Ziying Hong, , , Yu Zhang, , , Meng Zhang, , , Nianxing Wang, , , Yanxiao Jiang, , , Hong Zhang, , , Kai Yu*, , and , Jie Jiang*,
{"title":"Mass Spectrometric Insight into the Sulfonated Polyaniline Polymerization Assisted by Aniline, Aniline Dimers and Perchloric Acid","authors":"Ziying Hong, , , Yu Zhang, , , Meng Zhang, , , Nianxing Wang, , , Yanxiao Jiang, , , Hong Zhang, , , Kai Yu*, , and , Jie Jiang*, ","doi":"10.1021/acs.jpclett.5c02172","DOIUrl":"10.1021/acs.jpclett.5c02172","url":null,"abstract":"<p >Sulfonated polyaniline (SPAN) has good water solubility and can be used as a proton reservoir to retain a high local H<sup>+</sup> concentration on the polymer backbone, making it valuable for water-soluble zinc batteries. However, the mechanism of SPAN by electrochemical synthesis lacks experimental data support. Here, the roles of aniline (ANI) and acid in electropolymerization of SPAN were mainly investigated by electrochemical-mass spectrometry, which can directly and in real time detect the target substances in complicated mixtures containing species. Under acid-free conditions, the chain growth of SPAN was mainly driven by ANI and ANI dimer (i.e., <i>N</i>-phenyl-p-phenylenediamine). After addition of perchloric acid, a chain growth pathway dominated by o-aminobenzenesulfonic acid (oASA) emerged during the reaction, indicating that the reactivity ratio of ANI and oASA was altered. Furthermore, experimental evidence were provided regarding the influence of antioxidant capacity and intramolecular hydrogen bonding on the oASA homopolymerizaiton. These results offer theoretical guidance for optimizing the electropolymerization process of SPAN.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9917–9924"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145036063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Engineering Interfacial Dual Vacancies in Heterostructured Electrocatalysts for Efficient Overall Water Splitting","authors":"Yinglong Weng, , , Ying Bo Kang*, , , Jianping Zhang, , , Nannan Li, , , Tengfei Yang, , , Chunyong Wang, , and , Xiaotong Han*, ","doi":"10.1021/acs.jpclett.5c02118","DOIUrl":"10.1021/acs.jpclett.5c02118","url":null,"abstract":"<p >Defect engineering has emerged as a pivotal strategy for tailoring the electrocatalytic activity of electrocatalysts, yet the fundamental mechanisms underlying the role of interfacial dual vacancies remain insufficiently understood. In this study, we rationally designed and synthesized a heterostructured electrocatalyst with interfacial oxygen and sulfur dual vacancies (V<sub>os</sub>-Co<sub>3</sub>O<sub>4</sub>@MoS<sub>2</sub>) via a hydrothermal–calcination approach, achieving high efficiency in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Combined experimental and theoretical investigations reveal that Co–O–S–Mo interfacial bonds, together with dual vacancies, synergistically modulate the local electronic environment by shifting the <i>d</i>-band center toward the Fermi level. This adjustment optimizes the adsorption energy of key intermediates, thereby accelerating the reaction kinetics. As a result, the V<sub>os</sub>-Co<sub>3</sub>O<sub>4</sub>@MoS<sub>2</sub> heterostructure demonstrates outstanding bifunctional activity in alkaline media, delivering low overpotentials of 81 mV for HER and 253 mV for OER at 10 mA cm<sup>–2</sup>. Additionally, it requires only 1.566 V to drive overall water splitting at 10 mA cm<sup>–2</sup> and maintains excellent stability for over 50 h. This work highlights the critical role of interfacial dual vacancies in enhancing electrocatalytic performance and provides valuable insights for the rational design of high-performance electrocatalysts for sustainable energy applications.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9864–9873"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"“Symmetry Breaking”-Assisted Distinct Molecular Packing in Self-Assembled Oligothiophenes Leading to Emissive Trap States and Enhanced Photocatalytic Solar H2 Production","authors":"Soham Ghosh, , , Amit Kumar, , , Subhajit Kar, , , Pandiselvi Durairaj, , , Sushila Kumari, , , Sunandan Sarkar*, , , Arijit K. De*, , and , Santanu Bhattacharyya*, ","doi":"10.1021/acs.jpclett.5c01824","DOIUrl":"10.1021/acs.jpclett.5c01824","url":null,"abstract":"<p >Two different types of self-assemblies have been fabricated from 2,2′-bithiophene-5,5′-dicarboxaldehyde (BTDA) and 2,2′:5′,2′′-terthiophene-5,5′′-dicarboxaldehyde (TTDA) molecules through reprecipitation methods. Unlike the BTDA molecule, one thiophene unit remains out of plane with respect to the other two thiophene units in TTDA. This results in partial face-to-face intermolecular interactions during self-assembly, causing the formation of a defect-mediated emissive trap state at longer wavelengths. These trap states are charge-transfer types with a longer lifetime compared to the pure TTDA molecule. Detailed computational studies and femtosecond transient absorption spectroscopy support the findings. The appearance of the charge transfer type trap state in TTDA self-assembly facilitates the photoinduced charge separation and free carrier accumulation, which helps to boost the photocatalytic solar H<sub>2</sub> production. However, highly defined head-to-tail molecular arrangements in BTDA self-assembly hinder the formation of such an emissive trap state, resulting in a decrease in the photocatalytic efficiency.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9906–9916"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145036078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nabankur Dasgupta, , , Kai Ito, , , Thomas M. Linker, , , Wataru Sugimoto, , , Seyedmahmoud Mortazavi, , , Rajiv K. Kalia, , , Aiichiro Nakano*, , , Alexander T. Radosevich, , , Kohei Shimamura, , , Fuyuki Shimojo, , , Adri van Duin, , and , Priya Vashishta,
{"title":"Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors","authors":"Nabankur Dasgupta, , , Kai Ito, , , Thomas M. Linker, , , Wataru Sugimoto, , , Seyedmahmoud Mortazavi, , , Rajiv K. Kalia, , , Aiichiro Nakano*, , , Alexander T. Radosevich, , , Kohei Shimamura, , , Fuyuki Shimojo, , , Adri van Duin, , and , Priya Vashishta, ","doi":"10.1021/acs.jpclett.5c02429","DOIUrl":"10.1021/acs.jpclett.5c02429","url":null,"abstract":"<p >While pyrolysis of polymeric precursors has gained attention for the additive manufacturing of ceramics, the high-temperature process is energy-inefficient and time-consuming. Recently, photochemistry has been suggested to reduce energy consumption and reaction time, but the microscopic mechanisms of such accelerated reactions remain elusive. Here, we reveal distinct photochemical and thermal reaction pathways at the initial stage of silicon–carbide ceramic formation from an acylsilane precursor, using a multiscale simulation approach that combines first-principles nonadiabatic and adiabatic quantum molecular dynamics simulations with semiempirical reactive molecular dynamics simulations. While photoexcitation causes scission of Si–C bonds within 100 fs driven by the localization of a photoexcited hole, the precursor remains stable at high temperatures up to 1800 K without photoexcitation. On longer time scales, we find thermal reaction pathways involving concerted motions of many atoms, including the formation of SiCO clusters, mainly resulting from oxygen of carbonyl carbon shifting and bonding with silicon. This microscopic understanding suggests synergistic use of photochemical and thermal pathways to design ultralow-energy and facile additive manufacturing of ceramics toward achieving a sustainable society.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9874–9883"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145036067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexey I. Chizhik, , , Damir I. Sakhapov, , , Ingo Gregor, , , Narain Karedla, , and , Jörg Enderlein*,
{"title":"Charge-Dependent Fluorescence Lifetime Modulation in a Plasmonic Nanocavity","authors":"Alexey I. Chizhik, , , Damir I. Sakhapov, , , Ingo Gregor, , , Narain Karedla, , and , Jörg Enderlein*, ","doi":"10.1021/acs.jpclett.5c01972","DOIUrl":"10.1021/acs.jpclett.5c01972","url":null,"abstract":"<p >Electric charges play a fundamental role in shaping the structure, function, and interactions of biomolecules, yet precisely measuring these charges at the single-molecule level remains a significant technical challenge. Here, we introduce a novel experimental methodology that utilizes plasmonic nanocavities to quantify molecular electric charges in solution with high sensitivity. Our approach exploits an externally applied electric field to induce the spatial redistribution of charged molecules confined within a planar metallic nanocavity while simultaneously leveraging nanocavity-induced fluorescence lifetime modulation as a highly sensitive readout. We demonstrate the feasibility of this method through proof-of-concept experiments, where we measure the fluorescence lifetimes of positively and negatively charged fluorescent dye molecules as a function of the applied electric field across the cavity. The experimental results are validated through a rigorous theoretical framework, incorporating statistical thermodynamics and electrodynamic modeling to accurately describe the observed data. The proposed method offers a calibration-free, experimentally simple, and rapid alternative to existing charge measurement techniques, opening new avenues for precise quantification of molecular electric charges down to the single-molecule level.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9900–9905"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145036065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Hierarchical Traps Modulated Charge Transport of Dielectric Polymers toward Enhanced Breakdown Performance","authors":"Yuanwei Zhu*, , , Haomiao Li, , , Yihang Jiang, , , Fenghua Cao, , , Jiahui Li, , , Jie Liu, , , Guochang Li, , , Yanhui Wei, , and , Shengtao Li*, ","doi":"10.1021/acs.jpclett.5c02256","DOIUrl":"10.1021/acs.jpclett.5c02256","url":null,"abstract":"<p >Charge carrier dynamics of trapping, detrapping, and transport dominate the electrical performance of dielectric polymers, which are vital for high-voltage equipment and electronic devices. The rich inhomogeneities in polymeric structure are manifested as distinct microphase crystallization regions, of which the contribution to charge dynamics remains as an unresolved frontier in dielectric physics, forming obstacles in designing high-performance dielectric polymers. Herein, we reveal the microscopic origin of inhomogeneity-generated intramolecular trap distributions and its modulation in charge transport. We find that under customized gradient branched structures, the generated rich deep traps build ordered trap blocks, forming hierarchical distributed energy levels where trap energy and density gradually decrease from the deepest trap block toward both chain terminals. We clarify that such a hierarchical configuration results in short-range transport of charge carriers, preventing energy accumulation from hopping through long-range free paths, leading to 12.5% enhanced breakdown performance of 701.1 kV/mm, as compared to the corresponding random copolymers. The proposed charge transport mechanism and intramolecular structure are expected to be utilized for developing next-generation dielectric polymers and customizing their electrical performance.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9884–9893"},"PeriodicalIF":4.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145036066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyu Liang, Yuanzheng Ren, Zhiwei Chen, Xinxin Zhang, Yan Liang, Bo Jiang, Hua Xie, Min Ji, Min Wang* and Xinkui Wang*,
{"title":"Construction of a Surface Hydroxyl Group on ZnIn2S4 Promotes Photocatalytic CO2 Reduction","authors":"Xiaoyu Liang, Yuanzheng Ren, Zhiwei Chen, Xinxin Zhang, Yan Liang, Bo Jiang, Hua Xie, Min Ji, Min Wang* and Xinkui Wang*, ","doi":"10.1021/acs.jpclett.5c02278","DOIUrl":"10.1021/acs.jpclett.5c02278","url":null,"abstract":"<p >Photocatalysis holds significant promise for the reduction of CO<sub>2</sub> to valued chemicals under mild conditions. However, its potential is severely limited by weak CO<sub>2</sub> adsorption and slow proton-coupled electron transfer (PCET) rates. In this work, ZnIn<sub>2</sub>S<sub>4</sub>-based catalysts with varying hydroxyl contents were synthesized via the solvothermal method. The hydroxyl group, acting as a basic site, improves CO<sub>2</sub> adsorption and inhibits the hydrogen evolution reaction (HER). Additionally, the hydroxyl group serves as a proton acceptor, facilitating proton transfer; the internal electric field formed by the redistribution of hydroxyl-induced charges promotes the separation of photogenerated carriers, jointly accelerating the PCET process. The hydroxyl-rich ZnIn<sub>2</sub>S<sub>4</sub> catalyst exhibits superior CO<sub>2</sub> reduction performance, with a CO generation rate of 4.55 mmol g<sup>–1</sup> h<sup>–1</sup>, 20 times that of ZnIn<sub>2</sub>S<sub>4</sub> with a lower hydroxyl content. Furthermore, the CO:H<sub>2</sub> ratio is increased by 18. This study highlights the critical roles of PCET and effective CO<sub>2</sub> adsorption in the CO<sub>2</sub> reduction reactions.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 37","pages":"9760–9767"},"PeriodicalIF":4.6,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145025723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Designing Ce–O–Ti Interface Bridge in CeOx/N–Ti3C2Ty Heterojunction for Electrochemical Hydrogen Evolution Reaction","authors":"Hau Quoc Pham, Quyen Huynh and Tai Thien Huynh*, ","doi":"10.1021/acs.jpclett.5c02063","DOIUrl":"10.1021/acs.jpclett.5c02063","url":null,"abstract":"<p >We herein construct the Ce–O–Ti interface bridge in the CeO<sub><i>x</i></sub>/N–Ti<sub>3</sub>C<sub>2</sub>T<sub><i>y</i></sub> heterojunction through an ultrasonic-assisted hydrothermal route as an efficient Pt-free hydrogen evolution electrocatalyst. The synergistic contribution of the heterogeneous Ce–O–Ti bridge and oxygen vacancies boosts the water dissociation and thus drastically reduces energy barriers of the hydrogen evolution reaction (HER). The optimal CeO<sub><i>x</i></sub>/N–Ti<sub>3</sub>C<sub>2</sub>T<sub><i>y</i></sub> material requires only a small overpotential (51.12 mV<sub>RHE</sub> at 10 mA cm<sup>–2</sup>) and has a low Tafel slope (51.87 mV dec<sup>–1</sup>) and long-term stability with negligible changes in structural and morphological properties after at least 50 h of testing.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 37","pages":"9849–9855"},"PeriodicalIF":4.6,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145026202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai-Ping Wang, Hui Liang, Xi-Meng Tang, Bo Wen, Chuan-Jia Tong* and Oleg V. Prezhdo,
{"title":"Interstitial Iodine Induced Deep-Trap-Pinning Suppresses Self-Healing at the TiO2/Perovskite Interface","authors":"Kai-Ping Wang, Hui Liang, Xi-Meng Tang, Bo Wen, Chuan-Jia Tong* and Oleg V. Prezhdo, ","doi":"10.1021/acs.jpclett.5c02430","DOIUrl":"10.1021/acs.jpclett.5c02430","url":null,"abstract":"<p >Defects significantly influence charge transport in CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> (MAPbI<sub>3</sub>) perovskite solar cells, particularly at interfaces. Using quantum dynamics simulation, we reveal a distinct interstitial iodine (I<sub>i</sub>) defect behavior at different positions in the TiO<sub>2</sub>/MAPbI<sub>3</sub> system. In the perovskite bulk-like region, I<sub>i</sub> exhibits high mobility and dissociates detrimental iodine trimers, facilitating small-to-large polaron transition and promoting shallow trap formation. In contrast, the interfacial I<sub>i</sub> defect enhances local structural rigidity due to its strong interaction with undercoordinated Ti atoms and MA molecular dipoles, which unexpectedly pins the deep trap state and suppresses its inherent self-healing capability. This leads to polaron localization and accelerates nonradiative recombination by 2 orders of magnitude. The results reveal the mechanism of deep-trap-pinning due to an interstitial I<sub>i</sub> defect at perovskite interfaces, which offers theoretical guidance for minimizing charge losses in highly efficient perovskite solar cells.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 37","pages":"9776–9784"},"PeriodicalIF":4.6,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145025722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jinfang Fan, Yufan Guo, Siyang Guo, Haiyang Jiang, Wei Zhao, Jihong Liu*, Shufang Wang and Shuang Qiao*,
{"title":"Doping and Polar Interface-Induced High-Position Sensing in the PEDOT:PSS/Si Heterojunction and Its Multifunctional Optical Imaging","authors":"Jinfang Fan, Yufan Guo, Siyang Guo, Haiyang Jiang, Wei Zhao, Jihong Liu*, Shufang Wang and Shuang Qiao*, ","doi":"10.1021/acs.jpclett.5c02476","DOIUrl":"10.1021/acs.jpclett.5c02476","url":null,"abstract":"<p >A highly sensitive, self-powered position-sensitive detector (PSD) based on a PEDOT:PSS/Si heterojunction is prepared. Band structure optimization via FS-300 additive doping significantly enhances the built-in electric field, achieving a maximum open-circuit voltage of 0.45 V (0.25 V for the undoped device) and a position sensitivity of 404.6 mV/mm (225.3 mV/mm for the undoped device). Remarkably, polar symmetry at the PEDOT:PSS/Si interface induces a pyroelectric field under pulsed light illumination, which dramatically boosts the position sensitivity to 778.8 mV/mm, representing an enhancement of 192.5%. Leveraging these properties, we designed an imaging system that exploits the distinct lateral photovoltaic responses and pyroelectric enhancements for different laser wavelengths to achieve high-resolution optical imaging. Furthermore, the PSD maintains a robust lateral photovoltaic response across electrode spacings from 0.5 to 9 mm, retaining a position sensitivity of 170 mV/mm even at a 9 mm spacing. This tunable performance across electrode spacings allows for adjustable imaging resolution, highlighting the device’s versatility for advanced optoelectronic applications.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 37","pages":"9815–9823"},"PeriodicalIF":4.6,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145026199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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