Physical Chemistry Chemical Physics最新文献

{"title":"Elucidating the role of lone-pair ns2 electrons in B-site cation-disordering of double halide perovskite Cs2AgBiCl6 and Cs2AgInCl6","authors":"Jingting Wei, Jiayin Wu, Yibin Yang, Le Huang, Bin Li","doi":"10.1039/d5cp01225b","DOIUrl":"https://doi.org/10.1039/d5cp01225b","url":null,"abstract":"Double perovskites, such as Cs2AgBiCl6 and Cs2AgInCl6, have been proposed as stable, nontoxic (or low toxic) and inorganic alternatives of lead halide perovskites. While their electronic structures should be modulated to achieve improved performance of corresponding optoelectronic and photovoltaic devices. Herein, we performed first-principles calculations to explore the accessibility of B-site cation disordering in Cs2AgBiCl6 and Cs2AgInCl6 and its effects on the electronic structures of both double perovskites. It is revealed that lower energy cost is required to form cation-disordered Cs2AgBiCl6 than the latter. Lone-pair electrons of Bi3+ makes its electron configuration distinct from Ag+, which results in much higher energy cost for electronic relaxation during cation-disordering of Cs2AgBiCl6. Large ionic size difference between Bi3+ and Ag+ results in significant ionic relaxation during cation-disordering, effectively compensating the energy cost. Furthermore, the resulted remarkable ionic relaxation and change in electron redistribution in cation-disordered Cs2AgBiCl6 effectively protect its electronic structure from being influenced by cation-disordering. Otherwise, cation-disordering shows significant influence on the electronic structure of Cs2AgInCl6. Our results provide in-depth understanding on the lone-pair effect on cation-disordering and electronic properties of double halide perovskites, which may be useful to develop and design high-performance optoelectronic and photovoltaic devices based on double perovskites.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144334987","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":"Accurately predicting the thermal conductivity of boron arsenide due to phonon anharmonic renormalization: A critical revisit","authors":"Yongjun Wu, Yan Zhang, Zhen Tong","doi":"10.1039/d5cp01538c","DOIUrl":"https://doi.org/10.1039/d5cp01538c","url":null,"abstract":"Currently theoretical works fail to accurately reproduce experimental results of lattice thermal conductivity of boron arsenide (BAs, both the nature one or the isotopically enriched one). We investigate the microscopic mechanisms of ultrahigh lattice thermal conductivity (<em>κ</em><small>_L</small>) and its unexpectedly strong temperature dependence (<em>T</em>-dependence) in cubic <small>^nat</small>BAs by a first principles theory in the framework of the Wigner transport theory combined with temperature-dependent interatomic force constants (<em>T</em>-IFCs). We include the contributions of three- and four-phonon scattering processes to the phonon lifetime, and consider the phonon renormalization due to temperature. We find that <em>κ</em><small>_L</small> of <small>^nat</small>BAs has a strong <em>T</em>-dependence (<em>κ</em><small>_L</small>~<em>T</em><small>^-1.721</small>) and <em>T</em>-IFCs play important roles in accurately predicting <em>κ</em><small>_L</small> especially at high temperatures. We predict a room-temperature <em>κ</em><small>_L</small> of 1060.51 W/mK of <small>^nat</small>BAs, which aligns more closely with the recently measured value of 1000 ± 90 W/mK [Science, 361, 579-581 (2018)] than previously reported predictions. The superior accuracy of our predictions is attributed to the inclusion of <em>T</em>-IFCs in describing phonons and their scattering characteristics. Our results (i) resolve the discrepancy between theoretical and experimental <em>κ</em><small>_L</small>, (ii) explain the underlying mechanism of the ultra-high <em>κ</em><small>_L</small> of <small>^nat</small>BAs, and (iii) highlight the importance of considering the temperature-induced anharmonic renormalization effect at high temperatures. This work provides new insights into accurately predicting <em>κ</em><small>_L</small> for materials with relatively harmonic phonon dispersion but having strong high-order anharmonic effects.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"237 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329121","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":"Electrocatalytic Activity of PtAuPd/C Nano Multi-Principal Element Alloy Catalyst towards Oxygen Reduction Reaction","authors":"Hui Li, Zhiwei Zhang, Lianke Zhang, Hualiang Ni, Haiying Qin, Jing Zhang, Hong Zhong Chi, Jun-Jing He","doi":"10.1039/d5cp01935d","DOIUrl":"https://doi.org/10.1039/d5cp01935d","url":null,"abstract":"Developing highly stable, low-platinum electrocatalysts is crucial for advancing fuel cell technology. In this study, a PtAuPd/C nano multi-principal element alloy catalyst was synthesized by a carbothermal shock method. The average particle size of the PtAuPd/C alloy nanoparticles is around 2.2 nm and the PtAuPd/C exhibits superior catalytic activity and stability towards the oxygen reduction reaction (ORR) compared to the binary alloy catalysts (PtAu/C and PtPd/C). The PtAuPd/C displays a half-wave potential (E1/2) of 0.837 V and a Tafel slope of 53.1 mV dec-1. It demonstrates only a minimal E1/2 loss of 3.5 mV after 40,000 cycles and a mass activity retention rate of 78.2%. When employed as a cathode catalyst within a direct borohydride fuel cell, the PtAuPd/C catalyst exhibits a maximum power density of 438.3 mW cm-2. This improved ORR activity is attributed to synergistic electronic effects and modified surface strain within the PtAuPd nanoalloy.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329122","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":"Heterostructured CoFe/Co nanoalloys encapsulated in N-doped carbon as bifunctional oxygen-electrode catalysts for Zn-air batteries","authors":"Xiao-Wei Song, Min Lin, Hui Zhao, Ruoxuan Sun, Ye-Bin Guan","doi":"10.1039/d5cp00941c","DOIUrl":"https://doi.org/10.1039/d5cp00941c","url":null,"abstract":"Developing bifunctional oxygen electrocatalysts based on non-precious elements for the air electrodes of rechargeable Zn-air batteries (ZABs) remains a significant challenge. Herein, by adjusting the Co precursor content, we synthesized a bifunctional electrocatalyst (CoFe@NC-5) comprising CoFe/Co nanoalloys (~16 nm) encapsulated in N-doped carbon. The CoFe@NC-5 catalyst features the highest metal loading (37.24 wt% Co+Fe), uniform nanoalloy distribution, a unique encapsulated structure, and well-defined heterojunction interfaces between CoFe and Co phases. These characteristics endow CoFe@NC-5 with excellent bifunctional oxygen electrode activity, as evidenced by a low potential gap (ΔE) of 0.757 V between the half-wave potential for the oxygen reduction reaction (ORR, 0.84 V) and the potential for the oxygen evolution reaction (OER, 1.597 V) at 10 mA cm<small>⁻²</small>. Density functional theory (DFT) calculations further reveal that the heterojunction interfaces in the CoFe/Co heterostructure of the CoFe@NC-5 catalyst significantly enhance interfacial electron accumulation and shift the d-band center closer to the Fermi level, thereby boosting its ORR and OER activities. Furthermore, a rechargeable ZAB assembled with CoFe@NC-5 as the air electrode exhibits a high power density of 363.7 mW cm<small>⁻²</small>, a specific capacity of 785.8 mAh g<small>_Zn</small><small>⁻¹</small> at 50 mA cm<small>⁻²</small>, and stable charge-discharge cycling for 330 hours.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329119","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":"Photon upconversion sensitized by earth-abundant transition metal complexes.","authors":"Pengyue Jin,Cui Wang","doi":"10.1039/d5cp00333d","DOIUrl":"https://doi.org/10.1039/d5cp00333d","url":null,"abstract":"Sensitized triplet-triplet annihilation upconversion (sTTA-UC) converts two lower-energy absorbed photons into one emitting photon of higher-energy, and has become a popular approach for a wide range of applications. Current photosensitizers rely mostly on transition metal complexes made of expensive platinum group elements, such as palladium, platinum, and osmium, due to their strong absorption in the visible range, unity intersystem crossing, and long-lived triplet excited lifetimes. In recent years, fundamental breakthroughs have been made with photoactive complexes based on earth-abundant 3d metals including chromium, manganese, iron, cobalt, copper, and zinc, and 4d elements like zirconium and molybdenum. These novel complexes offer advantages, such as cost-effectiveness, sustainability, low toxicity, scalability for industrial use, and potential for innovative research in areas including catalysis and energy conversion, making them promising alternatives to noble metal-based photosensitizers in sTTA-UC and other fields. In this review, we delineate the recent advancements in sTTA-UC utilizing photoactive earth-abundant transition metal complexes. We explore their energy transfer mechanisms, evaluate their upconversion performance, discuss their applications, and outline the challenges and perspectives, aiming to offer insights for the development of novel photosensitizers based on earth-abundant metals for future research and applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328926","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":"Probing “hydridic hydrogen bonds” using energy decomposition analysis based on absolutely localized molecular orbitals","authors":"David W. Roberts, Yuezhi Mao","doi":"10.1039/d5cp01581b","DOIUrl":"https://doi.org/10.1039/d5cp01581b","url":null,"abstract":"The concept of \"hydridic hydrogen bonds (HBs)\" was recently proposed by Hobza and co-workers (Civiš et al., <em>J. Am. Chem. Soc.</em>, 2023, <strong>145</strong>, 8550) to describe X–H···Y interactions where the X atom is more electropositive than hydrogen. Here, we investigate prototypical \"hydridic HBs\" formed between trimethylsilane (MeSiH) and various electrophilic acceptors using energy decomposition analysis methods based on absolutely localized molecular orbitals (ALMO-EDA). New insights into the physical origin of these interactions and the associated vibrational frequency shifts are obtained. Compared to conventional, protonic HBs, \"hydridic HB\" complexes feature a more pronounced contribution from dispersion interactions to binding, and the key polarization and charge-transfer effects originate from the electron-rich Si–H bond rather than from the H-acceptor. Using the adiabatic ALMO-EDA approach, we further reveal the dominant role of permanent electrostatics (along with charge transfer in some cases) in driving the redshifts in the Si–H stretching frequency, differing from the factors leading to red- or blueshifts in conventional HBs. These findings clearly demonstrate that the apparent similarities between \"hydridic HBs\" and conventional, protonic HBs arise from fundamentally different physical origins, suggesting that alternative terminology, such as halogen, pnictogen, and tetrel bonds (based on the character of the H-acceptor), or hydride bonds (to retain an H-centered perspective), should be considered for complexes involving hydridic H-donors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"233 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319570","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":"Mechanistic Diversity in the Reactive Adsorption of Chlorine Trifluoride on Monohydrogenated Silicon","authors":"Henry Thake, Stephen J. Jenkins","doi":"10.1039/d5cp01331c","DOIUrl":"https://doi.org/10.1039/d5cp01331c","url":null,"abstract":"We present first-principles molecular dynamic simulations of chlorine trifluoride impinging upon the monohydrogenated Si{001} surface. Our computed trajectories reveal a rich variety of reactive adsorption events, most of which differ considerably from the behaviour predicted in previous quasistatic transition state calculations for the dihydrogenated surface. In addition to reactions involving the abstraction of adsorbed hydrogen, we find that direct interaction of the molecule's equatorial fluorine atom with silicon atoms as deep as the third layer may also lead to reactive adsorption. Amongst the surface defects induced by these processes, we find cationic bridges of Si--H--Si or Si--F--Si type; anionic motifs of Si--Si--F type; and silicon dangling bonds, which may be of cationic, anionic, or radical character. Chlorine monofluoride is evolved in the majority of reactive trajectories, with hydrogen fluoride, hydrogen chloride, and difluorochlorate species generated on occasion.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319563","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":"Variable-temperature token sampling in decoder-GPT molecule-generation can produce more robust and potent virtual screening libraries","authors":"Mauricio Cafiero","doi":"10.1039/d5cp00692a","DOIUrl":"https://doi.org/10.1039/d5cp00692a","url":null,"abstract":"Token generation in generative pretrained transformers (GPTs) that produce text, code, or molecules often use conventional approaches such as greedy decoding, temperature-based sampling, or top-k or top-p techniques. This work shows that for a model trained to generate inhibitors of the enzyme HMG-Coenzyme-A reductase, a variable temperature approach using a temperature ramp during the inference process produces larger sets of molecules (screening libraries) than those produced by either greedy decoding or single-temperature-based sampling. These libraries also have lower predicted IC50 values, lower docking scores, and lower synthetic accessibility scores than libraries produced by the other sampling techniques, especially when used with very short prompt-lengths. This work explores several variable-temperature schemes when generating molecules with a GPT and recommends a sigmoidal temperature ramp early in the generation process.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319568","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":"Probing the Hydroxyl in [2,2,2]-Cryptand/KF/Choline Chloride Non-Covalent Host-Guest Complex in Solution by 19F-NMR Spectroscopy: Structural Correlation and Thermodynamic Reversal of Host-Guest Configurations in Solution and in the Gas Phase","authors":"So Yeon Lee, Young-Ho Oh, Han Bin Oh, Sungyul Lee","doi":"10.1039/d5cp01548k","DOIUrl":"https://doi.org/10.1039/d5cp01548k","url":null,"abstract":"We study the structures of the [2,2,2]-cryptand/KF/choline chloride ([2,2,2]/KF/ChCl) non-covalent host-guest complex in solution using <small>¹⁹</small>F-NMR spectroscopy. We examine the environment around the hydroxyl group in the ChCl guest, to determine whether the functional group forms a hydrogen bond with the [2,2,2]/KF host or interacts with solvent molecules (dimethyl sulfoxide (DMSO), ethylene glycol (EG)). We find that the <small>¹⁹</small>F peaks are characteristic of the structural features of the complex, showing that the –OH group in the ChCl guest is solvated away from the [2,2,2]/KF host in EG-<em>d</em><small>₆</small>, and that it forms a hydrogen bond with F<small>^-</small> in DMSO-<em>d</em><small>₆</small> isolated from the solvent. By carrying out density functional theory (DFT) calculations, we find that a gas-phase [2,2,2]/KF/Ch<small>⁺</small> conformer (with a ‘naked –OH group) of higher Gibbs free energy (by 13.6 kcal/mol) is structurally connected to the solution-phase configuration, where the –OH forms H-bonds with EG-<em>d</em><small>₆</small> molecules. On the other hand, the global minimum Gibbs energy gas-phase complex (featuring the [F<small>^-</small>…HO-] H-bond) is structurally correlated with the configuration observed in DMSO-<em>d</em><small>₆</small>. These observations of ‘thermodynamic reversal’ and structural correlation of the [2,2,2]/KF/ChCl complexes in the two phases, connected by the electrospray ionization/mass spectroscopy (ESI/MS) procedure, are discussed in relation to the potential for explicating host-guest-solvent interactions in solution from gas-phase host - guest configurations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319571","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 gemini ionic liquid as a corrosion inhibitor for carbon steel in petroleum pipelines","authors":"Ashraf M. Ashmawy, Yousef A. Selim, M. Abd-El-Raouf, Kh. Zakaria, Yasser M. Moustafa, Ahmed Z. Sayed, Odeh A. O. Alshammari, Reda Abdel-Hameed","doi":"10.1039/d5cp00349k","DOIUrl":"https://doi.org/10.1039/d5cp00349k","url":null,"abstract":"We conducted an experiment to test the effectiveness of a new gemini ionic liquid, labeled as <em>N</em><small>₁</small>,<em>N</em><small>₁</small>,<em>N</em><small>₃</small>,<em>N</em><small>₃</small>-tetramethyl-<em>N</em><small>₁</small>,<em>N</em><small>₃</small>-bis(4-nitrobenzyl) propane 1,3-diaminium chloride, in prohibiting carbon steel corrosion in a 1 M hydrochloric acid solution. We successfully synthesized this compound and characterized it using various analytical techniques, comprising elemental examinations, mass spectroscopy, FT-IR spectroscopy and <small>¹</small>H-NMR spectroscopy. To assess corrosion and corrosion inhibition efficiency, we utilized electrochemical techniques. The trials were performed at a temperature of 298 K, with adjustments made to the inhibitor concentrations. We maintained standardized conditions to maximize the inhibition efficiency. Additionally, AFM, SEM, and EDAX analyses were employed to identify the surface morphology. Our results showed that the inhibition efficiency increased with increasing inhibitor concentrations, reaching up to 90.6% at 200 ppm of the synthesized compound at 298 K. Notably, the formed gemini ionic liquid operated as a mixed inhibitor, adopted a physico-chemisorption mechanism, and fitted well with the Langmuir adsorption model.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319564","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}