Tailoring the Reactive Oxygen Species in Mesoporous NiO for Selectivity-Controlled Aerobic Oxidation of 5-Hydroxymethylfurfural on a Loaded Pt Catalyst

Abstract

The base-free aerobic oxidation of 5-hydroxymethylfurfural (HMF) in water to 2,5-furandicarboxylic acid (FDCA) is a sustainable upgrading process for cellulosic carbohydrates. A mesoporous NiO-supported Pt nanoparticle (ca. 3 nm) catalyst was reported, which can achieve 100% selectivity to FDCA at a full conversion of HMF without the assistance of any base under mild conditions, that is, 100 °C, 10 bar O2, and 12 h. The catalyst efficiency in terms of productivity reached 22.2 molFDCA molPt –1 h–1, which is the highest value among all the supported Pt catalysts to date in literature. Moreover, the Pt/NiO catalyst showed a remarkably stable and reusable performance during five consecutive cycling. X-ray diffraction, N2 physisorption, transmission electron microscopy, X-ray photoelectron spectroscopy, CO-adsorbed diffuse reflectance Fourier transform infrared spectroscopy, temperature-programed reduction of hydrogen, temperature-programed desorption of oxygen, and electron paramagnetic resonance techniques were used to comprehensively analyze the catalysts. It was disclosed that tailoring the reactive oxygen species in NiO is an effective way to control the initial reaction rate of HMF as well as the derived intermediates (i.e., a reflection of product distribution). This can be manipulated by varying the aging temperature during the preparation of NiO; thus, the role of different oxygen species (i.e., Oads. and Olatt.) in NiO was clarified. The interaction between the metallic Pt active sites and the mobile oxygen species was found to be critical to the excellent catalytic performance.

Research Progress of Highly Efficient Noble Metal Catalysts for the Oxidation of 5‐Hydroxymethylfurfural

“…[14,52,63] Zhang et al reported a mesoporous NiO-supported Pt nanoparticle catalyst (Pt/Ni 25a ) (Scheme 4). [64] After 12 h reaction under optimum conditions (100 °C, 10 mPa O 2 ), HMF could be completely converted and FDCA could be produced in 100 % selectivity. In addition, the Pt/NiO catalyst exhibited a great stability and reusability after 5 runs.…”

Current Advances in the Sustainable Conversion of 5‐Hydroxymethylfurfural into 2,5‐Furandicarboxylic Acid

“…The maximum yield in FDCA reached 96.7 % in 12 h (2 MPa and 140 °C), good recyclability was also demonstrated (5 catalytic cycles). Au/Pd alloy supported on nNiO was prepared by Bonincontro et al [60] The authors reported a high conversion (95 %), a high yield in FDCA (70 %), and a good level of stability using 1 MPa O 2 at 90 °C in 6 h. NiO was also used as support for Pt-based catalyst by Zhang et al [61] The catalyst reached the highest values ever reported among all the supported Pt catalysts in terms of FDCA productivity (22.2 mol mol Pt À 1 h À 1 ) and high stability (5 catalytic cycles) in water, 1 MPa O 2 at 100 °C. Promising results in basefree aqueous conditions (5 bar O 2 , 110 °C) were achieved also using Pt and Pt/Sn nanoparticles prepared from carbonyl cluster precursor on TiO 2 as support.…”

Catalytic Conversion of 5‐Hydroxymethylfurfural to High‐Value Derivatives by Selective Activation of C−O, C=O, and C=C Bonds

“…Initial reaction rate and the derived intermediates can be manipulated by varying the aging temperature during the preparation of NiO, and the interaction between the metallic Pt active sites and the mobile oxygen species was found to be critical to the excellent catalytic performance. [88] HMF oxidation reaction is generally performed at high O 2 pressure ranging from 1 to 40 bar to increase the solubility of gaseous oxygen. However, the employment of high-pressure conditions could cause the risk of explosion, hindering industrial applications.…”

“…However, Au catalyst is less active for the oxidation of the alcohol group in HMF. [88,91] In order to further enhance the activity of catalysts, product selectivity, and catalyst stability, bimetallic catalysts have been extensively examined for the transformation of HMF into oxidation products in aqueous and organic solvents. The bimetallic catalysts can be dual noble metal, precious metal and transition metal, as well as dual transition metal.…”