Metal Single-Atom and Nanoparticle Double-Active-Site Relay Catalysts: Design, Preparation, and Application to the Oxidation of 5-Hydroxymethylfurfural

Abstract

For tandem reactions with several intermediate products, improving the reaction rate of each step is vital for accelerating the entire reaction. However, simultaneously enhancing the conversions of different intermediates using a single-active-site catalyst remains a challenge because the catalyst commonly promotes only one type of reaction. Herein, a Co-based double-active-site relay catalyst (denoted as (Co1→Cop)/N-CNTs) is reported. Due to the preferable catalytic activities of Co single atoms (Co1) and Co nanoparticles (Cop) for the oxidation of hydroxyls to aldehyde groups and aldehydes to carboxyl groups, respectively, the prepared (Co1→Cop)/N-CNTs exhibited good catalytic performance for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The catalyst achieved 100% HMF conversion efficiency and 96% FDCA yield under a 0.1 MPa O2 atmosphere at 100 °C for 8 h. The presented strategy offers prospects for the development of highly active catalysts for complex tandem reactions.

Hierarchical Pores‐Confined Ultrasmall Cu Nanoparticles for Efficient Oxidation of 5‐Hydroxymethylfurfural

“…Accordingly, the as-prepared metalÀ carbon composites were composed of nanoconfined metal nanoparticles (NPs) and porous carbons featuring adjustable morphologies (e. g., hollow, core-shell, and yolk-shell nanostructures), and exhibited enhanced catalytic performance in comparison with their solid counterparts. [14][15][16][17][18][19][20] Despite the advances achieved, most of the reported strategies suffered from complicated operation procedures, costly templates, harsh preparation conditions, and limited versatilities, which get in the way of practical applications. In a word, it is still of urgent need to develop facile, cost-effective, and versatile protocols for the controllable synthesis of MOF-derived metalÀ carbon composites for highly efficient catalysis.…”

“…In order to overcome these shortcomings, various synthetic strategies, including hard/soft/self‐templating, and reagent‐oriented methods, have been developed to suppress the metal agglomeration and strengthen the morphology modulation of organic ligands derived carbons during the pyrolysis. Accordingly, the as‐prepared metal−carbon composites were composed of nanoconfined metal nanoparticles (NPs) and porous carbons featuring adjustable morphologies (e. g., hollow, core‐shell, and yolk‐shell nanostructures), and exhibited enhanced catalytic performance in comparison with their solid counterparts [14–20] . Despite the advances achieved, most of the reported strategies suffered from complicated operation procedures, costly templates, harsh preparation conditions, and limited versatilities, which get in the way of practical applications.…”

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

“…However, considering their global availability and the sustainability of their extraction process, the use of cobalt should be preferred. And it is precisely a cobalt-based catalyst that Yang et al [39] focused their activities on, developing a catalytic system consisting of two different cobalt active sites: the Co single atoms and the highly dispersed Co nanoparticles. The former favored the oxidation of the alcoholic group to the aldehyde functionality, while the latter promoted the oxidation of aldehyde groups to carboxylic derivatives, thanks to the different acidity of the two active sites.…”

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

“…Co p )/N-CNTs] was also prepared from ZnCo-ZIF and applied for HMF oxidation, and the synthesis process was shown in Figure 17. Outstanding catalytic performance was exhibited due to the preferable catalytic activities of Co single atoms (Co 1 ) and Co nanoparticles (Co p ), and the catalyst achieved 100 % HMF conversion efficiency and 96 % FDCA yield under 0.1 MPa O 2 atmosphere at 100 °C for 8 h. [101] Manganese oxides have been extensively investigated in broad fields, such as use as catalysts [99,102] or the supports of active metal, [94,95] owing to their low cost, Earth abundance, and specific chemical properties. It is generally acknowledged that manganese oxides have diverse crystal structures and a redox cycle between + 2 and + 4 oxidation states, providing outstanding redox reactions of Mn 2 + /Mn 3 + or Mn 3 + /Mn 4 + , and oxygen mobility within the oxide lattice.…”

“…Recently, Co‐based double active‐site relay catalyst [denoted as (Co 1 →Co p )/N‐CNTs] was also prepared from ZnCo‐ZIF and applied for HMF oxidation, and the synthesis process was shown in Figure 17. Outstanding catalytic performance was exhibited due to the preferable catalytic activities of Co single atoms (Co 1 ) and Co nanoparticles (Co p ), and the catalyst achieved 100 % HMF conversion efficiency and 96 % FDCA yield under 0.1 MPa O 2 atmosphere at 100 °C for 8 h [101] …”