Pub Date : 2024-06-29DOI: 10.1021/acs.inorgchem.4c01314
Gopabandhu Panigrahi, Anna A. Berseneva, Gregory Morrison, Adam A. King, Robin L. Conner, Luiz G. Jacobsohn, Hans-Conrad zur Loye
We report on the detailed structural analysis of a series of 11 new quaternary rare earths containing thiosilicates, AkRE2Si2S8 (Ak = Ca and Sr; RE = La, Ce, Pr, Nd, Sm, Gd, and Tb), synthesized using the flux-assisted boron chalcogen mixture method. High quality crystals were grown and used to determine their crystal structures by single crystal X-ray diffraction. All members of the AkRE2Si2S8 series crystallize in the trigonal crystal system with space group R3̅c (space group no. 167). Polycrystalline powders were used for physical property measurements, including magnetic susceptibility, diffuse reflectance in the UV–visible range, and scintillation. Magnetic measurements indicated that CaRE2Si2S8 (RE = Nd and Tb) exhibits paramagnetic behavior with a slightly negative Weiss constant. The band gaps of the materials were determined from diffuse reflectance data, and optical band gaps were estimated to be 2.5(1) and 2.9(1) eV for CaCe2Si2S8 and CaGd2Si2S8, respectively. CaCe2Si2S8, CaTb2Si2S8, and SrCe2Si2S8 exhibited intense green luminescence upon irradiation with 375 nm ultraviolet light and, furthermore, scintillated when exposed to X-rays. Radioluminescence measurements of CaCe2Si2S8 powder revealed green emission with an intensity approximately 14% of that emitted by bismuth germanium oxide powder.
{"title":"Crystal Growth of Quaternary AkRE2Si2S8 (Ak = Ca and Sr; RE = La–Tb) Thiosilicates Using Flux-Assisted Boron Chalcogen Mixture Method: Exploring X-ray Scintillation, Luminescence, and Magnetic Properties","authors":"Gopabandhu Panigrahi, Anna A. Berseneva, Gregory Morrison, Adam A. King, Robin L. Conner, Luiz G. Jacobsohn, Hans-Conrad zur Loye","doi":"10.1021/acs.inorgchem.4c01314","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01314","url":null,"abstract":"We report on the detailed structural analysis of a series of 11 new quaternary rare earths containing thiosilicates, AkRE<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> (Ak = Ca and Sr; RE = La, Ce, Pr, Nd, Sm, Gd, and Tb), synthesized using the flux-assisted boron chalcogen mixture method. High quality crystals were grown and used to determine their crystal structures by single crystal X-ray diffraction. All members of the AkRE<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> series crystallize in the trigonal crystal system with space group <i>R</i>3̅<i>c</i> (space group no. 167). Polycrystalline powders were used for physical property measurements, including magnetic susceptibility, diffuse reflectance in the UV–visible range, and scintillation. Magnetic measurements indicated that CaRE<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> (RE = Nd and Tb) exhibits paramagnetic behavior with a slightly negative Weiss constant. The band gaps of the materials were determined from diffuse reflectance data, and optical band gaps were estimated to be 2.5(1) and 2.9(1) eV for CaCe<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> and CaGd<sub>2</sub>Si<sub>2</sub>S<sub>8</sub>, respectively. CaCe<sub>2</sub>Si<sub>2</sub>S<sub>8</sub>, CaTb<sub>2</sub>Si<sub>2</sub>S<sub>8</sub>, and SrCe<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> exhibited intense green luminescence upon irradiation with 375 nm ultraviolet light and, furthermore, scintillated when exposed to X-rays. Radioluminescence measurements of CaCe<sub>2</sub>Si<sub>2</sub>S<sub>8</sub> powder revealed green emission with an intensity approximately 14% of that emitted by bismuth germanium oxide powder.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-29DOI: 10.1021/acs.inorgchem.4c00369
Monika Motlochová, Xenia Vislocká, Sven Lidin, Mária Čaplovičová, Roman Maršálek, Jan Šubrt
The manuscript focuses on an original method of preparation of metatitanic acid when only environmentally safe base substances are used in the synthesis process. The synthesis is based on the reaction of solid titanyl sulfate in an aqueous solution of sodium hydroxide. This method allows for (i) a full preservation of the morphology of the starting titanyl sulfate and (ii) a preparation of metatitanic acid substances with specific parameters. This can be achieved via a precise control of the alkali metal/titanyl sulfate ratio resulting in substances with varying contents of alkali metals or even sulfate anions. The prepared metatitanic acid then also contains very small weakly crystalline particles (2–3 nm) and forms pseudomorphic aggregates whose shape and dimensions correspond to those of the starting titanyl sulfate. These aggregates exhibit regular nanoporosity with a high surface area of up to 500 m2·g–1, have no tendency to form colloids, and are mechanically highly resistant even by high-energy ultrasound. The characterization of the resulting products is done via their chemical composition and methods of structural analysis, as well as by electron microscopy and local analysis. The mechanism of product formation is discussed based on the structure of the precursor, including the so far unknown structure of metatitanic acid.
{"title":"A Metatitanic Acid Particulate Xerogel: Green Synthesis, Structure Determination, and Detailed Characterization","authors":"Monika Motlochová, Xenia Vislocká, Sven Lidin, Mária Čaplovičová, Roman Maršálek, Jan Šubrt","doi":"10.1021/acs.inorgchem.4c00369","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c00369","url":null,"abstract":"The manuscript focuses on an original method of preparation of metatitanic acid when only environmentally safe base substances are used in the synthesis process. The synthesis is based on the reaction of solid titanyl sulfate in an aqueous solution of sodium hydroxide. This method allows for (i) a full preservation of the morphology of the starting titanyl sulfate and (ii) a preparation of metatitanic acid substances with specific parameters. This can be achieved via a precise control of the alkali metal/titanyl sulfate ratio resulting in substances with varying contents of alkali metals or even sulfate anions. The prepared metatitanic acid then also contains very small weakly crystalline particles (2–3 nm) and forms pseudomorphic aggregates whose shape and dimensions correspond to those of the starting titanyl sulfate. These aggregates exhibit regular nanoporosity with a high surface area of up to 500 m<sup>2</sup>·g<sup>–1</sup>, have no tendency to form colloids, and are mechanically highly resistant even by high-energy ultrasound. The characterization of the resulting products is done via their chemical composition and methods of structural analysis, as well as by electron microscopy and local analysis. The mechanism of product formation is discussed based on the structure of the precursor, including the so far unknown structure of metatitanic acid.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel organo sulfur and selenium-controlled emission behavior in discrete copper(I) clusters has been demonstrated for the first time. The pentanuclear [Cu5Br5(L1)2] (1), trinuclear [Cu3Br3(L2)2] (2), dinuclear [Cu2I2(L1)2] (3), and tetranuclear [Cu4I4(L2)2CH3CN] (4) copper(I) discrete clusters have been synthesized from the reaction between L1 [L1 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] or L2 [L2 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] chelating ligands and corresponding copper(I) halide salts. These new clusters have been characterized by FT-IR, UV–visible, thermogravimetric analysis, and fluorescence spectroscopy techniques. Single-crystal X-ray diffraction studies reveal that 1–4 consists of abundant d10–d10 interactions. The structural and bonding features of clusters have been investigated using density functional theory calculations. Notably, the L2-ligated 2 and 4 are poorly emissive, while L1-ligated 1 and 3 showed strong emission in the orange and green regions, respectively. The time-dependent density functional theory natural transition orbital calculations of 1 and 3 reveal the nature of the transitions contributed by 3MLCT/3LLCT/3ILCT. Photoluminescence quantum yields of 1 and 3 are 19 and 11%, with average lifetimes of 21.55 and 6.57 μs, respectively. 1 and 3 were coated on prototype LED bulbs for light-emitting performance.
{"title":"Organo Chalcogenone-Triggered Luminescent Copper(I) Clusters for Light Emitting Applications","authors":"Sabari Veerapathiran, Gopendra Muduli, Arushi Rawat, Kumar Siddhant, Joginder Singh, Kohsuke Matsumoto, Osamu Tsutsumi, Ganesan Prabusankar","doi":"10.1021/acs.inorgchem.3c04637","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.3c04637","url":null,"abstract":"A novel organo sulfur and selenium-controlled emission behavior in discrete copper(I) clusters has been demonstrated for the first time. The pentanuclear [Cu<sub>5</sub>Br<sub>5</sub>(<b>L</b><sup><b>1</b></sup>)<sub>2</sub>] (<b>1</b>), trinuclear [Cu<sub>3</sub>Br<sub>3</sub>(<b>L</b><sup><b>2</b></sup>)<sub>2</sub>] (<b>2</b>), dinuclear [Cu<sub>2</sub>I<sub>2</sub>(<b>L</b><sup><b>1</b></sup>)<sub>2</sub>] (<b>3</b>), and tetranuclear [Cu<sub>4</sub>I<sub>4</sub>(<b>L</b><sup><b>2</b></sup>)<sub>2</sub>CH<sub>3</sub>CN] (<b>4</b>) copper(I) discrete clusters have been synthesized from the reaction between <b>L</b><sup><b>1</b></sup> [<b>L</b><sup><b>1</b></sup> = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] or <b>L</b><sup><b>2</b></sup> [<b>L</b><sup><b>2</b></sup> = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] chelating ligands and corresponding copper(I) halide salts. These new clusters have been characterized by FT-IR, UV–visible, thermogravimetric analysis, and fluorescence spectroscopy techniques. Single-crystal X-ray diffraction studies reveal that <b>1–4</b> consists of abundant <i>d<sup>10</sup>–d<sup>10</sup></i> interactions. The structural and bonding features of clusters have been investigated using density functional theory calculations. Notably, the <b>L</b><sup><b>2</b></sup>-ligated <b>2</b> and <b>4</b> are poorly emissive, while <b>L</b><sup><b>1</b></sup>-ligated <b>1</b> and <b>3</b> showed strong emission in the orange and green regions, respectively. The time-dependent density functional theory natural transition orbital calculations of <b>1</b> and <b>3</b> reveal the nature of the transitions contributed by <sup>3</sup>MLCT/<sup>3</sup>LLCT/<sup>3</sup>ILCT. Photoluminescence quantum yields of <b>1</b> and <b>3</b> are 19 and 11%, with average lifetimes of 21.55 and 6.57 μs, respectively. <b>1</b> and <b>3</b> were coated on prototype LED bulbs for light-emitting performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c01568
Zhilin Liang, Maria Batuk, Fabio Orlandi, Pascal Manuel, Joke Hadermann, Michael A. Hayward
Binary metal hydrides can act as low-temperature reducing agents for complex oxides in the solid state, facilitating the synthesis of anion-deficient oxide or oxyhydride phases. The reaction of LaSrCoRuO6, with CaH2 in a sealed tube yields the face-centered cubic phase LaSrCoRuO3.2H1.9. The reaction with LiH under similar conditions converts LaSrCoRuO6 to a mixture of tetragonal LaSrCoRuO4.8H1.2 and cubic LaSrCoRuO3.3H2.13. The formation of the LaSrCoRuOxHy oxyhydride phases proceeds directly from the parent oxide, with no evidence for anion-deficient LaSrCoRuO6–x intermediates, in contrast with many other topochemically synthesized transition-metal oxyhydrides. However, the reaction between LaSrCoRuO6 and LiH under flowing argon yields a mixture of LaSrCoRuO5 and the infinite layer phase LaSrCoRuO4. The change to all-oxide products when reactions are performed under flowing argon is attributed to the lower hydrogen partial pressure under these conditions. The implications for the reaction mechanism of these topochemical transformations is discussed along with the role of the hydrogen partial pressure in oxyhydride synthesis. Magnetization measurements indicate the LaSrCoRuOxHy phases exhibit local moments on Co and Ru centers, which are coupled antiferromagnetically. In contrast, LaSrCoRuO4 exhibits ferromagnetic behavior with a Curie temperature above 350 K, which can be rationalized on the basis of superexchange coupling between the Co1+ and Ru2+ centers.
{"title":"Competition between Anion-Deficient Oxide and Oxyhydride Phases during the Topochemical Reduction of LaSrCoRuO6","authors":"Zhilin Liang, Maria Batuk, Fabio Orlandi, Pascal Manuel, Joke Hadermann, Michael A. Hayward","doi":"10.1021/acs.inorgchem.4c01568","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01568","url":null,"abstract":"Binary metal hydrides can act as low-temperature reducing agents for complex oxides in the solid state, facilitating the synthesis of anion-deficient oxide or oxyhydride phases. The reaction of LaSrCoRuO<sub>6</sub>, with CaH<sub>2</sub> in a sealed tube yields the face-centered cubic phase LaSrCoRuO<sub>3.2</sub>H<sub>1.9</sub>. The reaction with LiH under similar conditions converts LaSrCoRuO<sub>6</sub> to a mixture of tetragonal LaSrCoRuO<sub>4.8</sub>H<sub>1.2</sub> and cubic LaSrCoRuO<sub>3.3</sub>H<sub>2.13</sub>. The formation of the LaSrCoRuO<sub><i>x</i></sub>H<sub><i>y</i></sub> oxyhydride phases proceeds directly from the parent oxide, with no evidence for anion-deficient LaSrCoRuO<sub>6–<i>x</i></sub> intermediates, in contrast with many other topochemically synthesized transition-metal oxyhydrides. However, the reaction between LaSrCoRuO<sub>6</sub> and LiH under flowing argon yields a mixture of LaSrCoRuO<sub>5</sub> and the infinite layer phase LaSrCoRuO<sub>4</sub>. The change to all-oxide products when reactions are performed under flowing argon is attributed to the lower hydrogen partial pressure under these conditions. The implications for the reaction mechanism of these topochemical transformations is discussed along with the role of the hydrogen partial pressure in oxyhydride synthesis. Magnetization measurements indicate the LaSrCoRuO<sub><i>x</i></sub>H<sub><i>y</i></sub> phases exhibit local moments on Co and Ru centers, which are coupled antiferromagnetically. In contrast, LaSrCoRuO<sub>4</sub> exhibits ferromagnetic behavior with a Curie temperature above 350 K, which can be rationalized on the basis of superexchange coupling between the Co<sup>1+</sup> and Ru<sup>2+</sup> centers.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c01856
Cailang Lu, Qian Jia, Linlin Yu, Bin Zhang, Ruoyu Chen
Silica nanotubes have significant applications in various fields, including thermal insulation, self-cleaning, and catalysis. Currently, the synthesis methods of silica nanotubes are mostly limited to the template method. In this work, a template-free strategy and vapor-phase approach were used to prepare silica nanotubes. Poly(methylhydrosiloxane) (PMHS) was hydrolyzed and condensed in a high-temperature closed reactor by using ammonia as a catalyst. The resulting product was then subjected to template-free self-assembly to synthesize silica nanotubes incorporating methyl groups. The silica nanotubes were synthesized under varying conditions, resulting in lengths ranging from 50 nm to several micrometers, exterior diameters between 40 and 120 nm, and wall thicknesses varying from 7 to 30 nm. The synthesized products underwent morphology analysis using TEM and FESEM for morphology analysis, elemental composition analysis using XPS, and chemical structure identification using FTIR, and the possible formation mechanism of silica nanotubes formation was also speculated. Furthermore, the coatings formed by silica nanotubes exhibited remarkable superhydrophobic self-cleaning properties with a water contact angle of 162° and a rolling angle of less than 1°.
{"title":"Mechanistic Insight into the Synthesis and Morphological Evolution of Superhydrophobic Silica Nanotubes","authors":"Cailang Lu, Qian Jia, Linlin Yu, Bin Zhang, Ruoyu Chen","doi":"10.1021/acs.inorgchem.4c01856","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01856","url":null,"abstract":"Silica nanotubes have significant applications in various fields, including thermal insulation, self-cleaning, and catalysis. Currently, the synthesis methods of silica nanotubes are mostly limited to the template method. In this work, a template-free strategy and vapor-phase approach were used to prepare silica nanotubes. Poly(methylhydrosiloxane) (PMHS) was hydrolyzed and condensed in a high-temperature closed reactor by using ammonia as a catalyst. The resulting product was then subjected to template-free self-assembly to synthesize silica nanotubes incorporating methyl groups. The silica nanotubes were synthesized under varying conditions, resulting in lengths ranging from 50 nm to several micrometers, exterior diameters between 40 and 120 nm, and wall thicknesses varying from 7 to 30 nm. The synthesized products underwent morphology analysis using TEM and FESEM for morphology analysis, elemental composition analysis using XPS, and chemical structure identification using FTIR, and the possible formation mechanism of silica nanotubes formation was also speculated. Furthermore, the coatings formed by silica nanotubes exhibited remarkable superhydrophobic self-cleaning properties with a water contact angle of 162° and a rolling angle of less than 1°.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c00740
Shengnan Bi, Junwei Ye, Peng Tian, Guiling Ning
Complex morphologies in nature often arise from the assembly of elemental building blocks, leading to diverse and intricate structures. Understanding the mechanisms that govern the formation of these complex morphologies remains a significant challenge. In particular, the edge-base plate growth of biogenic crystals plays a crucial role in directing the development of intricate bioskeleton morphologies. However, the factors and regulatory processes that govern edge-base plate growth remain insufficiently understood. Inspired by biological skeletons and based on the soluble property of boric acid (BA) in both water and alcohols, we obtained a series of novel BA morphologies, including coccolith, and anemone biological skeletons. Here, we unveil the “inscribed circle effect”, a concise mathematical model that reveals the underlying causative factors and regulatory mechanisms driving edge-base plate growth. Our findings illuminate how variations in solvent environments can exert control over the edge-base plate growth pathways, thereby resulting in the formation of diverse and complex morphologies. This understanding holds significant potential for guiding the chemical synthesis of bioskeleton materials.
{"title":"Insight from Boric Acid into Bioskeleton Formation: Inscribed Circle Effect on the Edge-Base Plate Growth","authors":"Shengnan Bi, Junwei Ye, Peng Tian, Guiling Ning","doi":"10.1021/acs.inorgchem.4c00740","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c00740","url":null,"abstract":"Complex morphologies in nature often arise from the assembly of elemental building blocks, leading to diverse and intricate structures. Understanding the mechanisms that govern the formation of these complex morphologies remains a significant challenge. In particular, the edge-base plate growth of biogenic crystals plays a crucial role in directing the development of intricate bioskeleton morphologies. However, the factors and regulatory processes that govern edge-base plate growth remain insufficiently understood. Inspired by biological skeletons and based on the soluble property of boric acid (BA) in both water and alcohols, we obtained a series of novel BA morphologies, including coccolith, and anemone biological skeletons. Here, we unveil the “inscribed circle effect”, a concise mathematical model that reveals the underlying causative factors and regulatory mechanisms driving edge-base plate growth. Our findings illuminate how variations in solvent environments can exert control over the edge-base plate growth pathways, thereby resulting in the formation of diverse and complex morphologies. This understanding holds significant potential for guiding the chemical synthesis of bioskeleton materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c02346
Hongmei Luo, Min Ouyang, Hongchen Li, Saiqun Nie, Dong Xu, Tian Zhao
Chemical equilibrium stands as a fundamental principle governing the dynamics of chemical systems. However, it may become intricate when it refers to nanomaterials because of their unique properties. Here, we invesitigated concave gold nanocubes (CGNs) subjected to an akaline Au3+/H2O2 solution, which exhibit both etching and growth in a monotonic solution. When CGNs were subjected to an increasingly alkaline Au3+/H2O2 solution, their dimensions increased from 107 to 199 nm and then decreased to 125 nm. Transmission electron microscopy (TEM) demonstrated that their morphology undergoes intricate alternations from concave to mutibranch and finally to concave again. Real-time ultraviolet–visible spectroscopy and time-dependent TEM also demonstrated reduction first and then oxidation in one solution. Among the nanomaterials, the obtained carpenterworm-like gold nanoparticles revealed the best catalytic performance in p-nitrophenol reduction by NaBH4, with a chemical rate that continues to increase until the reaction reaches completion. Growth leading to atomic dislocation, distortion, and exposure on nanoparticles and the redox of H2O2 plausibly account for the further etching due to the Ostwald ripening effect. Our study may spur more interest in the tuning of the properties, engineering, investigation, and design of new kinds of nanomaterials.
{"title":"Concave Gold Nanocubes Exhibit Growth-Etching Behavior: Unexpected Morphological Transformations","authors":"Hongmei Luo, Min Ouyang, Hongchen Li, Saiqun Nie, Dong Xu, Tian Zhao","doi":"10.1021/acs.inorgchem.4c02346","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02346","url":null,"abstract":"Chemical equilibrium stands as a fundamental principle governing the dynamics of chemical systems. However, it may become intricate when it refers to nanomaterials because of their unique properties. Here, we invesitigated concave gold nanocubes (CGNs) subjected to an akaline Au<sup>3+</sup>/H<sub>2</sub>O<sub>2</sub> solution, which exhibit both etching and growth in a monotonic solution. When CGNs were subjected to an increasingly alkaline Au<sup>3+</sup>/H<sub>2</sub>O<sub>2</sub> solution, their dimensions increased from 107 to 199 nm and then decreased to 125 nm. Transmission electron microscopy (TEM) demonstrated that their morphology undergoes intricate alternations from concave to mutibranch and finally to concave again. Real-time ultraviolet–visible spectroscopy and time-dependent TEM also demonstrated reduction first and then oxidation in one solution. Among the nanomaterials, the obtained carpenterworm-like gold nanoparticles revealed the best catalytic performance in <i>p</i>-nitrophenol reduction by NaBH<sub>4</sub>, with a chemical rate that continues to increase until the reaction reaches completion. Growth leading to atomic dislocation, distortion, and exposure on nanoparticles and the redox of H<sub>2</sub>O<sub>2</sub> plausibly account for the further etching due to the Ostwald ripening effect. Our study may spur more interest in the tuning of the properties, engineering, investigation, and design of new kinds of nanomaterials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Enantioselective synthesis of homochiral rare earth clusters is still a great challenge. In this work, we developed an efficient “cluster to cluster” approach, that is, a pair of enantiomerical R/S-{Nd8Fe3}-oxo clusters were successfully obtained from the presynthesized racemic {Nd9Fe2}-oxo cluster. R/S-hydrobenzoin ligands trigger the transformation of the pristine clusters by an SN2-like mechanism. Compared to the pristine cluster with an achiral core, the new cluster exhibits hierarchical chirality, from ligand chirality to interface chirality, then to helix chirality, and finally to supramolecular double helix chirality. The spectral experiments monitored the transformation and confirmed distinctly structure-related optical activity. The enantiomeric pure cluster also exhibits a potential asymmetric catalytic activity.
{"title":"Enantioselective Synthesis of Homochiral Hierarchical Nd8Fe3-Oxo Cluster from Racemic Nd9Fe2-Oxo Cluster","authors":"Ying Lu, Xiu-Xia Ding, Ju-Suo Zhong, Zhan-Guo Jiang, Cai-Hong Zhan","doi":"10.1021/acs.inorgchem.4c01635","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01635","url":null,"abstract":"Enantioselective synthesis of homochiral rare earth clusters is still a great challenge. In this work, we developed an efficient “cluster to cluster” approach, that is, a pair of enantiomerical <i>R</i>/<i>S</i>-{Nd<sub>8</sub>Fe<sub>3</sub>}-oxo clusters were successfully obtained from the presynthesized racemic {Nd<sub>9</sub>Fe<sub>2</sub>}-oxo cluster. <i>R</i>/<i>S</i>-hydrobenzoin ligands trigger the transformation of the pristine clusters by an SN<sub>2</sub>-like mechanism. Compared to the pristine cluster with an achiral core, the new cluster exhibits hierarchical chirality, from ligand chirality to interface chirality, then to helix chirality, and finally to supramolecular double helix chirality. The spectral experiments monitored the transformation and confirmed distinctly structure-related optical activity. The enantiomeric pure cluster also exhibits a potential asymmetric catalytic activity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c01552
Xinyue Hong, Youting Fang, Duobin Chao
Molecule/semiconductor hybrid catalysts, which combine molecular metal complexes with semiconductors, have shown outstanding performances in photocatalytic CO2 reduction. In this work, we report two hybrid catalysts for the selective photoreduction of CO2 to CO. One is composed of carbon nitride and a terpyridine–Lu complex (denoted as LutpyCN), and the other is composed of carbon nitride and a terpyridine–Ce complex (denoted as CetpyCN). Compared with pristine carbon nitride, the hybrid catalysts LutpyCN and CetpyCN display a noteworthy increase in CO generation, boosting the yield by approximately 176 times and 106 times, respectively. Mechanistic studies demonstrate that such significant enhancement in photocatalysis is primarily due to more efficient separation of photogenerated carriers for hybrid catalysts after modifying CN with molecular terpyridine–lanthanide species.
分子/半导体杂化催化剂将分子金属复合物与半导体结合在一起，在光催化二氧化碳还原过程中表现出卓越的性能。在这项工作中，我们报告了两种用于将 CO2 选择性光还原为 CO 的混合催化剂。其中一种由氮化碳和铽吡啶-Lu 复合物（简称 LutpyCN）组成，另一种由氮化碳和铽吡啶-Ce 复合物（简称 CetpyCN）组成。与原始氮化碳相比，混合催化剂 LutpyCN 和 CetpyCN 的 CO 生成量显著增加，分别提高了约 176 倍和 106 倍。机理研究表明，光催化效果之所以有如此显著的提高，主要是由于用分子铽镧系物种修饰 CN 后，混合催化剂能更有效地分离光生载体。
{"title":"Molecular Terpyridine–Lanthanide Complexes Modified Carbon Nitride for Enhanced Photocatalytic CO2 Reduction","authors":"Xinyue Hong, Youting Fang, Duobin Chao","doi":"10.1021/acs.inorgchem.4c01552","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01552","url":null,"abstract":"Molecule/semiconductor hybrid catalysts, which combine molecular metal complexes with semiconductors, have shown outstanding performances in photocatalytic CO<sub>2</sub> reduction. In this work, we report two hybrid catalysts for the selective photoreduction of CO<sub>2</sub> to CO. One is composed of carbon nitride and a terpyridine–Lu complex (denoted as LutpyCN), and the other is composed of carbon nitride and a terpyridine–Ce complex (denoted as CetpyCN). Compared with pristine carbon nitride, the hybrid catalysts LutpyCN and CetpyCN display a noteworthy increase in CO generation, boosting the yield by approximately 176 times and 106 times, respectively. Mechanistic studies demonstrate that such significant enhancement in photocatalysis is primarily due to more efficient separation of photogenerated carriers for hybrid catalysts after modifying CN with molecular terpyridine–lanthanide species.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.inorgchem.4c01299
Minh N. Tran, Rafaella Saa Rodriguez, Joseph R. Geniesse, Kajini Sandrakumar, Iver J. Cleveland, Eray S. Aydil
Bismuth-based halide perovskites are nontoxic alternatives to widely studied lead-based perovskites for optoelectronic applications. Here, we synthesized Cs2NaBiCl6 thin films and attempted to synthesize Cs2NaBiBr6 using physical vapor deposition. While Cs2NaBiCl6 forms a stable cubic structure with a 3.4 eV band gap and could be synthesized successfully, Cs2NaBiBr6 does not form and is unstable with respect to dissociation into Cs3–xNaxBi2Br9 and Cs3–xNaxBiBr6. Furthermore, the close X-ray diffraction patterns of Cs3–xNaxBi2Br9 and Cs2NaBiBr6 raise doubts about the previous reports of the latter’s formation based on X-ray diffraction alone.
铋基卤化物包晶是光电应用中无毒的替代品，可替代广泛研究的铅基包晶。在这里，我们合成了 Cs2NaBiCl6 薄膜，并尝试用物理气相沉积法合成 Cs2NaBiBr6。Cs2NaBiCl6 形成了稳定的立方结构，具有 3.4 eV 的带隙，可以成功合成，而 Cs2NaBiBr6 却没有形成，而且不稳定，无法解离成 Cs3-xNaxBi2Br9 和 Cs3-xNaxBiBr6。此外，Cs3-xNaxBi2Br9 和 Cs2NaBiBr6 的 X 射线衍射图样非常接近，这使人们对之前仅根据 X 射线衍射就得出 Cs3-xNaxBi2Br9 和 Cs2NaBiBr6 的报告产生了怀疑。
{"title":"Stability of Cs2NaBiBr6 and Cs2NaBiCl6","authors":"Minh N. Tran, Rafaella Saa Rodriguez, Joseph R. Geniesse, Kajini Sandrakumar, Iver J. Cleveland, Eray S. Aydil","doi":"10.1021/acs.inorgchem.4c01299","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01299","url":null,"abstract":"Bismuth-based halide perovskites are nontoxic alternatives to widely studied lead-based perovskites for optoelectronic applications. Here, we synthesized Cs<sub>2</sub>NaBiCl<sub>6</sub> thin films and attempted to synthesize Cs<sub>2</sub>NaBiBr<sub>6</sub> using physical vapor deposition. While Cs<sub>2</sub>NaBiCl<sub>6</sub> forms a stable cubic structure with a 3.4 eV band gap and could be synthesized successfully, Cs<sub>2</sub>NaBiBr<sub>6</sub> does not form and is unstable with respect to dissociation into Cs<sub>3–<i>x</i></sub>Na<sub><i>x</i></sub>Bi<sub>2</sub>Br<sub>9</sub> and Cs<sub>3–<i>x</i></sub>Na<sub><i>x</i></sub>BiBr<sub>6</sub>. Furthermore, the close X-ray diffraction patterns of Cs<sub>3–<i>x</i></sub>Na<sub><i>x</i></sub>Bi<sub>2</sub>Br<sub>9</sub> and Cs<sub>2</sub>NaBiBr<sub>6</sub> raise doubts about the previous reports of the latter’s formation based on X-ray diffraction alone.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：