Atomic Insights into Synergistic Nitroarene Hydrogenation over Nanodiamond‐Supported Pt₁−Fe₁ Dual‐Single‐Atom Catalyst

Abstract

Fundamental understanding of the synergistic effect of bimetallic catalysts is of extreme significance in heterogeneous catalysis, but a great challenge lies in the precise construction of uniform dual‐metal sites. Here, we develop a novel method for constructing Pt1−Fe1/ND dual‐single‐atom catalyst, by anchoring Pt single atoms on Fe1−N4 sites decorating a nanodiamond (ND) surface. Using this catalyst, the synergy of nitroarenes selective hydrogenation is revealed. In detail, hydrogen is activated on the Pt1−Fe1 dual site and the nitro group is strongly adsorbed on the Fe1 site via a vertical configuration for subsequent hydrogenation. Such synergistic effect decreases the activation energy and results in an unprecedented catalytic performance (3.1 s−1 turnover frequency, ca. 100 % selectivity, 24 types of substrates). Our findings advance the applications of dual‐single‐atom catalysts in selective hydrogenations and open up a new way to explore the nature of synergistic catalysis at the atomic level.

Pt Nanoclusters Supported on Ti3C2Tx Nanosheets for the Selective Hydrogenation of Halogenated Nitroarenes under Mild Conditions

“…As shown in Figure S10, the H 2 reaction orders over Pt/Ti 3 C 2 T x and 1% Pt/C catalysts were nearly 0.48 and 0.61, respectively. The smaller reaction order of Pt/Ti 3 C 2 T x indicated that it was easier for H 2 activation. , In comparison with 1% Pt/C, Pt/Ti 3 C 2 T x exhibited higher desorption temperature that reflected the stronger adsorption capacity and lower activation energy of H 2 . In addition, Pt 4f core level spectra of the Pt/Ti 3 C 2 T x and 1% Pt/C catalysts after the reaction were also investigated (Figure e,f).…”

“…Organic synthesis has gradually developed toward being green, safe, and with high efficiency. The hydrogenation of halogenated nitroarenes is regarded as a crucial reaction in organic synthesis and has wide applications in medicines, insecticides, pigments, and chemical reagents. − However, the traditional methods always utilize sulfurated alkali, iron powder, and hydrazine hydrate as reductants, which have caused huge environmental problems and are inconsistent with the sustainable concept of organic synthesis. , The hydrogenation reaction with H 2 as a hydrogen atom source over heterogeneous catalysts exhibits green and efficient features, which have attracted extensive attention. − For instance, non-noble catalysts such as Co, Ni, and Cu have been developed for the hydrogenation of halogenated nitroarenes, attributed to their abundant reserves and low cost. − However, these catalysts usually need to be used under high hydrogen pressure and high reaction temperature conditions that will consume considerable energy and pose safety risks . Noble metal catalysts such as Pt, Pd, and Ru are capable of excellent hydrogenation performance under mild reaction conditions, but the stubbornly high cost cannot satisfy their large-scale application. − In addition, noble metal catalysts also exhibit imperfect selectivity because of their strong hydrodechlorination capabilities that will generate the dechlorination byproducts inevitably .…”

Synergistic effect between Co single atoms and Pt nanoparticles for efficient alkaline hydrogen evolution

“…Such limitation highlights the pressing need for innovative catalyst designs and material modifications via fine-tuning catalyst-electrolyte interaction to expedite the reaction kinetics. For instance, creating an acid-like local environment could accelerate water dissociation and H 3 O + generation in alkaline media [10][11][12][13].…”

Structural Ni0–Niδ+ Pair Sites for Highly Active Hydrogenation of Nitriles to Primary Amines

“…The supported metal pair sites contain pairs of metal centers with proper spatial intimacy. ,, These pair metal centers have distinct properties for the activation and transformation of reactant molecules, which could meet the requirements of cooperative active sites for highly efficient catalysis. The pair metal centers can be constructed in different structures and forms, including synthesizing dual single atoms, , atomically dispersing metals and metal oxides on the support, and grafting metal particles onto metal oxide nanocrystals . Once the metal centers are isolated metal atoms, the pair sites in fact are dual single atom sites .…”