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

Abstract

Atomically dispersed metal catalysts maximize atom e ciency and display unique catalytic properties compared to regular metal nanoparticles. However, achieving high reactivity while still preserving high stability at high loadings remains as a grand challenge. Here we solve the challenge by synergizing strong metal-support interactions and spatial con nement, which enable to fabricate highly loaded (3.1 wt%), active and stable atomic Ni and dense atomic Cu grippers (8.1 wt%) on a graphitic C 3 N 4 support.For semi-hydrogenation of acetylene in excess of ethylene, the fabricated catalyst shows 11 times higher activity than the atomic Ni alone, high ethylene selectivity (90%), and high stability against both sintering and coke formation for 350 h. Comprehensive microscopic and spectroscopic characterization and theoretical calculations reveal the active site of the bridging Ni con ned in two hydroxylated Cu grippers, whose structure changes dynamically by breaking interfacial Ni-support bonds upon reactant adsorption and making these bonds upon product desorption. Such a dynamic effect confers high activity/selectivity and high stability, providing an avenue to rational design of e cient, stable, highly loaded, yet atomically dispersed catalysts.

Supported Sub‐Nanometer Clusters for Electrocatalysis Applications

“…XAS and HAADF‐STEM are two typical techniques to characterize the atomic structure of SNCCs and SACs. Besides, to reveal the more complex SNC, more advanced techniques such as atom probe tomography and atomic‐resolution electron energy‐loss spectroscopy could be considered (Figure 9i), [ 103,120 ] which are powerful tools to reveal the atomic configuration of SNC from chemical composition and 3D imaging at the atomic level.…”

“…Unfortunately, the manipulation and structure analysis of such kind of sub‐nanometer cluster's configuration is still fairly complex because it is very challenging to stabilize the precise numbers and different kinds of atoms in a single cluster. As a successful example, the Ni 1 Cu 2 linear trimers on a graphitic carbon nitride support was recently synthesized and clearly characterized, [ 103 ] in which the spatial confinement and synergizing metal–support interactions endow them with excellent performances in the semihydrogenation of acetylene. For electrocatalysis, Yao and co‐workers recently identified the dynamical structure of dinuclear Ni 2 on a N‐doped carbon support during electrochemical CO 2 reduction, [ 104 ] and they revealed a O–Ni 2 –N 6 structure with enhanced Ni–Ni interaction for significantly promoting CO 2 activation.…”

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

“…The same results can be seen in nickel–copper bimetallic AFCs (≈10 atoms nm −2 ) on graphitic carbon nitride, where the linear Cu–Ni–Cu (with bridging O atoms) tri‐atom stereo structures is formed (Figure 3F). [ 37 ] The transferred paradigm of 3D metal atomic foam materials is of great significance in both material science and nanoscience, by which the traditional metal foam micro/nano‐materials have entered the atomic structure era.…”

Bi/trinuclear Pt1,2Cu cluster assembly from isolated metal atoms

“…Several bimetallic clusters with bi-/tri-atoms, such as Zn–Co, Co–Fe, Ni–Fe, and Cu–Ni, have been synthesized. 6,9–11 It should be noted, however, that the metal atoms in most reported bimetallic clusters are typically in positively charged ionic states and stabilized by coordination of negatively charged heteroatoms such as oxygen and nitrogen. In addition, single metal atoms or metallic particles coexist with bimetallic clusters in the literature.…”

“…In addition, single metal atoms or metallic particles coexist with bimetallic clusters in the literature. 11,12 Preparing sub-nanometer-sized bimetallic clusters with relatively uniform and dispersed atomic distributions is still the focus of on-going research efforts.…”