Synthesis Of Single-atom Catalysts Research Articles

Stable single-atom platinum catalyst trapped in carbon onion graphitic shells for improved chemoselective hydrogenation of nitroarenes

Supported platinum (Pt) catalysts present excellent chemoselectivity for a variety of hydrogenation reactions. Minimizing the use of such expensive catalysts while retaining their catalytic activities has been one of the most challenging topics in recent years. The construction of well dispersed, stable Pt single atom catalysts both increases the density of catalytically active sites while reducing Pt usage. Here we report the synthesis of Pt single atoms trapped in carbon onion graphitic shells by arc-discharge in aqueous solution. Such graphitic shells not only limit the chemical/thermal coarsening of Pt single atoms, but also enhance the conductivity for accelerating the penetration and exchange of ions and electrons during the catalytic process. Experimental results demonstrate that the Pt single atom catalysts show superior performance and no detectable loss of activity and selectivity over 10 cycles (both remain >99%) for the hydrogenation of p-chloronitrobenzene. This novel atomically dispersed form of Pt catalyst is indicative of a new avenue towards efficient synthesis of single atom catalysts with improved performance.

Atomic engineering of high-density isolated Co atoms on graphene with proximal-atom controlled reaction selectivity

Controllable synthesis of single atom catalysts (SACs) with high loading remains challenging due to the aggregation tendency of metal atoms as the surface coverage increases. Here we report the synthesis of graphene supported cobalt SACs (Co1/G) with a tuneable high loading by atomic layer deposition. Ozone treatment of the graphene support not only eliminates the undesirable ligands of the pre-deposited metal precursors, but also regenerates active sites for the precise tuning of the density of Co atoms. The Co1/G SACs also demonstrate exceptional activity and high selectivity for the hydrogenation of nitroarenes to produce azoxy aromatic compounds, attributable to the formation of a coordinatively unsaturated and positively charged catalytically active center (Co–O–C) arising from the proximal-atom induced partial depletion of the 3d Co orbitals. Our findings pave the way for the precise engineering of the metal loading in a variety of SACs for superior catalytic activities.

Harnessing the Wisdom in Colloidal Chemistry to Make Stable Single-Atom Catalysts.

Research on single-atom catalysts (SACs), or atomically dispersed catalysts, has been quickly gaining momentum over the past few years. Although the unique electronic structure of singly dispersed atoms enables uncommon-sometimes exceptional-activities and selectivities for various catalytic applications, developing reliable and general procedures for preparing stable, active SACs in particular for applications under reductive conditions remains a major issue. Herein, the challenges associated with the synthesis of SACs are highlighted semiquantitatively and three stabilization techniques inspired by colloidal science including steric, ligand, and electrostatic stabilization are proposed. Some recent examples are discussed in detail to showcase the power of these strategies in the synthesis of stable SACs without compromising catalytic activity. The substantial further potential of steric, ligand, and electrostatic effects for developing SACs is emphasized. A perspective is given to point out opportunities and remaining obstacles, with special attention given to electrostatic stabilization where little is done so far. The stabilization strategies presented herein have a wide applicability in the synthesis of a series of new SACs with improved performances.

Recent advances in the precise control of isolated single-site catalysts by chemical methods

Abstract The search for constructing high-performance catalysts is an unfailing topic in chemical fields. Recently, we have witnessed many breakthroughs in the synthesis of single-atom catalysts (SACs) and their applications in catalytic systems. They have shown excellent activity, selectivity, stability, efficient atom utilization and can serve as an efficient bridge between homogeneous and heterogenous catalysis. Currently, most SACs are synthesized via a bottom-up strategy; however, drawbacks such as the difficulty in accessing high mass activity and controlling homogeneous coordination environments are inevitably encountered, restricting their potential use in the industrial area. In this regard, a novel top-down strategy has been recently developed to fabricate SACs to address these practical issues. The metal loading can be increased to 5% and the coordination environments can also be precisely controlled. This review highlights approaches to the chemical synthesis of SACs towards diverse chemical reactions, especially the recent advances in improving the mass activity and well-defined local structures of SACs. Also, challenges and opportunities for the SACs will be discussed in the later part.

General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MN4C4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical prediction of MN4C4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.

Electronic Metal–Support Interactions in Single‐Atom Catalysts

The synthesis of single-atom catalysts and the control of the electronic properties of catalytic sites to arrive at superior catalysts is a major challenge in heterogeneous catalysis. A stable supported single-atom silver catalyst with a controllable electronic state was obtained by anti-Ostwald ripening. An electronic perturbation of the catalytic sites that is induced by a subtle change in the structure of the support has a strong influence on the intrinsic reactivity. The higher depletion of the 4d electronic state of the silver atoms causes stronger electronic metal-support interactions, which leads to easier reducibility and higher catalytic activity. These results may improve our understanding of the nature of electronic metal-support interactions and lead to structure-activity correlations.