Facile Synthesis of Kilogram-Scale Co-Alloyed Pt Single-Atom Catalysts via Ball Milling for Hydrodeoxygenation of 5-Hydroxymethylfurfural

Abstract

Catalytic conversion of biomass-derived 5-hydroxymethylfurfural (HMF) into high-quality biofuel 2,5-dimethylfuran (DMF) is significant for the utilization of biomass but remains a substantial challenge. Herein, we report a straightforward, eco-friendly, and scalable ball milling method for the synthesis of Co-alloyed Pt (Pt1/Co) single-atom alloy (SAA) catalysts at kilogram levels. The catalysts exhibit superior catalytic performance for the hydrodeoxygenation of HMF to DMF, obtaining 100% HMF conversion and 92.9% selectivity to DMF under 1.0 MPa H2 at 180 °C for 2 h. The reaction pathway is also investigated, which shows that the hydrogenolysis of the CO bond in HMF to form 2,5-dihydroxymethylfuran is the main route during the hydrodeoxygenation and promoted by the synergistic effect of Pt and Co. Pt1/Co SAA catalysts display excellent stability without aggregation after five successive runs. More inspiringly, our method achieves the mass production of Pt1/Co at the kilogram scale, rendering its potential for practical applications. Moreover, by varying acetylacetonate precursors, we show the general synthesis of different Co-supported noble metal SAA catalysts (M1/Co, M = Pd, Ru, Ir, and Rh). Our findings not only offer a facile and readily scalable synthetic approach of SAA catalysts but also open new avenue to the exploitation of biomass.

Intrinsic Electrocatalytic Activity Regulation of M–N–C Single‐Atom Catalysts for the Oxygen Reduction Reaction

“…For instance, the SACs based on other substrates (e.g., MXene, MoS 2 , and TiO 2 ) and the SACs with dual‐metal sites are potential modulated objects. On the other hand, this regulation principle is also applicable to other types of catalytic processes, including electrocatalysis (e.g., HER, CO 2 RR, and NRR), thermal catalytic processes (e.g., hydrogenation of furfural [98] and Fischer–Tropsch synthesis [99] ), metal catalysis in organic chemistry (e.g. Suzuki–Miyaura reaction [100] ), photo(electro)catalysis, and even enzyme catalysis.…”

“…Specifically,the essence of the proposed regulation strategies is to consider the electronic structure of the center metal atom as the crucial factor,a nd that its chemical environment can be regulated by nearby coordinated atoms as well as more distant groups.Based on the above principle,t he intrinsic activity of other types of SACs can also be adjusted as long as the basic building units (especially for the coordinated and environmental atoms) are redefined. Fori nstance,t he SACs based on other substrates (e.g., MXene,M oS 2 ,a nd TiO 2 )a nd the SACs with dual-metal sites are potential modulated objects.O nt he other hand, this regulation principle is also applicable to other types of catalytic processes, including electrocatalysis (e.g., HER, CO 2 RR, and NRR), thermal catalytic processes (e.g.,h ydrogenation of furfural [98] and Fischer-Tropsch synthesis [99] ), metal catalysis in organic chemistry (e.g.S uzuki-Miyaura reaction [100] ), photo(electro)catalysis,a nd even enzyme catalysis.N evertheless,t he differences between the reactions should be seriously considered;s imply transplanting the strategy may not result in improved catalysis. 4) Other aspects besides reactivity.…”

Single-Atom Catalysts: A Perspective toward Application in Electrochemical Energy Conversion

“…Moreover, flammable organic solvent can react vigorously with metal catalysts, leading to safety problems. 49 , 50 , 52 , 53 Among the methods surveyed above, the dry impregnation-based mechanochemical method allows for solvent-free processes, engendering of process simplicity, and cost effectiveness.…”

From double‐atom catalysts to single‐cluster catalysts: A new frontier in heterogeneous catalysis

“…Moreover, Ji et al. [ 126 ] reported a simple and scalable ball milling method for the synthesis of kilogram‐level coal‐made Pt (Pt 1 /Co) monoatomic alloy catalyst. Ma et al.…”