RESUMEN
The construction of doped molecular clusters is an intriguing way to perform bimetallic doping for electrocatalysts. However, efficiently harnessing the benefits of a doping strategy and alloy engineering to create a nanostructure for electrocatalytic application at the molecular level has consistently posed a challenge. Here we propose an in situ reconstruction strategy aimed at producing an alloy nanostructure through a pyrolysis process, originating from bowknot-like heterometallic clusters. The Schiff base, denoted as ligand L1 (o-vanillin ethylenediamine), was introduced as a precursor to coordinate Fe and Co metals, thereby yielding a heteronuclear metal cluster [(FeCo)(L1)2O]CH3CN. Subsequently, a comprehensive investigation of the in situ reconstruction process [(FeCo)(L1)2O](CH3CN) â [(FeCo)(L1)2O] â [M-O-M/M-O] [CH3+/CH3O+/H2CâN/C2H5+/C4H4+] â [FeCo/Fe3O4/Fe2O3/Co3O4][carbon layer] led to the formation of MOx/CoFe@NC-700 during the pyrolysis. This process reveals that the metals Fe and Co in the clusters undergo partly in situ evolution into FeCo alloys, resulting in the successful preparation of MOx/CoFe@NC (M = Fe, Co) nanomaterials that leverage the advantages of both doping strategies and alloy engineering. The synergistic interaction between alloy particles and metal oxides establishes active sites that contribute to the excellent oxygen evolution (OER) and hydrogen evolution (HER) catalytic behaviors. Notably, these materials exhibit outstanding OER and HER properties under alkaline conditions, with overpotentials of 191 and 88 mV for OER and HER, respectively, at 10 mA cm-2. Investigation of the in situ conversion of Schiff base bimetal clusters into alloy materials through pyrolysis offers a novel strategy for advancing electrocatalytic applications.
RESUMEN
The development of novel catalyst with high catalytic activity is important for electrochemical non-enzymatic glucose sensing. Here, iridium single-atom/nickel oxide nanoparticle/N-doped graphene nanosheet (Ir1/NiO/NG) with the loading of 1.13 wt% Ir was successfully synthesized for constructing electrochemical non-enzymatic glucose sensor for the first time. The morphology and structure of Ir1/NiO/NG were characterized by XRD, SEM, TEM, HRTEM, and XPS, and the presence of Ir SAs was confirmed by AC-HAADF-STEM. The Ir1/NiO/NG shows 65 mV lower oxidation potential and 3.3 times higher response current than Ni(OH)2/NG. In addition, Ir1/NiO/NG exhibits high sensitivity (70.09 µA mM-1 cm-2), excellent selectivity, low detection limit (2.00 µM), and great stability (91.53% current remaining after 21 days) for electrochemical non-enzymatic glucose sensing. The outstanding catalytic and sensing performance of Ir1/NiO/NG is mainly attributed to synergistic effect of Ir SAs, NiO nanoparticles, and highly conductive NG, which modulate the electronic and geometric structure of Ir1/NiO/NG. This work shows the promising potential of SACs in electrochemical sensing.
Asunto(s)
Técnicas Electroquímicas , Glucosa , Grafito , Iridio , Límite de Detección , Níquel , Níquel/química , Grafito/química , Iridio/química , Catálisis , Técnicas Electroquímicas/métodos , Glucosa/análisis , Glucosa/química , Técnicas Biosensibles/métodosRESUMEN
The development of cost-effective and highly efficient electrocatalysts is critical to help electrochemical non-enzymatic sensors achieve high performance. Here, a new class of catalyst, Ru single atoms confined on Cu nanotubes as a single-atom alloy (Ru1Cu NTs), with a unique electronic structure and property, was developed to construct a novel electrochemical non-enzymatic glucose sensor for the first time. The Ru1Cu NTs with a diameter of about 24.0 nm showed a much lower oxidation potential (0.38 V) and 9.0-fold higher response (66.5 µA) current than Cu nanowires (Cu NWs, oxidation potential 0.47 V and current 7.4 µA) for glucose electrocatalysis. Moreover, as an electrochemical non-enzymatic glucose sensor, Ru1Cu NTs not only exhibited twofold higher sensitivity (54.9 µA mM-1 cm-2) and wider linear range (0.5-8 mM) than Cu NWs, but also showed a low detection limit (5.0 µM), excellent selectivity, and great stability. According to theoretical calculation results, the outstanding catalytic and sensing performance of Ru1Cu NTs could be ascribed to the upshift of the d-band center that helped promote glucose adsorption. This work presents a new avenue for developing highly active catalysts for electrochemical non-enzymatic sensors.
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Aleaciones , Cobre , Técnicas Electroquímicas , Glucosa , Nanotubos , Rutenio , Cobre/química , Nanotubos/química , Técnicas Electroquímicas/métodos , Glucosa/análisis , Aleaciones/química , Rutenio/química , Límite de Detección , Catálisis , Técnicas Biosensibles/métodos , Oxidación-ReducciónRESUMEN
It is critical to develop high-performance electrocatalyst for electrochemical nonenzymatic glucose sensing. In this work, a single-atom Pt supported on Cu@CuO core-shell nanowires (Pt1 /Cu@CuO NWs) for electrochemical nonenzymatic glucose sensor is designed. Pt1 /Cu@CuO NWs exhibit excellent electrocatalytic oxidation toward glucose with 70 mV lower onset potential (0.131 V) and 2.4 times higher response current than Cu NWs. Sensors fabricated using Pt1 /Cu@CuO NWs also show high sensitivity (852.163 µA mM-1 cm-2 ), low detection limit (3.6 µM), wide linear range (0.01-5.18 µM), excellent selectivity, and great long-term stability. The outstanding sensing performance of Pt1 /Cu@CuO NWs, investigated by experiments and density functional theory (DFT) calculations, is attributed to the synergistic effect between Pt single atoms and Cu@CuO core-shell nanowires that generates strong binding energy of glucose on the nanowires. The work provides a new pathway for exploring highly active SACs for electrochemical nonenzymatic glucose sensor.
RESUMEN
Conventional nanomaterials in electrochemical nonenzymatic sensing face huge challenge due to their complex size-, surface-, and composition-dependent catalytic properties and low active site density. In this work, we designed a single-atom Pt supported on Ni(OH)2 nanoplates/nitrogen-doped graphene (Pt1/Ni(OH)2/NG) as the first example for constructing a single-atom catalyst based electrochemical nonenzymatic glucose sensor. The resulting Pt1/Ni(OH)2/NG exhibited a low anode peak potential of 0.48 V and high sensitivity of 220.75 µA mM-1 cm-2 toward glucose, which are 45 mV lower and 12 times higher than those of Ni(OH)2, respectively. The catalyst also showed excellent selectivity for several important interferences, short response time of 4.6 s, and high stability over 4 weeks. Experimental and density functional theory (DFT) calculated results reveal that the improved performance of Pt1/Ni(OH)2/NG could be attributed to stronger binding strength of glucose on single-atom Pt active centers and their surrounding Ni atoms, combined with fast electron transfer ability by the adding of the highly conductive NG. This research sheds light on the applications of SACs in the field of electrochemical nonenzymatic sensing.
Asunto(s)
Grafito , Nanoestructuras , Electrodos , Glucosa/química , Grafito/química , Nanoestructuras/química , Níquel/químicaRESUMEN
Terahertz focal plane array imaging methods, direct camera imaging and conventional light field imaging methods are incapable of resolving and separating layers of multilayer objects. In this paper, for the purpose of fast, high-resolution and layer-resolving imaging of multilayer structures with different reflection characteristics, a novel angular intensity filtering (AIF) method based on terahertz light-field imaging is purposed. The method utilizes the extra dimensional information from the 4D light field and the reflection characteristics of the imaging object, and the method is capable to resolve and reconstruct layers individually. The feasibility of the method is validated by experiment on both "idealized" and "practical" multilayer samples, and the advantages in performance of the method are proven by quantitative comparison with conventional methods.
RESUMEN
Layered transition metal dichalcogenide (TMD) nanomaterials are promising alternatives to platinum (Pt) for the hydrogen evolution reaction (HER). However, the family of layered TMDs is mainly limited to Group IV-VII transition metals, while the synthesis of layered TMDs based on metals from other groups still remains a challenge. Herein, we demonstrate by atomic-resolution transmission electron microscopy that hexagonal RuSe2 (h-RuSe2 ) nanosheets with a mixture of 2H and 1T phases can be obtained by a facile bottom-up colloidal synthetic approach. The obtained h-RuSe2 , which can be transformed into the thermodynamically favorable phase of cubic RuSe2 (c-RuSe2 ) only after annealing at 600 °C, exhibits Pt-like HER performance, with a fivefold turnover frequency enhancement compared to the c-RuSe2 in alkaline media. Experimental results and density functional theory (DFT) calculations reveal that the enhanced adsorption free energies of H2 O (ΔG H 2 O * ), optimized adsorption free energies of H (ΔGH* ), and increased conductivity of h-RuSe2 contribute to its superior HER activity.
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Searching for efficient, low-cost, and durable electrocatalysts toward the hydrogen evolution reaction (HER) is extremely urgent for future energy conversion systems. Herein, the colloidal synthesis of 2D tungsten-doped nickel selenide nanosheets by using Ni(acac)2 (acac=aceylacetonate), [W(CO)6 ], and selenium powder as precursors in oleylamine is reported. The introduction of tungsten is essential for the formation of 2D nanosheets. As a result, by taking the advantage of the unique layered structure and strong synergistic electronic effect between nickel, tungsten, and selenium, the as-synthesized Ni0.54 W0.26 Se nanosheets exhibit superior catalytic activity toward the HER in alkaline media, with an overpotential of 162â mV (η10 ), which is much lower than those of NiSe2 (η10 =330â mV) and WSe2 (η10 =378â mV), and higher than that of most previously reported selenide-based electrocatalysts.
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To study the telomerase activity change in patients with CML different phases, telomerase PCR-ELISA method was used. Results showed that telomerase activity of normal bone marrow cells was low. The telomerase activity in CML at any phase was higher than that in normal bone marrow (P < 0.05). The telomerase activity in accelerated and acute transformation phases was higher than that in chronic phase (P < 0.05), but there was no significant difference between accelerated phase and acute transformation phase. It was concluded that telomerase activity could be used as an useful marker for evaluating development of course and curative effect of CML.