ChemPlusChem最新文献

Why Including Solvation is Paramount: First-Principles Calculations of Electrochemical CO2 Reduction to CO on a Cu Electrocatalyst. 为什么溶解至关重要？在铜电催化剂上将 CO2 还原成 CO 的电化学第一原理计算。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-19 DOI: 10.1002/cplu.202400346

Reza Gholizadeh, Matic Pavlin, Blaz Likozar, Matej Huš

{"title":"Why Including Solvation is Paramount: First-Principles Calculations of Electrochemical CO2 Reduction to CO on a Cu Electrocatalyst.","authors":"Reza Gholizadeh, Matic Pavlin, Blaz Likozar, Matej Huš","doi":"10.1002/cplu.202400346","DOIUrl":"https://doi.org/10.1002/cplu.202400346","url":null,"abstract":"Electrochemical reduction reaction of CO2 (eCO2RR) to produce valuable chemicals offers an attractive strategy to solve energy and environmental problems simultaneously. We have mapped out entire reaction pathways of eCO2RR to CO on Cu(100), including all intermediates and transition states using first-principles simulations. To accurately account for the solvent effect, the reaction was investigated with and without explicit water molecules, highlighting the limitations of the often (mis)used vacuum reaction pathway simplification. The results show that the reduction reaction was initiated under neutral pH conditions at an applied potential of -0.11 V (RHE, reversible hydrogen electrode) and all elementary reactions were thermodynamically favorable, while an applied potential of -1.24 V is required to ensure that all reactions exhibit spontaneous behavior. Detailed analysis revealed that solvation significantly influences the stability of the adsorbates and intermediates. Its inclusion notably alters the calculated reaction kinetics and energetic parameters by lowering the barrier energies and Gibbs free energies of all reactions. CO production proceeded mainly via the COOH* pathway (CO2-->trans-COOH*-->cis-COOH*-->CO*+OH*-->CO*-->CO). The use of water as a more sustainable and cost-effective solvent is compared to other options such as organic solvents, ionic liquids and mixed solvent systems, which are less sustainable and more expensive.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400346"},"PeriodicalIF":3.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674658","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Modelling Lithium-ion Transport Properties in Sulfoxides and Sulfones with Polarizable Molecular Dynamics and NMR Spectroscopy. 利用可极化分子动力学和核磁共振波谱模拟氧化硫和砜中的锂离子传输特性。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-19 DOI: 10.1002/cplu.202400629

Vanessa Piacentini, Cataldo Simari, Emanuela Mangiacapre, Isabella Nicotera, Sergio Brutti, Adriano Pierini, Enrico Bodo

引用次数: 0

Bipyridyl Functionalized NHC-Sulfenyl, Selenenyl Cations; Potential Species for Alkylation Reactions and Ligands in Copper(I) Catalysis. 双吡啶基功能化 NHC-亚磺酰基和亚硒酰基阳离子；烷基化反应的潜在物种和铜（I）催化的配体。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-18 DOI: 10.1002/cplu.202400623

Bhagyashree Das, Amiya Kumar Sahoo, Maksood Alam, Subhra Jyoti Panda, Chandra Shekhar Purohit, Adinarayana Doddi

{"title":"Bipyridyl Functionalized NHC-Sulfenyl, Selenenyl Cations; Potential Species for Alkylation Reactions and Ligands in Copper(I) Catalysis.","authors":"Bhagyashree Das, Amiya Kumar Sahoo, Maksood Alam, Subhra Jyoti Panda, Chandra Shekhar Purohit, Adinarayana Doddi","doi":"10.1002/cplu.202400623","DOIUrl":"10.1002/cplu.202400623","url":null,"abstract":"Reactions of bipyridyl-functionalized imidazole-thiones and selones with MeX (X = I, OTf) afforded sulfenyl and selenenyl cations [(NNC)EMe]X (2/3, E = S, Se). Further reactions of these main-group cations with [Cu(CH3CN)4]BF4, Cu(OTf) furnished dicationic [{Cu(µ-I)(NNC)EMe}2][Y]2 (5/6, Y = BF4, OTf) and tricationic copper(I) complexes [Cu{(NNC)EMe}2](OTf)2BF4 (7a/7b) when employed [(NNC)EMe]I and [(NNC)EMe]OTf respectively. All these cationic complexes were characterized by various spectroscopic techniques, including X-ray diffraction analysis. The solid-state structures revealed novel bonding modes of the cations. The cationic nature of new complexes was analyzed by the 77Se NMR spectroscopy, which indicated different electronic environments around the selenium centers. The cations [(NNC)EMe]X (X= I, OTf), and (NNC)SMe bearing copper complex [{Cu(µ-I)(NNC)EMe}2][Y]2 proved as potential candidates for alkylation of various Lewis bases and as molecular catalyst in aldehyde-alkyne-amine coupling reactions, respectively. The latter catalytic reactions yielded a range of three-component products in good to excellent yields with low catalyst loading under solvent-free conditions, which demonstrate the potential utility of group-16 cations as ancillary ligands in homogeneous catalysis.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400623"},"PeriodicalIF":3.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Thermoresponsive Polymers as Viscosity Modifiers: Innovative Nanoarchitectures as Lubricant Additives. 作为粘度调节剂的热致伸缩性聚合物：作为润滑油添加剂的创新纳米结构。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-18 DOI: 10.1002/cplu.202400611

Raffaele Carfora, Marcello Notari, Giulio Assanelli, Sara Caramia, Andrea Nitti, Dario Pasini

{"title":"Thermoresponsive Polymers as Viscosity Modifiers: Innovative Nanoarchitectures as Lubricant Additives.","authors":"Raffaele Carfora, Marcello Notari, Giulio Assanelli, Sara Caramia, Andrea Nitti, Dario Pasini","doi":"10.1002/cplu.202400611","DOIUrl":"https://doi.org/10.1002/cplu.202400611","url":null,"abstract":"The world of lubricants is driven by the constant pursuit of improved performance in response of the requests of new engine generations. Engine oils play a critical role as lubricants in mitigating wear, reducing friction and ensuring optimal engine operation under diverse conditions. Modern commercial engine oils are complex formulations, comprising of a base oil, generally coming from petroleum sources, formulated with specific, important additives able to optimize the viscosity, thickening and shear stress in the operating temperature range. Such additives are produced in the thousand tons per year scale range. The most important class of additives for modern lubrication is made of organic polymers with variable architectures and topologies, generally referred as \"viscosity modifiers\" (VMs): they act as \"moderators\" of viscosity at different working temperatures. The tremendous advances in polymer science have been reflected in the realm of VMs, allowing the commercialization of products obtained by controlled polymerization techniques, and the experimentation of a broad variety of different macromolecular architectures and topologies as VMs. In this review we introduce the reader, together with the basic principles of viscosity modification and thermal-dependent rheological response, to the fascinating chemistry towards the improvement of VMs, through optimization of macromolecular design and architecture.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400611"},"PeriodicalIF":3.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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: Excited Charge Transfer Promoted Electron Transfer in all Perylenediimide Derived, Wide-Band Capturing Conjugates: A Mimicry of the Early Events of Natural Photosynthesis (ChemPlusChem 11/2024) 封面：所有派生过二亚胺宽带捕获共轭物中的受激电荷转移促进了电子转移：模仿自然光合作用的早期过程（ChemPlusChem 11/2024）

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-17 DOI: 10.1002/cplu.202481101

Dr. Ana M. Gutiérrez-Vílchez, Chamari V. Ileperuma, Valeria Navarro-Pérez, Prof. Dr. Paul A. Karr, Prof. Dr. Fernando Fernández-Lázaro, Prof. Dr. Francis D'Souza

引用次数: 0

Cover Feature: Amino-Functionalizing Ce-Based MOF UiO-66 for Enhanced CO2 Adsorption and Selectivity (ChemPlusChem 11/2024) 封面专题：胺官能化 Ce 基 MOF UiO-66 增强二氧化碳吸附性和选择性（ChemPlusChem 11/2024）

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-17 DOI: 10.1002/cplu.202481103

John Senith Ravishan Fernando, Shivani S. Asaithambi, Sachin Maruti Chavan

引用次数: 0

Cover Feature: Production of Acetylene from Viable Feedstock: Promising Recent Approaches (ChemPlusChem 11/2024) 封面专题：利用可行原料生产乙炔：前景广阔的最新方法（ChemPlusChem 11/2024）

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-17 DOI: 10.1002/cplu.202481102

Dr. Yulia V. Gyrdymova, Andrei N. Lebedev, Prof. Yan-Jun Du, Dr. Konstantin S. Rodygin

引用次数: 0

Green Synthesis of Urea from Carbon Dioxide and Ammonia Catalyzed by Ultraporous Permanently Polarized Hydroxyapatite. 超多孔永久极化羟基磷灰石催化二氧化碳和氨气合成尿素的绿色方法。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-14 DOI: 10.1002/cplu.202400705

Marc Arnau, Júlia Sanz, Pau Turon, Carlos Alemán, Jordi Sans

{"title":"Green Synthesis of Urea from Carbon Dioxide and Ammonia Catalyzed by Ultraporous Permanently Polarized Hydroxyapatite.","authors":"Marc Arnau, Júlia Sanz, Pau Turon, Carlos Alemán, Jordi Sans","doi":"10.1002/cplu.202400705","DOIUrl":"https://doi.org/10.1002/cplu.202400705","url":null,"abstract":"The sustainable synthesis of urea from ammonia (NH3) and carbon dioxide (CO2) using ultraporous permanently polarized hydroxyapatite (upp-HAp) as catalyst has been explored as an advantageous CO2-revalorization strategy. As the simultaneous activation of N2 and CO2 (single-step) demands an increase of the reaction conditions, we have re-visited the industrial two-step Bazarov reaction. upp-HAp has been designed as a stable multifunctional catalyst capable of promoting both CO2 and NH3 adsorption for their subsequent C-N bond formation. Herein we report the synthesis of 1 mmol/gcat of urea with a selectivity of 97% under strictly mild conditions (95-120 ºC and 1 bar of CO2; without applying any electrical currents or UV irradiation) which represents an efficiency of ~2% and ~30% with respect to the NH3 and CO2 content, respectively. The study of the NH3 content, products adsorbed in the catalyst, presence of intermediates and temperature of the reaction allows unveiling the great potential of upp-HAp as a green catalyst for sustainable Bazarov reactions. Results suggest that the double-step approach could be more advantageous for both synthesizing urea and as a CO2-revalorization strategy, which in turn promotes the development of specific technologies for the independent synthesis of green NH3.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400705"},"PeriodicalIF":3.0,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Solvothermal Synthesis of Medium-Entropy Oxide Spheres for Thermocatalytic Conversion of CO2 to Methanol. 溶热合成中等熵氧化物球体，用于热催化二氧化碳转化为甲醇。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-13 DOI: 10.1002/cplu.202400691

Monika Mielniczuk, Amy Knorpp, Rishabh Shukla, Rolf Erni, Dariusz Kata, Thomas Graule, Ewa Drożdż, Michael Stuer

{"title":"Solvothermal Synthesis of Medium-Entropy Oxide Spheres for Thermocatalytic Conversion of CO2 to Methanol.","authors":"Monika Mielniczuk, Amy Knorpp, Rishabh Shukla, Rolf Erni, Dariusz Kata, Thomas Graule, Ewa Drożdż, Michael Stuer","doi":"10.1002/cplu.202400691","DOIUrl":"https://doi.org/10.1002/cplu.202400691","url":null,"abstract":"New chemical compositions and structures for medium- and high-entropy oxides (HEOs) currently represent a promising new avenue in materials research for a wide range of applications including catalysis, energy storage, and ceramics. To speed up further development, synthesis methods for multicationic oxides are needed for controlling features like morphology, porosity, and chemical compositions. In this work, mesoporous spinel oxide spheres with five cations are synthesized using solvothermal synthesis techniques. The targeted chemistry included Co, Al, Fe, and Cr as the first four cations, where the fifth cation was varied by increasing cation radii (Ga, In, Yb, Ho, or Ce). After calcination, all as-synthesized precursors led to mesoporous oxide spheres with spinel oxide structures. In order to demonstrate an example of applicability for targeting different M3+ cations, the sample containing Co, Al, Fe, Cr, and In was tested in a model reaction of thermocatalytic CO2 hydrogenation and is shown to be active with a preference to methanol formation (58% selectivity, 7.8% conversion at 300 °C). The synthesis of multicationic mesoporous spheres appears to be quite flexible in terms of possible M3+ cations compositions and is a potential material to combine targeted chemistry for applications like catalysis.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400691"},"PeriodicalIF":3.0,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Optimization across-the-Board: Centro-Arylated Push-Pull Tetraene Chromophores and Guest-Host Polymers for Electro-Optics. 全面优化：中心芳基推挽四烯色团和用于电光学的客座聚合物。

IF 3 4区化学

ChemPlusChem Pub Date : 2024-11-12 DOI: 10.1002/cplu.202400551

Di Zhang, Jingdong Luo

{"title":"Optimization across-the-Board: Centro-Arylated Push-Pull Tetraene Chromophores and Guest-Host Polymers for Electro-Optics.","authors":"Di Zhang, Jingdong Luo","doi":"10.1002/cplu.202400551","DOIUrl":"https://doi.org/10.1002/cplu.202400551","url":null,"abstract":"The research and development of push-pull tetraene chromophores (PPT-phores) have contributed greatly to the field of organic electro-optic (EO) materials and devices since the inauguration of CLD-1 in 2001. This study is thus a systematic contribution to synthesize and characterize a series of centro-arylated PPT-phores based on strong electron-donating tetrahydroquinolinyl groups and variable strong electron-accepting tricyanofuran derivatives. In particular, we report the crystallographic data to show various packing modes of these PPT-phores with detailed information about bond length alternation and intermolecular interactions, the optical absorption edges of guest-host polymers by the Tauc model, and the anisotropy and dispersion of Pockels tensors for the poled polymers by attenuated total reflection spectroscopy. Such analyses have not been addressed to any significant extent previously and are fundamentally important to the future development of PPT-phore-based EO materials and devices. The poled films of several centro-arylated PPT-phores in polycarbonates exhibited large EO activities, excellent thermal stability, and tunable optical transparency at the telecom O- and C-band. The study demonstrates the effectiveness of π-bridge centro-arylation enabled by molecular shape modification and rigidity enhancement, over the relatively flexible and labile thioether or alkoxy groups, in rational design of hyperpolarizable PPT-phores for high-performance EO polymers.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400551"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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