Pub Date : 2025-04-21DOI: 10.1021/acs.jpcc.5c00130
Ashwin Srinivasan, Nadine van Westrenen, Zachary Benmamoun, Matthew Feldman, Dongjin Seo, William A. Ducker
The equilibrium height of a meniscus in a truncated trapezoidal capillary was examined by theory and experiment. Experiments focused on the limit of larger separation between the parallel sides than the sloped sides, where the capillary rise was dominated by the gap between the sloped sides. The capillary was constructed from hydrophilic borosilicate glass slides, and the liquid was pure water or ethanol–water solutions. Theoretical results were obtained by numerical solution of the Young–Laplace equation to obtain the shape of the vapor–liquid interface as a function of the height above the surrounding liquid. We found good agreement between experiment and theory for wall angles, α, in the range 0–30°, a variety of submerged depths of the capillary, and ethanol solutions in the range 0–30% v/v. Experiment and theory showed that the meniscus rose less for greater angles of the trapezoid, and the rise is much more sensitive to α than to the contact angle, θ, for the small angles explored in this work. The rise is particularly sensitive to variation of α in the range 0–4°. In general, the criterion for the meniscus to rise in a capillary with inclined sides is (θ + α)< 90°, which is in contrast to θ < 90° for a capillary with parallel walls. The inclination of the wall provides an additional control variable, and a useful variable because of the high sensitivity to α at small angles. Capillaries with angled walls occur in natural and engineered systems, such as in porous media, where many wall inclinations can be found. In addition to capillary rise, these results have potentially useful applications to wetting of patterned surfaces, and to filtration.
{"title":"Capillary Rise for Inclined Walls","authors":"Ashwin Srinivasan, Nadine van Westrenen, Zachary Benmamoun, Matthew Feldman, Dongjin Seo, William A. Ducker","doi":"10.1021/acs.jpcc.5c00130","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00130","url":null,"abstract":"The equilibrium height of a meniscus in a truncated trapezoidal capillary was examined by theory and experiment. Experiments focused on the limit of larger separation between the parallel sides than the sloped sides, where the capillary rise was dominated by the gap between the sloped sides. The capillary was constructed from hydrophilic borosilicate glass slides, and the liquid was pure water or ethanol–water solutions. Theoretical results were obtained by numerical solution of the Young–Laplace equation to obtain the shape of the vapor–liquid interface as a function of the height above the surrounding liquid. We found good agreement between experiment and theory for wall angles, α, in the range 0–30°, a variety of submerged depths of the capillary, and ethanol solutions in the range 0–30% v/v. Experiment and theory showed that the meniscus rose less for greater angles of the trapezoid, and the rise is much more sensitive to α than to the contact angle, θ, for the small angles explored in this work. The rise is particularly sensitive to variation of α in the range 0–4°. In general, the criterion for the meniscus to rise in a capillary with inclined sides is (θ + α)< 90°, which is in contrast to θ < 90° for a capillary with parallel walls. The inclination of the wall provides an additional control variable, and a useful variable because of the high sensitivity to α at small angles. Capillaries with angled walls occur in natural and engineered systems, such as in porous media, where many wall inclinations can be found. In addition to capillary rise, these results have potentially useful applications to wetting of patterned surfaces, and to filtration.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"108 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853383","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 : 2025-04-21DOI: 10.1021/acs.jpcc.5c00183
Edirisuriya M. Dilanga Siriwardane, Rongzhi Dong, Jianjun Hu, Deniz Çakır
Ultralow compressible materials, which have a high bulk modulus (K), are invaluable in extreme conditions due to their ability to undergo significant compression without structural failure. As a large number of borides can be found with high K, this study develops a computational framework to scan the vast chemical space to identify the ultralow compressible borides. Transformer-based networks are helpful to generate new chemical compositions due to their self-attention mechanism, scalability, and ability to capture long-range dependencies. First, we developed a transformer-based network to generate new binary and ternary boride compositions based on the known boride compositions. Next, we trained a hybrid model based on AdaBoost and Gradient Boosting algorithms with a mean absolute error (MAE) of 14.1 GPa to scan the high K borides. The CALYPSO code was used to find the possible structures for those materials. After predicting K for a broad chemical domain, we found that Re–B and W–B systems are promising ultralow compressible materials. We then performed density functional theory (DFT) calculations to investigate the stability of the high K materials. Our computations suggest that W3B2, W2B3, W5VB4, and Re5CrB4 materials exhibit K > 300 GPa with a negative formation energy and energy-above-hull less than 40 meV. These materials are mechanically and dynamically stable based on the elastic constant calculations and the phonon dispersion.
{"title":"Exploiting Transformer-Based Networks and Boosting Algorithms for Ultralow Compressible Boride Design","authors":"Edirisuriya M. Dilanga Siriwardane, Rongzhi Dong, Jianjun Hu, Deniz Çakır","doi":"10.1021/acs.jpcc.5c00183","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00183","url":null,"abstract":"Ultralow compressible materials, which have a high bulk modulus (<i>K</i>), are invaluable in extreme conditions due to their ability to undergo significant compression without structural failure. As a large number of borides can be found with high <i>K</i>, this study develops a computational framework to scan the vast chemical space to identify the ultralow compressible borides. Transformer-based networks are helpful to generate new chemical compositions due to their self-attention mechanism, scalability, and ability to capture long-range dependencies. First, we developed a transformer-based network to generate new binary and ternary boride compositions based on the known boride compositions. Next, we trained a hybrid model based on AdaBoost and Gradient Boosting algorithms with a mean absolute error (MAE) of 14.1 GPa to scan the high <i>K</i> borides. The CALYPSO code was used to find the possible structures for those materials. After predicting <i>K</i> for a broad chemical domain, we found that Re–B and W–B systems are promising ultralow compressible materials. We then performed density functional theory (DFT) calculations to investigate the stability of the high <i>K</i> materials. Our computations suggest that W<sub>3</sub>B<sub>2</sub>, W<sub>2</sub>B<sub>3</sub>, W<sub>5</sub>VB<sub>4</sub>, and Re<sub>5</sub>CrB<sub>4</sub> materials exhibit <i>K</i> > 300 GPa with a negative formation energy and energy-above-hull less than 40 meV. These materials are mechanically and dynamically stable based on the elastic constant calculations and the phonon dispersion.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853384","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 : 2025-04-21DOI: 10.1021/acs.jpcc.5c00625
Hozumi Takahashi, Hiroshi Y. Yoshikawa
This study investigates the crystallization behavior of the ionic liquid 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) induced by focused irradiation with ultrashort laser pulses with the pulse duration of 100 fs or 5 ps. The crystallization was significantly enhanced through scanning irradiation compared to single-point irradiation, probably due to an increase in numbers of laser-induced bubbles and less temperature elevation. The scanning irradiation with 5 ps laser pulses resulted in a higher crystallization probability than that with 100 fs laser pulses, which is attributed to the larger bubbles generated by 5 ps pulses (≥1 mm) compared to those with 100 fs pulses (≪1 mm). Our findings that focused scanning irradiation with 5 ps laser pulses can efficiently induce crystal nucleation will offer a guiding principle for the efficient crystal nucleation of various compounds, impacting a broad range of scientific and industrial fields such as crystal engineering and materials science.
{"title":"Enhancement of Crystallization of Ionic Liquids by Scanning Irradiation with Focused Ultrashort Laser Pulses","authors":"Hozumi Takahashi, Hiroshi Y. Yoshikawa","doi":"10.1021/acs.jpcc.5c00625","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00625","url":null,"abstract":"This study investigates the crystallization behavior of the ionic liquid 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) induced by focused irradiation with ultrashort laser pulses with the pulse duration of 100 fs or 5 ps. The crystallization was significantly enhanced through scanning irradiation compared to single-point irradiation, probably due to an increase in numbers of laser-induced bubbles and less temperature elevation. The scanning irradiation with 5 ps laser pulses resulted in a higher crystallization probability than that with 100 fs laser pulses, which is attributed to the larger bubbles generated by 5 ps pulses (≥1 mm) compared to those with 100 fs pulses (≪1 mm). Our findings that focused scanning irradiation with 5 ps laser pulses can efficiently induce crystal nucleation will offer a guiding principle for the efficient crystal nucleation of various compounds, impacting a broad range of scientific and industrial fields such as crystal engineering and materials science.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"26 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853385","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}
We have developed a chemically constrained micro reverse Monte Carlo (CC-MRMC) method and have statistically determined the three-dimensional (3D) structure of single-atom Cu species dispersed on a 3-thiophene carboxylic acid (TCA)-premodified flat single-crystal oxide surface using a polarization-dependent total reflection fluorescent X-ray absorption fine structure (PTRF-XAFS) technique. The CC-MRMC analysis of the PTRF-XAFS data indicated that an S–Cu–O sandwich structure was adsorbed on the TiO2(110) surface at three equivalent sites of TiO2(110). We carried out density functional theory (DFT) calculations to select one structure among the three candidates. The Cu has a linear structure sandwiched with S in TCA and the bridging oxygen (OB) of TiO2. The TCA is adsorbed onto the TiO2(110) surface as a monodentate carboxylate species, CO(–Ti)O–, with a loss of H+. The advantages and disadvantages of the combination of the PTRF-XAFS + CC-MRMC and DFT methods are discussed.
{"title":"3D Precise Structure Determination of Single-Atom Cu Species on TiO2 Using Polarization-Dependent Total Reflection Fluorescent X-ray Absorption Fine Structure Empowered by Chemically Constrained Micro Reverse Monte Carlo and Density Functional Theory","authors":"Yunli Lin, Kai Oshiro, Jun-ya Hasegawa, Satoru Takakusagi, Wang-Jae Chun, Masao Tabuchi, Kiyotaka Asakura","doi":"10.1021/acs.jpcc.4c08367","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08367","url":null,"abstract":"We have developed a chemically constrained micro reverse Monte Carlo (CC-MRMC) method and have statistically determined the three-dimensional (3D) structure of single-atom Cu species dispersed on a 3-thiophene carboxylic acid (TCA)-premodified flat single-crystal oxide surface using a polarization-dependent total reflection fluorescent X-ray absorption fine structure (PTRF-XAFS) technique. The CC-MRMC analysis of the PTRF-XAFS data indicated that an S–Cu–O sandwich structure was adsorbed on the TiO<sub>2</sub>(110) surface at three equivalent sites of TiO<sub>2</sub>(110). We carried out density functional theory (DFT) calculations to select one structure among the three candidates. The Cu has a linear structure sandwiched with S in TCA and the bridging oxygen (O<sub>B</sub>) of TiO<sub>2</sub>. The TCA is adsorbed onto the TiO<sub>2</sub>(110) surface as a monodentate carboxylate species, CO(–Ti)O<sup>–</sup>, with a loss of H<sup>+</sup>. The advantages and disadvantages of the combination of the PTRF-XAFS + CC-MRMC and DFT methods are discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853387","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 : 2025-04-20DOI: 10.1021/acs.jpcc.4c08813
Zhe Feng, Xin Liu, Huimin Guo, Changgong Meng
Ga/ZSM-5 is among the most promising catalysts for propane dehydrogenation (PDH) to selectively produce propylene, which is one of the most important feedstocks in chemical industry. PDH over Ga/ZSM-5 operates at harsh conditions (T > 800 K), limiting the in-depth and in situ characterization of the catalysts. The Ga speciation and the structures of active sites on Ga/H-ZSM-5 in dehydrogenation have remained in active discussion as they have not been solved clearly. Furthermore, Ga species stabilized by mono-Al sites would be the most abundant Ga species; the PDH pathways over them would be different from those of Ga-oxo or reduced Ga species trapped by dual-Al sites in Ga/ZSM-5, and were reported to exhibit unexpectedly high performance. To bridge these gaps, the potential catalytic roles and evolution of [Ga]+, [GaH2]+, and [Ga]3+ in the channel and on the surface of ZSM-5 in PDH were investigated with first-principles-based calculations. We showed that dynamically generated undercoordinated [GaH2]+ (Sin-[GaH2]+) would exhibit superior catalytic performance as compared with other mononuclear reduced Ga species stabilized by mono-Al sites at the operation conditions. Though [Ga]+ is thermodynamically more plausible, [GaH2]+ is also kinetically favored on PDH pathways. A catalytic cycle of PDH was proposed connecting the concerted pathway over [Ga]+ and the alkyl pathway over [GaH2]+, showing the strong coupling between the evolution of Ga species and the conversion of propane. We also proposed that, competing with PDH and the interconversion, [Ga]+ and [GaH2]+ may also evolve and transport to form [Ga]3+ in channels or on the surface of zeolites, and this transportation also changes the Ga/Al ratio, forming Ga species that are more active than [GaH2]+ and [Ga]+ in situ and may account for the observed PDH performance of Ga/ZSM-5. The findings may help to rationalize the understanding of PDH performance of Ga/ZSM-5 and benefit the design of novel catalysts with superior PDH performance.
{"title":"Evolution of [Ga]+ and [GaH2]+ at Propane Dehydrogenation Conditions in MFI Zeolite: A Theoretical Investigation","authors":"Zhe Feng, Xin Liu, Huimin Guo, Changgong Meng","doi":"10.1021/acs.jpcc.4c08813","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08813","url":null,"abstract":"Ga/ZSM-5 is among the most promising catalysts for propane dehydrogenation (PDH) to selectively produce propylene, which is one of the most important feedstocks in chemical industry. PDH over Ga/ZSM-5 operates at harsh conditions (<i>T</i> > 800 K), limiting the in-depth and in situ characterization of the catalysts. The Ga speciation and the structures of active sites on Ga/H-ZSM-5 in dehydrogenation have remained in active discussion as they have not been solved clearly. Furthermore, Ga species stabilized by mono-Al sites would be the most abundant Ga species; the PDH pathways over them would be different from those of Ga-oxo or reduced Ga species trapped by dual-Al sites in Ga/ZSM-5, and were reported to exhibit unexpectedly high performance. To bridge these gaps, the potential catalytic roles and evolution of [Ga]<sup>+</sup>, [GaH<sub>2</sub>]<sup>+</sup>, and [Ga]<sup>3+</sup> in the channel and on the surface of ZSM-5 in PDH were investigated with first-principles-based calculations. We showed that dynamically generated undercoordinated [GaH<sub>2</sub>]<sup>+</sup> (Sin-[GaH<sub>2</sub><sup>]+</sup>) would exhibit superior catalytic performance as compared with other mononuclear reduced Ga species stabilized by mono-Al sites at the operation conditions. Though [Ga]<sup>+</sup> is thermodynamically more plausible, [GaH<sub>2</sub>]<sup>+</sup> is also kinetically favored on PDH pathways. A catalytic cycle of PDH was proposed connecting the concerted pathway over [Ga]<sup>+</sup> and the alkyl pathway over [GaH<sub>2</sub>]<sup>+</sup>, showing the strong coupling between the evolution of Ga species and the conversion of propane. We also proposed that, competing with PDH and the interconversion, [Ga]<sup>+</sup> and [GaH<sub>2</sub>]<sup>+</sup> may also evolve and transport to form [Ga]<sup>3+</sup> in channels or on the surface of zeolites, and this transportation also changes the Ga/Al ratio, forming Ga species that are more active than [GaH<sub>2</sub>]<sup>+</sup> and [Ga]<sup>+</sup> in situ and may account for the observed PDH performance of Ga/ZSM-5. The findings may help to rationalize the understanding of PDH performance of Ga/ZSM-5 and benefit the design of novel catalysts with superior PDH performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"2 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853388","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 : 2025-04-19DOI: 10.1021/acs.jpcc.5c01618
Danielle R. Lustig, Fangqi Chen, Wentao Zhang, Olivia F. Bird, Javier Fajardo, Jr., Shane Ardo, Shu Hu, Gordana Dukovic, A. Alec Talin, Rohini Bala Chandran, Justin B. Sambur
Nanowire arrays present many unique advantages for solar-to-chemical energy conversion. One possible advantage is that photon recycling between neighboring nanowires has the potential to increase solar energy conversion efficiencies. Here, we explore three underlying mechanisms of optical and electronic coupling between neighboring nanowires─incident photon scattering, photon recycling, and charge-carrier transport from the photoexcited nanowire to the neighboring nanowire via the underlying substrate─using single nanowire-level microscopy and spectroscopy measurements. We present a comprehensive analysis of light absorption and emission of a single nanowire at open circuit, and subsequent re-absorption and re-emission by a neighboring nanowire. We developed a novel correlated single nanowire microspectroscopy and widefield imaging methodology to spatially resolve photon communication pathways between neighboring nanowires and selectively image re-emitted and reflected photons. We developed unique multiphysics models to couple wave optics and semiconductor photophysics to especially isolate contributions from photon recycling and electronic transport to photon emission from neighboring nanowires. By systematically varying the morphologies of the nanowires modeled, we identified pathways to maximize photon recycling between neighboring nanowires. We concluded that the measured photoluminescence is more strongly influenced by the diffusion of charge carriers as compared to photon recycling in materials with moderate-to-large charge-carrier mobilities (>10 cm2 V–1 s–1), and that photon recycling dictates photoluminescence intensity only when the charge-carrier mobility is low (<1 cm2 V–1 s–1). The experimental and simulation platforms developed herein for photon management strategies can be leveraged by the semiconductor photocatalysis community to enhance solar-to-chemical conversion efficiencies in semiconductor nanowire arrays.
{"title":"Models and Measurements Quantify Photon Recycling, Charge-Carrier Diffusion and Photon Scattering Contributions to Photoluminescence in InP Nanowire Arrays","authors":"Danielle R. Lustig, Fangqi Chen, Wentao Zhang, Olivia F. Bird, Javier Fajardo, Jr., Shane Ardo, Shu Hu, Gordana Dukovic, A. Alec Talin, Rohini Bala Chandran, Justin B. Sambur","doi":"10.1021/acs.jpcc.5c01618","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01618","url":null,"abstract":"Nanowire arrays present many unique advantages for solar-to-chemical energy conversion. One possible advantage is that photon recycling between neighboring nanowires has the potential to increase solar energy conversion efficiencies. Here, we explore three underlying mechanisms of optical and electronic coupling between neighboring nanowires─incident photon scattering, photon recycling, and charge-carrier transport from the photoexcited nanowire to the neighboring nanowire via the underlying substrate─using single nanowire-level microscopy and spectroscopy measurements. We present a comprehensive analysis of light absorption and emission of a single nanowire at open circuit, and subsequent re-absorption and re-emission by a neighboring nanowire. We developed a novel correlated single nanowire microspectroscopy and widefield imaging methodology to spatially resolve photon communication pathways between neighboring nanowires and selectively image re-emitted and reflected photons. We developed unique multiphysics models to couple wave optics and semiconductor photophysics to especially isolate contributions from photon recycling and electronic transport to photon emission from neighboring nanowires. By systematically varying the morphologies of the nanowires modeled, we identified pathways to maximize photon recycling between neighboring nanowires. We concluded that the measured photoluminescence is more strongly influenced by the diffusion of charge carriers as compared to photon recycling in materials with moderate-to-large charge-carrier mobilities (>10 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>), and that photon recycling dictates photoluminescence intensity only when the charge-carrier mobility is low (<1 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>). The experimental and simulation platforms developed herein for photon management strategies can be leveraged by the semiconductor photocatalysis community to enhance solar-to-chemical conversion efficiencies in semiconductor nanowire arrays.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"34 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853761","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 : 2025-04-18DOI: 10.1021/acs.jpcc.5c01172
Paul Vosshage, Camila M. Otero, Francis Schuknecht, María Ana Huergo, Jochen Feldmann, Theobald Lohmüller
In this work, we analyze the motion of gold nanospheres in orbital angular momentum (OAM)-carrying optical vortex traps in real time using darkfield microscopy and high-speed video analysis. Notably, we observe that optical binding between gold nanoparticles within the ring-shaped laser trap leads to increased orbiting speeds at a lower focal plane for gold nanoparticle dimers compared to monomers. This behavior is attributed to stronger optical scattering forces acting on the dimers driven by the emergence of a coupled plasmon mode. As the particles move closer together, this mode red-shifts, becoming more resonant with the laser wavelength, eventually causing the system to transition from optical trapping to optical printing. This finding suggests a general mechanism for one-step dimer printing based on plasmonic coupling in vortex beams by adjusting the laser wavelength or modifying the dielectric environment of the nanoparticles via a molecular coating. The feasibility of this approach is demonstrated for optical printing and subsequent surface-enhanced Raman scattering (SERS) spectroscopy on gold nanoparticle dimers coated with 4-nitrothiophenol.
{"title":"Dynamic Trapping and Printing of Plasmonic Dimers with Optical Vortex Beams","authors":"Paul Vosshage, Camila M. Otero, Francis Schuknecht, María Ana Huergo, Jochen Feldmann, Theobald Lohmüller","doi":"10.1021/acs.jpcc.5c01172","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01172","url":null,"abstract":"In this work, we analyze the motion of gold nanospheres in orbital angular momentum (OAM)-carrying optical vortex traps in real time using darkfield microscopy and high-speed video analysis. Notably, we observe that optical binding between gold nanoparticles within the ring-shaped laser trap leads to increased orbiting speeds at a lower focal plane for gold nanoparticle dimers compared to monomers. This behavior is attributed to stronger optical scattering forces acting on the dimers driven by the emergence of a coupled plasmon mode. As the particles move closer together, this mode red-shifts, becoming more resonant with the laser wavelength, eventually causing the system to transition from optical trapping to optical printing. This finding suggests a general mechanism for one-step dimer printing based on plasmonic coupling in vortex beams by adjusting the laser wavelength or modifying the dielectric environment of the nanoparticles via a molecular coating. The feasibility of this approach is demonstrated for optical printing and subsequent surface-enhanced Raman scattering (SERS) spectroscopy on gold nanoparticle dimers coated with 4-nitrothiophenol.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846472","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 : 2025-04-18DOI: 10.1021/acs.jpcc.5c01083
Andres Robles-Navarro, Shaun Cooper, Odile R. Smits, Peter Schwerdtfeger
By introducing appropriate lattice parameters for a bilattice smoothly connecting the hexagonal close-packed (hcp) structure with the cuboidal structures, namely the body-centered cubic (bcc) and the face-centered cubic (fcc) lattices, we were able to map out the minimum energy path for a Burgers-Bain type of phase transition. We demonstrate that for three different models applied, i.e., the kissing hard-sphere model, the Lennard-Jones potential, and density functional theory for metallic lithium, the direct transition path is always from hcp to fcc, with a separate path leading from fcc to bcc. This resolves, at least for the models considered here, a long-standing controversy regarding whether or not fcc acts as an intermediate phase in martensitic types of phase transitions.
{"title":"Exploring the Mechanism of Phase Transitions between the Hexagonal Close-Packed and the Cuboidal Structures","authors":"Andres Robles-Navarro, Shaun Cooper, Odile R. Smits, Peter Schwerdtfeger","doi":"10.1021/acs.jpcc.5c01083","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01083","url":null,"abstract":"By introducing appropriate lattice parameters for a bilattice smoothly connecting the hexagonal close-packed (hcp) structure with the cuboidal structures, namely the body-centered cubic (bcc) and the face-centered cubic (fcc) lattices, we were able to map out the minimum energy path for a Burgers-Bain type of phase transition. We demonstrate that for three different models applied, i.e., the kissing hard-sphere model, the Lennard-Jones potential, and density functional theory for metallic lithium, the direct transition path is always from hcp to fcc, with a separate path leading from fcc to bcc. This resolves, at least for the models considered here, a long-standing controversy regarding whether or not fcc acts as an intermediate phase in martensitic types of phase transitions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"54 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846471","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 : 2025-04-18DOI: 10.1021/acs.jpcc.4c08009
Shyam Deo, Thomas Ludwig, Melinda L. Jue, Nathan C. Ellebracht, Mathew J. Rasmussen, James M. Crawford, Matthew M. Yung, Sneha A. Akhade, Simon H. Pang
Carbon capture and storage (CCS) technologies, along with CO2 capture and conversion methods, have emerged as crucial research areas to address rising CO2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO2 conversion and CH4 production rates over the synthesized catalysts “Ru/TiO2” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO2”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. This comprehensive approach offers key insights into the role of the amine-CO2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO2 capture and conversion processes.
{"title":"Theoretical and Experimental Insights into CO2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts","authors":"Shyam Deo, Thomas Ludwig, Melinda L. Jue, Nathan C. Ellebracht, Mathew J. Rasmussen, James M. Crawford, Matthew M. Yung, Sneha A. Akhade, Simon H. Pang","doi":"10.1021/acs.jpcc.4c08009","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08009","url":null,"abstract":"Carbon capture and storage (CCS) technologies, along with CO<sub>2</sub> capture and conversion methods, have emerged as crucial research areas to address rising CO<sub>2</sub> emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO<sub>2</sub> conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO<sub>2</sub> into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO<sub>2</sub> methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO<sub>2</sub> conversion and CH<sub>4</sub> production rates over the synthesized catalysts “Ru/TiO<sub>2</sub>” and the amine (<i>N</i>-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO<sub>2</sub>”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO<sub>2</sub> uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO<sub>2</sub> coverage at all temperatures. The MKM simulations consistently confirmed these trends. This comprehensive approach offers key insights into the role of the amine-CO<sub>2</sub> bond in methanation, highlighting a pathway toward lower-energy, more efficient CO<sub>2</sub> capture and conversion processes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846470","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 : 2025-04-18DOI: 10.1021/acs.jpcc.4c08535
Samuele Pelatti, Stefania Benedetti, Giuseppe Ammirati, Patrick O’Keeffe, Daniele Catone, Stefano Turchini, Xinchao Huang, Yohei Uemura, Frederico Lima, Christopher Jackson Milne, Paola Luches
Niobium oxide can be stabilized in three distinct stoichiometries, each exhibiting unique physicochemical properties relevant to various technological applications. This study presents a novel procedure for fabricating niobium oxide films and tuning their stoichiometry among the three most stable oxide phases. Starting with a magnetron-sputtered film predominantly composed of Nb2O5, its structure and stoichiometry are optimized through thermal treatment in an O2/N2 flux. A vacuum reduction treatment transforms the as-grown film into the NbO phase, which can then be reoxidized under controlled oxygen partial pressure to achieve the NbO2 phase. The films are characterized in terms of surface composition using X-ray photoemission spectroscopy, structure through X-ray diffraction, optical properties via UV–vis spectrophotometry, and morphology using scanning electron microscopy. Additionally, we show that X-ray absorption near-edge spectroscopy at the Nb K-edge, performed with X-ray free-electron laser radiation, can provide insights into the electronic structure and subsurface stoichiometry of the films. The ultrafast mechanisms underlying photoinduced processes in NbO2 are also discussed.
{"title":"Niobium Oxide Films with Variable Stoichiometry: Structure, Morphology, and Ultrafast Dynamics","authors":"Samuele Pelatti, Stefania Benedetti, Giuseppe Ammirati, Patrick O’Keeffe, Daniele Catone, Stefano Turchini, Xinchao Huang, Yohei Uemura, Frederico Lima, Christopher Jackson Milne, Paola Luches","doi":"10.1021/acs.jpcc.4c08535","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08535","url":null,"abstract":"Niobium oxide can be stabilized in three distinct stoichiometries, each exhibiting unique physicochemical properties relevant to various technological applications. This study presents a novel procedure for fabricating niobium oxide films and tuning their stoichiometry among the three most stable oxide phases. Starting with a magnetron-sputtered film predominantly composed of Nb<sub>2</sub>O<sub>5</sub>, its structure and stoichiometry are optimized through thermal treatment in an O<sub>2</sub>/N<sub>2</sub> flux. A vacuum reduction treatment transforms the as-grown film into the NbO phase, which can then be reoxidized under controlled oxygen partial pressure to achieve the NbO<sub>2</sub> phase. The films are characterized in terms of surface composition using X-ray photoemission spectroscopy, structure through X-ray diffraction, optical properties via UV–vis spectrophotometry, and morphology using scanning electron microscopy. Additionally, we show that X-ray absorption near-edge spectroscopy at the Nb K-edge, performed with X-ray free-electron laser radiation, can provide insights into the electronic structure and subsurface stoichiometry of the films. The ultrafast mechanisms underlying photoinduced processes in NbO<sub>2</sub> are also discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846469","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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