The Journal of Physical Chemistry C最新文献

{"title":"Fragmenting the Kagomé Lattice: Pressure-Tuned Anisotropy of Cu2+ Triangles in a Novel Atacamite Relative CaCu(OH)3Cl","authors":"Scott D. Ambos, Nicholas S. Manganaro, Matthew DeCapua, Dongzhou Zhang, Phuong Q. H. Nguyen, Jun Yan, James P. S. Walsh","doi":"10.1021/acs.jpcc.4c07695","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07695","url":null,"abstract":"The atacamite family of copper halide minerals contains several prominent quantum spin liquid candidate materials, chiefly herbertsmithite. Unfortunately, an intrinsic chemical disorder in herbertsmithite complicates attempts to perform magneto-structural correlations that deconvolute the fundamental magnetic exchange terms that underpin frustration. We sought to synthesize disorder-free zero-dimensional analogues of the atacamites that retain the basic local geometry required for frustration (i.e., triangular arrangements of spins) while avoiding the extended lattices that are prone to site disorder. We present here the synthesis of a novel trimetallic compound, CaCu(OH)₃Cl, that is reminiscent in composition and structure to the known atacamites. CaCu(OH)₃Cl features mildly Jahn–Teller distorted copper triangles that represent zero-dimensional analogues to the triangles that comprise the kagomé layers in herbertsmithite. We present a high-pressure synchrotron single crystal X-ray diffraction study of CaCu(OH)₃Cl up to 10.1(2) GPa and show that pressure counteracts the magnetic Jahn–Teller distortion of the square planar Cu(OH)₄ units that comprise the copper triangles, offering a new direction for optimizing magnetic frustration.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"12 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797819","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":"Multifunctionality and Processability of a Thermoplastic Based Gel Electrolyte Cell for the Realization of Structural Batteries","authors":"Martin Krammer, Susan Montes, Helmut Kühnelt, Qixiang Jiang, Daniel Lager, Alexander Bismarck, Alexander Beutl","doi":"10.1021/acs.jpcc.4c07301","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07301","url":null,"abstract":"In this work, a battery layup consisting of a poorly flammable ionic liquid electrolyte and a poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) (PVdF-HFP) thermoplastic has been developed along with composite anode and cathode electrodes. The developed gel electrolyte exhibits feasible ionic conductivity of about 1 mS/cm at 30 °C. State-of-the-art active electrode materials, i.e., LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) and graphite, have been employed. Full cells were tested in coin and pouch cell format, obtaining capacities of about 120 and 100 mA h/g_NMC811, respectively, at a C-rate of C/10. Thereby, it was observed that good contact between the individual cell layers is crucial. Recently, it was shown that the mechanical properties of structural batteries, realized by integrating battery cells into carbon fiber-reinforced polymer (CFRP) laminates, depend significantly on the mechanical properties of the cell itself. Hence, to promote the realization of such a structural battery concept, tensile tests were carried out to investigate the mechanical properties of cells as well as the individual components developed in this work. The full cell showed values of 10 GPa and 49 MPa for the Young’s modulus and tensile strength, respectively. Thus, feasible multifunctionality could be verified on the cell level. However, regarding the contributions of the different components, it could be shown that mainly the current collector foils contribute to the mechanical properties, in contrast to the electrode loadings and the gel electrolyte. Additionally, the thermal and chemical stability of the developed system was evaluated, highlighting the importance of these secondary properties for the fabrication of structural batteries, i.e., the integration of cells into load-bearing CFRP laminates. Specifically, it was observed that the developed system is thermally stable up to 150 °C and no HF release was detected upon exposure to ambient conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"12 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805102","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":"Multifunctionality and Processability of a Thermoplastic Based Gel Electrolyte Cell for the Realization of Structural Batteries","authors":"Martin Krammer*,&nbsp;Susan Montes,&nbsp;Helmut Kühnelt,&nbsp;Qixiang Jiang,&nbsp;Daniel Lager,&nbsp;Alexander Bismarck and Alexander Beutl,&nbsp;","doi":"10.1021/acs.jpcc.4c0730110.1021/acs.jpcc.4c07301","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07301https://doi.org/10.1021/acs.jpcc.4c07301","url":null,"abstract":"<p >In this work, a battery layup consisting of a poorly flammable ionic liquid electrolyte and a poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) (PVdF-HFP) thermoplastic has been developed along with composite anode and cathode electrodes. The developed gel electrolyte exhibits feasible ionic conductivity of about 1 mS/cm at 30 °C. State-of-the-art active electrode materials, i.e., LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) and graphite, have been employed. Full cells were tested in coin and pouch cell format, obtaining capacities of about 120 and 100 mA h/g_NMC811, respectively, at a C-rate of C/10. Thereby, it was observed that good contact between the individual cell layers is crucial. Recently, it was shown that the mechanical properties of structural batteries, realized by integrating battery cells into carbon fiber-reinforced polymer (CFRP) laminates, depend significantly on the mechanical properties of the cell itself. Hence, to promote the realization of such a structural battery concept, tensile tests were carried out to investigate the mechanical properties of cells as well as the individual components developed in this work. The full cell showed values of 10 GPa and 49 MPa for the Young’s modulus and tensile strength, respectively. Thus, feasible multifunctionality could be verified on the cell level. However, regarding the contributions of the different components, it could be shown that mainly the current collector foils contribute to the mechanical properties, in contrast to the electrode loadings and the gel electrolyte. Additionally, the thermal and chemical stability of the developed system was evaluated, highlighting the importance of these secondary properties for the fabrication of structural batteries, i.e., the integration of cells into load-bearing CFRP laminates. Specifically, it was observed that the developed system is thermally stable up to 150 °C and no HF release was detected upon exposure to ambient conditions.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"128 50","pages":"21317–21330 21317–21330"},"PeriodicalIF":3.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpcc.4c07301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-Principles Investigation of Surface pKa and the Behavior of Acids at Aqueous–Metal Interfaces","authors":"Basil Raju Karimadom, Dan Meyerstein, Amir Mizrahi, Haya Kornweitz","doi":"10.1021/acs.jpcc.4c06554","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06554","url":null,"abstract":"Several computational methods were reported for the accurate determination of p<i>K</i>_a values in a solvent medium, but the research on surfaces and interfaces is limited. This study reports a new method for accurately determining the surface p<i>K</i>_a (*p<i>K</i>_a) of acids on surfaces. The *p<i>K</i>_a is defined as the function of the adsorption energies of neutral acids and their deprotonated form. In the suggested method, the estimated proton solvation-free energy value is not required, a fact that increases the accuracy of the results. The *p<i>K</i>_a values of various organic and inorganic acids on the (111) surfaces of Ag, Au, and Pt were evaluated. The results are validated with available experimental results on various surface coverage ratios. The results point out that weak acids adsorbed on the metal-aqueous interface are orders of magnitude stronger acids than those in homogeneous solutions. The shift of the p<i>K</i>_as is largest on platinum. These results are of major importance in electrochemistry and heterogeneous catalysis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797851","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":"Novel Heterostructure as a H2-Evolving Photocatalyst Boosting the Z-Scheme Overall Water Splitting Performance under Visible Light Irradiation","authors":"Yu Qi, Yuanfeng Zhu, Tengfeng Xie, Fuxiang Zhang","doi":"10.1021/acs.jpcc.4c06607","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06607","url":null,"abstract":"Tantalum nitride (Ta₃N₅) has been widely investigated as an extremely promising photocatalyst or photoanode for solar water splitting, but its performance is blocked by inefficient charge separation regardless of using a one-step or two-step excitation method. Here, we demonstrate significantly enhanced proton reduction on the particulate Ta₃N₅ photocatalyst with an effort for the promotion of charge separation via forming a solid solution-based heterostructure composite. One-pot nitridation was adopted to synthesize this novel heterostructure, which is composed of Ta₃N₅ and BaZrO₃–BaTaO₂N solid solution. The as-obtained composite (BaZrO₃–BaTaO₂N/Ta₃N₅) is found to exhibit superior charge separation and transfer ability compared with Ta₃N₅ and BaZrO₃–BaTaO₂N. As a result, the visible-light-driven Z-scheme overall water splitting (OWS) activity using the optimal BaZrO₃–BaTaO₂N/Ta₃N₅ composite as the H₂-evolving photocatalyst can be promoted by about 20 times. This work not only gives the first example to fabricate heterostructures based on solid solution for enhanced charge separation but also offers a new avenue to improve the photocatalytic OWS performance of Ta₃N₅.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"228 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805073","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":"Nanoarchitectonics with Expired Carbon Fiber Reinforced Polymer-Derived Carbon Layer@Carbon Fiber Coaxial Electrodes for Superior Supercapacitor Performance","authors":"Chunhua Zhao, Wenjie Gao, Yipeng Zhao, Mingkun Li, Xiangzhi Tong, Huiming Guo, Yunpeng Zhu, Chongjun Zhao","doi":"10.1021/acs.jpcc.4c05557","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05557","url":null,"abstract":"Inspired by the double demands of both collection/storage from new energy devices and storage/supply for consumption tools, energy storage attracts much attention, and electrodes play a crucial role. In our work, by using an expired carbon fiber reinforced polymer (CFRP) as the raw material, when the epoxy resin component is removed through pretreatment at 350 °C and retained epoxy resin on the surface of carbon fibers (CFs) is carbonized/activated at 650 °C, a coaxial structure of carbon layer@carbon fiber (C@CF) is acquired (specific area: 786 m² g^–1). This C@CF can be directly used as a supercapacitor electrode, which exhibits good electrochemical performance: a specific capacitance of 202 F g^–1 at 1 A g^–1 for its electrode (vs 11.1 F g^–1 for bare CF), while an energy density of 9.75 Wh kg^–1 and a specific capacitance retention of 93.27% after 10,000 cycles for its symmetric supercapacitor (SSC).","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793347","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":"Oxidation Temperature-Dependent Electrochemical Doping of WO3 Deposited via Atomic Layer Deposition","authors":"Alexandria R. C. Bredar, Hannah R. M. Margavio, Carrie Donley, Neil Spinner, Nyaan Amin, Gregory N. Parsons, Jillian L. Dempsey","doi":"10.1021/acs.jpcc.4c06105","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06105","url":null,"abstract":"Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO₂ reduction but suffer from instability under photoelectrochemical conditions relevant to CO₂ reduction. Coating silicon electrodes with thin layers of metal oxides has shown promise to passivate unstable silicon surfaces, and many different metal oxides can be deposited on silicon using various techniques. In this study, we investigate the fundamental photoelectrochemical performance of WO₃-coated silicon photoelectrodes, which were generated by oxidation of W-metal films deposited via atomic layer deposition on both degenerately doped (nSi⁺) and low-doped (pSi) silicon. Two different oxidation temperatures were investigated (400 and 600 °C), and it was found that the monoclinic phase of WO₃ predominates at both temperatures but that more grain boundaries are present in the 600 °C film. From X-ray photoelectron spectroscopy, the stoichiometry of both films was found to be 1:3 W:O, and low electron energy loss experiments indicate band gaps of 3.0 and 3.1 eV for 400 and 600 °C films, respectively. Cyclic voltammetry experiments showed that the electron transfer kinetics increased after continued redox cycling, particularly for the material produced at 400 °C. X-ray photoelectron spectra suggest that the observed increase in electrode conductivity is due to the formation of oxygen vacancies in the film. Electrochemical impedance spectroscopy indicated that charge transport through the films was impacted by the grain boundaries that formed during oxidation of the film. Photoelectrochemical studies on pSi/WO₃ electrodes were highly variable, only producing a photocurrent and photovoltage with some samples. Our best sample, formed at 400 °C, produced a photovoltage of 180 mV, which is lower than what has previously been reported for WO₃-coated silicon (500 mV). We hypothesize that the variability in photoelectrochemical experiments arose from a roughened WSiO_<i>x</i> interface that is generated during film preparation. WO₃ shows promise as a metal oxide coating for silicon, but our results suggest that formation of a high-quality interface between Si and WO₃ is vital for best performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"83 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793656","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":"Assessing the Sensitivity of Pourbaix Diagrams to Computational Protocols: Electrochemical Stability of Ni Oxides as a Case Study","authors":"Wenyu Sun, Nitish Govindarajan, Aditya Prajapati, Jeremy T. Feaster, Christopher Hahn, Sneha A. Akhade","doi":"10.1021/acs.jpcc.4c06788","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06788","url":null,"abstract":"Pourbaix diagrams stand as a useful tool in assessing and visualizing materials’ electrochemical stability and are widely used for electrocatalyst design. However, their reliability hinges on the accuracy of the chemical potentials of involved phases, which may bear uncertainties and can be significantly impacted by decision-making steps in the computational protocol. This study introduces a robust sensitivity analysis framework, exemplified through a detailed examination of the computational Pourbaix diagram of Ni, the oxides of which are used as high-activity and cost-friendly catalysts for many electrochemical reactions. Quantities of interest derived from the Pourbaix diagram include the appearance and stability domain of the catalytically active Ni oxide phases along with the onset electrochemical potentials of phase transitions. These metrics can guide the design of operational conditions for Ni oxide electrocatalysts. We find that the employed DFT exchange-correlation functional has the most significant influence on the computed Pourbaix diagram. Uncertainties on crystal structures, along with their related ab initio energetics, are also found to affect the size of the phase stability domain. Higher-order coupling among input parameters is found to play a crucial role in influencing the appearance and distribution of Ni phases in the diagram. Our findings suggest a need to consider variations and uncertainties associated with the computational procedures on predicted Pourbaix diagrams for materials design.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793686","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":"Interface-Based FeSiCr/MXene Heterostructure for High-Performance Electromagnetic Wave Absorption","authors":"Zhengxing Li,&nbsp;Lei Wang*,&nbsp;Juan Liu*,&nbsp;Wenmiao Zhang,&nbsp;Shuqi Shen,&nbsp;Weiwei Dong,&nbsp;Yuzhi Wang and Tongxiang Liang*,&nbsp;","doi":"10.1021/acs.jpcc.4c0637410.1021/acs.jpcc.4c06374","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06374https://doi.org/10.1021/acs.jpcc.4c06374","url":null,"abstract":"<p >An electrostatic self-assembly method is used to synthesize FeSiCr/MXene, and the effect of MXene on the wave-absorbing properties is studied in this paper. The electromagnetic parameters of the composites are adjusted by optimizing the amount of MXene to improve the dielectric polarization and achieving impedance matching in order to enhance the microwave-absorbing properties. The lowest reflection loss (RL_min) of FeSiCr/MXene composites is −50.34 dB at 13.75 GHz. When the quantity of MXene composite is 15 wt % and the matching thickness is only 1.32 mm, the effective absorption bandwidth (EAB) at 2.00 mm approaches 11.05 GHz. The improved FeSiCr impedance matching, together with synergistic effects such as dielectric loss and interfacial polarization, results in outstanding microwave absorption performance for the FeSiCr/MXene composites. This paper proposes a new approach to developing and synthesizing materials with lightweight and efficient electromagnetic wave absorption.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"128 50","pages":"21292–21301 21292–21301"},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842913","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":"Oxygen Potential, Uranium Diffusion, and Defect Chemistry in UO2±x: A Density Functional Theory Study","authors":"William D. Neilson*,&nbsp;Jason Rizk,&nbsp;Michael W. D. Cooper and David A. Andersson,&nbsp;","doi":"10.1021/acs.jpcc.4c0658010.1021/acs.jpcc.4c06580","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06580https://doi.org/10.1021/acs.jpcc.4c06580","url":null,"abstract":"<p >Point defects play a crucial role in controlling the thermodynamic and kinetic properties of materials; in UO₂ nuclear fuel, they impact critical engineering-scale fuel performance properties, such as creep, fission gas release, and thermal conductivity. This work builds a point defect model informed using defect energies calculated by density functional theory (DFT) and vibrational entropies calculated by empirical potential calculations to predict point defect concentrations in UO_2±<i>x</i>. The DFT methodology uses large supercells and considers dispersion interactions, spin–orbit coupling, and noncollinear magnetic contributions. The result is a model that enables quantitative investigation of UO₂ defect chemistry over a wide range of conditions. Experimental validation is achieved in the deviation of <i>x</i> in UO_2±<i>x</i> as a function of temperature and partial pressure of oxygen, being facilitated by oxygen-type defects. By considering lattice thermal expansion when calculating the mobility of uranium vacancies, we have also been able to validate the model against experimentally measured uranium self-diffusivity; the calculated temperature dependence in the activation energy of uranium self-diffusion prompts interesting implications for future studies of defect transport in materials more generally.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"128 50","pages":"21559–21571 21559–21571"},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842984","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}