Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study

Mkhohlakali, AFuku, XSeo, MHModibedi, Remegia MKhotseng, LMathe, M2023-02-262023-02-262022-10Mkhohlakali, A., Fuku, X., Seo, M., Modibedi, R.M., Khotseng, L. & Mathe, M. 2022. Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study. Nanomaterials, 12(20). http://hdl.handle.net/10204/126172079-4991doi: 10.3390/nano12203607http://hdl.handle.net/10204/12617An alternative electrosynthesis of PdTe, using the electrochemical atomic layer deposition (E-ALD) method, is reported. The cyclic voltammetry technique was used to analyze Au substrate in copper (Cu2+), and a tellurous (Te4+) solution was used to identify UPDs and set the E-ALD cycle program. Results obtained using atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques reveal the nanometer-sized flat morphology of the systems, indicating the epitaxial characteristics of Pd and PdTe nanofilms. The effect of the Pd:Te ratio on the crystalline structure, electronic properties, and magnetic properties was investigated using a combination of density functional theory (DFT) and X-ray diffraction techniques. Te-containing electrocatalysts showed improved peak current response and negative onset potential toward ethanol oxidation (5 mA; -0.49 V) than Pd (2.0 mA; -0.3 V). Moreover, DFT ab initio calculation results obtained when the effect of Te content on oxygen adsorption was studied revealed that the d-band center shifted relative to the Fermi level: -1.83 eV, -1.98 eV, and -2.14 eV for Pd, Pd3Te, and Pd3Te2, respectively. The results signify the weakening of the CO-like species and the improvement in the PdTe catalytic activity. Thus, the electronic and geometric effects are the descriptors of Pd3Te2 activity. The results suggest that Pd2Te2 is a potential candidate electrocatalyst that can be used for the fabrication of ethanol fuel cells.FulltextenDFT calculationEthanol oxidation reactionOxygen binding energyPdTe nanofilmsUnderpotential depositionElectro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based StudyArticleMkhohlakali, A., Fuku, X., Seo, M., Modibedi, R. M., Khotseng, L., & Mathe, M. (2022). Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study. Nanomaterials, 12(20), http://hdl.handle.net/10204/12617Mkhohlakali, A, X Fuku, MH Seo, Remegia M Modibedi, L Khotseng, and M Mathe "Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study." Nanomaterials, 12(20) (2022) http://hdl.handle.net/10204/12617Mkhohlakali A, Fuku X, Seo M, Modibedi RM, Khotseng L, Mathe M. Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study. Nanomaterials, 12(20). 2022; http://hdl.handle.net/10204/12617.TY - Article AU - Mkhohlakali, A AU - Fuku, X AU - Seo, MH AU - Modibedi, Remegia M AU - Khotseng, L AU - Mathe, M AB - An alternative electrosynthesis of PdTe, using the electrochemical atomic layer deposition (E-ALD) method, is reported. The cyclic voltammetry technique was used to analyze Au substrate in copper (Cu2+), and a tellurous (Te4+) solution was used to identify UPDs and set the E-ALD cycle program. Results obtained using atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques reveal the nanometer-sized flat morphology of the systems, indicating the epitaxial characteristics of Pd and PdTe nanofilms. The effect of the Pd:Te ratio on the crystalline structure, electronic properties, and magnetic properties was investigated using a combination of density functional theory (DFT) and X-ray diffraction techniques. Te-containing electrocatalysts showed improved peak current response and negative onset potential toward ethanol oxidation (5 mA; -0.49 V) than Pd (2.0 mA; -0.3 V). Moreover, DFT ab initio calculation results obtained when the effect of Te content on oxygen adsorption was studied revealed that the d-band center shifted relative to the Fermi level: -1.83 eV, -1.98 eV, and -2.14 eV for Pd, Pd3Te, and Pd3Te2, respectively. The results signify the weakening of the CO-like species and the improvement in the PdTe catalytic activity. Thus, the electronic and geometric effects are the descriptors of Pd3Te2 activity. The results suggest that Pd2Te2 is a potential candidate electrocatalyst that can be used for the fabrication of ethanol fuel cells. DA - 2022-10 DB - ResearchSpace DP - CSIR J1 - Nanomaterials, 12(20) KW - DFT calculation KW - Ethanol oxidation reaction KW - Oxygen binding energy KW - PdTe nanofilms KW - Underpotential deposition LK - https://researchspace.csir.co.za PY - 2022 SM - 2079-4991 T1 - Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study TI - Electro-design of bimetallic PdTe electrocatalyst for ethanol oxidation: Combined experimental approach and ab initio Density Functional Theory (DFT)-Based Study UR - http://hdl.handle.net/10204/12617 ER -26455