A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ac900937kDOI Listing

Publication Analysis

Top Keywords

electrocatalytic activity
20
glassy carbon
12
carbon nanotubes
8
carbon surface
8
metal nanoparticle
8
nanoparticle deposition
8
activity oxygen
8
oxygen reduction
8
orr phosphate
8
phosphate buffer
8

Similar Publications

Covalent organic frameworks (COFs) are often employed in oxygen reduction reactions (ORR) for hydrogen peroxide production due to their tunable structures and compositions. However, COF electrocatalysts require precise structural engineering, such as heteroatoms or metal site doping, to modulate the reaction pathway during the ORR process. In this work, we designed a tetraphenyl-p-phenylenediamine based COF electrocatalyst, namely TPDA-BDA, which exhibited excellent two-electron (2e) ORR performance with high H2O2 selectivity of 89.

View Article and Find Full Text PDF

Super-Resolved Mapping of Electrochemical Reactivity in Single 3D Catalysts.

Nano Lett

January 2025

Institute of Nanochemistry and Nanobiology, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, P.R. China.

Crystals with three-dimensional (3D) stereoscopic structures, characterized by diverse shapes, crystallographic planes, and morphologies, represent a significant advancement in catalysis. Differentiating and quantifying the catalytic activity of specific surface facets and sites at the single-particle level is essential for understanding and predicting catalytic performance. This study employs super-resolution radial fluctuations electrogenerated chemiluminescence microscopy (SRRF-ECLM) to achieve high-resolution mapping of electrocatalytic activity on individual 3D CuO crystals, including cubic, octahedral, and truncated octahedral structures.

View Article and Find Full Text PDF

Ligand-induced changes in the electrocatalytic activity of atomically precise Au nanoclusters.

Chem Sci

January 2025

School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University Chongqing 401331 China

Atomically precise gold nanoclusters have shown great promise as model electrocatalysts in pivotal electrocatalytic processes such as the hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CORR). Although the influence of ligands on the electronic properties of these nanoclusters is well acknowledged, the ligand effects on their electrocatalytic performances have been rarely explored. Herein, using [Au(SR)] nanoclusters as a prototype model, we demonstrated the importance of ligand hydrophilicity hydrophobicity in modulating the interface dynamics and electrocatalytic performance.

View Article and Find Full Text PDF

Design Criteria for Active and Selective Catalysts in the Nitrogen Oxidation Reaction.

ACS Phys Chem Au

January 2025

University of Duisburg-Essen, Faculty of Chemistry, Theoretical Catalysis and Electrochemistry, Universitätsstraße 5, Essen 45141, Germany.

The direct conversion of dinitrogen to nitrate is a dream reaction to combine the Haber-Bosch and Ostwald processes as well as steam reforming using electrochemistry in a single process. Regrettably, the corresponding nitrogen oxidation (NOR) reaction is hampered by a selectivity problem, since the oxygen evolution reaction (OER) is both thermodynamically and kinetically favored in the same potential range. This opens the search for the identification of active and selective NOR catalysts to enable nitrate production under anodic reaction conditions.

View Article and Find Full Text PDF

We report on the synthesis and characterization of an imine-type nickel complex produced the complexation of an generated 2-(iminomethyl)phenol ligand with Ni ion. The use of this complex as an electrocatalyst for H evolution in a DMF solution, with acetic acid as the proton source, was investigated in detail, employing both experimental analyses (electrochemical analysis, spectroscopy analysis) and theoretical analysis (plateau current analysis). The overpotential required for H evolution is about 590 mV with a faradaic efficiency of 49% after 3 hours bulk electrolysis, competing with the two-electron reduction of free-imine groups in the ligand.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!