Chemphyschem最新文献

Behavior of Crystalline Water During Cation Adsorption and Desorption in Layered Zirconium Phosphate 层状磷酸锆中结晶水对阳离子的吸附和解吸行为。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-15 DOI: 10.1002/cphc.70565

Masakuni Yamaguchi, Takahiro Toyoshima, Akira Takahashi, Tohru Kawamoto, Hisashi Tanaka

{"title":"Behavior of Crystalline Water During Cation Adsorption and Desorption in Layered Zirconium Phosphate","authors":"Masakuni Yamaguchi, Takahiro Toyoshima, Akira Takahashi, Tohru Kawamoto, Hisashi Tanaka","doi":"10.1002/cphc.70565","DOIUrl":"10.1002/cphc.70565","url":null,"abstract":"This study explores the behavior of crystalline water during the adsorption of Na+, K+, and NH4+ ions onto layered zirconium phosphate (ZrP) using powder X-ray diffraction (XRD) and thermogravimetric analysis (TG). Cation uptake proceeded via two discrete adsorption steps, each accompanied by distinct structural transformations and water-related phenomena. For Na+, water molecules were incorporated into the interlayer region during the second adsorption stage. In contrast, adsorption of K+ and NH4+ involved the release of crystalline water during the first stage, followed by water incorporation in the second stage. Notably, ZrP exhibited no measurable dissolution under the analytical conditions employed even under strongly alkaline conditions (pH ≈ 12). Furthermore, acid-induced desorption followed by readsorption confirmed that the layered structure of ZrP remained intact and fully regenerable. These findings demonstrate that ion-dependent migration of crystalline water plays a critical role in the adsorption mechanism and indicate that the dynamic behavior of interlayer water must be considered in the rational design of layered inorganic materials.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 20","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70565","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191681","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}

引用次数: 0

Mechanistic Insights and Catalytic Performance of Transition-Metal-Decorated PtS2 Catalysts for Electrocatalytic Reduction of Nitrate 过渡金属修饰PtS2催化剂电催化还原硝酸盐的机理及催化性能研究。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-15 DOI: 10.1002/cphc.70591

Faiza Shafiq, Lei Yang, Weihua Zhu

{"title":"Mechanistic Insights and Catalytic Performance of Transition-Metal-Decorated PtS2 Catalysts for Electrocatalytic Reduction of Nitrate","authors":"Faiza Shafiq, Lei Yang, Weihua Zhu","doi":"10.1002/cphc.70591","DOIUrl":"10.1002/cphc.70591","url":null,"abstract":"Electrocatalytic reduction of hazardous water-pollutant nitrate offers an efficient and green approach for ammonia (NH3) generation, which is a sustainable alternative of Haber–Bosch process. However, the absence of a mechanistic understanding of the extremely complicated nitrate reduction reaction (NO3RR) and NH3 selectivity makes it difficult to discover reliable catalysts. We performed first-principles calculations to comprehensively examine the activity and selectivity of a single-atom catalyst (SAC) based on PtS2 for NO3RR. Based on the stability of catalysts, the adsorption energy of key intermediates, and the inhibition of the hydrogen evolution reaction (HER), two efficient systems, Ni/PtS2 and Cu/PtS2, with low value of limiting potentials (−0.18 and −0.21 V, respectively), were selected as promising candidates of electrocatalysts for NO3RR. Mechanistic analysis shows that the N-end pathway is most suitable with minimum energy barrier for ammonia generation. The partial density of state and charge transfer study confirm the effective activation of nitrate on the catalysts. Furthermore, ab initio molecular dynamics simulations were conducted to check the thermal stability of Ni/PtS2 and Cu/PtS2. Our findings reveal the design principle for more effective catalysts for NO3RR under ambient circumstances and present efficient catalysts for the generation of ammonia from nitrate.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 20","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191631","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}

引用次数: 0

Structure–Reactivity Relationships in Methylaluminoxane: Ionization Potentials Across Compositions and Morphologies 甲基铝氧烷的结构-反应性关系：跨组成和形态的电离势。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-15 DOI: 10.1002/cphc.70583

Xiaotong Mao, Wei Hu, Scott Collins, Mikko Linnolahti

{"title":"Structure–Reactivity Relationships in Methylaluminoxane: Ionization Potentials Across Compositions and Morphologies","authors":"Xiaotong Mao, Wei Hu, Scott Collins, Mikko Linnolahti","doi":"10.1002/cphc.70583","DOIUrl":"10.1002/cphc.70583","url":null,"abstract":"Methylaluminoxane (MAO) is the most widely used cocatalyst in metallocene-catalyzed olefin polymerization, yet its structural basis for reactivity remains poorly understood. Here, we present a computational survey of ionization potentials across 118 MAO species with the general formula (AlOMe)n(AlMe3)m (n = 4–10), covering over 1100 aluminum sites classified by local coordination environment. The analysis is extended to experimentally relevant sizes through evaluation of sheet and cage models up to n = 18, including an ovalene-type sheet model and crystallographically characterized 26,9 species. All energies are evaluated at the RI-MP2 level. Ionization potentials become systematically more negative with increasing oligomer size, and sheet structures are more reactive than cages across the sizes studied. At experimentally relevant sizes, the reactive site landscape converges to two characteristic types: one for methide abstraction and one for dimethylaluminum cation cleavage, with the latter pathway becoming exceptionally favorable for the ovalene-type sheet topology that matches the crystallographically confirmed MAO structure. The identification of specific sheet-type species as the most reactive MAO components is consistent with the experimental observation that the catalytically active component of MAO is a minor species within the bulk material, providing a quantitative basis for understanding structure–reactivity relationships in this industrially important cocatalyst.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 20","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70583","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191706","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}

引用次数: 0

Front Cover: Polarized ATR-FTIR Spectroscopy Reveals Light-Induced Peptide Insertion of LAH4 Into Photoswitchable Membranes (ChemPhysChem 20/2026) 封面：极化ATR-FTIR光谱揭示光诱导肽插入到光开关膜（chemphysche20 /2026）

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-14 DOI: 10.1002/cphc.70601

Celine Eckert, Selina Mertens, Karin Hauser

引用次数: 0

Proton-Coupled Electron Transfer in Reaction of Catecholamines: Experimental and Computational Approach 儿茶酚胺反应中的质子耦合电子转移：实验与计算方法。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-13 DOI: 10.1002/cphc.70579

Ana Karković Marković, Mia Jovanić, Dijana Kolezarić, Viktor Pilepić

{"title":"Proton-Coupled Electron Transfer in Reaction of Catecholamines: Experimental and Computational Approach","authors":"Ana Karković Marković, Mia Jovanić, Dijana Kolezarić, Viktor Pilepić","doi":"10.1002/cphc.70579","DOIUrl":"10.1002/cphc.70579","url":null,"abstract":"Biogenic catecholamines (dopamine, noradrenaline, adrenaline) exhibit a dual role in biological systems, acting as both endogenous antioxidants and potential sources of oxidative stress. The core of their antiradical activity is the catechol moiety that enables efficient radical scavenging via hydrogen and/or electron transfer. In this study, the reactivity of catecholamines toward the DPPH• radical was investigated experimentally and computationally in predominantly nonpolar 1,4-dioxane–water media. Experimental rate constants, kinetic isotope effects, and thermodynamic activation parameters suggest that, under these conditions, the reactions proceed via a concerted hydrogen transfer mechanism, best described as proton-coupled electron transfer (PCET). The proposed PCET-like reaction mechanism is supported by intrinsic bond orbital analysis along the intrinsic reaction coordinate path. Average local ionization energy (ALIE) analysis showed that the most reactive electron-donating sites are associated with π electrons above and below the aromatic ring of the catecholamine compounds. Additionally, kinetic isotope effects and anomalous Arrhenius parameters provide evidence for the involvement of hydrogen tunneling. Complementary pH-dependent kinetic studies with dopamine suggest a mechanistic shift toward a faster sequential proton loss-electron transfer pathway with increasing catecholate formation. These findings offer new insight into the antioxidant mechanisms of catecholamines and provide the first experimental indication of hydrogen tunneling in their radical-scavenging reactions.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13661290/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179617","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}

引用次数: 0

Inertness of a Planar Ni7O6+ Cluster in CO Adsorption Revealed by Ion Mobility–Mass Spectrometry 离子迁移-质谱法研究平面Ni7O6 +簇在CO吸附中的惰性。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-12 DOI: 10.1002/cphc.70599

Hiroya Sakakura, Yuto Nakajima, Keijiro Ohshimo, Fuminori Misaizu

{"title":"Inertness of a Planar Ni7O6+ Cluster in CO Adsorption Revealed by Ion Mobility–Mass Spectrometry","authors":"Hiroya Sakakura, Yuto Nakajima, Keijiro Ohshimo, Fuminori Misaizu","doi":"10.1002/cphc.70599","DOIUrl":"10.1002/cphc.70599","url":null,"abstract":"A previous mass spectrometry study reported that the CO adsorption rate constant for the Ni7O6+ cluster is anomalously smaller than those of adjacent sizes. In this study, the origin of this remarkable inertness was revealed using a combination of ion mobility–mass spectrometry (IM–MS) and theoretical calculations. IM–MS measurements clearly resolved two distinct structural isomers of Ni7O6+: three-dimensional (3D) and two-dimensional (2D) structures. The CO adsorption rate constant for the 2D isomer of Ni7O6+ was determined to be <6 × 10−12 cm3 molecule−1 s−1, which is significantly smaller than that of the 3D isomer (1.3 × 10−10 cm3 molecule−1 s−1). Molecular orbital analysis reveals that the π-back donation cannot occur between the 2D isomer of Ni7O6+ and a CO molecule due to the absence of dyz orbital character on the Ni atoms. We conclude that the extraordinary stability of Ni7O6+ originates directly from the character of its constituent Ni atomic orbitals in the 2D isomer.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149165492","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}

引用次数: 0

Computational Design of Neutral Heteronuclear Alkaline-Earth Metal Complexes Featuring a 2c─3e Bond and Their Application in CO2 Activation 含2c─3e键的中性异核碱土金属配合物的计算设计及其在CO2活化中的应用。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-11 DOI: 10.1002/cphc.70587

Jiahui Chen, Lifang Yan, Zhuanliang Zhang, Xingman Liu, Xiaomeng Wang, Zhongmin Su

{"title":"Computational Design of Neutral Heteronuclear Alkaline-Earth Metal Complexes Featuring a 2c─3e Bond and Their Application in CO2 Activation","authors":"Jiahui Chen, Lifang Yan, Zhuanliang Zhang, Xingman Liu, Xiaomeng Wang, Zhongmin Su","doi":"10.1002/cphc.70587","DOIUrl":"10.1002/cphc.70587","url":null,"abstract":"In contrast to electron-paired bonds, odd-electron bonding systems have garnered significant interest due to their distinctive bonding and radical properties. A series of neutral heteronuclear (AEM–AEM′)AMD (AEM = Be, Mg, and Ca) complexes was theoretically designed by binding two distinct alkaline-earth-metal (AEM) atoms with amidinate radical ligands (AMD) via side-on coordination. Upon one-electron transfer from AEM–AEM′ to AMD, the electron occupies an AMD nonbonding orbital, avoiding destabilization from rising ligand orbital energy, while a two-center three-electron (2c─3e) bond forms between the two AEMs. Subsequent CO2 activation studies show that (Mg─Ca)AMD exhibits the highest activity, a net electron transfer of 1.46 |e| derived from a two-electron redox process, accompanied by activation indicators: elongation of the C─O bond length (from 1.160 to 1.248 Å), reduction of the Wiberg bond index (from 1.816 to 1.454) and decrease of the flexible force constant (from 16.667 to 6.410 mDyn/Å). Investigation of CO2 conversion reveals CO formation with monotonically decreasing free energies. Although methane is the thermodynamically more favorable product, its formation encounters three energy-consuming steps, making the free-energy profile nonmonotonic. This work extends heteronuclear odd-electron bonding into the s-block and provides a route for CO2 activation using alkaline-earth systems beyond transition-metal or main-group catalysts.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149165998","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}

引用次数: 0

Efficient Separation of Xe/Kr by Induced Polarization on Single-Atom Modified Ti3C2O2: A DFT Study 单原子修饰Ti3C2O2诱导极化高效分离Xe/Kr的DFT研究

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-11 DOI: 10.1002/cphc.70584

Qu Mengnan, Aijun Du, Sun Qiao

{"title":"Efficient Separation of Xe/Kr by Induced Polarization on Single-Atom Modified Ti3C2O2: A DFT Study","authors":"Qu Mengnan, Aijun Du, Sun Qiao","doi":"10.1002/cphc.70584","DOIUrl":"10.1002/cphc.70584","url":null,"abstract":"The efficient separation of radioactive xenon (Xe) and krypton (Kr) is challenging due to their similar sizes and chemical inertness. To address this, dispersing metal atoms as single sites on a substrate can utilize their highly localized electronic structure and concentrated charge to enhance polarization of noble gas atoms, thereby achieving effective Xe/Kr adsorption and separation. Two-dimensional MXene materials, with their large specific surface areas and tunable surface terminal groups, offer promising substrates for supporting metal atoms. In this study, we performed ab initio density functional theory (DFT) calculations to systematically evaluate the adsorption and separation capabilities of transition metal (TM) functionalized Ti3C2O2 (TM-Ti3C2O2) for Xe and Kr. Among the tested metals, Cu–Ti3C2O2 exhibited the strongest adsorption toward both gases. Charge density difference and partial density of states analyses revealed that the supported Cu atom induce significant polarization of Xe and Kr, facilitating pronounced interactions between the p orbitals of the gas atoms and the d orbitals of Cu. Furthermore, Cu–Ti3C2O2 showed the largest difference in adsorption energy between Xe and Kr, demonstrating its strong potential as an effective material for Xe/Kr separation.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149165045","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}

引用次数: 0

The Eu3+-Based Luminescent Marker—A Powerful Tool for Fast Monitoring of Ce4+/Ce3+ Transitions in Ru/Ceria-Based Catalysts 基于Eu3+的发光标记——快速监测Ru/ ceria基催化剂中Ce4+/Ce3+跃迁的有力工具

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-07 DOI: 10.1002/cphc.70580

Oleksii Bezkrovnyi, Maja Szymczak, Piotr Kraszkiewicz, Damian Szymański, Leszek Kępiński, Małgorzata Małecka, Mirosława Pawlyta, Michael Vorochta, Iva Matolínová, Lukasz Marciniak

引用次数: 0

Molecular Fe2O3 Ion-Pair Adducts in Ionic-Liquid Environments: A Computational Study 离子-液体环境中Fe2O3离子对加合物的计算研究。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-10-07 DOI: 10.1002/cphc.70574

Leonard Komando, Maciej Bobrowski

{"title":"Molecular Fe2O3 Ion-Pair Adducts in Ionic-Liquid Environments: A Computational Study","authors":"Leonard Komando, Maciej Bobrowski","doi":"10.1002/cphc.70574","DOIUrl":"10.1002/cphc.70574","url":null,"abstract":"Ionic environments modify the redox and magnetic behavior of iron oxides through dielectric polarization and specific first-shell interactions. Dispersion-corrected, spin-unrestricted density functional theory combined with the solvation model based on density for generic ionic liquids was used to examine molecular Fe2O3 adducts. Three room-temperature ionic liquids were represented by one explicit ion pair each, while [CH3NH3][BF4] adducts containing one to four pairs provided a loading model for this high-melting salt. Alternative neutral arrangements were optimized for every composition, and calculations without explicit ions provided a reference. The selected adducts are antiferromagnetic singlets when neutral, antiferromagnetic doublets after reduction, and ferromagnetic detects after oxidation. In the single ion pair systems, reduction localizes charge at one Fe center and contracts the di-μ-oxo core, whereas oxidation expands the Fe─O─Fe hinges and gives magnetic exchange constants of +140 to +216 cm−1. Increasing [CH3NH3][BF4] loading shifts the +1/0 and 0/−1 potentials to more positive values by 0.60 and 0.56 V, respectively. Thus, anion coordination, cation-mediated contacts, proton relocation, and crowding modulate the intrinsic Fe2O3 response beyond dielectric polarization alone.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149126745","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}

引用次数: 0