Hydrogen Evolution Electrocatalyst Design: Turning Inert Gold into Active Catalyst by Atomically Precise Nanochemistry

Abstract

Electrocatalytic hydrogen evolution reaction (HER) holds promise in the renewable clean energy scheme. Crystalline Au and Ag are, however, poor in catalyzing HER, and the ligands on colloidal nanoparticles are generally another disadvantage. Herein, we report a thiolate (SR)-protected Au 36 Ag 2 (SR) 18 nanocluster with low coverage of ligands and a core composed of three icosahedral (I h ) units for catalyzing HER efficiently. This trimeric structure, together with the monomeric I h Au 25 (SR) 18− and dimeric I h Au 38 (SR) 24 , constitutes a unique series, providing an opportunity for revealing the correlation between the catalytic properties and the catalyst's structure. The Au 36 Ag 2 (SR) 18 surprisingly exhibits high catalytic activity at lower overpotentials for HER due to its low ligand-to-metal ratio, low-coordinated Au atoms and unfilled superatomic orbitals. The current density of Au 36 Ag 2 (SR) 18 at −0.3 V vs RHE is 3.8 and 5.1 times that of Au 25 (SR) 18 − and Au 38 (SR) 24 , respectively. Density functional theory (DFT) calculations reveal lower hydrogen binding energy and higher electron affinity of Au 36 Ag 2 (SR) 18 for an energetically feasible HER pathway. Our findings provide a new strategy for constructing highly active catalysts from inert metals by pursuing atomically precise nanoclusters and controlling their geometrical and electronic structures.

Identifying Highly Photoelectrochemical Active Sites of Two Au21 Nanocluster Isomers toward Bright Near-Infrared Electrochemiluminescence

“…The physical insights into structure–performance relationships can be extended to catalysis, as revealed by Tian, Lin, and Sun et al on high-index-facet and high-surface-energy nanocrystals of metals and metal oxides for highly efficient catalysts and by Zheng et al on carbene-stabilized gold nanoclusters with high robustness and surface reactivity . Recently, Jin and co-workers investigated electrocatalytic activity of three nanoclusters, i.e., Au 25 (SC 2 H 4 Ph) 18 , Au 38 (SC 2 H 4 Ph) 24 , and Au 36 Ag 2 (SC 10 H 15 ) 18 , for the hydrogen evolution reaction (HER) . Interestingly, the later nanocluster revealed higher electrocatalytic activity with a lower hydrogen generation overpotential, which have been correlated to the nanoclusters’ active sites.…”

“…83 Recently, Jin and co-workers investigated electrocatalytic activity of three nanoclusters, i.e., Au 25 (SC 2 H 4 Ph) 18 , Au 38 (SC 2 H 4 Ph) 24 , and Au 36 Ag 2 (SC 10 H 15 ) 18 , for the hydrogen evolution reaction (HER). 84 Interestingly, the later nanocluster revealed higher electrocatalytic activity with a lower hydrogen generation overpotential, which have been correlated to the nanoclusters' active sites. The presence of the active sites in such nanclusters depends on exposed facets in the nanostructures.…”

Free Energy Landscape and Isomerization Rates of Au$_4$ Clusters at Finite Temperature

“…[26] Apart from interconversion within one cluster's multiple isomers, catalysis processes have more complicated cluster-to-cluster transformations, [74] which make interesting targets for applications of these coupled ab initio and advanced sampling methods. Importantly, industrial catalysis widely uses alloy clusters, [75][76][77] and handling the thermodynamic and structural properties of complex alloys is thus essential and challenging. New advances in artificial intelligence and machine learning, [78,79] have offered new solutions to study structural and transitional properties on complicated metal and alloy systems with faster computational speed while retaining accuracy, and offer the potential to build on the framework established here to study complex physical processes in nanoparticles.…”

Atomically Precise Cun(n=3, 6 and 11) Nanocatalysts for Alkyne‐Haloalkane‐Amine (AHA) Coupling Reaction

“…Recently, atomically precise nanoclusters have attracted a considerable attention in the area of catalysis, exhibiting remarkable catalytic performance in various chemical reactions. [21][22][23][24] Furthermore, nanoclusters(NCs) offer a new perspective for understanding the structure/activity relationships at the molecular level owning to their perfect monodispersion and well-defined structures. [25,26] For example: Jin and co-workers reported the oxide-supported spherical Au 25 (SR) 18 and rod-shaped Au 25 (PPh 3 ) 10 (C�CPh) 5 X 2 (X=Cl, Br) NCs for the semihydrogenation process of alkynes and identified a new alkyne-activation pathway.…”

“…Recently, atomically precise nanoclusters have attracted a considerable attention in the area of catalysis, exhibiting remarkable catalytic performance in various chemical reactions [21–24] . Furthermore, nanoclusters(NCs) offer a new perspective for understanding the structure/activity relationships at the molecular level owning to their perfect monodispersion and well‐defined structures [25,26] .…”