A novel three-component radical cyclization/haloazidation of enynones, employing TMSN as the azide source and NIS (NBS or NCS) as the halogen source, has been developed under metal-free conditions for the efficient synthesis of various 1-indanones with moderate yields and acceptable / ratio. The reaction progresses through a sequence involving radical addition, 5- cyclization, and radical coupling, ultimately resulting in the formation of three new chemical bonds and a new ring in a single step. The synthetic benefits of this method have been proven by large-scale experiments and late-stage modification.
View Article and Find Full Text PDFNickel-based electrocatalysts are promising for industrial water electrolysis, but the dense hydroxyl oxide layer formed during the oxygen evolution reaction (OER) limits active sites accessibility and presents challenges in balancing structural stability with effective charge transfer. Based on this, an efficient in situ leaching strategy is proposed to construct grain boundary-rich catalyst structure with high charge transfer ability and a deep catalytic active layer reached >200-nm. Under OER conditions, stable sub-nano NiAl particles are embedded in Ni(Fe)OOH, originating from leaching out the unstable NiAl phase of the initial NiAl/NiAl alloy doped with Fe.
View Article and Find Full Text PDFWe present a Cu/PTFE electrode for the CO reduction reaction with a high coverage of *OH which facilitates both the activation of CO and the C-C coupling, leading to a faradaic efficiency for ethylene exceeding 50% at an exceptionally low potential of -246 mV RHE, with the maximum FE reaching 60.3%.
View Article and Find Full Text PDFSuitable biomaterials with seed cells have promising potential to repair bone defects. However, bone marrow mesenchymal stem cells (BMSCs), one of the most common seed cells used in tissue engineering, cannot differentiate efficiently and accurately into functional osteoblasts. In view of this, a new tissue engineering technique combined with BMSCs and scaffolds is a major task for bone defect repair.
View Article and Find Full Text PDFHydrogen obtained from electrochemical water splitting is the most promising clean energy carrier, which is hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Thus, the development of an efficient OER electrocatalyst using nonprecious 3d transition elements is desirable. Multielement synergistic effect and lattice oxygen oxidation are two well-known mechanisms to enhance the OER activity of catalysts.
View Article and Find Full Text PDFReversible solid oxide cells (rSOCs) have significant potential as efficient energy conversion and storage systems. Nevertheless, the practical application of their conventional air electrodes, such as LaSrMnO (LSM), BaSrCoFeO (BSCF), and PrBaCaCoO (PBCC), remains unsatisfactory due to interface delamination during prolonged electrochemical operation. Using micro-focusing X-ray absorption spectroscopy (µ-XAS), a decrease (increase) in the co-valence state from the electrode surface to the electrode/electrolyte interface is observed, leading to the above delamination.
View Article and Find Full Text PDFThe solid oxide electrolysis cell (SOEC) is an advanced electrochemical device with a promising future in reducing CO emissions. Currently, the insufficient oxygen evolution reaction activity in conventional anode materials severely restricts the development of electrolytic CO. Herein, the PNCO-LSC composite oxygen electrode was exploited by impregnating PrNiCoO (PNCO) on the surface of LaSrCoO (LSC) oxygen electrode.
View Article and Find Full Text PDFModulating the coordination environment of the metal active center is an effective method to boost the catalytic performances of metal-organic frameworks (MOFs) for oxygen evolution reaction (OER). However, little attention has been paid to the halogen effects on the ligands engineering. Herein, a series of MOFs X─FeNi-MOFs (X = Br, Cl, and F) is constructed with different coordination microenvironments to optimize OER activity.
View Article and Find Full Text PDFWith the rapid development of nuclear energy, problems with uranium supply chain and nuclear waste accumulation have motivated researchers to improve uranium separation methods. Here we show a paradigm for such goal based on the in-situ formation of π-f conjugated two-dimensional uranium-organic framework. After screening five π-conjugated organic ligands, we find that 1,3,5-triformylphloroglucinol would be the best one to construct uranium-organic framework, thus resulting in 100% uranium removal from both high and low concentration with the residual concentration far below the WHO drinking water standard (15 ppb), and 97% uranium capture from natural seawater (3.
View Article and Find Full Text PDFThe photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo- and radio-induced luminescence of a series of lanthanide-bearing organic-inorganic hybrids and their potential as a platform for X-ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6-di(1H-pyrazol-1-yl)isonicotinate (bppCOO) ligands affords six new materials with three distinct structures.
View Article and Find Full Text PDFProtonic ceramic fuel cells with high efficiency and low emissions exhibit high potential as next-generation sustainable energy systems. However, the practical proton conductivity of protonic ceramic electrolytes is still not satisfied due to poor membrane sintering. Here, we show that the dynamic displacement of Y adversely affects the high-temperature membrane sintering of the benchmark protonic electrolyte BaZrCeYYbO, reducing its conductivity and stability.
View Article and Find Full Text PDFCrystalline organic-inorganic hybrids, which exhibit colorimetric responses to ionizing radiation, have recently been recognized as promising alternatives to conventional X-ray dosimeters. However, X-ray-responsive organic-inorganic hybrids are scarce and the strategy to fine-tune their detection sensitivity remains elusive. Herein, an unprecedented mixed-ligand strategy is reported to modulate the X-ray detection efficacy of organic-inorganic hybrids.
View Article and Find Full Text PDFMXene-supported noble metal alloy catalysts exhibit remarkable electrocatalytic activity in various applications. However, there is no facile one-step method for synthesizing these catalysts, because the synthesis of MXenes requires a strongly oxidizing environment and the preparation of platinum nanoalloys requires a strongly reducing environment and high temperatures. Hence, achieving coupling in one step is extremely challenging.
View Article and Find Full Text PDFA novel radio-photoluminescence material featuring fluorochromic responses toward UV or X-ray irradiation has been obtained. Such a unique monomer- to excimer-based luminescence transition allows for dosimetry of ionizing radiation in a ratiometric manner. Rather than quenching the luminescence, the radiation-induced radical species of Th-105 boost the excimer emission, rendering it as a rare material possessing radical-excimers.
View Article and Find Full Text PDFActinide-bearing metal-organic frameworks (MOFs) encompass intriguing structures and properties, but the radioactivity of actinide cripples their applications. Herein, we have constructed a new thorium-based MOF () as a bifunctional platform for the adsorption and detection of radioiodine, a more radioactive fission product that can readily spread through the atmosphere in its molecular form or via solution as anionic species. The iodine capture within the framework of from both the vapor phase and the cyclohexane solution has been verified, showing that features maximum adsorption capacities () of 959 and 1046 mg/g, respectively.
View Article and Find Full Text PDFDesigning efficient catalyst for the oxygen evolution reaction (OER) is of importance for energy conversion devices. The anionic redox allows formation of O-O bonds and offers higher OER activity than the conventional metal sites. Here, we successfully prepare LiNiO with a dominant 3dL configuration (L is a hole at O 2p) under high oxygen pressure, and achieve a double ligand holes 3dL under OER since one electron removal occurs at O 2p orbitals for Ni oxides.
View Article and Find Full Text PDFMembranes with fast and selective ion transport are essential for separations and electrochemical energy conversion and storage devices. Metal-coordinated polymers are promising for fabricating ion-conducting membranes with molecular channels, however, the structures and ion transport channels remain poorly understood. Here, we reported mechanistic insights into the structures of metal-ion coordinated polybenzimidazole membranes and the preferential K transport.
View Article and Find Full Text PDFDeveloping ultraviolet (UV) radiation sensors featuring high sensitivity, ease of operation, and rapid readout is highly desired in diverse fields. However, the strategies to enhance sensitivity of UV detection remain limited particularly for photochromic materials, which show colorimetric response toward UV irradiation. Guided by our initial goal of facilitating easier handling, we formulated a viologen derivative () incorporating hydrogel-based UV sensor which not only inherits the photochromism of but also engenders an unprecedented reversible photoelectrochromic response that is absent in either or hydrogel alone.
View Article and Find Full Text PDFSimple synthetic modulation based on thorium nitrate and tris((4-carboxyl)phenylduryl)amine (HTCBPA) gives rise to a new thorium-based metal-organic framework, Th-TCBPA, which features excellent hydrolytic and thermal stabilities. Incorporating electron-rich TCBPA linkers not only endows Th-TCBPA with high adsorption capacity toward radioiodine vapor, but also makes it a luminescence sensor for the highly sensitive and selective detection of Cr(VI) anions.
View Article and Find Full Text PDFPrevious reports have confirmed that crude saponins (ginsenosides) in Panax ginseng have a preventive effect on chemotherapy-induced intestinal injury. However, the protective effects and possible mechanisms of ginsenoside Re (G-Re, a maker saponin in ginseng) against chemotherapy-induced intestinal damage have not been thoroughly studied. In this work, a series of experiments and on the intestinal toxicity caused by cisplatin have been designed to verify the improvement effect of G-Re, focusing on the levels of Wnt3a and [Formula: see text]-catenin.
View Article and Find Full Text PDFMonitoring and shielding of X-ray radiation are of paramount importance across diverse fields. However, they are frequently realized in separate protocols and a single material integrating both functions remained elusive. Herein, a hexanuclear cluster [Th (µ -OH) (µ -O) (H O) ](pba) (HCOO) (Th-pba-0D) incorporating high-Z thorium cations and 3-(pyridin-4-yl)benzoate ligands that can function as a brand-new dual-module platform for visible detection and efficient shielding of ionizing radiation is demonstrated.
View Article and Find Full Text PDFWith maximum atomic utilization, transition metal single atom catalysts (SACs) show great potential in electrochemical reduction of CO to CO. Herein, by a facile pyrolysis of zeolitic imidazolate frameworks (ZIFs) assembled with tiny amounts of metal ions, a series of metal-nitrogen-carbon (M-N-C) based SACs (M = Fe, Ni, Mn, Co and Cu), with metal single atoms decorated on a nitrogen-doped carbon support, have been precisely constructed. X-ray photoelectron spectroscopy (XPS) for M-N-C showed that the N 1s spectrum was deconvoluted into five peaks for pyridinic (∼398.
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