The unclear p-type conduction mechanism and lack of reliable p-type Ga2O3 severely hinder Ga2O3-based high-voltage electronics. Here, we demonstrate in situ nitrogen (N) doping via metal–organic chemical vapor deposition homoepitaxy using N2O as oxygen source and acceptor dopant. Structural and compositional analyses confirm efficient N incorporation (favored by N–Ga bonding) compensating residual Si/H donors without compromising crystallinity. The Ga2O3:N epilayers achieve excellent p-type performance: 1.04 × 1018 cm–3 hole concentration, 0.47 cm2 V–1 s–1 mobility at room temperature, and 0.168 eV activation energy. A completely new insight into the p-type conduction mechanism in Ga2O3 is introduced, focusing on the crystallographic visualization of acceptors (N2–) and holes (O–), as well as the hole excitation process. It is suggested that careful suppression of the donor compensation effect and precise control of the N chemical potential, which leads to the fabrication of trace O– species solid-dissolved within Ga2O3, are essential for achieving high-hole-concentration p-type conduction in oxides.
{"title":"Insight into the High Hole Concentration of p-Type Ga2O3 via In Situ Nitrogen Doping","authors":"Yaoping Lu, Lemin Jia, Duanyang Chen, Titao Li, Hongji Qi, Xiaorui Xu, Xiaohang Li, Minmin Zhu, Haizhong Zhang, Xiaoqiang Lu","doi":"10.1021/acs.jpclett.5c00318","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00318","url":null,"abstract":"The unclear p-type conduction mechanism and lack of reliable p-type Ga<sub>2</sub>O<sub>3</sub> severely hinder Ga<sub>2</sub>O<sub>3</sub>-based high-voltage electronics. Here, we demonstrate in situ nitrogen (N) doping via metal–organic chemical vapor deposition homoepitaxy using N<sub>2</sub>O as oxygen source and acceptor dopant. Structural and compositional analyses confirm efficient N incorporation (favored by N–Ga bonding) compensating residual Si/H donors without compromising crystallinity. The Ga<sub>2</sub>O<sub>3</sub>:N epilayers achieve excellent p-type performance: 1.04 × 10<sup>18</sup> cm<sup>–3</sup> hole concentration, 0.47 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup> mobility at room temperature, and 0.168 eV activation energy. A completely new insight into the p-type conduction mechanism in Ga<sub>2</sub>O<sub>3</sub> is introduced, focusing on the crystallographic visualization of acceptors (N<sup>2–</sup>) and holes (O<sup>–</sup>), as well as the hole excitation process. It is suggested that careful suppression of the donor compensation effect and precise control of the N chemical potential, which leads to the fabrication of trace O<sup>–</sup> species solid-dissolved within Ga<sub>2</sub>O<sub>3</sub>, are essential for achieving high-hole-concentration p-type conduction in oxides.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"39 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853376","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 : 2025-04-21DOI: 10.1021/acs.jpclett.5c00828
Jiaxing Lv, Ying Jiang, Guozhong Lu, Xiaobing Lou, Bingwen Hu
The authors wish to note that the following relevant article, which is under review, will be of interest to the reader: Dutoit, C.-E.; Soleti, R.; Doux, J.-M.; Pelé, V.; Boireau, V.; Jordy, C.; Pondaven, S.; Vezin, H. Innovative L-band electron paramagnetic resonance investigation of solid-state pouch cell batteries. Magn. Reson. Discuss., in review, 10.5194/mr-6-113-2025. The authors also wish to note that the following patent is pending under review: Hu, B.; Jiang, Y.; Lu, G.; Geng, F. A battery mold for electron paramagnetic resonance imaging. CN 202310612686.9, May 2023 (In Chinese). This article has not yet been cited by other publications.
{"title":"Addition to “A Ring-Shaped Lithium Metal Anode Enables High-Performance All-Solid-State Batteries Revealed by In Situ L-Band EPR Imaging”","authors":"Jiaxing Lv, Ying Jiang, Guozhong Lu, Xiaobing Lou, Bingwen Hu","doi":"10.1021/acs.jpclett.5c00828","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00828","url":null,"abstract":"The authors wish to note that the following relevant article, which is under review, will be of interest to the reader: <contrib-group person-group-type=\"allauthors\"><span>Dutoit, C.-E.</span>; <span>Soleti, R.</span>; <span>Doux, J.-M.</span>; <span>Pelé, V.</span>; <span>Boireau, V.</span>; <span>Jordy, C.</span>; <span>Pondaven, S.</span>; <span>Vezin, H.</span></contrib-group> Innovative L-band electron paramagnetic resonance investigation of solid-state pouch cell batteries. <cite><i>Magn. Reson. Discuss.</i></cite>, in review, 10.5194/mr-6-113-2025</pub-id>. The authors also wish to note that the following patent is pending under review: <contrib-group person-group-type=\"allauthors\"><span>Hu, B.</span>; <span>Jiang, Y.</span>; <span>Lu, G.</span>; <span>Geng, F.</span></contrib-group> A battery mold for electron paramagnetic resonance imaging. CN 202310612686.9</patent>, May 2023 (In Chinese). This article has not yet been cited by other publications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"56 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853381","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 : 2025-04-20DOI: 10.1021/acs.jpclett.5c00849
Haotian Chen, Huanxin Li, Bedřich Smetana, Vlastimil Novák, Richard G. Compton
The importance of electrode shape, alongside electrode size, as key factors in controlling the reversibility or otherwise of electrochemical responses, is recognized at the microscopic level but is explored here via finite-element simulation on the macroscopic scale. Reduced overpotential is seen for concave surfaces relative to flat or convex surfaces, providing an unexplored avenue for the design and fabrication of electrodes, including composites for diverse applications where enhanced reversibility is desirable, such as in sensors and battery materials where the promotion of electrocatalytic responses is important.
{"title":"Promoting Electrochemical Reversibility: Concave versus Convex Electrodes","authors":"Haotian Chen, Huanxin Li, Bedřich Smetana, Vlastimil Novák, Richard G. Compton","doi":"10.1021/acs.jpclett.5c00849","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00849","url":null,"abstract":"The importance of electrode shape, alongside electrode size, as key factors in controlling the reversibility or otherwise of electrochemical responses, is recognized at the microscopic level but is explored here via finite-element simulation on the macroscopic scale. Reduced overpotential is seen for concave surfaces relative to flat or convex surfaces, providing an unexplored avenue for the design and fabrication of electrodes, including composites for diverse applications where enhanced reversibility is desirable, such as in sensors and battery materials where the promotion of electrocatalytic responses is important.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853753","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 : 2025-04-20DOI: 10.1021/acs.jpclett.5c00259
Ahmad Ostovari Moghaddam, Seyedsaeed Mehrabi-Kalajahi, Mohammad Moaddeli, Amin Abdollahzadeh, Seyed Amir Hossein Vasigh, Segun Ahemba Akaahimbe, Mahya Nangir, Rahele Fereidonnejad, Behrouz Shaabani, Mariappan Anandkumar, Sergey A. Aksenov, Andrey S. Vasenko, Andreu Cabot
Electrocatalytic CO2 reduction reaction (CO2RR) to valuable multicarbon (C2+) fuels and chemicals presents a promising strategy to mitigate atmospheric CO2 accumulation and promote the closure of the carbon cycle. However, significant challenges persist in achieving both high product selectivity and sustained stability in the CO2RR. In this study, the catalytic performance of (Fe,Co,Ni,Cu)3O4 medium entropy oxide (MEO) nanoparticles anchored on reduced graphene oxide (rGO) was evaluated for the CO2RR. The MEO–rGO catalyst exhibited remarkable activity, achieving a cathodic current density of −0.5 A cm–2 at −1.7 V, significantly outperforming bare nickel foam (−0.15 A cm–2). Additionally, the catalyst demonstrated a high total Faradaic efficiency (FE) of 60.3% for C2+ products, comprising 30.6% C5H12O and 29.7% C5H10O. This exceptional selectivity toward long-chain hydrocarbons is attributed to the enhanced C–C coupling on the MEO–rGO surface, facilitated by reduced energy barriers. Density functional theory (DFT) calculations further revealed that the adsorption and reduction of CO2 on the (Fe,Co,Ni,Cu)3O4 MEO surface are energetically favorable processes.
{"title":"Electrocatalytic Reduction of CO2 to Long-Chain Hydrocarbons on (FeCoNiCu)3O4 Medium Entropy Oxide Nanoparticles","authors":"Ahmad Ostovari Moghaddam, Seyedsaeed Mehrabi-Kalajahi, Mohammad Moaddeli, Amin Abdollahzadeh, Seyed Amir Hossein Vasigh, Segun Ahemba Akaahimbe, Mahya Nangir, Rahele Fereidonnejad, Behrouz Shaabani, Mariappan Anandkumar, Sergey A. Aksenov, Andrey S. Vasenko, Andreu Cabot","doi":"10.1021/acs.jpclett.5c00259","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00259","url":null,"abstract":"Electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to valuable multicarbon (C<sub>2+</sub>) fuels and chemicals presents a promising strategy to mitigate atmospheric CO<sub>2</sub> accumulation and promote the closure of the carbon cycle. However, significant challenges persist in achieving both high product selectivity and sustained stability in the CO<sub>2</sub>RR. In this study, the catalytic performance of (Fe,Co,Ni,Cu)<sub>3</sub>O<sub>4</sub> medium entropy oxide (MEO) nanoparticles anchored on reduced graphene oxide (rGO) was evaluated for the CO<sub>2</sub>RR. The MEO–rGO catalyst exhibited remarkable activity, achieving a cathodic current density of −0.5 A cm<sup>–2</sup> at −1.7 V, significantly outperforming bare nickel foam (−0.15 A cm<sup>–2</sup>). Additionally, the catalyst demonstrated a high total Faradaic efficiency (FE) of 60.3% for C<sub>2+</sub> products, comprising 30.6% C<sub>5</sub>H<sub>12</sub>O and 29.7% C<sub>5</sub>H<sub>10</sub>O. This exceptional selectivity toward long-chain hydrocarbons is attributed to the enhanced C–C coupling on the MEO–rGO surface, facilitated by reduced energy barriers. Density functional theory (DFT) calculations further revealed that the adsorption and reduction of CO<sub>2</sub> on the (Fe,Co,Ni,Cu)<sub>3</sub>O<sub>4</sub> MEO surface are energetically favorable processes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"33 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853382","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 : 2025-04-18DOI: 10.1021/acs.jpclett.5c00713
Dongmei Wu, Jianwu Wei, Binbin Luo, Liya Zhou, Peican Chen, Jie Tian, Jiahong Pan, Alexei V Emeline, Jin Zhong Zhang, Qi Pang
A chiral bidentate ligand, (R)-(−)-1-amino-2-propanol (denoted as R1) or (R)-(−)-2-amino-1-propanol (denoted as R2), was used to modify achiral 2D tin-based perovskite HDASnBr4 (HDA: 1,6-hexamethylenediamine) to form R1-HDASnBr4 or R2-HDASnBr4 by an acid precipitation method. R1-HDASnBr4 exhibits a near-unity photoluminescence quantum yield (PLQY) and strong yellow circularly polarized luminescence (CPL) with a luminescence asymmetry g-factor (|glum|) of 8.3 × 10–3, while R2-HDASnBr4 shows a PLQY of 95% and |glum| of 3.2 × 10–3. Both exhibit strong CPL activities, attributed to the significant centro-asymmetric distortion induced by the interaction between the chiral ligand and the inorganic lattice of 2D perovskites. The |glum| of R1-HDASnBr4 is 2.6× that of R2-HDASnBr4, resulting from the direct coordination of the hydroxyl group attached to the chiral carbons in R1 with the [SnBr6]4– inorganic framework, which induces a higher degree of distortion than the amino group in R2. Furthermore, we explored the potential of R1-HDASnBr4 as a chiral inducer and a CPL source to facilitate asymmetric polymerization. This work offers a simple strategy to introduce chirality to achiral perovskites.
{"title":"Circularly Polarized Luminescence in Achiral Tin-Based Perovskites via Structural Isomer-Driven Coordination Interaction","authors":"Dongmei Wu, Jianwu Wei, Binbin Luo, Liya Zhou, Peican Chen, Jie Tian, Jiahong Pan, Alexei V Emeline, Jin Zhong Zhang, Qi Pang","doi":"10.1021/acs.jpclett.5c00713","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00713","url":null,"abstract":"A chiral bidentate ligand, (<i>R</i>)-(−)-1-amino-2-propanol (denoted as R<sub>1</sub>) or (<i>R</i>)-(−)-2-amino-1-propanol (denoted as R<sub>2</sub>), was used to modify achiral 2D tin-based perovskite HDASnBr<sub>4</sub> (HDA: 1,6-hexamethylenediamine) to form R<sub>1</sub>-HDASnBr<sub>4</sub> or R<sub>2</sub>-HDASnBr<sub>4</sub> by an acid precipitation method. R<sub>1</sub>-HDASnBr<sub>4</sub> exhibits a near-unity photoluminescence quantum yield (PLQY) and strong yellow circularly polarized luminescence (CPL) with a luminescence asymmetry g-factor (|<i>g</i><sub>lum</sub>|) of 8.3 × 10<sup>–3</sup>, while R<sub>2</sub>-HDASnBr<sub>4</sub> shows a PLQY of 95% and |<i>g</i><sub>lum</sub>| of 3.2 × 10<sup>–3</sup>. Both exhibit strong CPL activities, attributed to the significant centro-asymmetric distortion induced by the interaction between the chiral ligand and the inorganic lattice of 2D perovskites. The |<i>g</i><sub>lum</sub>| of R<sub>1-</sub>HDASnBr<sub>4</sub> is 2.6× that of R<sub>2</sub>-HDASnBr<sub>4</sub>, resulting from the direct coordination of the hydroxyl group attached to the chiral carbons in R<sub>1</sub> with the [SnBr<sub>6</sub>]<sup>4–</sup> inorganic framework, which induces a higher degree of distortion than the amino group in R<sub>2</sub>. Furthermore, we explored the potential of R<sub>1</sub>-HDASnBr<sub>4</sub> as a chiral inducer and a CPL source to facilitate asymmetric polymerization. This work offers a simple strategy to introduce chirality to achiral perovskites.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"61 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849902","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 lithium-ion batteries (LIBs) used for deep-space exploration, LiCoO2 cathode materials face significant challenges in high-radiation environments, including structural degradation and ion migration. This study investigates the dynamic structural evolution of LiCoO2 under irradiation using the electron-temperature-dependent deep potential (ETD-DP) model. Compared with traditional ab initio molecular dynamics (AIMD) simulations, the ETD-DP method extends both the spatial and temporal scales by several orders of magnitude. The results reveal that LiCoO2’s response to irradiation occurs on the nanosecond time scale, divided into three stages: ion traversal, intense local structural adjustment, and structure relaxation. During the intense adjustment stage, irradiation induces the migration of transition metal ions toward the lithium layers. In the structure relaxation stage, cobalt ions displaced from their equilibrium positions form a dumbbell structure with adjacent Co ions. The simulation results were validated through high-energy electron beam experiments using aberration-corrected electron microscopy. This study provides valuable insights for improving the irradiation tolerance of LIB cathode materials and offers new perspectives on the application of high-energy particle-beam-based fine structural characterization techniques in advanced battery applications.
{"title":"Revealing Irradiation-Induced Dynamic Structural Failure in LiCoO2 Cathodes via Electron-Temperature-Dependent Deep Potential Molecular Dynamics","authors":"Pengfei Liu, Yuanyuan Liu, Xiaoya Zhang, Wei He, Hong Zhang, Qingshui Xie, Jingli Ren, Zi-Zhong Zhu, Dong-Liang Peng","doi":"10.1021/acs.jpclett.5c00486","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00486","url":null,"abstract":"In lithium-ion batteries (LIBs) used for deep-space exploration, LiCoO<sub>2</sub> cathode materials face significant challenges in high-radiation environments, including structural degradation and ion migration. This study investigates the dynamic structural evolution of LiCoO<sub>2</sub> under irradiation using the electron-temperature-dependent deep potential (ETD-DP) model. Compared with traditional ab initio molecular dynamics (AIMD) simulations, the ETD-DP method extends both the spatial and temporal scales by several orders of magnitude. The results reveal that LiCoO<sub>2</sub>’s response to irradiation occurs on the nanosecond time scale, divided into three stages: ion traversal, intense local structural adjustment, and structure relaxation. During the intense adjustment stage, irradiation induces the migration of transition metal ions toward the lithium layers. In the structure relaxation stage, cobalt ions displaced from their equilibrium positions form a dumbbell structure with adjacent Co ions. The simulation results were validated through high-energy electron beam experiments using aberration-corrected electron microscopy. This study provides valuable insights for improving the irradiation tolerance of LIB cathode materials and offers new perspectives on the application of high-energy particle-beam-based fine structural characterization techniques in advanced battery applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"136 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846468","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 : 2025-04-18DOI: 10.1021/acs.jpclett.5c00419
Kun Xie, Dongbin Wang, Long Lin, Pengtao Wang, Xiangyu Guo, Shengli Zhang
In recent years, the TMN4 moieties have demonstrated significant catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in graphene, CxNy, and other carbon-based two-dimensional (2D) support materials. Modifying the coordination number and species of N atoms in the TMN4 moieties has proven to be an effective approach to regulate their catalytic activity. In this research, by incorporating different triphenylene ligands, we have successfully constructed TMA2B2 (TM = Co, Rh, Ir; A/B = N, O, S, Se) moieties with varying coordination environments within 2D metal organic frameworks (MOFs), which are linked by TM and triphenylene. These moieties serve as an effective model to elucidate the structure–property relationship of two-dimensional 2D-MOFs in OER and ORR. Our findings confirm that alterations in the coordination environment can finely tune the d-band electron distribution of the TM within the TMA2B2 unit, particularly activating the dyz and dz2 orbitals of O2, thereby influencing the interactions between TM and key intermediates. We discovered that the regulatory effect of the coordination environment is closely linked to the electronegativity of the coordinating atoms, which led us to establish reliable descriptors such as φ1 and φ2 to elucidate the impact of coordination environments on the performance of OER/ORR. This criterion can be applied to numerous other 2D-MOFs and provides an in-depth understanding of the structure–activity relationship facilitates the development of highly efficient bifunctional electrocatalysts for OER and ORR applications.
{"title":"Ligand Regulated the Coordination Environment of Cobalt-Group-MOF for Efficient Electrocatalytic Oxygen Reduction/Evolution Catalysis","authors":"Kun Xie, Dongbin Wang, Long Lin, Pengtao Wang, Xiangyu Guo, Shengli Zhang","doi":"10.1021/acs.jpclett.5c00419","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00419","url":null,"abstract":"In recent years, the TMN<sub>4</sub> moieties have demonstrated significant catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in graphene, CxNy, and other carbon-based two-dimensional (2D) support materials. Modifying the coordination number and species of N atoms in the TMN<sub>4</sub> moieties has proven to be an effective approach to regulate their catalytic activity. In this research, by incorporating different triphenylene ligands, we have successfully constructed TMA<sub>2</sub>B<sub>2</sub> (TM = Co, Rh, Ir; A/B = N, O, S, Se) moieties with varying coordination environments within 2D metal organic frameworks (MOFs), which are linked by TM and triphenylene. These moieties serve as an effective model to elucidate the structure–property relationship of two-dimensional 2D-MOFs in OER and ORR. Our findings confirm that alterations in the coordination environment can finely tune the <i>d</i>-band electron distribution of the TM within the TMA<sub>2</sub>B<sub>2</sub> unit, particularly activating the <i>d</i><sub><i>yz</i></sub> and <i>d</i><sub>z<sup>2</sup></sub> orbitals of O<sub>2</sub>, thereby influencing the interactions between TM and key intermediates. We discovered that the regulatory effect of the coordination environment is closely linked to the electronegativity of the coordinating atoms, which led us to establish reliable descriptors such as φ<sub>1</sub> and φ<sub>2</sub> to elucidate the impact of coordination environments on the performance of OER/ORR. This criterion can be applied to numerous other 2D-MOFs and provides an in-depth understanding of the structure–activity relationship facilitates the development of highly efficient bifunctional electrocatalysts for OER and ORR applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"61 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849897","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 : 2025-04-18DOI: 10.1021/acs.jpclett.5c00641
Haixia Zhu, Zhaozhe Chen, Hua Zhang, Jin Dai, Jie Zhang, Zhihui Chen, Si Xiao, Jun He
Exploring strong nonlinear optical (NLO) response and high NLO anisotropy materials is crucial for nonlinear nanophotonic devices with a polarization function. Here, we report a quasi-one-dimensional (quasi-1D) ZrS3 nanobelt exhibiting ultrastrong third harmonics generation (THG) with a maximum third-order susceptibility (χ(3)) of 67.9 × 10–18 m2/V2 for a 24.3 nm thickness, which is approximately 3 orders of magnitude higher than most 2D materials. This thickness-dependent NLO coefficient (χ(3)) decreases from 4.88 × 10–18 to 1.14 × 10–18 m2/V2 with the variation in nanobelt thickness from 15.6 to 131 nm, which is explained by the phase matching confinement effect. More importantly, an anisotropic ratio of THG as large as 61.5 is confirmed, with the b-axis being the high THG polarization orientation. This orientation-dependent giant THG in quasi-1D ZrS3 crystals will provide potential for the development of future nonlinear nanophotonics with a polarization function.
{"title":"Orientation-Related Giant Third Harmonics Generation in Quasi-One-Dimensional ZrS3 Crystals","authors":"Haixia Zhu, Zhaozhe Chen, Hua Zhang, Jin Dai, Jie Zhang, Zhihui Chen, Si Xiao, Jun He","doi":"10.1021/acs.jpclett.5c00641","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00641","url":null,"abstract":"Exploring strong nonlinear optical (NLO) response and high NLO anisotropy materials is crucial for nonlinear nanophotonic devices with a polarization function. Here, we report a quasi-one-dimensional (quasi-1D) ZrS<sub>3</sub> nanobelt exhibiting ultrastrong third harmonics generation (THG) with a maximum third-order susceptibility (χ<sup>(3)</sup>) of 67.9 × 10<sup>–18</sup> m<sup>2</sup>/V<sup>2</sup> for a 24.3 nm thickness, which is approximately 3 orders of magnitude higher than most 2D materials. This thickness-dependent NLO coefficient (χ<sup>(3)</sup>) decreases from 4.88 × 10<sup>–18</sup> to 1.14 × 10<sup>–18</sup> m<sup>2</sup>/V<sup>2</sup> with the variation in nanobelt thickness from 15.6 to 131 nm, which is explained by the phase matching confinement effect. More importantly, an anisotropic ratio of THG as large as 61.5 is confirmed, with the <i>b</i>-axis being the high THG polarization orientation. This orientation-dependent giant THG in quasi-1D ZrS<sub>3</sub> crystals will provide potential for the development of future nonlinear nanophotonics with a polarization function.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"37 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849899","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 : 2025-04-18DOI: 10.1021/acs.jpclett.5c01029
Yilang Liu, Dongzheng Yang, Hua Guo, Daiqian Xie
Two mistakes have recently been identified in the original paper, (1) which lead to some changes in the calculation results. First, the initial rotational state of the aligned H2 molecule in eq 2 was defined with the order of subscripts m1 and 0 reversed in the reduced Wigner rotation matrix elements dm1,0j1(β). The correct eq 2 should read The second mistake is concerned with the azimuthal angle dependence (2,3) of the scattering amplitude and differential cross section (DCS) in eqs 1 and 3, which was neglected in the original publication. The azimuthal angle (ϕ) is depicted in Figure S1 of the Supporting Information. The correct eqs 1 and 3 should read respectively Figure 1. Integral cross sections for para-H2 (v1 = 1, j1 = 2) + HF (v2 = 0, j2 = 0) → para-H2 (v′1 = 1, j′1 = 0) + HF (v′2 = 0, j′2 = 3). (a) Partial wave resolved ICSs. (b) ICSs for different initially aligned H2. Figure S3. Integral cross sections for the collisional process para-H2 (v1 = 1, j1 = 2) + HF (v2 = 0, j2 = 0) → para-H2 (v′1 = 1, j′1 = 0) + HF (v′2 = 0, j′2 = 0, 1, 2). Left panels: Partial wave resolved ICSs. Right panels: ICSs for different initially aligned H2. These errors did not change the scientific conclusions in the original paper. This article references 4 other publications. This article has not yet been cited by other publications.
{"title":"Correction to “Visualizing Stereodynamics in Cold Collisions through Shape Resonance Wavefunctions”","authors":"Yilang Liu, Dongzheng Yang, Hua Guo, Daiqian Xie","doi":"10.1021/acs.jpclett.5c01029","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01029","url":null,"abstract":"Two mistakes have recently been identified in the original paper, (1) which lead to some changes in the calculation results. First, the initial rotational state of the aligned H<sub>2</sub> molecule in eq 2 was defined with the order of subscripts <i>m</i><sub>1</sub> and 0 reversed in the reduced Wigner rotation matrix elements <i>d</i><sub><i>m</i><sub>1</sub>,0</sub><sup><i>j</i><sub>1</sub></sup>(β). The correct eq 2 should read The second mistake is concerned with the azimuthal angle dependence (2,3) of the scattering amplitude and differential cross section (DCS) in eqs 1 and 3, which was neglected in the original publication. The azimuthal angle (ϕ) is depicted in Figure S1 of the Supporting Information. The correct eqs 1 and 3 should read respectively Figure 1. Integral cross sections for <i>para</i>-H<sub>2</sub> (<i>v</i><sub>1</sub> = 1, <i>j</i><sub>1</sub> = 2) + HF (<i>v</i><sub>2</sub> = 0, <i>j</i><sub>2</sub> = 0) → <i>para</i>-H<sub>2</sub> (<i>v′</i><sub>1</sub> = 1, <i>j′</i><sub>1</sub> = 0) + HF (<i>v′</i><sub>2</sub> = 0, <i>j′</i><sub>2</sub> = 3). (a) Partial wave resolved ICSs. (b) ICSs for different initially aligned H<sub>2</sub>. Figure S3. Integral cross sections for the collisional process <i>para</i>-H<sub>2</sub> (<i>v</i><sub>1</sub> = 1, <i>j</i><sub>1</sub> = 2) + HF (<i>v</i><sub>2</sub> = 0, <i>j</i><sub>2</sub> = 0) → <i>para</i>-H<sub>2</sub> (<i>v′</i><sub>1</sub> = 1, <i>j′</i><sub>1</sub> = 0) + HF (<i>v′</i><sub>2</sub> = 0, <i>j′</i><sub>2</sub> = 0, 1, 2). Left panels: Partial wave resolved ICSs. Right panels: ICSs for different initially aligned H<sub>2</sub>. These errors did not change the scientific conclusions in the original paper. This article references 4 other publications. This article has not yet been cited by other publications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849900","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}
Aqueous electrolyte additives are effective to improve the Zn anode performance, but their structural effect on electric double layer and Zn plating remains elusive. By comparing several additives with varied compositions and polarities, we reveal that the dipole moment plays an important role in modulating the electrode interface, while zincophilic functional groups are crucial to Zn stripping/plating kinetics. A strongly dipolar inner salt, L-α-glycerylphosphorylcholine, is screened as a favorable additive to stabilize the hydrophobic surface of the Zn anode and act as a Zn2+-migration bridge for fast desolvation. An aqueous 2 M ZnSO4 electrolyte containing 75 mM L-α-glycerylphosphorylcholine results in the restriction of parasitic hydrogen evolution, zinc sulfation hydroxylation, and dendrite formation. Consequently, the Zn anodes achieve a high Coulombic efficiency of 99.8% in Zn||Cu cells at 1 mA cm–2 and sustain 1800 h of cycling at 50% depth of discharge at 3 mA cm–2. This study underscores the screening and mechanistic understanding of dipolar inner salt additives to formulate better aqueous electrolytes.
{"title":"Strong Dipole Inner Salt Molecule as Interface Ion Bridge for Rechargeable Aqueous Zn-Anode Batteries","authors":"Zhaodong Wang, Yang Dong, Linlin Xue, Fengming Zhang, Meng Yu, Fangyi Cheng","doi":"10.1021/acs.jpclett.5c00594","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00594","url":null,"abstract":"Aqueous electrolyte additives are effective to improve the Zn anode performance, but their structural effect on electric double layer and Zn plating remains elusive. By comparing several additives with varied compositions and polarities, we reveal that the dipole moment plays an important role in modulating the electrode interface, while zincophilic functional groups are crucial to Zn stripping/plating kinetics. A strongly dipolar inner salt, L-α-glycerylphosphorylcholine, is screened as a favorable additive to stabilize the hydrophobic surface of the Zn anode and act as a Zn<sup>2+</sup>-migration bridge for fast desolvation. An aqueous 2 M ZnSO<sub>4</sub> electrolyte containing 75 mM L-α-glycerylphosphorylcholine results in the restriction of parasitic hydrogen evolution, zinc sulfation hydroxylation, and dendrite formation. Consequently, the Zn anodes achieve a high Coulombic efficiency of 99.8% in Zn||Cu cells at 1 mA cm<sup>–2</sup> and sustain 1800 h of cycling at 50% depth of discharge at 3 mA cm<sup>–2</sup>. This study underscores the screening and mechanistic understanding of dipolar inner salt additives to formulate better aqueous electrolytes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"6 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841817","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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