Pub Date : 2024-01-27DOI: 10.3390/inorganics12020044
Jordan L. Appleton, Nolwenn Le Breton, Sylvie Choua, Romain Ruppert
The syntheses of a series of copper(II) porphyrins and their dimers linked by palladium(II) or platinum(II) are reported. Their electronic properties and their magnetic properties were studied. In particular, the effect of the linking unit on these properties was evaluated. It was discovered that three factors influence the electronic and magnetic interactions between the two metalloporphyrins: the nature of the linking metal ion, the nature of the external coordination site of the porphyrin, and also the nature of the metal ion present in the central core of the aromatic macrocycle.
{"title":"The Effect of the Linking Unit on the Electronic and Magnetic Interactions in Copper(II) Porphyrin Dimers Linked by Metal Ions","authors":"Jordan L. Appleton, Nolwenn Le Breton, Sylvie Choua, Romain Ruppert","doi":"10.3390/inorganics12020044","DOIUrl":"https://doi.org/10.3390/inorganics12020044","url":null,"abstract":"The syntheses of a series of copper(II) porphyrins and their dimers linked by palladium(II) or platinum(II) are reported. Their electronic properties and their magnetic properties were studied. In particular, the effect of the linking unit on these properties was evaluated. It was discovered that three factors influence the electronic and magnetic interactions between the two metalloporphyrins: the nature of the linking metal ion, the nature of the external coordination site of the porphyrin, and also the nature of the metal ion present in the central core of the aromatic macrocycle.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140491861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-27DOI: 10.3390/inorganics12020042
H. Idriss
The reduction of Ce cations in CeO2 can be enhanced by their partial substitution with Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for the thermal water-splitting reaction when compared to CeO2 alone. This mixed oxide has a smaller crystallite size when compared to CeO2, in addition to a smaller lattice size. In this work, two Fe-substituted Ce oxides are studied (Ce0.95Fe0.05O2-δ and Ce0.75Fe0.25O2-δ; δ < 0.5) by core and valence level spectroscopy in their as-prepared and Ar-ion-sputtered states. Ar ion sputtering substantially increases Ce4f lines at about 1.5 eV below the Fermi level. In addition, it is found that the XPS Ce5p/O2s ratio is sensitive to the degree of reduction, most likely due to a higher charge transfer from the oxygen to Ce ions upon reduction. Quantitatively, it is also found that XPS Ce3d of the fraction of Ce3+ (uo, u′ and vo, v′) formed upon Ar ion sputtering and the ratio of Ce5p/O2s lines are higher for reduced Ce0.95Fe0.05O2-δ than for reduced Ce0.75Fe0.25O2-δ. XPS Fe2p showed, however, no preferential increase for Fe3+ reduction to Fe0 with increasing time for both oxides. Since water splitting was higher on Ce0.95Fe0.05O2-δ when compared to Ce0.75Fe0.25O2-δ, it is inferred that the reaction centers for the thermal water splitting to hydrogen are the reduced Ce cations and not the reduced Fe cations. These reduced Ce cations can be tracked by their XPS Ce5p/O2s ratio in addition to the common XPS Ce3d lines.
CeO2 中 Ce 阳离子的还原性可通过用 Fe 阳离子部分取代而得到增强。与单独的 CeO2 相比，Ce 阳离子的还原性增强使得热分水反应的反应速率大大提高。与 CeO2 相比，这种混合氧化物除了晶格尺寸较小之外，结晶尺寸也较小。在这项工作中，通过核光谱和价级光谱研究了两种 Fe 取代的 Ce 氧化物（Ce0.95Fe0.05O2-δ 和 Ce0.75Fe0.25O2-δ；δ < 0.5）的制备状态和氩离子溅射状态。氩离子溅射大大增加了费米级以下约 1.5 eV 处的 Ce4f 线。此外，研究还发现 XPS Ce5p/O2s 比率对还原程度很敏感，这很可能是由于还原时氧向铈离子的电荷转移较多。定量研究还发现，氩离子溅射时形成的 Ce3+ 部分（uo，u′ 和 vo，v′）的 XPS Ce3d 以及 Ce5p/O2s 线的比率，还原 Ce0.95Fe0.05O2-δ 要高于还原 Ce0.75Fe0.25O2-δ。然而，XPS Fe2p 显示，随着时间的延长，两种氧化物中的 Fe3+ 还原成 Fe0 的比例并没有增加。与 Ce0.75Fe0.25O2-δ 相比，Ce0.95Fe0.05O2-δ 上的水分裂率更高，因此可以推断，热水分裂成氢的反应中心是还原的 Ce 阳离子，而不是还原的 Fe 阳离子。除了常见的 XPS Ce3d 线之外，还可以通过其 XPS Ce5p/O2s 比值跟踪这些还原的 Ce 阳离子。
{"title":"A Core and Valence-Level Spectroscopy Study of the Enhanced Reduction of CeO2 by Iron Substitution—Implications for the Thermal Water-Splitting Reaction","authors":"H. Idriss","doi":"10.3390/inorganics12020042","DOIUrl":"https://doi.org/10.3390/inorganics12020042","url":null,"abstract":"The reduction of Ce cations in CeO2 can be enhanced by their partial substitution with Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for the thermal water-splitting reaction when compared to CeO2 alone. This mixed oxide has a smaller crystallite size when compared to CeO2, in addition to a smaller lattice size. In this work, two Fe-substituted Ce oxides are studied (Ce0.95Fe0.05O2-δ and Ce0.75Fe0.25O2-δ; δ < 0.5) by core and valence level spectroscopy in their as-prepared and Ar-ion-sputtered states. Ar ion sputtering substantially increases Ce4f lines at about 1.5 eV below the Fermi level. In addition, it is found that the XPS Ce5p/O2s ratio is sensitive to the degree of reduction, most likely due to a higher charge transfer from the oxygen to Ce ions upon reduction. Quantitatively, it is also found that XPS Ce3d of the fraction of Ce3+ (uo, u′ and vo, v′) formed upon Ar ion sputtering and the ratio of Ce5p/O2s lines are higher for reduced Ce0.95Fe0.05O2-δ than for reduced Ce0.75Fe0.25O2-δ. XPS Fe2p showed, however, no preferential increase for Fe3+ reduction to Fe0 with increasing time for both oxides. Since water splitting was higher on Ce0.95Fe0.05O2-δ when compared to Ce0.75Fe0.25O2-δ, it is inferred that the reaction centers for the thermal water splitting to hydrogen are the reduced Ce cations and not the reduced Fe cations. These reduced Ce cations can be tracked by their XPS Ce5p/O2s ratio in addition to the common XPS Ce3d lines.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140492805","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-17DOI: 10.3390/inorganics12010033
Sara Ghomi, A. Lamperti, M. Alia, C. Casari, C. Grazianetti, A. Molle, C. Martella
Developing a method for the growth of ultrathin metal chalcogenides, potentially targeting the two-dimensional (2D) limit, has a pivotal impact on various nanotechnological device applications. Here, we employed a vapor deposition scheme, based on tellurization, to induce the heterogenous chemical reaction between solid Ag and Au precursors, in the form of ultrathin films, and Te vapors. We characterized the morphological and structural properties of the grown tellurides by using atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques. The developed tellurization methodology provides a key advancement in the picture of growing ultrathin noble metal tellurides and holds great potential for applications in different technological fields.
开发一种可能达到二维（2D）极限的超薄金属铬化物生长方法，对各种纳米技术设备的应用有着举足轻重的影响。在此，我们采用了一种基于碲化的气相沉积方案，以超薄薄膜的形式诱导固体银和金前体与碲蒸气之间的异质化学反应。我们利用原子力显微镜、拉曼光谱、X 射线光电子能谱和 X 射线衍射技术对生长出的碲化物的形态和结构特性进行了表征。所开发的碲化方法为超薄贵金属碲化物的生长提供了一个关键进展，在不同技术领域具有巨大的应用潜力。
{"title":"Large Area Growth of Silver and Gold Telluride Ultrathin Films via Chemical Vapor Tellurization","authors":"Sara Ghomi, A. Lamperti, M. Alia, C. Casari, C. Grazianetti, A. Molle, C. Martella","doi":"10.3390/inorganics12010033","DOIUrl":"https://doi.org/10.3390/inorganics12010033","url":null,"abstract":"Developing a method for the growth of ultrathin metal chalcogenides, potentially targeting the two-dimensional (2D) limit, has a pivotal impact on various nanotechnological device applications. Here, we employed a vapor deposition scheme, based on tellurization, to induce the heterogenous chemical reaction between solid Ag and Au precursors, in the form of ultrathin films, and Te vapors. We characterized the morphological and structural properties of the grown tellurides by using atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques. The developed tellurization methodology provides a key advancement in the picture of growing ultrathin noble metal tellurides and holds great potential for applications in different technological fields.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139526992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-16DOI: 10.3390/inorganics12010031
R. Irankunda, Jairo Andrés Camaño Echavarría, Cédric Paris, K. Selmeczi, Loic Stefan, Sandrine Boschi-Muller, Laurence Muhr, L. Canabady-Rochelle
Various peptides can be obtained through protein enzymatic hydrolysis. Immobilized metal ion affinity chromatography (IMAC) is one of the methods which can be used to separate metal chelating peptides (MCPs) in a hydrolysate mixture. In this context, this work aims to understand deeply the interactions in IMAC and surface plasmon resonance (SPR) in order to validate experimentally the analogy between both technologies and to be further able to perform IMAC modeling in the next work using peptide sorption isotherm parameters obtained from SPR. Indeed, chromatography modeling can be used to predict separation of MCPs in IMAC and the knowledge of peptide sorption isotherm obtained from SPR is a crucial step. For this purpose, 22 peptides were selected and investigated in IMAC using HisTrap X-Ni2+ and HiFliQ NTA-Ni2+ columns and were also studied in SPR as well. Results showed that peptides with histidine residues had good affinity to Ni2+, while the high positive charge of peptides was responsible of ionic interactions. Further, most of the peptides with good retention time in IMAC showed a good affinity in SPR as well, which validated experimentally the SPR-IMAC analogy.
{"title":"Deciphering Interactions Involved in Immobilized Metal Ion Affinity Chromatography and Surface Plasmon Resonance for Validating the Analogy between Both Technologies","authors":"R. Irankunda, Jairo Andrés Camaño Echavarría, Cédric Paris, K. Selmeczi, Loic Stefan, Sandrine Boschi-Muller, Laurence Muhr, L. Canabady-Rochelle","doi":"10.3390/inorganics12010031","DOIUrl":"https://doi.org/10.3390/inorganics12010031","url":null,"abstract":"Various peptides can be obtained through protein enzymatic hydrolysis. Immobilized metal ion affinity chromatography (IMAC) is one of the methods which can be used to separate metal chelating peptides (MCPs) in a hydrolysate mixture. In this context, this work aims to understand deeply the interactions in IMAC and surface plasmon resonance (SPR) in order to validate experimentally the analogy between both technologies and to be further able to perform IMAC modeling in the next work using peptide sorption isotherm parameters obtained from SPR. Indeed, chromatography modeling can be used to predict separation of MCPs in IMAC and the knowledge of peptide sorption isotherm obtained from SPR is a crucial step. For this purpose, 22 peptides were selected and investigated in IMAC using HisTrap X-Ni2+ and HiFliQ NTA-Ni2+ columns and were also studied in SPR as well. Results showed that peptides with histidine residues had good affinity to Ni2+, while the high positive charge of peptides was responsible of ionic interactions. Further, most of the peptides with good retention time in IMAC showed a good affinity in SPR as well, which validated experimentally the SPR-IMAC analogy.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139527950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-02DOI: 10.3390/inorganics12010022
Huahua Zhao, Tingyu Ji, Yanping Wu, Huanling Song, Jianfeng Wu, L. Chou
A series of ZnO-doped nitrogen-carbon materials (xZnO-N-C) with ZnO contents of 5–40% are prepared by a vacuum curing–carbonization strategy using polyamide-imide as the N-C source and zinc nitrate as the metal source for propane dehydrogenation (PDH). 20ZnO-N-C exhibits outstanding initial activity (propane conversion of 35.2% and propene yield of 24.6%) and a relatively low deactivation rate (0.071 h−1) at 600 °C. The results of detailed characterization show that small ZnO nanoparticles (5.5 nm) with high dispersion on the catalyst can be obtained by adjusting the ZnO loading. Moreover, more nitrogen-based species, especially ZnNx species, are formed on 20ZnO-N-C in comparison with 20ZnO-N-C-air prepared via curing carbonization without vacuum, which may contribute to the higher product selectivity and catalytic stability of 20ZnO-N-C. The active sites for the PDH reaction on the catalyst system are proposed to be C=O species and Zn2+ species. Moreover, the carbon deposition and the aggregation of ZnO nanoparticles are the causes of activity loss on this catalyst system.
{"title":"Exploration of ZnO-Doped Nitrogen-Carbon Materials Derived from Polyamide-Imide for Propane Dehydrogenation","authors":"Huahua Zhao, Tingyu Ji, Yanping Wu, Huanling Song, Jianfeng Wu, L. Chou","doi":"10.3390/inorganics12010022","DOIUrl":"https://doi.org/10.3390/inorganics12010022","url":null,"abstract":"A series of ZnO-doped nitrogen-carbon materials (xZnO-N-C) with ZnO contents of 5–40% are prepared by a vacuum curing–carbonization strategy using polyamide-imide as the N-C source and zinc nitrate as the metal source for propane dehydrogenation (PDH). 20ZnO-N-C exhibits outstanding initial activity (propane conversion of 35.2% and propene yield of 24.6%) and a relatively low deactivation rate (0.071 h−1) at 600 °C. The results of detailed characterization show that small ZnO nanoparticles (5.5 nm) with high dispersion on the catalyst can be obtained by adjusting the ZnO loading. Moreover, more nitrogen-based species, especially ZnNx species, are formed on 20ZnO-N-C in comparison with 20ZnO-N-C-air prepared via curing carbonization without vacuum, which may contribute to the higher product selectivity and catalytic stability of 20ZnO-N-C. The active sites for the PDH reaction on the catalyst system are proposed to be C=O species and Zn2+ species. Moreover, the carbon deposition and the aggregation of ZnO nanoparticles are the causes of activity loss on this catalyst system.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139536751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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