Impact of Rare-EarthPhosphate as a Hydrophilic Promoteron Boosting Electrooxidation of 5‑Hydroxymethylfurfural: ADyPO<sub>4</sub>/Ni<sub>2</sub>P Example

The hydrophilic property of the catalytic interface has been seldom focused on particularly, although many green and sustainable catalysis transformations involve water. Addressing the issue, we prepared Dy–Ni–P catalysts for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) to 2,5-furandicarboxylic acid (2,5-FDCA) in this work. The catalysts were clarified as (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P composites with molar ratio <i>m</i> within 0.08–0.28 by ICP-OES, XRD, XPS, and HRTEM characterizations. The catalytic performance of samples was comprehensively analyzed by the HPLC technique, <sup>1</sup>H NMR spectra, and various electrochemical tests, indicating that the introduction of DyPO<sub>4</sub> in a proper amount (<i>m</i> = 0.16) would significantly enhance the catalytic efficiency versus singular Ni<sub>2</sub>P in terms of 2,5-FDCA yield (91 vs 26%), selectivity (99 vs 47%), and Faradaic Efficiency (F.E.: 98 vs 70%). The enhancements were accompanied by improved kinetic features such as the Tafel slope (53 vs 95 mV dec<sup>–1</sup>) and intrinsic activity (3.3 vs 1.7 mA cm<sup>–2</sup>). The boosting endowment (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P stands among the top members of reported Ni-based HMFOR catalysts. The promoter effect of DyPO<sub>4</sub> was further investigated by H<sub>2</sub>O-TPD, contact angle, zeta potential, OCP, and EIS measurements. It was testified that the nonhydrophilic Ni<sub>2</sub>P surface would be converted to a hydrophilic composite interface with the introduction of DyPO<sub>4</sub>; in line with the essential change, transfer of reactants and activation of water were obviously intensified with the lowered charge transfer resistance along the catalytic interface, which was responsible for the enhanced catalytic behavior of (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P versus Ni<sub>2</sub>P. The above discovery made the topic regarding water indicate that the hydrophilic property of the catalytic interface played a significant role in facilitating heterogeneous catalysis transformations involving water; exampled by the current (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P for HMFOR, rare-earth phosphate could be referred to as an outstanding hydrophilic promoter to innovate excellent catalysts for technology-important chemical engineering involving water.

Publication Details

Journal
Figshare
Published
2025-03-21
DOI
https://doi.org/10.1021/acsaem.5c00318.s001
Primary Topic
Catalysis for Biomass Conversion
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article
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article

Impact of Rare-EarthPhosphate as a Hydrophilic Promoteron Boosting Electrooxidation of 5‑Hydroxymethylfurfural: ADyPO4/Ni2P Example

Figshare
Catalysis for Biomass Conversion
article

Impact of Rare-EarthPhosphate as a Hydrophilic Promoteron Boosting Electrooxidation of 5‑Hydroxymethylfurfural: ADyPO4/Ni2P Example

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Abstract

The hydrophilic property of the catalytic interface has been seldom focused on particularly, although many green and sustainable catalysis transformations involve water. Addressing the issue, we prepared Dy–Ni–P catalysts for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) to 2,5-furandicarboxylic acid (2,5-FDCA) in this work. The catalysts were clarified as (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P composites with molar ratio <i>m</i> within 0.08–0.28 by ICP-OES, XRD, XPS, and HRTEM characterizations. The catalytic performance of samples was comprehensively analyzed by the HPLC technique, <sup>1</sup>H NMR spectra, and various electrochemical tests, indicating that the introduction of DyPO<sub>4</sub> in a proper amount (<i>m</i> = 0.16) would significantly enhance the catalytic efficiency versus singular Ni<sub>2</sub>P in terms of 2,5-FDCA yield (91 vs 26%), selectivity (99 vs 47%), and Faradaic Efficiency (F.E.: 98 vs 70%). The enhancements were accompanied by improved kinetic features such as the Tafel slope (53 vs 95 mV dec<sup>–1</sup>) and intrinsic activity (3.3 vs 1.7 mA cm<sup>–2</sup>). The boosting endowment (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P stands among the top members of reported Ni-based HMFOR catalysts. The promoter effect of DyPO<sub>4</sub> was further investigated by H<sub>2</sub>O-TPD, contact angle, zeta potential, OCP, and EIS measurements. It was testified that the nonhydrophilic Ni<sub>2</sub>P surface would be converted to a hydrophilic composite interface with the introduction of DyPO<sub>4</sub>; in line with the essential change, transfer of reactants and activation of water were obviously intensified with the lowered charge transfer resistance along the catalytic interface, which was responsible for the enhanced catalytic behavior of (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P versus Ni<sub>2</sub>P. The above discovery made the topic regarding water indicate that the hydrophilic property of the catalytic interface played a significant role in facilitating heterogeneous catalysis transformations involving water; exampled by the current (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P for HMFOR, rare-earth phosphate could be referred to as an outstanding hydrophilic promoter to innovate excellent catalysts for technology-important chemical engineering involving water.

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