Ions Tuning Interfacial Reaction Enhancing Electrocatalytic Activities of Aromatic Icosahedral [B12H6]2  Borane Nanomaterials For Synthesis of Zingerone Via Vanillin Upgrading In Acid Environment

Abstract

Herein, high performance aromatic icosahedral [B12H6]2- borophene catalysts based on ions tuning interfacial reaction environment were screened for the synthesis of zingerone using vanillin and acetone. The electrochemical of [B12H6]2- in the acid micro-environment form of interfacial environment switches from halogen (F-, Cl-, Br-, and F-) to alkali (Na+, Mg2+, K+, and Ca2+) atoms were investigated using density functional theory (DFT) calculations. These calculations revealed these candidates based on their small energy barrier (UL) values of zingerone synthesis, suggesting that three ions (Cl-, K+ and Ca2+) tuning interfacial reaction environment candidates with superior zingerone synthesis activity than other reaction medium, due to a UL > −0.4 V can guarantee high activity and low energy consumption during zingerone synthesis. Cl- (acid), K+ (acid), and Ca2+ (acid) exhibited higher catalytic activity than other candidates, and their performances were competitive for zingerone synthesis, with low UL barrier of −0.15, −0.24, and −0.32 V, respectively. Zingerone synthesis via the protolysis reaction between vanillin and acetone includes two paths, i.e., induced protolysis and direct protolysis via the aldol condensation reaction. Multiple descriptors were used to evaluate and screen promising candidates for the synthesis of zingerone. For example, ΔG(*vanillin) and Bader charge analyses revealed the origin of zingerone synthesis activity based on binding energy. Importantly, binding energy of intermediates have a strong intrinsic linear scaling relationship that can be used to screen for the optimal catalyst by controlling the scaling relationship, indicating a scaling relationship was established based on G(*vanillin) and G[*zingiberone]. Finally, we proposed a method for directly inducing protolysis during the aldol condensation reaction, which may be widely applicable to different biomass-derived carbonyl compounds, yielding chemicals and medicinal compounds through biomass valorization. Final, we utilize ab initio molecular dynamics simulation (AIMD) calculation to insight into the dehydration hydrodeoxygenation of halogen (F-, Cl-, Br-, and F-) to alkali (Na+, Mg2+, K+, and Ca2+) atoms, the stability of the different coordination in acid and ions induced micro-environments. Our calculations suggest Cl- and K+ significant enhance in the HDO and provide insight into how they modulated by pH dependents.

Keywords: Tuning interfacial, [B12H6]2- boron, Aldol condensation reaction, Vanillin and acetone, Ions tuning interfacial reaction