Pub Date : 2025-04-12DOI: 10.1021/acs.jpcc.4c08302
Piqiang Tan, Zhiyong Chen, Xiang Liu, Chaojie Yao
High-nickel layered oxide materials have become some of the most important cathode materials for lithium–ion batteries (LIBs). Despite their high capacity, they also intensify safety concerns, resulting in reduced reliability of LIBs. Hence, NCM811 was developed to stabilize the structure, enhance reliability, and ensure a high energy density. Herein, we proposed a new criterion for assessing the reliability of LIBs, focusing on lattice distortion, oxygen evolution, and cation mixing of NCM811 under high voltage and elevated temperature conditions. To validate the evaluation criteria, NCM811 was further doped, with the optimal dopant determined through a stepwise pruning process by using density functional theory calculations. Specifically, a consecutive stepwise screening process is implemented for 39 candidate dopants to inspect their validity in reducing lattice distortion and inhibiting oxygen evolution and cation mixing. Furthermore, the role of dopants is examined through electronic structure analysis, highlighting their influence on the materials. Our work not only puts forward a paradigm for the highly effective screening of dopants in NCM811 materials but also clarifies the role of dopants and provides valuable insights for improving the reliability of LIBs.
{"title":"Stepwise Screening Process for Further Dopant of NCM811 Cathode Material to Enhance the Reliability of Lithium–Ion Batteries","authors":"Piqiang Tan, Zhiyong Chen, Xiang Liu, Chaojie Yao","doi":"10.1021/acs.jpcc.4c08302","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08302","url":null,"abstract":"High-nickel layered oxide materials have become some of the most important cathode materials for lithium–ion batteries (LIBs). Despite their high capacity, they also intensify safety concerns, resulting in reduced reliability of LIBs. Hence, NCM811 was developed to stabilize the structure, enhance reliability, and ensure a high energy density. Herein, we proposed a new criterion for assessing the reliability of LIBs, focusing on lattice distortion, oxygen evolution, and cation mixing of NCM811 under high voltage and elevated temperature conditions. To validate the evaluation criteria, NCM811 was further doped, with the optimal dopant determined through a stepwise pruning process by using density functional theory calculations. Specifically, a consecutive stepwise screening process is implemented for 39 candidate dopants to inspect their validity in reducing lattice distortion and inhibiting oxygen evolution and cation mixing. Furthermore, the role of dopants is examined through electronic structure analysis, highlighting their influence on the materials. Our work not only puts forward a paradigm for the highly effective screening of dopants in NCM811 materials but also clarifies the role of dopants and provides valuable insights for improving the reliability of LIBs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"218 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823031","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}
Perovskite solar cells (PSCs) have gained considerable attention in recent years as highly efficient and low-cost alternative to conventional photovoltaic technologies. In this study, we focus on CsPbBr3-based PSCs, through a combination of numerical simulations and experimental validation to explore their potential under illumination. We systematically investigated various charge transport layers, the highest PCE of 8.34% achieved using TiO2 as the ETL with Spiro-OMeTAD serving as the HTL in combination with the CsPbBr3 absorber layer. By analyzing energy band diagrams, we assessed the influence of absorber layer thickness, acceptor density, and defect densities on device efficiency, presenting the results as contour plots. We optimized these parameters, including interfacial defect densities at both the ETL/absorber and absorber/HTL interfaces using a simulation approach. Furthermore, we examined the effects of electron affinity, temperature, series and shunt resistance, capacitance, Mott–Schottky characteristics, generation rate, and recombination rate to gain a deeper understanding of the optimized device’s performance. Subsequently, we experimentally fabricated CsPbBr3-based PSC devices using a one-step spin deposition technique, which is the first attempt of its kind for this material system, to the best of our knowledge. The CsPbBr3 films were analyzed by using XRD, SEM with EDX, UV–visible, and PL spectroscopy. We then fabricated the devices based on the optimized design from our simulations and measured J–V characteristics and EQE curves. The performance of the experimental devices was further validated by the simulation outcomes for the CsPbBr3-based PSC device. The present work underscores the potential of PSCs based on CsPbBr3 and offers significant perspectives for their enhancement and subsequent progress in the field of photovoltaics.
{"title":"Numerical and Experimental Validation of CsPbBr3 Perovskite Solar Cells: Insights on a One-Step Deposition Technique","authors":"Soumya Sundar Parui, Krishnapressad Vijayan, Nithin Xavier, R Ramesh Babu, Vipul Kheraj","doi":"10.1021/acs.jpcc.4c07209","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07209","url":null,"abstract":"Perovskite solar cells (PSCs) have gained considerable attention in recent years as highly efficient and low-cost alternative to conventional photovoltaic technologies. In this study, we focus on CsPbBr<sub>3</sub>-based PSCs, through a combination of numerical simulations and experimental validation to explore their potential under illumination. We systematically investigated various charge transport layers, the highest PCE of 8.34% achieved using TiO<sub>2</sub> as the ETL with Spiro-OMeTAD serving as the HTL in combination with the CsPbBr<sub>3</sub> absorber layer. By analyzing energy band diagrams, we assessed the influence of absorber layer thickness, acceptor density, and defect densities on device efficiency, presenting the results as contour plots. We optimized these parameters, including interfacial defect densities at both the ETL/absorber and absorber/HTL interfaces using a simulation approach. Furthermore, we examined the effects of electron affinity, temperature, series and shunt resistance, capacitance, Mott–Schottky characteristics, generation rate, and recombination rate to gain a deeper understanding of the optimized device’s performance. Subsequently, we experimentally fabricated CsPbBr<sub>3</sub>-based PSC devices using a one-step spin deposition technique, which is the first attempt of its kind for this material system, to the best of our knowledge. The CsPbBr<sub>3</sub> films were analyzed by using XRD, SEM with EDX, UV–visible, and PL spectroscopy. We then fabricated the devices based on the optimized design from our simulations and measured <i>J</i>–<i>V</i> characteristics and EQE curves. The performance of the experimental devices was further validated by the simulation outcomes for the CsPbBr<sub>3</sub>-based PSC device. The present work underscores the potential of PSCs based on CsPbBr<sub>3</sub> and offers significant perspectives for their enhancement and subsequent progress in the field of photovoltaics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"60 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820025","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 : 2025-04-11DOI: 10.1021/acs.jpcc.4c08516
Takashi Tsuji, Yoshihito Machida, Steven De Feyter, Kazukuni Tahara, Yoshito Tobe
One of the important aspects of self-assembled molecular networks (SAMNs) formed at the liquid–solid interfaces is the structural switching of SAMNs induced by external adsorbates, which serve as supramolecular guest molecules. However, guest-induced structural changes are not diverse, mostly switching from close-packed, nonporous patterns to porous patterns through an increase in the number and ordering of adsorbed alkyl chains of the stretched configuration accompanying few changes in the number of guest molecules. To achieve structural switching in response to multiguest molecules, we designed a building block DBA-DYN which has three alkyl chains. Each chain contains a stiff 1,3-butadiyne unit and a carbonyl group, imparting conformational dynamism and enabling hydrogen bonding, respectively. At the 1-phenyloctane–graphite interface, DBA-DYN forms closely packed networks in the absence of guests, with its alkyl chains adopting different conformations. In the presence of coronene (COR) used as a guest molecule, however, the SAMN structure transforms into a porous form comprising six DBA-DYN molecules in all-transoid geometry, where a large number of COR molecules are confined. Conversely, six molecules of triangular guest (DBA) are immobilized in a smaller space of the network formed by three DBA-DYN molecules in which alkyl chains are hydrogen-bonded, adopting an all-cisoid geometry. For the guest-dependent SAMN structure switching to occur, the carbonyl group of the diynone unit plays a crucial role through specific hydrogen bonds, both between DBA-DYN molecules and between DBA-DYN and COR guest molecules.
{"title":"Multiguest-Induced Structural Switching in a Self-Assembled Monolayer Network at the Liquid–Solid Interface","authors":"Takashi Tsuji, Yoshihito Machida, Steven De Feyter, Kazukuni Tahara, Yoshito Tobe","doi":"10.1021/acs.jpcc.4c08516","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08516","url":null,"abstract":"One of the important aspects of self-assembled molecular networks (SAMNs) formed at the liquid–solid interfaces is the structural switching of SAMNs induced by external adsorbates, which serve as supramolecular guest molecules. However, guest-induced structural changes are not diverse, mostly switching from close-packed, nonporous patterns to porous patterns through an increase in the number and ordering of adsorbed alkyl chains of the stretched configuration accompanying few changes in the number of guest molecules. To achieve structural switching in response to multiguest molecules, we designed a building block <b>DBA-DYN</b> which has three alkyl chains. Each chain contains a stiff 1,3-butadiyne unit and a carbonyl group, imparting conformational dynamism and enabling hydrogen bonding, respectively. At the 1-phenyloctane–graphite interface, <b>DBA-DYN</b> forms closely packed networks in the absence of guests, with its alkyl chains adopting different conformations. In the presence of coronene (<b>COR</b>) used as a guest molecule, however, the SAMN structure transforms into a porous form comprising six <b>DBA-DYN</b> molecules in all-transoid geometry, where a large number of <b>COR</b> molecules are confined. Conversely, six molecules of triangular guest (<b>DBA</b>) are immobilized in a smaller space of the network formed by three <b>DBA-DYN</b> molecules in which alkyl chains are hydrogen-bonded, adopting an all-cisoid geometry. For the guest-dependent SAMN structure switching to occur, the carbonyl group of the diynone unit plays a crucial role through specific hydrogen bonds, both between <b>DBA-DYN</b> molecules and between <b>DBA-DYN</b> and <b>COR</b> guest molecules.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"274 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823041","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 : 2025-04-11DOI: 10.1021/acs.jpcc.5c00763
Akrema, Ruby Phul, Ahmet Faruk Yazıcı, Zeynep Senel, Talha Erdem
Electrostatic self-assembly is one of the important self-assembly mechanisms that found use in optoelectronics. Although this method enables realizing unconventional architectures, producing complicated architectures in large areas requires local control over the self-assembly process. One of the ways to achieve this control is to provide enough kinetic energy to the self-assembling nanoparticles so that they can escape electrostatic attraction. We hypothesize that this energy can be delivered to the nanoparticles by treating them with light that can be absorbed by the particles. Here, we test this idea to tailor the electrostatic self-assembly of semiconductor quantum dots (QDs) using a laser. Employing fluorescence and atomic force microscopy, we demonstrate that the QDs are not attached to the substrate in regions where they are exposed to light while they are coated in the absence of optical excitation. We further conduct theoretical analysis to show that elevated temperatures indeed allow the QDs to escape the electrostatic attraction of the charged polymers on the surface. We also demonstrate that increasing the temperature during the coating process without irradiating the sample gives similar results as the case when the sample was irradiated. Finally, we fabricate an uncoated region on the self-assembled QD film with dimensions of ∼200 μm × 0.5 cm to demonstrate the feasibility of our approach to control the bottom-up self-assembly. We believe that our results may pave the way for a cost-effective and sustainable approach for the fabrication of nanoelectronic and optoelectronic devices.
{"title":"Light-Controlled Electrostatic Self-Assembly of Quantum Dots","authors":"Akrema, Ruby Phul, Ahmet Faruk Yazıcı, Zeynep Senel, Talha Erdem","doi":"10.1021/acs.jpcc.5c00763","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00763","url":null,"abstract":"Electrostatic self-assembly is one of the important self-assembly mechanisms that found use in optoelectronics. Although this method enables realizing unconventional architectures, producing complicated architectures in large areas requires local control over the self-assembly process. One of the ways to achieve this control is to provide enough kinetic energy to the self-assembling nanoparticles so that they can escape electrostatic attraction. We hypothesize that this energy can be delivered to the nanoparticles by treating them with light that can be absorbed by the particles. Here, we test this idea to tailor the electrostatic self-assembly of semiconductor quantum dots (QDs) using a laser. Employing fluorescence and atomic force microscopy, we demonstrate that the QDs are not attached to the substrate in regions where they are exposed to light while they are coated in the absence of optical excitation. We further conduct theoretical analysis to show that elevated temperatures indeed allow the QDs to escape the electrostatic attraction of the charged polymers on the surface. We also demonstrate that increasing the temperature during the coating process without irradiating the sample gives similar results as the case when the sample was irradiated. Finally, we fabricate an uncoated region on the self-assembled QD film with dimensions of ∼200 μm × 0.5 cm to demonstrate the feasibility of our approach to control the bottom-up self-assembly. We believe that our results may pave the way for a cost-effective and sustainable approach for the fabrication of nanoelectronic and optoelectronic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"218 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820151","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 : 2025-04-11DOI: 10.1021/acs.jpcc.5c00445
Wei Wang, Daniel Rosenmann, Yuzi Liu, Xuedan Ma, Wooje Cho, Joshua Portner, Ruiming Lin, Dmitri V. Talapin, Ralu Divan, David J. Gosztola, Stephen K. Gray, Gary P. Wiederrecht
Exciton-plasmon coupling in nanomaterials produces many relevant phenomena for photonics applications including increased light-matter interactions, enhanced radiative rates of quantum emitters, and coherent energy exchange. In the case of exciton coupling to surface plasmon polaritons (SPPs), dispersive interactions controlled by the wavevector of optical excitation create the opportunity for tunable optical emission. Strong temporal impacts on exciton lifetimes can also occur in coupled systems, creating the opportunity for ultrafast control of exciton lifetime via changes in electronic coupling magnitude to a dispersive SPP. The coupling strength can be impacted by the morphology of the nanomaterials. Here, we utilize colloidal semiconductor nanoplatelets deposited onto thin silver plasmonic films, and compare the results to semiconductor quantum dots deposited on the silver films. We map the dispersion of the coupled systems and measure the ultrafast transient absorption response of the coupled systems. Due to the larger interaction areas of the nanoplatelets that lie flat on the silver films, a greater degree of coupling is found for the nanoplatelets, and much faster temporal responses are found as compared to quantum dots. Fresnel theory calculations that incorporate heavy and light hole features can reproduce the dispersion of the nanoplatelet-silver film, and a simple three-state model is developed to provide insights into the nature of the coupling at different photon energies along the dispersion curve.
{"title":"Ultrafast Dynamics of Plasmon-Coupled Excitons in Semiconducting Nanoplatelets","authors":"Wei Wang, Daniel Rosenmann, Yuzi Liu, Xuedan Ma, Wooje Cho, Joshua Portner, Ruiming Lin, Dmitri V. Talapin, Ralu Divan, David J. Gosztola, Stephen K. Gray, Gary P. Wiederrecht","doi":"10.1021/acs.jpcc.5c00445","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00445","url":null,"abstract":"Exciton-plasmon coupling in nanomaterials produces many relevant phenomena for photonics applications including increased light-matter interactions, enhanced radiative rates of quantum emitters, and coherent energy exchange. In the case of exciton coupling to surface plasmon polaritons (SPPs), dispersive interactions controlled by the wavevector of optical excitation create the opportunity for tunable optical emission. Strong temporal impacts on exciton lifetimes can also occur in coupled systems, creating the opportunity for ultrafast control of exciton lifetime via changes in electronic coupling magnitude to a dispersive SPP. The coupling strength can be impacted by the morphology of the nanomaterials. Here, we utilize colloidal semiconductor nanoplatelets deposited onto thin silver plasmonic films, and compare the results to semiconductor quantum dots deposited on the silver films. We map the dispersion of the coupled systems and measure the ultrafast transient absorption response of the coupled systems. Due to the larger interaction areas of the nanoplatelets that lie flat on the silver films, a greater degree of coupling is found for the nanoplatelets, and much faster temporal responses are found as compared to quantum dots. Fresnel theory calculations that incorporate heavy and light hole features can reproduce the dispersion of the nanoplatelet-silver film, and a simple three-state model is developed to provide insights into the nature of the coupling at different photon energies along the dispersion curve.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820150","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}
Calcium sulfide (CaS) is a semiconductor with excellent optoelectronic properties and its electronic structures are readily modulated by applying pressure. Here, we conduct in situ X-ray diffraction and ultraviolet–visible light spectroscopy experiments to investigate the evolution of band gap across the phase transition from B1 to B2 type structures. Upon pressurizing to 50 GPa, we observe the band gap decreased from the initial 3.51 to 1.18 eV. Through first-principles calculations, we reveal that the band gap narrowing is driven by a pressure-induced direct-to-indirect transition, accompanied by enhanced interactions between S 3p and Ca 3d states. Releasing pressure to ambient conditions recover the band gap, implying a fully reversible phase transition. Our results suggest that pressure-induced polymorphism and bandgap engineering tune the electronic properties of CaS, making it a promising optoelectronic material in the visible to deep-ultraviolet spectral regions.
{"title":"Bandgap Engineering in Pressurized Calcium Sulfide","authors":"Longfei Gong, Songsong Han, Songhao Guo, Zhikai Zhu, Hongliang Dong, Yihuai Li, Zihua Wu, Xujie Lü, Qingyang Hu","doi":"10.1021/acs.jpcc.5c00061","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00061","url":null,"abstract":"Calcium sulfide (CaS) is a semiconductor with excellent optoelectronic properties and its electronic structures are readily modulated by applying pressure. Here, we conduct in situ X-ray diffraction and ultraviolet–visible light spectroscopy experiments to investigate the evolution of band gap across the phase transition from B1 to B2 type structures. Upon pressurizing to 50 GPa, we observe the band gap decreased from the initial 3.51 to 1.18 eV. Through first-principles calculations, we reveal that the band gap narrowing is driven by a pressure-induced direct-to-indirect transition, accompanied by enhanced interactions between S 3p and Ca 3d states. Releasing pressure to ambient conditions recover the band gap, implying a fully reversible phase transition. Our results suggest that pressure-induced polymorphism and bandgap engineering tune the electronic properties of CaS, making it a promising optoelectronic material in the visible to deep-ultraviolet spectral regions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820026","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 : 2025-04-11DOI: 10.1021/acs.jpcc.5c01131
Philipp Werner, Andika Asyuda, Adrian Wiesner, Martin Kind, Michael Zharnikov, Andreas Terfort
We present a series of custom-designed, perfluorophenyl (PFP)-based molecular films on gold, in which the terminal PFP unit, coupled to the thiolate anchoring group via a cystamine linker (CA), is additionally decorated with various polar groups (R), such as −CF3, −SCF3, −CN, and −CH3. The basic characterization of the series with several complementary experimental tools shows that, on Au(111), the CA-R molecules form self-assembled monolayers (SAMs) with dense packing and high orientation. The structural parameters of these SAMs are nearly independent of R, implying that their work function (WF) can be exclusively associated with the identity of R. This was indeed the case, with the WF value varying from 5.5 to 5.6 eV for the electron-withdrawing −CF3 and −SCF3 groups to ∼4.9 eV for the electron-donating −CH3 group. Surprisingly, the CA-CN SAM, bearing electron-withdrawing nitrile groups, showed a similar work function as CA-CH3 – an effect that was observed earlier for other CN-terminated aromatic SAMs as well, and is tentatively explained by a redistribution of electron density due to the conjugation of the CN orbitals with the adjacent aromatic ring. This SAM features lower hydrophobicity than the other CA-R monolayers, which might be useful to provide a better match to a deposited organic material.
{"title":"Tail Group Engineering in Perfluorophenyl-Based Self-Assembled Monolayers","authors":"Philipp Werner, Andika Asyuda, Adrian Wiesner, Martin Kind, Michael Zharnikov, Andreas Terfort","doi":"10.1021/acs.jpcc.5c01131","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01131","url":null,"abstract":"We present a series of custom-designed, perfluorophenyl (PFP)-based molecular films on gold, in which the terminal PFP unit, coupled to the thiolate anchoring group via a cystamine linker (CA), is additionally decorated with various polar groups (R), such as −CF<sub>3</sub>, −SCF<sub>3</sub>, −CN, and −CH<sub>3</sub>. The basic characterization of the series with several complementary experimental tools shows that, on Au(111), the CA-R molecules form self-assembled monolayers (SAMs) with dense packing and high orientation. The structural parameters of these SAMs are nearly independent of R, implying that their work function (WF) can be exclusively associated with the identity of R. This was indeed the case, with the WF value varying from 5.5 to 5.6 eV for the electron-withdrawing −CF<sub>3</sub> and −SCF<sub>3</sub> groups to ∼4.9 eV for the electron-donating −CH<sub>3</sub> group. Surprisingly, the CA-CN SAM, bearing electron-withdrawing nitrile groups, showed a similar work function as CA-CH<sub>3</sub> – an effect that was observed earlier for other CN-terminated aromatic SAMs as well, and is tentatively explained by a redistribution of electron density due to the conjugation of the CN orbitals with the adjacent aromatic ring. This SAM features lower hydrophobicity than the other CA-R monolayers, which might be useful to provide a better match to a deposited organic material.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"19 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820027","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 : 2025-04-11DOI: 10.1021/acs.jpcc.5c02312
Basil Raju Karimadom, Dan Meyerstein, Amir Mizrahi, Haya Kornweitz
The calculated surface pKa (*pKa) values were originally underestimated (contained in Table 1, Table 2, Table 3, Table S4 and Figure 2), and the corrected values are given in Table 1 and the corrected Figure 2 below. The correction in values is due to the usage of the incorrect value of gas constant R in eq 10 for calculating *pKa. The recalculated values shifted toward lower values than the previous values, and it shows the strong acid behavior of weak acids on the metal–aqueous interface than those in the homogeneous solution. Hence, the corrections do not change the data conclusion in the original manuscript. Figure 2. Corrected *pKa of acids on M(111) surfaces. The *pKa cannot be calculated on the Au surface as H3O+ is not adsorbed on the Au surface. The *pKa at 0.019 particle/Å coverage is −10.62 and at 0.038 particle/Å coverage is 8.68. This article has not yet been cited by other publications.
{"title":"Correction: “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.5c02312","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02312","url":null,"abstract":"The calculated surface p<i>K</i><sub>a</sub> (*p<i>K</i><sub>a</sub>) values were originally underestimated (contained in Table 1, Table 2, Table 3, Table S4 and Figure 2), and the corrected values are given in Table 1 and the corrected Figure 2 below. The correction in values is due to the usage of the incorrect value of gas constant <i>R</i> in eq 10 for calculating *p<i>K</i><sub>a</sub>. The recalculated values shifted toward lower values than the previous values, and it shows the strong acid behavior of weak acids on the metal–aqueous interface than those in the homogeneous solution. Hence, the corrections do not change the data conclusion in the original manuscript<named-content content-type=\"anchor\" r type=\"simple\"></named-content>. Figure 2. Corrected *p<i>K</i><sub>a</sub> of acids on M(111) surfaces. The *p<i>K</i><sub>a</sub> cannot be calculated on the Au surface as H<sub>3</sub>O<sup>+</sup> is not adsorbed on the Au surface. The *p<i>K</i><sub>a</sub> at 0.019 particle/Å coverage is −10.62 and at 0.038 particle/Å coverage is 8.68. This article has not yet been cited by other publications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"25 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820152","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 : 2025-04-11DOI: 10.1021/acs.jpcc.5c00275
Bin Wang, Edurne Redondo, Lewis W. Le Fevre, Adam Brookfield, Eric J. L. McInnes, Robert A. W. Dryfe
The rapid voltage and capacity fade of the otherwise promising Ni-rich layered LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode are the primary obstacles to its successful commercialization in lithium-ion batteries (LIBs). Here, in situ electrochemical electron paramagnetic resonance (EPR) spectroscopy is employed to gain insight into the cation redox behavior of the NMC811 cathode during the cell charge/discharge process. Different oxidation states of Ni ions are detected by variations in the signal of the EPR spectra. Ex situ studies of NMC811 at different SOC levels also confirm changes in the local Mn–Ni environment. A comparison of in situ studies on fresh and cycled NMC811 electrodes demonstrates that the fundamental redox processes remain unchanged upon cycling of the material. Finally, dissolved Mn and Co ions from the bulk are found using ex situ EPR characterization of the cycled cathode and separator. The dissolution of these metal ions can accelerate the degradation of the entire battery.
{"title":"Evolution of LiNi0.8Mn0.1Co0.1O2 (NMC811) Cathodes for Li-Ion Batteries: An In Situ Electron Paramagnetic Resonance Study","authors":"Bin Wang, Edurne Redondo, Lewis W. Le Fevre, Adam Brookfield, Eric J. L. McInnes, Robert A. W. Dryfe","doi":"10.1021/acs.jpcc.5c00275","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00275","url":null,"abstract":"The rapid voltage and capacity fade of the otherwise promising Ni-rich layered LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NMC811) cathode are the primary obstacles to its successful commercialization in lithium-ion batteries (LIBs). Here, <i>in situ</i> electrochemical electron paramagnetic resonance (EPR) spectroscopy is employed to gain insight into the cation redox behavior of the NMC811 cathode during the cell charge/discharge process. Different oxidation states of Ni ions are detected by variations in the signal of the EPR spectra. <i>Ex situ</i> studies of NMC811 at different SOC levels also confirm changes in the local Mn–Ni environment. A comparison of <i>in situ</i> studies on fresh and cycled NMC811 electrodes demonstrates that the fundamental redox processes remain unchanged upon cycling of the material. Finally, dissolved Mn and Co ions from the bulk are found using <i>ex situ</i> EPR characterization of the cycled cathode and separator. The dissolution of these metal ions can accelerate the degradation of the entire battery.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"90 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820149","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}
In order to enhance the performance of microwave-absorbing materials, the development of light, broad, and strong wave-absorbing solid materials has become a research focus at present. In recent years, Prussian blue analogs (PBAs), as members of MOFs, have received widespread attention as precursors for absorbing materials due to their adjustable composition and simple synthesis. We created a ZnO/ZnFe2O4/rGO aerogel by mixing ZnFe-PBA with a light GO aerogel using a basic carbonization and hydrothermal reaction. It has the advantage of ferrite’s high magnetic loss, while overcoming the disadvantages of its high density and narrow absorption bandwidth. The ZnO/ZnFe2O4/rGO aerogel is effective at absorbing waves because they have a three-dimensional network structure and interfaces made up of different types of materials. By introducing different ratios of ZnFe-PBA to GO, the electromagnetic parameters and impedance matching were modified, giving the material excellent microwave absorbing properties in the 2−40 GHz range. The lowest reflection loss (RL) of −61.6 dB with a maximum effective absorption bandwidth (EAB) of 26.78 GHz can be achieved by adjusting the absorber thickness with a filling volume of only 15 wt %. The results show that the ZnO/ZnFe2O4/rGO will enrich the research on MOF derivatives in microwave absorption.
{"title":"High-Performance Microwave-Absorbing Materials Based on Bimetallic Organic Framework/Graphene Composite","authors":"Heng Gao, Danfeng Zhang, Ruhao Yang, Guoxun Zeng, Qibai Wu, Haiyan Zhang","doi":"10.1021/acs.jpcc.4c08313","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08313","url":null,"abstract":"In order to enhance the performance of microwave-absorbing materials, the development of light, broad, and strong wave-absorbing solid materials has become a research focus at present. In recent years, Prussian blue analogs (PBAs), as members of MOFs, have received widespread attention as precursors for absorbing materials due to their adjustable composition and simple synthesis. We created a ZnO/ZnFe<sub>2</sub>O<sub>4</sub>/rGO aerogel by mixing ZnFe-PBA with a light GO aerogel using a basic carbonization and hydrothermal reaction. It has the advantage of ferrite’s high magnetic loss, while overcoming the disadvantages of its high density and narrow absorption bandwidth. The ZnO/ZnFe<sub>2</sub>O<sub>4</sub>/rGO aerogel is effective at absorbing waves because they have a three-dimensional network structure and interfaces made up of different types of materials. By introducing different ratios of ZnFe-PBA to GO, the electromagnetic parameters and impedance matching were modified, giving the material excellent microwave absorbing properties in the 2−40 GHz range. The lowest reflection loss (RL) of −61.6 dB with a maximum effective absorption bandwidth (EAB) of 26.78 GHz can be achieved by adjusting the absorber thickness with a filling volume of only 15 wt %. The results show that the ZnO/ZnFe<sub>2</sub>O<sub>4</sub>/rGO will enrich the research on MOF derivatives in microwave absorption.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"37 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823032","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：