The Journal of Physical Chemistry C最新文献_第8页

Seeded-Surface Plasmonic Nanocavity with Enhanced Field Localization for Exciton–Plasmon Coupling 用于激子-等离子体耦合的增强场定位的种子表面等离子体纳米腔

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-12 DOI: 10.1021/acs.jpcc.6c03611

Lin Luo,Xin Shu,Xiaobo Han,Liang Ma,Xiaohong Li

{"title":"Seeded-Surface Plasmonic Nanocavity with Enhanced Field Localization for Exciton–Plasmon Coupling","authors":"Lin Luo,Xin Shu,Xiaobo Han,Liang Ma,Xiaohong Li","doi":"10.1021/acs.jpcc.6c03611","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03611","url":null,"abstract":"Achieving strong light–matter interaction in monolayer transition metal dichalcogenides (TMDCs) at room temperature requires plasmonic nanocavities with extreme field confinement and minimized mode volume. Although conventional nanoparticle-on-mirror (NPoM) cavities support strong gap-mode plasmon confinement, further compression of the electromagnetic field is desirable for enhancing exciton–plasmon interactions with smaller excitonic ensembles. Here, we developed a seeded-surface NPoM (SS-NPoM) nanocavity consisting of a 50 nm Au nanocube decorated with 10 nm Au nanospheres, separated from an Au mirror by a 10 nm Al2O3 spacer and integrated with monolayer WS2. The surface nanoseeds introduce additional nanoscale protrusions that redistribute and compress the gap-plasmon field into highly localized subhotspots. Dark-field scattering measurements revealed a systematic detuning-dependent anticrossing with mode splitting of 106 meV. Because this value is comparable to the stringent loss-based threshold, the system is conservatively classified as operating in an intermediate-coupling regime close to the onset of strong coupling. Quasinormal-mode calculations show that surface seeding can reduce the optical mode volume by 1 order of magnitude, corresponding to an estimated minimum of ∼14 coupled excitons in the most strongly confined configuration. Experimentally, the area-corrected photoluminescence enhancement reaches ∼690, compared with ∼220 for conventional NPoM cavities. These results demonstrate that seeded-surface engineering provides an effective strategy for constructing highly localized plasmonic nanocavities and offers a promising platform for room-temperature TMDC polaritonics and efficient nanoscale light sources.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152182","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}

引用次数: 0

Largely NegativeEnergy Difference between the Singletand Triplet Excited States and Ultrafast Delayed Fluorescence 单态和三重态激发态与超快延迟荧光之间的巨大负能量差

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-10 DOI: 10.1021/acs.jpcc.6c05966

Guanhao Liu,Ryutaro Komatsu,Kazushi Enomoto,Retno Miranti,Yong-Jin Pu

{"title":"Largely Negative\u0000Energy Difference between the Singlet\u0000and Triplet Excited States and Ultrafast Delayed Fluorescence","authors":"Guanhao Liu,Ryutaro Komatsu,Kazushi Enomoto,Retno Miranti,Yong-Jin Pu","doi":"10.1021/acs.jpcc.6c05966","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c05966","url":null,"abstract":"Abstract Molecules exhibiting inversion of the lowest singlet and triplet excited states, referred to as inverted singlet–triplet (IST) molecules, can show a short delayed lifetime below 1 μs and are therefore promising candidates for next-generation emitters in organic light-emitting diodes. However, the structural factors that govern this inversion remain insufficiently understood, limiting the rational molecular design of compounds with tunable photophysical properties. Here, we analyzed the relationships between excited-state energy levels and frontier molecular-orbital energy levels in heptazine derivatives. The results indicate that degenerate HOMOs and LUMOs are key factors for reducing ΔEST through enhanced mixing of multiple excitation configurations, whereas phenyl groups slightly increase ΔEST by enhancing the exchange interaction, K. Wave function-based quantum chemical calculations using EOM-CCSD estimated large negative ΔEST values of −0.244 eV and −0.238 eV for the heptazine derivatives, HzDA3 and HzTFE3, respectively. Temperature-dependent time-resolved photoluminescence, together with the onsets analysis of photoluminescence and phosphorescence spectra, confirmed their negative ΔEST values. HzDA3 and HzTFE3 exhibited fast reverse intersystem crossing rate constants exceeding 107 s–1, resulting in ultrafast delayed lifetimes of 76 and 341 ns, respectively. These results clarify the key factors governing inverted singlet–triplet (IST) gap in heptazine derivatives and provide a basis for the development of IST molecules.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151176","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}

引用次数: 0

ALD of Tantalumand Titanium Phosphates Using Tris(dimethylamino)phosphine 三（二甲氨基）膦对钽和磷酸钛ALD的影响

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-10 DOI: 10.1021/acs.jpcc.6c05418

Ruben Blomme,Aditya Chalishazar,Andreas Werbrouck,Arnout Van Kerckhoven,Lowie Henderick,Frans Munnik,Christophe Detavernier,Jolien Dendooven

{"title":"ALD of Tantalum\u0000and Titanium Phosphates Using Tris(dimethylamino)phosphine","authors":"Ruben Blomme,Aditya Chalishazar,Andreas Werbrouck,Arnout Van Kerckhoven,Lowie Henderick,Frans Munnik,Christophe Detavernier,Jolien Dendooven","doi":"10.1021/acs.jpcc.6c05418","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c05418","url":null,"abstract":"Abstract Atomic layer deposition (ALD) of metal phosphates is increasingly explored for energy applications, yet the mechanisms governing phosphorus incorporation remain poorly understood. In this work, we introduce two novel ALD processes for amorphous tantalum phosphate and titanium phosphate thin films using tris(dimethylamino)phosphine (TDMAP) as the phosphorus precursor and metal alkylamides as precursors. Both processes employ a four-step ALD cycle, consisting of TDMAP/O2-plasma and metal alkylamide/O2-plasma subcycles, and exhibit a pronounced temperature dependence, with the growth per cycle decreasing as the temperature increases from 150 to 300 °C. In situ characterization indicates ligand exchange reactions during the TDMAP pulse and enhanced P uptake at lower temperatures due to higher reactive site density. The resulting films deposited at 150 °C are a tantalum oxyphosphate and a phosphate-containing titanium oxide, both exhibiting substantially higher phosphorus-to-oxygen and phosphorus-to-metal ratios than their trimethylphosphate-based counterparts. A key finding of this work is that phosphorus incorporation can be further increased by replacing the O2-plasma pulse following the TDMAP exposure with a H2O pulse, shifting the composition toward phosphate-rich stoichiometries intermediate between ortho- and metaphosphates. In situ measurements suggest that less extensive ligand removal during hydrolysis reduces the availability of active sites for subsequent metal precursor adsorption, thereby lowering metal incorporation. These findings demonstrate that tuning the surface chemistry established between the TDMAP and metal precursor exposures provides a straightforward and effective approach for tailoring the composition of metal phosphate films.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151177","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}

引用次数: 0

Anion Immobilization-InducedEnhancement of Li+ Transport at the Polymer Electrolyte–SeparatorInterface 阴离子固定化诱导的聚合物电解质-分离器界面Li+输运增强

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-10 DOI: 10.1021/acs.jpcc.6c01338

Xiaoning Wang,Jingang Zheng,Weichen Han,Hongxu Zhou,Hongwei Zhao,Han Zhang,Lixiang Li,Weimin Zhou,Baigang An,Chengguo Sun

{"title":"Anion Immobilization-Induced\u0000Enhancement of Li+ Transport at the Polymer Electrolyte–Separator\u0000Interface","authors":"Xiaoning Wang,Jingang Zheng,Weichen Han,Hongxu Zhou,Hongwei Zhao,Han Zhang,Lixiang Li,Weimin Zhou,Baigang An,Chengguo Sun","doi":"10.1021/acs.jpcc.6c01338","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c01338","url":null,"abstract":"Abstract In situ polymerized electrolytes have garnered widespread attention owing to their high ionic conductivity and excellent interface compatibility. However, conventional polyethylene (PE) or polypropylene (PP) separators incorporated to maintain structural integrity typically serve merely as mechanical scaffolds, lacking interfacial functionalities to facilitate ion transport and thereby limiting Li+ transport. Herein, we propose an anion immobilization strategy by employing a PP separator coated with aramid layers on both sides (AP) as the supporting scaffold, followed by in situ polymerization to construct an anion-immobilizing polymer electrolyte (APVD). In this composite architecture, the N–H groups in the aramid layers immobilize TFSI– through hydrogen-bonding interactions, establishing a local Li+ concentration gradient at the electrolyte/separator interfaces that assists Li+ transport. Benefiting from the anion immobilization effect, APVD delivers a high Li+ transference number of 0.78, representing an approximately 81% increase over that of the control sample (0.43). Moreover, the Li||APVD||Li symmetric cell maintains a stable polarization voltage below 100 mV after 900 cycles at 0.3 mA cm–2, demonstrating efficient Li+ transport and robust interfacial stability. This work highlights the potential of transforming supporting separators from passive mechanical scaffolds into active ion-transport-regulating interfaces, providing an effective strategy for the rational design of high-performance in situ polymerized electrolytes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"20 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151219","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}

引用次数: 0

Intrinsic DefectEnergetics and Fluorine Doping Effectsin Li2CO3 and Li2O2: AFirst-Principles Study Li2CO3和Li2O2的内在缺陷、能学和氟掺杂效应：第一性原理研究

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-10 DOI: 10.1021/acs.jpcc.6c04090

Youjeong Choi,Tasuku Sugiura,Keisuke Mukai,Nanako Ishihara,Shuji Nakanishi,Teruyasu Mizoguchi

{"title":"Intrinsic Defect\u0000Energetics and Fluorine Doping Effects\u0000in Li2CO3 and Li2O2: A\u0000First-Principles Study","authors":"Youjeong Choi,Tasuku Sugiura,Keisuke Mukai,Nanako Ishihara,Shuji Nakanishi,Teruyasu Mizoguchi","doi":"10.1021/acs.jpcc.6c04090","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c04090","url":null,"abstract":"Abstract Lithium carbonate, Li2CO3, is a thermodynamically stable carbonate phase whose defect energetics are closely related to its stability and decomposition behavior in various lithium-based electrochemical systems. These properties of Li2CO3 are particularly important in lithium–oxygen battery environments. In these systems, Li2CO3 can form as a parasitic discharge product alongside Li2O2, the primary discharge product, leading to performance degradation. However, compared with Li2O2, the intrinsic defect thermodynamics of Li2CO3 and how chemical doping modifies its defect energetics remain insufficiently understood. In this study, first-principles calculations were performed to systematically analyze the intrinsic point-defect energetics of Li2CO3 and to evaluate the effects of fluorine doping on vacancy formation energies in Li2CO3 and Li2O2. Intrinsic defect analysis reveals that defect behavior is predominantly governed by lithium-related defects. Upon fluorine doping, the carbon vacancy formation energies decrease selectively, destabilizing the carbonate framework. Lithium vacancy formation energies decrease partially in Li2CO3 under certain conditions, while a reduction in neutral lithium vacancy formation energy is observed in Li2O2. These results suggest that fluorine doping modulates the defect energetics of both discharge products, potentially providing a thermodynamic basis for controlling the stability of Li2CO3 and Li2O2 under thermodynamic conditions representative of lithium–oxygen batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151175","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}

引用次数: 0

In Situ UV–Vis SpectroscopyInsights into the Role of Hole Scavengers during the Photodepositionof Uniform Gold Nanoparticles on Zinc Oxide 在原位紫外可见光谱中洞悉孔清除剂在氧化锌上均匀金纳米颗粒光沉积过程中的作用

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-10 DOI: 10.1021/acs.jpcc.6c03740

Roos L. Grote,Elaina Galvin,Nico van Mil,Ariq Attallah,Emiel J. M. Hensen,Erik C. Garnett,Bert M. Weckhuysen,Eline M. Hutter

{"title":"In Situ\u0000 UV–Vis Spectroscopy\u0000Insights into the Role of Hole Scavengers during the Photodeposition\u0000of Uniform Gold Nanoparticles on Zinc Oxide","authors":"Roos L. Grote,Elaina Galvin,Nico van Mil,Ariq Attallah,Emiel J. M. Hensen,Erik C. Garnett,Bert M. Weckhuysen,Eline M. Hutter","doi":"10.1021/acs.jpcc.6c03740","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03740","url":null,"abstract":"Abstract Photodeposition has emerged as a promising technique to grow metal nanoparticles (NPs) on semiconductors through the reduction of metal ions by photoexcited electrons. It is known that metal NPs become more uniform when holes are subtracted by a hole scavenger. However, mechanistic insights into the effect of hole scavengers on the growth kinetics and resulting material properties and the effect of the type of hole scavenger are lacking. In this work, we use in situ UV–vis transmission spectroscopy to investigate the oxygen-deficient photodeposition of Au on ZnO. These measurements reveal that the presence of ethanol as a hole scavenger leads to faster nucleation and substantially accelerates the growth of Au NPs compared to the nonscavenged case. Although the effect of adding a hole scavenger is significant, the type of hole scavenger does not play a significant role in the final Au NP morphology. Therefore, adding a hole scavenger results in a higher density of Au NPs with a well-defined localized surface plasmon resonance (LSPR) band and a homogeneous size distribution of 9 ± 3 nm. By capturing real-time NP growth dynamics, inaccessible to ex situ methods, this study shows why a hole scavenger plays a significant role in the kinetics of Au NPs formation and why they lead to better-defined Au NPs with more controlled plasmonic properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151218","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}

引用次数: 0

Unveiling PhosphorusVacancy-Mediated Resistive Switchingin Cu/HfO2/BP/Pt Memristors: Experimental and First-PrinciplesInvestigations 揭示Cu/HfO2/BP/Pt记忆电阻器中磷空位介导的电阻开关：实验和第一性原理研究

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-09 DOI: 10.1021/acs.jpcc.6c05460

Daiyang Jiang,Zihao Yan,Changtian Cao,Ouwen Zhang,Wenhao Li,Zuhao Shi,Niannian Yu,Xiangshui Miao,Huajun Sun

{"title":"Unveiling Phosphorus\u0000Vacancy-Mediated Resistive Switching\u0000in Cu/HfO2/BP/Pt Memristors: Experimental and First-Principles\u0000Investigations","authors":"Daiyang Jiang,Zihao Yan,Changtian Cao,Ouwen Zhang,Wenhao Li,Zuhao Shi,Niannian Yu,Xiangshui Miao,Huajun Sun","doi":"10.1021/acs.jpcc.6c05460","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c05460","url":null,"abstract":"Abstract Memristors integrating 2D materials are promising for neuromorphic computing, yet their microscopic resistive switching mechanisms require further clarification. In this study, a Cu/HfO2/BP/Pt memristor was fabricated to investigate its electrical characteristics and conductive filament (CF) dynamics. The device exhibits compliance-dependent behavior, enabling unipolar volatile switching at 100 μA and bipolar nonvolatile switching at 200 μA. In nonvolatile mode, it demonstrates a concentrated switching voltage distribution (Vset ≈ −1.491 V, Vreset ≈ 1.669 V), stable endurance exceeding 150 cycles, and an ON/OFF ratio of ∼104. The low- and high-resistance states follow ohmic conduction (a hybrid ohmic conduction of electron capture/decapture under negative bias) and Schottky emission, respectively. Furthermore, first-principles CI-NEB calculations indicate that intrinsic phosphorus vacancies (Vp) within the BP layer facilitate directional Cu+ migration (1.54 eV barrier) and spontaneous Pt atom trapping (0.1 eV barrier). This defect-mediated interfacial interaction promotes stable orbital hybridization, anchoring localized CFs. This work provides experimental and theoretical insights for designing oxide/2D material-based neuromorphic hardware.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"32 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151179","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}

引用次数: 0

Realization ofReversible Regulation of Thermal Conductivityin 2D Materials through Engineered Acoustic Mismatch 利用工程声学失配实现二维材料热导率的可逆调节

IF 4.126 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-09 DOI: 10.1021/acs.jpcc.6c03973

H. F. Feng,S. R. Zhu,Z. Y. Xu,B. Liu,Z. X. Song,Zhi-Xin Guo

{"title":"Realization of\u0000Reversible Regulation of Thermal Conductivity\u0000in 2D Materials through Engineered Acoustic Mismatch","authors":"H. F. Feng,S. R. Zhu,Z. Y. Xu,B. Liu,Z. X. Song,Zhi-Xin Guo","doi":"10.1021/acs.jpcc.6c03973","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03973","url":null,"abstract":"Abstract In modern electronic devices, active control of heat transport is essential for performance and reliability, yet most existing approaches to thermal conductivity modulation are irreversible and fixed after synthesis. Here, we propose a reversible thermal conductivity regulation strategy based on engineered junctions in two-dimensional (2D) materials. By locally coupling the central region of a 2D heat-conducting layer to a substrate, we create a junction that exhibits distinct out-of-plane acoustic phonon (ZA mode) properties relative to the surrounding uncoupled region, thereby introducing an engineered acoustic mismatch to dynamically regulate heat transport. Using homogeneous nonequilibrium molecular dynamics (HNEMD) and nonequilibrium molecular dynamics (NEMD) simulations with a graphene/hexagonal boron nitride (Gr/h-BN) junction as a model system, we show that tuning the interlayer coupling in the junction region can suppress the thermal conductivity of graphene by up to a factor of 49 at 100 K. At room temperature (300 K), the modulation ratio can still reach 6.5. This effectiveness of this architecture is not limited by the type of substrates and heat-conducting layer, demonstrating excellent versatility and robustness. The proposed architecture offers a promising route toward dynamic, reversible thermal management in 2D materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"20 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151178","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}

引用次数: 0

Methyl Viologen Groups Bound to Pseudo-Two-Dimensional Cadmium Selenide Nanocrystals as X-Type Ligands Are More Effective Quenchers Than When Bound as L-Type Ligands 甲基紫基与伪二维硒化镉纳米晶体结合作为x型配体比作为l型配体更有效的猝灭剂

IF 3.4 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-08 Epub Date: 2026-09-24 DOI: 10.1021/acs.jpcc.6c05014

Hailey M. Meyer, Jie Chen, Timothy J. Krogmeier, Anthony W. Schlimgen, Kade Head-Marsden, William E. Buhro, Richard A. Loomis

{"title":"Methyl Viologen Groups Bound to Pseudo-Two-Dimensional Cadmium Selenide Nanocrystals as X-Type Ligands Are More Effective Quenchers Than When Bound as L-Type Ligands","authors":"Hailey M. Meyer, Jie Chen, Timothy J. Krogmeier, Anthony W. Schlimgen, Kade Head-Marsden, William E. Buhro, Richard A. Loomis","doi":"10.1021/acs.jpcc.6c05014","DOIUrl":"10.1021/acs.jpcc.6c05014","url":null,"abstract":"Oleylamine-ligated wurtzite CdSe quantum platelets (QPs)and quantumbelts (QBs) are exchanged with carboxylate-terminated, methyl-viologen-containingMV2+(CH2)nCO2– ligands (where n = 2,4, or 6), resulting in the progressive quenching of the QP and QBphotoluminescence (PL). Spectroscopic and compositional analyses indicatethat the initial ligand exchange responsible for PL quenching occurson the nonpolar, thin, long-edge nanocrystal facets. The X-type MV2+(CH2)nCO2– ligands are shown to be more-effective PL quenchersthan the corresponding L-type MV2+(CH2)nNH2 ligands studied previously[ Meyer, H. M.; et al.J. Phys. Chem. C2023, 127, 18506–18517.]. Transient-absorptionspectroscopy measurements reveal electron transfer to the ligandsoccurs for fully quenched QPs, but not for the fully quenched QBs,establishing that electron transfer occurs selectively at the polar,thin, short-edge facets of the nanocrystals. The electron transferoccurs in <50 fs for the X-type ligation and within 100 fs forthe L-type ligation. This difference is ascribed to the greater preferencefor the binding of X-type over L-type ligands on polar facets, andthis results in a significant contribution of electron transfer tothe overall PL quenching.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13853–13862"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049370","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}

引用次数: 0

Beyond Optical Basicity: Role of O–Cl Bond Formation in CaCl2-Induced Silicate Network Disruption in Weathered Biotite 超越光学碱度：O-Cl键形成在风化黑云母中cacl2诱导的硅酸盐网络破坏中的作用

IF 3.4 3区化学

The Journal of Physical Chemistry C Pub Date : 2026-10-08 Epub Date: 2026-09-29 DOI: 10.1021/acs.jpcc.6c03362

Iwao Shimoyama, Yuji Baba

{"title":"Beyond Optical Basicity: Role of O–Cl Bond Formation in CaCl2-Induced Silicate Network Disruption in Weathered Biotite","authors":"Iwao Shimoyama, Yuji Baba","doi":"10.1021/acs.jpcc.6c03362","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03362","url":null,"abstract":"The optical basicity framework has long served as a guidingprinciplefor predicting chemical reactivity in silicate systems, yet it failsto explain a striking experimental observation: despite its extremelylow optical basicity, CaCl2 uniquely induces the phasetransformation of weathered biotite (WB) at 600 °C–700°C, whereas high-basicity additives such as CaO and CaCO3 do not. Here, we address this paradox by combining Cl K-edgenear-edge X-ray absorption fine structure (NEXAFS) spectroscopy, thermaldesorption spectroscopy (TDS), and molecular orbital (MO) calculations.Cl K-edge NEXAFS indicates the coexistence of Cl– and positively polarized O-coordinated Cl environments, while TDSshows Cl-containing desorption products consistent with the formationof oxychlorine-containing species below the onset of phase transformation.In contrast, NaCl produces no detectable O–Cl bonding speciesand fails to induce structural transformation under vacuum conditions.MO calculations indicate that O–Cl bonds destabilize silicateframeworks by weakening Si–O–Si linkages more effectivelythan Si–Cl bonds. These findings suggest that O–Cl bondformation provides a fundamentally distinct mechanism for low-temperaturesilicate network disruption beyond conventional optical basicity theory.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13924–13935"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124945","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}

引用次数: 0