Electrocatalytic Biomass Upgrading of Furfural using Transition‐Metal Borides via Density Functional Theory Investigation

Abstract

Electrocatalytic biomass upgrading has proven to be an effective technique for generating value‐added products. Herein, the design and development of furfural upgrading using transition‐metal borides (MBenes) with simultaneous production of hydrogen are presented. Using density functional theory, the stabilities, selectivities, and activities of 13 MBene candidates are systematically evaluated for furfural upgrading. This research suggests that Fe2B2 can serve as a promising electrocatalyst for the formation of furoic acid (FAC), with a limiting potential of −0.15 V, and 5‐hydroxy‐2(5H)‐furanone (HFO), with a limiting potential of −0.93 V. Furthermore, Fe2B2 and Mn2Fe2 are shown to exhibit favorable limiting potentials of −1.35 and −1.36 V, respectively, for producing 6‐hydroxy‐2.3‐dihydro‐6H‐pyrano‐3‐one (HDPO), indicating that they may also serve as electrocatalysts. Based on Sabatier's principle, a descriptor (φ) of material properties is developed for screening catalysts with high catalytic activity considering the electronegativities and d‐electron number of metals. Additionally, surface redox potential, electronic properties, and charge‐density differences are determined for Fe2B2, which is estimated to exhibit high catalytic activity for the oxidation of furfural to FAC and HFO.

Recent Advances on Transition‐Metal‐Based Layered Double Hydroxides Nanosheets for Electrocatalytic Energy Conversion

“…[ 190 ] Alternatively, Fur electrochemical oxidation is an attractive replacement to the conventional thermocatalytic technique since the new oxidation process can be operated in normal pressure and temperature without adding external oxygen. [ 191 ] As seen in Figure a, Fur could be electro‐oxidized to furoic acid (FurAc) by converting the aldehyde group to carboxylic acid. [ 192 ] However, Cannizzaro reaction is always proceeded in Fur electro‐oxidation process under alkaline condition, leading to an undesired FurAc yield (<50%).…”

Electroreforming injects a new life into solid waste

“…Theoretical simulations are also used to realize a high-throughput screening of catalysts towards electrooxidation of solid-waste-derived feedstocks. Li et al 294 calculated the limiting potentials for furoic acid (FAC), 6-hydroxy-2,3-dihydro-6 H -pyrano-3-one (HDPO), and 5-hydroxy-2(5 H )-furanone (HFO) over all the transition-metal boride (MBene) catalysts and established three scaling relations (the limiting potential as a function of ϕ ) based on Sabatier's principle (Fig. 11d–f).…”

Comprehensive Study Addressing the Challenge of Efficient Electrocatalytic Biomass Upgrading of 5‐(Hydroxymethyl)Furfural (HMF) with a CH3NH2 Ionic Liquid on Metal‐Embedded Mo2B2 MBene Nanosheets

“…Furthermore, biomass is a renewable carbon source that is widely distributed in nature, which is ecofriendly, atom economic, and cost-effective. [12,13] Various biomass platform molecules are used in electrocatalytic biomass upgrading, [14] including furfural, [15] 5-hydroxymethyfurfural (5-HMF), [] glycolaldehyde, [16] and phenol;, [17] these are widely available from lignocellulosic biomass, which can be substituted for fossil-based feedstock in the production of valuable chemical compounds. Recently, electrocatalytic biomass upgrading has received considerable attention as a strategy to sustainably obtain high-value ammonia-containing chemicals.…”