The Journal of Physical Chemistry C最新文献

{"title":"Does Electronic Strong Light-Matter Coupling Affect the Ground-State Energy Landscape? An Experimental Study Using Spin-Crossover Molecules","authors":"Ayman Hoblos, Stéphane Calvez, Lionel Salmon, Gábor Molnár, Karl Ridier, Azzedine Bousseksou","doi":"10.1021/acs.jpcc.4c08198","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08198","url":null,"abstract":"The effect of strong light-matter coupling on the electronic ground-state energy landscape of a large ensemble of coupled molecules remains an open question, even at the theoretical level, which still suffers from the lack of experimental studies. In the present work, we have conducted a very careful study of the thermodynamic phase equilibrium between the low-spin (LS) and high-spin (HS) states of a molecular spin-crossover (SCO) thin film, strongly coupled to the vacuum field inside a Fabry–Pérot cavity. While the cavity was tuned to be resonant with the intense charge-transfer bands of the SCO complexes in the LS state, allowing a strong-coupling regime to be achieved with a Rabi splitting of up to 670 meV, molecules in the nonabsorbing HS state remain uncoupled to the cavity. Importantly, no significant change in the spin-transition temperature is observed between the LS and HS states under light-matter coupling within the precision limit (1 °C) of our measurements. The present results demonstrate that, although collective strong coupling to electronic excitations can significantly perturb the excited states of molecules, the effect on the ground-state energy levels remains largely negligible (<0.6 meV).","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"33 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071785","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}

{"title":"Plasma-Enhanced Spatial Atomic Layer Deposition on 2D and 3D Surface Topologies: The Case of Amorphous and Crystalline TiO2","authors":"Mike van de Poll, Jie Shen, James Hilfiker, Marcel Verheijen, Paul Poodt, Fieke van den Bruele, Wilhelmus Kessels, Bart Macco","doi":"10.1021/acs.jpcc.4c08281","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08281","url":null,"abstract":"Plasma-enhanced spatial ALD (PE-s-ALD) is an interesting technique for high-volume manufacturing of thin films at low-temperature. This technique is particularly appealing for conformal depositions on 3D surfaces for various applications, such as optical coatings, electrolyzers, and batteries. However, various crystallization and growth effects can influence the final film profile and properties, and understanding these effects and their interplay is key. This study investigates the complex growth mechanism of TiO₂ using PE-s-ALD. TiO₂ films are deposited on both planar and 3D substrates, while systematically varying the number of cycles, deposition temperature, and exposure times. Thickness, crystallinity, and composition are determined as a function of depth inside the structures. Conditions that result in the anatase phase on a planar surface only partially form this phase inside 3D structures, with the deepest part of the film being amorphous. This partial crystallization is ascribed to the film thickness inside the 3D structure gradually dropping below the critical thickness for crystallization. In turn, the partial crystallization is shown to have a significant effect on the resulting thickness profile, due to a difference in growth per cycle between the two phases. A framework of the interplay between effects is proposed, offering insights that enable better control of crystallinity and thickness throughout the entirety of coated surfaces of 3D structures by PE-s-ALD. Additionally, the recombination probability of oxygen radicals during this atmospheric-pressure PE-s-ALD process at 200 °C is determined to be 3 × 10^–5. This value is similar to low-pressure PE-ALD, indicating that differences in conformality between the two types of ALD are not the result of differences in recombination probability, but rather of differences in initial radical density and diffusion behavior.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"75 1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071786","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}

{"title":"Electronic and Optical Properties of Highly Complex Ga2O3 and In2O3 Polymorphs Using Approximate Quasiparticle DFT + A – 1/2","authors":"Claudio Ribeiro da Silva, Friedhelm Bechstedt, Lara Kühl Teles, Marcelo Marques","doi":"10.1021/acs.jpcc.4c06718","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06718","url":null,"abstract":"Ga₂O₃ and In₂O₃ are among the most important wide-bandgap semiconductors for transparent electronics and ultraviolet optoelectronics. Their pronounced polymorphism necessitates a deeper understanding. In addition to assessing the stability of specific crystal structures, the central goal is to investigate the variation of material properties as a function of the actual crystal structure. The underlying atomic geometries are determined through total energy optimizations within density functional theory (DFT) using the AM05 exchange-correlation functional. To account for excitation effects in electronic systems, the formation of quasiparticles, and the underestimation of band gaps, we employ the fast, efficient, but approximate DFT + <i>A –</i> 1/2 method. This approach accurately predicts fundamental gaps, interband transition energies, and <i>d</i>-level positions for five Ga₂O₃ and five In₂O₃ polymorphs, even for structures with up to 160 atoms in the unit cell. The resulting electronic structures are further used to predict dielectric and optical spectra. The effective band masses and dielectric tensors are subsequently employed to estimate the binding energies of band-edge excitons. All results are discussed in the context of polymorph geometry and symmetry, and they are compared with available experimental and theoretical data.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071779","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}

{"title":"Elucidating the Dynamic Changes in the Mechanism of the Potential-Dependent Alkaline Hydrogen Evolution Reaction on Platinum","authors":"Mengting Li, Zhuoyang Xie, Jin Liu, Jingtian Ni, Mingming Deng, Yunchuan Tu, Shangkun Jiang, Jiawei Liu, Guohua Chen, Li Li, Zidong Wei","doi":"10.1021/acs.jpcc.4c08707","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08707","url":null,"abstract":"Platinum is widely regarded as the most efficient catalyst for the hydrogen evolution reaction (HER). However, as the overpotential increases, the kinetics of the HER significantly declines and the mechanism exhibits potential-dependent behavior. Through a combination of theoretical simulations and experimental testing, we investigated the changes in the HER mechanism and the underlying kinetic reasons within the kinetic control potential region. The results revealed that at a low cathodic overpotential, the HER follows the Volmer–Tafel mechanism at the Pt(111)/water interface, while at a high cathodic overpotential, it follows the Volmer–Heyrovsky mechanism. The transition and shift in the rate-determining step from the Tafel step to the Volmer step are attributed to the reduced density of active sites and the accumulation of OH generated from water dissociation. Excessive accumulation of OH can promote the desorption of H₂ but can also raise the energy barrier of the Volmer step. This occurs because it weakens the adsorption of species and disrupts the orientation of interfacial water on the Pt(111) surface, thus hindering the HER. These findings clarify the significant role of local OH enrichment and its effect on interfacial water in modulating the HER mechanism and enhancing HER kinetics under kinetic control conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"39 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143072847","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}

{"title":"Sensitization of Ti3+ Persistent Luminescent Lifetime-Based Thermometer by Ln3+ Co-Doping","authors":"Wojciech M. Piotrowski","doi":"10.1021/acs.jpcc.4c07883","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07883","url":null,"abstract":"Co-doping of phosphors to induce energy transfers is a recognized approach to sensitize lifetime-based luminescent thermometers. However, introducing an additional depopulation channel is usually associated with a significant shortening of lifetime over the entire temperature range, which hinders the reliability of the temperature readout with respect to unco-doped counterparts. In this work, I analyzed the influence of the co-doping of lanthanide (Ln³⁺) ions on the thermometric performance of the LaAlO₃: 10% Ti³⁺ phosphor, in which the average lifetime of the ²E excited state reaches almost 30 ms at room temperature. To optimize the sensitization strategy, I discuss the role of Ti³⁺ → Ln³⁺ and Ln³⁺ → Ti³⁺ energy transfers in the thermal evolution of Ti³⁺ lifetimes, where Ln³⁺ = Pr³⁺, Nd³⁺, Eu³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, and Yb³⁺. The next step is the verification of the effect of the concentration of Tm³⁺ and Pr³⁺ ions as co-dopants on thermal quenching. The research allowed improvement of the relative sensitivity of the luminescent thermometer by more than 250%, exceeding 5% K^–1.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"20 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071783","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}

{"title":"Force-Matching-Based Approach for the Generation of Polarizable and Nonpolarizable Force Fields Applied to CsPbI3","authors":"Cecilia Vona, Mathias Dankl, Ariadni Boziki, Martin P. Bircher, Ursula Rothlisberger","doi":"10.1021/acs.jpcc.4c04979","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04979","url":null,"abstract":"Lead halide perovskites have emerged as highly efficient solar cell materials. However, to date, the most promising members of this class are polymorphs in which a wide-band-gap δ phase competes with the photoactive perovskite α form and the intrinsic physical interactions that stabilize one phase over the other are currently not well understood. Classical molecular dynamics simulations based on suitably parametrized force fields (FF) enable computational studies over broad temperature (and pressure) ranges and can help to identify the underlying factors that govern relative phase stability at the atomic level. In this article, we present a force-matching-based approach for the automatized generation of polarizable (<i>pol</i>) as well as nonpolarizable (<i>npol</i>) FFs from high-level reference data and apply it to the all-inorganic lead halide material CsPbI₃ as a prototype system exhibiting a δ/α polymorphism. These force-matched <i>npol</i> and <i>pol</i> FFs have been determined based on extensive reference data from first-principles molecular dynamics simulations over a wide range of temperatures. While both FFs are able to describe the perovskite as well as the nonperovskite δ phase, finer structural details, as well as the relative phase stability, are better reproduced with the polarizable version. A comparison of these ab initio-derived interatomic potentials allows direct insight into the physical origin of the interactions that govern the interplay between the two competing phases. It turns out that explicit polarization is the essential factor that stabilizes the strongly anisotropic δ phase over the high-symmetry (cubic) perovskite α phase at lower temperatures. This fundamental difference between α and δ phases appears universal and might thus also hold for other perovskite compounds with δ/α polymorphism providing rational guidance for synthetic efforts to stabilize the photoactive perovskite phase at room temperature.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"18 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056858","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}

{"title":"Chiral Gold Nanoprisms by Tuning the Wavelength and Handedness of Light","authors":"Tsumugi Miyashita, Sumon Hati, Sarah R. Langlais, Brekke Pattison, Tian Qiao, Rajesh Sardar, Ming Lee Tang","doi":"10.1021/acs.jpcc.4c08741","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08741","url":null,"abstract":"Plasmonic nanoparticles with chiral resonances in the visible wavelengths complement optical dissymmetry in the ultraviolet and near-infrared wavelengths in natural products and metamaterials respectively. Here, we show that under oxidative conditions, hot holes photogenerated with circularly polarized light in gold nanoprisms can spatially direct the photodeposition of lead oxide (PbO₂), resulting in chiral nanostructures tunable with the polarization and wavelength of light. We observe a <i>g</i>-factor of 3.6 × 10^–3, which can be attributed to the enhanced optical dissymmetry with PbO₂ deposition of the side of nanoprisms upon illumination with green 532 nm light. Our finite-difference time-domain calculations support the site-specific photodeposition of PbO₂ onto nanoprisms. This work shows that plasmonic nanoparticles can have tunable chiral properties imbued as a function of the wavelength and polarization of light.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"79 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056862","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}

{"title":"Prediction of the Pressure-Resistant Hardest AlFeO3","authors":"Runqing Zhang, Lingling Bai, JingYi Zhang, Junzhao Li, Minru Wen, Fugen Wu, Huafeng Dong, Lei Shen","doi":"10.1021/acs.jpcc.4c07134","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07134","url":null,"abstract":"Perovskite iron-oxide AlFeO&lt;sub&gt;3&lt;/sub&gt; is an environmentally friendly (lead-free) multiferroic material that simultaneously exhibits ferromagnetism and the potential magnetoelectric coupling, making it ideal for next-generation spintronic devices. Recently, high pressure has emerged as an effective approach in achieving superior physical properties of perovskite structures. Here, we systematically study the phase diagram and physical properties of AlFeO&lt;sub&gt;3&lt;/sub&gt; under pressure. Using an &lt;i&gt;ab initio&lt;/i&gt; evolutionary algorithm, we explore all of the potential stable phases of bulk AlFeO&lt;sub&gt;3&lt;/sub&gt; between 0 and 50 GPa, and we successfully discover two new stable phases (&lt;i&gt;P&lt;/i&gt;2&lt;sub&gt;1&lt;/sub&gt;/&lt;i&gt;c&lt;/i&gt; and &lt;i&gt;R&lt;/i&gt;32). We identify three pressure-induced phase transition sequences &lt;i&gt;&lt;/i&gt;&lt;span style=\"color: inherit;\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;mi&gt;n&lt;/mi&gt;&lt;mi&gt;a&lt;/mi&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mi mathvariant=\"normal\"&gt;&amp;#x2010;A&amp;#x2010;AFM&lt;/mi&gt;&lt;mover&gt;&lt;mrow&gt;&lt;mo stretchy=\"true\"&gt;&amp;#x2192;&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;mi&gt;GPa&lt;/mi&gt;&lt;/mrow&gt;&lt;/mover&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;mi mathvariant=\"normal\"&gt;&amp;#x2010;G&amp;#x2010;AFM&lt;/mi&gt;&lt;mover&gt;&lt;mrow&gt;&lt;mo stretchy=\"true\"&gt;&amp;#x2192;&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;15&lt;/mn&gt;&lt;mi&gt;GPa&lt;/mi&gt;&lt;/mrow&gt;&lt;/mover&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;mi mathvariant=\"normal\"&gt;&amp;#x2010;FM&lt;/mi&gt;&lt;/math&gt;' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"&gt;&lt;nobr aria-hidden=\"true\"&gt;&lt;span style=\"width: 23.128em; display: inline-block;\"&gt;&lt;span style=\"display: inline-block; position: relative; width: 21.026em; height: 0px; font-size: 110%;\"&gt;&lt;span style=\"position: absolute; clip: rect(1.139em, 1021.03em, 2.901em, -999.997em); top: -2.554em; left: 0em;\"&gt;&lt;span&gt;&lt;span style=\"font-family: STIXMathJax_Normal-italic;\"&gt;𝑃&lt;span style=\"display: inline-block; overflow: hidden; height: 1px; width: 0.116em;\"&gt;&lt;/span&gt;&lt;/span&gt;&lt;span style=\"font-family: STIXMathJax_Normal-italic;\"&gt;𝑛&lt;/span&gt;&lt;span style=\"font-family: STIXMathJax_Normal-italic;\"&gt;𝑎&lt;/span&gt;&lt;span&gt;&lt;span style=\"display: inline-block; position: relative; width: 0.912em; height: 0px;\"&gt;&lt;span style=\"position: absolute; clip: rect(3.128em, 1000.46em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"&gt;&lt;span&gt;&lt;span style=\"font-family: STIXMathJax_Main;\"&gt;2&lt;/span&gt;&lt;/span&gt;&lt;span style=\"display: inline-block; width: 0px;","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057321","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}

{"title":"Modulated Electronic and Thermal Transport Properties in Cu-Based Diamond-like Chalcogenides by Point Defect Engineering","authors":"Taras Parashchuk","doi":"10.1021/acs.jpcc.4c07317","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07317","url":null,"abstract":"The electronic and thermal transport properties of thermoelectric materials are always affected by the presence of native defects. However, the importance of these defects remains unclear due to the complex nature of their identification. In this study, we demonstrate that powder X-ray diffraction can provide the necessary point defect scheme to explain the transport properties of quaternary Cu-based diamond-like materials. In particular, the mixed cation occupancy of Co, Ge, and Cu in Cu₂CoGeSe₄ and the mixed occupancy of Sn and Cu in Cu₂CoSnSe₄, as determined by Rietveld refinement, have been successfully used to elucidate the influence of point defects on the carrier concentration and the lattice thermal conductivity. This approach allows for a quantitative prediction of the lattice thermal conductivity, which reaches a very low value below 0.6 W m^–1 K^–1 at 773 K for the investigated Cu-based diamond-like selenides. Furthermore, substitutional defects were identified as a means to improve the electronic transport properties, namely, by modulating the carrier concentration and increasing the power factor up to 5–6 μW cm^–1 K^–2. The improved power factor and low lattice thermal conductivity observed in the Cu-based diamond-like selenides Cu₂CoGeSe₄ and Cu₂CoSnSe₄ result in a significantly higher thermoelectric figure of merit <i>ZT</i> than that of the sulfides Cu₂CoGeS₄ and Cu₂CoSnS₄. At 773 K, the undoped materials exhibit a <i>ZT</i> value of 0.75. In addition to identifying the exceptional thermoelectric properties of Cu-based diamond-like materials, this research demonstrates the effectiveness of powder X-ray diffraction as a simple yet effective method for investigating point defects in thermoelectric materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"50 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071787","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}

{"title":"Chemical Reaction Pathways during Laser Fragmentation of Metallic Microparticles in Organic Solvents","authors":"Theo Fromme, Rutger Müller, Lars Krenz, Lucie K. Tintrop, Ignacio Sanjuán, Torsten C. Schmidt, Katharine M. Tibbetts, Corina Andronescu, Sven Reichenberger, Stephan Barcikowski","doi":"10.1021/acs.jpcc.4c06653","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06653","url":null,"abstract":"Laser synthesis and processing of colloids (LSPC) allows the scaled production of nanomaterials for applications in catalysis, biomedicine, and additive manufacturing. However, the processed raw material reacts with the solvent during nanoparticle formation, resulting in byproducts. Despite several studies on byproduct formation during LSPC in organic solvents, the reaction mechanisms are still unknown. To fill this knowledge gap, this study focuses on the microparticle laser fragmentation (MP-LFL) of four different metal microparticles in five different C₆ solvents in ambient and oxygen-depleted atmospheres. The influence of the solvent, metal, and dissolved oxygen on the gas formation rates, gas and liquid compositions, and nanoparticle properties is investigated. The gas and hydrogen formation rates were found to be dependent on the atmosphere and chemical properties of the solvent and metal. In contrast, the formation of liquid byproducts was independent of the metal and the atmosphere and is instead determined by the solvent. Based on this, solvent decomposition pathways during MP-LFL were proposed, providing general selection rules to suppress or enhance the formation of byproduct species.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056861","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}