Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation

Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation

© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.

Bibliographische Detailangaben
Veröffentlicht in:Advanced materials (Deerfield Beach, Fla.). - 1998. - 35(2023), 48 vom: 21. Nov., Seite e2305573
1. Verfasser: Yang, Yuwei (VerfasserIn)
Weitere Verfasser: Lie, William Hadinata, Unocic, Raymond R, Yuwono, Jodie A, Klingenhof, Malte, Merzdorf, Thomas, Buchheister, Paul Wolfgang, Kroschel, Matthias, Walker, Anne, Gallington, Leighanne C, Thomsen, Lars, Kumar, Priyank V, Strasser, Peter, Scott, Jason A, Bedford, Nicholas M
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2023
Zugriff auf das übergeordnete Werk:Advanced materials (Deerfield Beach, Fla.)
Schlagworte:Journal Article Ni-based layered double hydroxide biomass electrooxidation defective engineering electron transfer processes metal-oxygen covalency proton transfer processes structural evolution
Beschreibung
Zusammenfassung:© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.
Ni-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts' deprotonation propensity and Faradic efficiency of 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA, FEFDCA ) is revealed by thorough density functional theory (DFT) simulations and atomic-scale characterizations, including in situ synchrotron diffraction and spectroscopy methods. The deprotonation capability of ultrathin layer-double hydroxides (UT-LDHs) is regulated by tuning the covalency of metal (M)-oxygen (O) motifs through defect site engineering and selection of M3+ co-chemistry. NiMn UT-LDHs show an ultrahigh FEFDCA of 99% at 1.37 V versus reversible hydrogen electrode (RHE) and retain a high FEFDCA of 92.7% in the OER-operating window at 1.52 V, about 2× that of NiFe UT-LDHs (49.5%) at 1.52 V. Ni-O and Mn-O motifs function as dual active sites for HMF electrooxidation, where the continuous deprotonation of Mn-OH sites plays a dominant role in achieving high selectivity while suppressing OER at high potentials. The results showcase a universal concept of modulating competing anodic reactions in aqueous biomass electrolysis by electronically engineering the deprotonation behavior of metal hydroxides, anticipated to be translatable across various biomass substrates
Beschreibung:Date Revised 28.11.2023
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1521-4095
DOI:10.1002/adma.202305573