Physical Chemistry Chemical Physics最新文献_第7页

Preparation of high-performance quasi-two-dimensional (Q-2D) perovskite solar cells by fluorinated benzylamine groups at different substitution positions

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04357j

Longtao Du, Jianhua Liao, Kegui Li, Yuge Chang, Qiang Huang, Xiaoyan Gan, Liling Guo, Hanxing Liu

{"title":"Preparation of high-performance quasi-two-dimensional (Q-2D) perovskite solar cells by fluorinated benzylamine groups at different substitution positions","authors":"Longtao Du, Jianhua Liao, Kegui Li, Yuge Chang, Qiang Huang, Xiaoyan Gan, Liling Guo, Hanxing Liu","doi":"10.1039/d4cp04357j","DOIUrl":"https://doi.org/10.1039/d4cp04357j","url":null,"abstract":"Quasi-two-dimensional (Q-2D) perovskite solar cells have garnered significant attention due to their unique hydrophobic organic cations and commendable stability. However, there is currently no established set of criteria for selecting the appropriate organic cations to fabricate highly efficient and stable Q-2D perovskite solar cells. This work systematically examines the organic interstitial cations containing fluorine atoms at various substitution positions in phenylmethylamine, focusing on crystal orientation, film morphology, and the photoelectric conversion efficiency (PCE) of n = 5 perovskite films. Through density functional theory (DFT) calculations and crystal structure analysis, it is revealed that compared to PMA-F, oFPMA-F and mFPMA-F, pFPMA-F exhibits the largest dipole moment. Additionally, (pFPMA)2PbI4 demonstrates a larger effective mass and greater layer spacing compared to (PMA)2PbI4. The findings revealed that in comparison to PMA-F, oFPMA-F and mFPMA-F, the pFPMA-F 2D perovskite film exhibits a preferential in-plane orientation, superior crystallinity, and higher carrier mobility. Consequently, the Q-2D perovskite solar cell device utilizing pFPMA-F achieved a PCE of 15.88%, which markedly surpassed those of the PMA-F (9.15%), oFPMA-F (12.62%), and mFPMA-F (7.8%) counterparts. Additionally, the device architecture based on pFPMA-F demonstrated exceptional stability.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393729","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

Steric effects in the adsorption of O2 on a Cu(111) surface

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04595e

Lok Yiu Wu, Maksymilian Jakub Roman, Brianna R Heazlewood, Mitsunori Kurahashi

{"title":"Steric effects in the adsorption of O2 on a Cu(111) surface","authors":"Lok Yiu Wu, Maksymilian Jakub Roman, Brianna R Heazlewood, Mitsunori Kurahashi","doi":"10.1039/d4cp04595e","DOIUrl":"https://doi.org/10.1039/d4cp04595e","url":null,"abstract":"Probing the stereodynamics of a gas-surface interaction is a useful tool to investigate the mechanisms responsible for adsorption. Experimental results are provided on the adsorption of alignment-controlled O2 interacting with a Cu(111) surface for the first time, across a range of incident energies (65–550 meV) and angles of incidence (0–60°). Molecules of O2 in a supersonic beam are prepared in a single spin-rotational state, and aligned with a Cu(111) surface so that the rotational angular momentum of O2 is either parallel or perpendicular to the surface. A strong steric effect is observed, where the initial sticking probability is higher in case of a \"side-on\" (or \"broadside\") collision, with measurable adsorption appearing at normal incident energies of 100 meV. The onset of sticking occurs at incident energies of approximately 200 meV in case of an \"end-on\" collision. The results also indicate that the adsorption of O2 on Cu(111) is predominantly due to an activated process in the energy range probed, corroborating previous experimental and theoretical results","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"63 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393726","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

Engineering Topological Phases in Transition-Metal-Doped Penta-Hexa-Graphene: Towards Spintronics Applications

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04426f

Rongrong Chen, Kun Tao, Lei Yang, Jin Gao, Desheng Xue, Chenlong Jia

{"title":"Engineering Topological Phases in Transition-Metal-Doped Penta-Hexa-Graphene: Towards Spintronics Applications","authors":"Rongrong Chen, Kun Tao, Lei Yang, Jin Gao, Desheng Xue, Chenlong Jia","doi":"10.1039/d4cp04426f","DOIUrl":"https://doi.org/10.1039/d4cp04426f","url":null,"abstract":"The exploration of topological properties in two-dimensional (2D) materials has opened new avenues for spintronics and quantum computing applications. In this study, we investigate the electronic structure and topological characteristics of penta-hexa-graphene (PH-G) doped with transition metals, Pd and Pt, using ﬁrst-principles calculations. We demonstrate that the band topology of PH-G can be eﬀectively manipulated by doping with Pd and Pt, leading to the emergence of nontrivial topological phases. Notably, the introduction of spin-orbit coupling (SOC) results in a ’W-shaped’ band at the Γ point, signifying potential topological properties, with band gaps of 13.00 meV and 74.80 meV for PH-CPd and PH-CPt, respectively. Further analysis reveals signiﬁcant Rashba splitting under tensile strain, with high Rashba coeﬃcients of 5.067 eV.˚A and 2.604 eV.˚A for PH-CPd and PH-CPt, respectively, suggesting promising potential for ﬁeld-eﬀect transistors and other electronic devices. Our ﬁndings not only extend the design concept of doping to form 2D topological materials but also provide valuable insights into the manipulation of topological properties in 2D systems, paving the way for novel electronic and spintronics applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393980","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

Correction: Effects of pressure and temperature on topological electronic materials X2Y3 (X = As, Sb, Bi; Y = Se, Te) using first-principles 更正：利用第一原理研究压力和温度对拓扑电子材料 X2Y3（X = As、Sb、Bi；Y = Se、Te）的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d5cp90009c

Le Fang, Chen Chen, Xionggang Lu, Wei Ren

引用次数: 0

Solid state NMR and DFT studies of azo-hydrazone tautomerism in azo dyes and chitosan-dye films

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04159c

Coral Hillel, Sarah Collins, Amanpreet Parihar, Ozzy Mermut, Christopher J Barrett, William Joseph Pietro, Linda Reven

{"title":"Solid state NMR and DFT studies of azo-hydrazone tautomerism in azo dyes and chitosan-dye films","authors":"Coral Hillel, Sarah Collins, Amanpreet Parihar, Ozzy Mermut, Christopher J Barrett, William Joseph Pietro, Linda Reven","doi":"10.1039/d4cp04159c","DOIUrl":"https://doi.org/10.1039/d4cp04159c","url":null,"abstract":"The properties of materials containing azobenzene depend strongly on the dynamics of cis and trans isomerization which in turn is influenced by the presence of the different possible tautomers. Two commonly used food azo dyes, Allura Red (ALR) and Amaranth (AMA) were studied by NMR spectroscopy to experimentally determine their tautomeric forms and then theoretically rationalized. Variable temperature 2D 1H-15N HMBC NMR provided a direct measure of the hydrazone percentage of the dyes in solution which was complimented by 1H ultrafast magic-angle spinning (MAS) and 13C CPMAS solid state NMR to characterize the structures of the solid dyes alone and incorporated into chitosan films designed to disassemble upon exposure to light and water. Density functional theory (DFT) calculations were carried out to predict tautomeric equilibria in comparison to NMR measurements and rationalize the observed equilibrium in terms of electronic structure effects computed in the Natural Bond Orbital analysis framework. In agreement with NMR results, the hydrazone form was strongly favored in a polar solvent, driven primarily by stabilizing resonance delocalization and favourable electrostatic interactions with solvent. Our observations show that the ALR and AMA dyes exist predominantly in the hydrazone form of their tautomeric equilibrium in solution, in the solid-state, and in a chitosan-dye film. These results indicate that since disassembly of the chitosan-dye films, potential substitutes for petrol-based polymer films, is based on cis-trans isomerization of the azo form, other water soluble food dyes with a higher azo contents should be explored.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393979","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

Computer-aided design of triazolo-cages as anion receptors

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04589k

Minwei Che, Sibali Debnath, Amar H. Flood, Krishnan Raghavachari

{"title":"Computer-aided design of triazolo-cages as anion receptors","authors":"Minwei Che, Sibali Debnath, Amar H. Flood, Krishnan Raghavachari","doi":"10.1039/d4cp04589k","DOIUrl":"https://doi.org/10.1039/d4cp04589k","url":null,"abstract":"Molecular cages with three-dimensional cavities have garnered significant interest due to their enhanced encapsulation abilities. In this study, we computationally investigate the binding behavior of a triazolo-cage receptor composed of alternating triazole and phenyl building blocks. With six different anions, including atomic (F−, Cl−, Br−, and I−), linear (SCN−), and trigonal planar (NO3−) geometries, we analyze the binding selectivity of the parent cage with DFT calculations. The influence of solvation on binding strength is investigated by calculating binding free energies in both gas phase and six solvent environments of progressively increasing dielectric constants. Symmetry-Adapted Perturbation Theory (SAPT) analysis reveals that electrostatic interactions dominate the binding process. Additionally, we perform computer-aided design to generate a series of new cage receptors with diverse functionalities, and our findings highlight the tunable chloride affinity achieved by adjusting various cage properties. Overall, this study offers insights into the design of novel cage receptors with versatile functionalities and provides a strategic approach to the rational design of anion receptors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393730","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

Role of explicit solvation and level of theory in predicting the aqueous reduction potential of carbonate radical anion by DFT

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04487h

Michael R. Dooley, Shubham Vyas

{"title":"Role of explicit solvation and level of theory in predicting the aqueous reduction potential of carbonate radical anion by DFT","authors":"Michael R. Dooley, Shubham Vyas","doi":"10.1039/d4cp04487h","DOIUrl":"https://doi.org/10.1039/d4cp04487h","url":null,"abstract":"Chemical oxidation reactions, a key class of electron transfer processes, have broad applications, including the treatment of persistent and mobile pollutants. Marcus theory, paired with density functional theory (DFT) simulations, enables quantification of thermodynamic properties in these reactions. However, accurately modeling species with complex solvent interactions, especially radicals, requires careful selection of computational methods. Reduction potentials provide critical benchmarks for evaluating solvent models and functional choices by comparing simulated values to literature data. In this study, we used the carbonate radical, known for its strong intermolecular interactions, as a model to assess solvation models and computational functionals. Implicit solvation methods significantly underperformed, predicting only one-third of the measured reduction potential. Accurate results were obtained using explicit solvation with 18 water molecules for ωB97xD/6-311++G(2d,2p) and 9 water molecules for M06-2X/6-311++G(2d,2p). B3LYP/6-311++G(2d,2p) showed improvement with additional explicit solvation but failed to match literature benchmarks. Functional performance differences, analyzed through natural bond orbital (NBO) and charge transfer calculations, emphasized the critical role of dispersion corrections. Testing various dispersion correction methods revealed consistent improvements in reduction potential accuracy. These findings highlight the necessity of explicit solvation for modeling electron transfer reactions with extensive solvent interactions and underscore the importance of selecting appropriate functionals and dispersion corrections for reliable predictions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"55 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393724","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

Atomic insights into the ion-conducting channels of poly(arylene piperidinium) anion exchange membranes

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp03406f

Weiwen Pu, Zhaoru Sun

{"title":"Atomic insights into the ion-conducting channels of poly(arylene piperidinium) anion exchange membranes","authors":"Weiwen Pu, Zhaoru Sun","doi":"10.1039/d4cp03406f","DOIUrl":"https://doi.org/10.1039/d4cp03406f","url":null,"abstract":"Anion exchange membranes (AEMs) are crucial in green energy devices such as water electrolyzers, fuel cells, and CO2 electroreduction. Among the reported AEMs, the quaternary ammonia poly(N-methyl-piperidine-co-p-terphenyl) (QAPPT) AEM is notable for its high OH− conductivity. However, the underlying mechanisms responsible for this high OH− conductivity have remained elusive. Recent experiments have developed the poly(p-quaterphenyl dimethyl piperidinium) (QAQPP) AEM, which has a similar structure to the QAPPT AEM but exhibits much lower conductivity. This discrepancy further complicates our understanding of the superior performance of the QAPPT AEM. To clarify the origin of QAPPT AEM's enhanced conductivity, we perform molecular dynamics simulations to investigate the differences in the underlying causes of the OH− conductivity between QAPPT and QAQPP AEMs. We observe higher OH− diffusion with larger ion-conducting channels in the QAPPT AEM, which is in good agreement with experimental results. Further analysis of the conformations with varying water contents shows that the ion-conducting channels in QAPPT AEMs become larger due to polymer chain folding and dispersion, thereby enhancing OH− transport. In contrast, the channels in QAQPP remain limited in size because the chains maintain their compactness regardless of the water content. Such pronounced conformational changes in QAPPT compared to QAQPP are essentially due to the greater sensitivity of its backbone phenyl rings to water. These findings highlight that conformational evolution in response to water is key to the enhanced conductivity of QAPPT AEMs, providing new insights for more efficient AEM design.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393733","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

Mobility of thiolates on Au(111) surfaces

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp03709j

Daniël R. Duijnstee, Wesley R. Browne, Moniek Tromp, Aleksandar Staykov

{"title":"Mobility of thiolates on Au(111) surfaces","authors":"Daniël R. Duijnstee, Wesley R. Browne, Moniek Tromp, Aleksandar Staykov","doi":"10.1039/d4cp03709j","DOIUrl":"https://doi.org/10.1039/d4cp03709j","url":null,"abstract":"Self-assembled monolayers (SAMs), especially those based on thiol containing compounds on gold, are of both practical and fundamental interest. Thiols and thiolates can bind to gold in several ways due to the presence of holes and edges on the surfaces. The variety of binding motifs is increased by the presence of adatoms, i.e. gold atoms present on the surface, that sit between the thiolate and the surface. Although these motifs bind strongly to gold surfaces, they are sufficiently mobile to allow for self-assembly of thiols, either by movement across the surface or by desorption/re-adsorption. The motifs have been investigated primarily in the context of high surface coverage, with some attention given to the mobility of these motifs. Here we focus on the binding in the low-coverage regime, i.e. the initial stage of SAM formation, using theoretical methods. We determine the relative stability of the motifs formed with methane thiolate in the low-coverage regime, and rationalize their relative mobilities. Methane thiolate is used to minimize contributions of intermolecular interactions. Competition between the rates of adsorption, movement, and formation of the motifs can influence the formation of SAMs. In this work we expand the understanding of the early stages of monolayer formation and conclude that the type of motif formed depends strongly on the availability of gold adatoms and defects (edges and holes) on the surface at the point of adsorption.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393728","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

Dissociation and aggregation behaviors of starch in choline amino acid ionic liquid solvents: the anion structure effect

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp03626c

Jin Chen, Xixi Zeng, Ling Chen

{"title":"Dissociation and aggregation behaviors of starch in choline amino acid ionic liquid solvents: the anion structure effect","authors":"Jin Chen, Xixi Zeng, Ling Chen","doi":"10.1039/d4cp03626c","DOIUrl":"https://doi.org/10.1039/d4cp03626c","url":null,"abstract":"To fully explore choline amino acid ([Cho][AA]) ionic liquids (ILs) as starch solvents to meet various application needs, the effects of anion structure (reflected from choline lysine ([Cho][Lys]) and choline aspartic acid ([Cho][Asp]) of [Cho][AA]-water solvents on the dissociation and aggregation behaviors of starch were investigated. Compared with water (66.05 °C), the decreased gelatinization temperatures of starch were achieved at water/IL (w:IL) ratios of 5:5 (64.09 °C) and 4:6 (46.96 °C) of [Cho][Lys] solvents, indicating the promoted dissociation behaviors of starch (also indicated by large tan δG'max values). However, all ratios (w:IL-9:1 ~ 2:8) of [Cho][Asp] solvents inhibited the dissociation behaviors of starch, leading to increased gelatinization temperatures (above 85 °C). Moreover, after dissolution, comparison with [Cho][Asp], the viscosity and G' values of starch-[Cho][Lys] solutions were lower, indicating the reduced aggregation of starch molecules. These differences arose from the structure differences of AA- anions. Compared to acidic [Cho][Asp], the longer side chain and the basic NH2 group of Asp-, which has weaker hydrogen bonding ability compared to the -COOH group of Asp-, endowed [Cho][Lys] solvents with high pH, weaker Cho+-Lys- interactions (indicated by low viscosity), and stronger starch-[Cho][Lys] ion interactions. This allowed [Cho][Lys] ions to interact strongly with starch, thereby promoting dissociation and inhibiting aggregation of starch molecules. These findings could pave the way for designing solvent media with [Cho][AA] ILs for specific applications of starch.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"129 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393981","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