Physical Chemistry Chemical Physics最新文献

{"title":"Enhanced Hydrogen Evolution Reaction Catalysis via Ruthenium Single-Atom Decoration on Biphenylene: A DFT Study","authors":"Sun Shikai, Manman Liu, David J. Singh, Wei Tao Zheng, Xiaofeng Fan","doi":"10.1039/d5cp02045j","DOIUrl":"https://doi.org/10.1039/d5cp02045j","url":null,"abstract":"The development of efficient, cost-effective, and durable electro-catalysts for the hydrogen evolution reaction (HER) remains a cornerstone for realizing sustainable hydrogen energy. However, the highly efficient catalysts with low cost for HER are still very limited. In this study, we employ spin-polarized density functional theory calculations to investigate the catalytic performance of ruthenium (Ru) single-atom catalysts (SACs) anchored on a biphenylene (BPN) substrate. It is found that the unique two-dimensional architecture and electronic characteristics of BPN offer a promising platform for hosting isolated metal atoms. The Ru atom is found to preferentially anchor at the C₄ hollow site, yielding a ΔGH* of -0.093 eV, comparable to H on Pt(111). Furthermore, Two Ru decorated BPN (2Ru-BPN) is energetically stable and provided to be as a double atoms catalyst (DACs). The active sit in 2Ru-BPN can lead to the multi-hydrogen adsorptions with Gibbs free energy change of about -0.12 eV, and thus promote the H₂ evolution along Tafel pathway under thermoneutral condition. Thus, this work provides a theoretical blueprint for designing high-performance Ru-based SACs and reinforces the potential of BPN as a next-generation catalyst support in hydrogen production.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"73 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140986","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":"Desorption of fragments upon electron impact on adsorbates: implications for electron beam induced deposition","authors":"Chinmai Sai Jureddy, Jakub Jurczyk, Krzysztof Mackosz, Hlib Lyschuk, Jaroslav Kocisek, Piotr Weber, Michelle Ernst, Alexey Verkhovtsev, Andrey V. Solov'yov, Juraj Fedor, Ivo Utke","doi":"10.1039/d5cp02552d","DOIUrl":"https://doi.org/10.1039/d5cp02552d","url":null,"abstract":"A molecular level understanding of surface chemistry involved in the focused electron beam induced deposition (FEBID) with metalorganic molecules is crucial for enhancing metal content in the nanostructures. Here we investigate the FEBID process of trimethyl(methylcyclopentadienyl)platinum(IV) [MeCpPtMe₃] using focused electron beam induced mass spectrometry (FEBiMS), a recently developed in situ analytical technique. A comparison with gas-phase electron impact fragmentation, along with density-functional-theoretical calculations and molecular dynamics simulations are presented. The results indicate that charged fragments generated via dissociative ionization exhibit strong adsorption to the substrate and lack sufficient kinetic energy to desorb, suggesting that the most observed charged species during FEBID originate from gasphase fragmentation above the surface. Furthermore, this study proposes processes like charge neutralization and dissociative recombination, mechanisms not previously considered in FEBID, could be significant contributors for increasing metal content in the resulting nanostructures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"95 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153857","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":"Chiral surface control in the Soai reaction: a DFT study of αquartz-induced enantioselective autocatalysis","authors":"Ivan I Murygin, Ilya D. Gridnev","doi":"10.1039/d5cp02751a","DOIUrl":"https://doi.org/10.1039/d5cp02751a","url":null,"abstract":"Mechanism of enantioselectivity generation in theSoai reaction induced by chiral α-quartz surfaces was modeled by DFT computations. Analyzing transition states for S-and R-products formation on d-and l-quartz, revealed key stabilizing interactions including hydrogen bonding and zinc coordination with the surface. Computed mirror-symmetric energy profiles for the reactions with d-and l-quartz systems correspond to the experimentally observed handedness of the product and demonstrate how the surface chirality controls stereochemistry of the reaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140978","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":"Unraveling the electronic properties of silicon carbide monolayers with Si/C vacancies","authors":"Ekaterina Vladimirovna Bartashevich, Sergey Sozykin, Vladimir G. Tsirelson","doi":"10.1039/d5cp02316e","DOIUrl":"https://doi.org/10.1039/d5cp02316e","url":null,"abstract":"This study discusses the structural features and electronic properties of silicon carbide monolayers (SiCML) in which the loss of a neutral Si or C atom leads to the formation of vacancy defects. 2D periodic models were compared from the standpoint of the energetic preference of their various metastable atomic configurations. The energy properties in SiCML models varies widely and depends on the type of ordering of silicon atoms in the layer plane. The electronic properties of SiCML were analyzed using the spin density distributions, electron localization function, and phase-space defined Fisher information density (PS-FID). It was discovered that PS-FID function allows distinguishing the domains of unpaired electrons from the domains of a lone electron pair. The study characterizes the types of C…C, C–Si, and Si–Si bonds forming between the atoms of defect selvedge. Some of C…C bonds can be attributed to typical tetrel bonds.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141099","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":"Theoretical and Machine Learning Exploration of Electronic Factors Governing Ni-Centered CO2 Reduction Catalysts","authors":"Shitong Nie, Lin Tao, Honglei Yu, Davoud Dastan, Wensen Wang, Lili Hong, Li-Xiang Li, Baigang An, Yaqiong Su","doi":"10.1039/d5cp02458g","DOIUrl":"https://doi.org/10.1039/d5cp02458g","url":null,"abstract":"Carbon-based electrocatalysts are promising candidates for CO2 reduction due to their intrinsic redox properties. However, achieving an in-depth understanding and rational design of the nickel site coordination environment and active site density remains a significant challenge. In this study, a single-atom catalyst supported on graphene was designed to reduce CO2 to CO or HCOOH, based on density functional theory. The catalytic activity of the Nin-CxNy-d monolayer was systematically evaluated through charge density, density of states, and molecular dynamics analyses, verifying the conductivity and stability. Furthermore, an analysis of the Gibbs free energy pathway and electronic structure revealed that Ni2-C3N1-1 exhibits excellent catalytic performance for CO production in the CO2 reduction reaction, while Ni2-C2N2-1 demonstrates superior performance for HCOOH, with relatively low limiting potentials of -0.27 V and -0.09 V, respectively. Molecular orbital theory analysis underscores the critical role of bonding states in explaining the adsorption energy of intermediate products. Moderate adsorption energy is shown to effectively suppress hydrogen evolution reactions, thereby enhancing both reaction activity and product selectivity. Leveraging the best-performing machine learning XGBoost model, the feature importance between HCOOH product and the Ni single-atom catalyst structure was predicted to be 0.568, allowing for the identification of optimal tuning strategies to achieve superior catalytic performance. This study provides novel theoretical insights and technological strategies for advancing sustainable CO2 reduction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140977","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":"Conducive ultra-flexible graphene-based films for electronic applications","authors":"Nikolay V. Petyakin, Artem Ilyich Ivanov, Anna A Buzmakova, Irina V. Antonova","doi":"10.1039/d5cp01806d","DOIUrl":"https://doi.org/10.1039/d5cp01806d","url":null,"abstract":"One of the priority tasks for development of flexible printed electronics is creation of stable conductive 2D printing inks that can form highly flexible films. For instance, development of wearable electronic devices requires materials able to withstand strain at the level of human skin elastisity. The structure, flexibility, and electrical properties of thin films of a graphene-based composite with addition of the conductive polymer PEDOT:PSS and polyvinyl alcohol (PVA) were studied. The films were produced by 2D inkjet printing. The high conductivity of all the samples is provided by graphene because its content significantly exceeds the percolation threshold. It has been found that the addition of 5 wt.% or more of PVA results in retainment of the film structure under strain of up to 40% (bending radius of 0.13 mm). At the same time, the resistance change under such deformations declines significantly (~3 times) compared to that of films without PVA. This is due to the formation of a PVA flexible network inside the composite films. Moreover, owing to this network, when no more than 30 wt.% of PVA is added, the initial specific resistance stays within 20% from that of the original composite without PVA. Besides that, at the addition of PVA, the resistance remains low under repeated significant mechanical strains (ε≈17%). Thus, graphene-based composites with the addition of PVA are promising conductive materials for flexible and wearable electronics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140980","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":"Isobaric phase equilibrium behavior and mechanism analysis for eliminating azeotropic phenomena of n-propanol and water with ionic liquids as entrainers.","authors":"Dongxiang Zhang,Yuxuan Xiao,Yue Wang,Hua Xin,Qinqin Zhang,Zhigang Zhang","doi":"10.1039/d5cp02301g","DOIUrl":"https://doi.org/10.1039/d5cp02301g","url":null,"abstract":"n-Propanol (NPA), extensively utilized in various fields including biomedicine and industrial production, forms an azeotrope with H2O. The azeotropic behavior impairs the purity of NPA, posing significant obstacles to the separation of the two substances via conventional distillation methods. Extractive distillation (ED), owing to its remarkable advantages, has become the prevalent technique for separating azeotropic mixtures. In the ED process, the entrainer has emerged as a crucial and indispensable component. Ionic liquids (ILs) are novel entrainers that have been developed recently and are employed as environmentally friendly solvents in the ED process. Based on the COSMO-RS theory, three ILs, [N1111][Ac], [EMMIM][Ac], and [BMMIM][Ac], were screened as entrainers according to the selectivity and solubility, and their capacity to influence the phase equilibrium behavior of the NPA-H2O system at atmospheric pressure was explored. Each of the three ionic liquids was found capable of disrupting the azeotropic behavior of the binary NPA-H2O system, with the reliability of the experimental results confirmed by the thermodynamic consistency test. Additionally, the vapor-liquid equilibrium (VLE) data were properly fitted through the nonrandom two-liquid (NRTL) model, and interaction parameters were derived that confirm that the three ILs break the azeotropy. Furthermore, through a series of quantum chemical (QC) studies, it was further confirmed at the theoretical level that the original hydrogen bonds (HB) are reorganized when ILs are used as entrainers. These results showed that the abilities of the three ILs to affect the azeotropy are in the order [N1111][Ac] > [EMMIM][Ac] > [BMMIM][Ac]. The experimental results are consistent with the predictions of the COSMO-RS model and QC calculations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"41 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140077","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":"Steric substitution in phenylazo indoles reveals interplay of steric and electronic effects on photophysical dynamics.","authors":"Christian A Guzman,Zachary J Knepp,Allen H Chen,Jacob Haber,Rachel Joh,Gabriel B Masso,Lisa A Fredin,Elizabeth R Young","doi":"10.1039/d5cp01953b","DOIUrl":"https://doi.org/10.1039/d5cp01953b","url":null,"abstract":"Indole-containing azo dyes have the potential to add photocontrol to pharmaceuticals, as substituted indoles are prevalent in biological systems. It is critical to understand the complex interplay substitution has on the photophysical properties in order to enable control of the on and off states of a drug. This work identifies the impact of steric and electronic effects of four steric R-groups on the photoisomerization and thermal reversion processes of a series of phenylazo indole dyes and demonstrates that protonation can be used to control bulk isomerization. Four phenylazo indole dyes were synthesized with varying steric bulk, a proton (H), a methyl group (Me), a tert-butyl group (tBu), or a phenyl group (Ph), at the C2 position of the indole adjacent to the azo bond. 2D NOESY NMR and computational methods were used to identify the rotational conformation of each trans-isomer as the anti-rotamer. The cis-isomer of the unsubstituted moiety accesses the eclipsed-rotamer while all other dyes adopt the anti-rotamer after photoexcitation. The Taft and Charton free energy models were employed to identify if the steric or electronic contributions of the steric R-group more strongly impact photoisomerization and thermal reversion dynamics. Surprisingly, in these indole dyes, electron donation strength, measured by the electronic Taft parameter of the steric R-group, correlated with the increasing photoisomerization rate. Thermal reversion rates were found to decrease with increasing steric substitution following the steric Taft parameter. However, the unsubstituted compound deviated from the trends in both photoisomerization and reversion dynamics. Acidity constants increase with increasing bulk of the steric R-group using the Charton steric model and protonation of the azo bond eliminated bulk photoisomerization. Thus, the impact of steric modification does not result in straightforward effects on the photophysical behavior, even when choosing a site close to the azo bond.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140146","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":"General integrated rate law for complex self-assembly reactions reveals the mechanism of amyloid-beta coaggregation.","authors":"Alexander J Dear,Georg Meisl,Emil Axell,Xiaoting Yang,Risto Cukalevski,Thomas C T Michaels,Sara Linse,L Mahadevan","doi":"10.1039/d5cp01288k","DOIUrl":"https://doi.org/10.1039/d5cp01288k","url":null,"abstract":"Analyzing kinetic experiments on protein aggregation using integrated rate laws has led to numerous advances in our understanding of the fundamental chemical mechanisms behind amyloidogenic disorders such as Alzheimer's and Parkinson's diseases. However, the description of biologically relevant processes may require rate equations that are too complex to solve using existing methods, hindering mechanistic insights into these processes. An example of significance is coaggregation in environments containing multiple amyloid-beta (Aβ) peptide alloforms, which may play a crucial role in the biochemistry of Alzheimer's disease but whose mechanism is still poorly understood. Here, we use the mathematics of Lie symmetry to derive a general integrated rate law valid for most plausible linear self-assembly reactions. We use it in conjunction with experimental data to determine the mechanism of coaggregation of the most physiologically abundant Aβ alloforms: Aβ42, Aβ40, Aβ38 and Aβ37 peptides. We find that Aβ42 fibril surfaces catalyze the formation of co-oligomers, which accelerate new Aβ40, Aβ38 and Aβ37 fibril formation whilst inhibiting secondary nucleation of new Aβ42 fibrils. The simplicity, accuracy and broad applicability of our general integrated rate law will enable kinetic analysis of more complex filamentous self-assembly reactions, both with and without coaggregation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140484","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":"Photoreduction preparation of PdPt/P2W18/rGO nanocomposite for alcohol electrooxidation","authors":"Peisong Yan, Bo Zhao, Xiangting Dong, Zhelin Liu","doi":"10.1039/d5cp01891a","DOIUrl":"https://doi.org/10.1039/d5cp01891a","url":null,"abstract":"Herein, palladium-platinum nanoparticles were assembled onto the surface of reduced graphene oxide with the assistance of polyoxometalate K<small>₆</small>P<small>₂</small>W<small>₁₈</small>O<small>₆₂</small> (abbreviated as P<small>₂</small>W<small>₁₈</small>) as photocatalyst via a facile and green photoreduction route. The as-prepared nanocomposites were investigated by characterizations including transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Motivated by the development of anode electrocatalyst of direct alcohol fuel cell, the assembled nanocomposite was developed as the electrocatalyst towards the electrooxidation of alcohol in alkaline electrolyte. Results show that the fabricated PdPt/P<small>₂</small>W<small>₁₈</small>/rGO nanocomposite exhibits enhanced electrocatalytic mass activity and stability compared with commercial 10% Pd/C catalyst, exhibiting potential practical prospect in fuel cell applications. The proposed fabrication approach can also be extended to the photoreduction preparation of other Pd alloy with the assistance of other polyoxometalate, and may spread the application in other fields.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"93 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140979","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}