Unveiling the Adsorption Behavior and Redox Properties of PtNi Nanowire for Biomass-Derived Molecules Electrooxidation

Abstract

Ni-based materials are auspicious electrocatalysts for 5-hydroxymethylfurfural oxidation reaction (HMFOR), including the adsorption and conversion of HMF and OHad on the electrocatalyst surface. However, the intrinsic HMFOR activity of Ni-based catalysts is far from satisfactory due to the weak adsorption of HMF and OHad species. Herein, a set of Pt x Ni100–x bundle nanowires (NWs) were prepared for HMFOR, which enables a low onset-potential and large current density. Operando methods reveal that Pt modulates the redox property of Ni in PtNi NWs and accelerates the oxidation of Ni2+–OH to Ni3+–O species during HMFOR. Moreover, the adsorption studies demonstrate the synergetic roles of Pt and Ni in enhancing the HMFOR activity by forming Pt–O–Ni bonds. In detail, Ni atoms modulate the d band of Pt to alter the adsorption behavior of HMF. Pt atoms promote the adsorption of OHad on Ni sites. This work provides design principles for HMFOR electrocatalysts by modulating the adsorption behaviors of organic molecules and OHad.

Promoted Formation of Catalytically Active Species in Ni Nanoparticles by Low Content Ru Doping for Electrocatalytic Oxidation of 5-Hydroxymethylfurfural

“…The other is indirect oxidation, which involves structural evolution and the valence state change of catalysts. As revealed by HRTEM and XPS results, Ni 2+ mainly exists in Ni@PCNS after HMF electrolysis, implying that both indirect oxidation and direct oxidation of HMF occur on Ni@PCNS catalyst. ,, For indirect oxidation of HMF, NiO is partially converted into NiOOH . For direct oxidation of HMF, Ni in Ni@PCNS is initially converted into NiO through electrooxidation reaction, and then HMF is adsorbed on the NiO surface (HMF ads ) and oxidized to generate the final product FDCA. , In our experiment, indirect oxidation mainly takes place on the NiRu@PCNS catalyst.…”

“…9,15,28 For indirect oxidation of HMF, NiO is partially converted into NiOOH. 28 For direct oxidation of HMF, Ni in Ni@PCNS is initially converted into NiO through electrooxidation reaction, and then HMF is adsorbed on the NiO surface (HMF ads ) and oxidized to generate the final product FDCA. 9,15 In our experiment, indirect oxidation mainly takes place on the NiRu@PCNS catalyst.…”

Tuning the adsorption behaviors of non-noble electrocatalysts to boost valorization of 5-hydroxymethylfurfural

“…4c and d present potential-dependent EIS evolutions of Ox-NiCuO z and Ox-NiCu(OH) z electrodes, respectively, along with the equivalent circuit. The corresponding resistance components, including the solution resistance ( R s ), electrode inner resistance ( R 1 ) and electrode/electrolyte interfacial resistance ( R 2 ), 14 are summarized in Tables S5, S6† and Fig. 4e.…”

“…11 For this reason, a variety of noble metals have been employed to prepare HMFOR catalysts due to their high conductivity and good adsorption capacity for various reactants. [12][13][14][15][16] For example, recently reported noble/non-noble-based hybrid catalysts, such as PdO-CuO, 12 Ir-Co 3 O 4 , 13 PtNi-NWs, 14 RuCu 15 and Pt-Ni(OH) 2 , 16 all remarkably outperform their non-noble counterparts for the HMFOR due to the enhanced adsorption of HMF. Nevertheless, the high cost of noble metals connes their further applications.…”

Regulating the Electronic Structure of Ni Sites in Ni(OH)2 by Ce Doping and Cu(OH)2 Coupling to Boost 5-Hydroxymethylfurfural Oxidation Performance

“…These results confirm that the HMFOR on the CuH_NWs@Ce:NiH_NSs/Cu electrocatalyst follows the indirect oxidation mechanism. 51 The hydroxyl and aldehyde groups in HMF enable two possible oxidation pathways (Figure 5a). Specifically, the hydroxyl or aldehyde group in the HMF molecule is first oxidized into an aldehyde or carboxyl group and generates intermediates of 2,5-diformylfuran (DFF) or 5-hydroxymethyl-2-furancarboxylic acid (HMFCA).…”