Physical Chemistry Chemical Physics最新文献

{"title":"A study on the construction of spherical MnCO3–Cu2O composites with enhanced electrochemical lithium storage performance","authors":"Lei Wang, Guifen Du, Piyu Gong, Chuansheng Cui, Shuo Tao, Haibo Li, Suyuan Zeng","doi":"10.1039/d4cp04509b","DOIUrl":"https://doi.org/10.1039/d4cp04509b","url":null,"abstract":"In this work, thermodynamic multifunctional MnCO<small>₃</small>–Cu<small>₂</small>O composites with coral sphere shaped and pompon-like microstructures were constructed using a one chemical co-precipitation solvothermal process. The synergistic effect, the pseudocapacitive contribution and the p–n heterojunction enhance the electrochemical lithium storage performance and cycling stability of the formed MnCO<small>₃</small>–Cu<small>₂</small>O composites. At a current density of 2.0 A g<small>⁻¹</small>, the coral sphere shaped MnCO<small>₃</small>–Cu<small>₂</small>O and pompon-like MnCO<small>₃</small>–Cu<small>₂</small>O electrodes exhibit discharge capacities of 804.6 mA h g<small>⁻¹</small> and 650.2 mA h g<small>⁻¹</small> after 400 cycles. The coral sphere shaped MnCO<small>₃</small>–Cu<small>₂</small>O microstructure exhibits excellent electrochemical performance. This study presents a design strategy for the construction of MnCO<small>₃</small>-based composites that can be used in novel lithium-ion batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758497","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":"Size-Selected Anion Photoelectron Spectroscopy and Density Functional Theory Calculations of Ferromagnetic Fe2Cn−/0 (n = 2–6) Clusters","authors":"Xi-Long Li, Zhen-Chao Long, Kai-Wen Liu, Baibai Wan, Xi-Ling Xu, Hong-Guang Xu, Weijun Zheng","doi":"10.1039/d5cp00662g","DOIUrl":"https://doi.org/10.1039/d5cp00662g","url":null,"abstract":"The structural and electronic properties of iron carbide clusters Fe2Cn−/0 (n = 2–6) were investigated using size-selected anion photoelectron spectroscopy and theoretical calculations. The adiabatic and vertical detachment energies of Fe2Cn− (n = 2–6) were obtained from their photoelectron spectra. The ground state structures of Fe2Cn− (n = 2–6) were determined by comparing the theoretical results with the experimental data. The most stable isomers of Fe2Cn− adopt planar structures, except for Fe2C5−, in which the carbon atoms deviate slightly from the plane. The ground state structures of neutral Fe2Cn clusters are generally similar to their corresponding anions, except for Fe2C3, which adopts a planar cyclic structure containing a C3 unit. The magnetic moments of the Fe2Cn− clusters are 7 µB for even sizes and 5 µB for odd sizes, whereas those of neutral Fe2Cn are 8 µB (6 µB for n = 2) for even sizes and 6 µB for odd sizes. The magnetic moments primarily originate from Fe atoms. The Fe–Fe bond lengths increase gradually with the growth of the cluster size, resulting in the transition from double-bond to single-bond character. The spin multiplicities and relative stabilities of Fe2Cn− exhibit odd-even alternations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"57 5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758503","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 Reaction of Sulfenic Acids with OH and HO2 Radicals in different Environments.","authors":"Josep M. Anglada, Ramon Crehuet, Marilia T.C. Martins-Costa, Joseph S Francisco, Manuel F. Ruiz-López","doi":"10.1039/d4cp04106b","DOIUrl":"https://doi.org/10.1039/d4cp04106b","url":null,"abstract":"Sulfenic acids are involved in major chemical processes occurring in the atmosphere, in food chemistry and in biological systems. In these diverse environments, oxidation reactions caused by reactive oxygen species, especially hydroxyl (OH) and hydroperoxyl (HO2) radicals, are very important, but their mechanisms remain poorly understood. To address this question, in this paper we present high-level theoretical results on selected reactions in gas phase and in aqueous solution. The study shows that the abstraction of the acidic hydrogen by OH or HO2 is the most important process in all cases. It leads to the formation of sulfinyl radicals and H2O or H2O2, respectively, following a proton-coupled electron transfer (pcet) mechanism. The associated rate constants depend on sulfenic acid derivative when the oxidizing species is HO2, but all processes are diffusion controlled in the case of reaction with OH. From structurally simple systems to a cysteine-derived model peptide, this work provides a systematic study that contributes to a comprehensive understanding of the reactivity of sulfenic acids with radicals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758504","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 Understanding of CO2 Reduction Products on Nitrogen-Doped Graphene Supported Dual-Atom Catalysts","authors":"Chunyuan Feng, Lixiang Zhong","doi":"10.1039/d5cp00875a","DOIUrl":"https://doi.org/10.1039/d5cp00875a","url":null,"abstract":"In recent years, nitrogen-doped graphene supported dual-atom catalysts (DAC@NC) for CO<small>₂</small> reduction reaction (CO<small>₂</small>RR) have attracted widespread research interest. Although some DAC structures for deep reduction C<small>₁</small> products and C<small>₂</small> products have been proposed in previous theoretical calculations, the desired products are still difficult to be realized in experiments. This work systematically investigates the reaction pathways and products of CO<small>₂</small> reduction on bimetallic DAC@NC (M<small>₁</small>-M<small>₂</small>@NC, M<small>₁</small>, M<small>₂</small> = Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, and Pt) by first-principles calculations. After excluding improper M<small>₁</small>-M<small>₂</small>@NC in terms of catalyst poisoning and hydrogen evolution competition, C−C coupling processes always have much higher free-energy increments than the corresponding hydrogenation, making it difficult to form multi-carbon structures. For most of the C<small>₁</small> intermediates on M<small>₁</small>-M<small>₂</small>@NC, the free-energy increments of C−C coupling are higher than 0.8 eV. Some C<small>₁</small> intermediates could couple with a second carbon, but it is much more difficult than hydrogenation toward C<small>₁</small> products. This work reveals why C<small>₂</small> products are still difficult to be achieved for CO<small>₂</small>RR on M<small>₁</small>-M<small>₂</small>@NC, and identifies the M<small>₁</small>-M<small>₂</small> combinations for deep reduction C<small>₁</small> products (methane and methanol), which is inspiring for the future design of CO<small>₂</small>RR catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758592","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":"Highly Sensitive Magnetostrictive NiZnCo Ferrites for Low Magnetic Field Sensor Applications","authors":"Yiyang Cui, Xiaokang Yang, Haofang Ma, Caiyun Qi, Baorui Xia, Daqiang Gao","doi":"10.1039/d4cp04520c","DOIUrl":"https://doi.org/10.1039/d4cp04520c","url":null,"abstract":"Ferrites with enhanced magnetostrictive strain and sensitivity possess significant potential for various multifunctional devices. Herein, the magnetostrictive ferrite (Ni0.8Zn0.2)1-xCoxFe2O4 (0 ≤ x ≤ 1) are prepared by a facile sintering method. The X-ray diffraction and scanning electron microscope results demonstrate that the lattice constant and mean grain size increase with the x while the porosity decreases. Through the magnetic measurements, it is found that the saturation magnetization, coercivity and magnetocrystalline anisotropy constant all increase with x. However, the permeability decreases due to the inherent hard magnetic nature of cobalt ferrite. Magnetostrictive strain measurements reveal that with the increasing x, the saturation magnetostrictive strain is elevated, owing to the strong magnetocrystalline anisotropy of the octahedrally coordinated Co2+. The strain sensitivity variation of the samples with 0.2 ≤ x ≤ 0.8 is consistent with the theoretical parameter. The maximum strain sensitivity is achieved in the sample with x = 0.4 (0.229 ppm/Oe), and the magnitude of the external magnetic field is also the smallest at this time, which indicates that this material may be applied in the field of low magnetic field magnetoelelctric sensors and devices. Finally, in order to further optimise the properties of magnetostrictive materials, an innovative approach is introduced.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"73 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758591","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":"Near Zero Singlet-Triplet Gap Through Nonfullerene Core Modification with Phenalene Derivatives Building Blocks","authors":"Leandro Benatto, Marlus Koehler, Rodrigo Capaz, Graziâni Candiotto","doi":"10.1039/d5cp00767d","DOIUrl":"https://doi.org/10.1039/d5cp00767d","url":null,"abstract":"Recent advances in data-driven machine learning have highlighted the critical importance of the singlet-triplet gap (ΔE<small>_ST</small>=E<small>_S1</small>-E<small>_T1</small>) in non-fullerene acceptors (NFAs) molecules as an useful figure of merit to predict the efficiency of organic photovoltaic devices. By reducing ΔE<small>_ST</small>, the photovoltaic performance can be improved through the suppression of triplet state channels for non-geminate charge recombination. Encouraged by this strategy, we propose and theoretically explore the properties (specially relative to ΔE<small>_ST</small>) of a new class of NFAs derived from modifications of the central core of the Y6 molecule (C<small>₈₂</small>H<small>₈₆</small>F<small>₄</small>N<small>₈</small>O<small>₂</small>S<small>₅</small>). The idea is to replace the benzothiadiazole chemical group by building blocks of phenalene derivatives, recognized for their unique inverted ΔE<small>_ST</small>. Using a computational analysis that incorporates double-hybrid exchange-correlation functional as a benchmark method, we anticipate a remarkable reduction of ΔE<small>_ST</small> upon phenalene derivatives substitution, with some molecules achieving near zero singlet-triplet gap. This is the first report that call attention to new chemical strategies to synthesize NFA molecules with very low (eventually zero) ΔE<small>_ST</small>. Moreover, some modified molecules exhibited higher E<small>_T1</small> compared to Y6, which is interesting to mitigate non-geminate recombination. The molecular modifications also improve the electron transfer properties, such as the intramolecular reorganization energy and the quadrupole moment, leading to more rigid and polarized molecules. The molecular modifications also lead to a decrease in intramolecular reorganization energy, thereby lowering the energy barrier for electron transfer. Additionally, a significant increase in the quadrupole moment component along the π-π stacking direction was observed—an essential property for strengthening quadrupole-quadrupole intermolecular interactions, which play a crucial role in molecular packing and charge transport. Overall, our research yields valuable insights into optimizing NFAs, opening the possibility of alternative molecular architectures to further development of high-efficiency organic photovoltaic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758501","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":"VUV threshold photoelectron spectroscopy of SiS","authors":"Myriam Drissi, Jean-Christophe Loison, Bérenger Gans, Séverine Boyé-Péronne, Hai-Linh Le, Mengxu Jiang, Laurent Nahon, Gustavo A. Garcia","doi":"10.1039/d5cp00494b","DOIUrl":"https://doi.org/10.1039/d5cp00494b","url":null,"abstract":"Silicon monosulfide (SiS) is an important molecule in astrochemistry likely linked to dust production through the formation of sulfide particles. This work presents the vacuum ultraviolet photoionisation of SiS formed <em>in situ</em> in a discharge flow reactor, in particular the threshold photoelectron spectrum covering the first three electronic states of the SiS<small>⁺</small> cation. The rich vibronic structure is assigned with the support of <em>ab initio</em> calculations and a spin orbit coupling constant of −323 ± 41 cm<small>⁻¹</small> is measured for the ground state. Adiabatic ionisation energies (10.453 ± 0.003, 10.515 ± 0.003 and 13.802 ± 0.003 eV for the ground, first and second excited state, respectively) and vibrational frequencies are also extracted from the spectra, and combined with the existing thermochemical values yields the SiS<small>⁺</small> dissociation energy (4.09 ± 0.01 eV).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758613","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":"Enhanced transdermal permeation of caffeine through skin model using electric field-induced lipid vesicles: a novel approach for drug transport","authors":"Herculano da Silva Martinho, Neila Machado, Daniele Ribeiro de Araújo, Carla Carolina Silva Bandeira, Roger Borges, Juan Jose Nogueira Perez, Lorena Ruano, Nuria Anguita, Vito F. Palmisano","doi":"10.1039/d4cp04377d","DOIUrl":"https://doi.org/10.1039/d4cp04377d","url":null,"abstract":"Caffeine is a highly beneficial compound for human health, known for its anticancer, anti-inflammatory, and antioxidant properties, particularly in protecting the skin from UVB radiation damage. Although caffeine shows excellent potential for transdermal delivery, its hydrophilic nature often requires a chemical enhancer for effective transport. Traditional methods like iontophoresis and electroporation utilize external electric fields to create micro-pores in the skin, enhancing the delivery of hydrophilic molecules. While electroporation is well understood, the molecular mechanisms of iontophoresis are unclear. This investigation presents an innovative mechanism for caffeine transport from an aqueous solution without chemical enhancers using lipid vesicles generated by external electric fields. To investigate the caffeine transdermal transport process, we combined our iontophoresis methodology with molecular dynamics simulations using Gromacs and the Martini force field alongside a practical custom experiment. Our approach employed a constant electric field of 22-25 mV/nm, successfully generating lipid vesicles that transport caffeine molecules. Notably, alternating electric fields at 306 K (physiological skin temperature) increased caffeine transport by 20%, and at 323 K, we achieved an impressive 300% increase compared to scenarios without electric fields. Our homemade Franz cell setup showed a permeation rate dependent on the electric field correlated with vesicle formation. Additionally, hyperspectral Raman mapping identified unsaturated carbon and C-N groups as key contributors to vesicle and pore instability. This groundbreaking approach offers significant potential for enhancing transdermal drug delivery systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766423","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":"Metal-Oxygen Bonding Characteristics Dictate Activity and Stability Differences of RuO2 and IrO2 in Acidic Oxygen Evolution Reaction","authors":"Longdan Tang, Li Li, Xia Chen, Zhuoyang Xie, Qiong Xiang, Jin Liu, Zidong Wei","doi":"10.1039/d5cp00666j","DOIUrl":"https://doi.org/10.1039/d5cp00666j","url":null,"abstract":"Ruthenium dioxide (RuO2) and iridium dioxide (IrO2) serve as benchmark electrocatalysts for the acidic oxygen evolution reaction (OER), yet their intrinsic activity-stability relationships remain elusive. Herein, we employ density functional theory (DFT) calculations to systematically investigate the origin of divergent OER catalytic behaviors between RuO2 and IrO2 in acidic media. Mechanistic analyses reveal that RuO2 follows the adsorbate evolution mechanism with superior activity (theoretical overpotential: 0.698 V vs. 0.909 V for IrO2), while IrO2 demonstrates enhanced stability due to a higher dissolution energy change (&gt;2.9 eV vs. -0.306 eV for RuO2). Electronic structure analysis uncovers that RuO2 exhibits ionic-dominated metal-oxygen bonds with delocalized electron distribution, facilitating intermediate desorption but promoting detrimental RuO42–dissolution. In contrast, IrO2 features covalent bonding characteristics with more electron filling in Ir-oxygen bonds (2.942 vs. 2.412 for RuO2), thereby stabilizing surface intermediates against dissolution at the expense of higher OER barriers. This work establishes a clear correlation between bonding nature and electrocatalytic performance metrics, offering fundamental insights for the rational design of acid-stable OER electrocatalysts with optimized activity-stability relationships.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"230 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758506","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":"Accounting for the Vibrational Contribution to the Configurational Entropy in Disordered Solids with Machine Learned Forcefields: A Case Study of Garnet Electrolyte Li7La3Zr2O12","authors":"Jack Yang, Ziqi Yin, Sean Li","doi":"10.1039/d5cp00138b","DOIUrl":"https://doi.org/10.1039/d5cp00138b","url":null,"abstract":"Accounting for lattice vibrations to accurately determine the phase stabilities of site-disordered solids is a long-standing challenge in computational material designs, due to the high computational cost associated with sampling the vast configurational space to obtain the converged thermodynamic quantities. One example is the garnet electrolyte Li7La3Zr2O12, the high-temperature and high-ion-mobility cubic phase of which is disordered in its Li+ site occupations, such that both the vibrational and configurational entropic contributions to its phase stability cannot be ignored. Understanding the subtle interplay between vibrational and configurational entropies in this material will therefore play a critical role in the rational manipulation of dopants and defects to stabilise cubic Li7La3Zr2O12 at room temperature for practical applications. Here, by developing machine learned forcefields based on an equivariant message-passing neural network SO3krates, we follow a strict statistical thermodynamic protocol to quantify the phase stability of cubic Li7La3Zr2O12 through structural optimisations, as well as molecular dynamic simulations at 300 and 1500 K, for a total of 70,120 configurations of cubic Li7La3Zr2O12. Although this only covers a tiny fraction of the configurational space (~7x10^34 configurations in total), we are able to deterministically show the vibrational contributions to the total configurational free energy at 1500 K are significant (on the order of 1 eV/atom) in correctly ordering the stability of the cubic Li7La3Zr2O12 over its tetragonal counterpart, thanks to the high data efficiency, accuracy, stability and good transferability of the transformer-based equivariant network architecture behind SO3krates. Therefore, our work opens up new avenue to accelerate the accurate computational designs of disordered solids, such as solid electrolytes, for technologically important applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"58 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766421","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}