Physical Chemistry Chemical Physics最新文献

{"title":"Synthesis of Hybrid BCN@Fe3O₄ Nanocomposites by Ultrasonication Technique as a Highly Efficient Photocatalysts for Solar Light-Driven CO₂ Conversion into Producing Sustainable Solar Chemical","authors":"Pragya Singh,Rajesh K. Yadav,Chinna Bathula,Shaifali Mishra,Kanchan Sharma,Surendra K. Jaiswal,Anurag Rai,Jin-Ook Baeg","doi":"10.1039/d6cp02372j","DOIUrl":"https://doi.org/10.1039/d6cp02372j","url":null,"abstract":"In this work, we report a simple, scalable, reproducible, and template-free in situ growth strategy assisted by ultrasonication for the fabrication of boron-doped graphitic carbon nitride–magnetic iron oxide (BCN@Fe₃O₄) hybrid nanocomposites. The method enables uniform anchoring of monodisperse Fe₃O₄ nanoparticles with an average size of ~20-22 nm onto BCN nanosheets, effectively suppressing particle aggregation and ensuring a stable interfacial architecture. The resulting BCN@Fe₃O₄ hybrid nanocomposite exhibits outstanding photocatalytic performance, achieving selective CO₂ reduction to formic acid 149 μM along with a high 1,4-NADH regeneration yield of 63.66%. This enhanced activity arises from the combined effects of strong visible-light absorption, efficient charge separation, and increased exposure of active surface sites. Furthermore, the synthesized nanocomposites superparamagnetic characteristics increase their potential for a variety of uses, especially in bio-nanotechnology and lithium storage systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152768","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":"Thermal Rectification by Nanoscale Design: Overcoming Bulk Limitations","authors":"Wei-Chao Wang,Zi-Qi Lin,Shuo-Wang Yang,Jin-Cheng Zheng,Huiqiong Wang","doi":"10.1039/d6cp02578a","DOIUrl":"https://doi.org/10.1039/d6cp02578a","url":null,"abstract":"Thermal rectification in bulk materials is generally weak because their thermal conductivities have similar temperature dependence. Here, we demonstrate a nanoscale design principle that overcomes the inherent efficiency limitations of bulk thermal rectifiers. By combining lattice-dynamics calculations with the Callaway transport model, we show that phonon–boundary scattering in nano crystalline silicon and diamond induces a nonmonotonic, size-dependent thermal conductivity, a behavior distinct from the monotonic dependence observed in bulk materials. Leveraging this effect, we achieve a maximum rectification ratio of 1.913 in a silicon-diamond junction, significantly exceeding the bulk value of approximately 1.044. The optimal design pairs a silicon segment with a 1000 nm grain size (d_g) with a diamond segment of 120–220 nm grain size (d_g), thereby maximizing the asymmetry in their temperature-dependent conductivities. The rectification exhibits a pronounced dependence on the operating temperature window, with the peak shifting toward lower temperatures and eventually giving way to a monotonically decreasing trend as the temperature bias increases. Extending this framework to other material combinations, we also evaluate carbon/silicon carbide (Diamond/SiC) and silicon carbide/silicon (SiC/Si) junctions in different grain size, achieving optimized rectification ratios of 1.749 and 1.296, respectively. Demonstrated by finite-difference time-domain simulations, this work establishes a general route for engineering phonon transport asymmetry via nanoscale structural design, enabling high-efficiency solid-state thermal management and phonon devices. Sensitivity analyses further show that the enhanced rectification remains robust against partial boundary specularity and a finite thermal boundary resistance, confirming that the dominant contribution arises from grain-size-induced asymmetry in the temperature-dependent thermal conductivities. This work establishes nanoscale structural engineering as a general strategy for breaking the intrinsic limitations of bulk thermal rectification, opening a new avenue for the rational design of high-performance thermal rectifiers and next-generation thermal-management technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151981","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":"Resonance Energies from Complex Absorbing Potentials: A Complex Basis Function Approach in the η → 0 Limit","authors":"Deepak Kumar,HRISHIKESH RAJBONGSHI,Ashish Kumar Gupta","doi":"10.1039/d6cp02831d","DOIUrl":"https://doi.org/10.1039/d6cp02831d","url":null,"abstract":"Complex Absorbing Potentials (CAP) are non-physical in nature, and they introduce artificial perturbations to the systems, resulting in unwanted shifts in the calculated resonance energies. This study presents a novel methodology for eliminating these artificial reflections using Complex Basis Functions (CBF). The eigenfunctions obtained at high CAP strength parameter(η) are used as CBF, and resonance energies are calculated in the limit of η → 0+ . This method not only generates perturbation-free resonance energies, but also produces the resonance wavefunction at η → 0+ . The resulting complex resonance energies obtained using these CBFs are independent of both the CAP box-size parameters and the optimal value of η. Consequently, the proposed approach eliminates the need to optimise the CAP-onset parameters while providing reliable and parameter-independent resonance energies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151978","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":"Preparing Small Gaussian Basis for Highly Accurate Ab Initio Description of Lithium Rydberg States","authors":"Jan Šmydke,Benjamín Andreides,Simona Dubcová","doi":"10.1039/d6cp03005j","DOIUrl":"https://doi.org/10.1039/d6cp03005j","url":null,"abstract":"A new small and highly accurate Gaussian basis set has been developed for the ab initio description of 2Li Rydberg excited states up to n = 7 and S, P, D, F, and G angular momentum symmetry, and the appropriate optimization protocol is presented. The obtained Rydberg excitation energies are compared with results from other highly accurate approaches. At the EOM-CCSD level of theory the new basis exhibits higher than 10-2 eV accuracy of the excitation energies and the ionization potential and provides superior results than an analogous universal Gaussian basis set, while utilizing even smaller number of basis functions. Plots of the 1-dimensional Rydberg-orbital cuts reveal a regular nodal structure along the logarithmic scale of the atomic radius reaching tens of Å far from the nucleus. The presented Rydberg basis set generation methodology is an important step towards routine ab initio Rydberg-state related investigations of more complex systems, such as large atoms and polyatomic molecules.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152770","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":"Beyond reflection: thickness-guided engineering of MXenes for green electromagnetic shielding.","authors":"Zhifang Liu, Luen Li, Huaqiang Cao, Yilin Sun","doi":"10.1039/d6cp03008d","DOIUrl":"https://doi.org/10.1039/d6cp03008d","url":null,"abstract":"<p><p>Rapid advancement of 5G/6G communication technologies has not only driven a paradigm shift in telecommunication systems, but also caused escalating electromagnetic (EM) pollution, which threatens the reliability of radio frequency (RF) devices and human health. Conventional EM shielding materials rely on reflection-dominated mechanisms enabled by high conductivity, which cause secondary EM pollution and conflict with sustainable development goals. Consequently, green EM shielding, emphasizing absorption-dominated attenuation with suppressed reflection, has emerged as a critical research direction. MXenes, a class of 2D transition metal carbides and nitrides, have attracted considerable attention for green EM shielding due to their high conductivity, layered architecture, tunable surface terminations, and solution processability. This review summarizes recent advances in MXene-based green EM shielding, focusing on shielding mechanisms, evaluation metrics, and thickness-dependent design principles. By distinguishing thin/ultrathin from thick shielding structures, we analyze intrinsic MXene regulation, interfacial engineering, composite architectures, and 3D designs that enhance impedance matching and promote absorption-dominated behavior. Synergistic contributions of conduction loss, dielectric/interfacial polarization, magnetic loss, and multiple reflections are discussed, alongside the applicability and limitations of the green shielding index (<i>g</i>_s). Finally, current challenges and future prospects are highlighted, including the performance trade-offs across frequency bands and underutilization of intrinsic MXene properties.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163476","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":"Eco-Friendly Cryolite-Type Cs 3 CeI 6 Halide: DFT+U Insights into Optoelectronic Properties and Defect-Modulated Deep-Blue Emission","authors":"Yuan Yin,Xiaoyao Shen,Yingying Cao,Hua Yang,Yu Wang,Zhongti Sun","doi":"10.1039/d6cp02849g","DOIUrl":"https://doi.org/10.1039/d6cp02849g","url":null,"abstract":"Eco-friendly rare-earth halide luminescent materials have emerged as promising candidates for deep-blue light-emitting devices, yet severe intrinsic luminescence quenching induced by intrinsic point defects severely limits their photoluminescence quantum yield (PLQY). In this work, we systematically investigate the optoelectronic properties, defect behavior, and carrier recombination mechanism of cryolite-type Ce 3 CeI 6 via first-principles calculations. The orbital composition of the valence band and conduction band of perfect Ce 3 CeI 6 is analyzed, and the intrinsic radiative limitation originating from low Γ-point transition probability and parityforbidden I 5p→Ce 4f transitions is clarified, which inherently results in weak deepblue emission. We further calculate the formation energies and charge transition energy levels of typical intrinsic point defects including V Cs and V I . The results reveal that V Cs defects act as detrimental deep acceptor traps within the bandgap, which can simultaneously capture photogenerated electrons and holes and dissipate excitation energy through multi-phonon relaxation, serving as the dominant source of nonradiative recombination and PLQY degradation. The density of deep quenching traps can be precisely regulated by tuning precursor chemical potentials: I-rich/Cs-poor growth environments reduce the formation energy of V Cs and promote trap aggregation, while Cs-rich conditions effectively suppress the generation of V Cs defects. Defect passivation can fully eliminate deep-level nonradiative traps, allowing photogenerated carriers to recombine through the parity-permitted Ce 5d→Ce 4f channel and significantly boost deep-blue luminescence efficiency. This work establishes a complete atomic-scale structure-defect-luminescence correlation for Ce 3 CeI 6 halides, providing fundamental theoretical guidance for optimizing precursor stoichiometry and developing efficient defect passivation strategies to fabricate high-performance, stable rare-earth halide deep-blue emitters.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151976","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":"An effective porous biochar adsorbent derived from Platanus orientalis leaves for removal of rhodamine B: Adsorption performance and mechanism insight","authors":"Yinuo Ye,Yanji Zhang,Wenqi Qin,Yiqian Lin,Luyu Liu,Xinxin Luo,Hong Lei,Ying Lei,Zhaoyang Ju","doi":"10.1039/d6cp02854c","DOIUrl":"https://doi.org/10.1039/d6cp02854c","url":null,"abstract":"In this study, a series of porous biochar materials (PoLC) were fabricated using platanus orientalis leaves as the raw precursor. The optimized PoLC-800 exhibited a high specific surface area of 1384 m2·g-1 and displayed an ultrahigh maximum adsorption capacity of 2761 mg·g-1 toward rhodamine B (RhB), which was remarkably superior to PoLC-600, PoLC-700 and most reported biomass-based adsorbents. Adsorption isotherms were systematically fitted by Langmuir, Freundlich, and Temkin models, while kinetic analysis confirmed that the adsorption process well complied with the pseudo-second-order model. After five consecutive adsorption-desorption cycles, PoLC-800 retained over 80% of its original adsorption efficiency. It also presented excellent adaptability to solution pH variation and coexisting interfering cations, and possessed broad adsorption applicability toward various anionic and cationic dyes. FT-IR and XPS characterization verified that abundant oxygen- and nitrogen-containing functional groups on the PoLC surface provided sufficient active sites for adsorption. Combined with density functional theory (DFT) calculations, hydrogen bonding, electrostatic attraction, as well as n–π and π–π stacking interactions were identified as the dominant adsorption mechanisms. This work combines experimental characterization with theoretical simulation to offer new molecular-level understanding for the removal of dye contaminants by low-cost biomass-derived porous biochar.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151974","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 dual topological phases in XAsTe (X = Zr, Hf) monolayers","authors":"Songsong Chen,Jie Li,Jie Liu,Zhixing He,Hongkuan Yuan,Minquan Kuang,Mingmin Zhong,Chunling Tian","doi":"10.1039/d6cp03069f","DOIUrl":"https://doi.org/10.1039/d6cp03069f","url":null,"abstract":"The quantum anomalous Hall effect (QAHE) and the quantum spin Hall effect (QSHE) hold great potential for advancing next-generation low-power, high-ruggedness electronic and quantum devices. Here, using first-principles calculations, we investigate the interplay between magnetic order and band topology in the two-dimensional (2D) semimetal system X3AsTe4 (X = Zr, Hf). We find that X3AsTe4 (X = Zr, Hf) is a promising material exhibiting ferromagnetic (FM) properties. The highly hybridized electronic orbitals near the Fermi level give rise to strong electronic correlations, leading to the formation of intriguing non-Dirac bands and rendering X3AsTe4 (X = Zr, Hf) a 2D semimetal. Upon including spin–orbit coupling (SOC), a QAH gap opens at the Fermi level. Within this QAH gap, two chiral edge states with the same propagation direction emerge, demonstrating that X3AsTe4 (X = Zr, Hf) is an ideal platform for realizing a high-Chern-number QAHE with C = 2. Meanwhile, X3AsTe4 (X = Zr, Hf) hosts a QSH gap at an energy of approximately 0.45 eV above the Fermi level, making X3AsTe4 (X = Zr, Hf) a dual-topological-phase material hosting both a high-Chern-number QAH state and a QSH state. Furthermore, we find that applying biaxial strain to X3AsTe4 (X = Zr, Hf) enables the tuning of the material's metallicity and the switching of its easy magnetization axis, and a slight biaxial tensile strain can effectively enlarge the QSH gap of monolayer Hf3AsTe4, thereby enhancing the stability of its QSHE. Our study greatly enriches the research on dual-topological-phase materials and provides a powerful route toward the realization of novel quantum devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151980","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":"Impact of ligand bulk on conformational rearrangement in supported organometallic complexes.","authors":"Jacob Mayer, Mita Halder, Da-Jiang Liu, Damien B Culver, Frédéric A Perras","doi":"10.1039/d6cp03084j","DOIUrl":"https://doi.org/10.1039/d6cp03084j","url":null,"abstract":"<p><p>Measuring the dynamics of surface organometallic species, let alone connecting these to catalysis, is highly challenging. We have applied surface-sensitive proton fast-magic-angle spinning double-quantum sideband NMR methods to probe the dynamics of supported metallocene complexes as a function of ligand size, metal identity, and confinement. It was found that dynamics of these species, which resemble olefin polymerization catalysts, are very sensitive to ligand size and that the complex's orientation is frozen once the bonded alkyl chain reaches a length greater than five carbons. Experimental measurements of motions are quantitatively reproduced by machine learning-accelerated molecular dynamics simulations, which provide clarity into the types of motions that are accessible across the complexes. Metal identity and confinement were found to have a lower influence on dynamics, as compared to ligand bulk.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163486","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":"Mesoscopic charge separation in mixtures of anisotropic Gay-Berne particles and Lennard-Jones spheres.","authors":"Katsuhiko Satoh, Giacomo Saielli","doi":"10.1039/d6cp03522a","DOIUrl":"https://doi.org/10.1039/d6cp03522a","url":null,"abstract":"<p><p>We present molecular dynamics (MD) simulations of binary mixtures of oppositely charged anisotropic Gay-Berne (GB) discotic particles and Lennard-Jones (LJ) spheres, with a GB : LJ stoichiometry of 1 : 2. At low scaled temperatures, the competition between two opposing driving forces, that is on the one hand the tendency of anisotropic particles to phase-separate, driven by excluded-volume and enthalpic effects, and on the other hand the long-range electrostatic repulsion that opposes macroscopic segregation of same-charge particles, gives rise to a mesoscopic charge separation. This is manifested as alternating thick layers of same-charge particles, constituting a novel microphase with a characteristic length scale spanning several particle diameters. The thickness of both the GB and LJ layers increases monotonically with decreasing scaled charge and it is well described by an inverse power law, <i>d</i>* = <i>A</i> + <i>B</i>/<i>q</i>*, where <i>d</i>* is the scaled thickness and <i>q</i>* the scaled charge. This result is consistent with a simple continuum electrostatic model based on stacked slabs of alternating charge density, which predicts a quadratic divergence of the electrostatic energy with layer thickness. Our results are directly relevant to the design of lyotropic liquid crystal phases in colloidal suspensions of anisotropic nanoparticles carrying opposite surface charges, and provide a microscopic understanding of the interplay between shape anisotropy, excluded-volume effects, and electrostatics in driving mesoscale charge separation.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163394","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}