Physical Chemistry Chemical Physics最新文献

{"title":"Damage-free separator engineering strategy via solvent-free in situ growth of Zn-MOF functional layers for long-cycling aqueous zinc-ion batteries","authors":"Juan Xu,Mengge Ding,Jiayi Li,Lingrui Zhu,Jiahui Zheng,Lei Wang,Pei Zhou,Zhiliang Chen,Zhongyang Li","doi":"10.1039/d6cp03692a","DOIUrl":"https://doi.org/10.1039/d6cp03692a","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) are promising for next-generation energy storage owing to high safety, low cost and environmental benignity. However, their practical application is hindered by uncontrollable zinc dendrite growth and parasitic side reactions at the anode interfaces. Separator modification is effective for addressing these issues, yet conventional solution-based or bladecoating methods may damage pristine separators and suffer from poor uniformity. Herein, a novel solvent-free in situ growth strategy is developed to construct the Zn-MOF functional layer on commercial separator, realizing the damage-free modification with ultrathin, conformal and thickness-controllable MOF coatings. The Zn-MOF-functionalized separator homogenizes Zn²⁺ flux, reduces interfacial charge transfer barriers, and guides uniform zinc deposition, as validated by electrochemical analyses COMSOL simulations. Consequently, the Zn||Zn symmetric cells with the Zn-MOF@NWF separator deliver stable cycling over 1800 h at 1 mA cm -2 for 1 mAh cm -2 . Moreover, the assembled full cells with a CuVO cathode demonstrate improved cycling stability and rate capability. This work establishes solvent-free MOF functionalization as a versatile and scalable platform for separator engineering, providing an alternative route to stabilize the anode interface and advance high-performance AZIBs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374939","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":"Conformational Fates and Secondary Kinetic Isotope Effects in Carbonic Acid and its Sulfur Analogues Mono-, Di-and Tri-thionic Acids at 10-300 K which Impact on their Lifetimes in the Interstellar Medium and Planetary Atmospheres","authors":"Judith Wurmel,Daniel J Cregg,John M Simmie","doi":"10.1039/d6cp03054h","DOIUrl":"https://doi.org/10.1039/d6cp03054h","url":null,"abstract":"Detailed chemical kinetics of the rotamerisation and hydrogen atom transfer reactions of gaseous carbonic acid and its sulfur analogues mono-, di-and tri-thiocarbonic acids are determined at temperatures between 10 K and 300 K all of which are largely driven by quantum mechanical tunnelling. Monte Carlo based simulations determine the conformational fate of the higher-energy species which in turn impact on the observational time that pertain to laboratory spectroscopic studies and detections in planetary atmospheres or in the interstellar medium. Secondary kinetic isotope effects resulting from the selective replacement of active and inactive hydrogen atoms by deuterium, are explored and it is shown that anomalous values are commonplace; validation of these results are provided by comparisons with cryogenic-matrix experiments on formic and acetic acids.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374916","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":"Pre-oxidation and molten salt activated semicoke carbon for zinc-ion hybrid capacitors","authors":"Na Wang,Tao Wang,Pengxu Ren,Haolan Wen,Gaojie Liu,Dongling Wu","doi":"10.1039/d6cp03030k","DOIUrl":"https://doi.org/10.1039/d6cp03030k","url":null,"abstract":"We propose a strategy for synthesizing semi-coke-derived porous carbon for zinc-ion hybrid capacitors (ZIHCs) via one-step air carbonization, using a K2CO3/KOH molten salt system as both a flame retardant and a functionalization agent, coupled with pre-oxidation. Pre-oxidation introduces oxygen groups that increase reactive sites and weaken π–π stacking. Above the salt melting point, the molten salts form a liquid encapsulation layer, providing condensed-phase flame retardancy to prevent excessive oxidation. During carbonization, KOH creates micropores through strong etching, while K2CO3 generates mesopores via mild widening, yielding a hierarchical micro/mesoporous structure. In situ oxidation introduces abundant oxygen functionalities, especially C–O–C bridges, whose steric hindrance synergizes with pre-oxidation to inhibit graphitic ordering and enhance disorder and defects. The optimal sample achieves a specific surface area of 2313 m2 g−1, pore sizes of 0.5–4 nm, and 42.24% sp3-C defects. As a ZIHC cathode, it delivers 216 mAh g−1 at 0.1 A g−1, an energy density of 173.4 Wh kg−1, and 99.2% capacity retention after 20 000 cycles. This work offers a cost-effective route for producing high-performance semi-coke-based porous carbons in air and provides experimental insights into synergistic structural modulation via pre-oxidation and molten-salt treatment.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374920","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":"Double halogenation controls the conformation of benzyl alcohol: does DFT fail to predict it even qualitatively?","authors":"Jannes N. Hasselhorn,Elisabeth Sennert,Martin A. Suhm,Daniel A. Obenchain","doi":"10.1039/d6cp03475f","DOIUrl":"https://doi.org/10.1039/d6cp03475f","url":null,"abstract":"Benzyl alcohol and its derivatives can occur in chiral and in more elusive mirror-symmetric structures. ortho-Halogenation (X) couples this structural duality with distorted OH⋯X vs. very weak CH⋯O/CH⋯X hydrogen bonding. We show by a combination of infrared and rotational spectroscopy in supersonic jets that additional para-halogenation introduces a particularly interesting halogen-sensitive conformational preference. While ortho-para-difluorobenzyl alcohol prefers the chiral OH⋯X arrangement, ortho-para-dichlorobenzyl alcohol favors the achiral structure with CH⋯O/CH⋯X contacts. Density functional (exemplified by dispersion corrected B3LYP) calculations fully support the infrared and rotational spectra of the competing conformations, but fail in predicting the energetic switch from F to Cl substitution, even when harmonic zero point energy is added or the electronic energy is replaced by its DLPNO-CCSD(T) counterpart. Only the combined effect of vibrational zero point energy and correlated wavefunction energetics is able to correctly predict the switch to mirror symmetry for Cl. Is there a density functional approach out there that predicts the correct structural switch on its own?","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"88 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374925","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":"Robust Two-dimensional Nodal-Loop Spin-Gapless Semimetal in a d0 Ferromagnet","authors":"Qian Zheng,AiNing Wang,Zikui Ye,Yuqiao Qu,Hongquan Zeng,Yu Chen,Liang Liu,Weiyao Jia,Huaxing Zhu,Junzhong Wang,Gang Yao","doi":"10.1039/d6cp03494b","DOIUrl":"https://doi.org/10.1039/d6cp03494b","url":null,"abstract":"Nodal-line spin-gapless semimetals (NLSGSMs), combining 100% spin polarization with gapless conducting channels, are highly sought after for low-dissipation spintronics. From both fundamental topology and spintronic application perspectives, two-dimensional (2D) ferromagnets that exhibit such a state along with high-temperature magnetic order and SOC-robustness are particularly desirable. Here, we theoretically identify monolayer NaN as a p-orbital ferromagnetic (FM) half-metal hosting a Type-B spin-gapless nodal loop exactly at the Fermi level (E F ). The loop is closed and completely immune to spin-orbit coupling (SOC). Magnetic anisotropy calculations reveal an easy-plane for the magnetic moments. Through symmetry analysis of an effective model, we reveal that the nodal loop is protected by n-glide symmetry, a mechanism verified by our first-principles calculations. This combination of a gapless nodal loop and above-room-temperature ferromagnetism persists under ±5% strain. Our discovery establishes a clean p-orbital platform for exploring dissipationless spin transport and topological spintronics beyond conventional d/f systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368261","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":"Electron momentum spectroscopy of benzonitrile: probing substitution effects on the molecular orbitals of benzene derivatives","authors":"David George Matalon,Darryl Bruce Jones,Samuel Eden,Kate Nixon","doi":"10.1039/d6cp03352k","DOIUrl":"https://doi.org/10.1039/d6cp03352k","url":null,"abstract":"This work applies experimental and theoretical electron momentum spectroscopy to the interstellar molecule benzonitrile for the first time. The results are presented both in position space (spatial orbital representations using orbital isomaps) and in momentum space (momentum distributions). Theoretical momentum distributions (TMDs, based on ωB97X-D/aug-cc-pVTZ model chemistry) complement the experimental measurements and good agreement is observed. Additionally, TMDs of benzene are compared with those of benzonitrile and fluorobenzene to investigate how resonance and inductive effects from two substituent groups (CN and F) influence the characteristics of the aromatic ring orbitals. Modifications to the TMDs upon substitutions are most strongly observed for molecular orbitals of a1 symmetry, with changes in orbital character and/or intensity at low momentum (<0.5 a.u.). It would be expected that benzonitrile, with a stronger inductive effect, would show greater deviation from the TMD of benzene. This trend is observed in the TMDs of the four MOs correlated to the 3e2g degenerate MOs of benzene and attributed to the varying inductive strengths of the substituents. The resonance electron withdrawing and donating effects of CN and F are not able to be unambiguously observed in the TMDs. The substitution effects are assessed for the molecules in their equilibrium geometries. This approach is supported by calculations using the harmonic analytical quantum mechanical (HAQM) method for benzonitrile which show that molecular vibrations have negligible effects on the majority of TMDs. The exception is the TMD for the unresolved sum of for 13a1, 5b2 and 12a1 which shows an increase in intensity at low momentum when vibrations are considered, bringing the TMD in closer agreement with the experimental data.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"44 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368264","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 Role of Water in the Thermal Decomposition of HXeCl in the HXeCl--H2O Complex: Spectator or Chemical Participant?","authors":"Arik Cohen,Masashi Tsuge,Robert Benny Gerber","doi":"10.1039/d6cp02395a","DOIUrl":"https://doi.org/10.1039/d6cp02395a","url":null,"abstract":"The role of water in chemical reactions is of fundamental importance across many areas of research. Here we investigate the role of water for the thermal decomposition of the noble-gas hydride HXeCl in the HXeCl--H/D2O complex. The study was carried out via ab initio calculations and Ab Initio Molecular Dynamics (AIMD) simulations. Results of the calculations for the isolated complex are compared with previous experiments carried out for the complex in a Xe matrix. The simulations show that the deuteration of water has a major effect on the reaction outcome, transforming the role of water essentially into that of a mere spectator, as was seen experimentally. When the simulations include H2O rather than D2O, a large fraction of the trajectories show H-exchange reaction between water and HXeCl during its decomposition process. This predicts a dramatic H/D isotopic effect on the role of water in the decomposition. Effects of a Xe matrix on the above dynamics were explored via a simplistic continuum model of the environment for which, the results were about the same. It is concluded that a simple model of an isolated complex can be useful for the analysis of corresponding processes in inert host matrices and clusters.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368262","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":"Hydrophilic Silica Surfaces Host a Hydrophobic-Like Two-Dimensional Water Network","authors":"Yijing Yang,Sana Bougueroua,Alvaro Cimas,Marie-Pierre Gaigeot","doi":"10.1039/d6cp02862d","DOIUrl":"https://doi.org/10.1039/d6cp02862d","url":null,"abstract":"Silica–water interfaces are widely considered prototypically hydrophilic due to surface silanol groups enabling hydrogen bonding with interfacial water. However, this description primarily accounts for vertical surface–water interactions and neglects the possible collective in-plane organization of interfacial water. Building on our previous observations of hydrophobic-like two-dimensional hydrogen-bonded water networks at selected oxide–water interfaces, here we investigate the robustness and limits of this organization across twelve structurally diverse crystalline and amorphous silica surfaces. Using DFT-based MD simulations combined with graph-theoretical analyses, we show that water within the Binding Interfacial Layer (BIL) predominantly organizes into such a collective 2D network at ten of the twelve investigated interfaces, while two exceptions reveal some limits of its prevalence. This lateral network coexists with heterogeneous vertical hydrogen-bonding motifs involving surface silanols, which anchor the network without disrupting its connectivity. These results establish the prevalence of a hydrophobic-like collective water organization across structurally diverse silica surfaces at PZC conditions, and show that silica wettability emerges from the interplay between vertical surface–water interactions and lateral collective water–water hydrogen-bond organization.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368281","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":"Machine-Learning Interatomic Potential-based Enhanced Sampling Simulations Reveal Dynamic Conformations and Small Molecule Activation on Au9 Nanocluster Confined in UiO-66-NH2 MOF","authors":"Dhananjay Gupta,Tarak Karmakar","doi":"10.1039/d6cp02396g","DOIUrl":"https://doi.org/10.1039/d6cp02396g","url":null,"abstract":"Atomically precise metal nanoclusters (NCs) confined within metal-organic frameworks (MOFs) have emerged as promising multifunctional porous crystalline nanocomposites (NC@MOFs) materials for applications in catalysis and sensing. Despite growing interest in these hybrid materials, the structural and dynamic behavior of NCs under MOF-confinement remains poorly understood because the relevant atomic-scale rearrangements are difficult to access experimentally. Here, we present a molecular-level investigation of a single gold nanocluster, Au9, encapsulated within the chemically distinct octahedral and tetrahedral pores of the Zr-based MOF, UiO-66-NH2, using machine learning interatomic potential (MLIP)–driven enhanced sampling simulations. Our approach combines textit{ab initio} molecular dynamics and well-tempered metadynamics (WTMetaD) in an iterative workflow to construct a reliable MLIP, thereby enabling simulations of the NC@MOF system over tens of nanoseconds. WTMetaD simulations of Au9 confined in the larger octahedral pore reveal a rich free-energy landscape characterized by pronounced confinement-induced fluxionality and multiple dynamically interconverting conformations. In contrast, the smaller tetrahedral pore accommodates the compact three-dimensional structure of Au9, providing a distinct confinement environment. The relative stability and interconversion of these structural motifs are strongly modulated by confinement, giving rise to quasi-planar or near-planar geometries. Furthermore, small-molecule adsorption studies probe the activation of H2 and CO on accessible Au9 conformations. H2 binds weakly to all five conformations, with average adsorption energies ranging from −0.13 to −0.19 eV, indicative of physisorption, whereas CO exhibits significantly stronger average adsorption energies of −0.94 to −1.23 eV, suggesting chemisorption. These results establish a direct connection between confinement-induced fluxionality, electronic properties, and the adsorption behavior of MOF-confined nanoclusters, with implications for their catalytic relevance. This study provides fundamental insight into confinement-driven nanocluster dynamics and establishes a generalizable computational framework for studying nanostructured NC@MOF materials with tailored properties.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368266","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":"Experimental and theoretical study on the kinetics of chlorine atom recombination with fluoroformyl radicals","authors":"María P. Badenes,Larisa L. B. Bracco,Carlos J. Cobos,Adela E. Croce,María E. Tucceri","doi":"10.1039/d6cp03757g","DOIUrl":"https://doi.org/10.1039/d6cp03757g","url":null,"abstract":"This work presents an experimental and theoretical investigation of the Cl + FCO + M → ClFCO + M recombination reaction and its dependence on the pressure and temperature. Both reactants, chlorine atoms and FCO radicals, were generated by 193 nm laser flash photolysis of (FCO)2/Cl2/CF4 mixtures at 296 K. The experimental measurements were found to correspond to the high-pressure limit, yielding an average recombination rate coefficient of (1.8 ± 0.4) × 10−10 cm3 molecule−1 s−1. The limiting high-pressure rate coefficient was analyzed using the statistical adiabatic channel model combined with classical trajectory calculations (SACM/CT) and its simplified version (SSACM), employing an ab initio potential energy surface derived at the G4//B3LYP/6-311+G(3df) level. Both approaches yield values in good agreement with the experiments. The limiting low-pressure rate coefficient was estimated to be 7.5 × 10−29 [CF4] cm3 molecule−1 s−1 at 296 K using the factorized low-pressure rate theory. Structural parameters, harmonic vibrational frequencies, and thermochemical properties of ClFCO were also computed using several levels of theory. A value of −98.5 ± 2.1 kcal mol−1 was obtained for the enthalpy of formation of ClFCO at 298 K from isodesmic and isogyric reactions computed at the G4//B3LYP/6-311++G(3df,3pd) level. The present results provide reliable kinetic and thermochemical parameters and contribute to a better understanding of pressure-dependent halogen-atom recombination reactions relevant to atmospheric chemistry.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368284","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}