Tuning the Electronic Structures of Anchor Sites to Achieve Zero-Valence Single-Atom Catalysts for Advanced Hydrogenation.

Single-atom catalysts (SACs) have recently become highly attractive for selective hydrogenation reactions owing to their remarkably high selectivity. However, compared to their nanoparticle counterparts, atomically dispersed metal atoms in SACs often show inferior activity and are prone to aggregate under reaction conditions. Here, by theoretical calculations, we show that tuning the local electronic structures of metal anchor sites on g-CN by doping B atoms (BCN) with relatively lower electronegativity allows achieving zero-valence Pd SACs with reinforced metal-support orbital hybridizations for high stability and upshifted Pd 4d orbitals for high activity in H activation.

Formation of a Porous Crystalline MgAlO Overlayer on Metal Catalysts via Controlled Solid-State Reactions for High-temperature Stable Catalysis.

Catalyst deactivation by sintering and coking is a long-standing issue in metal-catalyzed harsh high-temperature hydrocarbon reactions. Ultrathin oxide coatings of metal nanocatalysts have recently appeared attractive to address this issue, while the porosity of the overlayer is difficult to control to preserve the accessibility of embedded metal nanoparticles, thus often leading to a large decrease in activity. Here, we report that a nanometer-thick alumina coating of MgAlO-supported metal catalysts followed by high-temperature reduction can transform a nonporous amorphous alumina overlayer into a porous MgAlO crystalline spinel structure with a pore size of 2-3 nm and weakened acidity.

Dehydrogenation of Ammonia Borane by Platinum-Nickel Dimers: Regulation of Heteroatom Interspace Boosts Bifunctional Synergetic Catalysis.

Regulation of the atom-atom interspaces of dual-atom catalysts is essential to optimize the dual-atom synergy to achieve high activity but remains challenging. Herein, we report an effective strategy to regulate the Pt -Ni interspace to achieve Pt Ni dimers and Pt +Ni heteronuclear dual-single-atom catalysts (HDSACs) by tailoring steric hindrance between metal precursors during synthesis. Spectroscopic characterization reveals obvious electron transfers in Pt Ni oxo dimers but not in Pt +Ni HDSAC.

Synergizing metal-support interactions and spatial confinement boosts dynamics of atomic nickel for hydrogenations.

Atomically dispersed metal catalysts maximize atom efficiency and display unique catalytic properties compared with regular metal nanoparticles. However, achieving high reactivity while preserving high stability at appreciable loadings remains challenging. Here we solve the challenge by synergizing metal-support interactions and spatial confinement, which enables the fabrication of highly loaded atomic nickel (3.

Synthesis of Quasi-Bilayer Subnano Metal-Oxide Interfacial Cluster Catalysts for Advanced Catalysis.

Planar metal clusters possess high metal utilization, distinct electronic properties, and catalytic functions from their 3D counterparts. However, synthesis of these materials is challenging due to much elevated surface free energies. Here it is reported that silica supported planar bilayer Pt-CoO subnano clusters, consisting of approximately one atomic layer of Pt and one CoO layer on top, can be achieved by employing strong-electrostatic interactions during impregnation and precisely-controlled CoO coating using atomic layer deposition.