Abstract
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.
| Original language | English |
|---|---|
| Article number | 2305573 |
| Journal | Advanced Materials |
| Volume | 35 |
| Issue number | 48 |
| DOIs | |
| State | Published - Nov 28 2023 |
Funding
Y.Y. would like to acknowledge scholarship support funded by the Faculty of Engineering at UNSW and the Australian Renewable Energy Agency (ARENA) Hydrogen Program (2018/RND015). XAS and ex situ HE‐XRD measurements were performed at the 10‐ID‐B and 11‐ID‐B beamlines of the Advanced Photon Source respectively, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. This research used the mail‐in program 11‐ID‐B, while operations at 10‐ID‐B were further supported by the Materials Research Collaborative Access Team and its member institutions. The authors would like to thank Dr. Joshua Wright for his assistance at 10‐ID‐B. The soft X‐ray spectroscopy experiment was undertaken on the SXR beamline at the Australian Synchrotron, part of ANSTO, and the authors would like to thank Dr. Bruce Cowie, the principal scientist of SXR, for his generous help in the experiments. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association (HGF) for the provision of PETRA‐III for in situ electrocatalytic PDF measurements performed at the P21 beamline under proposal I‐20200433. The authors would like to thank Dr. Soham Banerjee, Dr. Philipp Glaevecke, and Dr. Ann‐Christin Dippel for assistance in using beamline P21. The authors acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities, and they would like to thank Dr. Blanka Detlefs for assistance and support in using the ID26 beamline for XAS measurements and Mrs. Haira Hackbarth for sample preparation support. The authors acknowledge the use of the facilities and the scientific and technical assistance of the ORNL's Center for Nanophase Materials Sciences (CNMS), Mark Wainwright Analytical Centre (MWAC), and the Electron Microscope Unit (EMU) at UNSW, Sydney. N.M.B would like to acknowledge support from the UNSW Digital Grid Futures Institute. The financial support by the federal ministry for education and research (Bundesministerium für Bildung und Forschung, BMBF) under Grant Numbers 03SF0613D “AEMready”, 03HY108D “HyThroughGen” and 03HY3002Q “H2Mare” are gratefully acknowledged. The research was undertaken with the assistance of computational resources provided by National Computational Infrastructure (NCI) Australia. Y.Y. would like to acknowledge scholarship support funded by the Faculty of Engineering at UNSW and the Australian Renewable Energy Agency (ARENA) Hydrogen Program (2018/RND015). XAS and ex situ HE-XRD measurements were performed at the 10-ID-B and 11-ID-B beamlines of the Advanced Photon Source respectively, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used the mail-in program 11-ID-B, while operations at 10-ID-B were further supported by the Materials Research Collaborative Access Team and its member institutions. The authors would like to thank Dr. Joshua Wright for his assistance at 10-ID-B. The soft X-ray spectroscopy experiment was undertaken on the SXR beamline at the Australian Synchrotron, part of ANSTO, and the authors would like to thank Dr. Bruce Cowie, the principal scientist of SXR, for his generous help in the experiments. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association (HGF) for the provision of PETRA-III for in situ electrocatalytic PDF measurements performed at the P21 beamline under proposal I-20200433. The authors would like to thank Dr. Soham Banerjee, Dr. Philipp Glaevecke, and Dr. Ann-Christin Dippel for assistance in using beamline P21. The authors acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities, and they would like to thank Dr. Blanka Detlefs for assistance and support in using the ID26 beamline for XAS measurements and Mrs. Haira Hackbarth for sample preparation support. The authors acknowledge the use of the facilities and the scientific and technical assistance of the ORNL's Center for Nanophase Materials Sciences (CNMS), Mark Wainwright Analytical Centre (MWAC), and the Electron Microscope Unit (EMU) at UNSW, Sydney. N.M.B would like to acknowledge support from the UNSW Digital Grid Futures Institute. The financial support by the federal ministry for education and research (Bundesministerium für Bildung und Forschung, BMBF) under Grant Numbers 03SF0613D “AEMready”, 03HY108D “HyThroughGen” and 03HY3002Q “H2Mare” are gratefully acknowledged. The research was undertaken with the assistance of computational resources provided by National Computational Infrastructure (NCI) Australia. Open access publishing facilitated by University of New South Wales, as part of the Wiley - University of New South Wales agreement via the Council of Australian University Librarians.
Keywords
- Ni-based layered double hydroxide
- biomass electrooxidation
- defective engineering
- electron transfer processes
- metal-oxygen covalency
- proton transfer processes
- structural evolution