Chemphyschem最新文献_第3页

17O NMR spectroscopy reveals CO2 speciation and dynamics in hydroxide-based carbon capture materials. 17O NMR 光谱揭示了基于氢氧化物的碳捕获材料中的 CO2 分类和动力学。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-20 DOI: 10.1002/cphc.202400941

Benjamin Rhodes, Lars Schaaf, Mary Zick, Suzi Pugh, Jordon Hilliard, Shivani Sharma, Casey Wade, Phillip Milner, Gábor Csányi, Alexander Forse

{"title":"17O NMR spectroscopy reveals CO2 speciation and dynamics in hydroxide-based carbon capture materials.","authors":"Benjamin Rhodes, Lars Schaaf, Mary Zick, Suzi Pugh, Jordon Hilliard, Shivani Sharma, Casey Wade, Phillip Milner, Gábor Csányi, Alexander Forse","doi":"10.1002/cphc.202400941","DOIUrl":"https://doi.org/10.1002/cphc.202400941","url":null,"abstract":"Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO2 capture systems by 17O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO2 capture products, finding that 17O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs): MFU-4l and KHCO3-cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning forcefields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO3-CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO2 capture materials by 17O NMR.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400941"},"PeriodicalIF":2.3,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674718","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

Commercial silica materials functionalized with a versatile organocatalyst for the catalysis of acylation reactions in liquid media. 用一种多功能有机催化剂功能化的商用二氧化硅材料，用于催化液体介质中的酰化反应。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-19 DOI: 10.1002/cphc.202400936

Raoul D Brand, Mareike Maass, Anatoliy G Grebenyuk, Alexander A Golub, Bernd M Smarsly

{"title":"Commercial silica materials functionalized with a versatile organocatalyst for the catalysis of acylation reactions in liquid media.","authors":"Raoul D Brand, Mareike Maass, Anatoliy G Grebenyuk, Alexander A Golub, Bernd M Smarsly","doi":"10.1002/cphc.202400936","DOIUrl":"https://doi.org/10.1002/cphc.202400936","url":null,"abstract":"Silica materials represent a promising material for the application in heterogeneous organocatalysis due to their readily modifiable surface and chemical inertness. To achieve high catalyst loadings, usually, porous carriers with high surface areas are used, such as special silica monoliths or spherical particles for backed bed reactors. Yet, their synthesis is elaborate, and thus less complex and cheaper alternatives are of interest, especially considering scaling up. In this work, two commercial silica materials functionalized with the organocatalyst 4-(dimethylamino)pyridine (DMAP) were used in catalytic acylation reactions: a mesoporous silica gel (Siliabond®-DMAP) and non-porous silica nanoparticles (Ludox®). Both were successfully used in the acylation of phenylethanol, but the latter required significantly longer reaction times, presumably due to mass-transfer limitations as a consequence of substantial agglomeration that limits the accessible amount of catalyst. Furthermore, it was shown that the influence of the linker molecule is negligible, since both reaction yields and the activation energy remain largely similar. As main result the commercial material Siliabond-DMAP, despite the non-uniform particles, exhibited significant yield in a flow setup, thus demonstrating the potential as support material for application in heterogeneous organocatalysis.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400936"},"PeriodicalIF":2.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674722","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

Front Cover: Formation of Paraldehyde (C6H12O3) in Interstellar Analog Ices of Acetaldehyde Exposed to Ionizing Radiation (ChemPhysChem 22/2024) 封面：暴露于电离辐射的乙醛星际模拟冰中副醛 (C6H12O3) 的形成（ChemPhysChem 22/2024）

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-19 DOI: 10.1002/cphc.202482201

Jia Wang, Andrew M. Turner, Joshua H. Marks, Ryan C. Fortenberry, Ralf I. Kaiser

引用次数: 0

Cover Feature: Exploration of Optimization Strategies for Locking Sulfur in 2D Layered/Polymer-Enveloped Cathode Composite for High Power Li-S Batteries (ChemPhysChem 22/2024) 封面专题：用于大功率锂离子电池的二维层状/聚合物开发型阴极复合材料中锁硫的优化策略探索（ChemPhysChem 22/2024）

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-19 DOI: 10.1002/cphc.202482202

M. Johnsi, V. J. Asha Shalini, M. Azhagulakshmi, B. Kavin Kumar, N. Balasubramanian

引用次数: 0

Cover Feature: Attraction versus Repulsion between Methyl and Related Groups: (CH3NHCH3)2 and (CH3SeBr2CH3)2 (ChemPhysChem 22/2024) 封面专题：甲基和相关基团之间的吸引力与排斥力：(CH3NHCH3)2 和 (CH3SeBr2CH3)2 （ChemPhysChem 22/2024）

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-19 DOI: 10.1002/cphc.202482203

Mariusz Michalczyk, Steve Scheiner, Wiktor Zierkiewicz

引用次数: 0

Density Functional Theory Study on Screening and Key Metrics for Non-metallic Oxygen Reduction Catalysts. 非金属氧还原催化剂筛选和关键指标的密度泛函理论研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-18 DOI: 10.1002/cphc.202400830

Jinlong Wang, Jinmin Guo, Weiwei Shao, Bingling He, Daping Liu, Wei Song, Xiao-Chun Li

{"title":"Density Functional Theory Study on Screening and Key Metrics for Non-metallic Oxygen Reduction Catalysts.","authors":"Jinlong Wang, Jinmin Guo, Weiwei Shao, Bingling He, Daping Liu, Wei Song, Xiao-Chun Li","doi":"10.1002/cphc.202400830","DOIUrl":"10.1002/cphc.202400830","url":null,"abstract":"This study systematically investigates the oxygen reduction reaction (ORR) catalytic activity of graphene doped with various non-metallic impurities. The non-metal elements include boron (B), silicon (Si), nitrogen (N), phosphorus (P), arsenic (As), oxygen (O), sulfur (S), selenium (Se), tellurium (Te), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). We found that adsorbates tend to adsorb on positively charged impurity atoms. We identified several substrates with good catalytic activity, all of which have an ORR overpotential of around 0.6 V. We further verified the thermodynamic stability of these substrates and found them to be very stable. We summarized the optimal adsorption energies for ORR intermediates O2H, O, and OH to be -1.9, -3.4, and -2.4 eV, respectively, and validated their reasonableness. Finally, we used simple linear functions to fit the relationship between the adsorption energies of O2H, O, and OH and the charge and magnetic moment of the adsorption site atoms. This model can roughly predict the ORR catalytic activity of doped graphene, facilitating the faster screening of excellent ORR catalysts.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400830"},"PeriodicalIF":2.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142667240","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

On the Nature of the Out-Of-Plane Distortions in Subporphyrins. 关于亚卟啉中平面外畸变的性质。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-16 DOI: 10.1002/cphc.202400836

Pattath D Pancharatna, J Haripriya, A Anjana, J Harikrishnan

{"title":"On the Nature of the Out-Of-Plane Distortions in Subporphyrins.","authors":"Pattath D Pancharatna, J Haripriya, A Anjana, J Harikrishnan","doi":"10.1002/cphc.202400836","DOIUrl":"https://doi.org/10.1002/cphc.202400836","url":null,"abstract":"The field of subporphyrins has garnered great interest in recent years owing to its unique structure and associated properties. They exhibit spectroscopic features similar to porphyrins and find applications in various optoelectronic devices, photodynamic therapy etc. Most of the synthesized subporphyrins have boron coordination with an axial ligand and exhibits a bowl-shaped geometry. The first isolation of a stable free-base subporphyrin is achieved recently with mesityl groups at two of the meso positions and anthracene at the other. X-ray studies reveal a markedly non-planar structure different from the bowl shape and is attributed to the steric hindrance of the inner N-H bonds. Herein, we report a systematic quantum chemical investigation assisted by symmetry principles on molecular models to characterize the out-of-plane (OOP) distortions observed so far in subporphyrins and unveil the electronic reasons. Correlation of the frontier molecular orbital (FMO) landscape between the D4h porphyrin and D3h subporphyrin gives insight into their electronic structure relative to one another and the nature of OOP distortions. Further the effect of a π-donor cum σ-acceptor substituent at the meso/beta positions of the subporphyrin ring as well as the impact of boron incorporation in the central cavity on the OOP distortions are also discussed.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400836"},"PeriodicalIF":2.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643780","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

Enantioselective complexation of protonated tyrosine by a chiral crown-ether: the nature of the Hydrogen bonds makes the difference. 手性冠醚对质子化酪氨酸的对映选择性络合：氢键的性质决定了区别。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-15 DOI: 10.1002/cphc.202400880

Anne Zehnacker, Kien Xuan Vo, Keisuke Hirata, Bruno Martínez-Haya, Jos Oomens, Shun-Ichi Ishiuchi, Masaaki Fujii

{"title":"Enantioselective complexation of protonated tyrosine by a chiral crown-ether: the nature of the Hydrogen bonds makes the difference.","authors":"Anne Zehnacker, Kien Xuan Vo, Keisuke Hirata, Bruno Martínez-Haya, Jos Oomens, Shun-Ichi Ishiuchi, Masaaki Fujii","doi":"10.1002/cphc.202400880","DOIUrl":"https://doi.org/10.1002/cphc.202400880","url":null,"abstract":"The complexes formed between (18-crown-6)-tetracarboxylic acid, denoted as 18C6TA, and the two enantiomers of protonated tyrosine, L- and D-Tyr, are studied in a cryogenic ion trap by combining mass spectrometry, laser spectroscopy, and DFT calculations. Both UV and IR photodissociation spectra indicate the formation of multiple isomers for each complex, some of them interconverting upon IR irradiation. Conformer-selective vibrational spectroscopy reveals that all structures involve an internally hydrogen-bonded folded structure of the crown ether. The complexes formed with L-Tyr involve two NH…O interactions with the ether oxygen atoms,and two hydrogen bonds to the crown ether carboxylic function, one from the NH group and the other from the COOH group of tyrosine. The D-Tyr complexesshow more conformational mobility: two out of the three lowest energy conformers observed are tripodal, with three NH…O interactions between the amino acid ammonium and the crown ether oxygens. An additional conformer shows only one NH…O interaction, but has two interactions involving one of the cavity COOH moieties, one with the NH and one with the phenol OH. The increased calculated stability of the complex made from (-) 18C6TA and L-Tyr parallels its higher abundance in the mass spectrum of an isotopically labelled racemic mixture.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400880"},"PeriodicalIF":2.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638497","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

Substrate-induced strain upshot on the optical and optoelectronic properties of trilayer MoS2. 基底诱导应变对三层 MoS2 光学和光电特性的影响。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-15 DOI: 10.1002/cphc.202400829

Sourav Mondal, Durga Basak

{"title":"Substrate-induced strain upshot on the optical and optoelectronic properties of trilayer MoS2.","authors":"Sourav Mondal, Durga Basak","doi":"10.1002/cphc.202400829","DOIUrl":"https://doi.org/10.1002/cphc.202400829","url":null,"abstract":"The characteristics of 2D layered MoS2 film are highly dependent on the substrate it is grown on which leaves us privileged to achieve unique and tunable properties. In this study, trilayer MoS2 films have been grown on fused quartz, crystalline quartz (z-cut), sapphire (0001), and silicon (100) substrates. MoS2 film grows as freestanding on amorphous fused quartz, while it experiences an in-plane tensile strain on the sapphire and silicon. Unprecedentedly we show that due to a large mismatch in the lattice parameter as well as in the thermal expansion coefficient, MoS2 grows with a significant compressive strain both along both in-plane on the crystalline quartz. The developed strain causes an alteration in its electronic structure, causing a 30 meV blue shift in the photoluminescence peak and an increased band gap in addition to fewer sulphur vacancies. Comparatively, the film on sapphire having tensile strain along the in-plane exhibits more sulphur vacancies increasing the electron density. The photoresponse time, photosensitivity, and charge separation distinctly vary for the MoS2 films depending on the substrates. This study underscores the influence of substrate on MoS2 film opening further research scopes on tunable properties owing to 2D layer-substrate interactions.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400829"},"PeriodicalIF":2.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638499","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

Cation-lone pair interaction in Alkali/alkaline earth metal ion-heavier borazine analogue complexes. 碱/碱土金属离子-重硼嗪类似物配合物中的阳离子-孤对相互作用。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-11-15 DOI: 10.1002/cphc.202400869

Bapan Saha

引用次数: 0