Physical Chemistry Chemical Physics最新文献_第2页

Revealing catalytic oxidation mechanism of CO on a-Fe2O3 surface: An ab initio thermodynamic study

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp04247f

Yun-Hyok Song, Yun-Hyok Kye, Myong-Il Pang, Yong-Min Ho, Hyon-Chol Choe, Chol-Jun Yu, Chol-Yong Ri

{"title":"Revealing catalytic oxidation mechanism of CO on a-Fe2O3 surface: An ab initio thermodynamic study","authors":"Yun-Hyok Song, Yun-Hyok Kye, Myong-Il Pang, Yong-Min Ho, Hyon-Chol Choe, Chol-Jun Yu, Chol-Yong Ri","doi":"10.1039/d4cp04247f","DOIUrl":"https://doi.org/10.1039/d4cp04247f","url":null,"abstract":"Signiﬁcant research efforts have been devoted to improving the efﬁciency of catalytic carbon monoxide (CO) oxidation over a-Fe2O3-based catalysts, but detailed underlying mechanism is still under debate. Here we apply the ab initio thermodynamic method (AITM) within the density functional theory framework to investigate phase diagram of a-Fe2O3 (0001) surface with various terminations and catalytic mechanism of CO oxidation on these surfaces. By extending the conventional AITM to consider the charge state of surface defect, we build the phase diagram of a-Fe2O3 (0001) surface in relation with the Fermi energy as well as the oxygen chemical potential, which makes it possible to explain the inﬂuence of point defects on the surface morphology and to predict the existence of the experimentally observed functional sites such as ferryl group (Fe−−O) and oxygen vacancy. Our calculations reveal that the surface with the ferryl-termination exhibits the highest catalytic activity for CO adsorption and oxidation with remarkably low activation energy (0.05 eV) and the largest exothermic reaction energy along the Eley-Rideal mechanism, while other surface with different terminations are inadequate with relatively high activation energies and different mechanisms. Furthermore, the electronic density of states and partial atomic charges are carefully analyzed, demonstrating that some electrons are transferred from CO molecule to the substrate on the event of CO adsorption and oxidation. Our work provides new fundamental insights into CO oxidation chemistry and mechanism, thereby contributing to a design of new catalysts with high performance and low cost.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"64 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874062","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

Balancing Enthalpy and Entropy in Inhibitors binding to the Prostate-Specific Membrane Antigen (PSMA)

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp04137b

Yuqing Xiong, Xinlin Wang, Mengchao Cui, Ya-Jun Liu, Beibei Wang

{"title":"Balancing Enthalpy and Entropy in Inhibitors binding to the Prostate-Specific Membrane Antigen (PSMA)","authors":"Yuqing Xiong, Xinlin Wang, Mengchao Cui, Ya-Jun Liu, Beibei Wang","doi":"10.1039/d4cp04137b","DOIUrl":"https://doi.org/10.1039/d4cp04137b","url":null,"abstract":"Understanding the molecular mechanism of inhibitor binding to Prostate-specific membrane antigen (PSMA) is of fundamental importance for designing targeted drug for prostate cancer. Here we designed a series of PSMA-targeting inhibitors with distinct molecular structures, which were synthesized and characterized using both experimental and computational approaches. Microseconds of molecular dynamics simulations revealed the structural and thermodynamic details of PSMA-inhibitor interactions. Our findings emphasize the pivotal role of the inhibitor's P1 region in modulating binding affinity and selectivity, and shed light on the binding-induced conformational shifts of two key loops (the Entrance Lid and the Interface Loop). Binding energy calculations demonstrate the enthalpy-entropy balancing in the thermodynamic driving force of different inhibitors. The binding of inhibitors in monomeric form is entropy-driving, in which the solvation entropy from the binding-induced water restraints play a key role, while the binding of inhibitors in dimeric form is enthalpy-driving, due to the promiscuous PSMA-inhibitor interactions. This insights about the molecular driving force of protein-ligand binding offer valuable guidance for rational drug design targeting PSMA.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874058","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

The formation mechanism of metal cluster fullerenes Sc3N@Cn: force field development and molecular dynamics simulations

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp03280b

Huichen Fan, Li-Hua Gan, Chun-Ru Wang

{"title":"The formation mechanism of metal cluster fullerenes Sc3N@Cn: force field development and molecular dynamics simulations","authors":"Huichen Fan, Li-Hua Gan, Chun-Ru Wang","doi":"10.1039/d4cp03280b","DOIUrl":"https://doi.org/10.1039/d4cp03280b","url":null,"abstract":"Metal cluster fullerenes are a class of molecular nanomaterials with complex structures and novel properties. An in-depth study of their formation mechanism is a key topic for developing new high-yield synthesis methods and promoting the practical application of such molecular nanomaterials. To elucidate the formation mechanism of Sc3N@Cn, a representative sub-class of metal cluster fullerenes, this study developed a ReaxFF force field parameter set CNSc.ff using a single parameter optimization method and conducted systematic molecular dynamics simulations on a C–N–Sc mixed system using the newly developed force field parameter set. The results show that atomic nitrogen has strong attraction to both C and Sc atoms, and it plays a key role in the formation of Sc3N@Cn; the formation of Sc3N@Cn includes carbon cluster growth, Sc-based cluster growth and their encapsulation; temperature, carbon density, and atomic ratio all affect the relative yield of Sc3N@Cn; and the final products are a mixture of amorphous carbon, fullerenes, metallofullerenes, and metal cluster fullerenes. This study rationalizes the phenomena observed in the synthesis experiments and provides insights for the development of selective and high-yield synthesis methods for metal cluster fullerenes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874032","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

Optimizing Nonlinearity in C6O6Li6-Doped Alkalides via Group I/III Doping for Unprecedented Charge Transfer and Breakthrough in Optoelectronics

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp03890h

Naveen Kosar, Khurshid Ayub, Abdulaziz A. Al-Saadi, Muhammad Imran, Tariq Mahmood

{"title":"Optimizing Nonlinearity in C6O6Li6-Doped Alkalides via Group I/III Doping for Unprecedented Charge Transfer and Breakthrough in Optoelectronics","authors":"Naveen Kosar, Khurshid Ayub, Abdulaziz A. Al-Saadi, Muhammad Imran, Tariq Mahmood","doi":"10.1039/d4cp03890h","DOIUrl":"https://doi.org/10.1039/d4cp03890h","url":null,"abstract":"The design and synthesis of nonlinear optical (NLO) materials are fast-growing fields in optoelectronics. Keeping in view the high demand of newly designed materials with superior optoelectronic characteristics, herein we have investigated doping Group-IIIA elements (namely, B, Al and Ga) on alkali metals (AM = Li, Na and K) supported C6O6Li6 (AM@C6O6Li6) complexes to enhance the NLO response. The AM-C6O6Li6 complexes sustained their structural features after interaction with Group-IIIA elements. Interaction energies as high as -109 kcal mol-1 demonstrated a high thermodynamic stability of the complexes. An exceptional charge transfer behavior is predicted in these complexes where the electronic density of Group-III metals shifts toward the alkali metals, making such complexes as alkalides. The π conjugation of C6O6Li6 withdraws excess electrons from Group IIIA metals in these alkalides, which are subsequently transferred to Group IA metals. The frontier molecular orbitals (FMOs) energy gap of AM-C6O6Li6 is notably reduced after alkalide formation. UV-Visible analysis explicitly described the bathochromic shift inside the alkalides. The first hyperpolarizability (βo) is calculated to confirm the NLO properties of these alkalides. B-C6O6Li6-K has the highest βo value of 1.75×105 au. These properties reflect the promising NLO response of our designed alkalides and their use in the field of optics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874034","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

2D P-Doped Carbon Nitride as an Effective Artificial Solid Electrolyte Interphase for the Protection of Li Anodes

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp04183f

Franco Eroles, Yesica Celeste Villagrán López, María Beatriz López, Martín Zoloff Michoff, Guillermina Leticia Luque, Fernando Pablo Cometto

{"title":"2D P-Doped Carbon Nitride as an Effective Artificial Solid Electrolyte Interphase for the Protection of Li Anodes","authors":"Franco Eroles, Yesica Celeste Villagrán López, María Beatriz López, Martín Zoloff Michoff, Guillermina Leticia Luque, Fernando Pablo Cometto","doi":"10.1039/d4cp04183f","DOIUrl":"https://doi.org/10.1039/d4cp04183f","url":null,"abstract":"Metallic lithium plays an important role in the development of next-generation lithium metal-based batteries. However, the uncontrolled growth of lithium dendrites limits the use of lithium metal as an anode. In this context, a stable solid electrolyte interphase (SEI) is crucial for regulating dendrite formation, stability, and cyclability of lithium metal anodes. This article proposes an artificial protective layer of P-doped carbon nitride on the lithium anode surface to address these issues. A thin film of P-doped carbon nitride (CNP) was created through a simple drop-casting method using synthesized CNP powder, forming an artificial SEI on the lithium electrode. The resulting symmetric CNP-modified Li/Li cells exhibited remarkable cyclability with low overpotentials of around 40 mV over 500 cycles at a current density of 3 mA/cm2. Anode degradation and SEI composition were thoroughly studied for cycled electrodes to gain insight into the mechanisms underlying this modified surface. Furthermore, these CNP-modified anodes were successfully utilized in a Li-S coin cell battery, achieving high capacity and capacity retention at a high current density (1C). First-principles calculations indicate that P-doping in the carbon nitride structure significantly enhances the surface diffusion of lithium and promotes a more homogeneous lithium plating.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"83 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874033","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

Quantification of vehicular versus uncorrelated Li+–solvent transport in highly concentrated electrolytes via solvent-related Onsager coefficients

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI: 10.1039/d4cp04209c

Hendrik Kilian, Tabita Pothmann, Martin Lorenz, Maleen Middendorf, Stefan Seus, Monika Schönhoff, Bernhard Roling

{"title":"Quantification of vehicular versus uncorrelated Li+–solvent transport in highly concentrated electrolytes via solvent-related Onsager coefficients","authors":"Hendrik Kilian, Tabita Pothmann, Martin Lorenz, Maleen Middendorf, Stefan Seus, Monika Schönhoff, Bernhard Roling","doi":"10.1039/d4cp04209c","DOIUrl":"https://doi.org/10.1039/d4cp04209c","url":null,"abstract":"Highly concentrated salt solutions are promising electrolytes for battery applications due to their low flammability, their high thermal stability, and their good compatibility with electrode materials. Understanding transport processes in highly concentrated electrolytes is a challenging task, since strong ion–ion and ion–solvent interactions lead to highly correlated movements on the microscopic scale. Here, we use an experimental overdetermination method to obtain accurate Onsager transport coefficients for concentrated binary electrolytes composed of either sulfolane (SL) or dimethyl carbonate (DMC) as solvent and either LiTFSI or LiFSI as salt. NMR-based electrophoretic mobilities demonstrate that volume conservation applies as a governing constraint for the transport. This fact allows to calculate the Onsager coefficients σ+0, σ−0 and σ00 related to the solvent. A parameter γ is then defined, which is a measure for the relevance of a vehicular Li+–solvent transport mechanism. We analyze the influence of the salt anion and of the solvent on dynamic correlations and transport mechanisms. In the case of the sulfolane-based electrolytes, the γ parameter reaches values up to 0.38, indicating that Li+–sulfolane interactions are stronger than Li+–anion interactions and that vehicular Li+–sulfolane transport plays a significant role. In the case of DMC-based electrolytes, the γ parameter is close to zero, suggesting balanced Li+–DMC vs. Li+–anion interactions and virtually uncorrelated movements of Li+ ions and DMC molecules.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874060","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

Laser Ablation Syntheses of OThS and OCeS and their Characterization by Rotational Spectroscopy

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-21 DOI: 10.1039/d4cp04382k

Joshua E. Isert, Alexander Davies, Smitty Grubbs II, Stephen Cooke

引用次数: 0

Investigation of Novel All-Inorganic Perovskites Ba3PX3 (X = F, Cl, Br, I) with Efficiency Above 29%

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-21 DOI: 10.1039/d4cp04276j

Md. Al Ijajul Islam, Md. Ferdous Rahman, Md. Monirul Islam, Mustafa K. A. Mohammed, Ahmad Irfan

引用次数: 0

Concurrent ultrafast twisting and proton transfer photoreactions in new pyrano[2,3-c]pyrazole derivatives

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-20 DOI: 10.1039/d4cp03805c

Marius Navickas, Karolis Gineitis, Arminas Urbonavičius, Sonata Krikštolė, Vytas Martynaitis, Eglė Arbačiauskienė, Miglė Dagilienė, Algirdas Šačkus, Mikas Vengris

引用次数: 0

Tunable electronic band structure of AlP3/Cs3Bi2I6Cl3 van der Waals heterostructure induced by electric field: a first-principles study

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-20 DOI: 10.1039/d4cp03918a

Cheng-Sheng Liao, Qiu-yi Wang, Lin Lang, Yu-Qing Zhao, Yu Zhuoliang

{"title":"Tunable electronic band structure of AlP3/Cs3Bi2I6Cl3 van der Waals heterostructure induced by electric field: a first-principles study","authors":"Cheng-Sheng Liao, Qiu-yi Wang, Lin Lang, Yu-Qing Zhao, Yu Zhuoliang","doi":"10.1039/d4cp03918a","DOIUrl":"https://doi.org/10.1039/d4cp03918a","url":null,"abstract":"Constructing van der Waals heterostructures (vdWHs) have emerged as an attractive strategy to combine and enhance the optoelectronic properties of stacked materials. Herein, by means of first-principles calculations, we investigate the geometric and electronic structures of the AlP3/Cs3Bi2I6Cl3 vdWH as well as its tunable band structure via external electric field. The AlP3/Cs3Bi2I6Cl3 vdWH is structurally and thermodynamically stable due to the low binding energy and the small energy fluctuation at room temperature. Our band structure calculations demonstrate that the AlP3/Cs3Bi2I6Cl3 vdWH possesses an indirect bandgap and a type-I band alignment with the band edges both dominated by AlP3 layer. Notably, the band alignment of heterostructure can be flexibly tuned between type-I and type-II by employing an external electric field. Besides, an indirect-to-direct bandgap transition can be observed by increasing the intensity of negative electric field. These results reveal the potential of AlP3/Cs3Bi2I6Cl3 vdWH as a novel candidate material for the experimental designs of multi-functional devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857899","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