Pub Date : 2025-01-21DOI: 10.1021/acs.jpclett.4c03275
Jürgen E. K. Schawe, Min Kyung Kwak, Mihai Stoica, Eun Soo Park, Jörg F. Löffler
The behavior of supercooled glass-forming metals depends on the cooperative atomic fluctuations caused by dynamic heterogeneities in the melt. These spatial and temporal heterogeneities form dynamic clusters, which are regions of cooperative rearrangement (CRR). In this study, the macroscopic kinetics and the correlation length ξ, of the CRR, are derived for Pt57.4Cu14.7Ni5.3P22.6 and Pd43Cu27Ni10P20 metallic glass-formers by fast differential scanning calorimetry near the glass transition. While the alloy composition influences the α-relaxation and vitrification kinetics, typically defined by the glass transition, as well as the limiting temperature of the Vogel–Fulcher–Tammann–Hesse equation and the fragility index, it has no significant influence on the correlation length of the cooperative atomic motions. In agreement with many other materials, ξ is about 3 nm at the glass transition for both metallic glasses. The temperature dependence of ξ correlates with the apparent activation energy of the α-relaxation and is the reason for its non-Arrhenius behavior.
{"title":"The Cooperativity of Atomic Fluctuations in Highly Supercooled Glass-Forming Metallic Melts","authors":"Jürgen E. K. Schawe, Min Kyung Kwak, Mihai Stoica, Eun Soo Park, Jörg F. Löffler","doi":"10.1021/acs.jpclett.4c03275","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03275","url":null,"abstract":"The behavior of supercooled glass-forming metals depends on the cooperative atomic fluctuations caused by dynamic heterogeneities in the melt. These spatial and temporal heterogeneities form dynamic clusters, which are regions of cooperative rearrangement (CRR). In this study, the macroscopic kinetics and the correlation length <i>ξ</i>, of the CRR, are derived for Pt<sub>57.4</sub>Cu<sub>14.7</sub>Ni<sub>5.3</sub>P<sub>22.6</sub> and Pd<sub>43</sub>Cu<sub>27</sub>Ni<sub>10</sub>P<sub>20</sub> metallic glass-formers by fast differential scanning calorimetry near the glass transition. While the alloy composition influences the α-relaxation and vitrification kinetics, typically defined by the glass transition, as well as the limiting temperature of the Vogel–Fulcher–Tammann–Hesse equation and the fragility index, it has no significant influence on the correlation length of the cooperative atomic motions. In agreement with many other materials, <i>ξ</i> is about 3 nm at the glass transition for both metallic glasses. The temperature dependence of <i>ξ</i> correlates with the apparent activation energy of the α-relaxation and is the reason for its non-Arrhenius behavior.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"74 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990805","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}
Pub Date : 2025-01-21DOI: 10.1021/acs.jpclett.4c03570
Abrahan J. Martinez, Ankai Wang, Mariam Khvichia, Jin Z. Zhang, Shengli Zou
The coupling between excitons in semiconductors or molecules and metal nanoparticles has been well-studied, primarily for nanoparticles in their ground electronic state. However, less attention has been given to exciton–nanoparticle interactions when the nanoparticle generates surface plasmons upon incident excitation. In this study, we explore the coupling and energy transfer dynamics between an exciton and the surface plasmon of a metal nanoparticle, forming a “plexciton”. Significant mutual energy exchange between the exciton and the plasmon leads to unexpected effects on the exciton lifetime and coupling strength. The interaction at varying wavelengths, orientations, magnitudes, and phases was studied. Our results show that the exciton decay rate can be quenched entirely when the plasmon’s energy compensates for that of the exciton radiative decay, even at separation distances of several hundred nanometers. These findings highlight the impact of surface plasmons on exciton dynamics, opening new possibilities for enhancing charge carrier dynamics in coupled systems.
{"title":"Coupling and Energy Transfer between an Exciton in a Semiconductor Quantum Dot and a Surface Plasmon in a Metal Nanoparticle","authors":"Abrahan J. Martinez, Ankai Wang, Mariam Khvichia, Jin Z. Zhang, Shengli Zou","doi":"10.1021/acs.jpclett.4c03570","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03570","url":null,"abstract":"The coupling between excitons in semiconductors or molecules and metal nanoparticles has been well-studied, primarily for nanoparticles in their ground electronic state. However, less attention has been given to exciton–nanoparticle interactions when the nanoparticle generates surface plasmons upon incident excitation. In this study, we explore the coupling and energy transfer dynamics between an exciton and the surface plasmon of a metal nanoparticle, forming a “plexciton”. Significant mutual energy exchange between the exciton and the plasmon leads to unexpected effects on the exciton lifetime and coupling strength. The interaction at varying wavelengths, orientations, magnitudes, and phases was studied. Our results show that the exciton decay rate can be quenched entirely when the plasmon’s energy compensates for that of the exciton radiative decay, even at separation distances of several hundred nanometers. These findings highlight the impact of surface plasmons on exciton dynamics, opening new possibilities for enhancing charge carrier dynamics in coupled systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992605","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}
Pub Date : 2025-01-21DOI: 10.1021/acs.jpclett.4c03144
Lina Wang, Zhenhai Wen, Guangfu Luo
Single-atom catalysts have attracted a significant amount of attention due to their exceptional atomic utilization and high efficiency in a range of catalytic reactions. However, these systems often face thermodynamic instability, leading to agglomeration under the operational conditions. In this study, we investigate the interactions of 12 types of catalytic atoms (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au, and Bi) on three crystalline phases (1T, 1T′, and 2H) of six transition metal dichalcogenide layers (MoS2, MoSe2, MoTe2, WS2, WSe2, and WTe2) using first-principles calculations. We ultimately identify 82 stable single-atom systems that thermodynamically prevent the formation of metal clusters on these substrates. Notably, our findings reveal that the metastable 1T and 1T′ phases significantly enhance the binding strength with single atoms and promote their thermodynamic stability. This research offers valuable insights into the design of stable single-atom systems and paves the way for the discovery of innovative catalysts.
{"title":"Stabilizing Single-Atom Catalysts on Metastable Phases of Transition Metal Dichalcogenides","authors":"Lina Wang, Zhenhai Wen, Guangfu Luo","doi":"10.1021/acs.jpclett.4c03144","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03144","url":null,"abstract":"Single-atom catalysts have attracted a significant amount of attention due to their exceptional atomic utilization and high efficiency in a range of catalytic reactions. However, these systems often face thermodynamic instability, leading to agglomeration under the operational conditions. In this study, we investigate the interactions of 12 types of catalytic atoms (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au, and Bi) on three crystalline phases (1T, 1T′, and 2H) of six transition metal dichalcogenide layers (MoS<sub>2</sub>, MoSe<sub>2</sub>, MoTe<sub>2</sub>, WS<sub>2</sub>, WSe<sub>2</sub>, and WTe<sub>2</sub>) using first-principles calculations. We ultimately identify 82 stable single-atom systems that thermodynamically prevent the formation of metal clusters on these substrates. Notably, our findings reveal that the metastable 1T and 1T′ phases significantly enhance the binding strength with single atoms and promote their thermodynamic stability. This research offers valuable insights into the design of stable single-atom systems and paves the way for the discovery of innovative catalysts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"10 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992603","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}
In the CO2 reduction reactions (CO2RR), the product selectivity is strongly dependent on the binding energy differences of the key intermediates. Herein, we systematically evaluated the CO2RR reaction pathways on single transition metal atom doped catalysts TM1Cu/Cu2O by density functional theory (DFT) methods and found that *CO is more likely to undergo C–O bond cleavage rather than be hydrogenated on TM1Cu/Cu2O (TM = Sc, Ti, V, Cr, Mn, Fe, Co), which facilitates C2+ production with a low-energy pathway of OC–C coupling, while it prefers to be hydrogenated to form CHO on TM1Cu/Cu2O (TM = Ni, Cu). The defects of Cu in TM1Cu/Cu2O were confirmed to enhance the production of ethanol. Furthermore, we established a scaling relationship between binding free energies of the key intermediates with the Bader charges of the active sites TM on TM1Cu/Cu2O and defective TM1Cu/Cu2O surfaces. This relationship facilitates a rational and efficient design of Cu/Cu2O-based catalysts.
{"title":"Understanding the CO2 Reduction Selectivity toward Ethanol on Single Atom Doped Cu/Cu2O Catalysts: Insights from Bader Charge as a Descriptor","authors":"Yunchen Qian, Jinshan Liang, Lijuan Xie, Ke Zheng, Weixin Lin, Lizhi Jiang","doi":"10.1021/acs.jpclett.4c03269","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03269","url":null,"abstract":"In the CO<sub>2</sub> reduction reactions (CO<sub>2</sub>RR), the product selectivity is strongly dependent on the binding energy differences of the key intermediates. Herein, we systematically evaluated the CO<sub>2</sub>RR reaction pathways on single transition metal atom doped catalysts TM<sub>1</sub>Cu/Cu<sub>2</sub>O by density functional theory (DFT) methods and found that *CO is more likely to undergo C–O bond cleavage rather than be hydrogenated on TM<sub>1</sub>Cu/Cu<sub>2</sub>O (TM = Sc, Ti, V, Cr, Mn, Fe, Co), which facilitates C<sub>2+</sub> production with a low-energy pathway of OC–C coupling, while it prefers to be hydrogenated to form CHO on TM<sub>1</sub>Cu/Cu<sub>2</sub>O (TM = Ni, Cu). The defects of Cu in TM<sub>1</sub>Cu/Cu<sub>2</sub>O were confirmed to enhance the production of ethanol. Furthermore, we established a scaling relationship between binding free energies of the key intermediates with the Bader charges of the active sites TM on TM<sub>1</sub>Cu/Cu<sub>2</sub>O and defective TM<sub>1</sub>Cu/Cu<sub>2</sub>O surfaces. This relationship facilitates a rational and efficient design of Cu/Cu<sub>2</sub>O-based catalysts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"12 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992604","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}
Pub Date : 2025-01-21DOI: 10.1021/acs.jpclett.4c02940
Joseph P. Heindel, Lukas Kim, Martin Head-Gordon, Teresa Head-Gordon
This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion–water and ion–ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range. This motivates an environment-dependent atomic polarizability parameter that depends on the strength of the local electric field experienced by the ions to account for strong damping, with anisotropy introduced by atomic multipoles. The resulting CMM model for ions provides accurate dimer surfaces and three-body polarization and charge transfer compared to EDA, and shows excellent performance on various ion benchmarks including vibrational frequencies and cluster geometries.
{"title":"Completely Multipolar Model for Many-Body Water–Ion and Ion–Ion Interactions","authors":"Joseph P. Heindel, Lukas Kim, Martin Head-Gordon, Teresa Head-Gordon","doi":"10.1021/acs.jpclett.4c02940","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02940","url":null,"abstract":"This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion–water and ion–ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range. This motivates an environment-dependent atomic polarizability parameter that depends on the strength of the local electric field experienced by the ions to account for strong damping, with anisotropy introduced by atomic multipoles. The resulting CMM model for ions provides accurate dimer surfaces and three-body polarization and charge transfer compared to EDA, and shows excellent performance on various ion benchmarks including vibrational frequencies and cluster geometries.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"3 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992622","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}
Pub Date : 2025-01-20DOI: 10.1021/acs.jpclett.4c03285
Ke Ye, Yulan Han, Min Hu, P. Hu, Mårten S. G. Ahlquist, Guozhen Zhang
Heterogenous single-atom catalysts (SACs) are reminiscent of homogeneous catalysts because of the similarity of structural motif of active sites, showing the potential of using the advantage of homogeneous catalysts to tackle challenges in hetereogenous catalysis. In heterogeneous oxygen electrocatalysis, the homogeneity of adsorption patterns of reaction intermediates leads to scaling relationships that limit their activities. In contrast, homogeneous catalysts can circumvent such limits by selectively altering the adsorption of intermediates through secondary coordination effects (SCEs). This inspired us to explore potential SCEs in metal–nitrogen-carbon (M–N-C), a promising type of oxygen evolution electrocatalyst. We introduced SCEs with a neighboring metal site that can modulate the adsorption strengths of oxygen-containing intermediates. First-principles calculations show that the second site in the heteronuclear duo four-nitrogen-coordinated metal center can induce SCEs that selectively stabilize the OOH intermediate but with minor effects on the OH intermediate and, thereby, disrupt the scaling relation between oxygen species and eventually increase the catalytic activity in oxygen evolution reactions. Additionally, the activity of oxygen reduction reaction of selected M–N-C is also enhanced by such SCE. Our computational work underscored the critical role SCEs can have in shaping activities of SACs, particularly in favorably altering scaling relationships, and demonstrated its potential to address catalytic challenges in heterogeneous catalysis.
{"title":"Secondary Coordination Effects of Adjacent Metal Center in Metal–Nitrogen-Carbon Improve Scaling Relation of Oxygen Electrocatalysis","authors":"Ke Ye, Yulan Han, Min Hu, P. Hu, Mårten S. G. Ahlquist, Guozhen Zhang","doi":"10.1021/acs.jpclett.4c03285","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03285","url":null,"abstract":"Heterogenous single-atom catalysts (SACs) are reminiscent of homogeneous catalysts because of the similarity of structural motif of active sites, showing the potential of using the advantage of homogeneous catalysts to tackle challenges in hetereogenous catalysis. In heterogeneous oxygen electrocatalysis, the homogeneity of adsorption patterns of reaction intermediates leads to scaling relationships that limit their activities. In contrast, homogeneous catalysts can circumvent such limits by selectively altering the adsorption of intermediates through secondary coordination effects (SCEs). This inspired us to explore potential SCEs in metal–nitrogen-carbon (M–N-C), a promising type of oxygen evolution electrocatalyst. We introduced SCEs with a neighboring metal site that can modulate the adsorption strengths of oxygen-containing intermediates. First-principles calculations show that the second site in the heteronuclear duo four-nitrogen-coordinated metal center can induce SCEs that selectively stabilize the OOH intermediate but with minor effects on the OH intermediate and, thereby, disrupt the scaling relation between oxygen species and eventually increase the catalytic activity in oxygen evolution reactions. Additionally, the activity of oxygen reduction reaction of selected M–N-C is also enhanced by such SCE. Our computational work underscored the critical role SCEs can have in shaping activities of SACs, particularly in favorably altering scaling relationships, and demonstrated its potential to address catalytic challenges in heterogeneous catalysis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"5 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990047","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}
Pub Date : 2025-01-20DOI: 10.1021/acs.jpclett.4c03116
Ramesh Jarupula, Haiwang Yong
Chirality is crucial due to its role in biological and chemical systems, where molecular handedness impacts structure and function. Chiral molecules with nonsuperimposable mirror images exhibit distinct biological activities pivotal in drug design and catalysis. This theoretical study explores X-ray circular dichroism (XCD) as a tool for probing the local structures of chiral molecules. We calculated the XCD signals at the chlorine, oxygen, and nitrogen K edges in various molecular systems. Our results show that electron delocalization plays an important role in the sensitivity of XCD to X-ray chromophore–chiral center distance. Furthermore, the XCD signals at multiple X-ray chromophores could offer multidimensional insights to pinpoint chiral center, providing spatial information about the local structures of complex chiral molecules.
手性在生物和化学系统中的作用至关重要，因为分子的手性会影响结构和功能。手性分子具有不可叠加的镜像，表现出独特的生物活性，在药物设计和催化方面举足轻重。本理论研究探讨了 X 射线圆二色性（XCD）作为探测手性分子局部结构的工具。我们计算了各种分子体系中氯、氧和氮 K 边的 XCD 信号。我们的结果表明，电子析出在 XCD 对 X 射线发色团-手性中心距离的敏感性中起着重要作用。此外，多个 X 射线发色团上的 XCD 信号可为精确定位手性中心提供多维视角，从而提供有关复杂手性分子局部结构的空间信息。
{"title":"Revealing Local Structures of Chiral Molecules via X-ray Circular Dichroism","authors":"Ramesh Jarupula, Haiwang Yong","doi":"10.1021/acs.jpclett.4c03116","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03116","url":null,"abstract":"Chirality is crucial due to its role in biological and chemical systems, where molecular handedness impacts structure and function. Chiral molecules with nonsuperimposable mirror images exhibit distinct biological activities pivotal in drug design and catalysis. This theoretical study explores X-ray circular dichroism (XCD) as a tool for probing the local structures of chiral molecules. We calculated the XCD signals at the chlorine, oxygen, and nitrogen K edges in various molecular systems. Our results show that electron delocalization plays an important role in the sensitivity of XCD to X-ray chromophore–chiral center distance. Furthermore, the XCD signals at multiple X-ray chromophores could offer multidimensional insights to pinpoint chiral center, providing spatial information about the local structures of complex chiral molecules.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"205 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990045","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}
Intentional doping plays a pivotal role in customizing metal halides’ electronic and optical features. This work manipulates the incorporation and distribution of Mn2+ in Cu(I) halide by controlling the elemental steps involved in the growth-doping kinetics as well as investigates the localized lattice and electronic structures in different doping configurations. Complementary experimental and theoretical results demonstrate that a uniform and relatively high Mn2+ doping level can be achieved by a step-tailored strategy that encompasses reducing the growth rate of the halide matrix, enhancing the surface adsorption of Mn2+, and facilitating the incorporation of the dopants. The optimized doping configuration mitigates severe lattice distortion and decreases the non-radiative transition rate, resulting in explicit dual-band emission and an enhanced photoluminescence quantum yield. This work underscores an effective synthesis strategy to harness the full potential of Mn2+-doped metal halides beyond Cu(I)-based ones and also showcases a new working paradigm of separately controlling the doping procedures for obtaining metal halides with customized optical/optoelectronic properties.
{"title":"Unveiling Doping Kinetics in Cu(I) Metal Halides for Customized Luminescent Performance","authors":"Ning Wan, Jiahong Chen, Xinxin Yan, Zhenxiong Yang, Qingyu Hu, Qi Pang, Zhao-Qing Liu, Yibo Chen","doi":"10.1021/acs.jpclett.4c03255","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03255","url":null,"abstract":"Intentional doping plays a pivotal role in customizing metal halides’ electronic and optical features. This work manipulates the incorporation and distribution of Mn<sup>2+</sup> in Cu(I) halide by controlling the elemental steps involved in the growth-doping kinetics as well as investigates the localized lattice and electronic structures in different doping configurations. Complementary experimental and theoretical results demonstrate that a uniform and relatively high Mn<sup>2+</sup> doping level can be achieved by a step-tailored strategy that encompasses reducing the growth rate of the halide matrix, enhancing the surface adsorption of Mn<sup>2+</sup>, and facilitating the incorporation of the dopants. The optimized doping configuration mitigates severe lattice distortion and decreases the non-radiative transition rate, resulting in explicit dual-band emission and an enhanced photoluminescence quantum yield. This work underscores an effective synthesis strategy to harness the full potential of Mn<sup>2+</sup>-doped metal halides beyond Cu(I)-based ones and also showcases a new working paradigm of separately controlling the doping procedures for obtaining metal halides with customized optical/optoelectronic properties.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"32 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990807","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}
Pub Date : 2025-01-20DOI: 10.1021/acs.jpclett.4c03415
Yuqi Wu, Xiao Han, Jinlu He
Understanding the mechanism of the nitrogen reduction reaction (NRR) is essential for designing highly efficient catalysts. In this study, we investigated the effects of the metal–support interaction (MSI) on NRR using density functional theory. The simulations revealed that the MSI is weak in the Au13/BiOCl system, with charge accumulation and depletion primarily occurring within the Au13 cluster. By replacement of one Au atom with either a Ag or Pt atom, the MSI becomes stronger compared to that in the Au13/BiOCl system. The is because doping breaks the symmetry of the Au13 cluster, leading to charge accumulation and depletion at the interface. Specifically, this enhanced MSI reduces the energy barriers of the rate-determining step from 1.07 eV in the Au13/BiOCl system to 0.91 eV in Au12Ag/BiOCl and 0.87 eV in Au12Pt/BiOCl, respectively. Our study uncovers the critical role of MSI in the activity of NRR, providing theoretical insights for the development of highly efficient NRR catalysts.
{"title":"Unraveling the Effects of Metal–Support Interaction on Nitrogen Reduction: A Theoretical Study in Au13/BiOCl","authors":"Yuqi Wu, Xiao Han, Jinlu He","doi":"10.1021/acs.jpclett.4c03415","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03415","url":null,"abstract":"Understanding the mechanism of the nitrogen reduction reaction (NRR) is essential for designing highly efficient catalysts. In this study, we investigated the effects of the metal–support interaction (MSI) on NRR using density functional theory. The simulations revealed that the MSI is weak in the Au<sub>13</sub>/BiOCl system, with charge accumulation and depletion primarily occurring within the Au<sub>13</sub> cluster. By replacement of one Au atom with either a Ag or Pt atom, the MSI becomes stronger compared to that in the Au<sub>13</sub>/BiOCl system. The is because doping breaks the symmetry of the Au<sub>13</sub> cluster, leading to charge accumulation and depletion at the interface. Specifically, this enhanced MSI reduces the energy barriers of the rate-determining step from 1.07 eV in the Au<sub>13</sub>/BiOCl system to 0.91 eV in Au<sub>12</sub>Ag/BiOCl and 0.87 eV in Au<sub>12</sub>Pt/BiOCl, respectively. Our study uncovers the critical role of MSI in the activity of NRR, providing theoretical insights for the development of highly efficient NRR catalysts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"37 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990808","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}
Pub Date : 2025-01-20DOI: 10.1021/acs.jpclett.4c03585
Jiaxing Lv, Ying Jiang, Guozhong Lu, Xiaobing Lou, Bingwen Hu
In traditional operations of all-solid-state lithium metal batteries (ASSLMBs), a small thin lithium metal circular disk is employed as a lithium metal anode (LMA). However, ASSLMBs with a circular-disk LMA often fail in <150 cycles with low capacity retention. In this work, we developed a new ring-shaped LMA to improve cyclability. Full cells consisting of a ring-shaped LMA, a LiCoO2 cathode, and a Li6PS5Cl electrolyte maintain good capacity retention of 83.65% at 0.3C after 300 cycles. Moreover, in situ L-band electron paramagnetic resonance imaging (EPRI) showed that fewer Li dendrites are formed on a ring-shaped LMA. This work highlights the importance of the design of the shape of the LMA to mitigate the growth of lithium dendrites and shows that L-band EPRI is a useful technique for ASSLMBs.
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