Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

Zhao, Wei; Bajdich, Michal; Carey, Spencer; Vojvodic, Aleksandra; Nørskov, Jens K.; Campbell, Charles T.

doi:10.1021/acscatal.6b01997

Title: Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

Journal Article · Mon Sep 19 00:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b01997· OSTI ID:1348873

Zhao, Wei ^[1]; Bajdich, Michal ^[2]; Carey, Spencer ^[1]; Vojvodic, Aleksandra ^[2]; Nørskov, Jens K. ^[2]; Campbell, Charles T. ^[1]

Univ. of Washington, Seattle, WA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Density functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1348873

Journal Information:: ACS Catalysis, Vol. 6, Issue 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 56 works

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Title: Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

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