Chemistry of Materials最新文献

{"title":"Tuning Electronic Properties of II–VI and III–V Narrow Band Gap Nanocrystals through Exposure to Alkali","authors":"Dario Mastrippolito, Mariarosa Cavallo, Houman Bahmani Jalali, Guncem Ozgun Eren, Erwan Bossavit, Huichen Zhang, Tommaso Gemo, Albin Colle, Adrien Khalili, Clément Gureghian, Yoann Prado, Mathieu G. Silly, Debora Pierucci, Francesco Di Stasio, Emmanuel Lhuillier","doi":"10.1021/acs.chemmater.4c02795","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02795","url":null,"abstract":"The use of nanocrystals in optoelectronics strongly relies on the ability to design photodiodes, which requires advanced knowledge of their electronic structure and offers even greater potential when that structure can be finely tuned. For traditional semiconductors, this degree of freedom is achieved through doping, obtained mostly via the introduction of extrinsic impurities. When it comes to colloidal quantum dots, this capacity is mostly lost and carrier density control is best obtained thanks to surface ligand exchanges. Tuning the capping molecule enables the generation of a surface dipole and a consequent charge transfer, which shifts the relative position of the bands with respect to the Fermi and vacuum level. However, the most efficient ligands (<i>i.e</i>., the one associated with the largest dipole) are not necessarily compatible with charge conduction, which rather prefers short molecules; therefore, new strategies are needed. Here, we explore how such a surface dipole can be obtained through alkali deposition as an alternative approach. We apply this method to a broad range of nanocrystals relevant to infrared optoelectronics, which are HgTe (with two different sizes) and InAs, including a ZnSe shell. Potassium deposition leads to a significant shift of the material work function that can be as large as 1.3 eV. We also bring clear evidence that this dipole arises from the polarization of the adatoms with no charge transfer involved (<i>i.e</i>., no shift in the core levels is measured). This method appears to be quite general and is very promising as a path to shift the absolute energy of a band gap, which may ease future integration of colloidal materials in high-performance diodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753163","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}

{"title":"Area-Selective Etching of Poly(lactic acid) Films via Catalytic Hydrogenolysis and Cracking","authors":"Valtteri Lasonen, Viivi Rajamäki, Mykhailo Chundak, Eva Tois, Sami Hietala, Mikko Ritala","doi":"10.1021/acs.chemmater.4c02744","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02744","url":null,"abstract":"Fabrication of future semiconductor devices requires new and inventive self-aligning patterning processes. One such process is area-selective etching (ASE) of polymers, which exploits different catalytic properties of different surfaces. In ASE, a polymer film is decomposed only from the top of catalytically active materials, while the polymer stays intact on catalytically inactive materials. This means that the patterning is self-aligned, thus avoiding edge placement errors. So far, patterning by ASE of polymers has been demonstrated in oxidative atmospheres. Here, we study the ASE of poly(lactic acid) (PLA) in two nonoxidative atmospheres: inert atmosphere where decomposition by cracking occurs, and H₂ atmosphere where the polymer is decomposed by hydrogenolysis. Ni, NiO, Ir, and Pt films were identified as hydrogenolysis catalysts in the decomposition of PLA, whereas Co and CoO films catalyzed the decomposition of PLA both under an inert atmosphere and in the presence of H₂. Further studies revealed, however, that it is the native Co oxide or hydroxide, rather than metallic Co, that promotes the decomposition of PLA. We also compared a commercially available amorphous PLA and self-synthesized semicrystalline PLA. The semicrystalline PLA showed less flow during the ASE process, due to its higher melting temperature, as compared to the amorphous PLA. The semicrystalline PLA inhibited 1000 atomic layer deposition (ALD) cycles of Cu, whereas clear Cu growth was observed on the amorphous PLA after 1000 cycles. Additionally, the amorphous PLA film was decomposed during the Cu deposition, unlike the semicrystalline PLA film which stayed intact. The results give further confidence that ASE of polymers can be achieved with various surface combinations by carefully choosing the right catalytic material, polymer, and atmosphere.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"69 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753155","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}

{"title":"Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag2O","authors":"Leanna Schulte, Shihan Qin, Wonil Jung, Christy George, Jarrett D. Dillenburger, Akshay Venkatesh, Muhammad K. Ishak, Nichole M. Wonderling, Sariah Marth, Heemin Park, Chulsung Bae, Andrew M. Rappe, Thomas E. Mallouk","doi":"10.1021/acs.chemmater.4c02082","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02082","url":null,"abstract":"Silver(I) oxide, Ag₂O, precipitated as microcrystals by combining aqueous silver(I) nitrate and KOH solutions, was found to be a solid-state hydroxide ion conductor with ionic conductivity on the order of 10^–3 S/cm. The proton chemical shifts at 4.87 and −7.35 ppm measured by solid-state ¹H NMR experiments are attributed to water molecules and in-lattice OH^– coordinated to silver, respectively. The lack of spinning sidebands around the 4.87 ppm peak indicates rapid reorientation on the NMR time scale, suggesting that the water molecules are adsorbed to the surface of the Ag₂O crystals. Pulsed field gradient measurements gave similar diffusion coefficients (2 × 10^–7 cm²/s at 298 K) for all three proton environments, indicating chemical exchange between sites on the millisecond time scale. The activation energy for OH^– diffusion measured by NMR (0.18 eV) was comparable to that obtained by conductivity measurements and density functional theory (DFT) electronic structure calculations. The calculated Pourbaix diagram of Ag₂O is consistent with the slightly lower sample density observed in He pycnometry and thermogravimetric measurements.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142712994","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}

{"title":"Manipulating Backbone Planarity of Ester Functionalized Conjugated Polymer Constitutional Isomer Derivatives Blended with Molecular Acceptors for Controlling Photovoltaic Properties","authors":"Sina Sabury,&nbsp;Austin L. Jones,&nbsp;Nora Schopp,&nbsp;Sadisha Nanayakkara,&nbsp;Thomas P. Chaney,&nbsp;Veaceslav Coropceanu,&nbsp;Seth R. Marder,&nbsp;Michael F. Toney,&nbsp;Jean-Luc Brédas,&nbsp;Thuc-Quyen Nguyen and John R. Reynolds*,&nbsp;","doi":"10.1021/acs.chemmater.4c0275110.1021/acs.chemmater.4c02751","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02751https://doi.org/10.1021/acs.chemmater.4c02751","url":null,"abstract":"<p >Exploring both electron donor and acceptor phase components in bulk heterojunction structures has contributed to the advancement of organic photovoltaics (OPV) realizing power conversion efficiencies reaching 20%. Being able to control backbone planarity of the donor polymer, while understanding its effects on the polymer conformation and photophysical properties, fosters the groundwork for further achievements in this realm. In this report, three isomeric PM7 derivatives are designed and synthesized where the benzodithiophene-4,8-dione structure is replaced by a quaterthiophene bridge carrying two ester moieties. The placement of these two ester groups varies among three configurational isomers, which ultimately influences the chain conformations and aggregation behavior of each polymer. Specifically, PM7-D3 has ester groups attached to the inner positions of the outer thiophenes showing moderate solution aggregation; PM7-D4 has ester groups attached to the inner positions of the inner thiophenes featuring a twisted backbone with no solution aggregation behavior; and PM7-D5 has ester groups attached to the outer positions of the inner thiophenes with strong solution aggregation. PM7-D5 shows the highest average power conversion efficiency of 11.4% paired with the molecular acceptor L8-BO. In addition, the differences among the polymer backbones are expressed by their state energies and carrier mobility in the corresponding fabricated OPV devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11656–11668 11656–11668"},"PeriodicalIF":7.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02751","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Area-Selective Etching of Poly(lactic acid) Films via Catalytic Hydrogenolysis and Cracking","authors":"Valtteri Lasonen*,&nbsp;Viivi Rajamäki,&nbsp;Mykhailo Chundak,&nbsp;Eva Tois,&nbsp;Sami Hietala and Mikko Ritala*,&nbsp;","doi":"10.1021/acs.chemmater.4c0274410.1021/acs.chemmater.4c02744","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02744https://doi.org/10.1021/acs.chemmater.4c02744","url":null,"abstract":"<p >Fabrication of future semiconductor devices requires new and inventive self-aligning patterning processes. One such process is area-selective etching (ASE) of polymers, which exploits different catalytic properties of different surfaces. In ASE, a polymer film is decomposed only from the top of catalytically active materials, while the polymer stays intact on catalytically inactive materials. This means that the patterning is self-aligned, thus avoiding edge placement errors. So far, patterning by ASE of polymers has been demonstrated in oxidative atmospheres. Here, we study the ASE of poly(lactic acid) (PLA) in two nonoxidative atmospheres: inert atmosphere where decomposition by cracking occurs, and H₂ atmosphere where the polymer is decomposed by hydrogenolysis. Ni, NiO, Ir, and Pt films were identified as hydrogenolysis catalysts in the decomposition of PLA, whereas Co and CoO films catalyzed the decomposition of PLA both under an inert atmosphere and in the presence of H₂. Further studies revealed, however, that it is the native Co oxide or hydroxide, rather than metallic Co, that promotes the decomposition of PLA. We also compared a commercially available amorphous PLA and self-synthesized semicrystalline PLA. The semicrystalline PLA showed less flow during the ASE process, due to its higher melting temperature, as compared to the amorphous PLA. The semicrystalline PLA inhibited 1000 atomic layer deposition (ALD) cycles of Cu, whereas clear Cu growth was observed on the amorphous PLA after 1000 cycles. Additionally, the amorphous PLA film was decomposed during the Cu deposition, unlike the semicrystalline PLA film which stayed intact. The results give further confidence that ASE of polymers can be achieved with various surface combinations by carefully choosing the right catalytic material, polymer, and atmosphere.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11645–11655 11645–11655"},"PeriodicalIF":7.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02744","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Celebrating the Life and Scientific Legacy of Professor Francis J. DiSalvo","authors":"Song Jin, Jing Li, Cora Lind, Richard Dronskowski","doi":"10.1021/acs.chemmater.4c03037","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03037","url":null,"abstract":"“If you want to catch a fish, you have to become a fish and adopt its behavior. The fish is looking for prey, but it will become prey itself if you only know what it will or must do. This is your chance.” That is how Francis J. “Frank” DiSalvo more than once summed up his advice on fishing, an activity that he loved, which of course also serves as a metaphor to many aspects of life. He was not only an excellent fisherman, but also a highly educated and talented physicist, industrial scientist, and self-trained chemist; ultimately an extremely accomplished solid-state chemist and materials scientist, a highly renowned educator, a fantastic colleague─and a beloved friend to us all. When it came to hunting for big scientific accomplishments, hardly anyone could compete with him. He was a great scientist, and an even greater person, a mentor, and inspiration for many who had the privilege of knowing him. He was the John A. Newman Professor Emeritus at Cornell University before his passing on October 27, 2023. Frank is survived by his wife, Barbara DiSalvo, two daughters, four grandchildren, and hundreds of students, postdocs, and collaborators who were fortunate enough to have interacted with him. Frank DiSalvo’s career is quickly told and may be listened to in an interview (https://www.youtube.com/watch?v=yH7BrgXBrD4): Frank was born on July 20, 1944, in Montreal, Canada, the oldest of seven children, and his family moved to Reading, Massachusetts, during his childhood. He received a BS from MIT in 1966 (first studying chemistry and then physics) and then his PhD in Applied Physics from Stanford in 1971, working with Prof. Theodore H. Geballe. He then joined the AT&amp;T Bell Laboratories where he later led the Solid State and Physics of Materials research department. He greatly valued his time at Bell Labs because it taught him how to collaborate with others given very limited funding. In 1986, Frank was recruited by Prof. Roald Hoffmann, then Chair of the Department of Chemistry, to join Cornell to follow in the footsteps of the late Prof. Mike Sienko. From 2000 to 2005, Frank DiSalvo served as the director of the Cornell Center for Materials Research, and helped establish the Cornell Fuel Cell Institute with Prof. Héctor (Tito) Abruña. He also served as the inaugural director of the Cornell Center for a Sustainable Future from 2005 to 2015, which has grown into the flourishing Cornell Atkinson Center for Sustainability. He was awarded the International Prize for New Materials by the American Physical Society (APS) in 1991 and elected to the National Academy of Sciences. He was also a fellow of the American Academy of Arts and Sciences, the American Association for the Advancement of Science, the APS, and the Materials Research Society (MRS). Frank’s research centered around the discovery and understanding of new chemical and physical phenomena in solids. One of Frank DiSalvo’s particular strengths was his ability to “feel out” unknown compounds a","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713001","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}

{"title":"Celebrating the Life and Scientific Legacy of Professor Francis J. DiSalvo","authors":"Song Jin,&nbsp;Jing Li,&nbsp;Cora Lind and Richard Dronskowski,&nbsp;","doi":"10.1021/acs.chemmater.4c0303710.1021/acs.chemmater.4c03037","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03037https://doi.org/10.1021/acs.chemmater.4c03037","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 22","pages":"10937–10938 10937–10938"},"PeriodicalIF":7.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713465","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}

{"title":"Manipulating Backbone Planarity of Ester Functionalized Conjugated Polymer Constitutional Isomer Derivatives Blended with Molecular Acceptors for Controlling Photovoltaic Properties","authors":"Sina Sabury, Austin L. Jones, Nora Schopp, Sadisha Nanayakkara, Thomas P. Chaney, Veaceslav Coropceanu, Seth R. Marder, Michael F. Toney, Jean-Luc Brédas, Thuc-Quyen Nguyen, John R. Reynolds","doi":"10.1021/acs.chemmater.4c02751","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02751","url":null,"abstract":"Exploring both electron donor and acceptor phase components in bulk heterojunction structures has contributed to the advancement of organic photovoltaics (OPV) realizing power conversion efficiencies reaching 20%. Being able to control backbone planarity of the donor polymer, while understanding its effects on the polymer conformation and photophysical properties, fosters the groundwork for further achievements in this realm. In this report, three isomeric PM7 derivatives are designed and synthesized where the benzodithiophene-4,8-dione structure is replaced by a quaterthiophene bridge carrying two ester moieties. The placement of these two ester groups varies among three configurational isomers, which ultimately influences the chain conformations and aggregation behavior of each polymer. Specifically, PM7-D3 has ester groups attached to the inner positions of the outer thiophenes showing moderate solution aggregation; PM7-D4 has ester groups attached to the inner positions of the inner thiophenes featuring a twisted backbone with no solution aggregation behavior; and PM7-D5 has ester groups attached to the outer positions of the inner thiophenes with strong solution aggregation. PM7-D5 shows the highest average power conversion efficiency of 11.4% paired with the molecular acceptor L8-BO. In addition, the differences among the polymer backbones are expressed by their state energies and carrier mobility in the corresponding fabricated OPV devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"247 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142712998","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}

{"title":"Tuning Electronic Properties of II–VI and III–V Narrow Band Gap Nanocrystals through Exposure to Alkali","authors":"Dario Mastrippolito,&nbsp;Mariarosa Cavallo,&nbsp;Houman Bahmani Jalali,&nbsp;Guncem Ozgun Eren,&nbsp;Erwan Bossavit,&nbsp;Huichen Zhang,&nbsp;Tommaso Gemo,&nbsp;Albin Colle,&nbsp;Adrien Khalili,&nbsp;Clément Gureghian,&nbsp;Yoann Prado,&nbsp;Mathieu G. Silly,&nbsp;Debora Pierucci,&nbsp;Francesco Di Stasio and Emmanuel Lhuillier*,&nbsp;","doi":"10.1021/acs.chemmater.4c0279510.1021/acs.chemmater.4c02795","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02795https://doi.org/10.1021/acs.chemmater.4c02795","url":null,"abstract":"<p >The use of nanocrystals in optoelectronics strongly relies on the ability to design photodiodes, which requires advanced knowledge of their electronic structure and offers even greater potential when that structure can be finely tuned. For traditional semiconductors, this degree of freedom is achieved through doping, obtained mostly via the introduction of extrinsic impurities. When it comes to colloidal quantum dots, this capacity is mostly lost and carrier density control is best obtained thanks to surface ligand exchanges. Tuning the capping molecule enables the generation of a surface dipole and a consequent charge transfer, which shifts the relative position of the bands with respect to the Fermi and vacuum level. However, the most efficient ligands (<i>i.e</i>., the one associated with the largest dipole) are not necessarily compatible with charge conduction, which rather prefers short molecules; therefore, new strategies are needed. Here, we explore how such a surface dipole can be obtained through alkali deposition as an alternative approach. We apply this method to a broad range of nanocrystals relevant to infrared optoelectronics, which are HgTe (with two different sizes) and InAs, including a ZnSe shell. Potassium deposition leads to a significant shift of the material work function that can be as large as 1.3 eV. We also bring clear evidence that this dipole arises from the polarization of the adatoms with no charge transfer involved (<i>i.e</i>., no shift in the core levels is measured). This method appears to be quite general and is very promising as a path to shift the absolute energy of a band gap, which may ease future integration of colloidal materials in high-performance diodes.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11669–11675 11669–11675"},"PeriodicalIF":7.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843421","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}

{"title":"Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag2O","authors":"Leanna Schulte,&nbsp;Shihan Qin,&nbsp;Wonil Jung,&nbsp;Christy George,&nbsp;Jarrett D. Dillenburger,&nbsp;Akshay Venkatesh,&nbsp;Muhammad K. Ishak,&nbsp;Nichole M. Wonderling,&nbsp;Sariah Marth,&nbsp;Heemin Park,&nbsp;Chulsung Bae,&nbsp;Andrew M. Rappe* and Thomas E. Mallouk*,&nbsp;","doi":"10.1021/acs.chemmater.4c0208210.1021/acs.chemmater.4c02082","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02082https://doi.org/10.1021/acs.chemmater.4c02082","url":null,"abstract":"<p >Silver(I) oxide, Ag₂O, precipitated as microcrystals by combining aqueous silver(I) nitrate and KOH solutions, was found to be a solid-state hydroxide ion conductor with ionic conductivity on the order of 10^–3 S/cm. The proton chemical shifts at 4.87 and −7.35 ppm measured by solid-state ¹H NMR experiments are attributed to water molecules and in-lattice OH^– coordinated to silver, respectively. The lack of spinning sidebands around the 4.87 ppm peak indicates rapid reorientation on the NMR time scale, suggesting that the water molecules are adsorbed to the surface of the Ag₂O crystals. Pulsed field gradient measurements gave similar diffusion coefficients (2 × 10^–7 cm²/s at 298 K) for all three proton environments, indicating chemical exchange between sites on the millisecond time scale. The activation energy for OH^– diffusion measured by NMR (0.18 eV) was comparable to that obtained by conductivity measurements and density functional theory (DFT) electronic structure calculations. The calculated Pourbaix diagram of Ag₂O is consistent with the slightly lower sample density observed in He pycnometry and thermogravimetric measurements.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11440–11448 11440–11448"},"PeriodicalIF":7.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843826","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}