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

Abstract

Because water is involved in the formation of furfural (FFR), aqueous-phase selective hydrogenation of FFR to furfuryl alcohol (FOL) has the potential for industrial applications, but it has not yet been well exploited. Here, partially reduced TiO x -modified Ni nanocatalysts were studied. The Ni–TiO2 interaction adjusts the Ni electron structure and affects the catalyst adsorption properties. FFR is adsorbed on the TiO x oxygen vacancy (OV) by CO, and the FOL selectivity is positively correlated with the surface OV content. The active H atoms dissociated on Ni spillover to the TiO x surface and then attack the adsorbed FFR CO. The precise synergistic effect of Ni and OV improves the comprehensive performance of FFR hydrogenation. Under mild conditions, FFR conversion can reach 92.5% and FOL selectivity can be as high as 96.8%. This is an extremely excellent performance of aqueous-phase FFR selective hydrogenation, and thus, the TiO x -modified Ni nanocatalyst is a very promising candidate for industrial applications.

Highly Efficient Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime over NiTi-Layered Double Hydroxide: The Key Role of Oxygen Vacancies

“…The negative value of the Eads implies that the adsorption of the substrate is endothermic and thermodynamically permissive. Moreover, the higher the negative value, the more stable the adsorption of the substrate. , As shown in Figure , the active site for NCH binding, while H 2 molecules tend to bind the Ni sites. The maximum adsorption energies of NCH on Ni-loaded TiO 2 and Ni-loaded TiO 2 –Ov are −3.4 and −13.3 eV, respectively.…”

“…Moreover, the higher the negative value, the more stable the adsorption of the substrate. 61,62 As shown in Figure 14 This study provides an efficient and economical catalyst for the preparation of CHO from NCH, and it is valuable for promoting the industrial production of caprolactam toward resource conservation and environment friendliness.…”

Recent Advances on Heterogeneous Non-noble Metal Catalysts toward Selective Hydrogenation Reactions

“…Second, the synergetic effect between the electrophilic sites (e.g., the metal oxide supports, the second metals, and some additives) and metal sites would improve the catalytic performance toward the hydrogenation of unsaturated aldehydes to unsaturated alcohols . For example, Zhang et al reported that TiO x -modified Ni nanocatalysts (Ni-TiO 2 ) showed excellent selectivity (96.8%) to FOL in aqueous-phase selective hydrogenation of FAL under mild reaction conditions . In addition to the effect of the electron-rich Ni created by the electron transfer from TiO x , they also found that the CO group tends to experience activation adsorption on O V of TiO x and reacts with H dissociated on Ni sites.…”

“…151 For example, Zhang et al reported that TiO xmodified Ni nanocatalysts (Ni-TiO 2 ) showed excellent selectivity (96.8%) to FOL in aqueous-phase selective hydrogenation of FAL under mild reaction conditions. 152 In addition to the effect of the electron-rich Ni created by the electron transfer from TiO x , they also found that the C�O group tends to experience activation adsorption on O V of TiO x and reacts with H dissociated on Ni sites. Actually, in addition to the production of α,β-unsaturated aldehydes, most of the supported Ni-based catalysts are also used to synthesize decarbonylation products, and the strong interaction between the furan ring and Ni sites leads to the formation of furan ring hydrogenation and ring-opening products.…”

Photocatalytic and photoelectrocatalytic H2 evolution combined with valuable furfural production

“…Many studies, instead, investigated the reverse reaction, i.e. the hydrogenation of furfural to furfuryl alcohol, with H2 consumption [20][21][22][23][24]. In particular, in this work the photocatalytic activity of TiO2-based photocatalysts prepared in the laboratory was compared with that of commercial samples.…”