Voltammetric Mapping of Hydrogen Evolution Reaction on Pt Locally via Scanning Electrochemical Cell Microscopy
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PROVIDER: S-EPMC9836041 | biostudies-literature | 2022 Apr
REPOSITORIES: biostudies-literature
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Project description:Hydrogen peroxide (H2O2) is a highly relevant metabolite in many biological processes, including the oral microbiome. To study this metabolite, we developed a 25 μm diameter, highly sensitive, nonenzymatic H2O2 sensor with a detection limit of 250 nM and a broad linear range of 250 nM to 7 mM. The sensor used the synergistic activity of the catalytically active Pt nanoparticles on a high surface area multiwalled carbon nanotube and conducting ionic liquid matrix to achieve high sensitivity (2.4 ± 0.24 mA cm-2 mM-1) for H2O2 oxidation. The unique composite allowed us to miniaturize the sensor and couple it with a Pt electrode (25 μm diameter each) for use as a dual scanning electrochemical microscopy probe. We could detect 65 ± 10 μM H2O2 produced by Streptococcus gordonii (Sg) in a simulated biofilm at 50 μm above its surface in the presence of 1 mM glucose and artificial saliva solution (pH 7.2 at 37 °C). Because of its high stability and low detection limit, the sensor showed a promising chemical image of H2O2 produced by Sg biofilms. We were also able to detect 30 μM H2O2 at 50 μm above the biofilm in the presence of the H2O2-decomposing salivary lactoperoxidase and thiocyanate, which would not otherwise be possible using an existing H2O2 assay. Thus, this sensor can potentially find applications in the study of other important biological processes in a complex matrix where circumstances demand a low detection limit in a compact space.
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Project description:Scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) were integrated in a single bifunctional probe for simultaneous mapping of the oxygen reduction current and the oxidation current of the produced H2O2. The dual probe is fabricated from a double-barrel θ capillary, comprising one open barrel filled with the electrolyte and another filled with pyrolytic carbon. Pt is deposited with a gas injection system (GIS) at the end of the carbon barrel. The probe integrates the advantages of both SECM and SECCM by forming an electrochemical droplet cell that embeds the Pt working electrode of the carbon barrel directly into the electrolyte meniscus formed upon sample contact from the electrolyte barrel. The versatility of the dual probe is demonstrated by mapping the oxygen reduction reaction (ORR) current and the H2O2 oxidation current of a Pt microstrip on a gold substrate. This allows simultaneous localized electrochemical measurements, highlighting the potential of the dual probe for broader applications in characterizing the electrocatalytic properties of materials.
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Project description:Transition-metal dichalcogenides (TMDs) materials have attracted much attention for hydrogen evolution reaction (HER) as a new catalyst, but they still have challenges in poor stability and high reaction over-potential. In this study, ultra-thin SnS2 nanocatalysts were synthesized by simple hydrothermal method, and low load of Pt was added to form stable SnS2-Pt-3 (the content of platinum is 0.5 wt %). The synergistic effect between ultra-thin SnS2 rich in active sites and individual dispersed Pt nanoclusters can significantly reduce the reaction barrier and further accelerate HER reaction kinetics. Hence, SnS2-Pt-3 exhibits a low overpotential of 210 mV at the current density of 10 mA cm-2. It is worth noting that SnS2-Pt-3 has a small Tafel slope (126 mV dec-1) in 0.5 M H2SO4, as well as stability. This work provides a new option for the application of TMDs materials in efficient hydrogen evolution reaction. Moreover, this method can be easily extended to other catalysts with desired two-dimensional materials.
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Project description:Platinum-based alloys with low cost transition metals have been considered as promising electrocatalysts in the field of sustainable energy conversion and storage. Herein, chloroplatinic acid, cobalt chloride, and carbon nanotubes are used as platinum, cobalt precursors, and carriers, respectively, to prepare rich Pt dealloying PtCo nanoparticles (SD-PtCo/CNT) via co-liquid phase reduction and chemical dealloying methods. The characterization and test results confirm that PtCo alloy nanoparticles are evenly dispersed on carbon nanotubes, further dealloying and resulting in the partial dissolving of cobalt, simultaneously generating a rich Pt layer and roughly active surface. Benefiting from the unique structure, the SD-PtCo/CNT catalyst displays obviously enhanced HER activity in both acidic and alkaline conditions. In 1.0 M KOH, SD-PtCo/CNT exhibits a low overpotential of 78 mV at 10 mA/cm2 and a small tafel slope (38.28 mV/dec). In 0.5 M H2SO4, SD-PtCo/CNT still shows the superior performance compared with un-dealloying PtCo/CNT, with an overpotential of 17 mV at 10 mA/cm2 and corresponding tafel slope of 21.35 mV/dec. The high HER activity of SD-PtCo/CNT can be attributed to the formation of a platinum rich layer and the uniformly dispersed PtCo nanoparticles supported on superior conductive carbon nanotubes, suggesting its great potential for hydrogen generation via water splitting.
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Project description:The oxidized platinum (Pt) can exhibit better electrocatalytic activity than metallic Pt0 in the hydrogen evolution reaction (HER), which has aroused great interest in exploring the role of oxygen in Pt-based catalysts. Herein, we select two structurally well-defined polyoxometalates Na5[H3Pt(IV)W6O24] (PtW6O24) and Na3K5[Pt(II)2(W5O18)2] (Pt2(W5O18)2) as the platinum oxide model to investigate the HER performance. Electrocatalytic experiments show the mass activities of PtW6O24/C and Pt2(W5O18)2/C are 20.175 A mg-1 and 10.976 A mg-1 at 77 mV, respectively, which are better than that of commercial 20% Pt/C (0.398 A mg-1). The in situ synchrotron radiation experiments and DFT calculations suggest that the elongated Pt-O bond acts as the active site during the HER process, which can accelerate the coupling of proton and electron and the rapid release of H2. This work complements the knowledge boundary of Pt-based electrocatalytic HER, and suggests another way to update the state-of-the-art electrocatalyst.
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