- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Rational design of manganese cobalt phosphide with yolk‐shell structure for overall water splitting
摘要： The development of low cost, earth-abundant and efficient catalysts for overall water splitting, involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), attracts tremendous attention in recent years. Herein, this work reports the preparation of Mn-Co phosphide (Mn-Co-P) bifunctional catalysts with a yolk-shell structure by a facile hydrothermal route. The as-prepared catalysts exhibit excellent catalytic activity with low overpotentials of 66 mV at 10 mA cm-2 for HER and 355 mV at 50 mA cm-2 for OER in 1 M KOH, along with outstanding stability. More importantly, the cell voltage of 1.74 V can achieve the current density of 10 mA cm-2 when assembled as an electrolyzer for overall water splitting. Such superior performance makes the Mn-Co-P being a promising candidate to replace Pt-based noble metal catalysts for electrocatalytic applications.
关键词： yolk-shell structure,electrochemistry,Mn-Co phosphide,overall water splitting,bifunctional catalyst
更新于2025-11-21 11:01:37
-
Monitoring plasmonic hot-carrier chemical reactions at the single particle level
摘要： Plasmon excitation in metal nanoparticles triggers the generation of highly energetic charge carriers that - properly manipulated and exploited - can mediate chemical reactions. Single-particle techniques are key to unearth the underlying mechanisms of hot-carrier generation, transport and injection as well as to disentangle the role of the temperature increase and the enhanced near-field at the nanoparticle-molecule interface. Gaining a nanoscopic insight of these processes and their interplay could aid in the rational design of plasmonic photocatalysts. Here, we present three different approaches to monitor hot-carrier reactivity at the single-particle level. We use a combination of dark-field microscopy and photo-electrochemistry to track a hot-hole driven reaction on a single Au nanoparticle. We image hot-electron reactivity with sub-particle spatial resolution using nanoscopy techniques. Finally, we push the limits looking for a hot-electron induced chemical reaction that generates a fluorescent product, which should enable imaging of active plasmonic photocatalysis at the single-particle and single-molecule levels.
关键词： dark-field microscopy,fluorescent product,single-particle techniques,Plasmonic hot-carriers,plasmonic photocatalysis,photo-electrochemistry,nanoscopy techniques
更新于2025-11-19 16:56:42
-
Effect of Unsymmetrically Branched Alkyl Chains on the Electrochemical Band Gap and Thermal Stability of the PCDTBT
摘要： This work introduces a modified poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyl-2’,1’,3’-benzothiadiazole)] (PCDTBT) with the unsymmetrically branched N-alkyl chain, which name as poly[N-9’-(2-hexyldecyl)-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyl-2’,1’,3’-benzothiadiazole)] (P1). The synthesis of P1 involves dimerization, cyclization, tosylation, N-alkylation, bromination, Stille’s and Suzuki’s coupling reactions. Suitable analysis techniques have used to study the chemical, physical, electrochemical, optical, and thermal properties of P1. The analysis results show that P1 possesses higher HOMO and LUMO energy levels than the previously reported PCDTBT, which have been narrowing the electrochemical band gap down to 1.58 eV. However, the P1 experiences 5% thermal degradation at 280 °C, which is relatively less favourable than the PCDTBT. Hence, the replacement of the symmetrically branched alkyl chains of PCDTBT with unsymmetrically branched alkyl chains results in both improvement and draw-back on the characteristics of the polymer.
关键词： bond energy,Alkylation,cyclic voltammetry,electrochemistry,polymerization
更新于2025-11-19 16:56:35
-
Luminescent rhenium(I) carbonyl complex with redox noninnocent ONS donor azo-phenol ligand: Synthesis, X-ray structure, photophysical properties and live cell imaging
摘要： Herein, we have synthesized a new fluorescent rhenium(I) carbonyl complex 1, bearing {Re(CO)3}+ core with ONS donor thioether containing azo-phenol redox noninnocent ligand. The distorted octahedral geometry of the complex is confirmed by single crystal X-ray diffraction method. Cyclic voltammogram in acetonitrile exhibits irreversible oxidation peak (Epa = 1.36 V) along with quasi-reversible reduction peak at E1/2 = -0.92 V (ΔE = 210 mV). The complex exhibits low energy emission band at 525 nm with high emission quantum yield (Φ = 0.115). Cytotoxicity of the complex is studied by MTT method with human breast cancer cell lines (MCF-7) and IC50 value is found to be 23.6 μM. In presence of the complex (10 μM) a bright green fluorescence image of MCF-7 cell lines is observed under fluorescence microscope.
关键词： Electrochemistry,ONS donor ligand,MTT assay,Rhenium(I) carbonyl complex,Live cell imaging
更新于2025-11-19 16:46:39
-
Probing Electrocatalytic CO2 Reduction at Individual Cu Nanostructures via Optically Targeted Electrochemical Cell Microscopy
摘要： Optically targeted electrochemical cell microscopy (OTECCM) was applied to measure electrocatalytic rates at individual Cu nanoparticles (NPs) under electrolyte conditions relevant to CO2 reduction. The electrocatalytic responses from individual NPs were found to exhibit a wide variation in behavior, with significant NP-to-NP variations in the magnitude of electrocatalytic currents and necessary overpotentials being observed. Correlations of these quantities with metrics of NP size suggest no significant variations in the inherent electrocatalytic activity of the NPs with size. Finite element simulations of diffusion in this system demonstrate the observed diffusion-limited currents are significantly smaller than expected, attributable to the presence of a significant amount of residual ligand on the surface of the Cu NPs, which were prepared via an organic phase synthesis. The results presented here further demonstrate the promise of techniques which employ correlated optical and electrochemical measurements, such as OTECCM, for studying electrocatalysis at individual NPs.
关键词： Nanoparticles,Electrochemical microscopy,Electrochemistry,CO2 reduction
更新于2025-11-14 17:03:37
-
Construction of a Biosensor Based on a Combination of Cytochrome c, Graphene, and Gold Nanoparticles
摘要： A biosensor based on a combination of cytochrome c (Cyt c), electrochemical reduced graphene oxides (ERGO), and gold nanoparticles (AuNPs) on a glassy carbon electrode (GCE) was fabricated. The proposed biosensor electrode was denoted as GCE/ERGO-Na?on/AuNPs/Cyt c/Na?on, where ERGO-Na?on was deposited by dropping graphene oxides-Na?on mixed droplet ?rst and following electrochemical reduction, AuNPs were directly deposited on the surface of the ERGO-Na?on modi?ed electrode by electrochemical reduction, and other components were deposited by the dropping-dry method. The effect of the deposition amount of AuNPs on direct electrochemistry of Cyt c in the proposed electrode was investigated. The hydrogen peroxide was taken to evaluate the performance of the proposed biosensor. The results showed that the biosensor has great analytical performance, including a high sensitivity, a wide linear range, a low detection limit, and good stability, reproducibility, and reliability.
关键词： gold nanoparticles,cytochrome c,graphene,direct electrochemistry,biosensor,hydrogen peroxide
更新于2025-09-23 15:23:52
-
Electrochromic and electrochemical properties of copolymer films based on EDOT and phenylthiophene derivatives
摘要： The poly(3,4-ethylenedioxythiophene-co-3-phenylthiophene) (P(EDOT-co-3PT)) and poly(3,4-ethylenedioxythiophene-co-3-(4-fluorophenyl)thiophene) (P(EDOT-co-FPT)) were electropolymerized with the application of 1.62 V and 1.95 V, respectively. Unpublished spectroelectrochemical and electrochromic properties of the conjugated copolymers with monomer ratio of 1:1 were investigated. A potential range of ? 1.0 to 2.0 V was found to be suitable for the device operation between blue to purple (P(EDOT-co-3PT)) and (P(EDOT-co-FPT)). The maximum transmittance difference (Δ% T) was determined to be 8.24 and 10.37%, and the time differences between oxidation and reduction were 2.14 and 2.94 s. The copolymers showed lower band gap energies than their original homopolymers (~ 1.4 eV).
关键词： Spectroelectrochemical,Electrochemistry,Electrochromism,Copolymer,Polythiophenes
更新于2025-09-23 15:23:52
-
Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)3X and Re(bpy)(CO)3X CO2 reduction catalysts linked via a saturated methylene bridge
摘要： Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI?? to 2*NDI?? results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy??)(CO)3X and Re(I)(bpy??)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy??)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.
关键词： Electrochemistry,CO2 reduction,Electron transfer,Radical anions,Femtosecond spectroscopy,Solar energy
更新于2025-09-23 15:23:52
-
Intracortical neural stimulation with untethered, ultrasmall carbon fiber electrodes mediated by the photoelectric effect
摘要： Objective: Neural stimulation with tethered, electrically activated probes is damaging to neural tissue and lacks good spatial selectivity and stable chronic performance. The photoelectric effect, which converts incident light into electric potential and heat, provides an opportunity for a tetherless stimulation method. We propose a novel stimulation paradigm that relies on the photoelectric effect to stimulate neurons around a free-floating, ultrasmall (7-8μm diameter) carbon fiber probe. Methods: A 2-photon microscope induced photo-stimulation with a laser. Chronoamperometry and chronopotentiometry were used to characterize the electrochemical properties of photo-stimulation, while the fluorescence of Rhodamine-B was used to quantify temperature changes. Results: Photo-stimulation caused a local cathodic potential pulse with minimal leakage current. Stimulation induced voltage deflections of 0.05 - 0.4V in vitro, varying linearly with the power of the laser source (5 – 40 mW). Temperature increases in the immediate vicinity of the electrode were limited to 2.5°C, suggesting that this stimulation modality can be used without inducing heat damage. Successful stimulation was supported in vivo by increased calcium fluorescence in local neurons at stimulation onset in a transgenic GCaMP-3 mouse model. Furthermore, cells activated by photo-stimulation were closer to the electrode than in electrical stimulation under similar conditions, indicating increased spatial precision. Conclusion: Our results support the hypothesis that the proposed photoelectric method is effective for neural stimulation. Significance: Photoelectric stimulation is precise and avoids the need for a potentially destructive tether, making it a promising alternative to electrical stimulation.
关键词： GCaMP,electrochemistry,neuromodulation,photovoltaic effect,2-photon microscopy,temperature-dependent,fluorescence
更新于2025-09-23 15:23:52
-
Hot electron-induced electrochemiluminescence at cellulose derivatives-based composite electrodes
摘要： The possibility of using cellulose derivative films as (i) insulating material on metal electrodes or (ii) in composite electrode films on metal to produce hot electron-induced electrochemiluminescence (HECL) was studied. It was shown that the luminophores known to produce HECL at thin insulating film coated cathodes (e.g. Si/SiO2 and Al2O3 electrodes) produced HECL with the present novel electrodes. In the case of composite films consisting of cellulose material doped with conducting carbon particles, the optimal cellulose/carbon black ratios were investigated by measuring the time-resolved HECL (TR-HECL) of an aromatic Tb(III) chelate. In addition to Tb(III) chelate, other well-known labels, fluorescein and Ru(bpy)3 2+ chelate, were demonstrated to produce strong HECL at the present composite electrodes, which are more environmental friendly in disposable assay cartridges as the plastic-based composites we have studied previously. Thus, it is now possible on the present basis to manufacture biodegradable paper-based assay cartridges with HECL detection of labels at biodegradable electrodes. It was shown that the present composite films are stable over wide pH range, and also time-resolved detection of Ru(bpy)3 2+ chelate is possible although its luminescence lifetime if quite short. The calibration curves were measured for presently used aromatic Tb(III) chelate and for Ru(bpy)3 2+. The detection limit (s/n = 3) was 2 · 10?10 M for the Tb(III)-chelate and 4 · 10?9 M for Ru(bpy)3 2+ in time-resolved detection mode. The relative standard deviation for Tb(III)-L1 (n = 5) emission at 10?5 M concentration was 2%. Wide linear range and low detection limits suggests that cellulose based composite electrodes can be used in HECL bioaffinity assays which was finally demonstrated here by an immunometric immunoassay.
关键词： Bioaffinity assays,Cellulose derivatives,Lanthanide electrochemiluminescence,Immunoassays,Electrochemiluminescence,Hot electron electrochemistry
更新于2025-09-23 15:23:52