Tunable and selective hydrogenation of furfural to furfuryl alcohol and cyclopentanone over Pt supported on biomass-derived porous heteroatom doped carbon

Abstract

The search for and exploitation of efficient catalytic systems for selective conversion of furfural into various high value-added chemicals remains a huge challenge for green synthesis in the chemical industry. Here, novel Pt nanoparticles supported on bamboo shoot-derived porous heteroatom doped carbon materials were designed as highly active catalysts for controlled hydrogenation of furfural in aqueous media. The porous heteroatom doped carbon supported Pt catalysts were endowed with a large surface area with a hierarchical porous structure, a high content of nitrogen and oxygen functionalities, a high dispersion of the Pt nanoparticles, good water dispersibility and reaction stability. Benefiting from these features, the novel Pt catalysts displayed a high activity and controlled tunable selectivity for furfural hydrogenation to produce furfuryl alcohol and cyclopentanone in water. The product selectivity could be easily modulated by controlling the carbonization temperature of the porous heteroatom doped carbon support and the reaction conditions (temperature and H pressure). Under mild conditions (100 °C, 1 MPa H), furfuryl alcohol was obtained in water with complete conversion of the furfural and an impressive furfuryl alcohol selectivity of >99% in the presence of Pt/NC-BS-500. A higher reaction temperature, in water, favored rearrangement of the furfural (FFA) with Pt/NC-BS-800 as the catalyst, which resulted in a high cyclopentanone yield of >76% at 150 °C and 3 MPa H. The surface properties and pore structure of the heteroatom doped carbon support, adjusted using the carbonization temperature, might determine the interactions between the Pt nanoparticles, carbon support and catalytic reactants in water, which in turn could have led to a good selectivity control. The effect of different reaction temperatures and reaction times on the product selectivity was also explored. Combined with exploration of the distribution of the reaction products, a reaction mechanism for furfural reduction has been proposed.

Effect of Self‐Doped Heteroatoms in Biomass‐Derived Activated Carbon for Supercapacitor Applications

“…The schematic diagram shown in Figure a represents the synthesis process of BFH‐850. As shown in Figure b, nitrogen contents were involved in quaternary nitrogen N‐Q (∼ 401.1 eV ), the pyrrolic nitrogen (∼ 399.6 eV ) and pyridinic nitrogen (∼ 398.4 eV ) . The obtained products with rich and uniform nitrogen (3.0 at %) exhibit large surface area (972 m 2 g −1 ), superb capacitance (412 F g −1 in KOH at current density of 0.9 A g −1 ), good rate stability (65.5% capacitance retention from 0.9 A g −1 to 5 A g −1 ) and excellent cycle stability (99.5% remained after 5000 times charge‐discharge) (Figure c).…”

Recent Advances in Catalytic Hydrogenation of Furfural

“…The catalytic performance of the obtained material significantly improved ( Table 5, entry 7). Modified carbon materials also showed an improvement on furfural selective hydrogenation [49,176]. For example, Liu et al prepared porous heteroatom-doped carbon materials, as supports for Pt nanoparticles.…”

“…For example, Liu et al prepared porous heteroatom-doped carbon materials, as supports for Pt nanoparticles. They observed more than 99% FA yield at 100 • C, and by performing the experiment at severe conditions, the reaction was selective towards cyclopentane via rearrangement [49]. Indeed, Pt supported on SiO 2 , without additional modification, only achieved 17% FA yield [99].…”

“…Catalysts 2019, 9, 796 3 of 33 Catalysts 2018, 8, x FOR PEER REVIEW 3 of 36 Scheme 1. Illustrative representation of reaction pathways in furfural hydrogenation.Other downstream products of furfural hydrogenation, such as (tetrahydro)furan [32], tetrahydrofurfural [33], lactones [34][35][36][37], levulinates [38,39], cyclopentanone(l) [40][41][42][43][44][45][46][47][48][49][50][51]. or diols [52][53][54][55], could also be employed as fuel additives, solvents, and platform molecules.…”

Defining Pt-compressed CO2synergy for selectivity control of furfural hydrogenation

“…18 Even if aqueous phase reactions are considered, which avoids potentially toxic and difficult to treat organic liquid waste, faces the problem of product separation, recovery and waste water treatment processes. Other options are electro-catalytic hydrogenation using different metals as electrode or electro-catalytic membrane.…”