A Resol‐Assisted Cationic Coordinative Co‐assembly Approach to Mesoporous ABO₃ Perovskite Oxides with Rich Oxygen Vacancy for Enhanced Hydrogenation of Furfural to Furfuryl Alcohol

Abstract

It is a challenge to obtain ABO3 perovskite oxides with favorable crystal phase and well‐defined porous structure via existing approaches. Here, we design an effective and versatile strategy to construct mesoporous ABO3 perovskite oxides with functionalized nanocrystal frameworks and abundant oxygen vacancy sites via a resol‐assisted cationic coordinative co‐assembly approach. The as‐prepared oxygen vacancy‐rich mesoporous LaMnO3 as heterogeneous catalyst exhibits remarkable catalytic activity and stability for hydrogenation of furfural to furfuryl alcohol, including over 99 % conversion and 96 % selectivity. Combined with density functional theory calculation, the catalytic mechanism is elucidated, revealing that porous LaMnO3 nanocrystal framework is conducive to expose oxygen deficiency sites, which can facilitate the interaction between catalyst surface and catalytic substrate, leading to lower barrier in hydrogenation process.

Industrially Applicable Aqueous-Phase Selective Hydrogenation of Furfural on an Efficient TiOx-Modified Ni Nanocatalyst

“…Similarly, as shown in Figure S8, Ni/TiO 2 -350 and Ni/TiO 2 -400 have more oxygen vacancies, so their corresponding FOL selectivities at different reaction temperatures are much higher than those over Ni/TiO 2 -300. Moreover, theoretically, more oxygen vacancies can reduce the energy barrier for FFR hydrogenation and promote the FFR conversion . However, the FFR conversion first increases and then decreases sharply with the increase in the O V content (Figure a).…”

“…In contrast, the Ni–TiO 2 interaction is slightly stronger than that of Ni–SiO 2 (Figure ). TiO 2 can be partially reduced to TiO x , and the surface properties of TiO x affect the adsorption and activation of reactants significantly. , Peculiarly, Zheng et al . revealed that exposed oxygen deficiency sites on the catalyst surface could promote the interaction between the catalyst surface and CO in FFR molecules and improve the FOL selectivity.…”

“…Moreover, theoretically, more oxygen vacancies can reduce the energy barrier for FFR hydrogenation and promote the FFR conversion. 45 However, the FFR conversion first increases and then decreases sharply with the increase in the O V content (Figure 8a). The effect of d-band electron structure of Ni on H 2 adsorption and activation should, therefore, be considered.…”

“…TiO 2 can be partially reduced to TiO x , and the surface properties of TiO x affect the adsorption and activation of reactants significantly. 5,19 Peculiarly, Zheng et al 45 revealed that exposed oxygen deficiency sites on the catalyst surface could promote the interaction between the catalyst surface and CO in FFR molecules and improve the FOL selectivity. In this study, O V exists in the reduced Ni/TiO 2 samples, and the surface O V content increases with increasing the reduction temperature (Figure 4c and Table 1).…”

Sustainable Conversion of Biomass-Derived d-Xylose to Furfuryl Alcohol in a Deep Eutectic Solvent–Water System

“…Commercially, FOL is being mainly manufactured via either liquid-phase or gas-phase catalytic hydrogenation of FAL. Recently, many attempts have been made to develop the synthesis of FOL by biocatalysis via bioreduction of FAL. , Compared to conventional chemical reduction methods, the bioreduction of FAL into FOL by biocatalysis is an environmentally friendly approach under the mild performance conditions . Currently, coupling of reductase with dehydrogenase for coenzyme regeneration has been favored during the bioreduction .…”