4.8 Article

3D Printed Nickel-Molybdenum-Based Electrocatalysts for Hydrogen Evolution at Low Overpotentials in a Flow-Through Configuration

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 17, Pages 20260-20268

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c05648

Keywords

hydrogen evolution reaction; electrocatalysis; 3D printing; alkaline electrolysis; NiMo; flow-through; electrochemistry; solar fuel

Funding

  1. US Department of Energy [DE-AC52-07NA27344]
  2. LDRD Awards [19-SI-005, 19-FS-047]
  3. IM review [LLNL-JRNL-816169]
  4. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub [DE-SC0021266]

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Three-dimensionally printed nickel molybdenum electrocatalysts with hierarchically porous structures were synthesized and evaluated for hydrogen evolution reaction in a flow-through configuration, showing efficient bubble removal and decreased overpotentials. An analytical model was developed to quantitatively evaluate voltage losses, while the electrochemical performance was systematically studied, achieving high electrochemical accessible surface areas and low overpotentials using the flow-through configuration.
Three-dimensional (3D) printed, hierarchically porous nickel molybdenum (NiMo) electrocatalysts were synthesized and evaluated in a flow-through configuration for the hydrogen evolution reaction (HER) in 1.0 M KOH(aq) in a simple electrochemical H-cell. 3D NiMo electrodes possess hierarchically porous structures because of the resol-based aerogel precursor, which generates superporous carbon aerogel as a catalyst support. Relative to a traditional planar electrode configuration, the flow-through configuration allowed efficient removal of the hydrogen bubbles from the catalyst surface, especially at high operating current densities, and significantly decreased the overpotentials required for HER. An analytical model that accounted for the electrokinetics of HER as well as the mass transport with or without the flow-through configuration was developed to quantitatively evaluate voltage losses associated with kinetic overpotentials and ohmic resistance due to bubble formation in the porous electrodes. The chemical composition, electrochemical surface area (ECSA), and roughness factor (RF) were also systematically studied to assess the electrocatalytic performance of the 3D printed, hierarchically porous NiMo electrodes. An ECSA of 25163 cm(2) was obtained with the highly porous structures, and an average overpotential of 45 mV at 10 mA cm(-2) was achieved over 24 h by using the flow-through configuration. The flow-through configuration evaluated in the simple H-cell achieved high electrochemical accessible surface areas for electrochemical reactions and provided useful information for adaption of the porous electrodes in flow cells.

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