Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c04678
Ivan Soldo, Paul Schweer, Marvin Quack, Nico Knüfer, David Olivenza, Daniel P. Miller, Karina Morgenstern
The adsorption of ions on metallic surfaces is a powerful method to alter their electronic structure and thus tune their reactivity. A prominent example is chlorine on Ag(111). We investigate chlorine created by the room-temperature adsorption of chloroform on Ag(111) at supersaturation and the structures it forms from individual monomers to a full layer by using low-temperature scanning tunneling microscopy. The data is supplemented by temperature-programmed desorption and X-ray photoelectron spectroscopy after low-temperature adsorption under ultrahigh-vacuum conditions. Data interpretation is supported by density functional theory (DFT) calculations that account for dispersion forces. At low chlorine coverages, each chlorine locally alters the electronic structure of the surface. The adsorbed chlorine-induced local environment modification thereby creates preferential adsorption sites for other chlorines in their vicinity, stabilizing extended chlorine structures on Ag(111). Oligomer formation leads to distance-dependent cooperative effects of the charge transfer and thus impacts the electronic structure of the surface beyond the change by individual chlorines. At intermediate chlorine coverage, chlorine forms meandering chains with atoms adsorbed in alternating hcp and fcc hollow sites at distinct chlorine–chlorine distances. The one-dimensional structures convert to an open network at intermediate coverages and a two-dimensional hexagonal superstructure at saturation coverage. The DFT calculations suggest that the charge density extracted from the surface into the chlorines and the interaction between chlorine and silver atoms is improved as chlorines are adjoined closer at intermediate and high coverages.
{"title":"Ordered Chlorine Layer Formation from a Supersaturation of Chloroform","authors":"Ivan Soldo, Paul Schweer, Marvin Quack, Nico Knüfer, David Olivenza, Daniel P. Miller, Karina Morgenstern","doi":"10.1021/acs.jpcc.4c04678","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04678","url":null,"abstract":"The adsorption of ions on metallic surfaces is a powerful method to alter their electronic structure and thus tune their reactivity. A prominent example is chlorine on Ag(111). We investigate chlorine created by the room-temperature adsorption of chloroform on Ag(111) at supersaturation and the structures it forms from individual monomers to a full layer by using low-temperature scanning tunneling microscopy. The data is supplemented by temperature-programmed desorption and X-ray photoelectron spectroscopy after low-temperature adsorption under ultrahigh-vacuum conditions. Data interpretation is supported by density functional theory (DFT) calculations that account for dispersion forces. At low chlorine coverages, each chlorine locally alters the electronic structure of the surface. The adsorbed chlorine-induced local environment modification thereby creates preferential adsorption sites for other chlorines in their vicinity, stabilizing extended chlorine structures on Ag(111). Oligomer formation leads to distance-dependent cooperative effects of the charge transfer and thus impacts the electronic structure of the surface beyond the change by individual chlorines. At intermediate chlorine coverage, chlorine forms meandering chains with atoms adsorbed in alternating hcp and fcc hollow sites at distinct chlorine–chlorine distances. The one-dimensional structures convert to an open network at intermediate coverages and a two-dimensional hexagonal superstructure at saturation coverage. The DFT calculations suggest that the charge density extracted from the surface into the chlorines and the interaction between chlorine and silver atoms is improved as chlorines are adjoined closer at intermediate and high coverages.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"14 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673607","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c04422
Reyna Méndez-Camacho, Máximo López-López, Elihu H. Sánchez-Martínez, Esteban Cruz-Hernández
Studies of Wigner crystals in semiconductor nanowires reveal significant electronic characteristics, especially in configurations where electron tunneling between adjacent wires occurs. This tunneling enables long-range coherence across nanowire arrays in both ground and excited states. We employ a Yukawa-like effective potential and the Kronig–Penney model along with matrix transfer methods to analyze coherence in N × N arrays, focusing on electronic distribution, resonant energies, and coherent superposition between adjacent wires. Our results demonstrate the formation of three-dimensional, noncontinuous charge distributions coherently connected by electronic tunneling. We discuss potential applications, methods for interacting with these distributions, and their experimental feasibility. These findings enable the formation of long-range coherent charge arrays, which can be externally tuned, paving the way for large-scale, high-density integration of coherent quantum systems.
对半导体纳米线中维格纳晶体的研究揭示了显著的电子特性，尤其是在相邻线之间发生电子隧道的配置中。这种隧道效应使得纳米线阵列在基态和激发态下都能产生长程相干性。我们采用类似于尤卡瓦的有效电势和克罗尼格-彭尼模型以及矩阵转移方法来分析 N × N 阵列中的相干性，重点研究相邻导线之间的电子分布、共振能量和相干叠加。我们的研究结果表明，三维非连续电荷分布的形成是通过电子隧道相干连接的。我们讨论了这些分布的潜在应用、相互作用方法及其实验可行性。这些发现使得长程相干电荷阵列的形成成为可能，它可以从外部进行调整，为大规模、高密度集成相干量子系统铺平了道路。
{"title":"Three-Dimensional Coherence in Arrays of Parallel One-Dimensional Wigner Crystals","authors":"Reyna Méndez-Camacho, Máximo López-López, Elihu H. Sánchez-Martínez, Esteban Cruz-Hernández","doi":"10.1021/acs.jpcc.4c04422","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04422","url":null,"abstract":"Studies of Wigner crystals in semiconductor nanowires reveal significant electronic characteristics, especially in configurations where electron tunneling between adjacent wires occurs. This tunneling enables long-range coherence across nanowire arrays in both ground and excited states. We employ a Yukawa-like effective potential and the Kronig–Penney model along with matrix transfer methods to analyze coherence in <i>N</i> × <i>N</i> arrays, focusing on electronic distribution, resonant energies, and coherent superposition between adjacent wires. Our results demonstrate the formation of three-dimensional, noncontinuous charge distributions coherently connected by electronic tunneling. We discuss potential applications, methods for interacting with these distributions, and their experimental feasibility. These findings enable the formation of long-range coherent charge arrays, which can be externally tuned, paving the way for large-scale, high-density integration of coherent quantum systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"99 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673606","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c05666
Guofei Chen, Lei Guan, Yang Chen, Huijie Xu, Jianqiu Zhou, Rui Cai
The contact loss and interface impedance of all-solid-state lithium-ion batteries (ASSLBs) have greatly restricted their commercial applications. This study simulates the ASSLB composed of a LiNi0.8Co0.1Mn0.1O2 (NMC811) cathode, silicon–carbon composite (SiC) anode, and Li10GeP2S12 (LGPS) solid electrolyte and analyzes the interfacial electrochemical and mechanical behavior. The electrical contact resistance and interface stress are obtained by the fractal network model and contact mechanics theory. According to the interface reaction kinetics and Nernst–Planck–Poisson equations, the analytical electric field of the space charge layer (SCL) in the case of symmetric carrier movement is acquired. In addition, the optimization effect of coating the porous poly(ethylene oxide) (PEO) layer on the interface is studied theoretically. Based on the equivalent circuit model (ECM), the electrochemical impedance spectra (EIS) of the whole cell are simulated by Comsol Multiphysics. To investigate the evolution of the SCL capacitance, the contact resistance, and the interfacial impedance, the relevant physical parameters are reasonably regulated. The results show that when the buffer layer of a higher initial porosity is taken with a thickness of 1.5–2.5 × 10–7m, the interface stress can be relieved and the actual contact can be improved. What’s more, the relative permittivity of the solid electrolytes in the range of 10–50 can reduce the interfacial impedance as well.
{"title":"Optimization Effect on the Interfacial Impedance and Contact Stress of the ASSLB with Porous Polymer Buffer Layer","authors":"Guofei Chen, Lei Guan, Yang Chen, Huijie Xu, Jianqiu Zhou, Rui Cai","doi":"10.1021/acs.jpcc.4c05666","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05666","url":null,"abstract":"The contact loss and interface impedance of all-solid-state lithium-ion batteries (ASSLBs) have greatly restricted their commercial applications. This study simulates the ASSLB composed of a LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NMC811) cathode, silicon–carbon composite (SiC) anode, and Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub> (LGPS) solid electrolyte and analyzes the interfacial electrochemical and mechanical behavior. The electrical contact resistance and interface stress are obtained by the fractal network model and contact mechanics theory. According to the interface reaction kinetics and Nernst–Planck–Poisson equations, the analytical electric field of the space charge layer (SCL) in the case of symmetric carrier movement is acquired. In addition, the optimization effect of coating the porous poly(ethylene oxide) (PEO) layer on the interface is studied theoretically. Based on the equivalent circuit model (ECM), the electrochemical impedance spectra (EIS) of the whole cell are simulated by Comsol Multiphysics. To investigate the evolution of the SCL capacitance, the contact resistance, and the interfacial impedance, the relevant physical parameters are reasonably regulated. The results show that when the buffer layer of a higher initial porosity is taken with a thickness of 1.5–2.5 × 10<sup>–7</sup>m, the interface stress can be relieved and the actual contact can be improved. What’s more, the relative permittivity of the solid electrolytes in the range of 10–50 can reduce the interfacial impedance as well.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"54 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671056","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}
Using antiferromagnetic order states to store information is desirable due to the high rate of data writing, large density of storage, and high anti-interference capability. Tuning magnetic anisotropy is required for data writing with a low energy consumption. In this work, we investigated the control of magnetism of antiferromagnetic two-dimensional MXene V2C(OH)2 based on density functional theory. We find that the magnetic anisotropy in V2C(OH)2 can be regulated by applying both in-plane tensile and vertical compression strain. With applying strain, the energy band gap can also be obviously varied. By the density of states and orbital-resolved magnetic anisotropy, we confirm that the strain-inducing changes of the distribution of the dz2 orbital states near the Fermi level, which form magnetic anisotropy with the dxz orbital by the spin–orbital coupling, have significant effects on the control of magnetic anisotropy. The results of this study show that the two-dimensional MXene material V2C(OH)2 with strain-tunable antiferromagnetism will have potential application in spintronics devices.
{"title":"Strain-Control Magnetic Anisotropy of Antiferromagnetism in Two-Dimensional MXene V2C(OH)2","authors":"Chengyang Zhao, Shiming Yan, Shiran Gao, Wen Qiao, Ru Bai, Tiejun Zhou","doi":"10.1021/acs.jpcc.4c04171","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04171","url":null,"abstract":"Using antiferromagnetic order states to store information is desirable due to the high rate of data writing, large density of storage, and high anti-interference capability. Tuning magnetic anisotropy is required for data writing with a low energy consumption. In this work, we investigated the control of magnetism of antiferromagnetic two-dimensional MXene V<sub>2</sub>C(OH)<sub>2</sub> based on density functional theory. We find that the magnetic anisotropy in V<sub>2</sub>C(OH)<sub>2</sub> can be regulated by applying both in-plane tensile and vertical compression strain. With applying strain, the energy band gap can also be obviously varied. By the density of states and orbital-resolved magnetic anisotropy, we confirm that the strain-inducing changes of the distribution of the d<sub><i>z</i><sup>2</sup></sub> orbital states near the Fermi level, which form magnetic anisotropy with the d<sub><i>xz</i></sub> orbital by the spin–orbital coupling, have significant effects on the control of magnetic anisotropy. The results of this study show that the two-dimensional MXene material V<sub>2</sub>C(OH)<sub>2</sub> with strain-tunable antiferromagnetism will have potential application in spintronics devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673621","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}
Energy storage is an effective means to address rising energy consumption, and phase change materials (PCMs) can effectively improve energy storage efficiency and utilize renewable energy. In this work, sliced paraffin (PS) and lauric acid (LA) were employed as phase change raw materials and blended with freeze-dried navel orange peel carbon (FNOP). PS-LA/FNOP was prepared by vacuum adsorption. NOP is carbonized at three temperatures. It is determined that FNOP900 has an optimal pore volume and a specific surface area of up to 0.165 cm3/g and 339.04 m2/g, respectively. The optimal load rate of FNOP900 reaches 65%. The phase transition enthalpy and temperature of PS-LA/FNOP900 are 61.95 J/g and 36.42 °C, respectively. PS-LA/FNOP900 has an excellent thermal storage capacity at a constant temperature of 10–55 °C. After 300 thermal cycles, the enthalpy of PS-LA/FNOP only decreased by 9.15 J/g. Meanwhile, PS-LA/FNOP900 maintains good thermal reliability; the thermal conductivity of PS-LA/FNOP900 is 0.42 W/m·K, which is 47.84% higher than that of PS-LA. Also, PS-LA/FNOP900 exhibits superior temperature control performance; the heating and cooling times of PS-LA/FNOP900 are reduced by 11.68 and 50.03%, respectively, compared with PS-LA.
{"title":"Pore Characteristics and Thermal Properties of a Binary Eutectic Adsorbed into Modified Waste Navel Orange Peels for Energy Storage","authors":"Fan Yong, Hua Fei, Yuanlin Li, Jiahong Zhou, Jianmin Tong, Liwen Chen","doi":"10.1021/acs.jpcc.4c06229","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06229","url":null,"abstract":"Energy storage is an effective means to address rising energy consumption, and phase change materials (PCMs) can effectively improve energy storage efficiency and utilize renewable energy. In this work, sliced paraffin (PS) and lauric acid (LA) were employed as phase change raw materials and blended with freeze-dried navel orange peel carbon (FNOP). PS-LA/FNOP was prepared by vacuum adsorption. NOP is carbonized at three temperatures. It is determined that FNOP900 has an optimal pore volume and a specific surface area of up to 0.165 cm<sup>3</sup>/g and 339.04 m<sup>2</sup>/g, respectively. The optimal load rate of FNOP900 reaches 65%. The phase transition enthalpy and temperature of PS-LA/FNOP900 are 61.95 J/g and 36.42 °C, respectively. PS-LA/FNOP900 has an excellent thermal storage capacity at a constant temperature of 10–55 °C. After 300 thermal cycles, the enthalpy of PS-LA/FNOP only decreased by 9.15 J/g. Meanwhile, PS-LA/FNOP900 maintains good thermal reliability; the thermal conductivity of PS-LA/FNOP900 is 0.42 W/m·K, which is 47.84% higher than that of PS-LA. Also, PS-LA/FNOP900 exhibits superior temperature control performance; the heating and cooling times of PS-LA/FNOP900 are reduced by 11.68 and 50.03%, respectively, compared with PS-LA.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673623","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c07452
Carina S. T. Peraça, Karla F. Andriani, Maurício J. Piotrowski, Juarez L. F. Da Silva
Unfortunately, we identified two errors in our paper related to the misapplication of the unity bond index–quadratic exponential potential (UBI–QEP) analysis, which became evident through discussions with Dr. Verónica Ganduglia-Pirovano and Dr. Breno L. Galvão (Private communication, March 15, 2024). The first error involves the results used to design Figure 5, where we obtained the activation energy values using the UBI-QEP approximation. In this analysis, we considered the most common adsorption sites reported in the literature for the CeO<sub>2</sub>(111) surface rather than the most stable ones on the ceria cluster. As a result, the dependence between the CH<sub>4</sub> adsorption site and the corresponding CH<sub>3</sub> and/or H sites was not maintained. A more appropriate approach for our purposes would be to conduct a systematic investigation of the coadsorption sites on (CeO<sub>2</sub>)<sub>10</sub>, using a specific adsorption site as a reference and mapping the most stable CH<sub>3</sub> or H sites. Therefore, we implemented the aforementioned approach by mapping the CH<sub>3</sub> sites and fixing the most stable H site as a reference; hence, the text and the related figure (Figure 5) on page 11944 should be updated based on the obtained new results. The second error concerns the formulation of Figure 6, where the transverse lines connecting the structures may give the reader the mistaken impression of a proposed reaction path. In reality, we present the reaction energy values for representative structures of each group selected by the <i>k-means</i> clustering method. Regarding the mistake in the production of Figures 5 and 6, the following changes must be applied: On page 11946, the sentence “The CH<sub>4</sub> molecule can adsorb on the nanocluster considering four adsorption configurations, [...]” must be replaced with “The CH<sub>4</sub> molecule can adsorb on the nanocluster considering three adsorption configurations, [...]” and the sentence “[...] C–H bond break on the (CeO<sub>2</sub>)<sub>10</sub> nanocluster can be related to the H adsorption site [...]” must be replaced with “[...] C–H bond break on the (CeO<sub>2</sub>)<sub>10</sub> nanocluster can be related to the coadsorption sites of CH<sub>3</sub> (H)[...]”. The original Figure 5 should be replaced by Figure 5 of this Correction. On page 11944, the sentence “We found four different adsorption modes for CH<sub>4</sub> on (CeO<sub>2</sub>)<sub>10</sub>, namely, umbrella, antiumbrella, scissoring, and modified antiumbrella, as indicated in Figure 5.<sup>66</sup> In the umbrella and antiumbrella modes, the calculated barrier (<i>E</i><sub>a</sub>) for the CH<sub>4</sub> dissociation (CH<sub>4</sub> → CH<sub>3</sub> + H*) indicates a higher cluster reactivity compared to the CeO<sub>2</sub>(111) surface. In this case, we obtained <i>E</i><sub>a</sub> equal to 0.54 eV (<i>E</i><sub>a</sub><sup>ZPE</sup> = 0.48 eV) and 0.59 eV (<i>E</i><sub>a</sub><sup>ZPE</sup> = 0.52 eV)
{"title":"Correction to “Ab Initio Investigation of CH4 Dehydrogenation on a (CeO2)10 Cluster”","authors":"Carina S. T. Peraça, Karla F. Andriani, Maurício J. Piotrowski, Juarez L. F. Da Silva","doi":"10.1021/acs.jpcc.4c07452","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07452","url":null,"abstract":"Unfortunately, we identified two errors in our paper related to the misapplication of the unity bond index–quadratic exponential potential (UBI–QEP) analysis, which became evident through discussions with Dr. Verónica Ganduglia-Pirovano and Dr. Breno L. Galvão (Private communication, March 15, 2024). The first error involves the results used to design Figure 5, where we obtained the activation energy values using the UBI-QEP approximation. In this analysis, we considered the most common adsorption sites reported in the literature for the CeO<sub>2</sub>(111) surface rather than the most stable ones on the ceria cluster. As a result, the dependence between the CH<sub>4</sub> adsorption site and the corresponding CH<sub>3</sub> and/or H sites was not maintained. A more appropriate approach for our purposes would be to conduct a systematic investigation of the coadsorption sites on (CeO<sub>2</sub>)<sub>10</sub>, using a specific adsorption site as a reference and mapping the most stable CH<sub>3</sub> or H sites. Therefore, we implemented the aforementioned approach by mapping the CH<sub>3</sub> sites and fixing the most stable H site as a reference; hence, the text and the related figure (Figure 5) on page 11944 should be updated based on the obtained new results. The second error concerns the formulation of Figure 6, where the transverse lines connecting the structures may give the reader the mistaken impression of a proposed reaction path. In reality, we present the reaction energy values for representative structures of each group selected by the <i>k-means</i> clustering method. Regarding the mistake in the production of Figures 5 and 6, the following changes must be applied: On page 11946, the sentence “The CH<sub>4</sub> molecule can adsorb on the nanocluster considering four adsorption configurations, [...]” must be replaced with “The CH<sub>4</sub> molecule can adsorb on the nanocluster considering three adsorption configurations, [...]” and the sentence “[...] C–H bond break on the (CeO<sub>2</sub>)<sub>10</sub> nanocluster can be related to the H adsorption site [...]” must be replaced with “[...] C–H bond break on the (CeO<sub>2</sub>)<sub>10</sub> nanocluster can be related to the coadsorption sites of CH<sub>3</sub> (H)[...]”. The original Figure 5 should be replaced by Figure 5 of this Correction. On page 11944, the sentence “We found four different adsorption modes for CH<sub>4</sub> on (CeO<sub>2</sub>)<sub>10</sub>, namely, umbrella, antiumbrella, scissoring, and modified antiumbrella, as indicated in Figure 5.<sup>66</sup> In the umbrella and antiumbrella modes, the calculated barrier (<i>E</i><sub>a</sub>) for the CH<sub>4</sub> dissociation (CH<sub>4</sub> → CH<sub>3</sub> + H*) indicates a higher cluster reactivity compared to the CeO<sub>2</sub>(111) surface. In this case, we obtained <i>E</i><sub>a</sub> equal to 0.54 eV (<i>E</i><sub>a</sub><sup>ZPE</sup> = 0.48 eV) and 0.59 eV (<i>E</i><sub>a</sub><sup>ZPE</sup> = 0.52 eV)","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"81 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671110","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c06090
Pallavi Singh, Davide Raffaele Ceratti, Yahel Soffer, Sudipta Bera, Yishay Feldman, Michael Elbaum, Dan Oron, David Cahen, Gary Hodes
Self-healing materials can become game changers for developing sustainable (opto)electronics. APbX3 halide (=X–) perovskites, HaPs, have shown a remarkable ability to self-heal damage. While we demonstrated self-healing in pure HaP compounds, in single crystals, and in polycrystalline thin films (as used in most devices), HaP compositions with multiple A+ (and X–) constituents are preferred for solar cells. We now show self-healing in mixed A+ HaPs. Specifically, if at least 15 atom % of the methylammonium (MA+) A cation is substituted for by guanidinium (Gua+) or acetamidinium (AA+), then the self-healing rate after damage is enhanced. In contrast, replacing MA+ with dimethylammonium (DMA+), comparable in size to Gua+ or AA+, does not alter this rate. Based on the times for self-healing, we infer that the rate-determining step involves short-range diffusion of A+ and/or Pb2+ cations and that the self-healing rate correlates with the strain in the material, the A+ cation dipole moment, and H-bonding between A+ and I–. These insights may offer clues for developing a detailed self-healing mechanism and understanding the kinetics to guide the design of self-healing materials. Fast recovery kinetics are important from the device perspective, as they allow complete recovery in devices during operation or when switched off (LEDs)/in the dark (photovoltaics).
{"title":"Guanidinium Substitution Improves Self-Healing and Photodamage Resilience of MAPbI3","authors":"Pallavi Singh, Davide Raffaele Ceratti, Yahel Soffer, Sudipta Bera, Yishay Feldman, Michael Elbaum, Dan Oron, David Cahen, Gary Hodes","doi":"10.1021/acs.jpcc.4c06090","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06090","url":null,"abstract":"Self-healing materials can become game changers for developing sustainable (opto)electronics. APbX<sub>3</sub> halide (=X<sup>–</sup>) perovskites, HaPs, have shown a remarkable ability to self-heal damage. While we demonstrated self-healing in pure HaP compounds, in single crystals, and in polycrystalline thin films (as used in most devices), HaP compositions with multiple A<sup>+</sup> (and X<sup>–</sup>) constituents are preferred for solar cells. We now show self-healing in mixed A<sup>+</sup> HaPs. Specifically, if at least 15 atom % of the methylammonium (MA<sup>+</sup>) A cation is substituted for by guanidinium (Gua<sup>+</sup>) or acetamidinium (AA<sup>+</sup>), then the self-healing rate after damage is enhanced. In contrast, replacing MA<sup>+</sup> with dimethylammonium (DMA<sup>+</sup>), comparable in size to Gua<sup>+</sup> or AA<sup>+</sup>, does not alter this rate. Based on the times for self-healing, we infer that the rate-determining step involves short-range diffusion of A<sup>+</sup> and/or Pb<sup>2+</sup> cations and that the self-healing rate correlates with the strain in the material, the A<sup>+</sup> cation dipole moment, and H-bonding between A<sup>+</sup> and I<sup>–</sup>. These insights may offer clues for developing a detailed self-healing mechanism and understanding the kinetics to guide the design of self-healing materials. Fast recovery kinetics are important from the device perspective, as they allow complete recovery in devices during operation or when switched off (LEDs)/in the dark (photovoltaics).","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"251 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673687","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c04982
Bruno Schmelz, Kazem Zhour, Susanna Krämer, Mariano Grünebaum, Diddo Diddens, Björn Braunschweig, Hadrián Montes-Campos, Masoud Baghernejad
The molecular arrangement of the electrode/electrolyte interface is crucial for enlarging the electrochemical stability of “water-in-salt” electrolytes in aqueous lithium-ion batteries. Using in situ vibrational sum-frequency generation (SFG) spectroscopy and molecular dynamics (MD) simulations, we investigated the interfacial structure and molecular orientation of water molecules and anions of a LiTFSI-based “water-in-salt” electrolyte as a function of electrode potential. Shifting the electrode potential from positive to negative values induces significant interfacial changes in the structure of the electrolyte species, transitioning from anion surface excess to a water-rich interface. Furthermore, TFSI anions undergo a conformational change from cis to trans at the interface at positive electrode potentials. The results of comprehensive MD simulations support the experimental observations, demonstrating a potentiodynamic change in the number densities of water molecules, TFSI anions, and Li-ions at the interface accompanied by increasing dihedral angles of TFSI anions at higher positive electrode potentials.
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Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c07233
Jinge Han, Jun Tang, Xiaoding Zhang, Yanru Guo, Haochen Tong, Zhigang Zang, Ru Li
In this report, the effect of A-site cations on the lattice thermal conductivity (κL) of nitride perovskites was comparatively studied by first-principles calculations in similar crystal structures, LaWN3 and YWN3. The A-site cation is found to induce notable differences in acoustic (0–125 cm–1) and low-lying optical phonons (125–500 cm–1), which translate into a large κL discrepancy (around 20%). It is worth mentioning that the higher κL of LaWN3 is contributed mostly by atom N in the [WN6] octahedron, although the average W–N bond length is almost identical for LaWN3 and YWN3. Faster group velocity, longer lifetime, and larger Grüneisen parameters in optical branches are observed in LaWN3, which should be ascribed to the longer distance between the cation La and the [WN6] octahedron. Our findings provide a deep understanding of the role of the A-site cation in the thermal conductivity of nitride perovskites.
在本报告中，通过对类似晶体结构 LaWN3 和 YWN3 的第一性原理计算，比较研究了 A 位阳离子对氮化物包晶石晶格热导率（κL）的影响。研究发现，A 位阳离子会引起声子（0-125 cm-1）和低频光学声子（125-500 cm-1）的显著差异，并转化为较大的 κL 差异（约 20%）。值得一提的是，尽管 LaWN3 和 YWN3 的平均 W-N 键长度几乎相同，但 LaWN3 的较高 κL 主要是由 [WN6] 八面体中的原子 N 造成的。在 LaWN3 中观察到了更快的群速度、更长的寿命和更大的光分支格吕尼森参数，这应该归因于阳离子 La 与 [WN6] 八面体之间更长的距离。我们的研究结果有助于深入了解 A 位阳离子在氮化物过氧化物导热性中的作用。
{"title":"Effect of the A-Site Cation on the Lattice Thermal Conductivity of Nitride Perovskites","authors":"Jinge Han, Jun Tang, Xiaoding Zhang, Yanru Guo, Haochen Tong, Zhigang Zang, Ru Li","doi":"10.1021/acs.jpcc.4c07233","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07233","url":null,"abstract":"In this report, the effect of A-site cations on the lattice thermal conductivity (κ<sub>L</sub>) of nitride perovskites was comparatively studied by first-principles calculations in similar crystal structures, LaWN<sub>3</sub> and YWN<sub>3</sub>. The A-site cation is found to induce notable differences in acoustic (0–125 cm<sup>–1</sup>) and low-lying optical phonons (125–500 cm<sup>–1</sup>), which translate into a large κ<sub>L</sub> discrepancy (around 20%). It is worth mentioning that the higher κ<sub>L</sub> of LaWN<sub>3</sub> is contributed mostly by atom N in the [WN<sub>6</sub>] octahedron, although the average W–N bond length is almost identical for LaWN<sub>3</sub> and YWN<sub>3</sub>. Faster group velocity, longer lifetime, and larger Grüneisen parameters in optical branches are observed in LaWN<sub>3</sub>, which should be ascribed to the longer distance between the cation La and the [WN<sub>6</sub>] octahedron. Our findings provide a deep understanding of the role of the A-site cation in the thermal conductivity of nitride perovskites.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"2 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673624","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}
Pub Date : 2024-11-18DOI: 10.1021/acs.jpcc.4c05815
Hongyue Yu, Minchao Liu, Qianqian Lu, Yan Yu, Dongyuan Zhao, Xiaomin Li
Mesoporous metal oxides, which combine the high specific surface area of mesoporous materials with the abundant physicochemical properties of metal elements, have shown significant potential in various fields. However, the development of effective methods for the synthesis of mesoporous metal oxide materials has faced numerous challenges, including rapid hydrolysis of metal precursors, difficulties in synthesis process control, and premature crystallization before mesoporous micelles can coassemble. This Review provides a systematic overview of the current synthesis methodologies for mesoporous metal oxide materials, focusing on two key dimensions: mesopore construction (including hard template, soft template, and template-free methods) and skeleton formation (such as the EISA method, the sol–gel method, and the grinding method). Additionally, this Review offers a detailed classification of mesoporous metal oxide materials based on their components. The current major challenges, along with an outlook on future developments in the synthesis methodologies for mesoporous metal oxides, are discussed.
{"title":"Mesoporous Metal Oxides","authors":"Hongyue Yu, Minchao Liu, Qianqian Lu, Yan Yu, Dongyuan Zhao, Xiaomin Li","doi":"10.1021/acs.jpcc.4c05815","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05815","url":null,"abstract":"Mesoporous metal oxides, which combine the high specific surface area of mesoporous materials with the abundant physicochemical properties of metal elements, have shown significant potential in various fields. However, the development of effective methods for the synthesis of mesoporous metal oxide materials has faced numerous challenges, including rapid hydrolysis of metal precursors, difficulties in synthesis process control, and premature crystallization before mesoporous micelles can coassemble. This Review provides a systematic overview of the current synthesis methodologies for mesoporous metal oxide materials, focusing on two key dimensions: mesopore construction (including hard template, soft template, and template-free methods) and skeleton formation (such as the EISA method, the sol–gel method, and the grinding method). Additionally, this Review offers a detailed classification of mesoporous metal oxide materials based on their components. The current major challenges, along with an outlook on future developments in the synthesis methodologies for mesoporous metal oxides, are discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"169 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665246","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}
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