Atomistic insight into the defect-induced tunable plasticity and electronic properties of tetragonal zirconia

Fazeli, Sara; Brault, Pascal; Caillard, Amaël; Thomann, Anne-Lise; Millon, Éric; Atmane, Soumya; Coutanceau, Christophe

doi:10.1016/j.mtcomm.2023.106731

Cited by 2 publications

(2 citation statements)

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“…For instance, increasing oxygen vacancy (V O ) concentration or combining ultrafine ZrO 2 nanoparticles (NPs) with nitrogen doping experimentally raised the onset potential for the (ORR) . In addition, the superior electronic properties of two defective t-ZrO 2 structures (t-ZrO 2 – x and t-ZrO 2 – x N x ) for catalytic applications compared to their pristine counterpart were highlighted in the previous work . Muhammady et al presented initial density functional theory (DFT) findings on the impact of V O and N doping on ORR catalytic activities in t-ZrO 2 (101).…”

Section: Introductionmentioning

confidence: 99%

“…24 In addition, the superior electronic properties of two defective t-ZrO 2 structures (t-ZrO 2d − x and t-ZrO 2d − x N x ) for catalytic applications compared to their pristine counterpart were highlighted in the previous work. 25 Muhammady et al 26 presented initial density functional theory (DFT) findings on the impact of V O and N doping on ORR catalytic activities in t-ZrO 2 (101). Their conclusion highlighted the minor role of defects in increasing the ORR catalytic activity on both defective surfaces.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl

Fazeli,

Brault,

Caillard

et al. 2024

J. Phys. Chem. C

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Accelerating the oxygen reduction reaction (ORR) is a main subject of electrocatalysis research. A key ORR step involves creating a hydroperoxyl functional group (OOH*) intermediate. This study examines the defect influence on the formation of the OOH* in a zirconia-based cathode during hydroxyl group (−OH) adsorption. Simulations on tetragonal pristine ZrO 2 (111) surfaces with introduced oxygen vacancy (t-ZrO 2−x ) and nitrogen dopant (ZrO 2−x N x ) are conducted using density functional theory (DFT). Results suggest that oxynitride t-ZrO 2−x N x has minimal −OH adsorption, while under-stoichiometric oxide t-ZrO 2d − x shows the highest affinity, potentially influencing OOH* formation. Minimum energy pathway (MEP) analysis using the nudged elastic band (NEB) approach shows the defects' significant impact on adjusting the barrier energy for OOH* formation in the presence of the −OH group. Analyzing natural bond orbital (NBO) data offers insights into electron distribution during the formation of the OOH* intermediate in reaction mechanisms. Our study demonstrates a competition between ZrO 2−x N x and t-ZrO 2−x with OHadsorbed in ORR acceleration. OOH* is favored on ZrO 2−x N x due to its lower barrier energy, while the stability of the OOH* is higher on the Zr site of t-ZrO 2−x , potentially influencing subsequent ORR steps. These study findings provide key insights for researchers developing nonplatinum-based cathode materials.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl

Fazeli,

Brault,

Caillard

et al. 2024

J. Phys. Chem. C

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Hydroxyl-Induced Modification of Oxygen Activation and Desorption Free Energy on Defective Tetragonal Zirconia Catalysts

Fazeli,

Brault,

Caillard

et al. 2024

J. Phys. Chem. C

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Describing the activation of O 2 on metal surfaces is crucial for understanding fundamental electrochemical processes, such as the oxygen reduction reaction (ORR) in hydrogen fuel cells. This study explores how defects influence O 2 adsorption mechanisms on a zirconia-based cathode. In the first step, we model O 2 adsorption on two defective surfaces: oxygen-deficient t-ZrO 2−x and oxynitride t-ZrO 2−x N x , in an aqueous solution. We describe various O 2 adsorption states by analyzing charge transfer and cohesive energy changes in O 2 molecules, Zr active sites, and defects. The results suggest that O 2 adsorption mechanisms on the surfaces of t-ZrO 2−x and t-ZrO 2−x N x occur through dissociative and associative pathways, respectively. Additionally, O 2 adsorption on t-ZrO 2−x N x leads to the departure of N dopants from the surface, which is unfavorable for catalytic activity. In the second step, we modified the surfaces of t-ZrO 2−x and t-ZrO 2−x N x with the hydroxyl (OH) group. Afterward, we simulate the O 2 activation process on these modified surfaces and identify the most probable active sites. Our findings reveal that OH groups stabilize N dopants on hydroxylated t-ZrO 2−x N x , preventing their loss. Moreover, OH groups influence the O 2 adsorption mechanism on t-ZrO 2−x , shifting toward associative O−O bond breaking. Conversely, O 2 adsorption on hydroxylated t-ZrO 2−x N x remains molecularly associative. Overall, on hydroxylated surfaces, O 2 adsorption involves stronger charge transfer among oxygen, defects, and Zr active sites. In the third step, we explored the trends of desorption of the O 2 from these surfaces. This entails analyzing O 2 desorption using steered molecular dynamics (SMD) to generate potential mean force (PMF) profiles and applying Jarzynski's equality to calculate the free energy of desorption. Herein, we find that the free energy of the desorption of O 2 from hydroxylated surfaces is lower, indicating a more spontaneous process compared to t-ZrO 2−x and t-ZrO 2−x N x . Moreover, we discover that oxygen has the highest tendency to desorb from the hydroxylated-ZrO 2−x surface, which is attributed to the lowest free energy involved in pulling oxygen from the surface, potentially influencing ORR acceleration. These findings offer valuable guidance for developing efficient nonplatinum-based cathode materials, particularly in catalysis applications.

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Atomistic insight into the defect-induced tunable plasticity and electronic properties of tetragonal zirconia

Cited by 2 publications

References 73 publications

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl

Hydroxyl-Induced Modification of Oxygen Activation and Desorption Free Energy on Defective Tetragonal Zirconia Catalysts

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Atomistic insight into the defect-induced tunable plasticity and electronic properties of tetragonal zirconia

Cited by 2 publications

References 73 publications

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO2 with Adsorbed-Hydroxyl

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO2 with Adsorbed-Hydroxyl

Hydroxyl-Induced Modification of Oxygen Activation and Desorption Free Energy on Defective Tetragonal Zirconia Catalysts

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Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl

Influence of Defects on Barrier Energy Formation for OOH* Intermediate in ORR on Tetragonal-ZrO₂ with Adsorbed-Hydroxyl