Chemistry of Materials最新文献_第8页

Fast Lithium Ion Conduction in Arsenides Li9AlAs4 and Li9GaAs4 砷化物 Li9AlAs4 和 Li9GaAs4 中的快速锂离子传导

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-10-24 DOI: 10.1021/acs.chemmater.4c02008

Luyao Qu, Xinmiao Liang, Li Yang, Ke Xu, Youyi Lei, Kaiqin Yang, Shenhui Li, Bin Jiang, Jiwen Feng

{"title":"Fast Lithium Ion Conduction in Arsenides Li9AlAs4 and Li9GaAs4","authors":"Luyao Qu, Xinmiao Liang, Li Yang, Ke Xu, Youyi Lei, Kaiqin Yang, Shenhui Li, Bin Jiang, Jiwen Feng","doi":"10.1021/acs.chemmater.4c02008","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02008","url":null,"abstract":"Understanding the structure–property relationship in ionic conductors is crucial for developing more efficient solid-state electrolytes and improving cell architecture. Here, we present two new arsenide-based fast ion conductors, Li9AlAs4 and Li9GaAs4, and compare them with two previously reported phosphide-based superionic conductors, Li9AlP4 and Li9GaP4, to study the substitution effect of element P by As. It is established that anion substitution dramatically enhances lithium-ion mobility and conductivity. In particular, the ionic conductivity and diffusion coefficient at room temperature of Li9GaAs4 reached remarkable levels of 6.5 mS cm–1 and 2.05 × 10–11 m2 s–1, respectively, achieving an order of magnitude increase compared with Li9GaP4. Multinuclear solid-state NMR chemical shifts reveal that As3– in [TrAs4]9– (Tr = Al, Ga) has a lower negative charge density than P3– in [TrP4]9–, which leads to a smaller Coulomb force between Li+ and As3– than between Li+ and P3–. This weakened Coulomb force on lithium ions, caused by As substitution, together with an enlarged lattice volume, lowers the activation barrier and promotes Li ion conductivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

CdSe-Dot/CdS-Rod/PbS-Dot Nanocrystals by Partial Cation Exchange Reaction 通过部分阳离子交换反应制备 CdSe-Dot/CdS-Rod/PbS-Dot 纳米晶体

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c02553

Vincent Mittag, Sebastian Schüttler, Christian Strelow, Tobias Kipp, Alf Mews

{"title":"CdSe-Dot/CdS-Rod/PbS-Dot Nanocrystals by Partial Cation Exchange Reaction","authors":"Vincent Mittag, Sebastian Schüttler, Christian Strelow, Tobias Kipp, Alf Mews","doi":"10.1021/acs.chemmater.4c02553","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02553","url":null,"abstract":"Dual-emissive nanorods with fluorescence in both the visible and infrared range are prepared by a combination of a CdSe-nanocrystal-seeded growth of CdS nanorods and a successive partial Cd-to-Pb cation exchange. We show that the exchange reaction, which involves Pb halides in oleylamine, starts at the tip of the rods, leading to the formation of CdSe-dot/CdS-rod/PbS-dot nanocrystals (DRDs). Besides these DRDs, the reaction product also contains shorter nanorods and spherical quantum dots. Their fraction strongly depends on the amount of lead halide precursor and the reaction time. The reaction mechanism is investigated in detail, such that by carefully adjusting the reaction conditions, it is possible to synthesize DRDs of distinct PbS-dot sizes with yields of over 95%. The resulting DRDs are crystalline and show a CdSe-fluorescence band in the visible range at 600 nm and also a fluorescence band in the near-infrared at 1440 nm, resulting from the PbS part of the rods. The dual emission is confirmed by single-DRD spectroscopy. For that, scanning fluorescence and transmission electron microscopy imaging are correlated, and time-resolved single-photon counting experiments simultaneously in the near-infrared and visible range are performed.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A-Site Cation Chemistry in Halide Perovskites 卤化物过氧化物中的 A 位阳离子化学

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0204310.1021/acs.chemmater.4c02043

Matthew P. Hautzinger*, Willa Mihalyi-Koch and Song Jin,

{"title":"A-Site Cation Chemistry in Halide Perovskites","authors":"Matthew P. Hautzinger*, Willa Mihalyi-Koch and Song Jin, ","doi":"10.1021/acs.chemmater.4c0204310.1021/acs.chemmater.4c02043","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02043https://doi.org/10.1021/acs.chemmater.4c02043","url":null,"abstract":"Metal halide perovskites are an important class of semiconductors now being implemented as photovoltaic absorbers and explored for light emission, among other device applications. The semiconducting properties of halide perovskites are deeply intertwined with their composition and structure. Specifically the symmetry, tilting, and distortions of the metal halide octahedra impact the band structure and other optoelectronic properties. In this review, we examine the various compositions of monovalent A-site cations in three-dimensional (3D) halide perovskites AMX3 (M = divalent metal; X = halide). We focus on how the A-site cation templates the inorganic metal-halide perovskite framework, resulting in changes in the crystal structure symmetry, as well as M–X bonding parameters, summarized in a comprehensive table of AMX3 structures. The A-site cation motion, effects of alloying, and 2D Ruddlesden–Popper perovskite structures with unique A-site cations are further overviewed. Correlations are shown between these A-site cation dominated structural parameters and the resulting optoelectronic properties such as band gap. This review should serve as a reference for the A-site cation structural chemistry of metal halide perovskites and inspire continued research into less explored metal halide perovskite compositions and structures.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

CdSe-Dot/CdS-Rod/PbS-Dot Nanocrystals by Partial Cation Exchange Reaction 通过部分阳离子交换反应制备 CdSe-Dot/CdS-Rod/PbS-Dot 纳米晶体

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0255310.1021/acs.chemmater.4c02553

Vincent Mittag, Sebastian Schüttler, Christian Strelow, Tobias Kipp* and Alf Mews,

{"title":"CdSe-Dot/CdS-Rod/PbS-Dot Nanocrystals by Partial Cation Exchange Reaction","authors":"Vincent Mittag, Sebastian Schüttler, Christian Strelow, Tobias Kipp* and Alf Mews, ","doi":"10.1021/acs.chemmater.4c0255310.1021/acs.chemmater.4c02553","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02553https://doi.org/10.1021/acs.chemmater.4c02553","url":null,"abstract":"Dual-emissive nanorods with fluorescence in both the visible and infrared range are prepared by a combination of a CdSe-nanocrystal-seeded growth of CdS nanorods and a successive partial Cd-to-Pb cation exchange. We show that the exchange reaction, which involves Pb halides in oleylamine, starts at the tip of the rods, leading to the formation of CdSe-dot/CdS-rod/PbS-dot nanocrystals (DRDs). Besides these DRDs, the reaction product also contains shorter nanorods and spherical quantum dots. Their fraction strongly depends on the amount of lead halide precursor and the reaction time. The reaction mechanism is investigated in detail, such that by carefully adjusting the reaction conditions, it is possible to synthesize DRDs of distinct PbS-dot sizes with yields of over 95%. The resulting DRDs are crystalline and show a CdSe-fluorescence band in the visible range at 600 nm and also a fluorescence band in the near-infrared at 1440 nm, resulting from the PbS part of the rods. The dual emission is confirmed by single-DRD spectroscopy. For that, scanning fluorescence and transmission electron microscopy imaging are correlated, and time-resolved single-photon counting experiments simultaneously in the near-infrared and visible range are performed.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02553","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogenolysis of Polyethylene by Metal–Organic Framework Confined Single-Site Ruthenium Catalysts 金属有机框架封闭单位钌催化剂对聚乙烯的氢解作用

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0218610.1021/acs.chemmater.4c02186

Manav Chauhan, Chhaya Thadhani, Bharti Rana, Poorvi Gupta, Biplab Ghosh and Kuntal Manna*,

{"title":"Hydrogenolysis of Polyethylene by Metal–Organic Framework Confined Single-Site Ruthenium Catalysts","authors":"Manav Chauhan, Chhaya Thadhani, Bharti Rana, Poorvi Gupta, Biplab Ghosh and Kuntal Manna*, ","doi":"10.1021/acs.chemmater.4c0218610.1021/acs.chemmater.4c02186","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02186https://doi.org/10.1021/acs.chemmater.4c02186","url":null,"abstract":"Upcycling polyolefins into value-added hydrocarbons via catalytic hydrogenolysis is challenging due to poor product selectivity, random C–C bond cleavage, and the formation of volatile alkanes. We have developed two isoreticular porous aluminum metal–organic framework (MOF) node-supported mononuclear ruthenium dihydride catalysts (DUT-5-RuH2 and MIL-53-RuH2), which are efficient in the hydrogenolysis of low-density polyethylene (LDPE) at 200 °C into a narrow distribution of liquid hydrocarbons (C8-C24). By systematic tuning of the pore sizes of the MOFs, high yields of desirable liquid alkanes were afforded with varying degrees of branching, achieving 80% selectivity. DUT-5-RuH2 produced a C22-centered bell-shaped alkane distribution with a polyethylene conversion of 98%, while MIL-53-RuH2, being selective for shorter alkanes, produced a C9-centered bell-shaped alkane distribution. Based on our spectroscopic and theoretical studies, the high catalytic activity and selectivity of these MOF catalysts are primarily attributed to the stabilization of single-site mono-RuH2 species at the MOF’s nodes via active-site isolation and the confinement of the active catalytic species within porous MOFs. Theoretical calculations suggest that RuH2-mediated polyolefin C–C bond cleavage primarily occurs via turnover-limiting σ-bond metathesis. This study underscores the significance of MOFs in the rational design of heterogeneous catalysts for the efficient upcycling of plastic waste.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Defect-Triggered Reversible Phase Transformation for Boosting Electrochemical Performance of Coordination Polymers 缺陷触发可逆相变，提升配位聚合物的电化学性能

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0195710.1021/acs.chemmater.4c01957

Yixiu Xu, Chenyu Yang, Yi Man, Xinwen Dou, Xin Xiao, Qiang Xu, Qiang Ju*, Qinghua Liu* and Zhenlan Fang*,

{"title":"Defect-Triggered Reversible Phase Transformation for Boosting Electrochemical Performance of Coordination Polymers","authors":"Yixiu Xu, Chenyu Yang, Yi Man, Xinwen Dou, Xin Xiao, Qiang Xu, Qiang Ju*, Qinghua Liu* and Zhenlan Fang*, ","doi":"10.1021/acs.chemmater.4c0195710.1021/acs.chemmater.4c01957","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01957https://doi.org/10.1021/acs.chemmater.4c01957","url":null,"abstract":"Coordination polymers (CPs) hold promise for reliable and powerful supercapacitors (SCs) to overcome the energy crisis. However, CP-SCs face the daunting challenge of maintaining high pseudocapacitance after long-term charge/discharge cycling. Generally, if introducing defects exerted a positive effect on the property, eliminating defects would show a negative effect, and vice versa. Contrary to this common sense, here we demonstrate that both implanting defects and eliminating defects can significantly boost the specific capacitance of the defect-engineered CPs (DECPs), which are about 1.23 and 1.62 times that of the pristine CP, respectively, without loss of rate capability even after 10,000 charge–discharge cycles. The aqueous (A-ASC) and solid-state asymmetric supercapacitor (SS-ASC) devices based on DECPs deliver high energy densities of 80.3 and 61.5 Wh kg–1, superb power densities of 8471.0 and 8430.6 W kg–1, and long cycling lifespan of up to 2000 cycles with 92.0 and 80.0% capacity retention, respectively. Moreover, the SS-ASC exhibits excellent flexibility, verified by 99.0% maintenance of its initial capacitance when it is twisted and bent at 180°. Importantly, this work has certified that stepwise increasing/decreasing the concentration of ordered defects gradually triggered reversible phase transformation of CP from nonporous to microporous by charge–discharge cycling, in situ addition of the modulator, and postsynthetic treatment. The mechanism of forming/eliminating defects and their effects on supercapacitive performances of CP-SCs have been unprecedentedly clarified. These findings offer insight into the relationship between defective structure and electrochemical behavior for developing efficient long-cycling CP-SCs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cooperative Transport of Lithium in Disordered Li10MP2S12 (M = Sn, Si) Electrolytes for Li-Ion Batteries 用于锂离子电池的无序 Li10MP2S12（M = Sn，Si）电解质中锂的协同传输

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0179110.1021/acs.chemmater.4c01791

Vinay Maithani, Sumantra Das and Sankha Mukherjee*,

{"title":"Cooperative Transport of Lithium in Disordered Li10MP2S12 (M = Sn, Si) Electrolytes for Li-Ion Batteries","authors":"Vinay Maithani, Sumantra Das and Sankha Mukherjee*, ","doi":"10.1021/acs.chemmater.4c0179110.1021/acs.chemmater.4c01791","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01791https://doi.org/10.1021/acs.chemmater.4c01791","url":null,"abstract":"Disorder in sulfide solid-state electrolytes significantly impacts chemical bonding, affecting electrochemical properties and interface stability. Li10GeP2S12, a prominent sulfide electrolyte, is expensive and has limited interfacial stability, so substituting Ge with earth-abundant elements, such as Sn and Si, could be more practical. However, a thorough understanding of the kinetics and chemical bonding nature of Li in the Sn/Si-substituted systems is missing owing to the complexity associated with disordered sublattice in these materials. We use isothermal–isobaric ensemble Car–Parrinello molecular dynamics to evaluate configuration-dependent tracer and charged diffusivities and activation energies for lithium-ion migration in disordered configurations of Li10SiP2S12 (LSiPS) and Li10SnP2S12 (LSnPS) obtained using ensemble statistics. The study uses Li-ion probability density and maximally localized Wannier orbital analysis to determine how temperature and Sn and Si cations affect Li-ion migration. Our findings indicate that higher temperatures enhance Li-ion mobility by enabling more diffusion pathways. The disordered LSiPS and LSnPS electronic structure shows a Kohn–Sham band gap of 2.4 eV for LSiPS and 2 eV for LSnPS, of the most probable configuration across 500 configurations, suggesting a wider electrolyte window for LSiPS. Additionally, Wannier function visualizations demonstrated the significant impact of locality and temperature on the dynamic nature of bonding states of migrating Li ions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discrete Ru(Sn)6 Octahedra Encapsulated in Oxoindate Channels: RuSn6In6O16 with Highly Ordered In/Sn Sites 封装在氧化茚酸盐通道中的离散 Ru(Sn)6 八面体：具有高度有序的 In/Sn 位点的 RuSn6In6O16

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c02253

Mohammed S. Abdelbassit, Zhanghao Ren, Samuel Yick, Kai Sun, Ziyun Wang, Tilo Söhnel

{"title":"Discrete Ru(Sn)6 Octahedra Encapsulated in Oxoindate Channels: RuSn6In6O16 with Highly Ordered In/Sn Sites","authors":"Mohammed S. Abdelbassit, Zhanghao Ren, Samuel Yick, Kai Sun, Ziyun Wang, Tilo Söhnel","doi":"10.1021/acs.chemmater.4c02253","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02253","url":null,"abstract":"A new transition metal–mixed main group element cluster compound, RuSn6In6O16, was prepared via the tin-flux method. Single-crystal structure refinements show that RuSn6In6O16 crystallizes in a monoclinic crystal system with a centrosymmetric C2/m space group. It shows a unique structure type reminiscent of metal–organic framework (MOF) structures. The structure exhibits a highly positive [Ru(Sn)6]14+ metallic cluster (guest) encapsulated in an oxoindate framework (host) formed by a combination of corner- and edge-sharing InO6/InO7 polyhedra. The oxidation states were experimentally and theoretically determined to be Ru2+ and Sn2+ in the metallic cluster and In3+ in the oxide layers. The cluster shows a direct band gap like that of semiconducting materials, which was also confirmed by band structure calculations. The photoluminescence spectrum exhibits a peak at 455 nm (blue emission), which may originate from oxygen vacancies in the microcrystalline powder. This indicates that RuSn6In6O16 has the potential to be used in light-emitting diodes (LEDs) and photovoltaic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and Evaluation of Polymer-Drug Conjugates as Potential Antioxidants and Cholinesterase Inhibitors for Neurodegenerative Diseases 合成和评估聚合物-药物共轭物作为神经退行性疾病的潜在抗氧化剂和胆碱酯酶抑制剂

IF 7.2 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c0176710.1021/acs.chemmater.4c01767

Nuruddin Mahadik, Gemma A. Barron, Paul Kong Thoo Lin and Colin J. Thompson*,

{"title":"Synthesis and Evaluation of Polymer-Drug Conjugates as Potential Antioxidants and Cholinesterase Inhibitors for Neurodegenerative Diseases","authors":"Nuruddin Mahadik, Gemma A. Barron, Paul Kong Thoo Lin and Colin J. Thompson*, ","doi":"10.1021/acs.chemmater.4c0176710.1021/acs.chemmater.4c01767","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01767https://doi.org/10.1021/acs.chemmater.4c01767","url":null,"abstract":"Polymer-drug conjugates (PDCs) may offer improved water-solubility and in vitro activity of potential antioxidant and cholinesterase (ChE) inhibitor drugs compared to the drugs alone. Conjugation of these potential drugs to water-soluble polymers could increase their therapeutic efficacy. Vanillin was conjugated to poly(allylamine hydrochloride) (NM10 and NM15) and naphthalimidohexylamine (HEXNAP) was conjugated to poly(acrylic acid) (N5 and N10). The antioxidant and cholinesterase inhibitory activities of these novel PDCs were evaluated and compared with those of their respective starting materials. Additionally, in silico molecular modeling studies were conducted to explore the potential cholinesterase inhibitory mechanisms of these conjugates. NM15 (unadjusted and adjusted value) showed significantly enhanced in vitro antioxidant activity (p ≤ 0.0001) compared to vanillin. The adjusted value of N5 compared to HEXNAP showed significantly enhanced in vitro cholinesterase inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) (p ≤ 0.0001). Kinetic and molecular modeling studies revealed that N5 was a competitive inhibitor of butyrylcholinesterase and interacted with the active sites of human acetylcholinesterase and human butyrylcholinesterase enzymes. NM15 and N5 were identified as lead PDCs based on their enhanced antioxidant and cholinesterase inhibitory activity, respectively. Overall, this work demonstrates the potential use of PDCs as treatment options for neurodegenerative diseases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c01767","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogenolysis of Polyethylene by Metal–Organic Framework Confined Single-Site Ruthenium Catalysts 金属有机框架封闭单位钌催化剂对聚乙烯的氢解作用

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-10-23 DOI: 10.1021/acs.chemmater.4c02186

Manav Chauhan, Chhaya Thadhani, Bharti Rana, Poorvi Gupta, Biplab Ghosh, Kuntal Manna

{"title":"Hydrogenolysis of Polyethylene by Metal–Organic Framework Confined Single-Site Ruthenium Catalysts","authors":"Manav Chauhan, Chhaya Thadhani, Bharti Rana, Poorvi Gupta, Biplab Ghosh, Kuntal Manna","doi":"10.1021/acs.chemmater.4c02186","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02186","url":null,"abstract":"Upcycling polyolefins into value-added hydrocarbons via catalytic hydrogenolysis is challenging due to poor product selectivity, random C–C bond cleavage, and the formation of volatile alkanes. We have developed two isoreticular porous aluminum metal–organic framework (MOF) node-supported mononuclear ruthenium dihydride catalysts (DUT-5-RuH2 and MIL-53-RuH2), which are efficient in the hydrogenolysis of low-density polyethylene (LDPE) at 200 °C into a narrow distribution of liquid hydrocarbons (C8-C24). By systematic tuning of the pore sizes of the MOFs, high yields of desirable liquid alkanes were afforded with varying degrees of branching, achieving 80% selectivity. DUT-5-RuH2 produced a C22-centered bell-shaped alkane distribution with a polyethylene conversion of 98%, while MIL-53-RuH2, being selective for shorter alkanes, produced a C9-centered bell-shaped alkane distribution. Based on our spectroscopic and theoretical studies, the high catalytic activity and selectivity of these MOF catalysts are primarily attributed to the stabilization of single-site mono-RuH2 species at the MOF’s nodes via active-site isolation and the confinement of the active catalytic species within porous MOFs. Theoretical calculations suggest that RuH2-mediated polyolefin C–C bond cleavage primarily occurs via turnover-limiting σ-bond metathesis. This study underscores the significance of MOFs in the rational design of heterogeneous catalysts for the efficient upcycling of plastic waste.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0