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The Effect of Interlayer Anion Grafting on Water Oxidation Electrocatalysis: A Comparative Study of Ni- and Co-Based Brucite-Type Layered Hydroxides, Layered Double Hydroxides and Hydroxynitrate Salts.

ABSTRACT: The urge for carbon-neutral green energy conversion and storage technologies has invoked the resurgence of interest in applying brucite-type materials as low-cost oxygen evolution reaction (OER) electrocatalysts in basic media. Transition metal layered hydroxides belonging to the brucite-type structure family have been shown to display remarkable electrochemical activity. Recent studies on the earth-abundant Fe³⁺ containing mössbauerite and Fe³⁺ rich Co-Fe layered oxyhydroxide carbonates have suggested that grafted interlayer anions might play a key role in OER catalysis. To probe the effect of such interlayer anion grafting in brucite-like layered hydroxides, we report here a systematic study on the electrocatalytic performance of three distinct Ni and Co brucite-type layered structures, namely, (i) brucite-type M(OH)₂ without any interlayer anions, (ii) LDHs with free interlayer anions, and (iii) hydroxynitrate salts with grafted interlayer anions. The electrochemical results indeed show that grafting has an evident impact on the electronic structure and the observed OER activity. Ni- and Co-hydroxynitrate salts with grafted anions display notably earlier formations of the electrocatalytically active species. Particularly Co-hydroxynitrate salts exhibit lower overpotentials at 10 mA cm^-2 (η=0.34 V) and medium current densities of 100 mA cm^-2 (η=0.40 V) compared to the corresponding brucite-type hydroxides and LDH materials.

SUBMITTER: Radha AV

PROVIDER: S-EPMC9291102 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. Herein, we report the syntheses of three iridium-doped zinc-aluminum LDHs (Ir-LDHs) nanomaterials (1-3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (∼0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO4, turnover number up to ∼10,000). Nanomaterials 1-3 display the highest ever reported turnover frequency values (up to 402 min-1) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3-1 μm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1-3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir-Ir scattering from second-nearest neighbors, excluding the presence of IrO2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

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The Effect of Interlayer Anion Grafting on Water Oxidation Electrocatalysis: A Comparative Study of Ni- and Co-Based Brucite-Type Layered Hydroxides, Layered Double Hydroxides and Hydroxynitrate Salts.

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