Furfural acquired from agricultural sources is receiving extensive attention in the petrochemical industry as it offers an alternative route to generate more valuable hydrocarbon compounds. Herein, we investigate the furfural hydrogenation to furfuryl alcohol catalyzed by Lewis acidic BEA zeolites at the molecular level by means of the M06-L density functional theory. The mechanistic pictures in the catalytic procedure are revealed. The possible reaction pathways are considered to proceed via either concerted or stepwise mechanisms. With the contribution of zeolite oxygen bridging for the H-H splitting, the rate determining step activation barrier for the stepwise mechanism is 14.7 kcal mol lower than that for the concerted mechanism. The stepwise reaction therefore seems to be favored compared to the concerted one. The catalytic effect of the defect zeolite framework on the stepwise mechanism is also investigated. The activation energy for the stepwise rate-determining step over this site is significantly lower than the corresponding step over the perfect one by 14.1 kcal mol. Finally, the catalytic activity of tetravalent metal centers (Sn, Ge, Zr and Hf) substituted in BEA is also preliminarily compared and it is found to follow the order of Hf > Zr > Sn > Ge based on activation energies and the reaction rate. The difference in the activation energy can be traced back to the difference in the charge transfer from the catalytic site to the adsorbed molecules.

The effect of an external electric field (EF) on the methane adsorption and its activation on iron‐embedded graphene (Fe‐GPs) are investigated by using the M06‐L density functional method. The EF is applied in the perpendicular direction to the graphene in the range of −0.015 to +0.015 a.u. with the interval of 0.005 a.u. The effects of EF on the adsorption, transition state and product complexes of the methane activation reaction are revealed. The binding energies of methane on Fe site in Fe‐GPs are increased from −12.9 to −15.3, −18.1 and −21.5 kcal/mol for the negative EF of −0.005, −0.010 and −0.015, respectively. By applying positive EF, the activation barriers for methane activation are reduced in range of 3–8 kcal/mol (around 12–31%) and the reaction energies are more exothermic. The positive EF kinetically favors the reaction compared to the system without EF. The adsorption and activation of methane on Fe‐GPs can be easily tuned by adjusting the external electric field for various applications. © 2019 Wiley Periodicals, Inc.