Mechanisms and selectivity of methanol oxidation on PtRuM3/C-MWCNT (M = Fe and Co) electrocatalysts.

Methanol oxidation efficiency and resistance to CO poisoning are the most challenging issues associated with direct methanol fuel cells. Much experimental effort has been undertaken, such as generating Pt-based binary and ternary nanoparticles, creating composite substrates, and fabricating nanoparticles with special shapes, to overcome these drawbacks. Our previous experiment showed that ternary PtRuM3/C-MWCNT (M = Fe and Co; C-MWCNT = carbon Vulcan-multiwalled carbon nanotube) electrocatalysts exhibited high methanol oxidation activity and tolerance to CO poisoning. However, reaction mechanisms on ternary PtRuM3/C-MWCNT (M = Fe and Co) electrocatalysts remain unknown. Therefore, this work is devoted to elucidating the problem using density functional theory calculations and thermodynamic models. Our present study showed that methanol oxidation proceeds via four possible reaction pathways on the surface of PtRuM3/C-MWCNTs, where the most favourable one follows a series of steps converting with a thermodynamic barrier of 0.513 eV for applied potentials of U = 0 V and 1.005 V on PtRuFe3/C-MWCNTs and 0.404 eV for U = 0 V and 0.167 eV for U = 1.005 V on PtRuCo3/C-MWCNTs. We also provide physical insights into the interaction between methanol oxidation intermediates and substrates' surface by analysing electronic properties. Our findings support the results of our previous experiment. The results of this study can be useful for rationally designing the anode for fuel cells.

Selectivity of volatile organic compounds on the surface of zinc oxide nanosheets for gas sensors.

The detection of volatile organic compounds by gas sensors is of great interest for environmental quality monitoring and the early-stage and noninvasive diagnosis of diseases. Experiments found hexane, toluene, aniline, butanone, acetone, and propanol gases in the exhaled breath of patients suffering from COVID-19, lung cancer, and diabetes. However, no studies are available to systematically elucidate the selectivity of these gases on nanosheets of zinc oxide for chemiresistive and direct thermoelectric gas sensors. Therefore, this work performed the elucidation by studying the electronic, electrical, and thermal properties of the bilayered ZnO nanosheets with polar (0001) and non-polar (112̄0) surfaces under the adsorption of the gases. The interaction between the gases and the nanosheets belongs to two groups: electrostatic attraction and charge exchange. The second one occurs due to the peak resonance of the same type of orbitals between the substrates and the gases along the surface normal and the first one for the other cases. The characteristics of the Seebeck coefficient exhibited distinct selectivity of butanone and acetone.