The Journal of Physical Chemistry Letters最新文献_第4页

Micrometer-Resolution Fluorescence and Lifetime Mappings of CsPbBr3 Nanocrystal Films Coupled with a TiO2 Grating 与 TiO2 光栅耦合的 CsPbBr3 纳米晶体薄膜的微米分辨率荧光和寿命图谱

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0254610.1021/acs.jpclett.4c02546

Viet Anh Nguyen, Ye Wu, Thi Thu Ha Do, Linh Thi Dieu Nguyen, Aleksandr A. Sergeev, Ding Zhu, Vytautas Valuckas, Duong Pham, Hai Xuan Son Bui, Duy Mai Hoang, Bui Son Tung, Bui Xuan Khuyen, Thanh Binh Nguyen, Hai Son Nguyen, Vu Dinh Lam, Andrey L. Rogach, Son Tung Ha and Quynh Le-Van*,

{"title":"Micrometer-Resolution Fluorescence and Lifetime Mappings of CsPbBr3 Nanocrystal Films Coupled with a TiO2 Grating","authors":"Viet Anh Nguyen, Ye Wu, Thi Thu Ha Do, Linh Thi Dieu Nguyen, Aleksandr A. Sergeev, Ding Zhu, Vytautas Valuckas, Duong Pham, Hai Xuan Son Bui, Duy Mai Hoang, Bui Son Tung, Bui Xuan Khuyen, Thanh Binh Nguyen, Hai Son Nguyen, Vu Dinh Lam, Andrey L. Rogach, Son Tung Ha and Quynh Le-Van*, ","doi":"10.1021/acs.jpclett.4c0254610.1021/acs.jpclett.4c02546","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02546https://doi.org/10.1021/acs.jpclett.4c02546","url":null,"abstract":"Enhancing light emission from perovskite nanocrystal (NC) films is essential in light-emitting devices, as their conventional stacks often restrict the escape of emitted light. This work addresses this challenge by employing a TiO2 grating to enhance light extraction and shape the emission of CsPbBr3 nanocrystal films. Angle-resolved photoluminescence (PL) demonstrated a 10-fold increase in emission intensity by coupling the Bloch resonances of the grating with the spontaneous emission of the perovskite NCs. Fluorescence lifetime imaging microscopy (FLIM) provided micrometer-resolution mapping of both PL intensity and lifetime across a large area, revealing a decrease in PL lifetime from 8.2 ns for NC films on glass to 6.1 ns on the TiO2 grating. Back focal plane (BFP) spectroscopy confirmed how the Bloch resonances transformed the unpolarized, spatially incoherent emission of NCs into polarized and directed light. These findings provide further insights into the interactions between dielectric nanostructures and perovskite NC films, offering possible pathways for designing better performing perovskite optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11291–11299 11291–11299"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640882","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}

引用次数: 0

Modulation of the Chirality and Dynamics of Self-Assembled Nanocellulose-Chiral C-Dot Film for Chiral Sensing Applications 用于手性传感应用的自组装纳米纤维素-手性 C 点薄膜的手性和动力学调制

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0256410.1021/acs.jpclett.4c02564

Sapna Waghmare, Umarfaruk S. Sayyad, Arunavo Chatterjee and Somen Mondal*,

{"title":"Modulation of the Chirality and Dynamics of Self-Assembled Nanocellulose-Chiral C-Dot Film for Chiral Sensing Applications","authors":"Sapna Waghmare, Umarfaruk S. Sayyad, Arunavo Chatterjee and Somen Mondal*, ","doi":"10.1021/acs.jpclett.4c0256410.1021/acs.jpclett.4c02564","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02564https://doi.org/10.1021/acs.jpclett.4c02564","url":null,"abstract":"The detection and sensing of chirality using chiral biomaterials are growing areas of research in advanced bioelectronics. As a result, chiral-controlled biomaterials are crucial for advancing current technologies in chiral sensing applications within biosystems. A chiral carbon dot (C-dot) modulated self-assembled emissive cellulose nanocrystal (CNC) film is developed where the chirality of the CNC film can be tempered between left-handed and right-handed chirality after being doped with chiral L/D-C-dots in CNCs (C-dot-CNC film), transferring the chirality from C-dots to CNCs. The interaction between C-dots, CNCs, and carrier dynamics is investigated using a variety of steady-state and time-resolved PL spectroscopy techniques. The chiral C-dot enhanced the protonic conductivity across the CNC via the formation of hydrogen bonds with its surface functional groups and water molecules. Further, the chiral CNC-C-dots photoelectrodes demonstrate an excellent ability to distinguish between left-handed and right-handed small molecules. These findings on the underlying mechanism of spin selectivity between chiral CNC-C-dot and chiral ligand hold promise for the development of efficient chiral-sensing electronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11275–11281 11275–11281"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640978","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}

引用次数: 0

Wave Function Localization Reduces the Bandgap of Disordered Double Perovskite Cs2AgBiBr6 波函数局部化降低了无序双包晶石 Cs2AgBiBr6 的带隙

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0294610.1021/acs.jpclett.4c02946

Dongyu Liu, Bayan Amer Abzakh, Elena A. Kazakova, Dmitrii A. Abrameshin, Pavel A. Troshin, Run Long and Andrey S. Vasenko*,

{"title":"Wave Function Localization Reduces the Bandgap of Disordered Double Perovskite Cs2AgBiBr6","authors":"Dongyu Liu, Bayan Amer Abzakh, Elena A. Kazakova, Dmitrii A. Abrameshin, Pavel A. Troshin, Run Long and Andrey S. Vasenko*, ","doi":"10.1021/acs.jpclett.4c0294610.1021/acs.jpclett.4c02946","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02946https://doi.org/10.1021/acs.jpclett.4c02946","url":null,"abstract":"Double perovskite Cs2AgBiBr6 is a promising alternative to lead-based perovskites with excellent stability and attractive optoelectronic properties. However, a relatively large bandgap severely limits its performance in many applications such as solar cells and photodetectors. It has been reported that a random distribution of Ag and Bi atoms in Cs2AgBiBr6 effectively reduces its bandgap without introducing dopants or impurities, while the mechanism remains unclear. Here, using density functional theory calculations, we demonstrate that the Ag–Bi disorder in Cs2AgBiBr6 generates localized electronic states as band edges to regulate the bandgap. The disordered structures segregate Ag and Bi atoms in the lattice, and the formed homoatomic clusters lead to wave function localization. Moreover, the bandgap decrease exhibits a non-monotonic dependence on the degree of disorder. Our results are comparable with experimental observations and provide crucial insights into understanding the order–disorder transition in double perovskites.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11268–11274 11268–11274"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640981","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}

引用次数: 0

Transferable and Interpretable Prediction of Site-Specific Dehydrogenation Reaction Rate Constants with NMR Spectra 利用核磁共振波谱预测特定位点脱氢反应速率常数的可转移性和可解释性

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0264710.1021/acs.jpclett.4c02647

Yanbo Li*, Fenfen Ma, Zhandong Wang and Xin Chen*,

{"title":"Transferable and Interpretable Prediction of Site-Specific Dehydrogenation Reaction Rate Constants with NMR Spectra","authors":"Yanbo Li*, Fenfen Ma, Zhandong Wang and Xin Chen*, ","doi":"10.1021/acs.jpclett.4c0264710.1021/acs.jpclett.4c02647","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02647https://doi.org/10.1021/acs.jpclett.4c02647","url":null,"abstract":"Accurate and efficient determination of site-specific reaction rate constants over a wide temperature range remains challenging, both experimentally and theoretically. Taking the dehydrogenation reaction as an example, our study addresses this issue by an innovative combination of machine learning techniques and cost-effective NMR spectra. Through descriptor screening, we identified a minimal set of NMR chemical shifts that can effectively determine reaction rate constants. The constructed model performs exceptionally well on theoretical data sets and demonstrates impressive generalization capabilities, extending from small molecules to larger ones. Furthermore, this model shows outstanding performance when applied to limited experimental data sets, highlighting its robust applicability and transferability. Utilizing the Sure Independence Screening and Sparsifying Operator (SISSO) algorithm, we also present an interpretable rate constant-temperature-NMR (k-T-NMR) relationship with a mathematical formula. This study reveals the great potential of combining machine learning with easily accessible spectroscopic descriptors in the study of reaction kinetics, enabling the rapid determination of reaction rate constants and promoting our understanding of reactivity.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11282–11290 11282–11290"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640828","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}

引用次数: 0

Selective Methods Promote Protein Solid-State NMR 促进蛋白质固态 NMR 的选择性方法

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0284110.1021/acs.jpclett.4c02841

Bin Han, Jun Yang* and Zhengfeng Zhang*,

引用次数: 0

Slope of the Delocalization Function Is Proportional to Analytical Hardness 脱焦函数的斜率与分析硬度成正比

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0226310.1021/acs.jpclett.4c02263

Bin Wang, Paul Geerlings, Farnaz Heidar-Zadeh, Paul W. Ayers and Frank De Proft*,

{"title":"Slope of the Delocalization Function Is Proportional to Analytical Hardness","authors":"Bin Wang, Paul Geerlings, Farnaz Heidar-Zadeh, Paul W. Ayers and Frank De Proft*, ","doi":"10.1021/acs.jpclett.4c0226310.1021/acs.jpclett.4c02263","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02263https://doi.org/10.1021/acs.jpclett.4c02263","url":null,"abstract":"Conceptual Density Functional Theory (CDFT) has been extended beyond its traditional role in elucidating chemical reactivity to the development of density functional theory methods, e.g., the investigation of the delocalization error. This delocalization error causes the dependence of the energy on the number of electrons (N) to deviate from its exact piecewise linear behavior, an error which is the basis of many well-known limitations of commonly used density-functional approximations (DFAs). Following our previous work on the analytical hardness η± for pure functionals, we extend its application to hybrid and range-separated functionals. A comparison is made between the analytical hardness and the slope of the delocalization function introduced by Hait and Head-Gordon. Our results show that there is a linear relationship between its slope and the analytical hardness. An approximate scheme is presented to construct the energy vs N curve without fractional occupation number calculations. The extension to densities is discussed.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11259–11267 11259–11267"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640984","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}

引用次数: 0

Inelastic Triatom-Atom Quantum Close-Coupling Dynamics in Full Dimensionality: All Rovibrational Mode Quenching of Water Due to the H Impact on a Six-Dimensional Potential Energy Surface 全维度非弹性三原子-原子量子紧密耦合动力学：六维势能面上的 H 影响导致的水的全振动模式淬火

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-04 DOI: 10.1021/acs.jpclett.4c0286510.1021/acs.jpclett.4c02865

Benhui Yang*, Chen Qu, J. M. Bowman, Dongzheng Yang, Hua Guo, N. Balakrishnan, R. C. Forrey and P. C. Stancil*,

{"title":"Inelastic Triatom-Atom Quantum Close-Coupling Dynamics in Full Dimensionality: All Rovibrational Mode Quenching of Water Due to the H Impact on a Six-Dimensional Potential Energy Surface","authors":"Benhui Yang*, Chen Qu, J. M. Bowman, Dongzheng Yang, Hua Guo, N. Balakrishnan, R. C. Forrey and P. C. Stancil*, ","doi":"10.1021/acs.jpclett.4c0286510.1021/acs.jpclett.4c02865","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02865https://doi.org/10.1021/acs.jpclett.4c02865","url":null,"abstract":"The rovibrational level populations, and subsequent emission in various astrophysical environments, are driven by inelastic collision processes. The available rovibrational rate coefficients for water have been calculated using a number of approximations. We present a numerically exact calculation for the rovibrational quenching for all water vibrational modes due to collisions with atomic hydrogen. The scattering theory implements a quantum close-coupling (CC) method on a high level ab initio six-dimensional (6D) potential energy surface (PES). Total rovibrational quenching cross sections for excited bending levels were compared with earlier results on a 4D PES with the rigid-bender close-coupling (RBCC) approximation. General agreement between 6D-CC and 4D-RBCC calculations are found, but differences are evident including the energy and amplitude of low-energy orbiting resonances. Quenching cross sections from the symmetric and asymmetric stretch modes are provided for the first time. The current 6D-CC calculation provides accurate inelastic data needed for astrophysical modeling.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11312–11319 11312–11319"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c02865","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Assessing the Influence of Illumination on Ion Conductivity in Perovskite Solar Cells 评估照明对 Perovskite 太阳能电池离子传导性的影响

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-03 DOI: 10.1021/acs.jpclett.4c0240310.1021/acs.jpclett.4c02403

Andreas Schiller*, Sandra Jenatsch, Balthasar Blülle, Miguel Angel Torre Cachafeiro, Firouzeh Ebadi, Nasim Kabir, Mostafa Othman, Christian Michael Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Wolfgang Tress and Beat Ruhstaller,

{"title":"Assessing the Influence of Illumination on Ion Conductivity in Perovskite Solar Cells","authors":"Andreas Schiller*, Sandra Jenatsch, Balthasar Blülle, Miguel Angel Torre Cachafeiro, Firouzeh Ebadi, Nasim Kabir, Mostafa Othman, Christian Michael Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Wolfgang Tress and Beat Ruhstaller, ","doi":"10.1021/acs.jpclett.4c0240310.1021/acs.jpclett.4c02403","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02403https://doi.org/10.1021/acs.jpclett.4c02403","url":null,"abstract":"Whether illumination influences the ion conductivity in lead-halide perovskite solar cells containing iodide halides has been an ongoing debate. Experiments to elucidate the presence of a photoconductive effect require special devices or measurement techniques and neglect possible influences of the enhanced electronic charge concentrations. Here, we assess the electronic-ionic charge transport using drift-diffusion simulations and show that the well-known increase in capacitance at low frequencies under illumination is caused by electronic currents that are amplified due to the screening of the alternating electric field by the ions. We propose a novel characterization technique to detect a potential photoinduced increase in ionic conductivity based on capacitance measurements on fully integrated devices. The method is applied to a range of perovskite solar cells with different active layer materials. Remarkably, all measured samples show a clear signature of photoenhanced ion conductivity, posing fundamental questions on the underlying nature of the photosensitive mechanism.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11252–11258 11252–11258"},"PeriodicalIF":4.8,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c02403","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Generation of Surface Ga-H Hydride and Reactivity toward CO2 表面氢化镓的生成和对二氧化碳的反应活性

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-01 DOI: 10.1021/acs.jpclett.4c0285410.1021/acs.jpclett.4c02854

Zhendong Feng, Qingnan Wang, Pengfei Zhang, Guanna Li, Jijie Wang, Zhaochi Feng* and Can Li*,

{"title":"Generation of Surface Ga-H Hydride and Reactivity toward CO2","authors":"Zhendong Feng, Qingnan Wang, Pengfei Zhang, Guanna Li, Jijie Wang, Zhaochi Feng* and Can Li*, ","doi":"10.1021/acs.jpclett.4c0285410.1021/acs.jpclett.4c02854","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02854https://doi.org/10.1021/acs.jpclett.4c02854","url":null,"abstract":"Hydrogen adsorption on gallium oxide was investigated by in situ infrared (IR) spectroscopy over a temperature range of 30–450 °C. Both hydroxyl groups and Ga-H hydrides with a pair of characteristic bands at 3685 (3532) cm–1 and 2011 (1988) cm–1 were detected on the surface gallium oxide. The formation and stability of surface Ga-H hydrides were found to be highly dependent on the temperature of H2 dissociation. Through a combination of density functional theory (DFT) calculations and isotopic experiments, a mechanism involving both heterolytic and homolytic pathways for hydrogen dissociation was proposed for the generation of Ga-H hydrides. Furthermore, the reactivity of surface Ga-H hydrides was explored by their interactions with various probe molecules such as carbon dioxide, oxygen, and nitrogen. A potential reaction mechanism involving the attraction between nucleophilic hydrogen and positively charged intermediates was suggested during those hydrogenations.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11194–11199 11194–11199"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640818","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}

引用次数: 0

Overlooked Role of Electrostatic Interactions in HER Kinetics on MXenes: Beyond the Conventional Descriptor ΔG ∼ 0 to Identify the Real Active Site 静电相互作用在二甲苯 HER 动力学中被忽视的作用：超越传统描述符 ΔG ∼ 0，识别真正的活性位点

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-01 DOI: 10.1021/acs.jpclett.4c0258810.1021/acs.jpclett.4c02588

Xiang Huang, Xiangting Hu, Jiong Wang and Hu Xu*,

{"title":"Overlooked Role of Electrostatic Interactions in HER Kinetics on MXenes: Beyond the Conventional Descriptor ΔG ∼ 0 to Identify the Real Active Site","authors":"Xiang Huang, Xiangting Hu, Jiong Wang and Hu Xu*, ","doi":"10.1021/acs.jpclett.4c0258810.1021/acs.jpclett.4c02588","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02588https://doi.org/10.1021/acs.jpclett.4c02588","url":null,"abstract":"Understanding the atomic-level mechanism of the hydrogen evolution reaction (HER) on MXene materials is crucial for developing affordable HER catalysts, while their complex surface terminations present a substantial challenge. Herein, employing constant-potential grand canonical density functional theory calculations, we elucidate the reaction kinetics of the HER on MXenes with various surface terminations by taking experimentally reported Mo2C as a prototype. We observe a contradictory scenario on Mo2C MXene when using conventional thermodynamic descriptor ΔGH* (hydrogen binding energy). Both competing surface phases that emerge close to the equilibrium potential meet the ΔGH* ∼ 0 criterion, while they exhibit distinctly different reaction kinetics. Contrary to previous studies that identified surface *O species as active sites, our research reveals that these *O sites are kinetically inert for producing H2 but are easily reduced to H2O. Consequently, the surface Mo atoms, exposed from the rapid reduction of the surface *O species, serve as the actual active sites catalyzing the HER via the Volmer–Heyrovsky mechanism, as confirmed by experimental studies. Our findings highlight the overlooked role of electrostatic repulsion in HER kinetics, a factor not captured by thermodynamic descriptor ΔGH*. This work provides new insights into the HER mechanism and emphasizes the importance of kinetic investigations for a comprehensive understanding of the HER.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11200–11208 11200–11208"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640873","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}

引用次数: 0