Physical Chemistry Chemical Physics最新文献

{"title":"Boosted photocatalytic water splitting over a direct Z-scheme CdTe/C₂N van der Waals heterojunction: a first-principles insight into photocatalytic activity.","authors":"Yi Li, Cheng Gong, Tong Chen, Dong-Lan Zhang, Ling-Ling Wang, Kejun Dong, Liang Xu","doi":"10.1039/d5cp02602d","DOIUrl":"10.1039/d5cp02602d","url":null,"abstract":"<p><p>The quest for sustainable and clean energy sources has led to significant research into photocatalytic water splitting, a process that converts solar energy into hydrogen fuel. This study demonstrates constructing a high-performance CdTe/C₂N van der Waals heterojunction for solar-driven water splitting hydrogen evolution. The proposed CdTe/C₂N heterojunction, investigated using first-principles calculations, integrates favorable structural stability and features a direct bandgap of 1.51 eV. The separation of photogenerated carriers is effectively facilitated by the built-in electric field oriented from CdTe to C₂N. The Gibbs free energy change (Δ<i>G</i>) for the hydrogen evolution reaction (HER) is found to be -0.11 eV, which is significantly closer to zero than that of the individual monolayers, thereby enabling near-ideal reaction kinetics. For the oxygen evolution reaction (OER), sufficient potential is provided by photogenerated holes in C₂N under illumination to overcome the energy barrier, ensuring spontaneous water splitting. Additionally, the enhanced visible light absorption, elevated electron mobility, and suppressed high energy carrier recombination <i>via</i> the Z-scheme mechanism make the heterojunction achieve a solar-to-hydrogen (STH) conversion efficiency of 10.04%, surpassing the industrial threshold of 10%. Therefore, this work presents a promising approach to achieving clean energy technologies through advanced photocatalysts.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"20199-20208"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022449","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":"Photocatalytic CO₂ reduction reaction on [TM(tpy)(ppy)]⁰ (TM = Re and Rh) species with a square pyramidal nitrogen-coordinated structure: a computational study.","authors":"Chengxu Hu, Donghua Zhang, Yunjie Chu, Xinyu Zuo, Min Zhang","doi":"10.1039/d5cp02175h","DOIUrl":"10.1039/d5cp02175h","url":null,"abstract":"<p><p>The photocatalytic performance of d-block metal complexes with unsaturated coordination circumstances after one dative-bond cleavage has become an emerging domain. Especially, the photocatalytic CO₂ reduction reaction (CO₂RR) on the active center of d-block metals in tridentate/bidentate ligands with square pyramidal nitrogen-coordinated atoms has been reported. In this study, the photocatalytic CO₂RR performance of six metals in [TM(tpy)(ppy)]⁰ as possible active candidates (TM = Fe, Co, Ru, Rh, Re, and Ir) for CO production was evaluated in detail using DFT computations. The theoretical data demonstrate that the screened-out [Re(tpy)(ppy)]⁰ exhibits superior photocatalytic CO₂RR activity to other identical species due to the only downhill process for CO₂ activation and the second one-electron photoreduction step as its lowest rate-limiting step of 38.41 kcal mol^-1. Besides, [Rh(tpy)(ppy)]⁰ also possesses comparable CO₂RR activity theoretically with the reported [Ir(tpy)(ppy)]⁰. In addition, our calculations reveal that the electron-transfer processes along the CO₂RR pathway on [TM(tpy)(ppy)]⁰ are mainly sourced from the tpy ligand. Therefore, our study paves the way for exploring the active species of metal complexes as photocatalysts for the CO₂RR before executing the targeted experimental exploration on their precursor complexes to discover other qualified ones.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"20185-20192"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013490","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":"Hot carriers decay dynamics of van der Waals room temperature ferroelectric α-In2Se3","authors":"Chunlian Li, Borong Cong, Jiajun Cao, Weizheng Liang, Bingsuo Zou","doi":"10.1039/d5cp02156a","DOIUrl":"https://doi.org/10.1039/d5cp02156a","url":null,"abstract":"In this paper, we investigated the hot carriers decay dynamics of two-dimensional room temperature ferroelectric α-In<small>₂</small>Se<small>₃</small> via femtosecond transient optical spectroscopy. The photo-excited hot carriers in α-In<small>₂</small>Se<small>₃</small> are decay via electron-phonon coupling (τ<small>₁</small>) and inter–layer charge transfer (τ<small>₂</small>). We observe the slope of the τ<small>₁</small><small>^-1</small>-T curve changed near 145 K, which indicating the change of temperature-dependent phonon excitation of α-In<small>₂</small>Se<small>₃</small>. Below 145 K, the dephase rate τ<small>₂</small><small>^-1</small> show an unusual temperature dependence, τ<small>₂</small><small>^-1</small> ∝ T<small>⁻¹</small>, while it exhibiting a linear increase with temperature above 145 K. The temperature-dependent variation of hot-carrier decay in In<small>₂</small>Se<small>₃</small> near 145 K may be related to a hidden phase transition. The dephase rate (τ<small>₁</small><small>^-1</small> ) exhibits a stronger temperature dependence below 145 K than above, which may arise from the more pronounced temperature dependence of optical phonon excitation at lower temperatures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"81 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127454","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":"Crystal structure and lithium-ion diffusion mechanism in the inverse spinel solid solution series, Li2+xNi2-2xCrxV2O8 (0 ≤ x ≤ 1)","authors":"Daniel ZC Martin, Rebecca Boston, Babatunde Adelowo Adedayo, Ronald Smith, Peter J Baker, Maria Diaz-Lopez, Veronica Celorrio, Nik Reeves-McLaren","doi":"10.1039/d5cp02385h","DOIUrl":"https://doi.org/10.1039/d5cp02385h","url":null,"abstract":"A new solid solution series based on substitution of Cr into LiNiVO4, with the stoichiometric formula Li2+xNi2-2xCrxV2O8 (0 ≤ x ≤ 1), is reported here for the first time. The materials crystallise in the Fd3-m space group as inverse spinels, with (at ambient temperatures) vanadium on the tetrahedral site and Li, Cr and/or Ni filling the octahedral interstices. High temperature neutron diffraction data are used to identify a continuous three-dimensional Li+-ion conduction pathway along 16c-8a-16c sites, with bulk activation energies ranging from 0.17 eV for powdered specimens to 0.53 eV for samples sintered at 550 - 650 °C. Lithium diffusion coefficients at 300 K were calculated from muon spectroscopy data to be in the region of 2 x 10-12 cm2 s-1. Preliminary electrochemical data show significant capacity loss after first discharge when employed as positive electrodes, as is common for similar inverse spinels, but show significant promise for anode applications with ca. 110 mAh g-1 in reversible specific capacity remaining after 50 cycles at an average operating potential of ~ 0.6 V.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127453","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":"Role of anharmonic correction in superconducting phase of two-dimensional alloy Al0.75Si0.25B2: insight from ab initio anisotropic Migdal-Eliashberg theory.","authors":"Prutthipong Tsuppayakorn-Aek,Wiwittawin Sukmas,Ryo Maezono,Thiti Bovornratanaraks","doi":"10.1039/d5cp02537k","DOIUrl":"https://doi.org/10.1039/d5cp02537k","url":null,"abstract":"Exploring emergent phases in monolayer alloy superconductors represents a forefront endeavor in contemporary quantum materials research. Following the successful exploration of AlB2 in a superconducting state, we provide a significant reference for examining superconductivity in Si-substituted AlB2 using first-principles predictions. This noteworthy outcome highlights that Al0.75Si0.25B2 is one of the energetically stable configurations within the Al1-xSixB2 system that exhibits the superconducting state. However, the anharmonic effects on this phase significantly impact its phonon spectra, potentially influencing dynamical stability. In specific cases, the application of the stochastic self-consistent harmonic approximation enables us to capture how thermally induced lattice vibrations impact the equilibrium structure of the material. It is observed that the inclusion of anharmonic corrections brings the predicted superconducting characteristics into closer agreement with those derived from the harmonic model, thereby resolving the issue of imaginary frequencies. As a result, we demonstrate that the Allen-Dynes modified McMillan scheme predicts a critical temperature (Tc) of approximately 15 K. This can be enhanced to 41 K through the utilization of the anisotropic Migdal-Eliashberg theory. Our findings reveal that the role of anharmonicity-arising from minor corrections in the acoustic regime contributed by the high atomic mass-in Al0.75Si0.25B2 theoretically leads to superconductivity, with Tc being consistent with values predicted within the harmonic approximation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127402","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":"Ligand-based virtual screening to discover potential inhibitors of SARS-CoV-2 main protease.","authors":"Gurmeet Kaur, Bhupesh Goyal","doi":"10.1039/d5cp01814e","DOIUrl":"10.1039/d5cp01814e","url":null,"abstract":"<p><p>The main protease (M^pro, also known as 3CL^pro), a pivotal enzyme of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has been considered a prime target for drug development due to its crucial role in viral replication and transcription. Importantly, a high degree of conservation in more than 13 million SARS-CoV-2 sequences affords M^pro as a promising target for antiviral therapy to impede the genetic evolution of SARS-CoV-2. In this work, ∼16 million compounds from various small molecule databases were screened using ligand-based virtual screening (LBVS) with boceprevir as the reference compound to identify new small molecule inhibitors of M^pro. Boceprevir [hepatitis C virus (HCV) drug] has been repurposed as a drug candidate against M^pro activity (IC₅₀ = 4.13 ± 0.61 μM). The lead compounds exhibiting higher binding affinities (-9.9 to -8.0 kcal mol^-1) than boceprevir (-7.5 kcal mol^-1) were identified from a library of 850 compounds using molecular docking. Furthermore, molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) analysis depicted ChEMBL144205 (C3), ZINC000091755358 (C5), and ZINC000092066113 (C9) with binding affinities of -65.2 ± 6.5, -66.1 ± 7.1, and -67.3 ± 5.8 kcal mol^-1, respectively, as high-affinity binders to M^pro. The identified compounds displayed a favourable drug-likeness profile without violating Lipinski's rule of five. Molecular dynamics (MD) simulations revealed the higher structural stability and reduced residue-level fluctuations in M^pro upon binding of C3, C5, and C9 as compared to apo-M^pro and M^pro-boceprevir. Notably, conformational clustering and FEL analyses depicted hydrogen bond interactions of C3 with Thr26, oxyanion hole residues (Asn142 and Gly143), the catalytic residue (Cys145), and Glu166 of M^pro, suggesting its strong binding affinity and potential inhibitory effect. The integrated computational methodology employed in this work identified promising lead compounds against M^pro activity, which warrants further experimental validation to develop them as antiviral agents against SARS-CoV-2.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"19877-19897"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936731","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":"Arriving at ultralow wear using cellulose/two-material composites.","authors":"Xuan Yin, Dingyao Zhang, Bing Zhang","doi":"10.1039/d5cp00527b","DOIUrl":"10.1039/d5cp00527b","url":null,"abstract":"<p><p>The development of environmentally friendly solid lubricants with exceptional wear resistance is imperative to address the escalating environmental concerns and performance limitations of conventional lubricants in demanding tribological applications. This study systematically investigated the wear resistance of hydroxypropyl methylcellulose (HPMC)/tungsten disulfide (WS₂)/graphene composites under normal applied loads (2 and 4 N) and varying solid lubricant contents (stoichiometric ratios of 0.2 referred to as CWG-0.2 and 10 referred to as CWG-10). Quantitative tribological tests revealed that the wear rate of HPMC composites exhibited distinct load dependence at fixed lubricant concentrations. Notably, CWG-0.2 and CWG-10 composites achieved an ultra-low wear rate below 10^-10 mm³, representing an approximately 95% reduction compared to pristine HPMC (10^-8 mm³). Surface characterization demonstrated that localized carbon phase clusters and interconnected carbon skeleton chains governed the ultra-low wear transition. Prolonged sliding (>10 000 cycles) induced the formation of a 10-50 nm-thick transfer film comprising WS₂ nanoflakes and a hybrid amorphous phase (C-O-W-S), as confirmed by X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The exceptional performance, quantified through rigorous parametric analysis, positions HPMC composites as sustainable solid lubricants for precision machinery, aerospace bearings, and biodegradable micro-electromechanical systems requiring eco-friendly superlubricity.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"19960-19969"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991039","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":"Axial engineering of bilayer single-atom catalysts for enhanced bifunctional oxygen electrocatalysis.","authors":"Xinge Wu, Wenzhu Tan, Zhaoying Yang, Chao Li, Shuai Shao, XiangYing Meng","doi":"10.1039/d5cp02199e","DOIUrl":"10.1039/d5cp02199e","url":null,"abstract":"<p><p>Axial ligand engineering is a promising strategy to enhance the performance of single-atom catalysts (SACs) in electrocatalysis. However, a single non-metallic axial coordination atom linked to monolayer SACs (MSACs) often exhibits insufficient stability. In this work, we designed a series of bilayer SACs (BSACs) with vertically stacked FeN₄ and MN₄ (M = Sc-Zn) layers bridged by axial non-metallic atoms (C, N, O, P, S, and Se). The bilayer structure stabilizes axial atom anchoring and redistributes electrons of dual-side metal atoms. As electrocatalysts for oxygen reduction (ORR) and evolution (OER) reactions, the introduction of axial ligands optimizes the binding strength of key intermediates and reduces the overpotentials. After high-throughput DFT screening of the ORR/OER pathways across 60 BSAC candidates, we found that FeN₄-P-MnN₄ (P-FeMn) and FeN₄-C-MnN₄ (C-FeMn) exhibit exceptional dual-sided bifunctional (ORR and OER) catalytic activity, with ORR overpotentials (Fe/Mn site) of 0.27/0.28 V and 0.37/0.29 V and OER overpotentials of 0.42/0.37 V and 0.31/0.42 V, respectively. Electronic structure analysis reveals that the axial P/C atoms induce a transition of the metal atoms from a high-spin state to a low-spin state, thereby shifting the d-band center and effectively weakening the metal-oxygen orbital hybridization (σ and π), leading to enhanced catalytic activity. This work advances axial ligand engineering in single-atom catalysts and offers new insights and strategies for designing stable and efficient bifunctional oxygen electrocatalysts.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"20039-20049"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144999232","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":"Toward a bottom-up understanding of the impact of high-entropy electrolyte components on the charge storage performance of lithium ion batteries.","authors":"Zihao Zeng, Tengxiang Qi, Bing-Ang Mei, Zhengxing Zuo, Huihua Feng, Rui Xiong","doi":"10.1039/d5cp01621e","DOIUrl":"10.1039/d5cp01621e","url":null,"abstract":"<p><p>High entropy electrolytes show great potential in the design of next generation batteries. Demonstrating how salt components of high entropy electrolytes influence the charge storage performance of batteries is essential in the tuning and design of such advanced electrolytes. This study investigates the transport and interfacial properties for lithium hexafluorophosphate (LiPF₆) in ethylene carbonate and dimethyl carbonate (EC/DMC) solvent with commonly used additives for high entropy electrolytes (LiTFSI, LiDFOB, and LiNO₃). Using a combination of experimental measurements and numerical simulations, transport properties including ionic conductivity, viscosity, transference numbers, and solvation structures of various electrolyte formulations are examined. The results show that the addition of LiTFSI improves ionic conductivity, while LiNO₃ may hinder ion migration due to the formation of aggregated Li-NO₃^- complexes. Both LiNO₃ and LiDFOB may result in an increase in near-surface reaction resistance. The addition of LiNO₃ and LiDFOB leads to an increase in capacity at low current rates but a decline at higher rates due to the coupled effect of additives on transport properties and interfacial properties. This study provides insights into the complex role of additives in optimizing the performance of lithium-ion batteries, particularly in terms of electrolyte conductivity and interfacial properties. This study establishes a general mechanistic design rule, showing that selecting electrolyte additives according to their effects on the solvation structure and aggregation enables predictive tailoring of salt combinations for either high-rate or low-rate lithium-ion battery applications.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"20209-20225"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022422","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 puzzle of high lifetime and low stabilization of HO₃˙: rationalization and prediction.","authors":"Philips Kumar Rai, Akash Gutal, Pradeep Kumar","doi":"10.1039/d5cp02134k","DOIUrl":"10.1039/d5cp02134k","url":null,"abstract":"<p><p>One of the most important puzzles in atmospheric chemistry is the long-lifetime of HO₃˙ in spite of its low-stabilization energy. In the present work, we have estimated the lifetime of HO₃˙ using classical dynamics simulations by coupling an available neural-network analytical potential energy surface with a chemical dynamics program. The simulation results clearly indicate that at room temperature, the lifetime of HO₃˙ can exceed 1 μs under collision-free conditions. In fact, at 200 K, the lifetime of HO₃˙ can enter the millisecond timescale. This suggests that HO₃˙ is indeed a stable enough intermediate that can affect the outcomes of crucial atmospheric processes.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"19684-19693"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022443","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}