Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO(2)/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO(2), which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.
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http://dx.doi.org/10.1038/nmat2359 | DOI Listing |
J Am Chem Soc
January 2025
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China.
Crystalline porous materials, known for their ordered structures, hold promise for efficient hydroxide conductivity in alkaline fuel cells with limited ionic densities. However, the rigid cross-linking of porous materials precludes their processing into membranes, while composite membranes diminish materials' conductivity advantage due to the interrupted phases. Here, we report a self-standing three-dimensional covalent organic framework (3D COF) membrane with efficient OH-transport through its interconnected 3D ionic nanochannels.
View Article and Find Full Text PDFAdv Mater
January 2025
School of Chemical and Biomolecular Engineering, The University of Sydney, Darlington, New South Wales, 2006, Australia.
Oxygen evolution reaction (OER) is a cornerstone of various electrochemical energy conversion and storage systems, including water splitting, CO/N reduction, reversible fuel cells, and rechargeable metal-air batteries. OER typically proceeds through three primary mechanisms: adsorbate evolution mechanism (AEM), lattice oxygen oxidation mechanism (LOM), and oxide path mechanism (OPM). Unlike AEM and LOM, the OPM proceeds via direct oxygen-oxygen radical coupling that can bypass linear scaling relationships of reaction intermediates in AEM and avoid catalyst structural collapse in LOM, thereby enabling enhanced catalytic activity and stability.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, c/Martí i Franquès 1-11, Barcelona 08028, Spain.
The oxygen reduction reaction (ORR) stands as a pivotal process in electrochemistry, finding applications in various energy conversion technologies such as fuel cells, metal-air batteries, and chlor-alkali electrolyzers. Hereby, a comprehensive density functional theory (DFT) investigation is presented into the proposed conventional and unconventional ORR mechanisms using single-atom catalysts (SACs) supported on nitrogen-doped graphene (NG) as model systems. Several reaction intermediates have been identified that appear to be more stable than the ones postulated in the conventional mechanism, which follows the *OOH, *O, and *OH intermediates.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China.
Polymer electrolyte membrane fuel cells (PEMFCs) are one of the most promising energy conversion devices due to their high efficiency and zero emission; however, two major challenges, high cost and short lifetime, have been hindering the commercialization of fuel cells. Achieving low-Pt or non-precious metal oxygen reduction reaction (ORR) electrocatalysts is one of the main research ideas in this field. In this review, the degradation mechanism of Pt-based catalysts is firstly explained and elucidated, and then five strategies are suggested for the reduction of Pt usage without loss of activity and durability: modulation of metal-support interactions, optimization of local ionomers and mass transport, modulation of composition, modulation of structure, and multi-site synergistic effects.
View Article and Find Full Text PDFHeliyon
January 2025
Amity Institute of Microbial Technology, Amity University Rajasthan, Kant Kalwar, Jaipur, 303002, Rajasthan, India.
The goal of this research is to develop and characterize low-cost NHI doped polyvinyl alcohol (PVA)-4-ethyl-4-methylmorpholiniumbromide (ionic liquid) anion exchange membranes (AEM) and its application for membrane cathode assembly. Physical characterization like FTIR, POM, and XRD notified the functional groups, basic structure, and amorphosity of the produced membrane, and it was employed in single-chambered microbial fuel cells (sMFCs) as a separator. The membranes in terms of oxygen diffusion, proton conductivity, and ion exchange capabilities were evaluated.
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