Journal of Solid State Chemistry最新文献

{"title":"Structural and optoelectronic properties of BA₂(MA)Pb₂I₇ and BDA(MA)Pb₂I₇ perovskites for solar cell applications: A DFT study on the role of organic cations","authors":"Traore Aboubacar ,&nbsp;Mohammadreza Hosseini ,&nbsp;Xing Li ,&nbsp;Jiahong Pan ,&nbsp;Xuepeng Liu ,&nbsp;Songyuan Dai ,&nbsp;Molang Cai","doi":"10.1016/j.jssc.2025.125185","DOIUrl":"10.1016/j.jssc.2025.125185","url":null,"abstract":"<div><div>Two-dimensional (2D) perovskites, renowned for their exceptional optical properties and stability, are increasingly explored for photovoltaic applications. However, the influence of interspace cations on the structural, optoelectronic, surface, water interaction, and mechanical properties of Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phases is still lacking. Using density functional theory (DFT), this study examines the effects of interspace butylammonium (BA) and butanediammonium (BDA) cations, alongside the intercage methylammonium (MA) cation, on the perovskites BA₂(MA)Pb₂I₇ and BDA(MA)Pb₂I₇. Our results show that the BDA cation, with its higher dielectric constant and reduced spatial occupation between inorganic layers, shifts electron absorption in the Pb 6p conduction orbitals to photon energies of 1.69 eV, resulting in improved light absorption, lower exciton binding energy, enhanced charge filtering, and reduced carrier recombination rates compared to the BA-based perovskite (1.86 eV). This feature of BDA lowers the work function, facilitating electron extraction. Additionally, reduced ionisation potentials and electron affinities suggest enhanced charge transport and extraction capabilities. The BDA-based perovskite, with reduced interlayer spacing and increased mass density, minimises voids and strengthens interlayer interactions, providing higher mechanical resistance and improved ductility, as indicated by higher values for Poisson's ratio, Young's modulus, and bulk modulus, as well as better surface resistance to water compared to BA-based perovskites. These attributes make BDA-based perovskites promising candidates for thin-film photovoltaic applications, surpassing BA-based variants in machinability. This study highlights cations' crucial role, spatial occupation, and characteristics in modulating optoelectronic and structural properties, paving the way to optimise 2D perovskites for high-performance photovoltaics.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125185"},"PeriodicalIF":3.2,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of bifunctional active sites in metal-organic framework for effective albendazole capture","authors":"Ting Wang ,&nbsp;Gan Li ,&nbsp;Jia Fu ,&nbsp;Yating Xue ,&nbsp;Bo Xue ,&nbsp;Pengtao Guo ,&nbsp;Chunhui Hu ,&nbsp;Dahuan Liu","doi":"10.1016/j.jssc.2025.125180","DOIUrl":"10.1016/j.jssc.2025.125180","url":null,"abstract":"<div><div>Developing efficient adsorbents for the capture of albendazole is of great significance but still faces challenges. Herein, an adsorbent (MIL-101(Cr)–SO₃H) with a dual-functional active site was synthesized. Benefiting from the abundant –SO₃H groups and unsaturated coordination Cr metal sites, the adsorbent exhibits excellent adsorption performance for albendazole. The maximum adsorption amount can reach 196.4 mg g⁻¹, higher compared to other reported adsorbents. The kinetic study reveals that saturation equilibrium is achieved within 500 min. The adsorption thermodynamics study indicates the adsorption process was spontaneous and endothermic. Experimental characterization and density functional theory calculation jointly demonstrate that coordination, electrostatic attraction, and π-π interactions play primary roles in albendazole adsorption. In addition, this adsorbent has outstanding chemical and thermal stability as well as good adsorption-desorption-regeneration cycle performance. Eventually, this work constructs an efficient adsorbent for the capture of albendazole.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125180"},"PeriodicalIF":3.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular-level regulation strategies for charge separation in conjugated polymer/polymeric carbon nitride heterojunction enabling efficient uranium photoreduction","authors":"Jialiang Kang ,&nbsp;Jianli Ouyang ,&nbsp;Fengtao Yu ,&nbsp;Zhiyong Chen ,&nbsp;Fangru Song ,&nbsp;Ruping Liang ,&nbsp;Jianding Qiu","doi":"10.1016/j.jssc.2024.125173","DOIUrl":"10.1016/j.jssc.2024.125173","url":null,"abstract":"<div><div>Construction of metal free conjugated polymer/polymeric carbon nitride heterojunction has been closely monitored as alternatives to traditional inorganic heterojunction photocatalysis, due to their molecular-level tunable electronic structure. Nevertheless, the realization of efficient photocatalytic is severely hindered by insufficient separation of photogenerated electrons and holes. To address the challenge, we report a general strategy for inserting thiophene units into electron acceptors to form novel donor-acceptor conjugated polymers/polymeric carbon nitride heterojunction (named YSS-2/CN). Combining experiments and theory calculations, it can be concluded that YSS-2/CN exhibits strong charge spatial separation, which is crucial for the photocatalytic process. As expected, the YSS-2/CN shows better photocatalytic reduction activity towards uranium (<em>k</em> = 0.043 min⁻¹), which is 1.16 and 2.87 times higher than those of YSS-1/CN and bulk carbon nitride (CN). This rational molecular design strategy provides a good platform for the development of efficient polymeric heterojunction photocatalysts for the removal and extraction of uranium.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125173"},"PeriodicalIF":3.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142800","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cu–Ir–B system: Phase equilibria, crystal structure, bonding and electronic structure of compounds","authors":"Oksana Sologub ,&nbsp;Leonid P. Salamakha ,&nbsp;Herwig Michor ,&nbsp;Neven Barisic ,&nbsp;Stepan Mudry ,&nbsp;Peter F. Rogl ,&nbsp;Ernst Bauer","doi":"10.1016/j.jssc.2024.125176","DOIUrl":"10.1016/j.jssc.2024.125176","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Phase relations in the ternary system Cu–Ir–B have been experimentally established for the isothermal section at 600 °C via electron microprobe and X-ray powder diffraction analyses. Reinvestigation of the binary systems pertinent to the concentration areas of the current study confirmed the existence and crystal structure of compounds &lt;em&gt;α&lt;/em&gt;-Ir&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;3-x&lt;/sub&gt; and Ir&lt;sub&gt;3&lt;/sub&gt;B&lt;sub&gt;4&lt;/sub&gt; and indicated slightly higher solubility of Ir in Cu as compared to literature data. The formation of &lt;em&gt;β&lt;/em&gt;-Ir&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;3-x&lt;/sub&gt; was observed from ternary alloys annealed at 800 °C. Phase equilibria at 600 °C involve two previously reported ternary compounds, CuIr&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;2-x&lt;/sub&gt; (x = 0.52; space group &lt;em&gt;Cmcm&lt;/em&gt;) and CuIrB (space group &lt;em&gt;Fdd&lt;/em&gt;2). In addition, a new ternary compound Cu&lt;sub&gt;5+x&lt;/sub&gt;Ir&lt;sub&gt;5-x&lt;/sub&gt;B&lt;sub&gt;2&lt;/sub&gt; (x = 1.05; space group &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;F&lt;/mi&gt;&lt;mover&gt;&lt;mn&gt;4&lt;/mn&gt;&lt;mo&gt;‾&lt;/mo&gt;&lt;/mover&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;) was identified in as cast alloys. CuIr&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;2-x&lt;/sub&gt; and CuIrB crystallize with their own structure types while the new compound Cu&lt;sub&gt;5+x&lt;/sub&gt;Ir&lt;sub&gt;5-x&lt;/sub&gt;B&lt;sub&gt;2&lt;/sub&gt; adopts the Pd&lt;sub&gt;5&lt;/sub&gt;Cu&lt;sub&gt;5&lt;/sub&gt;B&lt;sub&gt;2&lt;/sub&gt; structure type. The copper iridium borides obtained reveal different motifs of condensation of boron structural units. In the CuIr&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;2-x&lt;/sub&gt; structure, the Ir&lt;sub&gt;6&lt;/sub&gt; trigonal prisms (partly filled with B) inter-connect in two directions to form 2D layers; the blocks of three layers of prisms interchange along the longer axis of the unit cell with two stacked 4&lt;sup&gt;4&lt;/sup&gt; Cu nets. Closely related arrangements are found in other intermetallic phases such as MAB phases. The building unit of CuIrB is a [BIr&lt;sub&gt;4&lt;/sub&gt;] tetrahedron; the tetrahedra interconnect creating channels with interlinked and slightly waved chains of Cu. In the structure of Cu&lt;sub&gt;5+x&lt;/sub&gt;Ir&lt;sub&gt;5-x&lt;/sub&gt;B&lt;sub&gt;2&lt;/sub&gt;, the groups of four [BM&lt;sub&gt;6&lt;/sub&gt;] trigonal prisms (condensed through common edges) join via common vertices to form a framework enveloping extensive Cu structural units reminiscent to those, found in the fcc copper lattice (Cu&lt;sub&gt;6&lt;/sub&gt; octahedron augmented into tetrahedron by adding copper Cu&lt;sub&gt;4&lt;/sub&gt; tetrahedra). Two ternary compounds, CuIr&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;2-x&lt;/sub&gt; and CuIrB were targeted for analysis of their electronic and band structure, chemical bonding and physical properties (electrical resistivity as a function of temperature). The chemical bonding analysis revealed partially covalent Ir–B bonding in the metal boride subunits in both compounds. According to Bader charges analysis, copper atoms donate their electrons to more electronegative iridium atoms. CuIrB and CuIr&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;2-x&lt;/sub&gt; are expected to be metallic from the DFT calculations with number of bands crossing the Fermi level in both SO and non-SO case in good agreement with resistivity measurements. CuIrB is characterized","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125176"},"PeriodicalIF":3.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improvement of thermoelectric properties through meso-hierarchical engineering approach – Thermoelectric cooler modelling aided study","authors":"Elaf Abdelillah Ali Elhussein ,&nbsp;Aminu Yusuf ,&nbsp;Sedat Ballikaya ,&nbsp;Ismail Boz","doi":"10.1016/j.jssc.2024.125175","DOIUrl":"10.1016/j.jssc.2024.125175","url":null,"abstract":"<div><div>Exploiting materials with high thermoelectric performance (TEP) is crucial for improving energy conversion efficiency and addressing future energy needs. This study reports the influence of meso-hierarchical engineering approach on structural properties, and TEP of Bi/Sb–Te based compounds. The meso-hierarchical engineering approach is based on substitute a certain amount of single-crystalline <em>p</em>-type Sb₂Te₃ (ST) like-nanoplates into polycrystalline <em>p</em>- and <em>n</em>-types Sb_1.5Bi_0.5Te₃ (SBT) and Bi₂Te_0.3Se_2.7 (BTSe) nanoparticles, respectively. The characterizations showed that the incorporation of ST into the SBT increases the density of nano-micro grains and the number of interfaces. Thereby, for 10%ST/SBT the electric conductivity, Seebeck coefficient, and power factor parameters were improved by 56.41 %, 8.75 % and 57.93 %, at ambient temperature compared to bulk SBT alloy, respectively. The lattice and total thermal conductivities were achieved a significant drop of 20.83 % and 20.34 % for 10%ST/SBT alloys at ambient temperature. Furthermore, 5%ST/SBT and 10%ST/SBT showed a remarkable a peak figure of merit (<em>zT</em>) of 1.1 and 1.13 were obtained at 328 and 303 K, respectively. Based on the high TEP of 5%ST/SBT and BTSe in the temperature of 300–400 K were used as <em>p</em>-and <em>n</em>-type legs to analyze the certain sized TE cooler model. The numerical modeled TEC observed a maximum cooling temperature difference as 71.64 K at hot-side temperature of 379.46 K and cooling load of 0.2 W. Moreover, at optimal cooling load of 0.5 W the maximum cooling temperature difference was found to be 64.73K at hot-side temperature of 393.41 K.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125175"},"PeriodicalIF":3.2,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling porous channels in Ga-MOFs for hydrogen storage applications in membranes","authors":"E.A. Mukhanova ,&nbsp;V.O. Shevchenko ,&nbsp;M.V. Kalmakhelidze ,&nbsp;I.L. Fisli ,&nbsp;A.V. Penkova ,&nbsp;A.V. Soldatov","doi":"10.1016/j.jssc.2025.125179","DOIUrl":"10.1016/j.jssc.2025.125179","url":null,"abstract":"<div><div>In our study we investigate the topology and pore characteristics of Ga-based metal-organic frameworks (Ga-MOFs) with a focus on their potential applications in hydrogen storage. We analyzed various Ga-MOF structures from the QMOF database to understand how different topologies affect their ability to efficiently store and separate hydrogen using advanced modeling tools, such as ToposPro, MOFid and CrystalNets. Our results indicate that Ga-MOFs exhibiting the <strong>bpq, 3,3,4,4T9</strong>, and <strong>6,8T21</strong> topologies possess distinct one-dimensional pore channels, which enhance hydrogen adsorption capacity and facilitate molecular transport. By clarifying the relationship between crystal topology and hydrogen interaction properties, future developments in gas storage and separation technologies can be informed. This work highlights the critical role of the pore structure in optimizing the functionality of MOFs and sets the foundation for further exploration of Ga-MOFs in energy applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125179"},"PeriodicalIF":3.2,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An iron-based metal-organic framework with strong water stability and effective adsorption of methylene blue from wastewater","authors":"Wei Guo ,&nbsp;Shixiong Li","doi":"10.1016/j.jssc.2024.125174","DOIUrl":"10.1016/j.jssc.2024.125174","url":null,"abstract":"<div><div>The stability of iron-based metal-organic frameworks (MOFs) in water affects their performance in adsorbing pollutants from wastewater. In this paper, an ionic iron-based metal-organic framework {[NH₂(CH₃)₂][Fe₆(O)₂(HCOO)(CO₃)(L)₆(H₂O)₂]·17(H₂O)·13(DMF)}_n (<strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF</strong>) and its nano adsorbents (<strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong>) are synthesized by FeSO₄·7H₂O and 4,4′-biphenyldicarboxylic acid (H₂L) as raw materials. X-ray single crystal diffraction shows that L²⁻ and HCOO⁻ in <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF</strong> take the form of <em>μ</em>_<em>4</em>-η¹:η¹:η¹:η¹ and <em>μ</em>_<em>2</em>-η¹:η¹ to bridge adjacent iron ions to form a three-dimensional structure with pores (18.96 × 19.89 Å), respectively. The particles of <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong> are approximately 200 nm and they have broad pH (3.00–9.00) stability. The maximum equilibrium adsorption capacity of <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong> adsorbs methylene blue (MB) in wastewater under optimal conditions (pH = 6.00, T = 25 °C) is 162.46 mg/g, which is larger than most MOF adsorbents. This may be because <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong> can adsorbs MB through strong electrostatic attraction and hydrogen bonds. Adsorption thermodynamic shows <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong> adsorbs MB conforms to the pseudo-first-order adsorption kinetic equation. Moreover, adsorption kinetic also shows that <strong>Fe</strong>_{<strong>6</strong>}<strong>-MOF-N</strong> adsorbs MB at 25–45 °C is the process of decreasing Gibbs free energy (△G &lt; 0) and enthalpy change (△H &lt; 0). This study provides an example for the synthesis of iron-based MOFs with good thermal stability, water stability, and effectively adsorbs MB.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125174"},"PeriodicalIF":3.2,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New intergrowth compounds in the La–Co–Al system, La3Co5Al2, La6Co7Al7, and La4Co9.6Al3.4: Crystal structures, bonding, and magnetism","authors":"Ilja V. Chernyshev ,&nbsp;Anna I. Tursina ,&nbsp;Sergey N. Nesterenko ,&nbsp;André M. Strydom ,&nbsp;Alexey N. Kuznetsov","doi":"10.1016/j.jssc.2024.125177","DOIUrl":"10.1016/j.jssc.2024.125177","url":null,"abstract":"<div><div>Three new intergrowth compounds in the La–Co–Al system have been synthesized using arc-melting with subsequent annealing. La₃Co₅Al₂ and La₆Co₇Al₇ crystallize in the La₆Co₁₁Ga₃-type (<em>I</em>4/<em>mcm</em>, <em>tI</em>80) with stoichiometry defined by different filling of the two Co sites: <em>a</em> = 8.1959 (8), <em>c</em> = 23.082 (7) Å (La₃Co₅Al₂) and <em>a</em> = 8.2426 (13), <em>c</em> = 23.768 (10) Å (La₆Co₇Al₇). The structures present a stacking variant of the YNi₉In₂-, U₃Si₂-, and CuAl₂-type layers along the <em>c</em>-direction. La₄Co_9.6Al_3.4 compound crystallizes with its own type (<em>P</em>4/<em>mbm</em>, <em>tP</em>34, <em>a</em> = 8.2060 (13), <em>c</em> = 8.989 (2) Å) and represents an intergrowth structure composed of YNi₉In₂- and U₃Si₂-type slabs stacked along the <em>c</em>-axis. La₃Co₅Al₂ and La₆Co₇Al₇ compounds do not form a homogeneous region whereas for La₄Co_9.6Al_3.4 compound a narrow solid solubility range has been detected. DFT calculations predict all compounds to be metallic, with Co d-states playing a major role near the Fermi level. Bonding analysis reveals a large number of bonding contacts for each compound and indicates complex systems of delocalized bonding. Combined specific heat and magnetic susceptibility measurement data indicate low-temperature transition to a magnetic state for the La₄Co_9.6Al_3.4 compound.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125177"},"PeriodicalIF":3.2,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the two step spin transition of Fe(NCBH3)(4phpy)2(m-bpypz)2 with ab initio calculations","authors":"Koussai Lazaar ,&nbsp;Fatma Aouaini ,&nbsp;Fatemah H. Alkallas ,&nbsp;Haifa Alyousef ,&nbsp;Saber Gueddida","doi":"10.1016/j.jssc.2024.125167","DOIUrl":"10.1016/j.jssc.2024.125167","url":null,"abstract":"<div><div>Spin crossover complexes represent a fascinating class of molecular materials with potential applications in diverse fields ranging from information storage to molecular electronics. Here using density functional theory, we investigate the properties of the binuclear spin crossover complex Fe(<span><math><msub><mrow><mtext>NCBH</mtext></mrow><mrow><mn>3</mn></mrow></msub></math></span>)(4phpy)<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>(m-bpypz)<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, which presents the intriguing property that the two step magnetic transition occurs through an intermediate state made of low spin or high spin chains, as seen experimentally. We observe that the different magnetic configurations can be reproduced by our calculations, and that irons ions are coupled antiferromagnetically. This complex transition is further elucidated through nudged elastic band calculations and observation of the magnetization density, and opens the path towards more studies of polynuclear spin crossover complexes.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125167"},"PeriodicalIF":3.2,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effective adsorption separation of n-hexane/3-methylpentane by vapor-phase linker exchange of Zeolitic-imidazolate framework ZIF-8","authors":"Le Chen,&nbsp;An Xie,&nbsp;Nan Zhang,&nbsp;Jianjun Yin,&nbsp;Qun Chen,&nbsp;Mingyang He,&nbsp;Zhihui Zhang","doi":"10.1016/j.jssc.2024.125168","DOIUrl":"10.1016/j.jssc.2024.125168","url":null,"abstract":"<div><div>Zeolitic-Imidazolate Framework 8 (ZIF-8), a porous crystalline absorbent, could be synthesized from the coordination reaction of zinc ions and 2-methylimidazole (2-mIM). ZIF-8 has a large specific surface area and a high adsorption capacity for <em>n</em>-hexane (<em>n</em>HEX). However, ZIF-8 suffers from low selectivity for both linear and mono-chain alkanes. Therefore, ZIF-8 was modified through 2-mIM ligand being partly replaced by 2-nitroimidazole (2-nIM) through Vapor-Phase post-synthesis modification. The modified materials were denoted as ZIF-8-2-nIM-X (X = 24h, 48h, 72h). ZIF-8-2-nIM-X has a higher specific surface area and better thermal stability than ZIF-8. Further thermodynamic and kinetic calculations show that the affinity of hexane isomers on ZIF-8-2-nIM-X is spontaneous physical adsorption combined with an exothermic process. In contrast, kinetic studies show that the adsorption of hexane isomers on ZIF-8-2-nIM-X is a pseudo-second-order kinetic model. The batch and dynamic adsorption and separation properties of ZIF-8-2-nIM-X for hexane isomers were studied. The results of the one-component vapor adsorption equilibrium experiment show that ZIF-8-2-nIM-72h has the best adsorption separation coefficient at 293 K. The adsorption capacity of <em>n</em>HEX and 3-methylpentane (3 MP) were 211.63 mg/g and 33.91 mg/g, respectively. Compared with ZIF-8 (selectivity coefficient: 1.08), the adsorption selectivity coefficient of the modified material is greatly improved. The adsorption selectivity coefficient of <em>n</em>HEX/3 MP is 6.24 (ZIF-8-2-nIM-72h).</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125168"},"PeriodicalIF":3.2,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149995","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}