The Journal of Physical Chemistry C最新文献

{"title":"Correlated Mg-Ion and Electron Transport in Polyanionic Co and Ni Silicate Electrodes: A Paddle Wheel-like Rotation-Induced Process","authors":"Rachita Panigrahi, Bhabani S. Mallik","doi":"10.1021/acs.jpcc.4c06664","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06664","url":null,"abstract":"This study investigates polyanionic-based olivine MgMSiO₄ (M = Co and Ni) electrode materials using first-principles density functional theory (DFT) and classical molecular dynamics (CMD). The structural, electronic, and ionic dynamics of these orthosilicate materials are explored. Our findings demonstrate that polyanionic [SiO₄]^4– tetrahedra facilitate Mg²⁺ ionic mobility by forming channels and enabling the paddle-wheel mechanism through their coupled reorientation dynamics. Ionic diffusion studies reveal low-energy barriers for Mg²⁺ ions, indicating favorable ionic transport in these materials. Here, we establish a linear correlation between relaxation time and ionic conductivities. This can fill the gap in understanding how ions can move independently or decouple with the anionic polyhedra in the solid lattice. The correlated dynamics of cations and anions is crucial for controlling the ionic transport properties. Additionally, minimal volume changes during intercalation–deintercalation are observed, attributed to the stabilizing effect of strong Si–O bonds, which weaken M–O bonds through an inductive effect. These bonds help to maintain structural stability during battery operation. The average voltages are 2.85 V for MgCoSiO₄ and 3.27 V for MgNiSiO₄, making them promising candidates for MIB cathodes. Olivine silicates act as polaronic conductors, where the material properties influence charge carriers. DFT results reveal the electronic structure and polaron formation with spin polarization, providing detailed insight into the behavior of free polarons. This work will help us understand polyanionic cathode materials for high-capacity rechargeable batteries at the atomic level.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832985","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":"Reaction Mechanism Investigation of Hematite Photoanodes for Photoelectrochemical Water Splitting: Progress of In Situ and Operando Spectroscopy","authors":"Yi-Ping Zhao, Guang-Ping Yi, Wei Yu, Tiger H. Tao, Peng-Yi Tang","doi":"10.1021/acs.jpcc.4c06448","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06448","url":null,"abstract":"Hematite photoanodes, a promising candidate for photoelectrochemical (PEC) water splitting, are far from reaching their theoretical photocurrent limit. Further designing high-performance hematite-based photoanodes requires an in-depth understanding of the reaction mechanism of PEC water splitting. In situ and operando spectral characterizations facilitate the mechanism investigation, revealing the dynamic surface structures and intermediates of hematite photoanodes during the PEC water splitting process. Herein, in situ and operando spectroscopic techniques were applied for a mechanistic understanding of hematite-based photoanodes in the PEC water splitting system, such as UV–visible spectroscopy, Raman spectroscopy, infrared spectroscopy, transient absorption spectroscopy, transmission electron microscopy, X-ray absorption spectroscopy, atomic force microscope, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy. The recent progress on charge carrier dynamics and interfacial reaction intermediates of hematite photoanodes for oxygen evolution reaction (OER) is summarized. An outlook on challenges and prospects of in situ and operando spectroscopic techniques for PEC water splitting is given. This review will inspire future mechanism investigation of photoanodes for PEC water splitting to achieve higher performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"10 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832892","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":"Study of 5-Alkynylpyrimidines as Cobalt Superfilling Inhibitors","authors":"Haidi Li, Tao Zhang, Shiqi Song, Qian Li, Rongze Han, Qiaoxia Li, Yulin Min, Lina Qiu, Xixun Shen, Qunjie Xu","doi":"10.1021/acs.jpcc.4c05741","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05741","url":null,"abstract":"Electrodeposition technology is the key core technology for achieving micro/nanoscale interconnection in high-end chip manufacturing. Recently, cobalt interconnect structures have been the ideal choice for constructing electronic pathways in process nodes below 14 nm due to the fact that cobalt has a smaller electron mean free path compared to copper; thus, studying the electroplating filling behavior of cobalt in micronano scale space has become a hot topic in the field of chip manufacturing. In this article, an electroplating solution containing a new 5-alkynylpyrimidine (5-EP) as an inhibitor is designed for electrochemical tests, including cyclic voltammetry and linear sweep voltammetry. The results indicate that the 5-EP significantly inhibits cobalt electrodeposition. The change in the nucleation mode of cobalt in an electroplating solution with the inhibitor (5-EP) was revealed by chronoamperometry, where cobalt atoms nucleate in a three-dimensional continuous manner instead of three-dimensional instantaneous nucleation. In situ enhanced Raman spectroscopy is used to further analyze the adsorption of the inhibitor (5-EP) molecules on the cobalt surface during the electroplating process from a spectroscopic perspective. The energy gap value of the additive molecule obtained through quantum chemical calculations is △<i>E</i> = <i>E</i>_LUMO – <i>E</i>_HOMO = 3.302 eV, indicating that the additive molecule has high reactivity and higher adsorption strength at the metal interface. The calculated electrostatic potential (ESP) values of the molecule range from a minimum of −47.29 kJ/mol to a maximum of 70.89 kJ/mol. Lower ESP values imply higher electron density. Molecular dynamics simulations calculate the adsorption energy of the additive molecule (5-EP) on Co(100) to be −133.96 kcal/mol, indicating that the 5-EP molecule has good adsorption capability. Electroplating experiments reveal that the addition of 6 ppm 5-EP to the plating solution enables defect-free filling of blind holes. Finally, it is also revealed by characterization tests (scanning electron microscopy/atomic force microscopy/X-ray diffraction) that the inhibitor (5-EP) effectively reduces the surface roughness of the cobalt coating and, meantime, promotes the preferential growth of cobalt along the 100 and 110 crystal planes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"78 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832887","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":"Pore Engineering in γ-Fe2O3 Nanoparticles: Hierarchical Pores by Controlled Lixiviation Using Citrate Ligands","authors":"Ankita Singh, Sharvari P. Kulkarni, Ram S. Patel, R. Aravinda Narayanan, Balaji Gopalan","doi":"10.1021/acs.jpcc.4c05806","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05806","url":null,"abstract":"Porous magnetic nanomaterials are attracting increasing attention due to their potential applications in environmental remediation, catalysis, biomedical fields, and magnetic storage media. This paper presents a leaching-based pore engineering approach for the synthesis of porous γ-Fe₂O₃. This environmentally benign approach uses a citrate buffer for the leaching process. The citrate ligands play a role by binding to surface/interface ions and leaching them into the solution, affecting micropore widths. Concurrently, the citrate ligands also lixiviate smaller-sized particles in the size distribution, resulting in a 6% increase in the average mesopore size. A two-level hierarchical pore size regime is created. The smaller size regime results in a 33% increase in adsorption capacity, and the bigger size regime leads to a 36% enhancement in the mass transport rate of methylene blue (MB) in γ-Fe₂O₃ nanoparticles leached for 6 days. During ultrasonication for MB adsorption studies, a dynamic pore evolution is observed, leading to a remarkable 183% increase in the MB adsorption capacity for sixth-day leached samples after 60 min. Changes in the pore width influence interparticle magnetic interactions. The blocking temperature decreases from 126 K in the as-prepared sample to 116 K in the sixth-day sample. This study highlights the potential of the citrate leaching process for pore engineering.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832983","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":"Electronic Structure at the Perovskite/Rubrene Interface: The Effect of Surface Termination","authors":"Nicholas P. Sloane, Christopher G. Bailey, Jared H. Cole, Timothy W. Schmidt, Dane R. McCamey, Mykhailo V. Klymenko","doi":"10.1021/acs.jpcc.4c07074","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07074","url":null,"abstract":"Perovskite films have rapidly emerged as leading active materials in optoelectronic devices due to their strong optical absorption, high carrier mobility, and ease of fabrication. While proving to be promising materials for solar cells and light-emitting diodes, another application of perovskites, which makes effective use of their unique properties, is sensitization for photon upconversion. Consisting of a bulk perovskite sensitizer alongside an adjacent organic semiconductor film, the upconverting system can absorb multiple low-energy photons to emit high-energy photons. In this work, density functional theory, in conjunction with GW theory, is utilized to investigate the electronic structure at the MAPbI₃/rubrene interface for different surface terminations of MAPbI₃. From this investigation, we reveal that the surface termination of the perovskite layer greatly affects the charge density at the interface and within the rubrene layer, driven by the formation of interfacial dipole layers. The formation of a strong interfacial dipole for the lead-iodide-terminated perovskite alters the band alignment of the heterojunction and is expected to facilitate more efficient hole transfer, which should enhance triplet generation in rubrene through sequential charge transfer from the perovskite layer. The formation of this dipole layer is explained by the slight ionization of rubrene molecules due to the passivation of surface states and orbital hybridization. For the perovskite surface terminated with the methylammonium iodide layer, the highest occupied molecular orbital of the adjacent rubrene layer lies deep within the perovskite band gap. This termination type is further characterized by a lower density of states near the band edges and lower electron density, thereby acting as a spacer, which is anticipated to decrease the probability of charge transfer across the interface. Thus, based on our results, PbI₂-terminated perovskite surfaces are predicted to be favorable for applications where hole transfer to a rubrene layer is ideal, highlighting the significance of surface termination not only for upconverting systems but for all systems where the electronic environment at the interface is crucial to performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"201 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832683","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":"Crystal-Phase Engineering of PdCu Nanoparticles for Catalytic Reduction of NO by CO","authors":"Shuang Liu, Yong Li, Yuemin Wang, Wenjie Shen","doi":"10.1021/acs.jpcc.4c06088","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06088","url":null,"abstract":"Tuning the crystal phase of bimetallic nanoparticles has emerged as a promising strategy to boost their catalytic performance, but identifying the active site at the single-nanoparticle scale is rarely done and remains challenging. Here, the crystal phase of a PdCu single nanoparticle, spatially confined by a silica shell, was mediated between the ordered body-centered cubic (B2) phase and the disordered face-centered cubic (A1) phase. During the crystal-phase transition, the porous silica shell prevented the bimetallic nanoparticles from sintering under reactive gases and at elevated temperatures, enabling us to alter the crystal phase while keeping the particle size and atomic composition unchanged. Combined microscopic and spectroscopic characterizations revealed that the B2 particle was enclosed predominantly by the {110} facets over which Pd and Cu atoms were populated alternatively, while the A1 particle exposed mainly the {111} facets terminated by a random distribution of Pd and Cu atoms. When applied to catalyze NO reduction by CO, the B2 particle showed a much higher activity with a reaction rate of 4.5 times greater than that of the A1 particle. It was proposed that the orderly arranged Pd and Cu atoms on the {110} facets, exposed by the B2 particle, favored the coadsorption of NO and CO and further facilitated the dissociation of NO as the rate-determining step in the reaction network.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832984","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":"Revealing the Stability and Conductivity of 1D Structures in 2D Semiconducting Lattices","authors":"Hangbo Zhou, Viacheslav Sorkin, ZhiGen Yu, Yong-Wei Zhang","doi":"10.1021/acs.jpcc.4c06240","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06240","url":null,"abstract":"Recent experiments show that one-dimensional (1D) structures in two-dimensional (2D) semiconducting lattices exhibit either metallic or semiconducting behavior, but the underlying mechanisms are unclear. Our theoretical model predicts that couplings between the 1D structures and the 2D lattices via elastic support and electron transfer play crucial roles. The predicted phase diagram shows that elastic support stabilizes the metallic phase when electron transfer is present. Validated by first-principles calculations on MoS₂, we discover two new types of metallic grain boundaries. Our theory provides a robust framework for designing stable 1D metallic structures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832896","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":"Surface Charge Density Spectra: Complex Analysis of the Electrical Double Layer Developed from Measurements of Hexanol Adsorption Kinetics","authors":"Kazimierz Darowicki, Anna Karólkowska, Szymon Wysmułek","doi":"10.1021/acs.jpcc.4c06824","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06824","url":null,"abstract":"A procedure for deriving surface charge density spectra from differential capacitance data is presented in this study, providing a deeper analysis of the generated charge. A set of simulated differential capacitance spectra was determined for three types of adsorption process control: diffusion control, adsorption control, and mixed control. Based on the differential capacitance curves and spectra, surface charge density spectra were determined. Shapes characteristic of the three types of control of the adsorption process were identified. Using the Dynamic Electrochemical Impedance Spectroscopy (DEIS) technique, the kinetics of hexanol adsorption on a mercury electrode was analyzed. A change in the controlling step of the hexanol adsorption process from diffusion control to adsorption control was observed, based on the relaxation time values and differential capacitance spectra shape. Using a procedure developed on the basis of simulated data, the surface charge density spectra were determined over the entire range of investigated potentials. The developed procedure enabled the separation of the electric double layer (EDL) capacitance from the adsorption pseudocapacitance over a wide potential range. The charges associated with the EDL and generated by increasing pseudocapacitance were determined. The contribution of both charges to the total charge generated with a change in electrode potential varied with the electrode potential.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832987","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":"Facile Synthesis of Ultrathin 2D Tungsten Oxide Nanosheet as a Next-Generation Material for Enhanced Solar Conversion Efficiency","authors":"Mohammad Muaz, Farasha Sama, Tokeer Ahmad, M. Shahid, Absar Ahmad","doi":"10.1021/acs.jpcc.4c06897","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06897","url":null,"abstract":"The global energy crisis and dependency on fossil fuels have compelled us to rely on renewable energy-based technology, a more sustainable, eco-friendly energy source. Dye-sensitized solar cells (DSSCs) are one such promising technology. Owing to its unique features, the two-dimensional (2D) tungsten oxide nanosheet is a top-notch photoactive material for DSSC applications. However, their extensive commercialization is limited by cost-efficient and environmentally benign synthesis of an ultrathin 2D nanosheets. In this work, an easily scalable and high-yield mechanochemical synthesis of ultrathin nanosheets has been proposed at ambient temperature. The phase evolution and formation mechanism of the WO₃ nanosheet has been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) images. The as-synthesized WO₃ nanosheets were structurally characterized by multiple techniques like XRD, Fourier-transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), Raman, and ultraviolet–visible (UV–vis), while the nanoplate-like surface morphology was characterized by microscopic techniques like field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscope (HRTEM), and atomic force microscopy (AFM). The synthesized nanosheet was combined with a highly conductive graphene sheet (GS) in different doping percentages, and such modified hybrid systems were tested for DSSC application. Under the simulation of one-sun illumination, the DSSC using pristine photoelectrode material demonstrated a solar-power conversion efficiency of 9.31%, while the optimal doping of 0.6 wt % GS exhibited excellent performance with the highest power conversion efficiency of 10.47%, improved IPCE, and long term stability. A device prototype of the DSSC was developed utilizing the same, which continued to perform well for almost 3 months with a meagre loss in its performance. This work provides a promising approach for increasing the efficiency of solar cells by altering the WO₃ photoelectrode with GS, which acted as a next-generation material for commercializing DSSCs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832988","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":"Temperature-Dependent Formation of Carbon Nanodomains in Silicon Oxycarbide Glass─A Reactive Force Field MD Study","authors":"Bernhard M. Kriesche, Felix R. S. Purtscher, Benedikt E. Hörfarter, Teja Stüwe, Victoria Greussing, Bettina Friedel, Engelbert Portenkirchner, Thomas S. Hofer","doi":"10.1021/acs.jpcc.4c05132","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05132","url":null,"abstract":"Novel anode materials for lithium-ion batteries (LIBs) are constantly being explored to further improve battery performance. In this work, ReaxFF molecular dynamics (MD) simulations are performed to model the early stages in the synthesis of nanostructured silicon carbide (SiC), which is one such promising material. The focus lies on its precursor, silicon oxycarbide glass of composition (Si₅O₈C₁₆)_<i>x</i> (17 mol% Si, 28 mol% O, and 54 mol% C), in the following referred to as SiOC. The structure of the amorphous material is characterized via <i>NPT</i> MD simulations at temperatures ranging from 300 to 1000 K. To this end, a graph theoretical approach is employed to quantify the formation of segregated carbon nanodomains in the solid. Three algorithms for detecting nearest neighbors in the amorphous solid, a crucial prerequisite for the assembly of an atomic connectivity graph, are compared. It is shown that the temperature-dependent carbon aggregation follows an exponential trend, largely independent of the neighbor detection method. Also, the effects of variations in elemental composition are explored. Furthermore, the calculated powder X-ray diffraction patterns of the equilibrated silicon oxycarbide glasses are in good agreement with experimental measurements.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"6 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832982","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}