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1.
Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co2+ and Zr4+ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe3+ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst. 相似文献
2.
A general framework for describing photofission observables of actinides at an average excitation energy below 30 MeV 下载免费PDF全文
Guan-Lin Wang Hao-Yang Lan Xiao-Ming Shi Zhi-Chao Zhu Wen Luo 《中国物理C(英文版)》2022,46(8):084102-084102-14
A reasonable prediction of photofission observables plays a paramount role in understanding the photofission process and guiding various photofission-induced applications, such as short-lived isotope production, nuclear waste disposal, and nuclear safeguards. However, the available experimental data for photofission observables are limited, and the existing models and programs have mainly been developed for neutron-induced fission processes. In this study, a general framework is proposed for characterizing the photofission observables of actinides, including the mass yield distributions (MYD) and isobaric charge distributions (ICD) of fission fragments and the multiplicity and energy distributions of prompt neutrons (np) and prompt γ rays (γp). The framework encompasses various systematic neutron models and empirical models considering the Bohr hypothesis and does not rely on the experimental data as input. These models are then validated individually against experimental data at an average excitation energy below 30 MeV, which shows the reliability and robustness of the general framework. Finally, we employ this framework to predict the characteristics of photofission fragments and the emissions of prompt particles for typical actinides including 232Th, 235, 238U and 240Pu. It is found that the 238U(γ, f) reaction is more suitable for producing neutron-rich nuclei compared to the 232Th(γ, f) reaction. In addition, the average multiplicity number of both np and γp increases with the average excitation energy. 相似文献
3.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(2):212-217
A polydentate ligand bridged by a fluorene group, namely 9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene (L), has been prepared under solvothermal conditions in acetonitrile. Crystals of the three‐dimensional metal–organic framework (MOF) poly[[[μ3‐9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene‐κ3N:N′:O]bis(methanol‐κO)(μ‐sulfato‐κ2O:O′)nickel(II)] methanol disolvate], {[Ni(SO4)(C27H24N2O2)(CH3OH)]·2CH3OH}n, (I), were obtained by the solvothermal reaction of L and NiSO4 in methanol. The ligand L forms a two‐dimensional network in the crystallographic bc plane via two groups of O—H…N hydrogen bonds and neighbouring two‐dimensional planes are completely parallel and stack to form a three‐dimensional structure. In (I), the NiII ions are linked by sulfate ions through Ni—O bonds to form inorganic chains and these Ni‐containing chains are linked into a three‐dimensional framework via Ni—O and Ni—N bonds involving the polydentate ligand L. With one of the hydroxy groups of L coordinating to the NiII atom, the torsion angle of the hydroxyethyl group changes from that of the uncoordinated molecule. In addition, the adsorption properties of (I) with carbon dioxide were investigated. 相似文献
4.
Farah Naz Bibimaryam Mousavi Zhixiong Luo Christia Jabbour Philippe M. Heynderickx Somboon Chaemchuen Francis Verpoort 《应用有机金属化学》2019,33(5)
A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity. 相似文献
5.
Yu Ye Libo Sun Chenghui Zhang Jianfeng Du Yuchuan Liu Xiaowei Song Zhiqiang Liang 《应用有机金属化学》2019,33(12)
A novel luminescent metal–organic framework ( Zn‐TCPP/BPY ) with pillared structure based on 2,3,5,6‐tetrakis(4‐carboxyphenyl)pyrazine (H4TCPP) and 4,4′‐bipyridine (BPY) has been designed and synthesized through a solvothermal reaction. The [Zn2(COO)4] paddlewheel units are linked by TCPP4? ligands to form two‐dimensional layers and further connected by BPY ligands as pillars to construct the twofold interpenetrating three‐dimensional framework. Interestingly, Zn‐TCPP/BPY possesses outstanding stability in organic solvents and water as well as maintains its structural rigidity in aqueous solutions of different pH values (3–12). After activation, Zn‐TCPP/BPY possesses permanent porosity with Brunauer–Emmett–Teller surface area of 630 m2 g–1. Remarkably, Zn‐TCPP/BPY displays excellent fluorescent property in virtue of the aggregation‐induced emission effect of the H4TCPP ligand, which can be highly active and quenched by small amounts of 2,4,6‐trinitrophenol (TNP) and Fe3+ ions. Furthermore, the detection effect of Zn‐TCPP/BPY remains basically the same even after five cycles. The excellent stability, high sensitivity, and recyclability of Zn‐TCPP/BPY make it an outstanding chemical sensor for detecting TNP and Fe3+ ions. 相似文献
6.
Tim-Oliver Knedel Dr. Esther Ricklefs Carsten Schlüsener Prof. Dr. Vlada B. Urlacher Prof. Dr. Christoph Janiak 《ChemistryOpen》2019,8(11):1337-1344
CgL1 laccase from Corynebacterium glutamicum was encapsulated into the metal-organic framework (MOF) ZIF-8 which was synthesized in a rapid enzyme friendly aqueous synthesis, the fastest in situ encapsulation of laccases reported to date. The obtained enzyme/MOF, i. e. laccase@ZIF-8 composite showed enhanced thermal (up to 70 °C) and chemical (N,N-dimethylformamide) stability, resulting in a stable heterogenous catalyst, suitable for high temperature reactions in organic solvents. Furthermore, the defined structure of ZIF-8 produced a size selective substrate specificity, so that substrates larger than the pore size were not accepted. Thereby, 2’-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) was used to verify that the enzyme is immobilized inside the MOF versus the outside surface. The enzyme@MOF composite was analyzed by atomic absorption spectroscopy (ASS) to precisely determine the enzyme loading to 2.1 wt%. 相似文献
7.
Cycloparaphenylene (CPP) shows modulated photophysical and electronic properties due to its strained structure and radially oriented π-electron system. Incorporation of CPP into metal-organic frameworks (MOFs) could transfer its extensive properties in solution to porous solids. Moreover, with the unique arrangement of the macrocycles and their interactions with the framework, emerging characteristics are anticipated. As an example of “robust dynamics”, we synthesized the first MOF structure (FDM-1001) with CPP precisely anchored to the ordered framework by employing a [8]CPP-containing linear dicarboxylate linker. Metric relationship between the dynamic macrocycles and the robust backbone creates ideal π-π interactions between them, which leads to an essentially directional arrangement of [8]CPP in the three-dimensional space. Furthermore, the MOF with [8]CPP could be successfully oxidized to generate an infinite array of radicals that show enhanced air stability compared to its molecular analogue. 相似文献
8.
Covalent organic frameworks(COFs), as a class of crystalline porous materials with periodic lattices and porous structures, have received extensive attention in the fields of gas storage and separation, energy storage, catalysis and optoelectronics and so on. However, COFs are still in their infancy in the field of nuclear waste treatment, especially for sequestration of long-live problematic radionuclides, such as 99Tc. Battle of decontamination of pertechnetate(TcO4–), a main existence of 99Tc under aerobic environments, is far from finished. In this review, recent progresses of COFs and some relative materials in the sequestration of pertechnetate, and perspective on surmounting the unmet issues are elucidated. 相似文献
9.
Non-noble bifunctional electrocatalysts with robust activity and stability toward oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are greatly significant but challenging for Zn-air batteries. Here, in situ confinement of FeNx active sites in high porosity carbon framework (FeNx/CMCC) derived from chelate of carboxymethylcellulose (CMC) and iron ions were synthesized. Particularly, construction of FeNx within porous carbon framework accelerates the electron transfer and the sufficient utilization of active centers, and then expedites the reaction kinetics of ORR and OER. As expected, the optimized FeNx/CMCC exhibits superior ORR activity with a larger half-wave potential of 0.869 V. The rechargeable Zn-air battery delivers a higher power density of 99.6 mW/cm2 and a special capacity of 781.9 mA h/gZn at 10 mA/cm2, together with excellent durability of over 335 h. Remarkably, the as-assembled solid-state battery exhibits a higher open circuit voltage (OCV) of 1.5 V, a special capacity of 709.7 mA h/gZn, as well as prolonged cycling stability (90 h). Moreover, the flexible solid-state battery displays negligible loss of electrochemical performance under various bending angles, illustrating its potential application in flexible electronic devices. 相似文献
10.
Dr. Yulia Y. Enakieva Dr. Anna A. Sinelshchikova Prof. Mikhail S. Grigoriev Prof. Vladimir V. Chernyshev Dr. Konstantin A. Kovalenko Prof. Irina A. Stenina Prof. Andrey B. Yaroslavtsev Prof. Yulia G. Gorbunova Prof. Aslan Y. Tsivadze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10552-10556
The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10−3 S cm−1 at 75 °C and 80 % relative humidity). 相似文献