Dataset Information

Electro-Design of Bimetallic PdTe Electrocatalyst for Ethanol Oxidation: Combined Experimental Approach and Ab Initio Density Functional Theory (DFT)-Based Study.

ABSTRACT: 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.

SUBMITTER: Mkhohlakali A

PROVIDER: S-EPMC9610566 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Electro-Design of Bimetallic PdTe Electrocatalyst for Ethanol Oxidation: Combined Experimental Approach and Ab Initio Density Functional Theory (DFT)-Based Study.

Mkhohlakali Andile A Fuku Xolile X Seo Min Ho MH Modibedi Mmalewane M Khotseng Lindiwe L Mathe Mkhulu M

Nanomaterials (Basel, Switzerland) 20221014 20

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 (Cu<sup>2+</sup>), and a tellurous (Te<sup>4+</sup>) 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 epitax ...[more]

PMID: 36296796

Similar Datasets

Project description:Ligand field theory (LFT) is one of the cornerstones of coordination chemistry since it provides a conceptual framework in which a great many properties of d- and f-element compounds can be discussed. While LFT serves as a powerful qualitative guide, it is not a tool for quantitative predictions on individual compounds since it incorporates semiempirical parameters that must be fitted to experiment. One way to connect the realms of first-principles electronic structure theory that has emerged as particularly powerful over the past decade is the ab initio ligand field theory (AILFT). The original formulation of this method involved the extraction of LFT parameters by fitting the ligand field Hamiltonian to a complete active space self-consistent field (CASSCF) Hamiltonian. The extraction was shown to be unique provided that the active space consists of 5/7 metal d/f-based molecular orbitals (MOs). Subsequent improvements have involved incorporating dynamical correlation using second-order N-electron valence state perturbation theory (NEVPT2) or second-order dynamical correlation dressed complete active space (DCDCAS). However, the limitation of past approaches is that the method requires a minimal space of 5/7 metal d- or f-based molecular orbitals. This leads to a number of limitations: (1) neglect of radial or semicore correlation would arise from the effect of a second d-shell or an sp-shell in the active space, (2) a more balanced description of metal-ligand bond covalency is lacking because the bonding ligand-based counterparts of the metal d/f orbitals are not in the active space. This usually leads to an exaggerated ionicity of the M-L bonds. In this work, we present an extended active space AILFT (esAILFT) that circumvents these limitations and is, in principle, applicable to arbitrary active spaces, as long as these contain the 5/7 metal d/f-based MOs as a subset. esAILFT was implemented in a development version of the ORCA software package. In order to help with the application of the new method, various criteria for active space extension were explored for 3d, 4d, and 5d transition-metal ions with varying charge. An interpretation of the trends in the Racah B parameter for these ions is also presented as a demonstration of the capabilities of esAILFT.

Dataset Information

Electro-Design of Bimetallic PdTe Electrocatalyst for Ethanol Oxidation: Combined Experimental Approach and Ab Initio Density Functional Theory (DFT)-Based Study.

Publications

Electro-Design of Bimetallic PdTe Electrocatalyst for Ethanol Oxidation: Combined Experimental Approach and Ab Initio Density Functional Theory (DFT)-Based Study.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets