Pub Date : 2024-06-26DOI: 10.1021/acs.chemmater.4c01087
Ruiyu De, Tiantian Tao, Weiwei Tang, Junbo Gong
Biomineralization is an important strategy for constructing mineral materials with excellent structure and properties. Organic biominerals exquisitely manipulate light, whereas inorganic biominerals are known for their mechanical strength. This progress report discusses the latest advances in the discovery and development of bioorganic molecules and crystalline materials, biomineralization mechanisms, the principles and theory of how ultrastructures produce optical properties, and relevant functional applications in biological and material fields. In particular, the discovery of bioorganic photonic crystalline materials has been remarkably extended from guanine alone to purines, pteridines, and flavins. Additionally, ultrastructural materials that function as light scatterers in living organisms were found to be produced by the nonclassical crystallization mechanism via amorphous precursors and oriented attachment. Further, the new biological function of the ultracompact reflector, composed of isoxanthopterin hollow nanospheres, was disclosed to dynamically adapt to various habitat environments. This report integrates materials and biological sciences to achieve a comprehensive view of organic biomineralization, inspiring the future development of advanced optical materials.
{"title":"Emerging Biomineralization of Organic Photonic Crystalline Materials: Ultrastructure, Formation Mechanism, and Optical Function","authors":"Ruiyu De, Tiantian Tao, Weiwei Tang, Junbo Gong","doi":"10.1021/acs.chemmater.4c01087","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01087","url":null,"abstract":"Biomineralization is an important strategy for constructing mineral materials with excellent structure and properties. Organic biominerals exquisitely manipulate light, whereas inorganic biominerals are known for their mechanical strength. This progress report discusses the latest advances in the discovery and development of bioorganic molecules and crystalline materials, biomineralization mechanisms, the principles and theory of how ultrastructures produce optical properties, and relevant functional applications in biological and material fields. In particular, the discovery of bioorganic photonic crystalline materials has been remarkably extended from guanine alone to purines, pteridines, and flavins. Additionally, ultrastructural materials that function as light scatterers in living organisms were found to be produced by the nonclassical crystallization mechanism via amorphous precursors and oriented attachment. Further, the new biological function of the ultracompact reflector, composed of isoxanthopterin hollow nanospheres, was disclosed to dynamically adapt to various habitat environments. This report integrates materials and biological sciences to achieve a comprehensive view of organic biomineralization, inspiring the future development of advanced optical materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acs.chemmater.4c00555
Topias Jussila, Anish Philip, Víctor Rubio-Giménez, Kim Eklund, Sami Vasala, Pieter Glatzel, Johan Lindén, Teruki Motohashi, Antti J. Karttunen, Rob Ameloot, Maarit Karppinen
Advanced deposition routes are vital for the growth of functional metal–organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal–organic materials. An exquisite example is iron-terephthalate (Fe-BDC), which is one of the most appealing metal–organic framework (MOF) type materials and thus widely studied in bulk form owing to its attractive potential in photocatalysis, biomedicine, and beyond. Resolving the chemistry and structural features of new thin film materials requires an extended selection of characterization and modeling techniques. Here we demonstrate how the unique features of the ALD/MLD grown in situ crystalline Fe-BDC thin films, different from the bulk Fe-BDC MOFs, can be resolved through techniques such as synchrotron grazing-incidence X-ray diffraction (GIXRD), Mössbauer spectroscopy, and resonant inelastic X-ray scattering (RIXS) and crystal structure predictions. The investigations of the Fe-BDC thin films, containing both trivalent and divalent iron, converge toward a novel crystalline Fe(III)-BDC monoclinic phase with space group C2/c and an amorphous Fe(II)-BDC phase. Finally, we demonstrate the excellent thermal stability of our Fe-BDC thin films.
{"title":"Chemical Bonding and Crystal Structure Schemes in Atomic/Molecular Layer Deposited Fe-Terephthalate Thin Films","authors":"Topias Jussila, Anish Philip, Víctor Rubio-Giménez, Kim Eklund, Sami Vasala, Pieter Glatzel, Johan Lindén, Teruki Motohashi, Antti J. Karttunen, Rob Ameloot, Maarit Karppinen","doi":"10.1021/acs.chemmater.4c00555","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00555","url":null,"abstract":"Advanced deposition routes are vital for the growth of functional metal–organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal–organic materials. An exquisite example is iron-terephthalate (Fe-BDC), which is one of the most appealing metal–organic framework (MOF) type materials and thus widely studied in bulk form owing to its attractive potential in photocatalysis, biomedicine, and beyond. Resolving the chemistry and structural features of new thin film materials requires an extended selection of characterization and modeling techniques. Here we demonstrate how the unique features of the ALD/MLD grown in situ crystalline Fe-BDC thin films, different from the bulk Fe-BDC MOFs, can be resolved through techniques such as synchrotron grazing-incidence X-ray diffraction (GIXRD), Mössbauer spectroscopy, and resonant inelastic X-ray scattering (RIXS) and crystal structure predictions. The investigations of the Fe-BDC thin films, containing both trivalent and divalent iron, converge toward a novel crystalline Fe(III)-BDC monoclinic phase with space group <i>C</i>2/<i>c</i> and an amorphous Fe(II)-BDC phase. Finally, we demonstrate the excellent thermal stability of our Fe-BDC thin films.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acs.chemmater.4c00602
Torben Steenbock, Emilia Drescher, Tobias Dittmann, Gabriel Bester
Ultrasmall CdSe quantum dots (QDs) with diameters up to 2 nm show broad photoluminescence (PL) spectra presumably due to emission from band-edge excitons and defect states. However, the origin of the defect emission and the effect of defects on the band-edge excitons is not fully understood. Based on spin–orbit density functional theory and screened configuration interaction singles, we show that Cd-dimer and Se defects form in-gap defect states. In comparison with experiment, we discuss the role of deep and shallow defect states for the PL and cover the dependence of their contributions to the PL with respect to the QD size. Further, we observe that these defects lead to a localization of the molecular orbitals (MOs) involved in the band-edge excitons creating large electric dipoles in the MOs. In the excitonic states, these dipoles cause multiexponential PL decay from the band-edge states with a highly anisotropic polarization of the emission. The polarization is found to be very sensitive with respect to the exact composition of the surface.
直径达 2 纳米的超小型硒化镉量子点（QDs）显示出宽广的光致发光（PL）光谱，这可能是由于带边激子和缺陷态的发射所致。然而，缺陷发射的起源以及缺陷对带边激子的影响尚未完全明了。基于自旋轨道密度泛函理论和屏蔽构型相互作用单子，我们证明了镉-二聚体和硒缺陷会形成隙内缺陷态。通过与实验的比较，我们讨论了深缺陷态和浅缺陷态对光致发光的作用，并涵盖了它们对光致发光的贡献与 QD 尺寸的关系。此外，我们还观察到这些缺陷会导致参与带边激子的分子轨道（MO）局部化，从而在 MO 中产生大的电偶极子。在激子态中，这些偶极子会导致带边态多指数聚光衰减，并产生高度各向异性的极化发射。研究发现，偏振对表面的确切成分非常敏感。
{"title":"How Surface Defects Shape the Excitons and Photoluminescence of Ultrasmall CdSe Quantum Dots","authors":"Torben Steenbock, Emilia Drescher, Tobias Dittmann, Gabriel Bester","doi":"10.1021/acs.chemmater.4c00602","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00602","url":null,"abstract":"Ultrasmall CdSe quantum dots (QDs) with diameters up to 2 nm show broad photoluminescence (PL) spectra presumably due to emission from band-edge excitons and defect states. However, the origin of the defect emission and the effect of defects on the band-edge excitons is not fully understood. Based on spin–orbit density functional theory and screened configuration interaction singles, we show that Cd-dimer and Se defects form in-gap defect states. In comparison with experiment, we discuss the role of deep and shallow defect states for the PL and cover the dependence of their contributions to the PL with respect to the QD size. Further, we observe that these defects lead to a localization of the molecular orbitals (MOs) involved in the band-edge excitons creating large electric dipoles in the MOs. In the excitonic states, these dipoles cause multiexponential PL decay from the band-edge states with a highly anisotropic polarization of the emission. The polarization is found to be very sensitive with respect to the exact composition of the surface.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acs.chemmater.4c01444
Yuyin Li, Zhengtang Luo*, Sara E. Skrabalak* and Yujie Xiong*,
{"title":"High-Entropy Materials in Focus","authors":"Yuyin Li, Zhengtang Luo*, Sara E. Skrabalak* and Yujie Xiong*, ","doi":"10.1021/acs.chemmater.4c01444","DOIUrl":"10.1021/acs.chemmater.4c01444","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-24DOI: 10.1021/acs.chemmater.4c01009
Dhananjeya Kumaar, Matthias Can, Helena Weigand, Olesya Yarema, Simon Wintersteller, Rachel Grange, Vanessa Wood, Maksym Yarema
Phase-change memory (PCM) technology has recently attracted a vivid interest for neuromorphic applications, in-memory computing, and photonic integration due to the tunable refractive index and electrical conductivity between the amorphous and crystalline material states. Despite this, it is increasingly challenging to scale down the device dimensions of conventionally sputtered PCM memory arrays, restricting the implementation of PCM technology in mass applications such as consumer electronics. Here, we report the synthesis and structural study of sub-10 nm Cu–Ge–Te (CGT) nanoparticles as suitable candidates for low-cost and ultrasmall PCM devices. We show that our synthesis approach can accurately control the structure of the CGT colloids, such as composition-tuned CGT amorphous nanoparticles as well as crystalline CGT nanoparticles with trigonal α-GeTe and tetragonal Cu2GeTe3 phases. In situ characterization techniques such as high-temperature X-ray diffraction and X-ray absorption spectroscopy reveal that Cu doping in GeTe improves the thermal properties and amorphous phase stability of the nanoparticles, in addition to nanoscale effects, which enhance the nonvolatility characteristics of CGT nanoparticles even further. Moreover, we demonstrate the thin-film fabrication of CGT nanoparticles and characterize their optical properties with spectroscopic ellipsometry measurements. We reveal that CGT nanoparticle thin films exhibit a negative reflectivity change and have good reflectivity contrast in the near-IR spectrum. Our work promotes the possibility to use PCM in nanoparticle form for applications such as electro-optical switching devices, metalenses, reflectivity displays, and phase-change IR devices.
{"title":"Phase-Controlled Synthesis and Phase-Change Properties of Colloidal Cu–Ge–Te Nanoparticles","authors":"Dhananjeya Kumaar, Matthias Can, Helena Weigand, Olesya Yarema, Simon Wintersteller, Rachel Grange, Vanessa Wood, Maksym Yarema","doi":"10.1021/acs.chemmater.4c01009","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01009","url":null,"abstract":"Phase-change memory (PCM) technology has recently attracted a vivid interest for neuromorphic applications, in-memory computing, and photonic integration due to the tunable refractive index and electrical conductivity between the amorphous and crystalline material states. Despite this, it is increasingly challenging to scale down the device dimensions of conventionally sputtered PCM memory arrays, restricting the implementation of PCM technology in mass applications such as consumer electronics. Here, we report the synthesis and structural study of sub-10 nm Cu–Ge–Te (CGT) nanoparticles as suitable candidates for low-cost and ultrasmall PCM devices. We show that our synthesis approach can accurately control the structure of the CGT colloids, such as composition-tuned CGT amorphous nanoparticles as well as crystalline CGT nanoparticles with trigonal α-GeTe and tetragonal Cu<sub>2</sub>GeTe<sub>3</sub> phases. In situ characterization techniques such as high-temperature X-ray diffraction and X-ray absorption spectroscopy reveal that Cu doping in GeTe improves the thermal properties and amorphous phase stability of the nanoparticles, in addition to nanoscale effects, which enhance the nonvolatility characteristics of CGT nanoparticles even further. Moreover, we demonstrate the thin-film fabrication of CGT nanoparticles and characterize their optical properties with spectroscopic ellipsometry measurements. We reveal that CGT nanoparticle thin films exhibit a negative reflectivity change and have good reflectivity contrast in the near-IR spectrum. Our work promotes the possibility to use PCM in nanoparticle form for applications such as electro-optical switching devices, metalenses, reflectivity displays, and phase-change IR devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-24DOI: 10.1021/acs.chemmater.4c01265
Yuncong Xue, Yu Jin, Yifei Zhang, Fengmin Han, Feng Wang
Supramolecular polymers represent ordered nanostructures that are held together by highly directional noncovalent bonds and can undergo reversible self-assembly. Their noncovalent nature imparts stimuli-responsive character to supramolecular polymers, making them appealing for the development of intelligent soft materials. As compared to the inherent responsiveness originating from the noncovalent connection units, incorporating additional stimuli-responsive units into the monomeric structure allows customization of stimuli-responsiveness for supramolecular polymers. Stimuli-triggered changes at the molecular level can amplify into macroscopic effects at the supramolecular level due to the ordered arrangement of monomers. This review summarizes recent progress on stimuli-triggered transformations in supramolecular polymers, categorizing them into five types: (i) depolymerization into monomers, (ii) transformations within different types of supramolecular polymers, (iii) post-stabilization of supramolecular polymers, (iv) activation of dormant monomers for in situ polymerization, and (v) transient polymerization with programmable lifetimes. Additionally, recent progress in unconventional responsiveness due to coupled equilibria in complex supramolecular systems is outlined. Emphasis is on monomeric structure design principles and accumulated property changes in response to stimuli, aimed at stimulating further research in the stimuli-responsive supramolecular polymer field.
{"title":"Stimuli-Triggered Dynamic Transformations in Supramolecular Polymers","authors":"Yuncong Xue, Yu Jin, Yifei Zhang, Fengmin Han, Feng Wang","doi":"10.1021/acs.chemmater.4c01265","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01265","url":null,"abstract":"Supramolecular polymers represent ordered nanostructures that are held together by highly directional noncovalent bonds and can undergo reversible self-assembly. Their noncovalent nature imparts stimuli-responsive character to supramolecular polymers, making them appealing for the development of intelligent soft materials. As compared to the inherent responsiveness originating from the noncovalent connection units, incorporating additional stimuli-responsive units into the monomeric structure allows customization of stimuli-responsiveness for supramolecular polymers. Stimuli-triggered changes at the molecular level can amplify into macroscopic effects at the supramolecular level due to the ordered arrangement of monomers. This review summarizes recent progress on stimuli-triggered transformations in supramolecular polymers, categorizing them into five types: (i) depolymerization into monomers, (ii) transformations within different types of supramolecular polymers, (iii) post-stabilization of supramolecular polymers, (iv) activation of dormant monomers for <i>in situ</i> polymerization, and (v) transient polymerization with programmable lifetimes. Additionally, recent progress in unconventional responsiveness due to coupled equilibria in complex supramolecular systems is outlined. Emphasis is on monomeric structure design principles and accumulated property changes in response to stimuli, aimed at stimulating further research in the stimuli-responsive supramolecular polymer field.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-24DOI: 10.1021/acs.chemmater.4c01366
Memory Zikhali, Thabo Matthews, Cyril T. Selepe, Siyabonga P. Mbokazi, Nobanathi W. Maxakato
Renewable energy systems have gained remarkable attention as potential green energy sources with escalating energy demand and environmental issues. Direct alcohol fuel cells are potential energy sources with quick start-up, zero emissions, and high power density. However, current electrocatalysts’ poor efficiency and catalytic activity hinder their commercialization. In this study, Pd–Nb metal nanoparticles (MNPs) supported on carbon nano-onions (CNOs) were synthesized using the polyol method for the electro-oxidation of isopropanol and ethanol in an alkaline medium. An inexpensive CNO support was synthesized using the soot-based approach. High-resolution transmission electron microscopy analysis confirmed the successful synthesis of CNOs with a quasi-spherical structure and concentric rings resembling an onion. The Fourier transform infrared spectroscopy analysis confirmed the presence of oxygen moieties on the surface of the CNOs, which were used to anchor the MNPs to the surface of the support. The X-ray photoelectron spectroscopy analysis confirmed the composition of the electrocatalysts and the presence of Pd and Nb in different oxidation states. The synthesized Pd–Nb/CNOs exhibited high catalytic activity and stability for isopropyl alcohol and ethanol electro-oxidation. The addition of Nb to Pd reduced the loading of Pd, thus reducing the cost of the electrocatalyst and improving the physicochemical properties and electrocatalytic activity of Pd toward isopropanol and ethanol electro-oxidation. The increased electrocatalytic activity of Pd–Nb/CNOs is attributed to the increased active sites on the surface of the MNPs and the synergistic effects arising from the CNO support and the Pd–Nb MNPs.
{"title":"Studies on the Catalytic Properties of Palladium–Niobium Electrocatalysts Supported on Carbon Nano-onions toward Isopropanol and Ethanol Electro-oxidation in an Alkaline Medium","authors":"Memory Zikhali, Thabo Matthews, Cyril T. Selepe, Siyabonga P. Mbokazi, Nobanathi W. Maxakato","doi":"10.1021/acs.chemmater.4c01366","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01366","url":null,"abstract":"Renewable energy systems have gained remarkable attention as potential green energy sources with escalating energy demand and environmental issues. Direct alcohol fuel cells are potential energy sources with quick start-up, zero emissions, and high power density. However, current electrocatalysts’ poor efficiency and catalytic activity hinder their commercialization. In this study, Pd–Nb metal nanoparticles (MNPs) supported on carbon nano-onions (CNOs) were synthesized using the polyol method for the electro-oxidation of isopropanol and ethanol in an alkaline medium. An inexpensive CNO support was synthesized using the soot-based approach. High-resolution transmission electron microscopy analysis confirmed the successful synthesis of CNOs with a quasi-spherical structure and concentric rings resembling an onion. The Fourier transform infrared spectroscopy analysis confirmed the presence of oxygen moieties on the surface of the CNOs, which were used to anchor the MNPs to the surface of the support. The X-ray photoelectron spectroscopy analysis confirmed the composition of the electrocatalysts and the presence of Pd and Nb in different oxidation states. The synthesized Pd–Nb/CNOs exhibited high catalytic activity and stability for isopropyl alcohol and ethanol electro-oxidation. The addition of Nb to Pd reduced the loading of Pd, thus reducing the cost of the electrocatalyst and improving the physicochemical properties and electrocatalytic activity of Pd toward isopropanol and ethanol electro-oxidation. The increased electrocatalytic activity of Pd–Nb/CNOs is attributed to the increased active sites on the surface of the MNPs and the synergistic effects arising from the CNO support and the Pd–Nb MNPs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-24DOI: 10.1021/acs.chemmater.4c00756
Tzu-Yang Huang, Zijian Cai, Matthew J. Crafton, Raynald Giovine, Ashlea Patterson, Han-Ming Hau, Justin Rastinejad, Bernardine L. D. Rinkel, Raphaële J. Clément, Gerbrand Ceder, Bryan D. McCloskey
In situ carbon dioxide (CO2) outgassing is a common phenomenon in lithium-ion batteries (LiBs), primarily due to parasitic side reactions at the cathode–electrolyte interface. However, little is known about the chemical origins of the in situ CO2 released from emerging Li-excess cation-disordered rock salt (DRX) cathodes. In this study, we selectively labeled various carbon sources with 13C in cathodes containing a representative DRX material, Li1.2Mn0.4Ti0.4O2 (LMTO), and performed differential electrochemical mass spectrometry (DEMS) during galvanostatic cycling in a carbonate-based electrolyte. When charging LMTO cathodes, electrolyte solvent (EC) decomposition is the dominant source of the CO2 outgassing. The amount of EC-originated CO2 is strongly correlated with the total surface area of carbon black in the electrode, revealing the critical role of electron-conducting carbon additives in the electrolyte degradation mechanisms. In addition, unusual bimodal CO2 evolution during the first cycle is found to originate from carbon black oxidation. Overall, the underlying chemical origin of in situ CO2 release during battery cycling is highly voltage- and cycle-dependent. This work further provides insights into improving the stability of DRX cathodes in LiBs and is envisioned to help guide future relevant material design to mitigate parasitic reactions in DRX-based batteries.
{"title":"Chemical Origin of in Situ Carbon Dioxide Outgassing from a Cation-Disordered Rock Salt Cathode","authors":"Tzu-Yang Huang, Zijian Cai, Matthew J. Crafton, Raynald Giovine, Ashlea Patterson, Han-Ming Hau, Justin Rastinejad, Bernardine L. D. Rinkel, Raphaële J. Clément, Gerbrand Ceder, Bryan D. McCloskey","doi":"10.1021/acs.chemmater.4c00756","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00756","url":null,"abstract":"In situ carbon dioxide (CO<sub>2</sub>) outgassing is a common phenomenon in lithium-ion batteries (LiBs), primarily due to parasitic side reactions at the cathode–electrolyte interface. However, little is known about the chemical origins of the in situ CO<sub>2</sub> released from emerging Li-excess cation-disordered rock salt (DRX) cathodes. In this study, we selectively labeled various carbon sources with <sup>13</sup>C in cathodes containing a representative DRX material, Li<sub>1.2</sub>Mn<sub>0.4</sub>Ti<sub>0.4</sub>O<sub>2</sub> (LMTO), and performed differential electrochemical mass spectrometry (DEMS) during galvanostatic cycling in a carbonate-based electrolyte. When charging LMTO cathodes, electrolyte solvent (EC) decomposition is the dominant source of the CO<sub>2</sub> outgassing. The amount of EC-originated CO<sub>2</sub> is strongly correlated with the total surface area of carbon black in the electrode, revealing the critical role of electron-conducting carbon additives in the electrolyte degradation mechanisms. In addition, unusual bimodal CO<sub>2</sub> evolution during the first cycle is found to originate from carbon black oxidation. Overall, the underlying chemical origin of in situ CO<sub>2</sub> release during battery cycling is highly voltage- and cycle-dependent. This work further provides insights into improving the stability of DRX cathodes in LiBs and is envisioned to help guide future relevant material design to mitigate parasitic reactions in DRX-based batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-23DOI: 10.1021/acs.chemmater.4c00942
Andrzej Nowok, Mirosław Mączka, Anna Gągor, Maciej Ptak, Jan K. Zaręba, Daria Szewczyk, Swaroop Palai, Adam Sieradzki
Hybrid organic–inorganic halides have traditionally been viewed as materials that adopt well-ordered structural phases at low temperatures. In this article, we report a one-dimensional perovskitoid aminoguanidinium lead iodide (AGAPbI3) with a first-order phase transition at 400/369 K (during heating/cooling) that breaks away from this rule. Specifically, we demonstrate that the structural transformation to the low-temperature monoclinic C2/c phase does not entirely suppress the motions associated with the organic AGA+ cation, leading to a phenomenon which we call now a persistent disorder. Indeed, it is still possible to observe pronounced dynamics of its terminal NH2 group at least, which gradually slows down upon cooling and impacts the PbI64– octahedra. As a result, we observe an unusually high activation energy of 0.6 eV related to the low-temperature relaxation dynamics, which is approximately 1 order of magnitude higher than those observed in conventional hybrid halides. We illustrate that the ongoing dynamic processes profoundly influence the temperature-dependent third-harmonic generation response and photoluminescence, the latter of which is characterized by two broad emission peaks with large Stokes shifts. Lastly, we emphasize that AGA+ cations can adopt two symmetry-equivalent positions within the low-temperature phase of AGAPbI3, revealing the ongoing transition between the low-temperature static and high-temperature dynamic disorder types in this hybrid compound.
{"title":"Low-Temperature Persistent Disorder and Lattice Dynamics in a Luminescent 1D Hybrid Lead Halide: Implications and Insights","authors":"Andrzej Nowok, Mirosław Mączka, Anna Gągor, Maciej Ptak, Jan K. Zaręba, Daria Szewczyk, Swaroop Palai, Adam Sieradzki","doi":"10.1021/acs.chemmater.4c00942","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00942","url":null,"abstract":"Hybrid organic–inorganic halides have traditionally been viewed as materials that adopt well-ordered structural phases at low temperatures. In this article, we report a one-dimensional perovskitoid aminoguanidinium lead iodide (AGAPbI<sub>3</sub>) with a first-order phase transition at 400/369 K (during heating/cooling) that breaks away from this rule. Specifically, we demonstrate that the structural transformation to the low-temperature monoclinic <i>C</i>2/<i>c</i> phase does not entirely suppress the motions associated with the organic AGA<sup>+</sup> cation, leading to a phenomenon which we call now a persistent disorder. Indeed, it is still possible to observe pronounced dynamics of its terminal NH<sub>2</sub> group at least, which gradually slows down upon cooling and impacts the PbI<sub>6</sub><sup>4–</sup> octahedra. As a result, we observe an unusually high activation energy of 0.6 eV related to the low-temperature relaxation dynamics, which is approximately 1 order of magnitude higher than those observed in conventional hybrid halides. We illustrate that the ongoing dynamic processes profoundly influence the temperature-dependent third-harmonic generation response and photoluminescence, the latter of which is characterized by two broad emission peaks with large Stokes shifts. Lastly, we emphasize that AGA<sup>+</sup> cations can adopt two symmetry-equivalent positions within the low-temperature phase of AGAPbI<sub>3</sub>, revealing the ongoing transition between the low-temperature static and high-temperature dynamic disorder types in this hybrid compound.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Noble metals often exhibit excellent catalytic activity when downsized into two-dimensional (2D) metals owing to their high atomic utilization and unique electronic properties. However, the controllable formation of 2D metals/support composites with clean interfaces/surfaces for practical applications still remains a synthetic bottleneck, with rather limited cases of 2D metals prepared through metal–support bonds. Herein, we developed a built-in electronic interface-guided method for in situ reduction of preadsorbed Pt atoms into 2D Pt metals along the surface of 2D nitrogen-doped carbon (NC) support through the electronic interaction at nonbonded metal–support interface. The interfacial electron exchange, driven by the difference in work functions between 2D Pt metals and NC support, enables the controllable synthesis of 2D Pt-based Schottky heterojunctions with clean interfaces/surfaces and a mean Pt thickness of 1.3 nm. Both experimental and theoretical results confirm the enhanced electron exchange at the interface between 2D Pt and the 2D NC support, resulting in a doubled electron density for 2D Pt. Consequently, the electron-rich 2D Pt metals exhibit remarkable mass activity of 67.3 A mgPt–1 for the hydrogen evolution reaction (HER) and a turnover frequency (TOF) value of 117 h–1 in the electrocatalytic hydrogenation of phenol, notably outperforming those of the commercial Pt/C catalyst by a factor of 16.8 and 4.0, respectively. Our efficient built-in electronic interface-guided method not only facilitates the synthesis of novel 2D metal/2D support Schottky heterojunctions but also lays the groundwork for designing more powerful electronic interface catalysts with enhanced and diversified functionalities.
{"title":"2D Pt Metals at Rectifying Interface with Pronounced Negative Charge Density for Electrocatalytic Reduction Reactions","authors":"Peng Gao, Zhouhong Ren, Qi-Yuan Li, Shi-Nan Zhang, Qian-Yu Liu, Jing-Wen Li, Wei-Yao Hu, Panzhe Qiao, Dong Xu, Si-Yuan Xia, Xi Liu, Jie-Sheng Chen, Xin-Hao Li","doi":"10.1021/acs.chemmater.4c01226","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01226","url":null,"abstract":"Noble metals often exhibit excellent catalytic activity when downsized into two-dimensional (2D) metals owing to their high atomic utilization and unique electronic properties. However, the controllable formation of 2D metals/support composites with clean interfaces/surfaces for practical applications still remains a synthetic bottleneck, with rather limited cases of 2D metals prepared through metal–support bonds. Herein, we developed a built-in electronic interface-guided method for in situ reduction of preadsorbed Pt atoms into 2D Pt metals along the surface of 2D nitrogen-doped carbon (NC) support through the electronic interaction at nonbonded metal–support interface. The interfacial electron exchange, driven by the difference in work functions between 2D Pt metals and NC support, enables the controllable synthesis of 2D Pt-based Schottky heterojunctions with clean interfaces/surfaces and a mean Pt thickness of 1.3 nm. Both experimental and theoretical results confirm the enhanced electron exchange at the interface between 2D Pt and the 2D NC support, resulting in a doubled electron density for 2D Pt. Consequently, the electron-rich 2D Pt metals exhibit remarkable mass activity of 67.3 A mg<sub>Pt</sub><sup>–1</sup> for the hydrogen evolution reaction (HER) and a turnover frequency (TOF) value of 117 h<sup>–1</sup> in the electrocatalytic hydrogenation of phenol, notably outperforming those of the commercial Pt/C catalyst by a factor of 16.8 and 4.0, respectively. Our efficient built-in electronic interface-guided method not only facilitates the synthesis of novel 2D metal/2D support Schottky heterojunctions but also lays the groundwork for designing more powerful electronic interface catalysts with enhanced and diversified functionalities.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141441624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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