ACS Materials Au最新文献

{"title":"Self-Healing Engineered Multilayer Coatings for Corrosion Protection of Magnesium Alloy AZ31B.","authors":"Mario Aparicio, Jadra Mosa, Miguel Gómez-Herrero, Zainab Abd Al-Jaleel, Jennifer Guzman, Mihaela Jitianu, Lisa C Klein, Andrei Jitianu","doi":"10.1021/acsmaterialsau.4c00170","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00170","url":null,"abstract":"<p><p>Nonporous, crack-free hybrid glass coatings have provided excellent corrosion protection to the AZ31B magnesium alloy. However, if a crack develops in the coatings, then corrosion will proliferate at that point. The novelty of this study consists of engineering a bilayer protection system that combines the \"barrier\" properties of the hybrid glass coatings with the \"inhibitor\" or \"self-healing\" effect of an internal layer of mesoporous silica doped with cerium(III) ions. The mesoporous layer was obtained using a sol-gel solution with 1 mol % cerium(III) ions. The inner cerium-doped mesoporous coating has a thickness of 0.25 μm, and the electrochemical characterization through Open circuit potential (OCP) and Electrochemical Impedance Spectroscopy (EIS) indicates a corrosion inhibition process provided by cerium(III) ions triggered by the corrosion. The combination of the Ce-doped and hybrid glass coatings reaches a total thickness of 5.1 μm. The corrosion evaluation through OCP and EIS does not show any evidence of corrosion during the first 575 h of immersion. After this, there are several steps of a sudden drop in potential and subsequent recovery of the previous values, which could be associated with the activation of the corrosion inhibition mechanism provided by the Ce (III) ions. EIS show a maximum impedance module of 10^6.7 Ohm cm², a decrease of impedance values and phase angle fluctuations after the potential drops observed, and, then, a recovery of the previous values of impedance and phase angle. This behavior confirms activation of the corrosion inhibition mechanism. Polarization curves shows that the multilayer coating leads to a low current density (∼10^-11 A cm^-2), around 5 orders of magnitude lower in comparison with the bare substrate. A <i>post-mortem</i> SEM-EDX analysis study, performed on the cracks generated during electrochemical testing, shows the accumulation of cerium as a consequence of the corrosion inhibitory process.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"409-420"},"PeriodicalIF":5.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907293/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143651090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Healing Engineered Multilayer Coatings for Corrosion Protection of Magnesium Alloy AZ31B","authors":"Mario Aparicio*,&nbsp;Jadra Mosa,&nbsp;Miguel Gómez-Herrero,&nbsp;Zainab Abd Al-Jaleel,&nbsp;Jennifer Guzman,&nbsp;Mihaela Jitianu,&nbsp;Lisa C. Klein and Andrei Jitianu*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0017010.1021/acsmaterialsau.4c00170","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00170https://doi.org/10.1021/acsmaterialsau.4c00170","url":null,"abstract":"<p >Nonporous, crack-free hybrid glass coatings have provided excellent corrosion protection to the AZ31B magnesium alloy. However, if a crack develops in the coatings, then corrosion will proliferate at that point. The novelty of this study consists of engineering a bilayer protection system that combines the “barrier” properties of the hybrid glass coatings with the “inhibitor” or “self-healing” effect of an internal layer of mesoporous silica doped with cerium(III) ions. The mesoporous layer was obtained using a sol–gel solution with 1 mol % cerium(III) ions. The inner cerium-doped mesoporous coating has a thickness of 0.25 μm, and the electrochemical characterization through Open circuit potential (OCP) and Electrochemical Impedance Spectroscopy (EIS) indicates a corrosion inhibition process provided by cerium(III) ions triggered by the corrosion. The combination of the Ce-doped and hybrid glass coatings reaches a total thickness of 5.1 μm. The corrosion evaluation through OCP and EIS does not show any evidence of corrosion during the first 575 h of immersion. After this, there are several steps of a sudden drop in potential and subsequent recovery of the previous values, which could be associated with the activation of the corrosion inhibition mechanism provided by the Ce (III) ions. EIS show a maximum impedance module of 10^6.7 Ohm cm², a decrease of impedance values and phase angle fluctuations after the potential drops observed, and, then, a recovery of the previous values of impedance and phase angle. This behavior confirms activation of the corrosion inhibition mechanism. Polarization curves shows that the multilayer coating leads to a low current density (∼10^–11 A cm^–2), around 5 orders of magnitude lower in comparison with the bare substrate. A <i>post-mortem</i> SEM-EDX analysis study, performed on the cracks generated during electrochemical testing, shows the accumulation of cerium as a consequence of the corrosion inhibitory process.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"409–420 409–420"},"PeriodicalIF":5.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00170","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Digging into the Atomistic Details of the TaN/MgO Interface: An Ab Initio Study Supported by Transmission Electron Microscopy.","authors":"Victor Quintanar-Zamora, Joseph P Corbett, Rodrigo Ponce-Pérez, Armando Reyes Serrato, Carlos Antonio Corona-Garcia, Oscar Contreras-López, Jonathan Guerrero-Sanchez, Jesús Antonio Díaz","doi":"10.1021/acsmaterialsau.4c00173","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00173","url":null,"abstract":"<p><p>First-principles calculations of the TaN/MgO (001) interface were performed within the DFT framework. A thermodynamic stability analysis identified four stable interfaces. The most stable configuration for the interface consists of a TaO monolayer formed between the TaN and MgO layers. The density of states at <i>E</i> _F indicates that all interface models exhibit metallic behavior. The electron localization function reveals that all of these models exhibit ionic-type bonds at the interface. In addition to the computational simulations, epitaxial growth of the TaN thin films on FCC MgO (001) substrates was carried out by using pulsed laser deposition. Transmission electron microscopy images of the TaN/MgO (001) interface cross-section reveal that TaN film grows on the MgO substrate following the epitaxial relationship TaN [001] || MgO [001]. An FFT analysis of the TaN films demonstrates that the TaN lattice contracts at the interface with MgO conforming to the substrate lattice, corroborating the computational predictions. Our results provide evidence that strained TaO layers mediate the TaN/MgO (001) interface formation.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"421-429"},"PeriodicalIF":5.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907287/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143650208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Digging into the Atomistic Details of the TaN/MgO Interface: An Ab Initio Study Supported by Transmission Electron Microscopy","authors":"Victor Quintanar-Zamora,&nbsp;Joseph P. Corbett,&nbsp;Rodrigo Ponce-Pérez,&nbsp;Armando Reyes Serrato,&nbsp;Carlos Antonio Corona-Garcia,&nbsp;Oscar Contreras-López,&nbsp;Jonathan Guerrero-Sanchez and Jesús Antonio Díaz*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0017310.1021/acsmaterialsau.4c00173","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00173https://doi.org/10.1021/acsmaterialsau.4c00173","url":null,"abstract":"<p >First-principles calculations of the TaN/MgO (001) interface were performed within the DFT framework. A thermodynamic stability analysis identified four stable interfaces. The most stable configuration for the interface consists of a TaO monolayer formed between the TaN and MgO layers. The density of states at <i>E</i>_F indicates that all interface models exhibit metallic behavior. The electron localization function reveals that all of these models exhibit ionic-type bonds at the interface. In addition to the computational simulations, epitaxial growth of the TaN thin films on FCC MgO (001) substrates was carried out by using pulsed laser deposition. Transmission electron microscopy images of the TaN/MgO (001) interface cross-section reveal that TaN film grows on the MgO substrate following the epitaxial relationship TaN [001] || MgO [001]. An FFT analysis of the TaN films demonstrates that the TaN lattice contracts at the interface with MgO conforming to the substrate lattice, corroborating the computational predictions. Our results provide evidence that strained TaO layers mediate the TaN/MgO (001) interface formation.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"421–429 421–429"},"PeriodicalIF":5.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00173","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tunable Work Function and Surface Energy in Titanium Nitride (TiN) Thin Films through Quantum Well States","authors":"Angus Huang,&nbsp;Yee-Heng Teh,&nbsp;Chin-Hsuan Chen,&nbsp;Sheng-Hsiung Hung,&nbsp;Jer-Fu Wang,&nbsp;Chih-Piao Chuu and Horng-Tay Jeng*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0017610.1021/acsmaterialsau.4c00176","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00176https://doi.org/10.1021/acsmaterialsau.4c00176","url":null,"abstract":"<p >High work function metals are crucial in various semiconductor applications. Titanium nitride (TiN) is particularly noteworthy as a high work function material in metal gate structures, which significantly enhances the transistor performance and reliability in advanced semiconductor devices. In this study, we employ first-principles calculations to demonstrate that the TiN work function oscillates with thickness due to the quantum well state effect. Furthermore, we investigate the termination and surface dependence of the work function across different crystallographic orientations. We show that the work function can be enhanced to up to 8.04 eV for TiN(111) with N-termination at five monolayers (5 MLs). Our findings provide valuable insights for fine-tuning the high work function of TiN.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"430–437 430–437"},"PeriodicalIF":5.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00176","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tunable Work Function and Surface Energy in Titanium Nitride (TiN) Thin Films through Quantum Well States.","authors":"Angus Huang, Yee-Heng Teh, Chin-Hsuan Chen, Sheng-Hsiung Hung, Jer-Fu Wang, Chih-Piao Chuu, Horng-Tay Jeng","doi":"10.1021/acsmaterialsau.4c00176","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00176","url":null,"abstract":"<p><p>High work function metals are crucial in various semiconductor applications. Titanium nitride (TiN) is particularly noteworthy as a high work function material in metal gate structures, which significantly enhances the transistor performance and reliability in advanced semiconductor devices. In this study, we employ first-principles calculations to demonstrate that the TiN work function oscillates with thickness due to the quantum well state effect. Furthermore, we investigate the termination and surface dependence of the work function across different crystallographic orientations. We show that the work function can be enhanced to up to 8.04 eV for TiN(111) with N-termination at five monolayers (5 MLs). Our findings provide valuable insights for fine-tuning the high work function of TiN.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"430-437"},"PeriodicalIF":5.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907290/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143651106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamic Tailoring Porosity and Surface Chemistry of Ultramicroporous Carbon Spheres for Highly Selective Post-combustion CO₂ Capture.","authors":"Man Liu, Weiwei Shi, Huili Liu, Yanzhen Guo, Baocheng Yang, Binbin Chang","doi":"10.1021/acsmaterialsau.4c00168","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00168","url":null,"abstract":"<p><p>Carbon capture has emerged as a pivotal carbon neutrality technology for addressing greenhouse effect challenges. Porous carbons are one of the most promising adsorbents for CO₂ capture and separation from flue gas, yet their traditional synthesis necessitates inert atmospheres to avoid oxidation, which greatly restricts the large-scale production at a low cost and advanced industrial applications. Herein, we propose an innovative pathway for large-scale fabrication of porous carbons via one-step pyrolysis in an air environment. Porosity and surface chemistry can be concurrently tailored by controlling the air-assisted pyrolysis process, and the optimization mechanism is unveiled in detail. The resultant materials feature well-interconnected hierarchical porosity with highly proportioned ultramicroporosity, uniform spherical morphology, and high surface heteroatom doping levels. By leveraging porosity and surface chemistry, the optimal sample exhibits superior CO₂ capture behaviors of satisfactory CO₂ uptake and ultrahigh selectivity. CO₂/N₂ selectivity reaches up to 160 at 0.15 bar and 25 °C, and it still achieves up to 76 at 1.0 bar and 25 °C, ranking it in the top 5% of the reported porous carbons. We explore the correlations between porosity, surface heteroatoms, and CO₂ capture behaviors. Porosity has a decisive function on CO₂ capture capacity and selectivity, especially ultramicroporosity, and surface heteroatoms doping could have a positive promotion in selectivity caused by extra CO₂-philic sites. This work pioneers a feasible approach for large-scale directional design of functional porous carbons through air-assisted pyrolysis under mild conditions.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"397-408"},"PeriodicalIF":5.7,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907289/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143650224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamic Tailoring Porosity and Surface Chemistry of Ultramicroporous Carbon Spheres for Highly Selective Post-combustion CO2 Capture","authors":"Man Liu,&nbsp;Weiwei Shi,&nbsp;Huili Liu,&nbsp;Yanzhen Guo,&nbsp;Baocheng Yang* and Binbin Chang*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0016810.1021/acsmaterialsau.4c00168","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00168https://doi.org/10.1021/acsmaterialsau.4c00168","url":null,"abstract":"<p >Carbon capture has emerged as a pivotal carbon neutrality technology for addressing greenhouse effect challenges. Porous carbons are one of the most promising adsorbents for CO₂ capture and separation from flue gas, yet their traditional synthesis necessitates inert atmospheres to avoid oxidation, which greatly restricts the large-scale production at a low cost and advanced industrial applications. Herein, we propose an innovative pathway for large-scale fabrication of porous carbons via one-step pyrolysis in an air environment. Porosity and surface chemistry can be concurrently tailored by controlling the air-assisted pyrolysis process, and the optimization mechanism is unveiled in detail. The resultant materials feature well-interconnected hierarchical porosity with highly proportioned ultramicroporosity, uniform spherical morphology, and high surface heteroatom doping levels. By leveraging porosity and surface chemistry, the optimal sample exhibits superior CO₂ capture behaviors of satisfactory CO₂ uptake and ultrahigh selectivity. CO₂/N₂ selectivity reaches up to 160 at 0.15 bar and 25 °C, and it still achieves up to 76 at 1.0 bar and 25 °C, ranking it in the top 5% of the reported porous carbons. We explore the correlations between porosity, surface heteroatoms, and CO₂ capture behaviors. Porosity has a decisive function on CO₂ capture capacity and selectivity, especially ultramicroporosity, and surface heteroatoms doping could have a positive promotion in selectivity caused by extra CO₂-philic sites. This work pioneers a feasible approach for large-scale directional design of functional porous carbons through air-assisted pyrolysis under mild conditions.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"397–408 397–408"},"PeriodicalIF":5.7,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00168","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cold-Plasma-Driven Ammonia Synthesis over Porous Silica: The Role of the Morphology","authors":"Fnu Gorky,&nbsp;Vashanti Storr,&nbsp;Jacek B. Jasinski and Maria L. Carreon*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0015910.1021/acsmaterialsau.4c00159","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00159https://doi.org/10.1021/acsmaterialsau.4c00159","url":null,"abstract":"<p >Nonthermal plasma (NTP) has opened unexplored routes for small-scale, decentralized ammonia production. However, understanding the ammonia formation pathways when employing NTP-driven processes is challenging due to the complex nature of the process. In this work, we report the effects of the morphology and textural properties on ammonia production. Herein, we explore mesoporous and macroporous regimes in silica. Performance of mesoporous silica with a gyroid morphology displays the highest ammonia production rate of 160.7 μmol/min·g-cat at a plasma power of 15 W. The findings from this work provide insights into tailoring porous structures and morphology for ammonia production powered by NTP. This work presents significant progress in the development of earth-abundant materials, achieved by tailoring their morphology and porous structure to improve their efficiency in plasma ammonia production.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"385–396 385–396"},"PeriodicalIF":5.7,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00159","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cold-Plasma-Driven Ammonia Synthesis over Porous Silica: The Role of the Morphology.","authors":"Fnu Gorky, Vashanti Storr, Jacek B Jasinski, Maria L Carreon","doi":"10.1021/acsmaterialsau.4c00159","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00159","url":null,"abstract":"<p><p>Nonthermal plasma (NTP) has opened unexplored routes for small-scale, decentralized ammonia production. However, understanding the ammonia formation pathways when employing NTP-driven processes is challenging due to the complex nature of the process. In this work, we report the effects of the morphology and textural properties on ammonia production. Herein, we explore mesoporous and macroporous regimes in silica. Performance of mesoporous silica with a gyroid morphology displays the highest ammonia production rate of 160.7 μmol/min·g-cat at a plasma power of 15 W. The findings from this work provide insights into tailoring porous structures and morphology for ammonia production powered by NTP. This work presents significant progress in the development of earth-abundant materials, achieved by tailoring their morphology and porous structure to improve their efficiency in plasma ammonia production.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"385-396"},"PeriodicalIF":5.7,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907291/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143651149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}