Insights into the Synergistic Effect in Pd Immobilized to MOF-Derived Co-CoO_x@N-Doped Carbon for Efficient Selective Hydrogenolysis of 5-Hydroxylmethylfurfural

Abstract

Co-CoO x -containing N-doped porous carbon-supported palladium catalysts were prepared via a ZIF precursor calcination and a simple impregnation route. The material was employed for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). The Co-CoO x -containing N-doped porous carbon provides a high dispersion and anchoring effect on active metal as well as abundant surface defects with strong adsorption ability to the oxygenated groups and enhanced electron transfer capability, which could promote the activation and H2 spillover and the cascade reaction of HMF hydrogenolysis to DMF. As-obtained palladium-based nanocatalysts exhibited excellent catalytic hydrogenolysis performance, and there is no apparent change in activity in six runs. The reasonable synergism between surface defects and active metallic species is the primary reason for such excellent catalytic effects. Most importantly, the strategy proposed enables us to adjust the physicochemical properties of the catalyst surface to design new bifunctional catalysts with significantly improved performance.

Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran Over a Modified CoAl-Hydrotalcite Catalyst

“…The Cu 2p XPS spectrum showed three characteristic sets of peaks, each having a 2:1 area ration for the 2p 3/2 and 2p 1/2 peaks. The Cu 2p 3/2 ; Cu 2p 1/2 and satellite peaks at 932.6, 952.5 and 942.1 eV, respectively, indicate the presence of Cu species exists in the form of Cu 0 (2p 3/2 = 932.8 eV, 2p 1/2 = 952.5 eV) and Cu 2+ (2p 3/2 = 934.5 eV, 2p 1/2 = 954.3 eV) in CuO or Cu 2 AlO 4 ( Figure 5B ) ( Shang et al, 2020 ; Umasankar et al, 2020 ). The Co 2p XPS spectrum ( Figure 5C ) showed two distinct sets of peaks: Co 2+ (2p 3/2 = 781.9 eV, 2p 1/2 = 796.8 eV) and Co 3+ (2p 3/2 = 780.3 eV, 2p 1/2 = 795.2 eV).…”

Recent Advances on Heteroatom‐Doped Porous Carbon/Metal Materials: Fascinating Heterogeneous Catalysts for Organic Transformations

“…Subsequently, Pd NPs were loaded on these supports by incipient wetness impregnation and thermal treatment at 350 °C to gain the final Pd/Co‐CoO x @NC (PCNC) catalysts (Figure 56). [149] PCNC‐700 presented an outstanding catalytic performance for the hydrogenolysis of 5‐hydroxymethylfurfural (HMF) to 2,5‐dimethylfuran (DMF) (Scheme 91) without an obvious change in efficiency in six cycles. The intense interaction between the support with large surface area and Pd species promoted the Pd distribution and immobilization to the Co‐CoO x @NC by Pd‐N binding, ultimately led to the stability of the catalyst.…”

Recent Advances in Reductive Upgrading of 5‐Hydroxymethylfurfural via Heterogeneous Thermocatalysis

“…The generated H species spilled rapidly to the adjacent CoO x surface, which promoted the hydrogenolysis of HMF to DMF. [116] As mentioned above, to facilitate both the CÀ O bond activation and the hydrogenation of the reaction intermediates, one strategy is to construct a bifunctional catalytic system combining metal hydrogenating catalysts and acid support/ sites. Alternatively, alloying the hydrogenating metal with another metal to modulate the adsorption and desorption of the reactant and intermediates on the catalyst surface is also effective.…”

“…The Pd nanoparticles strongly interacting with CoO x efficiently dissociated H 2 into active H species. The generated H species spilled rapidly to the adjacent CoO x surface, which promoted the hydrogenolysis of HMF to DMF [116] …”