IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.007

{"title":"Kinetic sieving separation of a gating macrocyclic crystal for purification of propylene","authors":"","doi":"10.1016/j.chempr.2024.06.007","DOIUrl":"10.1016/j.chempr.2024.06.007","url":null,"abstract":"<div><div>Finding an energy-efficient alternative to cryogenic distillation for the room temperature, pressure-swing-adsorptive separation of propylene/propane (C3H6/C3H8) is challenging due to their physiochemical similarity. Herein, we report a gating macrocyclic crystal facilely prepared by the recrystallization of a macrocyclic arene (i.e., naphthyl-hexnutarene), which exhibits outstanding separation capabilities for C3H6/C3H8, with a remarkable kinetic selectivity of 76.7 and fast C3H6 adsorption kinetics with a diffusional time constant of 0.1727 min−1. The achievement is attributed to the transient motions of a gating methoxy group on the macrocycle that extend toward the contracted pore apertures, effectively amplifying the subtle distinction in guest transport. Furthermore, this crystal demonstrates great potential in actual pressure swing adsorption processes, showcasing energy-saving and efficient regeneration, as evidenced by a low heat of adsorption of 15.4 kJ mol−1 for C3H6 and full recovery of adsorption capacity through dynamic vacuum at room temperature, together with merited exclusions of co-present C2H6/C2H4/CH4/CO2/N2 for C3H6 purification.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3148-3158"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Enhancing backbone organization and photovoltaic performance of M-series acceptors by using partially fluorinated side chains 通过使用部分氟化侧链增强 M 系列受体的骨架组织和光伏性能

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.005

{"title":"Enhancing backbone organization and photovoltaic performance of M-series acceptors by using partially fluorinated side chains","authors":"","doi":"10.1016/j.chempr.2024.06.005","DOIUrl":"10.1016/j.chempr.2024.06.005","url":null,"abstract":"<div><div>Side-chain fluorination of nonfullerene acceptors (NFAs) has been rarely reported to enhance their photovoltaic performance, although it may improve their backbone organization and carrier mobilities. Here, we design new partially fluorinated side chains and incorporate them into M-series NFAs, which are featured with a ladder-type heteroheptacene-cored skeleton without sp3-hybridized carbons. Compared with the traditional M-series acceptor with non-fluorinated side chains (MC7F0), the NFA with partially fluorinated side chains (MC7F3) shows down-shifted energy levels, reduced miscibility, and more importantly, improved backbone organization, thereby leading to the formation of a 3D network packing structure with enhanced carrier transport. Consequently, the MC7F3-based device exhibits a power conversion efficiency of 17.61% and an excellent fill factor of 79.48%, both of which are among the best values for all A-D-A-type NFAs reported so far. The results highlight that side-chain fluorination can efficiently enhance π-conjugated backbone organization, improve intermolecular interaction, increase electron mobilities, and boost photovoltaic performance of NFAs.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3131-3147"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Electroreduction of alkaline/natural seawater: Self-cleaning Pt/carbon cathode and on-site co-synthesis of H2 and Mg hydroxide nanoflakes 碱性/天然海水的电还原：自清洁铂/碳阴极和 H2 与氢氧化镁纳米片的现场共合成

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.018

{"title":"Electroreduction of alkaline/natural seawater: Self-cleaning Pt/carbon cathode and on-site co-synthesis of H2 and Mg hydroxide nanoflakes","authors":"","doi":"10.1016/j.chempr.2024.05.018","DOIUrl":"10.1016/j.chempr.2024.05.018","url":null,"abstract":"<div><div>Distributed coastal/offshore seawater splitting plants can facilitate H2-based economy’s global deployment. Increasingly, studies emerge mostly focusing on inhibiting anodic oxidation of halide ions. Equally tricky cathodic precipitation in natural seawater reduction (NSR) is neglected due to the use of alkaline seawater in most studies. Herein, we explore possible strategies (introducing a proton sponge to change cathodic microenvironments, breaking local OH− gradients, employing self-cleaning cathodes) to alleviate surface precipitation. We introduce a famous H2 evolution-active metal, Pt, onto a self-cleaning carbon support with H2 gas evacuation capability. Our proposed binder-free Pt/carbon cathode is more robust than many previous Pt/C cathodes for NSR. Moreover, we highlight possibilities of co-electrosynthesizing nano-sized Mg hydroxides and H2 from natural seawater. This work suggests that designs of local environments, pH gradient disruption, and/or cathode architecture-based gas/liquid flows may suppress surface precipitation. We demonstrate in detail the various issues in NSR and possible solutions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3067-3087"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141334617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Operando electrochemical NMR spectroscopy reveals a water-assisted formate formation mechanism 操作电化学核磁共振光谱揭示了水辅助甲酸盐形成机制

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.001

{"title":"Operando electrochemical NMR spectroscopy reveals a water-assisted formate formation mechanism","authors":"","doi":"10.1016/j.chempr.2024.06.001","DOIUrl":"10.1016/j.chempr.2024.06.001","url":null,"abstract":"<div><div>The affinity of oxygen (O)-bound species is a key factor in CO2 reduction (CO2R) reactions (including C1 and C2+ products), although existing experimental methods cannot quantitatively track the O atoms active within CO2R reactions in real time. Among the diversified products from CO2R reactions, the formate (HCOO−) possesses the highest profit per mole of electrons. Here, we report an operando electrochemical nuclear magnetic resonance (NMR) method, which allows to quantitatively describe the complex species containing O atoms during the electrochemical CO2R reactions. Based on Cu and bimetallic Cu-based materials (Bi2CuO4 and In2Cu2O5) systems, we found that by introducing Bi and In metal adsorption sites, the O atoms of adsorbed H2O can directly involve in the formation of HCOO− through a water-assisted mechanism (∗COOH− regeneration), thereby improving the selectivity of liquid HCOO− product mostly from 34.2% to 98%. This strategy gives valuable insights into the design of HCOO−-favored catalysts.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3114-3130"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Elucidating the role of cathode identity: Voltage-dependent reversibility of anode-free batteries 阐明阴极特性的作用：无阳极电池的电压可逆性

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.008

{"title":"Elucidating the role of cathode identity: Voltage-dependent reversibility of anode-free batteries","authors":"","doi":"10.1016/j.chempr.2024.06.008","DOIUrl":"10.1016/j.chempr.2024.06.008","url":null,"abstract":"<div><div>The cathode material in a lithium (Li) battery determines the system cost, energy density, and thermal stability. In anode-free batteries, the cathode also serves as the source of Li for electrodeposition, thus impacting the reversibility of plating and stripping. Here, we show that the reason LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes deliver lower Coulombic efficiencies than LiFePO4 (LFP) is the formation of tortuous Li deposits, acidic species in the electrolyte, and accumulation of “dead” Li0. Batteries containing an LFP cathode generate dense Li deposits that can be reversibly stripped, but Li is lost to the solid electrolyte interphase (SEI) and corrosion according to operando 7Li NMR, which seemingly “revives” dead Li0. X-ray photoelectron spectroscopy (XPS) and in situ 19F/1H NMR indicate that these differences arise because upper cutoff voltage alters electrolyte decomposition, where low-voltage LFP cells prevent anodic decomposition, ultimately mitigating the formation of protic species that proliferate upon charging NMC811.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3159-3183"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Electrocatalytic reduction of nitrogen oxide species to ammonia 电催化氧化氮还原成氨

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.006

Huimin Liu , Lichen Bai , Arno Bergmann , Beatriz Roldan Cuenya , Jingshan Luo

引用次数: 0

Bioengineering of syrbactin megasynthetases for immunoproteasome inhibitor production 用于生产免疫蛋白酶体抑制剂的西林杆菌巨合成酶生物工程

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.013

Leonard Präve , Wolfgang Kuttenlochner , Werner W.A. Tabak , Chiara Langer , Markus Kaiser , Michael Groll , Helge B. Bode

{"title":"Bioengineering of syrbactin megasynthetases for immunoproteasome inhibitor production","authors":"Leonard Präve , Wolfgang Kuttenlochner , Werner W.A. Tabak , Chiara Langer , Markus Kaiser , Michael Groll , Helge B. Bode","doi":"10.1016/j.chempr.2024.07.013","DOIUrl":"10.1016/j.chempr.2024.07.013","url":null,"abstract":"<div><div>The natural product (NP) class of syrbactins are potent proteasome inhibitors produced by hybrids of non-ribosomal peptide synthetases (NRPSs) and polyketide synthases (PKSs). Here, we describe the stepwise reassembly of an entire NRPS/PKS hybrid to produce a new syrbactin derivative by utilizing the recently described “eXchange Unit between Thiolation domains” (XUTs) approach. Remarkably, XUT-based engineering allowed the direct assembly of PKS and NRPS modules to introduce an α,β-unsaturated Michael system in a macrolactam moiety, which represents the inhibitory warhead of syrbactins. The novel derivative was produced in E. coli, isolated, and examined for its ability to inhibit yeast (yCP), human constitutive (cCP), and immunoproteasome (iCP). The engineered NP maintained the inhibitory activities of the syrbactin class but, due to rational modifications, inhibited iCP most strongly. Moreover, analysis of the crystal structure of yCP in complex with the derivative revealed further design strategies for even more specific iCP inhibition.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3212-3223"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141998757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Promoting stimuli-responsive motion in soft matter by host-guest interactions 通过主客体相互作用促进软物质的刺激响应运动

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.016

引用次数: 0

Metal-cluster-powered ultramicropore alliance in pore-space-partitioned metal-organic frameworks for benchmark one-step ethylene purification 孔隙空间分区金属有机框架中的金属簇驱动超微孔联盟，实现基准一步法乙烯纯化

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.011

Shu-Yi Li, Shu-Cong Fan, Peng Zhang, Wen-Yu Yuan, Ying Wang, Quan-Guo Zhai

引用次数: 0

Post-synthetic tuning of metal coordination on entangled scaffolds 缠结支架上金属配位的合成后调整

IF 19.1 1区化学