Ultrafine Copper Oxide Particles Dispersed on Nitrogen‐Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass‐Derived 5‐Hydroxymethylfurfural

Abstract

One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/NÀ CÀ HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/NÀ CÀ HNSs was prepared through a template protection-sacrifice strategy using SiO 2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m 2 /g, the CuO/ NÀ CÀ HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP 3 CÀ H bond functionalization is also demonstrated using the same catalyst.

Hollow carbon-based materials for electrocatalytic and thermocatalytic CO2 conversion

“…In nature, cells with hollow structures are the fundamental unit of an organism, and this unique structure endows them with distinctive properties that allow for the adjustment of adsorption, separation, and exchange for substrates required to maintain vital life activities. 25,26 Inspired by nature, many encouraging hollow-structure nanoreactors have been developed for energy storage, [27][28][29][30][31] biomass conversion, 32,33 and environmental catalysis applications. 34,35 In recent years, hollowstructured carbon (HSC) and its derived nanomaterials have attracted considerable attention in the elds of thermocatalysis and electrocatalysis for CO 2 conversion due to their advantageous features.…”

Metal@hollow carbon sphere nanoreactors for sustainable biomass and CO2valorization

“…Many highly functionalized compounds like aldehydes, alcohols and carboxylic acids could be obtained from catalytic oxidation reactions, 10 which are one of the significant chemical reactions for the valorization of biomass and the production of fine chemicals, fragrances and drugs. 193 N-doped carbon hollow nanospheres (CuO/N–C-HNSs) loaded with ultrafine CuO particles were constructed using SiO 2 as the hard template and histidine as the C and N precursor for the direct generation of furan-2,5-dimethylcarboxylate in the oxidative esterification of 5-hydroxymethylfurfural 194 (Fig. 23a–g).…”