Physical Chemistry Chemical Physics最新文献

{"title":"Influence of Surface Oxidation on the Catalytic Activity of Topological Quantum Materials","authors":"Ashraf Abdelrahman Assadig Elameen, Rowa Mahjoub Yahia Elhassan","doi":"10.1039/d5cp01040c","DOIUrl":"https://doi.org/10.1039/d5cp01040c","url":null,"abstract":"Topological quantum materials (TQMs) have been extensively studied due to their exotic properties, as predicted by theory and confirmed by experiments. These properties, particularly protected surface states and high charge carrier mobility, make them promising candidates for applications where electron transport is crucial, such as catalysis. Recently, various TQMs have been experimentally demonstrated to enhance water splitting reactions, specifically the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), by establishing a correlation between topological surface states and catalytic activity. However, surface phenomena at the interface are complex and highly sensitive to factors such as surface termination, defects induced during exfoliation, and surface chemical reactivity. Therefore, further experimental and theoretical investigations are required to understand how surface reactivity influences the catalytic performance of TQMs. In this perspective, we analyse key studies on TQM-based catalysts, highlighting the role of surface modification, particularly surface oxidation, in catalytic activity.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087978","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":"Structure making and breaking effects of ions on the anomalous diffusion of water revealed by machine learning potentials","authors":"Jinfeng Liu, Xuchao Zhou, Xiao He","doi":"10.1039/d5cp01180a","DOIUrl":"https://doi.org/10.1039/d5cp01180a","url":null,"abstract":"The dynamics of water exhibits anomalous behavior in the solvation of ions, and understanding the perturbation that ions make on the hydrogen bond structure of water remains an open question. In this study, we investigate the anomalous diffusion behavior of water and its molecular origins in aqueous NaCl and CsI solutions using deep machine learning potentials developed at the MP2 level of theory. Our simulations reveal a suppression of water diffusion in NaCl solutions and whereas an enhancement of water diffusion in CsI solutions across various salt concentrations, perfectly reproducing the experimental observations. We further explore the microscopic origins of this anomalous diffusion behavior by examining the structural changes of water hydrogen bond network, as well as the vibrational properties of water molecules. Our findings highlight the distinct roles that different ions play in modulating the structure and dynamic behavior of water in salt solutions, and provide key insights into the fundamental mechanisms of structure making and breaking that govern the anomalous diffusion of water.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087980","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":"Substrate charge transfer drives the absorption site of metal-phthalocyanines and porphyrins on coinage metal surfaces","authors":"Silvia Carlotto, Iulia Cojocariu, Vitaliy Feyer, Luca Schio, Luca Floreano, Maurizio Casarin","doi":"10.1039/d5cp01576f","DOIUrl":"https://doi.org/10.1039/d5cp01576f","url":null,"abstract":"The frontier electronic structure of tetraphenylporphyrinato (TPP<small>^2-</small>) and phthalocyaninato (Pc<small>^2-</small>) square planar transition metal complexes (MTPP and MPc; M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) has been revisited through DFT calculations. The different symmetry and spin multiplicity between MPc and MTPP of the same M is shown to originate from the different Pc<small>^2-</small> and TPP<small>^2-</small> ligand field, stronger in the former ligand than in the latter. The corresponding spatial localization and symmetry of the unoccupied molecular orbitals postulate unescapable geometric constraints to their overlap with the electron cloud of a crystalline metal surface. From comparison with literature experimental evidence, we show that the adsorption geometry (atomic site and azimuthal orientation) of MTPPs and MPcs on the low index crystal planes of coinage metals (CM = Au, Ag, Cu) may be predicted when two conditions are satisfied: i) evidence of a surface → adsorbate charge transfer, ii) absence of significant distortion of the macrocycle upon adsorption. In this regard, the overall susceptibility to charge transfer is determined by the strength of the molecular ligand field (i.e., charge transfer to MPc is more favoured than to MTPP) and inversely linked to the electronegativity of the surface atoms (being Au the most inert CM substrate thanks to its highest electronegativity).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"77 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066170","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":"Persistence of Ce3+ Species on the Surface of Ceria during Redox Cycling: A Modulated Chemical Excitation Investigation","authors":"Cyril Hachemi, Hadi Dib, Mourad Debbichi, Michael Badawi, Calley Eads, Maya Ibrahim, Stéphane Loridant, Jan Knudsen, Helena Kaper, Luis Cardenas","doi":"10.1039/d5cp01283j","DOIUrl":"https://doi.org/10.1039/d5cp01283j","url":null,"abstract":"Operando Resonant Photoelectron Spectroscopy (RPES) combined with Modulated Chemical Excitation revealed the dynamic evolution of Ce<small>³⁺</small> and Ce<small>⁴⁺</small> redox states at the surface of CeO<small>₂</small> during the CO oxidation reaction. Using alternating CO and O<small>₂</small> pulses as chemically modulated signals, we monitored the surface states in the valence band region, unveiling the evolution of electronic structure during the catalytic process. The analysis with different gas flow ratios revealed that under CO-rich conditions (CO:O<small>₂</small> ≥ 1), only partial conversion from Ce<small>³⁺</small> to Ce<small>⁴⁺</small> occurred. In contrast, complete Ce<small>³⁺</small> to Ce<small>⁴⁺</small> conversion was achieved when pulsing O<small>₂</small> into O<small>₂</small>-rich environments. Furthermore, we find that intermediate oxygen species, such as peroxo and OH, impact the conversion of Ce<small>³⁺</small> and Ce<small>⁴⁺</small>. These oxygenated species coexist between 330 °C and 360 °C in pure O<small>₂</small>, while above 390 °C only OH groups remain stable on the ceria surface.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"78 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066135","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":"Excitations in Lanthanide Ions: A Systematic Evaluation of two-component CAS-CI and GW","authors":"Roman Zielke, Florian Weigend, Christof Holzer","doi":"10.1039/d5cp00780a","DOIUrl":"https://doi.org/10.1039/d5cp00780a","url":null,"abstract":"This paper presents a thorough prediction and investigation of ionization energies, atomic levels, and crystal-field splittings in lanthanide ions. We show that a two-component complete active space (CAS) configuration interaction (CI) approach based on two-component density functional theory (DFT) reference states is suitable to yield accurate excitation energies for lower energy terms. DFT references are further shown to be superior to Hartree-Fock (HF) references for predicting both atomic levels and ionization energies. Especially in the Greens function based GW method used to determine ionization energies, the deficiencies of the wave function based HF references are severe, leading to sizable errors. Two-electron contributions to spin-orbit coupling are found to be an important ingredient for obtaining accurate atomic levels. These contributions are taken into account using a screened-nuclear-spin-orbit (SNSO) approach, which is shown to be very accurate. DFT based CAS-CI is further used to calculate crystal-field splittings. The results are well suited to predict the subtle splittings in complexes with unpaired 4f electrons.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066136","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 molecular dynamics simulations of Shock Response and Spallation Behavior in PPTA Crystals","authors":"lei liu, Jingfu Shi, Di Song, Changqing Miao","doi":"10.1039/d5cp00251f","DOIUrl":"https://doi.org/10.1039/d5cp00251f","url":null,"abstract":"The shock response of poly(p-phenylene terephthalamide) (PPTA) crystals is investigated using molecular dynamics simulations combined with a machine learning potential. Considering the anisotropy of PPTA crystals, the directions dominated by hydrogen bonding and van der Waals forces are examined, respectively. First, a machine learning potential capable of simulating the shock behavior of PPTA is developed and validated. The potential is demonstrated to achieve excellent accuracy, showing high consistency with density functional theory results. Based on the established machine learning potential, multiscale shock techniques are employed to simulate shock compression at various particle velocities. The Hugoniot curves of PPTA crystals reveal three distinct stages of shock response: elastic, plastic, and cross-linking. With increasing particle velocity, the b axis of PPTA crystals is found to exhibit a greater tendency for plastic deformation. Plasticity along the a axis is characterized by the planarization of adjacent benzene rings within the chains, while along the b axis, it involves the breaking and reformation of hydrogen bonds. The spatiotemporal evolution of thermodynamic parameters and spallation during shock wave propagation is further uncovered through non-equilibrium molecular dynamics simulations. The shock response mechanisms of PPTA fibers are elucidated, providing a foundation for subsequent simulations and their application in impact protection structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066139","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":"Predicting accurate binding energies and vibrational spectroscopic features of interstellar icy species. A quantum mechanical study","authors":"Albert Rimola, Alicja Bulik, Berta Martínez-Bachs, Niccolò Bancone, Eric Mates-Torres, Marta Corno, Piero Ugliengo","doi":"10.1039/d5cp01151e","DOIUrl":"https://doi.org/10.1039/d5cp01151e","url":null,"abstract":"In the coldest, densest regions of the interstellar medium (ISM), dust grains are covered by thick ice mantles dominated mainly by water. Although more than 300 species have been detected in the gas phase of the ISM by their rotational emission lines within the radio frequency range, only a few were found in interstellar ices, e.g. CO, CO<small>₂</small>, NH<small>₃</small>, CH<small>₃</small>OH, CH<small>₄</small> and OCS, by means of infrared (IR) spectroscopy. Observations of ices require a background-illuminating source for absorption, constraining the available sight lines for investigation. Further challenges arise when comparing with laboratory spectra due to the influence of temperature, ice structure and the presence of other species. In the era of IR observations provided by the James Webb Space Telescope (JWST), it is crucial to provide reference spectral data confirming JWST's assigned features. For this purpose, this study addresses the adsorption of the aforementioned species on water ice surfaces and their IR features by means of quantum chemical computations grounded on the density functional theory (DFT) hybrid B3LYP-D3(BJ) functional, known to give reliable results for binding energy and vibrational frequency calculations, including IR spectra simulation. The calculated binding energies and IR spectral data are presented in the context of experimental spectra of ices and the new findings from the JWST, which have already proven to be insightful thanks to its unmatched sensitivity. We show that quantum chemistry is a powerful tool for accurate frequency calculations of ISM ice interfaces, providing unprecedented insights into their IR signatures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066137","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":"Tuning surface curvature in B and N co-doped CNT-derived Fe, Ru and Ir catalysts for electrochemical hydrogenation of N2 to NH3†","authors":"Deewan S. Teja and Bhabani S. Mallik","doi":"10.1039/D5CP00309A","DOIUrl":"10.1039/D5CP00309A","url":null,"abstract":"<p >Single-atom catalysts (SACs) have tremendous applications in enhancing the catalytic performance in the electrocatalytic nitrogen reduction reaction (NRR). Carbon-based substrates have superior properties that improve the catalytic performance either by forming defects or by doping heteroatoms, such as B,N-doped graphene, S-doped graphene, and defective carbon nanotubes. However, the carbon nanotube (CNT)-based electrocatalysts for NRR study are currently less explored. Here, we use the FeB<small>₂</small>N<small>₂</small>-(<em>n</em>,0) CNTs (<em>n</em> = 3–8) as representative electrocatalysts to study the different CNT curvatures and reveal their effects on the N<img>N triple bond activation and adsorption free energy (Δ<em>G</em>) of the *N<small>₂</small> molecule, with changes in the potential-determining step in NRR. Zigzag B<small>₂</small>N<small>₂</small>-(6,0) CNTs were selected as the efficient substrate, with three transition metal atoms (TM = Fe, Ru and Ir) anchored on the B<small>₂</small>N<small>₂</small>-(6,0) CNT to construct the NRR catalysts. Using first-principles calculation and the computational hydrogen electrode (CHE) model, we investigated their electrocatalytic performance in NRR. FeB<small>₂</small>N<small>₂</small>-(6,0) CNT is the most efficient catalyst and has a low limiting potential (<em>U</em><small>_L</small>) of −0.551 V for NRR. Further, the projected partial density of states and projected crystal orbital Hamilton population analyses illustrate that the N<small>₂</small> activation is due to strong π*-backbonding, which leads to effective charge transfer between the active site (metal d-orbital) and N<small>₂</small> molecule (p-orbital). The FeB<small>₂</small>N<small>₂</small>-(6,0) CNT also showed high NRR selectivity, inhibiting the competitive hydrogen evolution reaction. Our study provides a detailed mechanism of catalysis by the carbon-based, high-efficiency electrocatalyst for NRR and opens up the possibility for experimentalists to further explore the carbon-based one-dimensional electrocatalyst for NRR.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 21","pages":" 11221-11233"},"PeriodicalIF":2.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065656","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":"Fabrication of gold/polyaniline/copper oxide electrode for efficient photoelectrochemical hydrogen evolution†","authors":"Fahad Abdulaziz, Mohamed Zayed, Salman Latif, Yassin A. Jeilani, Mohamed Shaban, Raja Rama Devi Patel, Hussein A. Elsayed, Mohamed Rabia and Ashour M. Ahmed","doi":"10.1039/D5CP00350D","DOIUrl":"10.1039/D5CP00350D","url":null,"abstract":"<p >This study explores a novel photoelectrode composed of copper oxide (CuO), polyaniline (PANI), and gold (Au) for efficient hydrogen production through photoelectrochemical (PEC) water splitting. Structural and morphological analyses using various techniques confirm the successful fabrication of the ternary Au/PANI/CuO photoelectrode. The integration of Au, PANI, and CuO nanomaterials enhances light harvesting, facilitates charge transfer, and reduces charge recombination due to the plasmonic effect of Au and the synergistic interaction between PANI and CuO. The Au/PANI/CuO photoelectrode achieves a 300-fold increase in photocurrent density (15 mA cm<small>⁻²</small> at −0.39 V <em>vs.</em> RHE) compared to pure CuO. Additionally, it demonstrates superior operational stability for 5 hours and records an IPCE of 45% at 500 nm. These findings pave the way for the development of high-performance and durable plasmonic/polymer/semiconductor photoelectrodes for sustainable and clean hydrogen generation.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 21","pages":" 11177-11190"},"PeriodicalIF":2.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065957","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":"Nanoscale island manipulation and construction of heterojunctions by mechanical collision of 2D materials†","authors":"Xiongbai Cao, Liangguang Jia, Huixia Yang, Zhenru Zhou, Tingting Wang, Haolong Fan, Yan Li, Xiaoyu Hao, Lingtao Zhan, Qinze Yu, Liwei Liu, Teng Zhang, Quanzhen Zhang and Yeliang Wang","doi":"10.1039/D5CP01339A","DOIUrl":"10.1039/D5CP01339A","url":null,"abstract":"<p >Controllable phase transitions between distinct polymorphs in transition metal dichalcogenides (TMDs) hold great significance for applications in nanoscale electronics. Currently, constructing nanoscale heterojunctions with the desired TMD phase remains challenging due to insufficient control. In this study, we provided a new strategy of phase transitions by controllable mechanical collision of TMD islands containing over thousands of atoms. Using an <em>in situ</em> scanning tunneling microscopy (STM) tip manipulation technique, we can precisely control the fixed-axis rotation of nanoscale NbSe<small>₂</small> islands. Through mechanically colliding T- and H-NbSe<small>₂</small> with each other, we successfully triggered a phase transition from Mott insulator T-NbSe<small>₂</small> to semi-metal H-NbSe<small>₂</small>, thereby creating a high-quality heterojunction. We further unveiled the unusual electronic properties of this heterojunction, and provided new insights into the phase transition mechanisms in TMDs and their potential applications in nanoscale electronics.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 21","pages":" 10915-10922"},"PeriodicalIF":2.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065657","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}