ChemSusChem最新文献_第9页

Determination of pK_a Values of C-H Bonds in Polar Fluorinated Arenes Referred to a New CF₃SO₂-Substituted Anchor Compound. 测定极性氟化烷中 C-H 键的 pKa 值，涉及一种新的 CF3SO2 取代锚化合物。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-20 DOI: 10.1002/cssc.202402041

Xiangmei Kong, Yunfei Liang, Zhenbo Guo, Tianxing Lin, Shan Liu, Zhiyi Liu, Tianfei Liu, Jin-Pei Cheng

{"title":"Determination of pKa Values of C-H Bonds in Polar Fluorinated Arenes Referred to a New CF3SO2-Substituted Anchor Compound.","authors":"Xiangmei Kong, Yunfei Liang, Zhenbo Guo, Tianxing Lin, Shan Liu, Zhiyi Liu, Tianfei Liu, Jin-Pei Cheng","doi":"10.1002/cssc.202402041","DOIUrl":"10.1002/cssc.202402041","url":null,"abstract":"pKa values of C-H bonds remain unreported and challenging in fluorous solvents because of these solvents' unique physicochemical properties, although they have been measured, theorized and predicted successfully in water and common organic solvents. Herein, a new CF3SO2-substituted anchor compound designed for matching the physicochemical properties of polar fluorinated arenes is synthesized. Its self-dissociation constants in these solvents are used as bases for experimentally determining the pKa values of 36 C-H compounds in them. These experimentally determined pKa values exhibit excellent linear free-energy relationships and correlate well with their corresponding DFT-calculated values. These data indicate that the polar fluorinated arenes are thermodynamically more favorable for deprotonation of ketone derivatives than acetonitrile as reaction media, resulting in enhanced deprotonation-promoted CO2 fixation. The pKa values determined in this work can be used as an important guidance tool for reactions involving the formation and cleavage of C-H bonds in polar fluorinated arenes.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402041"},"PeriodicalIF":7.5,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Ni/PiNe Heterogeneous Catalyst from Biomass Waste: Low-Loading, Ligand-Free Suzuki-Miyaura Cross-Coupling. 从生物质废弃物中提取的 Ni/PiNe 异构催化剂：低负载、无配体的 Suzukii-Miyaura 交叉偶联。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-19 DOI: 10.1002/cssc.202402011

Federica Valentini, Shaomin Chen, Giulia Brufani, Yanlong Gu, Luigi Vaccaro

引用次数: 0

Elucidating 'Transfer-Lithiation' from Graphite to Si within Composite Anodes during Pre-Lithiation and Regular Charging. 阐明复合阳极在预锂化和常规充电过程中从石墨到硅的 "转移锂化"。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-19 DOI: 10.1002/cssc.202401290

Lars Frankenstein, Pascal Jan Glomb, Marvin Mohrhardt, Steffen Böckmann, Leon Focks, Aurora Gomez-Martin, Tobias Placke, Michael Ryan Hansen, Martin Winter, Johannes Kasnatscheew

{"title":"Elucidating 'Transfer-Lithiation' from Graphite to Si within Composite Anodes during Pre-Lithiation and Regular Charging.","authors":"Lars Frankenstein, Pascal Jan Glomb, Marvin Mohrhardt, Steffen Böckmann, Leon Focks, Aurora Gomez-Martin, Tobias Placke, Michael Ryan Hansen, Martin Winter, Johannes Kasnatscheew","doi":"10.1002/cssc.202401290","DOIUrl":"10.1002/cssc.202401290","url":null,"abstract":"Si-based anodes can increase specific energy and energy density of Li ion batteries. However, the volume-induced material stress and capacity loss necessitates only a partial Si utilization within composite anodes, typically with state-of-the-art graphite, so called Si/Gr composites. In this work, various Si nanowires (SiNWs), a promising Si architecture for these composites, are investigated and modified via pre-lithiation. Though, charged pre-lithiated anodes show potentials below 0 V vs. Li|Li+ in the initial cycles, they do not show indications for metallic Li, which is likely a hint for a triggered surface Li depletion in course of a continuous \"transfer-lithiation\" from lithiated Gr to Si, which is indicated by decreasing LiC6 and increasing LixSiy signals via nuclear magnetic resonance (NMR), X-ray diffraction (XRD) as well as shifts in capacities of respective voltage plateaus during discharge after storage. A relevant contribution of self-discharge is unlikely as shown by a stable open-circuit-voltage during storage in charged state and similar subsequent discharge capacities, being consequently a hint for an intra-electrode capacity shift. The process of transfer lithiation is finally validated via solid-state 7Li NMR for varied Si morphology, i. e., amorphous and crystalline, as well as during pre-lithiation with passivated lithium metal powder (PLMP).","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401290"},"PeriodicalIF":7.5,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Conceptualizing Surface-Like Diffusion for Ultrafast Ionic Conduction in Solid-State Materials. 固态材料中超高速离子传导的类表面扩散概念化。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-19 DOI: 10.1002/cssc.202401886

Jingxi Zhang, Yanhao Dong, Chang-An Wang

{"title":"Conceptualizing Surface-Like Diffusion for Ultrafast Ionic Conduction in Solid-State Materials.","authors":"Jingxi Zhang, Yanhao Dong, Chang-An Wang","doi":"10.1002/cssc.202401886","DOIUrl":"10.1002/cssc.202401886","url":null,"abstract":"Surface-like diffusion is a recently proposed concept to explain the mechanism of ultrafast ionic conduction in high-rate oxide (e. g., niobium oxides and their alloys with TiO2 and WO3) and framework materials (e. g., Prussian blue analogs). This perspective seeks to illustrate the structural origin, theoretical foundation, and experimental evidences of surface-like diffusion. Unlike classical lattice diffusion, which typically involves ionic hopping between adjacent interstitial sites in solids, surface-like diffusion occurs when ions-that are significantly smaller than the interstitials-migrate along the off-center path in the diffusion channel. This mechanism results in an exceptionally low activation energy (Ea) down to 0.2 eV, which is crucial for achieving high-rate performance in electrochemical devices such as lithium-ion and sodium-ion batteries. This concept review also discusses the criteria to identify materials with potential surface-like diffusion and outlines theoretical and experimental tools to capture such phenomenon. Several candidates for further investigation are proposed based on the current understanding of the mechanism.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401886"},"PeriodicalIF":7.5,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Boron Doping Induced Strong Anchor Effect Between Bimetal NiCo Alloy and Carbon Support for Efficient Electrocatalytic Nitrate Reduction to Ammonia. 硼掺杂诱导双金属镍钴合金与碳支撑之间产生强烈的锚定效应，从而实现高效电催化硝酸盐还原成氨。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202401979

Meng Zhang, Xuetao Cheng, Yun Duan, Junxiang Chen, Yan-Qin Wang

引用次数: 0

Methanol Activation: Strategies for Utilization of Methanol as C1 Building Block in Sustainable Organic Synthesis. 甲醇活化：在可持续有机合成中利用甲醇作为 C1 构件的策略。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202401974

Hung-Vu Tran, Tuan Thanh Dang, Nguyen Hoang Nguyen, Huyen Thu Tran, Dung Tien Nguyen, Dang Van Do, Thanh Son Le, Thuong Hanh Ngo, Yawa K E Late, Prince Nana Amaniampong, Eugene Fletcher, Tran Quang Hung, Yuran Cheng, Tuan-Khoa Nguyen, Tuan Sang Tran, Jun Zhang, Hongjie An, Nam-Trung Nguyen, Quang Thang Trinh

{"title":"Methanol Activation: Strategies for Utilization of Methanol as C1 Building Block in Sustainable Organic Synthesis.","authors":"Hung-Vu Tran, Tuan Thanh Dang, Nguyen Hoang Nguyen, Huyen Thu Tran, Dung Tien Nguyen, Dang Van Do, Thanh Son Le, Thuong Hanh Ngo, Yawa K E Late, Prince Nana Amaniampong, Eugene Fletcher, Tran Quang Hung, Yuran Cheng, Tuan-Khoa Nguyen, Tuan Sang Tran, Jun Zhang, Hongjie An, Nam-Trung Nguyen, Quang Thang Trinh","doi":"10.1002/cssc.202401974","DOIUrl":"10.1002/cssc.202401974","url":null,"abstract":"The development of efficient and sustainable chemical processes which use greener reagents and solvents, currently play an important role in current research. Methanol, a cheap and readily available resource from chemical industry, could be activated by transition metal catalysts. This review focuses in covering the recent five-years literature and provides a systematic summary of strategies for methanol activation and the use in organic chemistry. Based on these strategies, many new synthetic methods have been developed for methanol utilization as the C1 building block in methylation, hydromethylation, aminomethylation, formylation reactions, as well as the syntheses of urea derivatives and heterocycles. The achievements, synthetic applications, limitations, some advanced approaches, and future perspectives of the methanol activation methodologies have been described in this review.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401974"},"PeriodicalIF":7.5,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Enhancement of Selective Catalytic Oxidation of Lignin β-O-4 Bond via Orbital Modulation and Surface Lattice Reconstruction. 通过轨道调节和表面晶格重构增强木质素 β-O-4 键的选择性催化氧化作用

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202402194

Haonan Chen, Baolong Qin, Qi Zhang, Xiaohong Hu, Longlong Ma, Xinghua Zhang, Zhiyuan Tang, Lungang Chen

{"title":"Enhancement of Selective Catalytic Oxidation of Lignin β-O-4 Bond via Orbital Modulation and Surface Lattice Reconstruction.","authors":"Haonan Chen, Baolong Qin, Qi Zhang, Xiaohong Hu, Longlong Ma, Xinghua Zhang, Zhiyuan Tang, Lungang Chen","doi":"10.1002/cssc.202402194","DOIUrl":"10.1002/cssc.202402194","url":null,"abstract":"The orbital modulation and surface lattice reconstruction represent an effective strategy to regulate the interaction between catalyst interface sites and intermediates, thereby enhancing catalytic activity and selectivity. In this study, the crystal surface of Au-K/CeO2 catalyst can undergo reversible transformation by tuning the coordination environment of Ce, which enables the activation of the Cβ-H bond and the oxidative cleavage of the Cβ-O and Cα-Cβ bonds, leading to the cleavage of 2-phenoxy-1-phenylethanol. The t2g orbitals of Au 5d hybridize with the 2p orbitals of lattice oxygen in CeO2 via π-coordination, modulating the coordination environment of Ce 4 f and reconstructing the lattice oxygen in the CeO2 framework, as well as increasing the oxygen vacancies. The interface sites formed by the synergy between Au clusters in the reconstructed Ce-OL1-Au structure and doped K play dual roles. On the one hand, it activates the Cβ-H bond, facilitating the enolization of the pre-oxidized 2-phenoxy-1-phenylethanone. On the other hand, through single-electron transfer involving Ce3+ 4f1 and the adsorption by oxygen vacancies, it enhances the oxidative cleavage of the Cβ-O and Cα-Cβ bonds. This study elucidates the complex mechanistic roles of the structure and properties of Au-K/CeO2 catalyst in the selective catalytic oxidation of lignin β-O-4 bond.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402194"},"PeriodicalIF":7.5,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Allylation and Thermosetting of Acetosolv Wheat Straw Lignin. 乙缩醛小麦秸秆木质素的烯丙基化和热固性。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202402051

Alessio Truncali, Davide Di Francesco, Cristiana Margarita, Iuliana Ribca, Louise Brandt, Benedikt Sochor, Stephan V Roth, Mats Johansson, Helena Lundberg

引用次数: 0

Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to α, β Unsaturated Ketones and Aldehydes. 利用深共晶溶剂对 α、β 不饱和酮和醛进行区域选择性极性加成。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202402083

Andrew W J Platten, Iva Manasi, Mario Campana, Karen J Edler, Eva Hevia

{"title":"Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to α, β Unsaturated Ketones and Aldehydes.","authors":"Andrew W J Platten, Iva Manasi, Mario Campana, Karen J Edler, Eva Hevia","doi":"10.1002/cssc.202402083","DOIUrl":"10.1002/cssc.202402083","url":null,"abstract":"Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to α,β-unsaturated ketones and aldehydes using the deep eutectic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1 : 2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the bulk concentration, although the interfacial chalcone concentration is still relatively low in this system. The influence of aggregation of the organometallic reagent in the organic solvent employed has also been evaluated, revealing the importance of achieving a balance between activation (via de-aggregation) and stability (to avoid its decomposition in the DES). This DES approach has been successfully extended to double additions to α,β-unsaturated esters and for one pot sequential 1,4 and 1,2 additions to ketones, providing a new entry point to a range of tertiary-alcohols, minimising the use of organic solvents and avoiding intermediate time-consuming purification steps.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402083"},"PeriodicalIF":7.5,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Cerium Dioxide-Induced Abundant Cu⁺/Cu⁰ Sites for Electrocatalytic Reduction of Carbon Dioxide to C₂₊ Products. 二氧化铈诱导丰富的 Cu+/Cu0 位点，用于电催化将二氧化碳还原为 C2+ 产物。

IF 7.5 2区化学

ChemSusChem Pub Date : 2024-11-18 DOI: 10.1002/cssc.202402097

Yuwen Wang, Jiajun Wang, Shuang Liu, Xuan Zhang, Lin Jin, Lanlan Feng, Demeng Kong, Chenxi Zhang, Yajuan Wei, Jingbo Zhang

{"title":"Cerium Dioxide-Induced Abundant Cu+/Cu0 Sites for Electrocatalytic Reduction of Carbon Dioxide to C2+ Products.","authors":"Yuwen Wang, Jiajun Wang, Shuang Liu, Xuan Zhang, Lin Jin, Lanlan Feng, Demeng Kong, Chenxi Zhang, Yajuan Wei, Jingbo Zhang","doi":"10.1002/cssc.202402097","DOIUrl":"10.1002/cssc.202402097","url":null,"abstract":"In recent years, the electrochemical reduction of carbon dioxide (CO2RR) has made many advances in C2+ production. Cu+/Cu0 site is beneficial for C-C coupling process, but the oxidation state of copper cannot be well maintained during the reaction process, resulting in a decrease in catalyst activity. Based on this consideration, in this work, transition metal oxide CeO2 with a hollow cube structure and oxygen vacancies was introduced to stabilize and increase Cu+/Cu0 active sites (Ce1Cu2). The catalyst exhibits excellent CO2RR performance, with FEC2+ achieving 73.52 % and jC2+ >280 mA/cm2 at 1.26 V (vs. RHE). Ethanol is the main C2+ product and FEethanol reaches 39 % at 1.26 V. The experimental results indicate that the presence of CeO2 provides a large number of oxygen vacancies and forming Cu+-O2--Ce4+ structure by the strong interaction of CeO2 and Cu NPs. The structure of Cu+-O2--Ce4+ and abundant oxygen vacancies lay a good foundation for the CO2 adsorption. Moreover, it increases the content of Cu+/Cu0 sites, effectively inhibiting hydrogen evolution reaction, promoting the C-C coupling interaction, thereby facilitating the generation of C2+ products. The DFT theoretical calculation further demonstrates that Ce1Cu2 is more inclined towards the ethanol pathway, confirming its high selectivity for ethanol.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402097"},"PeriodicalIF":7.5,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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