</sup> ions is promoted by the formation of erbium oxide. The Er-NPs having diameters lower than 100 nm are made of Er<sub>2</sub>O<sub>3</sub>, whereas Er-NPs of larger dimensions are made of an oxidized erbium oxide matrix containing a large amount of excess Er, the concentration of which increases gradually inside the Er-NPs. The formation of this graded Er/Er<sub>2</sub>O<sub>3</sub> core–shell structure gives rise to a decrease in the Er visible photoluminescence emission. These findings shed light on the influence of the PLAL laser fluence on both the geometry and the composition of Er-NPs, as well as its consequence on their photoemission capacity, making them relevant for easy implementation with tunable properties in advanced photonics devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560907","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 : 2025-03-06DOI: 10.1021/acs.jpcc.4c08108
José L. C. Fajín, Amit Kumar Halder, M. Natália D. S. Cordeiro
The water gas shift (WGS) reaction is a critical process in various industrial applications, with its rate often governed by the activation energy of water dissociation on metal-based catalysts. In this work, we develop a machine learning model to predict the activation energy for water dissociation across diverse catalytic surfaces, including monometallic, bimetallic, and trimetallic surfaces, metallic nanotubes, and platinum nanoparticles. The model links activation energy to easily computable descriptors, such as adsorption energies or distances of the involved reaction species, derived from density functional theory (DFT) calculations. Our multilayer perceptron-based regression model demonstrates exceptional predictive accuracy. A Shapley additive explanation (SHAP) analysis discloses that all input variables contribute positively to the activation energy, with the adsorption energy of reaction products identified as the most influential feature. Remarkably, our model enables the prediction of activation energy for water dissociation and WGS on metal-based catalysts not included in the training set by simply DFT computing adsorption energies and distances, significantly reducing computational effort. This approach thus provides a powerful tool for the rapid screening and optimization of catalysts for the WGS reaction, paving the way for more efficient industrial processes.
{"title":"Machine Learning-Guided Prediction of Activation Energies for Catalyst Design in the Water Gas Shift Reaction","authors":"José L. C. Fajín, Amit Kumar Halder, M. Natália D. S. Cordeiro","doi":"10.1021/acs.jpcc.4c08108","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08108","url":null,"abstract":"The water gas shift (WGS) reaction is a critical process in various industrial applications, with its rate often governed by the activation energy of water dissociation on metal-based catalysts. In this work, we develop a machine learning model to predict the activation energy for water dissociation across diverse catalytic surfaces, including monometallic, bimetallic, and trimetallic surfaces, metallic nanotubes, and platinum nanoparticles. The model links activation energy to easily computable descriptors, such as adsorption energies or distances of the involved reaction species, derived from density functional theory (DFT) calculations. Our multilayer perceptron-based regression model demonstrates exceptional predictive accuracy. A Shapley additive explanation (SHAP) analysis discloses that all input variables contribute positively to the activation energy, with the adsorption energy of reaction products identified as the most influential feature. Remarkably, our model enables the prediction of activation energy for water dissociation and WGS on metal-based catalysts not included in the training set by simply DFT computing adsorption energies and distances, significantly reducing computational effort. This approach thus provides a powerful tool for the rapid screening and optimization of catalysts for the WGS reaction, paving the way for more efficient industrial processes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"32 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561234","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 : 2025-03-06DOI: 10.1021/acs.jpcc.5c00740
Olivia F. Bird, Kenneth M. Drbohlav, Evan K. Gowdy, Faith A. Flinkingshelt, Lauren M. Pellows, Benjamin F. Hammel, Bradley W. Layne, Shane Ardo, Jenny Y. Yang, Kenneth A. Miller, Gordana Dukovic
Anchoring of molecules to the surfaces of semiconductor nanocrystals (NCs) presents an opportunity to leverage the precise synthetic tunability of molecular function and the remarkable light harvesting properties of NCs to drive photochemical reactions. However, charge transfer between the two species depends not only on the energy level alignments but also on the details of their binding interactions, which are difficult to probe. Here, we characterize the binding between CdSe quantum dots (QDs) and a new phosphonated derivative of the electron acceptor methyl viologen, designed to attach to the QD surface via the phosphonate group. We use isothermal titration calorimetry to probe the thermodynamics of the QD–molecule interaction and use the parameters determined therein to analyze transient absorption spectroscopy measurements of forward and back electron transfer from QDs to the viologen. We find that the ligand-like phosphonate binding leads to an electron-transfer rate constant that is 3 orders of magnitude smaller than that for the face-on binding of the bipyridine ring of methyl viologen. Back electron transfer is also significantly slower in the derivative. Interestingly, a minor fraction of the phosphonated derivative also binds in the face-on configuration, with similar forward and back electron transfer kinetics as methyl viologen. Numerical simulations show that the ligand-like binding will lead to significantly improved quantum yields of photocatalysis over a wide range of reaction rates. By independently characterizing binding thermodynamics and charge transfer kinetics, this work reveals how the complexities underlying electron transfer at the NC–molecule interface determine photocatalytic outcomes. This work also represents a step toward controlling forward and back electron transfer kinetics via rational molecular design.
{"title":"Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen","authors":"Olivia F. Bird, Kenneth M. Drbohlav, Evan K. Gowdy, Faith A. Flinkingshelt, Lauren M. Pellows, Benjamin F. Hammel, Bradley W. Layne, Shane Ardo, Jenny Y. Yang, Kenneth A. Miller, Gordana Dukovic","doi":"10.1021/acs.jpcc.5c00740","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00740","url":null,"abstract":"Anchoring of molecules to the surfaces of semiconductor nanocrystals (NCs) presents an opportunity to leverage the precise synthetic tunability of molecular function and the remarkable light harvesting properties of NCs to drive photochemical reactions. However, charge transfer between the two species depends not only on the energy level alignments but also on the details of their binding interactions, which are difficult to probe. Here, we characterize the binding between CdSe quantum dots (QDs) and a new phosphonated derivative of the electron acceptor methyl viologen, designed to attach to the QD surface via the phosphonate group. We use isothermal titration calorimetry to probe the thermodynamics of the QD–molecule interaction and use the parameters determined therein to analyze transient absorption spectroscopy measurements of forward and back electron transfer from QDs to the viologen. We find that the ligand-like phosphonate binding leads to an electron-transfer rate constant that is 3 orders of magnitude smaller than that for the face-on binding of the bipyridine ring of methyl viologen. Back electron transfer is also significantly slower in the derivative. Interestingly, a minor fraction of the phosphonated derivative also binds in the face-on configuration, with similar forward and back electron transfer kinetics as methyl viologen. Numerical simulations show that the ligand-like binding will lead to significantly improved quantum yields of photocatalysis over a wide range of reaction rates. By independently characterizing binding thermodynamics and charge transfer kinetics, this work reveals how the complexities underlying electron transfer at the NC<b>–</b>molecule interface determine photocatalytic outcomes. This work also represents a step toward controlling forward and back electron transfer kinetics via rational molecular design.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570122","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}
Improving the productivity of photoelectrochemical water splitting hinges on discovering a viable method to facilitate bubble release from the surface of the photoelectrode, which, in turn, enhances the mass transfer of the resulting products. In this study, an experimental platform for photoelectrochemical water splitting to produce hydrogen by a coupled vibration system was built to realize the visualization of bubble behavior. By applying vibration to the electrode through a vibration exciter, this work explored how amplitude and frequency affect the photocurrent and geometric parameters during the bubble evolution process on the photoelectrode surface. Based on the expression of bubble coverage and gas evolution efficiency, mass transfer coefficients of gas products were deduced and calculated. The results showed that the increase in amplitude will increase the onset potential of nucleation, reducing the possibility of nucleation. Increasing the amplitude and frequency helps to release the bubbles from the electrode surface. For stationary electrodes, the mass transfer of gas products mainly depends on single-phase natural microconvection. For the vibrating electrode, macroscopic forced convection plays a dominant role. In this experiment, the average total mass transfer coefficient after applying vibration to the electrode can reach 11.16 × 10–5 m/s, which is about 7.6 times the mass transfer coefficient under static conditions. Therefore, vibration can significantly improve the reaction efficiency and mass transfer during the water splitting process for hydrogen generation.
{"title":"Vibration Promotes Mass Transfer of Products in Photoelectrochemical Water Splitting by Enhancing Forced Convection","authors":"Tengfei Nie, Qiang Xu, Yonglu She, Xinyi Luo, Mengsha Wang, Liejin Guo","doi":"10.1021/acs.jpcc.4c08219","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08219","url":null,"abstract":"Improving the productivity of photoelectrochemical water splitting hinges on discovering a viable method to facilitate bubble release from the surface of the photoelectrode, which, in turn, enhances the mass transfer of the resulting products. In this study, an experimental platform for photoelectrochemical water splitting to produce hydrogen by a coupled vibration system was built to realize the visualization of bubble behavior. By applying vibration to the electrode through a vibration exciter, this work explored how amplitude and frequency affect the photocurrent and geometric parameters during the bubble evolution process on the photoelectrode surface. Based on the expression of bubble coverage and gas evolution efficiency, mass transfer coefficients of gas products were deduced and calculated. The results showed that the increase in amplitude will increase the onset potential of nucleation, reducing the possibility of nucleation. Increasing the amplitude and frequency helps to release the bubbles from the electrode surface. For stationary electrodes, the mass transfer of gas products mainly depends on single-phase natural microconvection. For the vibrating electrode, macroscopic forced convection plays a dominant role. In this experiment, the average total mass transfer coefficient after applying vibration to the electrode can reach 11.16 × 10<sup>–5</sup> m/s, which is about 7.6 times the mass transfer coefficient under static conditions. Therefore, vibration can significantly improve the reaction efficiency and mass transfer during the water splitting process for hydrogen generation.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"131 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561235","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 development of the composite material based on poly(vinylidene fluoride) (PVDF) incorporating lithium salt of adipic acid (Li-AA) presents a promising avenue for sustainable and renewable energy generation via piezoelectric nanogenerators. In this study, PVDF/Li-AA composites were prepared through melt-mixing, followed by the fabrication of thin films using compression molding and solution casting techniques, with Li-AA concentration ranging from 1% to 10% by weight. Analysis via Fourier transform infrared spectroscopy (FTIR) confirmed hydrogen bonding interactions between −CF2 moieties of PVDF and the acid functional groups of Li-AA. Additionally, FTIR analysis revealed that the solution-cast PVDF/Li-AA composite containing 10 wt % Li-AA exhibited the highest polar phase amount (∼ 65%) among all the composites, with remnant polarization of ∼4.2 × 10–3 μC/cm2 (50 Hz and 500 V). Furthermore, the solution cast PVDF/Li-AA composite film containing 10 wt % Li-AA achieved the highest piezoelectric coefficient (d33 value ∼ 42 pm/V), indicating superior piezoelectric response. Energy harvesting devices fabricated using compression molded and solution-cast films demonstrated an output voltage of ∼80 and ∼100 V, respectively, obtained from PVDF/Li-AA composite containing 10 wt % Li-AA. Furthermore, devices fabricated with compression molded and solution-cast composite films containing 10 wt % Li-AA exhibited higher power densities of ∼80 and ∼100 μW/cm2, respectively. Finally, PVDF/Li-AA composite film based self-powered speed sensor was fabricated for speed detection of the vehicles.
{"title":"Li-Salt of Adipic Acid Incorporated Flexible Poly(vinylidene fluoride) Composite for Piezoelectric Energy Harvester with Superior Energy Density Toward Self-Powered Traffic Monitoring System","authors":"Ananya Aishwarya, Suvankar Mondal, Akanksha Adaval, Titas Dasgupta, Arup R. Bhattacharyya","doi":"10.1021/acs.jpcc.4c07023","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07023","url":null,"abstract":"The development of the composite material based on poly(vinylidene fluoride) (PVDF) incorporating lithium salt of adipic acid (Li-AA) presents a promising avenue for sustainable and renewable energy generation via piezoelectric nanogenerators. In this study, PVDF/Li-AA composites were prepared through melt-mixing, followed by the fabrication of thin films using compression molding and solution casting techniques, with Li-AA concentration ranging from 1% to 10% by weight. Analysis via Fourier transform infrared spectroscopy (FTIR) confirmed hydrogen bonding interactions between −CF<sub>2</sub> moieties of PVDF and the acid functional groups of Li-AA. Additionally, FTIR analysis revealed that the solution-cast PVDF/Li-AA composite containing 10 wt % Li-AA exhibited the highest polar phase amount (∼ 65%) among all the composites, with remnant polarization of ∼4.2 × 10<sup>–3</sup> μC/cm<sup>2</sup> (50 Hz and 500 V). Furthermore, the solution cast PVDF/Li-AA composite film containing 10 wt % Li-AA achieved the highest piezoelectric coefficient (<i>d</i><sub>33</sub> value ∼ 42 pm/V), indicating superior piezoelectric response. Energy harvesting devices fabricated using compression molded and solution-cast films demonstrated an output voltage of ∼80 and ∼100 V, respectively, obtained from PVDF/Li-AA composite containing 10 wt % Li-AA. Furthermore, devices fabricated with compression molded and solution-cast composite films containing 10 wt % Li-AA exhibited higher power densities of ∼80 and ∼100 μW/cm<sup>2</sup>, respectively. Finally, PVDF/Li-AA composite film based self-powered speed sensor was fabricated for speed detection of the vehicles.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560905","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 : 2025-03-06DOI: 10.1021/acs.jpcc.4c07712
Tristan Georges, Jacynthe Beaudoin, Mubassira Rahman, Alireza Nari, Jeffrey S. Ovens, David L. Bryce
This study focuses on 3,4-dicyano-1,2,5-selenadiazole and substituted 2,1,3-benzoselenadiazole-based cocrystals synthesized via mechanochemical methods and characterized by a combination of X-ray diffraction and solid-state NMR spectroscopy. Eight new single-crystal structures are reported, revealing a variety of chalcogen bond (ChB) geometries and binding motifs that are found to promote low-dimensional molecular architectures. We find that 77Se isotropic chemical shifts follow exponential decay or growth trends along with the ChB length, while also depending on the electrostatic contribution of the ChB donor. These trends are shown to be governed by changes to the intermediate selenium chemical shift tensor component, δ22. Such behavior is further exploited to estimate ChB lengths in compounds unsuitable for single-crystal structure determination. This methodology highlights the utility of solid-state NMR as a powerful alternative for probing ChB interactions, particularly in systems where traditional crystallographic techniques are not applicable. The results offer critical physical insights into the origins of the selenium chemical shift tensors of ChB-based materials.
{"title":"77Se Solid-State NMR Investigation of Selenium Chemical Shift Tensors of Chalcogen Bonds in Selenadiazole Cocrystals","authors":"Tristan Georges, Jacynthe Beaudoin, Mubassira Rahman, Alireza Nari, Jeffrey S. Ovens, David L. Bryce","doi":"10.1021/acs.jpcc.4c07712","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07712","url":null,"abstract":"This study focuses on 3,4-dicyano-1,2,5-selenadiazole and substituted 2,1,3-benzoselenadiazole-based cocrystals synthesized via mechanochemical methods and characterized by a combination of X-ray diffraction and solid-state NMR spectroscopy. Eight new single-crystal structures are reported, revealing a variety of chalcogen bond (ChB) geometries and binding motifs that are found to promote low-dimensional molecular architectures. We find that <sup>77</sup>Se isotropic chemical shifts follow exponential decay or growth trends along with the ChB length, while also depending on the electrostatic contribution of the ChB donor. These trends are shown to be governed by changes to the intermediate selenium chemical shift tensor component, δ<sub>22</sub>. Such behavior is further exploited to estimate ChB lengths in compounds unsuitable for single-crystal structure determination. This methodology highlights the utility of solid-state NMR as a powerful alternative for probing ChB interactions, particularly in systems where traditional crystallographic techniques are not applicable. The results offer critical physical insights into the origins of the selenium chemical shift tensors of ChB-based materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560908","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 : 2025-03-06DOI: 10.1021/acs.jpcc.5c0070410.1021/acs.jpcc.5c00704
Zhihua Wu, Jian-Feng Li* and Zhong-Qun Tian*,
{"title":"Celebrating 10 Years of the Collaborative Innovation Center of Chemistry for Energy Materials (iChEM)","authors":"Zhihua Wu, Jian-Feng Li* and Zhong-Qun Tian*, ","doi":"10.1021/acs.jpcc.5c0070410.1021/acs.jpcc.5c00704","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00704https://doi.org/10.1021/acs.jpcc.5c00704","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 9","pages":"4321–4322 4321–4322"},"PeriodicalIF":3.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547776","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 : 2025-03-06DOI: 10.1021/acs.jpcc.4c07912
Ashutosh Shukla, Rahul Chand, Sneha Boby, G. V. Pavan Kumar
Optical tweezers have revolutionized particle manipulation at the micro- and nanoscale, playing a critical role in fields such as plasmonics, biophysics, and nanotechnology. While traditional optical trapping methods primarily rely on optical forces to manipulate and organize particles, recent studies suggest that optothermal traps in surfactant solutions can induce unconventional effects such as enhanced trapping stiffness and increased diffusion. Thus, there is a need for further exploration of this system to gain a deeper understanding of the forces involved. This work investigates the behavior of gold nanoparticles confined in an optothermal trap around a heated anchor particle in a surfactant (CTAC) solution. We observe unexpected radial confinement and synchronized rotational diffusion of particles at micrometre-scale separations from the anchor particle. These dynamics differ from known optical binding and thermophoretic effects, suggesting unexplored forces facilitated by the surfactant environment. This study expands the understanding of optothermal trapping driven by anchor plasmonic particles. It introduces new possibilities for nanoparticle assembly, offering insights with potential applications in nanoscale fabrication and materials science.
{"title":"Synchronized Motion of Gold Nanoparticles in an Optothermal Trap","authors":"Ashutosh Shukla, Rahul Chand, Sneha Boby, G. V. Pavan Kumar","doi":"10.1021/acs.jpcc.4c07912","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07912","url":null,"abstract":"Optical tweezers have revolutionized particle manipulation at the micro- and nanoscale, playing a critical role in fields such as plasmonics, biophysics, and nanotechnology. While traditional optical trapping methods primarily rely on optical forces to manipulate and organize particles, recent studies suggest that optothermal traps in surfactant solutions can induce unconventional effects such as enhanced trapping stiffness and increased diffusion. Thus, there is a need for further exploration of this system to gain a deeper understanding of the forces involved. This work investigates the behavior of gold nanoparticles confined in an optothermal trap around a heated anchor particle in a surfactant (CTAC) solution. We observe unexpected radial confinement and synchronized rotational diffusion of particles at micrometre-scale separations from the anchor particle. These dynamics differ from known optical binding and thermophoretic effects, suggesting unexplored forces facilitated by the surfactant environment. This study expands the understanding of optothermal trapping driven by anchor plasmonic particles. It introduces new possibilities for nanoparticle assembly, offering insights with potential applications in nanoscale fabrication and materials science.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"53 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570121","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 : 2025-03-06DOI: 10.1021/acs.jpcc.4c08237
Neda Sadat Barekati, Eshagh Irandoost, Hossein Farsi, Shokufeh Moghiminia, Alireza Farrokhi, Emmanuel Albert Mensah, Zhihai Li
Recently, ultrathin two-dimensional (2D) MOF nanosheets with unique and superior dimension-related characteristics, inclusive of high surface areas, abundantly accessible active metal centers, and excellent electrical conductivity, have drawn intensive interest in a broad spectrum of functional electrochemical devices like rechargeable batteries and supercapacitors. Herein, we synthesized ultrathin 2D Co-MeIM (MeIM = 2-methylimidazole) through a facile one-pot hydrothermal approach with a thickness of about 1.5 nm. The prepared ultrathin 2D Co-MeIM nanosheet possesses highly exposed active cobalt sites, less charge transfer resistance, and quicker ionic transfer, enabling it to play a significant role as a propitious electrode candidate for outstanding execution supercapacitors. Notably, the ultrathin 2D Co-MeIM nanosheet displayed an elevated capacitance of 1589 F g–1 at a constant current of 0.6 A g–1, and it retained 91.6% of its specific capacitance after 4000 cycles, revealing superb long-term cycling performance.
{"title":"Development of Ultrathin Two-Dimensional Cobalt-Based Metal–Organic Framework Nanosheets for High-Performance Supercapacitors","authors":"Neda Sadat Barekati, Eshagh Irandoost, Hossein Farsi, Shokufeh Moghiminia, Alireza Farrokhi, Emmanuel Albert Mensah, Zhihai Li","doi":"10.1021/acs.jpcc.4c08237","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08237","url":null,"abstract":"Recently, ultrathin two-dimensional (2D) MOF nanosheets with unique and superior dimension-related characteristics, inclusive of high surface areas, abundantly accessible active metal centers, and excellent electrical conductivity, have drawn intensive interest in a broad spectrum of functional electrochemical devices like rechargeable batteries and supercapacitors. Herein, we synthesized ultrathin 2D Co-MeIM (MeIM = 2-methylimidazole) through a facile one-pot hydrothermal approach with a thickness of about 1.5 nm. The prepared ultrathin 2D Co-MeIM nanosheet possesses highly exposed active cobalt sites, less charge transfer resistance, and quicker ionic transfer, enabling it to play a significant role as a propitious electrode candidate for outstanding execution supercapacitors. Notably, the ultrathin 2D Co-MeIM nanosheet displayed an elevated capacitance of 1589 F g<sup>–1</sup> at a constant current of 0.6 A g<sup>–1</sup>, and it retained 91.6% of its specific capacitance after 4000 cycles, revealing superb long-term cycling performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561236","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 : 2025-03-06DOI: 10.1021/acs.jpcc.5c00327
R. A. B. van Bree, G. J. Kroes
The activated dissociative chemisorption (DC) of O<sub>2</sub> on Al(111) is a thoroughly studied benchmark system for oxygen–metal interactions. However, research based on density functional theory (DFT) has not yet been able to accurately determine the electronic structure, and theory as a whole has so far been unable to reproduce measured sticking probabilities with chemical accuracy. Previous work has argued that this is likely due to the inability of DFT at the generalized gradient approximation (GGA) level to describe the barriers to DC of O<sub>2</sub> on Al(111) correctly. The argument is that the most commonly applied electronic structure approach in surface science, which involves the use of GGA-DFT, yields too low reaction barriers for the DC of O<sub>2</sub> on Al(111). Moreover, it seems that GGAs will generally fail to accurately predict barriers for systems with low charge transfer energy, i.e., systems for which charge transfer from metal to molecule at the transition state is likely. Subsequent work on both O<sub>2</sub> + Al(111) and O<sub>2</sub> + Cu(111) has suggested that screened hybrid density functionals (DF) yield more accurate barrier heights for DC on metal surfaces. However, so far the use of only a screened hybrid DF was not enough to ensure a highly accurate description for O<sub>2</sub> + Al(111). Even though the onset of the sticking probability (<i>S</i><sub>0</sub>) curve was correctly described, the slope, or width, of the curve was not. The use of a nonlocal correlation DF combined with an increased fraction of exact exchange in the screened hybrid exchange DF was believed to further improve the description of the electronic structure by increasing the energetic corrugation of the barrier. This approach was assumed to increase the width of the sticking curve without lowering the incidence energy for the reaction onset, thus reducing the slope of the sticking curve. To test this, we present quasi-classical trajectory (QCT) calculations on the O<sub>2</sub> + Al(111) system based on a potential energy surface (PES) computed with the HSE06-1/2<i>x</i>-VdWDF2 screened hybrid van der Waals DF, using the Born–Oppenheimer static surface (BOSS) model. The resulting PES shows the presence of shallow van der Waals wells in the entrance channel. Furthermore, the barriers to DC show a slightly higher energetic corrugation than the previously used HSE03-1/3<i>x</i> screened hybrid DF, although most differences are smaller than 1 kcal/mol. These minor alterations in the PES with respect to previous work mean that the <i>S</i><sub>0</sub> computed for O<sub>2</sub> + Al(111) using the HSE06-1/2<i>x</i>-VdWDF2 DF are somewhat improved over the previous results. Specifically, the onset of the <i>S</i><sub>0</sub> curve is now somewhat better described and the curve is broadened a little compared to the HSE03-1/3<i>x</i> description. These results, in combination with previous studies, imply that future electronic structure met
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