Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

Abstract

The biomass-derived alcohol oxidation reaction (BDAOR) holds great promise for sustainable production of chemicals. However, selective electrooxidation of alcohols to value-added aldehyde compounds is still challenging. Herein, we report the electrocatalytic BDAORs to selectively produce aldehydes using single-atom ruthenium on nickel oxide (Ru 1 -NiO) as a catalyst in the neutral medium. For electrooxidation of 5-hydroxymethylfurfural (HMF), Ru 1 -NiO exhibits a low potential of 1.283 V at 10 mA cm À 2 , and an optimal 2,5-diformylfuran (DFF) selectivity of 90 %. Experimental studies reveal that the neutral electrolyte plays a critical role in achieving a high aldehyde selectivity, and the single-atom Ru boosts HMF oxidation in the neutral medium by promoting water dissociation to afford OH*. Furthermore, Ru 1 -NiO can be extended to selective electrooxidation of a series of biomass-derived alcohols to corresponding aldehydes, which are conventionally difficult to obtain in the alkaline medium.

Synergistic Regulation of S-Vacancy of MoS2-Based Materials for Highly Efficient Electrocatalytic Hydrogen Evolution

“…However, a decrease in both the size and number of CoS 2 with further increasing V ( Figures 4D–F ) can be explained as follows: introducing excessive Ru into the lattice of CoS 2 may induce an increase in the oxidation state of neighboring Co ions to maintain the charge neutrality. The similar result has been observed for other transition metal compounds, such as NiO ( Smyth, 2000 ; Ge et al, 2022 ). This implies that excessive dopant will hinder the formation of CoS 2 in turn.…”

“…The Raman spectrum of Ru-MoS 2-x -CoS 2 /CC ( Supplementary Figure S3 ) displays the typical E 1 2g and A 1g vibration models of the Mo-S bonds, further verifying the phase structure of 2H-MoS 2 in Ru-MoS 2-x -CoS 2 /CC. As shown in Figure 2B , the Ru 3p high-resolution X-ray photoelectron spectroscopy (XPS) spectrum of Ru-MoS 2-x -CoS 2 /CC is divided into two characteristic peaks at the binding energies of 462.4 and 484.7 eV, corresponding to Ru 3p 3/2 and Ru 3p 1/2 ( Ge et al, 2022 ). Nevertheless, no peak of Ru is detected in MoS 2 nanosheets coated with CoS 2 assembled on CC (MoS 2 -CoS 2 /CC) in Figure 2B .…”

Emerging Electrochemical Processes to Decarbonize the Chemical Industry

“…However, there are still challenges in biomass electrochemical partial oxidation. The product distribution has been found to be significantly affected by the catalyst type 146 and morphology, 147 electrolyte, and pH; 148 thus, achieving a high Faradaic efficiency toward a certain product and preventing full oxidation to CO 2 requires more insight into the reaction mechanism.…”

Earth‐Abundant Metal‐Based Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient Hydrogen Production: Recent Progress and Perspectives

“…Based on above statements, we realize that Ni‐based electrocatalysts are very popular for the HMF oxidation due to its abundance, unique electronic structure and high intrinsic activity, even comparable to most noble metal‐based electrocatalyts for the HMF oxidation. [ 33,42–44 ] Generally, most electrocatalysts drive the HMF oxidation via the HMFCA route in strong alkaline media (pH = 14) while a few experiences the DFF route at pH ≤ 13, suggesting the pH can affect the reaction pathway. Moreover, the in situ formation of NiOOH in Ni‐based materials during the HMF oxidation plays a key role for enhancing the overall performance.…”