The Journal of Physical Chemistry C最新文献

{"title":"Thermoelectric Properties of Flexible Bi–Sb–Mn Films and Output Power of the Generator","authors":"Zhihao Ben, Guihong Song, Lijing Peng, Yusheng Wu, Junhua You","doi":"10.1021/acs.jpcc.5c00421","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00421","url":null,"abstract":"In this work, the Bi–Sb films with different Mn-doping contents were prepared on polyimide (PI) substrates by high vacuum magnetron sputtering. The carrier transport process, thermoelectric properties, flexibility of the deposited Bi–Sb–Mn films, and output power of the thermoelectric generator were studied. Results showed that the carrier concentration increased and carrier mobility and energy gap decreased with increasing doping Mn content in deposited Bi–Sb–Mn films. The electrical conductivity, Seebeck coefficient, and power factor all first increased and then decreased with increasing doping Mn content. The deposited Bi–Sb–Mn film with 1.0 at % Mn doping content possessed a maximum electrical conductivity of 5.30 × 10⁴ S m^–1, a Seebeck coefficient of −105.86 μV·K^–1, and a power factor of 624.22 μW m^–1 K^–2. The loss of electrical conductivity increased with increasing bending angles and bending times, and the loss greatly decreased with Mn doping in Bi–Sb films. The bending flexibility of Bi–Sb films can be further improved by doping more Mn. The maximum output power density (<i>PD</i>_max) of the thermoelectric generator for the deposited Bi₈₂–Sb₁₇–Mn film with 1.0 at % Mn doping content was 1.64 and 3.22 W·m^–2 at Δ<i>T</i> = 30 and 45 K, respectively. The standardized maximum power density (<i>PD</i>_max·<i>L</i>/Δ<i>T</i>²) of the thermoelectric generator for the Bi₈₂–Sb₁₇–Mn (1.0 at % Mn) film reached 72.89 μW·m^–1·K^–2, which was approximately 2.44 times higher than that of the undoped Bi₈₄–Sb₁₆ film.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"57 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-Principles Study of Molecular Hydrogen Activation by Defects in Boron Nitride","authors":"Michel Sassi, Tom Autrey","doi":"10.1021/acs.jpcc.5c00806","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00806","url":null,"abstract":"We used density functional theory simulations in combination with ab initio thermodynamics to determine the H₂ partial pressure (<i>p</i>_H2)-dependent energetics associated with H₂ activation and recovery at various defect sites in hexagonal boron nitride (h-BN). We found that some defects are very reactive with hydrogen, thereby definitely trapping hydrogen in defective h-BN. However, depending on hydrogen partial pressure, less reactive defect sites can be populated. Because of the lower binding capability of these sites, they would allow hydrogen to be recycled and recovered. For small defect sizes, we found that hydrogen preferentially binds to nitrogen sites by forming N–H bonds, and if no N sites are available then boron sites would be the next to bind hydrogen. Hydrogen dissociation via frustrated Lewis pair is found to be more favorable than forming only N–H bonds but only if the defect size is large enough to accommodate steric effects. For specific conditions such as <i>T</i> = 400 K, <i>p</i>_H₂ = 1 bar, and only considering one molecular H₂ per defect, three defects, namely, the N monovacancy, 3V(1B2N), and hexagonal 6V(3B3N) could play a role in both the activation and recycling of H₂ as they would be reacting enough to allow a favorable splitting of H₂ while not binding too strongly to allow its recovery. More broadly, a range of <i>p</i>_H₂ and hydrogen loading conditions were investigated for different types of defects and the finding suggests that <i>p</i>_H₂ could be used to fine-tune the Gibbs free energy of hydrogenation, thereby allowing several types of defects at different hydrogen loading contents to play a role in the activation/recovery process of H₂ in defective h-BN.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of Nuclear Motion on the Photoinduced Interfacial Charge Transfer Dynamics at a NiO/P1 Photocathode","authors":"Titus de Haas, Kaijian Zhu, Joannes M. van der Sterre, Yusen Luo, Guido Mul, Francesco Buda, Annemarie Huijser","doi":"10.1021/acs.jpcc.4c08758","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08758","url":null,"abstract":"The performance of dye-sensitized photoelectrochemical cells is presently limited by the photocathode component. Here, we investigate the impact of nuclear dynamics on the photoinduced charge separation of the benchmark NiO/P1 system (P1 = 4-(bis-4-(5-(2,2-dicyano-vinyl)-thiophene-2-yl)-phenyl-amino)-benzoic acid). Transient absorption (TA) studies in aqueous environments with different viscosities show that photoinduced hole injection either proceeds ultrafast (&lt;100 fs) or in a sub-ps time window. We assign the fastest component to a surface species strongly coupled to the NiO. Interestingly, the slower injection component and charge recombination are slowed down considerably in more viscous media. Quantum-classical dynamics simulations of a system with the dye standing perpendicular to the surface yield an injection lifetime remarkably close to the slow component from kinetic modeling of the TA results. Simulations including nuclear thermal motion yield a 2-fold increase in hole transfer rate compared to simulations on fixed nuclei, highlighting the role of nuclear motion and providing new design principles for dye-sensitized photocathodes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hybrid Functional Study on the Intrinsic Defect, Extrinsic n- and p-type Doping in 6H-SiC","authors":"Jincheng Wang, Bo Kong, Ti-xian Zeng, Song Ling, Peitao Qu, Wentao Wang","doi":"10.1021/acs.jpcc.4c08290","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08290","url":null,"abstract":"6H-SiC has garnered significant attention due to its promising applications in high-power devices and high-temperature sensors. However, the presence and properties of intrinsic defects that could significantly impact the material’s performance and the mechanisms of n-type (N, P, and As) and p-type (B, Al, and Ga) doping and their performance optimization remain unclear. In this work, we conduct a comprehensive investigation into the intrinsic defect physics of 6H-SiC and assess the effects of both intentional n-type (Group VA) and p-type doping (Group IIIA) on its conductivity, electronic structure, and optical properties. Our findings reveal that intrinsic defects in 6H-SiC generally exhibit high formation energies and deep transition levels, making their impact on conductivity minimal. Most of them should only form under nonthermal equilibrium growth conditions, such as high-temperature annealing and strong radiation. Furthermore, most of these intrinsic defects will also introduce defect energy levels in the band gap, which could act as the trapping centers of the photogenerated electrons or the recombination centers of the photogenerated electron–hole pairs. Particularly, for n-type doping, N and P emerge as ideal dopants, with N yielding excellent n-type 6H-SiC under C-poor conditions and P showing optimal performance in C-rich environments. In contrast, among the p-type dopants, Al stands out as the only excellent and ideal dopant, demonstrating a superior p-type doping efficiency under Si-poor conditions. The p-type doping of B shows significantly less favorable results compared to the n-type doping of N, which may be related to the intrinsic donor property of the carbon vacancy in 6H-SiC. These findings enhance our understanding of the defect physics in 6H-SiC and offer valuable insights for developing and optimizing high-performance 6H-SiC materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"99 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-Principles Insights into Interlayer Distance, Strain, and Electric Field-Modulated Electronic Properties of FeCl3/WSi2N4 Heterostructures","authors":"Yingying Zhao, Dan Zhou, Xuewen Wang, Syed Awais Ahmad, Muhammad Hilal, Jie Guo, Weibin Zhang","doi":"10.1021/acs.jpcc.4c08311","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08311","url":null,"abstract":"In this work, the electronic properties of the FeCl₃/WSi₂N₄ van der Waals heterostructure (vdWH) are investigated via first-principles calculations, emphasizing the impacts of layer spacing, in-plane strain, and external electric fields. The vdWH band structure exhibits a remarkable response to the interlayer spacing between FeCl₃ and WSi₂N₄, with the bandgap first increasing from 0.18 eV (Δ<i>D</i> = 2.25 Å, where Δ<i>D</i> represents the interlayer distance) to a peak of 0.82 eV (Δ<i>D</i> = 3.368 Å) and then declining to 0.31 eV (Δ<i>D</i> = 4.48 Å). Meanwhile, the heterojunction shifts from type-II to type-I and then back to type-II. The bandgap increases from 0.27 eV (ε = −3%) to 1.58 eV (ε = −2%) and then decreases to 0.18 eV (ε = 4%) under in-plane strain, and the biaxial compressive strain can result in a change of the heterojunction type. Moreover, the applied electric field can also regulate the bandgap and alter the heterojunction from type-I to type-II. When the field direction is from FeCl₃ to WSi₂N₄, the bandgap gradually increases from 0.72 eV (<i>E</i> = −0.4 V/Å) to 0.76 eV (<i>E</i> = −0.1 V/Å). Conversely, the bandgap remains nearly constant at around 0.82 eV under the reverse direction. These tunable electronic properties indicate that FeCl₃/WSi₂N₄ vdWHs are highly adaptable and have substantial potential for future wearable devices, flexible electronics, and optoelectronic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Fingerprint Analysis of X-ray Absorption Spectra with the Machine-Learning Method Trained on the Multielement Experimental Library”","authors":"B. O. Protsenko, Y. Kakiuchi, S. A. Guda, D. Trummer, A. Zabilska, S. Shapovalova, A. V. Soldatov, O. V. Safonova, C. Copéret, A. A. Guda","doi":"10.1021/acs.jpcc.5c01357","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01357","url":null,"abstract":"The only change we want to make is related to the Acknowledgment section. Published version: A.V.S. and A.A.G. acknowledge the financial support by the Ministry of Science and Higher Education of the Russian Federation (agreement no. <b>075–15–2021–1363</b>). B.O.P. acknowledges the financial support by the Russian Science Foundation (agreement no. <b>075–15–2021–1363</b>) for developing software for ML analysis of synchrotron data. A.Z. and O.V.S. acknowledge the support of the Swiss National Science Foundation (SNSF) under project 200021_179132 “Uncovering dynamic structure of active sites in selective oxidation catalysts using time-resolved X-ray absorption spectroscopy”. We acknowledge I. E. Wachs (Lehigh University) for providing the bilayered 5% V2O5/15%TiO2/SiO2 catalyst. C.C. and O.V.S. acknowledge the support by the NCCR Catalysis (grant number 180544). Published version contains duplicated grant number. We ask to replace second grant number with a proper one number: A.V.S. and A.A.G. acknowledge the financial support by the Ministry of Science and Higher Education of the Russian Federation (agreement no. <b>075–15–2021–1363</b>). B.O.P. acknowledges the financial support by the Russian Science Foundation (agreement no. <b>24–43–00215</b>) for developing software for ML analysis of synchrotron data. A.Z. and O.V.S. acknowledge the support of the Swiss National Science Foundation (SNSF) under project 200021_179132 “Uncovering dynamic structure of active sites in selective oxidation catalysts using time-resolved X-ray absorption spectroscopy”. We acknowledge I. E. Wachs (Lehigh University) for providing the bilayered 5% V2O5/15%TiO2/SiO2 catalyst. C.C. and O.V.S. acknowledge the support by the NCCR Catalysis (grant number 180544). This article has not yet been cited by other publications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"18 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Potential-Dependent Electrocatalytic Nitrogen Reduction Catalysis on Ni-Anchored γ-Al2O3(110) Surface","authors":"Deewan S. Teja, Bhabani S. Mallik","doi":"10.1021/acs.jpcc.4c08378","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08378","url":null,"abstract":"The transition metal oxides (TMOs) as supports for metal clusters or nanoparticles with surface oxygen vacancies enhance charge transfer from the metal-oxide surface to the metal cluster. Experimental reports have shown that 5 wt % Ni loading on γ-Al₂O₃ enables N₂ activation with the presence of NH_<i>x</i> intermediates on the Ni surface. In this study, we investigated the electrocatalytic nitrogen reduction reaction mechanism (eNRR) on Ni₁ and Ni₄ clusters on γ-Al₂O₃(110) at room temperature by using the computational hydrogen electrode (CHE) model. Nickel atoms preferentially bind via oxygen atoms on the γ-Al₂O₃(110) surface. Moreover, Ni₄/γ-Al₂O₃(110) follows the enzymatic mechanism with a limiting potential (<i>U</i>_<i>L</i>) of −0.576 V, where **N₂ to *N*NH is the potential determining step (PDS). In contrast, Ni₁/γ-Al₂O₃(110) follows a mixed mechanism through an enzymatic route with a <i>U</i>_<i>L</i> of −1.272 V, also with **N₂ to *N*NH as the PDS. The electronic properties, such as the projected density of states (PDOS) and integrated crystal orbital Hamilton population (ICOHP), indicate effective overlap between the metal d-orbital and N₂ antibonding 2π<i>*</i> orbitals near the Fermi level in Ni₄/γ-Al₂O₃(110), whereas a weak interaction is observed in Ni₁/γ-Al₂O₃(110). The evaluation of NRR selectivity shows that Ni₁/Ni₄ sites are freely available for NRR rather than HER. Overall, the mechanistic investigation shows that Ni₄/γ-Al₂O₃(110) is a better electrocatalyst for NRR because of the strong electronic orbital overlaps between Ni metal and surface oxygen. This work highlights how the loading percentage of metal clusters on metal oxides affects catalysis and can be tuned to design better electrocatalysts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"18 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CO2 Adsorption on Variably Hydrated Cation-Exchanged Montmorillonite-Rich Clays","authors":"Niels Mendel, Diana Sîreţanu, Igor Sîreţanu, Derk W. F. Wim Brilman, Frieder Mugele","doi":"10.1021/acs.jpcc.4c07731","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07731","url":null,"abstract":"Layered swelling clay minerals like montmorillonite (MMT) can competitively and synergistically adsorb CO₂ and H₂O in their interlayer galleries. This work examines how different interlayer cations, relative humidity levels (and amount of cosorbed H₂O), and (de)hydration history affect CO₂ adsorption on MMT and MMT-rich bentonite at near-ambient pressure and temperature. For CO₂ to be adsorbed, the MMT requires either large (e.g., Cs⁺) or hydrated interlayer cations to provide a sufficiently wide interlayer gallery, and must not have too much H₂O adsorbed competitively with CO₂. Na-MMT and initially anhydrous Mg- and Ca-MMT studied under increasing relative humidity conditions adsorb little CO₂. However, Mg- and Ca-MMT can effectively adsorb CO₂ if first hydrated and then mildly dried such that the cations remain hydrated while the competitively adsorbed excess H₂O is removed. Because of their high stability and the favorable shape of their CO₂ adsorption isotherms, low-cost (near-)natural Mg- and Ca-bentonite can be used for (cyclic) CO₂ adsorption and separation purposes, similar to the more expensive Cs-bentonite.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"57 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-Principles Insights into Interlayer Distance, Strain, and Electric Field-Modulated Electronic Properties of FeCl3/WSi2N4 Heterostructures","authors":"Yingying Zhao,&nbsp;Dan Zhou,&nbsp;Xuewen Wang,&nbsp;Syed Awais Ahmad,&nbsp;Muhammad Hilal,&nbsp;Jie Guo* and Weibin Zhang*,&nbsp;","doi":"10.1021/acs.jpcc.4c0831110.1021/acs.jpcc.4c08311","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08311https://doi.org/10.1021/acs.jpcc.4c08311","url":null,"abstract":"<p >In this work, the electronic properties of the FeCl₃/WSi₂N₄ van der Waals heterostructure (vdWH) are investigated via first-principles calculations, emphasizing the impacts of layer spacing, in-plane strain, and external electric fields. The vdWH band structure exhibits a remarkable response to the interlayer spacing between FeCl₃ and WSi₂N₄, with the bandgap first increasing from 0.18 eV (Δ<i>D</i> = 2.25 Å, where Δ<i>D</i> represents the interlayer distance) to a peak of 0.82 eV (Δ<i>D</i> = 3.368 Å) and then declining to 0.31 eV (Δ<i>D</i> = 4.48 Å). Meanwhile, the heterojunction shifts from type-II to type-I and then back to type-II. The bandgap increases from 0.27 eV (ε = −3%) to 1.58 eV (ε = −2%) and then decreases to 0.18 eV (ε = 4%) under in-plane strain, and the biaxial compressive strain can result in a change of the heterojunction type. Moreover, the applied electric field can also regulate the bandgap and alter the heterojunction from type-I to type-II. When the field direction is from FeCl₃ to WSi₂N₄, the bandgap gradually increases from 0.72 eV (<i>E</i> = −0.4 V/Å) to 0.76 eV (<i>E</i> = −0.1 V/Å). Conversely, the bandgap remains nearly constant at around 0.82 eV under the reverse direction. These tunable electronic properties indicate that FeCl₃/WSi₂N₄ vdWHs are highly adaptable and have substantial potential for future wearable devices, flexible electronics, and optoelectronic devices.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 13","pages":"6432–6442 6432–6442"},"PeriodicalIF":3.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Understanding the New Crucial Role of a Calcium Ion as a Pillar Dopant in Stabilizing O3-Type Na[Ni1/3Fe1/3Mn1/3]O2 Cathodes","authors":"Zhenbo Sun, Maosheng Gong, Jiacheng Li, Mohan Dong, Ke Fan, Xuanming Chang, Feng Li, Peiyu Hou, Xijin Xu","doi":"10.1021/acs.jpcc.4c08703","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08703","url":null,"abstract":"The pillar dopants occupying the sodium sites show great potential for stabilizing O3-type oxide cathodes, but the specific mechanism of action needs to be further uncovered. Herein, a series of Ca²⁺-doped O3-type Na_{1–2<i>x</i>}Ca<i>_x</i>[Ni_1/3Fe_1/3Mn_1/3]O₂ compounds were synthesized using coprecipitation and solid-state reaction methods. Density functional theory calculation confirms a lower formation energy for the Ca dopant occupying the sodium sites compared to that of transition metal sites. In-situ XRD results reveal that pristine O3-type Na[Ni_1/3Fe_1/3Mn_1/3]O₂ cathodes undergo a similar O3 - O3/P3 - P3 - P3/O3 - O3 phase transition within the first and second cycles. Different from the pristine O3-type cathode, the Ca²⁺-doped counterpart shows a distinct O3 - O3/P3 - P3 - P3/O3 phase transition in the first cycle, indicating that the transformation from the P3 phase to the O3 phase is partly suppressed during discharging. In the second cycle, a reversible P3/O3 - P3 - P3/O3 phase transition with weak volume changes is observed for the Ca²⁺-doped electrode, suggesting improved structural stability. Consequently, the Ca²⁺-doped Na_0.94Ca_0.03[Ni_1/3Fe_1/3Mn_1/3]O₂ shows an enhanced cycling stability, retaining 92.4% of its initial capacity after 100 cycles at 0.1 C and 85% after 300 cycles at 1 C, which is much better than that of the pristine electrode. These results reveal a new crucial role of calcium ions as pillar dopants in regulating the phase transition and stabilizing the structure of O3-type cathodes for advanced sodium-ion batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"72 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}