Physical Chemistry Chemical Physics最新文献_第4页

Spectral mechanisms of solid/liquid interfacial heat transfer in the presence of a meniscus 半月板存在时固/液界面传热的光谱机制

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-01 DOI: 10.1039/d4cp04768k

Abdullah El-Rifai, Liudmyla Klochko, Viktor Mandrolko, Sreehari Perumanath, David Lacroix, Rohit Pillai, Mykola Isaiev

{"title":"Spectral mechanisms of solid/liquid interfacial heat transfer in the presence of a meniscus","authors":"Abdullah El-Rifai, Liudmyla Klochko, Viktor Mandrolko, Sreehari Perumanath, David Lacroix, Rohit Pillai, Mykola Isaiev","doi":"10.1039/d4cp04768k","DOIUrl":"https://doi.org/10.1039/d4cp04768k","url":null,"abstract":"In this study, we employ molecular simulations to investigate the enhancement in thermal conductance at the solid/liquid interface in the presence of a meniscus reported previously (Klochko et al., Phys. Chem. Chem. Phys., 2023, 25(4), 3298–3308). We vary the solid/liquid interaction strength at Lennard-Jones interfaces for both confined liquid and meniscus systems, finding that the presence of a meniscus yields an enhancement in the solid/liquid interfacial thermal conductance across all wettabilities. However, the magnitude of the enhancement is found to depend on the surface wettability, initially rising monotonously for low to moderate wettabilities, followed by a sharp rise between moderate and high wettabilities. The spectral decomposition of heat flux formalism was applied to understand the nature of this phenomenon further. By computing the in-plane and out-of-plane components of the heat fluxes within both the interfacial solid and liquid, we show that the initial monotonous rise in conductance enhancement predominantly stems from a rise in the coupling of out-of-plane vibrations within both the solid and the liquid. In contrast, the subsequent sharp rise at more wetting interfaces is linked to sharp increases in the utilization of the in-plane modes of the solid and liquid. These observations result from the interplay between the solid/liquid adhesive forces and the liquid/vapor interfacial tension. Our results can aid engineers in optimizing thermal transport at realistic interfaces, which is critical to designing effective cooling solutions for electronics, among other applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Uranyl fluorescence in acidic solution: quenching effects by tetramethylammonium (TMA+) 酸性溶液中的铀酰荧光：四甲基铵（TMA+）的猝灭效应

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp00577a

Thomas D. Persinger, Michael C. Heaven, Richard E. Wilson

{"title":"Uranyl fluorescence in acidic solution: quenching effects by tetramethylammonium (TMA+)","authors":"Thomas D. Persinger, Michael C. Heaven, Richard E. Wilson","doi":"10.1039/d5cp00577a","DOIUrl":"https://doi.org/10.1039/d5cp00577a","url":null,"abstract":"The quenching of uranyl luminescence by various cation species was studied in aqueous media at low pH. Solutions with different nitrate salts, held at constant uranyl nitrate, nitric acid, and ion concentration, were tested to examine the quenching effects of the cations from the nitrate salts. Alkali metal (Li+, Na+, Rb+) and quaternary ammonium cations (NH4+), (CH3)4N+ (TMA+), (C2H5)4N+ (TEA+) were investigated. Solutions containing TMA+ reduced the lifetime of uranyl fluorescence significantly more than the other cations. Uranyl emission spectra also showed that TMA+ increased the complex formation between uranyl and nitrate ions. Fluorescence decay lifetime measurements for most solutions yielded values between 1.4–1.9 μs at 20 °C, while 1.8 M TMA+ reduced the lifetime of uranyl fluorescence to 0.6 μs. Decay rate versus concentration data (Stern–Volmer plots) indicated a dynamic quenching process with increasing fluorescence decay rates at higher cation concentrations for Li+, TMA+, and TEA+. The temperature dependencies of the decay rates and the kinetics in D2O were also examined.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"91 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of anchoring groups on the photocatalytic performance of iridium(III) complexes in hydrogen production and their toxicological analysis 锚定基团对铱（III）配合物产氢光催化性能的影响及其毒理学分析

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d4cp04828h

Xiao YAO, Linyu Fan, Zhu Wu Jiang, Chaoqun Zheng, Jinfeng Chen, Yachen Jiang, Yisang Lu, Cheuk-Lam Ho, Yuanmei Chen

{"title":"Effect of anchoring groups on the photocatalytic performance of iridium(III) complexes in hydrogen production and their toxicological analysis","authors":"Xiao YAO, Linyu Fan, Zhu Wu Jiang, Chaoqun Zheng, Jinfeng Chen, Yachen Jiang, Yisang Lu, Cheuk-Lam Ho, Yuanmei Chen","doi":"10.1039/d4cp04828h","DOIUrl":"https://doi.org/10.1039/d4cp04828h","url":null,"abstract":"Three iridium(III) complexes (Ir1–Ir3) with different anchoring moieties, namely, 4,4'-dinitro-2,2'-bipyridine, tetraethyl [2,2ʹ‐bipyridine]‑4,4ʹ‐diylbis(phosphonate), and diethyl [2,2ʹ‐bipyridine]‑4,4ʹ‐dicarboxylate were designed, synthesised, and used as photosensitisers for water-splitting hydrogen generation. The effects of these anchoring moieties on the photophysical and electrochemical characteristics of the Ir(III) complexes were investigated via density functional theory (DFT) simulations and experimental methods. The hydrogen production efficiency of the Ir1@Pt-TiO2 system was as high as 4020.27 mol·μg−1·h−1. Among the three anchoring moieties, tetraethyl [2,2ʹ‑bipyridine]‑4,4ʹ‑diylbis(phosphonate) improved the performance of the complexes to a greater extent. In addition, toxicological investigation revealed that the toxicity of the Ir(III) complexes to luminous bacteria did not differ significantly from that of TiO2. This implies that the Ir(III) complexes synthesised in this study do not pose a significant threat to marine environments, similar to TiO2. This finding has potential implications in the development of highly efficient Ir(III) photosensitisers for the water-splitting process for hydrogen production.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"72 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Pressure-induced symmetry breaking and robust Mo3 clusters (S = 0) in kagome compounds M2Mo3O8 (M = Zn, Fe) kagome化合物M2Mo3O8 （M = Zn, Fe）中压力诱导对称破缺和强健Mo3簇（S = 0）

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp00514k

En Chen, Chen Li, Dequan Jiang, Yingying Ma, Haoming Cheng, Tianyao Pei, Chuanlong Lin, Yonggang Wang

{"title":"Pressure-induced symmetry breaking and robust Mo3 clusters (S = 0) in kagome compounds M2Mo3O8 (M = Zn, Fe)","authors":"En Chen, Chen Li, Dequan Jiang, Yingying Ma, Haoming Cheng, Tianyao Pei, Chuanlong Lin, Yonggang Wang","doi":"10.1039/d5cp00514k","DOIUrl":"https://doi.org/10.1039/d5cp00514k","url":null,"abstract":"This study explores the high-pressure behavior of Zn2Mo3O8 and Fe2Mo3O8, both composed of Mo3O13 clusters, through synchrotron X-ray diffraction, high-pressure Raman spectroscopy, and electrical transport measurements. The results reveal that both compounds undergo similar structural phase transitions from the hexagonal P63mc phase to the monoclinic P21 phase at elevated pressures. High-pressure Raman spectroscopy further shows the emergence of new vibrational modes and a gradual softening of the A1 mode, both of which are closely associated with the structural phase transition and potential breathing behavior of the Mo3 clusters. Thermal activation model analysis of resistivity measurements reveals pressure-dependent activation energy trends, including an anomalous trend reversal. Comparative experiments demonstrate that the presence or absence of magnetism in interlayer transition metal atoms does not affect the structural evolution, but seems to have an impact on transport properties under applied pressure. This suggests that the pressure-induced changes are primarily associated with the behavior of the Mo3 clusters in these compounds.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"107 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Uncovering the degradation kinetics and mechanisms of difluoroacetone in atmosphere and at air-water interface by OH radical and Cl atom: A theoretical investigation OH自由基和Cl原子在大气和空气-水界面降解二氟丙酮动力学和机理的理论研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp00279f

Xiao-Ming Song, Wan-Ying Yu, Ting-Ting Meng, Tai-Xing Chi, Xiang-Huan Liu, Shuang Ni, Feng-Yang Bai, Zhen Zhao

{"title":"Uncovering the degradation kinetics and mechanisms of difluoroacetone in atmosphere and at air-water interface by OH radical and Cl atom: A theoretical investigation","authors":"Xiao-Ming Song, Wan-Ying Yu, Ting-Ting Meng, Tai-Xing Chi, Xiang-Huan Liu, Shuang Ni, Feng-Yang Bai, Zhen Zhao","doi":"10.1039/d5cp00279f","DOIUrl":"https://doi.org/10.1039/d5cp00279f","url":null,"abstract":"The environmental and health risks of fluorinated compounds have attracted more and more attention because of their essential roles in the human body and potential contributions to greenhouse effects. Herein, the degradation mechanism, kinetic properties, subsequent transformation, and atmospheric lifetime of difluoroacetone (CF2HC(O)CH3) initiated by Cl atom and OH radical were investigated in the atmosphere and at the air-water interface. The reaction coefficients and product branching ratios (or regioselectivity) for H-abstraction channels were calculated and analyzed within 200-800 K by using multi-structural canonical variational transition state theory with small curvature tunneling (MS-CVT/SCT). At 297 K, the total rate coefficients of CF2HC(O)CH3 with OH radical and Cl atom are respectively 1.39×10-14 and 8.04×10-14 cm3 molecule-1 s-1, which are consistent with the existing experimental data. In the presence of HO2, O2, and NO, CF2HC(O)CH3 can convert into COF2 and CO2 as the end-products. Our findings indicate that the OH radical plays a more significant role in determining the atmospheric lifetime of CF2HC(O)CH3 than the Cl atom. At the air-water interface, the H-abstraction reaction of CF2HC(O)CH3 induced by OH radical occurs more rapidly at the -CH3 site (0.50 ps) than at the -CF2H site (2.50 ps), which is opposite to the selectivity of the gas-phase reaction. This study contributes to understanding the evolution mechanism of fluorinated acetone in a complex environment and improves our understanding of atmospheric chemical effects on aerosol surfaces.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"71 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cobalt-Free Cathode Material LiNi0.9Mn0.05Mg0.05O2 with High Cycle Stability Synthesized by Homogeneous Co-precipitation Method 均匀共沉淀法合成高循环稳定性无钴正极材料LiNi0.9Mn0.05Mg0.05O2

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp00910c

Jiatai Wang, XI Wen, Yan Tan, Yuanyuan Li

引用次数: 0

Computational investigation of silica-supported Pdn and Pdn(xO) nanoclusters 二氧化硅负载Pdn和Pdn（xO）纳米团簇的计算研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp00164a

Cornelius Lombard, Cornelia G. C. E. van Sittert, Jane Mugo, Christopher B Perry, David J Willock

{"title":"Computational investigation of silica-supported Pdn and Pdn(xO) nanoclusters","authors":"Cornelius Lombard, Cornelia G. C. E. van Sittert, Jane Mugo, Christopher B Perry, David J Willock","doi":"10.1039/d5cp00164a","DOIUrl":"https://doi.org/10.1039/d5cp00164a","url":null,"abstract":"Silica-supported Pd nanoclusters (Pdn/SiO2) are essential catalysts in methane oxidation for pollution abatement. These catalysts operate at high temperature for long periods exposed to the exhaust gases of combustion engines. For catalyst design to ensure the required longevity, insight into the interaction between nanoclusters and the SiO2 surface is essential. Accordingly, there is a need for well-defined, computationally inexpensive, quantum mechanical models of these structures from which cluster support interactions can be understood. In this work, we have found that a strong adsorption site for a single Pd1 atom on the hydroxlated α‑SiO2(101) surface can be formed when Pd adsorption is accompanied by the elimination of water. We show that this becomes a thermodynamically favourable process at the temperatures commonly used for calcination following catalyst synthesis using wet impregnation. Using this initial anchor point Pdn and Pdn(xO) nanoclusters are systematically constructed guided by the Mulliken charges of atoms at each stage. We then investigate the surface interactions of these Pdn and Pdn(xO) nanoclusters by considering the gas phase references of the same clusters. Our calculations show stability varies according to cluster size. Oxidation of the clusters leads to a weakening of cluster-surface interaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"70 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A dual-band mid-infrared polarization-insensitive perfect absorber 双波段中红外偏振不敏感的完美吸收器

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp01142f

Sijing Huang, Mousu Wan, Mingli Sun, Lin Lu, Xiaogang Wang, Bijun Xu

{"title":"A dual-band mid-infrared polarization-insensitive perfect absorber","authors":"Sijing Huang, Mousu Wan, Mingli Sun, Lin Lu, Xiaogang Wang, Bijun Xu","doi":"10.1039/d5cp01142f","DOIUrl":"https://doi.org/10.1039/d5cp01142f","url":null,"abstract":"We propose a dual-band mid-infrared polarization-insensitive perfect absorber utilizing a cross-shaped indium antimonide (InSb) metasurface. The absorber comprises a multilayer structure with an InSb cross-shaped thin film, dielectric layers (Si3N4 and Al2O3), and a titanium reflective substrate. Through finite-difference time-domain (FDTD) simulations, the optimized design achieves near-perfect absorption efficiencies of 99.3% and 99.8% at wavelengths of 4.91 μm and 5.94 μm, respectively, under normal incidence. Impedance matching theory and multipole decomposition reveal that the dual-band absorption is primarily contributed by electric dipole (ED) and magnetic dipole (MD) resonances. Crucially, the four-fold symmetry of the cross-shaped InSb layer ensures polarization insensitivity, with absorption spectra overlapping perfectly for transverse electric (TE) and transverse magnetic (TM) modes. Due to its simple design and ease of fabrication, the absorber can be widely applied in various fields, including infrared imaging, optical communication, gas detection, and thermal radiation control, offering new possibilities for the advancement of related technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889786","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

First-Principles Investigation of Auxetic Piezoelectric Effect in Nitride Perovskites 氮化钙钛矿中补充压电效应的第一性原理研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-30 DOI: 10.1039/d5cp01148e

Yanting Peng, Zunyi Deng, Siyu Song, Gang Tang, Jiawang Hong

{"title":"First-Principles Investigation of Auxetic Piezoelectric Effect in Nitride Perovskites","authors":"Yanting Peng, Zunyi Deng, Siyu Song, Gang Tang, Jiawang Hong","doi":"10.1039/d5cp01148e","DOIUrl":"https://doi.org/10.1039/d5cp01148e","url":null,"abstract":"The recently reported auxetic piezoelectric effect, which acts as the electrical counterpart of the negative Poisson’s ratio, is of significant technical importance for applications in acoustic wave devices. However, this electric auxetic effect has not yet been reported in perovskite systems. In this work, we employ first-principles calculations to investigate the piezoelectric properties of six polar nitride perovskites with the chemical formula ABN3 (A = La, Sc, Y; B = W, Mo). Among these, all compounds except ScMoN3 exhibit the auxetic piezoelectric effect, which is characterized by an unusually positive transverse piezoelectric coefficient, along with a positive longitudinal piezoelectric coefficient. This behavior is in sharp contrast to previously reported results in HfO2, where both the longitudinal and transverse piezoelectric coefficients are negative. These unusual positive transverse piezoelectric coefficients originate from the domination of the positive internal-strain contribution. We further confirm the auxetic piezoelectric effect with finite electric field calculations. Our research enriches the understanding of the piezoelectric properties of nitride perovskites and provides a new compositional space for the design of novel auxetic piezoelectric materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889787","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Lower Limits on Hydrogen Bond Strength. Charge of Bridging H Atom 氢键强度下限。桥接H原子的电荷

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-04-29 DOI: 10.1039/d5cp01314c

Steve Scheiner

引用次数: 0