4.8 Article

Platinum Modulates Redox Properties and 5-Hydroxymethylfurfural Adsorption Kinetics of Ni(OH)2 for Biomass Upgrading

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 42, Pages 22908-22914

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202109211

Keywords

5-hydroxymethylfurfural electro-oxidation; biomass upgrading; Ni(OH)(2); operando spectroscopies; platinum modulation

Funding

  1. National Key R&D Program of China [2020YFA0710000]
  2. National Natural Science Foundation of China [21902047, 21825201, U19A2017, 21972164]
  3. Natural Science Foundation of Hunan Province [2020JJ5045, 2019GK2031]

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In this study, platinum modification of nickel hydroxide improved the current density of the 5-hydroxymethylfurfural oxidation reaction (HMFOR) and optimized the formation of active Ni(OH)O species. Platinum also reduced the adsorption energy of HMF, enhancing the catalytic process.
Nickel hydroxide (Ni(OH)(2)) is a promising electrocatalyst for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) and the dehydronated intermediates Ni(OH)O species are proved to be active sites for HMFOR. In this study, Ni(OH)(2) is modified by platinum to adjust the electronic structure and the current density of HMFOR improves 8.2 times at the Pt/Ni(OH)(2) electrode compared with that on Ni(OH)(2) electrode. Operando methods reveal that the introduction of Pt optimized the redox property of Ni(OH)(2) and accelerate the formation of Ni(OH)O during the catalytic process. Theoretical studies demonstrate that the enhanced Ni(OH)O formation kinetics originates from the reduced dehydrogenation energy of Ni(OH)(2). The product analysis and transition state simulation prove that the Pt also reduces adsorption energy of HMF with optimized adsorption behavior as Pt can act as the adsorption site of HMF. Overall, this work here provides a strategy to design an efficient and universal nickel-based catalyst for HMF electro-oxidation, which can also be extended to other Ni-based catalysts such as Ni(HCO3)(2) and NiO.

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