• C Retna Raj

Articles written in Journal of Chemical Sciences

• Electrochemistry of surface wired cytochrome c and bioelectrocatalytic sensing of superoxide

Electrochemistry of cytochrome c (Cyt-c) wired on an electrode modified with the self-assemblies of 4,4'-dithio-dibutyric acid (DTB) and 2-pyrazineethane thiol (PET) by covalent and electrostatic binding and the amperometric sensing of superoxide (O$^−_2$) are described. Cyt-c wired on the mixed self-assembly of DTB and PET displays well-defined voltammetric response at 0.025V with a peak-to-peak separation ($\Delta E_p$) of 5mV. Pyrazine unit in the mixed self-assembly promotes the electron transfer in the redox reaction of surface wired Cyt-c. Cyt-c wired on the mixed self-assembly has been used for the amperometric sensing of superoxide. The enzymatically generated superoxide has been successfully detected using the Cyt-c wired electrode. High sensitivity and fast response for superoxide have been achieved. Uric acid does not interfere in the amperometric measurement of superoxide. The interference due to H2O2 has been eliminated by using enzyme catalase.

• Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway

Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior electrocatalytic performance of Pt-Pd bimetallic nanoelectrocatalyst of ultralow Pt content and tuning the reaction pathway by controlling the Pt content. Bimetallic nanoparticles of Pt4Pd96, Pt7Pd93 and Pt47Pd53 compositions are synthesized by electrochemical co-deposition method in aqueous solution. The nanoparticles of ultralow Pt content, Pt4Pd96, favour the CO-free dehydrogenation pathway for formic acid oxidation with an onset potential of 0 V (SHE) whereas the Pt47Pd53 nanoparticles favour the dehydration pathway involving the formation of CO at high positive potential. The Pt content of the bimetallic nanoparticles actually controls the oxidation peak potential and catalytic activity. Significant negative shift (∼350 mV) in the oxidation peak potential and remarkable enhancement in the current density (2.6 times) are observed for Pt4Pd96 nanoparticles with respect to Pt47Pd53. The absence of three adjacent Pt and Pd atoms could be the reason for the suppression of CO pathway. The electrochemical impedance measurements indirectly support the CO-free pathway for the formic acid oxidation on Pt4Pd96 nanoparticles.

• Facile Growth of Multi-twined Au Nanostructures

We describe a facile growth of chain-like Au nanostructures and their spontaneous transformation to multi-twined nanostructure using a mild reducing agent bisphenol A (BPA). The growth Au nanostructures involves the chemical reduction of HAuCl4 by BPA in the presence of cetyltrimethylammonium bromide (CTAB) as capping agent in alkaline condition without any seeds. Wire and chain-like Au nano-network structures with diameter in the range of 4 to 9 nm are obtained in the initial stage of the reaction. These chainlike nanostructures undergo spontaneous transformation into multi-twined nanostructures within 24 h. These nanocrystalline multi-twined structures have an average size of 80-90 nm. X-ray and selected area electron diffraction measurements reveal that the Au nanoparticles have (111), (200), (220) and (311) planes of a face centered cubic structure. High resolution transmission electron microscopic measurement shows that the nanostructures are mainly composed of (111) lattice plane with twin boundaries. The concentration of HAuCl4, BPA and CTAB has pronounced effect in the growth of nanostructures. The multi-twined nanostructures are highly stable at room temperature over a period of one month and can be used for catalytic applications.

• Journal of Chemical Sciences

Volume 135, 2023
All articles
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• Editorial Note on Continuous Article Publication

Posted on July 25, 2019