Physical Chemistry Chemical Physics最新文献

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Single-Atom Pd in ZSM 5 for Selective Oxidation of Methane-to-Methanol: A DFT-Based ONIOM Approach 单原子钯在zsm5中选择性氧化甲烷制甲醇：基于dft的ionom方法

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-13 DOI: 10.1039/d5cp02968f

Priyanka Dutta, Nishant Biswakarma, Dikshita Dowerah, Shilpa Neog, Nand Kishor Gour, Gaurisankar Phukan, Ramesh Deka

Single-atom catalysts are emerging as promising candidates for the selective oxidation of methane, providing distinctive opportunities to improve activity, selectivity, and atomic efficiency. In this study, we have applied the DFT-D3 based ONIOM approach to examine the potential energy surfaces of Pd single atoms, with oxidation states of 0, +1, and +2, enclosed within the ZSM-5 framework for the partial oxidation of methane to methanol employing N2O as the oxidant. We have incorporated dispersion correction using Grimme’s GD3 dispersion correction to account for the van der waals interaction within the zeolites framework. Depending on the oxidation states of the Pd atom, we have substituted Si atoms with an equivalent number of Al atoms to maintain the overall charge neutrality of the ZSM-5 framework. The mechanism of the reaction consists of three key steps mainly formation of active site by N2O, activation of C-H bond of methane and recombination of the CH3 and OH moieties to form methanol. Two-state reactivity has also been considered for the catalyst with close lying spin states. Furthermore, the inclusion of water during methanol desorption significantly reduces its desorption energy thereby preventing the risk of over-oxidation and increasing the selectivity. In terms of activation barrier, kinetic analysis and methanol desorption energies, siliceous ZSM-5 with Pd0 is found to be most favorable choice for partial oxidation of methane to methanol. Our findings offer significant insights into the oxidation state dependent reactivity of single atom Pd/ZSM-5 for direct conversion of methane to methanol.

单原子催化剂正在成为甲烷选择性氧化的有希望的候选者，为提高活性、选择性和原子效率提供了独特的机会。在这项研究中，我们应用了基于DFT-D3的ONIOM方法来检查氧化态为0、+1和+2的Pd单原子的势能表面，这些原子被封闭在ZSM-5框架内，以N2O作为氧化剂将甲烷部分氧化成甲醇。我们采用了格里姆GD3色散校正来解释沸石框架内的范德华相互作用。根据Pd原子的氧化态，我们用等量的Al原子取代了Si原子，以保持ZSM-5框架的整体电荷中性。反应机理主要包括N2O生成活性位点、甲烷C-H键活化、CH3和OH重组生成甲醇三个关键步骤。对于自旋态相近的催化剂，还考虑了双态反应性。此外，在甲醇脱附过程中，水的包裹显著降低了其脱附能量，从而防止了过度氧化的风险，提高了选择性。从活化势垒、动力学分析和甲醇解吸能等方面分析，发现含Pd0的硅质ZSM-5是甲烷部分氧化制甲醇的最佳选择。我们的研究结果对单原子Pd/ZSM-5直接将甲烷转化为甲醇的氧化态依赖性反应性提供了重要的见解。

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引用次数: 0

From fluorine chemistry to noncovalent interactions: celebrating Prof. Giuseppe Resnati. 从氟化学到非共价相互作用：庆祝Giuseppe Resnati教授。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp90211h

Antonio Frontera, Norio Shibata, Kamran T Mahmudov

引用次数: 0

Probing drug pharmacokinetics using neutron scattering techniques. 利用中子散射技术探测药物的药代动力学。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp03679h

Clara B Martins, Mona Sarter, Ana L M Batista de Carvalho, Victoria García-Sakai, Tilo Seydel, Jacques Ollivier, Luís A E Batista de Carvalho, Maria P M Marques

Quasi-elastic neutron scattering was applied to the study of human serum albumin metalation by anticancer drugs, with a specific focus on understanding the effects on the protein dynamics at the atomic scale. Two drugs were studied, a dinuclear Pd-complex and the clinical agent cisplatin. Both drugs prompted a decrease in the overall mobility of the protein, and this perturbation is closely associated with the protein's hydration layer. Opposite effects were detected for the Pt- and Pd-agents regarding the protein's local and internal dynamics. The influence of the Pd-compound at the nanosecond scale is particularly intriguing, as it reduced the observed backbone dynamics below 290 K. This enhanced knowledge on the drug's pharmacokinetics is expected to contribute to the design of improved anticancer agents (with lower toxicity and increased bioavailability at the target).

将准弹性中子散射技术应用于抗癌药物对人血清白蛋白金属化的研究，重点关注在原子尺度上对蛋白质动力学的影响。研究了两种药物，一种双核pd复合物和临床药物顺铂。这两种药物都促使蛋白质的整体流动性下降，这种扰动与蛋白质的水合层密切相关。Pt-和pd -制剂在蛋白质的局部和内部动力学方面检测到相反的作用。钯化合物在纳秒尺度上的影响特别有趣，因为它降低了观察到的290 K以下的主链动力学。这种对药物药代动力学的增强了解有望有助于设计改进的抗癌药物（具有更低的毒性和更高的靶标生物利用度）。

引用次数: 0

Facile Synthesis of Carbon-Supported PdAu Nanonetworks for Cinnamaldehyde Hydrogenation 肉桂醛加氢碳负载PdAu纳米网络的简易合成

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp02601f

Ruigang Xie, Xiaofang Ren, Wei Zhang, Lingli Zhou, Daixiang Chen, Shenghu Yan

Carbon-supported palladium-alloyed nanowires (PdAu NWs@C) were synthesized in an alcoholic solution containing carbon black without the use of surfactants or directing agents. The prepared nanomaterials exhibited excellent catalytic performance in the cinnamaldehyde hydrogenation reaction, reaching up to 93% selectivity for hydrogenated cinnamaldehyde at 98% conversion.

在不使用表面活性剂或导向剂的情况下，在含炭黑的酒精溶液中合成了碳负载钯合金纳米线（PdAu NWs@C）。制备的纳米材料在肉桂醛加氢反应中表现出优异的催化性能，在98%的转化率下，加氢肉桂醛的选择性高达93%。

引用次数: 0

Solvent-Dependent Electronic Dichotomy in Zinc Complexes with Non-Innocent Ligands: Divalent Zn(+II) vs. Monovalent Zn(+I) Forms 非无害配体锌配合物的溶剂依赖电子二分法：二价锌（+II）与单价锌（+I）形式

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp03669k

Mikaël Le Roch, Alejandro Perez-Luna, Hélène Gerard, Fabrice Chemla, Stéphanie Halbert

The relative stabilities and the electronic structures of zinc complexes bearing non-innocent ligands, associated with various oxidation states, are examined in this computational study, with a particular attention on the influence of solvent polarity, modeled by explicit, implicit, and hybrid solvation approaches. Notably, we show that the stabilities and the electronic configuration of both the divalent species, described as a Zn (II) center coordinated to a fully reduced ligand (dianion), and the monovalent Zn (+I) species, described as a Zn (I) center bound to a one-electron reduced ligand (radical anion), as a biradical, are highly sensitive to the polarity of the solvent. This study underscores the importance of performing geometry optimizations within the solvation model and highlights the use of structural features and bonding analysis tools in elucidating electronic structures.

在本计算研究中，研究了与各种氧化态相关的含非无害配体的锌配合物的相对稳定性和电子结构，特别关注溶剂极性的影响，通过显式、隐式和混合溶剂化方法建模。值得注意的是，我们发现两种物质的稳定性和电子构型都对溶剂的极性高度敏感，一种是锌（II）中心与完全还原的配体（离子）配合，一种是锌（+I）中心与单电子还原的配体（自由基阴离子）结合，一种是双自由基。这项研究强调了在溶剂化模型中进行几何优化的重要性，并强调了在阐明电子结构时使用结构特征和键合分析工具。

引用次数: 0

Silicon single atom anchored on α-BS monolayer for efficient electrocatalytic nitric oxide reduction to ammonia α-BS单层固载硅单原子高效电催化氧化氮还原制氨

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp04409j

yongxu Fu, Hu Li, Qingbo Kang, Jiangke Li, Minghui Wu, Liu Lei, Xiaobing Yan, Weichao Wang, Linxia Wang

The development of efficient, low-cost, and environmentally friendly metal-free electrocatalysts is crucial for the green conversion of nitric oxide (NO) into ammonia (NH3). Herein, we designed a series of non-metal single-atom catalysts (XS@BS, X = B, C, N, O, Si, P, As, and Se) by substituting a sulfur atom in the α-BS monolayer. Their structural stability, NO activation capability, and performance toward the electrocatalytic NO reduction reaction (eNORR) were systematically investigated using first-principles density functional theory (DFT) calculations. Among these systems, SiS@BS demonstrates the highest eNORR activity via the N-alternating pathway, with a positive limiting potential of 0.33 V, ensuring that the reaction can proceed spontaneously under standard conditions. Furthermore, SiS@BS effectively suppresses the competing hydrogen evolution reaction and prevents the formation of undesired byproducts (N2O and N2). The robustness of SiS@BS was further validated by AIMD simulations at room temperature. The superior performance is attributed to the balanced energy profile, enabled by the effective hybridization between the p orbital of Si and the 1π* orbital of NO, which facilitates efficient N-O bond activation while avoiding the over-stabilization of subsequent intermediates. This study provides theoretical guidance for the rational design of cost-effective metal-free eNORR catalysts.

开发高效、低成本、环保的无金属电催化剂是实现一氧化氮（NO）绿色转化为氨（NH3）的关键。在此，我们设计了一系列非金属单原子催化剂（XS@BS, X = B， C， N， O, Si， P, As, Se），通过在α-BS单层中替换一个硫原子。利用第一性原理密度泛函理论（DFT）计算系统地研究了它们的结构稳定性、NO活化能力和对电催化NO还原反应（eNORR）的性能。在这些体系中，SiS@BS通过n -交替途径表现出最高的eNORR活性，其正极限电位为0.33 V，确保在标准条件下反应可以自发进行。此外，SiS@BS有效地抑制了竞争性析氢反应，防止了不良副产物（N2O和N2）的形成。通过室温下的AIMD仿真，进一步验证了SiS@BS的鲁棒性。Si的p轨道和NO的1π*轨道之间的有效杂化使得能量分布平衡，从而促进了N-O键的有效激活，同时避免了后续中间体的过度稳定。该研究为合理设计高性价比的无金属eNORR催化剂提供了理论指导。

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引用次数: 0

Unraveling the stereoisomeric toxicity of V-series nerve agent VX on human acetylcholinesterase: a well-tempered metadynamics study. 揭示v系列神经毒剂VX对人类乙酰胆碱酯酶的立体异构体毒性：一项良好调节的元动力学研究。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp02194d

Dipankar Das, Shibaji Ghosh, Kalyanashis Jana, Bishwajit Ganguly

Highly toxic organophosphorus nerve agents exert their severe toxicity by inhibiting AChE irreversibly through the phosphonylation of Ser203 within the catalytic triad. The inhibition of AChE varies with stereoisomeric nerve agents. The inhibition mechanism of AChE by stereoselective nerve agents remains elusive. This study explores the mechanism of inhibition of hAChE by stereoselective nerve agents using well-tempered metadynamics (WT-MtD) simulations. The stereoisomeric nerve agent VX (in PS and PR forms) has been examined because it is known from the literature that the PS form of VX inhibits human AChE faster than the PR form. The 1D free energy surface profiles from the WT-MtD simulations reveal that the PS_VX nerve agent binds more strongly (∼4.0 kcal mol^-1) with hAChE than the PR_VX nerve agent. The WT-MtD simulation results showed that the catalytic triad residues Ser203, His447, and Glu334 play an important role in governing the inhibition process of hAChE by stereoisomeric VX nerve agents. The catalytic triad Ser203, His447, and Glu334 of hAChE aligns in a very similar fashion to that observed for the hydrolysis of acetylcholine (ACh) by PS_VX. The aligned triad residues assist in generating the nucleophilic center at Ser203 for attack on the electrophilic phosphorus center of PS_VX more effectively than PR_VX. The WT-MtD snapshots taken from basin I for both stereoisomers of the nerve agents, used for superimposition onto the apo crystal structure of hAChE, show that the catalytic triad of PR_VX bound hAChE is not aligned with the catalytic triad of the crystal structure. The role of water molecules in the slower inhibition of PR_VX has also been investigated.

高毒性有机磷神经毒剂通过催化三联体中Ser203的磷酸化不可逆地抑制乙酰胆碱酯酶发挥其严重毒性。对乙酰胆碱酯酶的抑制作用因立体异构体神经毒剂而异。立体选择性神经毒剂对乙酰胆碱酯酶的抑制机制尚不清楚。本研究通过调节元动力学（WT-MtD）模拟探讨了立体选择性神经毒剂抑制hAChE的机制。对立体异构体神经毒剂VX （PS和PR形式）进行了研究，因为从文献中得知，VX的PS形式比PR形式更快地抑制人类AChE。WT-MtD模拟的一维自由能表面谱显示，PS_VX神经毒剂比PR_VX神经毒剂与hAChE结合更强（约4.0 kcal mol-1）。WT-MtD模拟结果表明，催化三联体残基Ser203、His447和Glu334在控制立体异构体VX神经毒剂对hAChE的抑制过程中起重要作用。hAChE的催化三联体Ser203、His447和Glu334的排列方式与PS_VX对乙酰胆碱（ACh）水解的观察结果非常相似。与PR_VX相比，排列的三联体残基有助于在Ser203上产生亲核中心，从而更有效地攻击PS_VX的亲电性磷中心。在盆I中对用于叠加到hAChE载子晶体结构上的神经毒剂的两种立体异构体进行了WT-MtD快照，结果表明PR_VX结合的hAChE的催化三联体与晶体结构的催化三联体并不对齐。还研究了水分子在PR_VX的缓慢抑制中的作用。

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引用次数: 0

Disentangling effects of pH, potential, and cation concentration in cathodic corrosion of platinum. pH、电位和阳离子浓度在铂阴极腐蚀中的解缠效应。

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp03483c

Mark Aarts,Jamie A Trindell,Marc T M Koper

Cathodic corrosion concerns the electrochemical etching of metals at negative polarization. While this process is detrimental for electrode stability and lifetime, the mechanism responsible for etching has not yet been fully elucidated. In this work, we determine the potential at which signs of cathodic corrosion on platinum electrodes are observed for different aqueous electrolytes, varying bulk pH and cation concentration. From cyclic voltammetry, we find that typical indicators of cathodic corrosion roughening the surface always appear at the same potential with respect to the standard hydrogen electrode, irrespective of the electrolyte. In contrast, we observe from microscopy that the degree of etch pit formation is strongly determined by the cation concentration. This therefore separates potential-induced effects of surface roughening from the rate of cation-mediated dissolution. The electrolyte-independent onset potential reveals aspects of the underlying corrosion mechanism, and our results are discussed in terms of the different roles of the electrolyte components at the interface.

阴极腐蚀是指金属在负极化下的电化学腐蚀。虽然这一过程不利于电极的稳定性和寿命，但蚀刻的机制尚未完全阐明。在这项工作中，我们确定了在铂电极上观察到的阴极腐蚀迹象的电位，不同的水溶液电解质，不同的体积pH值和阳离子浓度。从循环伏安法中，我们发现阴极腐蚀表面的典型指标总是出现在相同的电位，相对于标准氢电极，无论电解质如何。相反，我们从显微镜观察到，蚀刻坑形成的程度强烈地取决于阳离子浓度。因此，这将潜在的表面粗化效应从阳离子介导的溶解速率中分离出来。与电解质无关的起始电位揭示了潜在腐蚀机制的各个方面，我们的结果根据电解质成分在界面上的不同作用进行了讨论。

引用次数: 0

Structural and Thermal Stability of B4C/Ru Multilayers with Carbon Barrier Layers 含碳阻挡层的B4C/Ru多层膜的结构和热稳定性

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp03527a

Aleksandr Bugaev, Sergei Sakhonenkov, Aidar Uralovich Gaisin, Roman Shaposhnikov, Vladimir Polkovnikov, Elena Olegovna Filatova

The chemical interaction between B 4 C and Ru layers in multilayer structures depending on the thickness ratio (Γ) was carried out using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and X-ray reflectometry (XRR). The results showed significant interaction of materials inside multilayer structures with the formation of ruthenium borides, with an increase in the B 4 C layer thickness (a decrease in the Γ parameter) leading to the formation of ruthenium borides of different stoichiometry. The introduction of a carbon barrier layer at the Ru-on-B 4 C interface resulted in significant suppression of ruthenium boride formation. The thermal stability of the B 4 C/Ru system was also studied upon annealing at 400 ℃ for 1 hour before and after the introduction of the carbon barrier layer. It was shown that the introduction of a carbon barrier layer at the Ru-on-B 4 C interface increases the thermal stability of the system, which makes this system more suitable for use in optical systems exposed to long-term radiation. The obtained results are important for the development of highly efficient multilayer mirrors used in EUV lithography and X-ray optics.

利用x射线光电子能谱（XPS）、x射线衍射（XRD）和x射线反射仪（XRR）研究了多层结构中b4c和Ru层之间随厚度比（Γ）的化学相互作用。结果表明，多层结构内部的材料与硼化钌的形成有明显的相互作用，b4c层厚度的增加（Γ参数的减小）导致不同化学计量的硼化钌的形成。在ru -on- b4c界面处引入碳阻挡层，显著抑制了硼化钌的形成。在引入碳阻挡层前后，对b4c /Ru体系在400℃下退火1h的热稳定性进行了研究。结果表明，在ru -on- b4c界面处引入碳势垒层提高了系统的热稳定性，使该系统更适合用于长期辐射的光学系统。所得结果对于开发用于EUV光刻和x射线光学的高效多层反射镜具有重要意义。

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Through-Space Magnetic Response of Noble-gases 稀有气体的全空间磁响应

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2025-12-12 DOI: 10.1039/d5cp03897a

Alvaro Muñoz-Castro

Noble gases remain a paramount notion of stability, guiding chemistry across the periodic table. In this letter, we describe the through-space magnetic behavior of noble gases from He to Rn, indicating an increasing averaged shielding region, which leads to long-range shielding with a complementary deshielding region under specific orientations of the external field, as a consequence of the electronic shell closure at the end of each period. Such behavior resembles the shielding cone, inherent to planar and spherical aromatic species, suggesting a fundamental origin of this behavior.

惰性气体仍然是稳定性的重要概念，指导着化学元素周期表。在这封信中，我们描述了稀有气体从He到Rn的穿越空间磁行为，表明平均屏蔽区域增加，这导致在特定外场方向下的远程屏蔽与互补的去屏蔽区域，这是每个周期结束时电子壳闭合的结果。这种行为类似于平面和球形芳香物种固有的屏蔽锥，这表明这种行为的基本起源。

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