Pub Date : 2025-06-14DOI: 10.1021/acs.inorgchem.5c00344
Arunaprabha Andipet, Prince Wesley Vanaraj, Lokeswaran Ravi, Kamala Bharathi Karuppanan, Krishnamoorthy Guruvidyathri, Suresh Perumal, Ravi kirana
High-entropy oxides (HEOs) have garnered significant attention as promising materials for sustainable energy applications due to their unique structural features, flexible chemical compositions, and tunable physicochemical and functional properties. This study explores the potential of (CuZnNiCoMg)O HEO for use in electrochemical and photocatalytic properties. Also, this study examines the role of magnesium (Mg) in enhancing the properties of (CuZnNiCo)O HEO. The (CuZnNiCo)O has formed a cubic rocksalt structure after calcination at 1473 K, while (CuZnNiCoMg)O achieved the same phase at a significantly lower temperature of 1173 K. The specific capacitance (Cs) values measured for the (CuZnNiCoMg)O and (CuZnNiCo)O electrodes were 276.69 and 257.88 Fg–1, respectively, in 1 M KOH at a scan rate of 1 mVs–1. Additionally, both compositions were employed as photocatalysts for the dye degradation of methylene blue (MB). The (CuZnNiCoMg)O photocatalyst achieved 81.14% degradation efficiency in one h, significantly outperforming the 64.16% efficiency achieved by the (CuZnNiCo)O photocatalyst under similar conditions. These findings underscore the superior multifunctional performance of (CuZnNiCoMg)O, highlighting its potential for energy storage and environmental remediation applications.
{"title":"High Electrochemical Performance and Photocatalytic Activity in Multicomponent Nanostructured (CuZnNiCoMg)O","authors":"Arunaprabha Andipet, Prince Wesley Vanaraj, Lokeswaran Ravi, Kamala Bharathi Karuppanan, Krishnamoorthy Guruvidyathri, Suresh Perumal, Ravi kirana","doi":"10.1021/acs.inorgchem.5c00344","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00344","url":null,"abstract":"High-entropy oxides (HEOs) have garnered significant attention as promising materials for sustainable energy applications due to their unique structural features, flexible chemical compositions, and tunable physicochemical and functional properties. This study explores the potential of (CuZnNiCoMg)O HEO for use in electrochemical and photocatalytic properties. Also, this study examines the role of magnesium (Mg) in enhancing the properties of (CuZnNiCo)O HEO. The (CuZnNiCo)O has formed a cubic rocksalt structure after calcination at 1473 K, while (CuZnNiCoMg)O achieved the same phase at a significantly lower temperature of 1173 K. The specific capacitance (<i>C</i><sub>s</sub>) values measured for the (CuZnNiCoMg)O and (CuZnNiCo)O electrodes were 276.69 and 257.88 Fg<sup>–1</sup>, respectively, in 1 M KOH at a scan rate of 1 mVs<sup>–1</sup>. Additionally, both compositions were employed as photocatalysts for the dye degradation of methylene blue (MB). The (CuZnNiCoMg)O photocatalyst achieved 81.14% degradation efficiency in one h, significantly outperforming the 64.16% efficiency achieved by the (CuZnNiCo)O photocatalyst under similar conditions. These findings underscore the superior multifunctional performance of (CuZnNiCoMg)O, highlighting its potential for energy storage and environmental remediation applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288434","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 : 2025-06-13DOI: 10.1021/acs.inorgchem.5c00009
Christine M. Morales, Annika L. Medrano, Thomas M. Gilbert
To investigate exceptions to the VSEPR principle that species with asymmetric lone pairs have bond angles smaller than those of their idealized molecular shapes, we computationally optimized the structures of a wide variety of small molecules and polyatomic anions, including as many experimentally characterized structures as possible, and applied a topological analysis of the electron localization function (ELF) as well as Natural Bond Orbital analysis (NBO). Species were chosen to represent each valence shell electron pair repulsion (VSEPR) shape with asymmetric lone pairs on the central atom. Results confirmed well-established precedents, including ligand close packing and Bent’s rule, clarifying our understanding of lone pair size in terms of volume per electron around the central atom: (a) lone pairs exclude more volume around the surface of a main–group central atom than a single covalent bond from the central atom to a substituent of similar size; (b) lone pairs exclude more volume around central atoms in lower oxidation states than in higher oxidation states; and (c) substituents larger than the central atom, multiply bonded to the central atom, and/or less electronegative than the central atom compete more effectively with lone pairs to expand bond angles and limit steric demands of lone pairs.
{"title":"Refining the VSEPR Model: Limits on the Lone Pair Size as Described by the Electron Localization Function","authors":"Christine M. Morales, Annika L. Medrano, Thomas M. Gilbert","doi":"10.1021/acs.inorgchem.5c00009","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00009","url":null,"abstract":"To investigate exceptions to the VSEPR principle that species with asymmetric lone pairs have bond angles smaller than those of their idealized molecular shapes, we computationally optimized the structures of a wide variety of small molecules and polyatomic anions, including as many experimentally characterized structures as possible, and applied a topological analysis of the electron localization function (ELF) as well as Natural Bond Orbital analysis (NBO). Species were chosen to represent each valence shell electron pair repulsion (VSEPR) shape with asymmetric lone pairs on the central atom. Results confirmed well-established precedents, including ligand close packing and Bent’s rule, clarifying our understanding of lone pair size in terms of volume per electron around the central atom: (a) lone pairs exclude more volume around the surface of a main–group central atom than a single covalent bond from the central atom to a substituent of similar size; (b) lone pairs exclude more volume around central atoms in lower oxidation states than in higher oxidation states; and (c) substituents larger than the central atom, multiply bonded to the central atom, and/or less electronegative than the central atom compete more effectively with lone pairs to expand bond angles and limit steric demands of lone pairs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"49 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278848","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 : 2025-06-13DOI: 10.1021/acs.inorgchem.5c01706
Justin Cado, Alexandre Abhervé, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic, Narcis Avarvari
Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4S,7R)camphor-2,2-bpp, the regioisomer bis(4S,7R)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic P21 space group for the enantiopure compounds and the centrosymmetric monoclinic P21/n space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors glum reaching up ±0.2 for the 7F1 ← 5D0 magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4S,7R)camphor-2,2-bpp and bis(4S,7R)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.
{"title":"Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes","authors":"Justin Cado, Alexandre Abhervé, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic, Narcis Avarvari","doi":"10.1021/acs.inorgchem.5c01706","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01706","url":null,"abstract":"Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp, the regioisomer bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic <i>P</i>2<sub>1</sub> space group for the enantiopure compounds and the centrosymmetric monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors <i>g</i><sub>lum</sub> reaching up ±0.2 for the <sup>7</sup>F<sub>1</sub> ← <sup>5</sup>D<sub>0</sub> magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp and bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278849","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 : 2025-06-13DOI: 10.1021/acs.inorgchem.5c01230
Samuel B. Zlotnikov, Nicholas J. Katzer, Patrick W. Smith, Elias Tanuhadi, Stefan Minasian, Polly L. Arnold
Isostructural, diamagnetic diluents are commonly used in magnetic investigations to eliminate interactions between neighboring electron spins. For divalent lanthanides, these diluents are currently limited to closed-shell ytterbium(II) complexes; ytterbium(II), however, is a poor size-match for the large early- and mid-lanthanides, precluding access to certain ligand frameworks. To aid in the study of lanthanide(II) complexes with unconventional electronic structures and magnetic properties, three strontium tris-cyclopentadienyl complexes, [K(2.2.2-cryptand)][SrCpR3], with common substituted cyclopentadienyl ligands, CpR = C5Me4H (Cptet), C5H4(SiMe3) (Cp′), and C5H3(SiMe3)2 (Cp″) were synthesized, characterized, and examined as diamagnetic diluents. En route to their synthesis, two new Sr metallocenes, [SrCpR2] CpR = Cptet, Cp′, were also prepared. [K(2.2.2-cryptand)][SrCptet3] was used to dilute the new complex [K(2.2.2-cryptand)][EuIICptet3], and the EPR spectra of the diluted material shows narrower linewidths than those of pure [K(2.2.2-cryptand)][EuIICptet3], suggesting an increase in the spin–spin relaxation time that enables determination of the europium hyperfine coupling constant.
{"title":"Strontium Tris(cyclopentadienyl) Complexes: Isostructural f0/d0 Analogues of Divalent Lanthanides","authors":"Samuel B. Zlotnikov, Nicholas J. Katzer, Patrick W. Smith, Elias Tanuhadi, Stefan Minasian, Polly L. Arnold","doi":"10.1021/acs.inorgchem.5c01230","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01230","url":null,"abstract":"Isostructural, diamagnetic diluents are commonly used in magnetic investigations to eliminate interactions between neighboring electron spins. For divalent lanthanides, these diluents are currently limited to closed-shell ytterbium(II) complexes; ytterbium(II), however, is a poor size-match for the large early- and mid-lanthanides, precluding access to certain ligand frameworks. To aid in the study of lanthanide(II) complexes with unconventional electronic structures and magnetic properties, three strontium tris-cyclopentadienyl complexes, [K(2.2.2-cryptand)][SrCp<sup>R</sup><sub>3</sub>], with common substituted cyclopentadienyl ligands, Cp<sup>R</sup> = C<sub>5</sub>Me<sub>4</sub>H (Cp<sup>tet</sup>), C<sub>5</sub>H<sub>4</sub>(SiMe<sub>3</sub>) (Cp′), and C<sub>5</sub>H<sub>3</sub>(SiMe<sub>3</sub>)<sub>2</sub> (Cp″) were synthesized, characterized, and examined as diamagnetic diluents. En route to their synthesis, two new Sr metallocenes, [SrCp<sup>R</sup><sub>2</sub>] Cp<sup>R</sup> = Cp<sup>tet</sup>, Cp′, were also prepared. [K(2.2.2-cryptand)][SrCp<sup>tet</sup><sub>3</sub>] was used to dilute the new complex [K(2.2.2-cryptand)][Eu<sup>II</sup>Cp<sup>tet</sup><sub>3</sub>], and the EPR spectra of the diluted material shows narrower linewidths than those of pure [K(2.2.2-cryptand)][Eu<sup>II</sup>Cp<sup>tet</sup><sub>3</sub>], suggesting an increase in the spin–spin relaxation time that enables determination of the europium hyperfine coupling constant.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288435","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 : 2025-06-12DOI: 10.1021/acs.inorgchem.5c01101
Yufeng Liu, Jiawei Cao, Jun Wu, Haoqi Liu, Ke Li, Xiaoling Lin, Guoping Yang
The quest to delve into high-nuclearity molecular metal-oxo clusters and unravel their reactivity presents a significant challenge in chemistry and materials science. In this work, we synthesized an unprecedented bowknot-like selenotungstates, [Ce7Se7W47O171(OH)(H2O)25(mal)]230- (Ce14W94, H3mal = dl-malic acid) via an in situ assembly strategy. The three building units, including tetravacant Keggin-{SeW8}, bivacant Dawson-{Se2W16}, and trivacant Keggin-{SeW9}, were self-assembled by the connection of {W1}, independent {SeO3} fragments, and seven mutually isolated Ce3+ ions to form the unique asymmetric structure, which was further extended to the bowknot-like dimeric structure and the 1D chain structure by symmetry. Due to the good photoelectric activity, Ce14W94 can serve as a highly efficient photocatalyst for the conversion of C–H to C–N bonds by hydroacylation of dialkyl azodicarboxylates, with a broad substrate scope and excellent reusability. This work enriches the assembly mode of POMs and provides a highly efficient photocatalyst.
{"title":"A Giant Ce3+-Bridged Selenotungstate Containing Three Different Building Blocks for Photocatalyzed C–N Bonds Formation","authors":"Yufeng Liu, Jiawei Cao, Jun Wu, Haoqi Liu, Ke Li, Xiaoling Lin, Guoping Yang","doi":"10.1021/acs.inorgchem.5c01101","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01101","url":null,"abstract":"The quest to delve into high-nuclearity molecular metal-oxo clusters and unravel their reactivity presents a significant challenge in chemistry and materials science. In this work, we synthesized an unprecedented bowknot-like selenotungstates, [Ce<sub>7</sub>Se<sub>7</sub>W<sub>47</sub>O<sub>171</sub>(OH)(H<sub>2</sub>O)<sub>25</sub>(mal)]<sub>2</sub><sup>30-</sup> (<b>Ce</b><sub><b>14</b></sub><b>W</b><sub><b>94</b></sub>, H<sub>3</sub>mal = <span>dl</span>-malic acid) via an <i>in situ</i> assembly strategy. The three building units, including tetravacant Keggin-{SeW<sub>8</sub>}, bivacant Dawson-{Se<sub>2</sub>W<sub>16</sub>}, and trivacant Keggin-{SeW<sub>9</sub>}, were self-assembled by the connection of {W<sub>1</sub>}, independent {SeO<sub>3</sub>} fragments, and seven mutually isolated Ce<sup>3+</sup> ions to form the unique asymmetric structure, which was further extended to the bowknot-like dimeric structure and the 1D chain structure by symmetry. Due to the good photoelectric activity, <b>Ce</b><sub><b>14</b></sub><b>W</b><sub><b>94</b></sub> can serve as a highly efficient photocatalyst for the conversion of C–H to C–N bonds by hydroacylation of dialkyl azodicarboxylates, with a broad substrate scope and excellent reusability. This work enriches the assembly mode of POMs and provides a highly efficient photocatalyst.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278852","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 : 2025-06-12DOI: 10.1021/acs.inorgchem.5c01349
Li Guo, Xinxin Han, Yuhan Li, Qiufeng Guo, Shanshan Fu, Honghui Hu, Xin Li, Yan Yang, Shixia Chen, Shuguang Deng, Jun Wang
Elucidating the role of electrolytes in steering CO2 electroreduction toward C2+ products is critical, yet impeded by dynamic electrocatalyst reconstruction during the CO2RR. Herein, we successfully prepared a novel Cu-based metal-organic framework (Cu-BDP, BDP = 1,4-benzenedipyrazolate) with robust Cu-N4 coordination. Bode phase analysis and contact angle measurements demonstrate that Cs+ cations facilitate interfacial charge transfer and establish local hydrophobic microenvironments to suppress hydrogen evolution reactions. Meanwhile, adsorbed I-anions generate more accessible active sites. As a result, in the optimized CsI electrolyte, a high C2 Faradaic efficiency of 50.34% is achieved at -1.6 V vs RHE. Density functional theory (DFT) calculations reveal that I- anions preferentially facilitate initial CO2 activation and stabilize single *CO intermediates, while Cs+ cations promote the enrichment of multi-CO intermediates and the hydrogenation of *OCCO to *OCCOH on the Cu-BDP surface. Furthermore, the synergistic effect of the Cs+/I- binary electrolyte system significantly reduces the energy barrier for C-C coupling compared to electrolytes containing only Cs+ or I- ions. This work provides insights into the synergistic effect of electrolyte cations and halide ions on CO2 electroreduction.
阐明电解质在将CO2电还原转向C2+产物中的作用是至关重要的，但在CO2RR过程中，动态电催化剂重构阻碍了电解质的作用。本文成功制备了一种新型cu基金属有机骨架（Cu-BDP, BDP = 1,4-苯二吡甲酸酯），具有良好的Cu-N4配位。波德相分析和接触角测量表明，Cs+阳离子促进界面电荷转移，建立局部疏水微环境，抑制析氢反应。同时，吸附的i -阴离子产生更多可接近的活性位点。结果表明，在优化后的CsI电解液中，在-1.6 V vs RHE下，C2法拉第效率高达50.34%。密度泛函理论（DFT）计算表明，I-阴离子优先促进初始CO2活化和稳定单*CO中间体，而Cs+阳离子促进多CO中间体在Cu-BDP表面的富集和*OCCO加氢成*OCCOH。此外，与仅含有Cs+或I-离子的电解质相比，Cs+/I-二元电解质体系的协同效应显著降低了C-C耦合的能量势垒。这项工作提供了对电解质阳离子和卤化物离子对CO2电还原的协同效应的见解。
{"title":"Elucidating the Effects of Electrolytes on a Robust MOF Interface for Enhanced CO<sub>2</sub> Electroreduction to C<sub>2</sub> Products.","authors":"Li Guo, Xinxin Han, Yuhan Li, Qiufeng Guo, Shanshan Fu, Honghui Hu, Xin Li, Yan Yang, Shixia Chen, Shuguang Deng, Jun Wang","doi":"10.1021/acs.inorgchem.5c01349","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01349","url":null,"abstract":"<p><p>Elucidating the role of electrolytes in steering CO<sub>2</sub> electroreduction toward C<sub>2+</sub> products is critical, yet impeded by dynamic electrocatalyst reconstruction during the CO<sub>2</sub>RR. Herein, we successfully prepared a novel Cu-based metal-organic framework (Cu-BDP, BDP = 1,4-benzenedipyrazolate) with robust Cu-N<sub>4</sub> coordination. Bode phase analysis and contact angle measurements demonstrate that Cs<sup>+</sup> cations facilitate interfacial charge transfer and establish local hydrophobic microenvironments to suppress hydrogen evolution reactions. Meanwhile, adsorbed I<sup>-</sup>anions generate more accessible active sites. As a result, in the optimized CsI electrolyte, a high C<sub>2</sub> Faradaic efficiency of 50.34% is achieved at -1.6 V vs RHE. Density functional theory (DFT) calculations reveal that I<sup>-</sup> anions preferentially facilitate initial CO<sub>2</sub> activation and stabilize single *CO intermediates, while Cs<sup>+</sup> cations promote the enrichment of multi-CO intermediates and the hydrogenation of *OCCO to *OCCOH on the Cu-BDP surface. Furthermore, the synergistic effect of the Cs<sup>+</sup>/I<sup>-</sup> binary electrolyte system significantly reduces the energy barrier for C-C coupling compared to electrolytes containing only Cs<sup>+</sup> or I<sup>-</sup> ions. This work provides insights into the synergistic effect of electrolyte cations and halide ions on CO<sub>2</sub> electroreduction.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281685","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 : 2025-06-12DOI: 10.1021/acs.inorgchem.5c01282
Doctor Stephen, Alexander Roseborough, Dhruba R. Paudel, Pere Miro, May Nyman
Polyoxopalladates (POPs) are an extension of classic polyoxometalates. The two most frequently observed POP topologies are the nanostar (Pd15) and the cube (Pd12), where the heterometal cation in the central cavity may influence topology selection. Here, we crystallize ten lanthanoid-centered, phenylphosphonate-capped POPs (YIII, LaIII, CeIII, PrIII, NdIII, SmIII, EuIII, GdIII, YbIII, and LuIII) and one actinide-centered (ThIV) POP. Single-crystal X-ray analysis reveals that most LnIII favors the Pd15 nanostar, while Yb and Lu favor the Pd12 cube. Between Tb and Tm, no single-crystal growth occurred, challenging our initial hypothesis that topology selection was entirely based on the central metal cation size. Computation supported this hypothesis; the transition from Pd15 to Pd12 as the favored topology occurs in the third quarter of the lanthanide series. On the other hand, PXRD of all the crystallized/precipitated bulk materials suggested Pd15 is always the favored topology, and inspection of the lattices reveals that Pd15–Na interactions likely promote incipient crystallization, while no such interactions are seen in the Pd12 lattices. Electrospray ionization mass spectrometry confirmed the presence of both Pd12 and Pd15 for the smaller lanthanides (Yb), only Pd15 for the larger lanthanides (Ce), and no clusters were observed between Tb and Tm, where crystal growth was also challenging.
{"title":"Lanthanoid-, Yttrium-, and Thorium-Centered Polyoxopalladates","authors":"Doctor Stephen, Alexander Roseborough, Dhruba R. Paudel, Pere Miro, May Nyman","doi":"10.1021/acs.inorgchem.5c01282","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01282","url":null,"abstract":"Polyoxopalladates (POPs) are an extension of classic polyoxometalates. The two most frequently observed POP topologies are the nanostar (Pd<sub>15</sub>) and the cube (Pd<sub>12</sub>), where the heterometal cation in the central cavity may influence topology selection. Here, we crystallize ten lanthanoid-centered, phenylphosphonate-capped POPs (Y<sup>III</sup>, La<sup>III</sup>, Ce<sup>III</sup>, Pr<sup>III</sup>, Nd<sup>III</sup>, Sm<sup>III</sup>, Eu<sup>III</sup>, Gd<sup>III</sup>, Yb<sup>III</sup>, and Lu<sup>III</sup>) and one actinide-centered (Th<sup>IV</sup>) POP. Single-crystal X-ray analysis reveals that most Ln<sup>III</sup> favors the Pd<sub>15</sub> nanostar, while Yb and Lu favor the Pd<sub>12</sub> cube. Between Tb and Tm, no single-crystal growth occurred, challenging our initial hypothesis that topology selection was entirely based on the central metal cation size. Computation supported this hypothesis; the transition from Pd<sub>15</sub> to Pd<sub>12</sub> as the favored topology occurs in the third quarter of the lanthanide series. On the other hand, PXRD of all the crystallized/precipitated bulk materials suggested Pd<sub>15</sub> is always the favored topology, and inspection of the lattices reveals that Pd<sub>15</sub>–Na interactions likely promote incipient crystallization, while no such interactions are seen in the Pd<sub>12</sub> lattices. Electrospray ionization mass spectrometry confirmed the presence of both Pd<sub>12</sub> and Pd<sub>15</sub> for the smaller lanthanides (Yb), only Pd<sub>15</sub> for the larger lanthanides (Ce), and no clusters were observed between Tb and Tm, where crystal growth was also challenging.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279002","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 : 2025-06-12DOI: 10.1021/acs.inorgchem.5c00458
Avery L. Blockmon, Jinhyeong Jo, Kiman Park, Emma Kirkman-Davis, Mark M. Turnbull, Minseong Lee, John Singleton, Stephen A. McGill, Heung-Sik Kim, Jun Hee Lee, Janice L. Musfeldt
The magnetic properties and phase diagrams of S = 1/2 quasi-one-dimensional Heisenberg antiferromagnets are well-established with copper-containing coordination polymers as the platform of choice due to their low energy scales and ease of chemical substitution. The inability to uncover orbitally resolved components of the magnetization has, however, been a long-standing barrier to greater understanding of high field spin state transitions. In this work, we combine pulsed field magnetization, optical spectroscopy, and magnetic circular dichroism with complementary electronic structure calculations to unravel orbital-specific contributions to the magnetism in the linear chain quantum magnet [CuL2(H2O)2(pyz)](ClO4)2 [L = 5-methyl-2-pyridone; pyz = pyrazine]. In addition to revealing a spin flop and field-driven transition to the fully saturated spin state, we untangle the green → teal color change across the 185 K structural phase transition and employ what we learn about the different Cu2+ → pyrazine charge transfer excitations to decompose the magnetic circular dichroism. Analysis reveals that both eg-derived Cu2+ 3d orbitals play a role in the field-driven transition to the fully saturated state, not just those formally hosting unpaired electrons. We attribute the surprisingly strong dichroic signature at room temperature to the presence of uncorrelated spin.
S = 1/2准一维海森堡反铁磁体的磁性和相图已经建立，含铜配位聚合物作为平台的选择，由于其低能尺度和易于化学取代。然而，无法发现轨道分辨的磁化分量，长期以来一直是更好地理解高场自旋态转变的障碍。在这项工作中，我们将脉冲场磁化、光谱学和磁性圆二色性与互补电子结构计算相结合，揭示了线性链量子磁体[CuL2(H2O)2(pyz)](ClO4)2 [L = 5-甲基-2-吡啶酮；Pyz =吡嗪]。除了揭示自旋翻转和场驱动到完全饱和自旋态的转变外，我们还解开了185k结构相变中绿色→青色的变化，并利用我们所了解的不同Cu2+→吡嗪电荷转移激发来分解磁圆二色性。分析表明，两个由egg衍生的Cu2+ 3d轨道在场驱动过渡到完全饱和状态中发挥了作用，而不仅仅是那些正式携带未配对电子的轨道。我们将室温下令人惊讶的强烈二色性特征归因于不相关自旋的存在。
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FeOOH polymorphs are valued in industrial catalysis for selective hydrogenation of organics in coal to high - value aromatics, yet the factors behind their differing efficiencies are still unclear. In this work, the synthesis of FeOOH nanopolymorphs with sizes from 80 to 300 nm was achieved through a simple, efficient, and environmentally friendly room temperature solid-phase chemical reaction. FeOOH polymorphs demonstrate different iron oxidation states and abundant surface hydroxyls. Among them, δ-FeOOH, with its lower iron oxidation state and rich surface hydroxyls, enhances hydrogen adsorption and lowers hydrogen activation energy through hydrogen bonding. Notably, δ-FeOOH achieved the complete conversion of benzyl phenyl ether, a typical α-O-4 linkage model compound in coal at 270 °C and 20 bar H2 for 2 h. This study provides valuable insights into the intricate relationship between FeOOH polymorphs and catalytic performance, contributing to the sustainable development of FeOOH-based hydrogenation catalysts.
FeOOH多晶型物在煤中有机物选择性加氢制高价值芳烃的工业催化中具有重要价值，但其不同效率背后的因素尚不清楚。在这项工作中，通过简单、高效、环保的室温固相化学反应，合成了尺寸从80到300 nm的FeOOH纳米多晶。FeOOH多晶表现出不同的铁氧化态和丰富的表面羟基。其中δ-FeOOH具有较低的铁氧化态和丰富的表面羟基，通过氢键作用增强氢吸附，降低氢活化能。值得注意的是，δ-FeOOH在270°C和20 bar H2条件下，在煤中实现了典型α-O-4连锁模型化合物苯并苯基醚的完全转化。该研究为FeOOH多晶型与催化性能之间的复杂关系提供了有价值的见解，有助于FeOOH基加氢催化剂的可持续发展。
{"title":"Synthesis of FeOOH Polymorphs by Room Temperature Solid-State Chemical Reaction: Effect on the Selective Cracking of Aromatic Hydrocarbons with C–O Bridge Bonds","authors":"Jinhua Wang, Yakun Tang, Xiaodong Guo, Lang Liu, Yue Zhang, Ting Liu, Jingmei Liu, Xiaodong Zhou, Xiaohui Li, Dianzeng Jia","doi":"10.1021/acs.inorgchem.5c00543","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00543","url":null,"abstract":"FeOOH polymorphs are valued in industrial catalysis for selective hydrogenation of organics in coal to high - value aromatics, yet the factors behind their differing efficiencies are still unclear. In this work, the synthesis of FeOOH nanopolymorphs with sizes from 80 to 300 nm was achieved through a simple, efficient, and environmentally friendly room temperature solid-phase chemical reaction. FeOOH polymorphs demonstrate different iron oxidation states and abundant surface hydroxyls. Among them, δ-FeOOH, with its lower iron oxidation state and rich surface hydroxyls, enhances hydrogen adsorption and lowers hydrogen activation energy through hydrogen bonding. Notably, δ-FeOOH achieved the complete conversion of benzyl phenyl ether, a typical α-O-4 linkage model compound in coal at 270 °C and 20 bar H<sub>2</sub> for 2 h. This study provides valuable insights into the intricate relationship between FeOOH polymorphs and catalytic performance, contributing to the sustainable development of FeOOH-based hydrogenation catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278850","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 : 2025-06-12DOI: 10.1021/acs.inorgchem.5c02265
Qingqing Guo, Tianyu Chen, Jing Ye, Fei-Yan Yi
This study demonstrates the successful fabrication of mixed-metal CoFePBA/NF with hierarchical 1D + 3D string-bead morphology through in situ conversion, followed by sulfidation to obtain highly active s-CoFePBA/NF. The optimized s-CoFePBA/NF (500 °C) demonstrates exceptional trifunctional electrocatalytic performance, achieving ultralow overpotentials of 226 mV (OER) and 127 mV (HER) at 10 mA cm–2, along with a remarkable UOR potential of 1.317 V. Remarkably, the assembled s-CoFePBA/NF (500 °C)||s-CoFePBA/NF (500 °C) electrolytic cell requires only 1.60 V for overall water splitting and 1.41 V for urea-assisted water splitting at 10 mA cm–2, significantly outperforming the commercial IrO2/NF||Pt/C/NF electrolytic cell (1.53 V). The system maintains excellent stability over 40 h of operation with ∼95% Faradaic efficiency for H2 production, offering an optimized strategy for urea–water electrolysis. Therefore, this work represents an advancement in developing multifunctional electrocatalysts for sustainable hydrogen production coupled with urea wastewater treatment.
本研究证明，通过原位转化，成功制备了具有分层1D + 3D串珠形态的混合金属CoFePBA/NF，然后进行硫化，获得了高活性的s-CoFePBA/NF。优化后的s-CoFePBA/NF（500°C）表现出优异的三功能电催化性能，在10 mA cm-2下实现了226 mV （OER）和127 mV （HER）的超低过电位，以及1.317 V的显著UOR电位。值得注意的是，组装的s-CoFePBA/NF(500°C)||s-CoFePBA/NF（500°C）电解槽在10 mA cm-2下的总水分解仅需1.60 V，尿素辅助水分解仅需1.41 V，明显优于商用IrO2/NF||Pt/C/NF电解槽（1.53 V）。该系统在40小时的运行过程中保持了优异的稳定性，产氢的法拉第效率为95%，为尿素-水电解提供了优化策略。因此，这项工作代表了开发用于可持续制氢和尿素废水处理的多功能电催化剂的进展。
{"title":"Fabricated CoFePBA/NF-Derived Mixed Metal Sulfide as Multifunctional Catalysts for Enhanced Urea–Water Electrolysis","authors":"Qingqing Guo, Tianyu Chen, Jing Ye, Fei-Yan Yi","doi":"10.1021/acs.inorgchem.5c02265","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02265","url":null,"abstract":"This study demonstrates the successful fabrication of mixed-metal CoFePBA/NF with hierarchical 1D + 3D string-bead morphology through in situ conversion, followed by sulfidation to obtain highly active s-CoFePBA/NF. The optimized s-CoFePBA/NF (500 °C) demonstrates exceptional trifunctional electrocatalytic performance, achieving ultralow overpotentials of 226 mV (OER) and 127 mV (HER) at 10 mA cm<sup>–2</sup>, along with a remarkable UOR potential of 1.317 V. Remarkably, the assembled s-CoFePBA/NF (500 °C)||s-CoFePBA/NF (500 °C) electrolytic cell requires only 1.60 V for overall water splitting and 1.41 V for urea-assisted water splitting at 10 mA cm<sup>–2</sup>, significantly outperforming the commercial IrO<sub>2</sub>/NF||Pt/C/NF electrolytic cell (1.53 V). The system maintains excellent stability over 40 h of operation with ∼95% Faradaic efficiency for H<sub>2</sub> production, offering an optimized strategy for urea–wa<sub>t</sub>er electrolysis. Therefore, this work represents an advancement in developing multifunctional electrocatalysts for sustainable hydrogen production coupled with urea wastewater treatment.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279005","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}
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