Biomimetic Design of a 3 D Transition Metal/Carbon Dyad for the One‐Step Hydrodeoxygenation of Vanillin

Abstract

Enzyme catalysts always show an excellent catalytic selectivity, which is important in biochemistry, especially in catalytic synthesis and biopharming. This selectivity is achieved by combining the binding effect induced by the electrostatic effect of the enzyme to attract a specific substrate and then the prearrangement of the substrates inside the enzyme pocket. Herein, we report a proof‐of‐concept application of an interfacial electrostatic field induced by constructing Schottky heterojunctions to mimic the electrostatic catalysis of an enzyme. In combination with the 3 D structure, a transition metal/carbon dyad was designed by nanoconfinement methods to promote the differential binding effect and the space‐induced organization of the reaction intermediate (vanillyl alcohol) to develop a new one‐step hydrogenolysis of vanillin for the production of 2‐methoxy‐4‐methylphenol with a remarkably high selectivity (>99 %).

Chemical and Enzymatic Routes for Lignocellulosic Bioproducts via Carbon Extension and Deoxygenation

“…The binding effect induced by the electrostatic effect of the enzyme to attract a specific substrate followed the prearrangement of the substrates inside the enzyme pocket based on the interfacial electrostatic field induced by the constructing Schottky junction which mimic an enzyme. Alcohol dehydrogenase enzymes are good candidates for deoxygenation of vanillin derivatives through hydrogenolysis which is a key step of hydrodeoxygenation under H 2 , and such hydrogenolysis can be dominated via the electrostatic effect induced by the enzyme active site by enhancing the magnitude of the electrostatic field to guide the stabilization of polar substrates or intermediates to the binding sites for an improved reaction rate by eliminating the diffusion-controlled limits . Since single-ring furan substrates are also good candidates as fuel additives as discussed in the section on deoxygenation, aerobic rearrangement for ring expansion of furans into ketoenal via a peroxidase enzyme-driven oxygen transfer process is an excellent offering of six-membered ring oxygenate which can be a good deoxygenation candidate …”

Improving the hydrodeoxygenation activity of vanillin and its homologous compounds by employing MoO3-incorporated Co-BTC MOF-derived MoCoOx@C

“…[30][31][32][33][34] Metalembedded carbon-based heterogeneous catalysts have also been developed for the HDO of vanillin and other biomassderived compounds. [34][35][36][37][38] Owing to the high cost of Pd and noble metals, robust and economical metal carbide-, phosphide-, nitride-, and oxide-based catalysts have been developed for the HDO process. [39][40][41][42][43] CoMo-supported Al 2 O 3 afforded insufficient activity and selectivity in vanillin reduction even under harsh reaction conditions (300 °C and 5 MPa H 2 ).…”

Electrochemical activation of C–H by electron-deficient W2C nanocrystals for simultaneous alkoxylation and hydrogen evolution

“…After the completion of adsorption, the residual volume of ethylbenzene in solution was obtained by extraction and analyzed in gas chromatography-mass spectrometry (GC-MS, Shimadzu QP2010SE) with dodecane as internal standard. And the adsorption volume for ethylbenzene on W 2 C/N x C (C ads ) was calculated using the equation of n ads = n ini -n res (n ini and n res represent the initial and residual contents in solution, respectively) 40 .…”