Subnano cluster catalysts, while highly promising due to unique activity, selectivity, and atom-efficiency, are limited in wider applications, as they are prone to deactivation via sintering. Even size-selection, which was previously shown to reduce sintering of nanoparticles, cannot reduce the sintering of highly fluxional subnano clusters, due to their inherent isomeric diversity. Here, we use a combination of theory and experiment to show that Pt clusters on Al2O3 exhibit size-dependent sintering resistance. We furthermore show that Pt4/Al2O3 and Pt7/Al2O3 are “magic” sinter-resistant cluster sizes. Their stability is attributed to the greater degree of bulk-like crystallinity of the dominant isomers. In addition, we identify different spatial signatures characteristic of the sintering of clusters with differing sintering stabilities.

We report the size-dependent activity and stability of FTO-supported Pt1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters are significantly more active than polycrystalline Pt, but also have stability under HER conditions that is size-dependent. To understand the mechanistic origin of the size effects, we carried out detailed DFT-based theory, accounting for the structural fluxionality under varying potentials. We show that, even under coverage of the simplest adsorbate H, the clusters can undergo drastic changes and populate a grand canonical ensemble of hydride states with diverse distributions of stoichiometry, structure, and thus reactivity. Both experiment and theory find that electrocatalysis mainly results from heavily hydrogenated states of the clusters (~2 H/Pt), and an ensemble-based kinetic model reproduces the experimental activity trend and provides detailed insights into the contributions from metastable configurations. The size-dependent stability trend is rationalized by chemical bonding analysis. The comparison of experiment and theory demonstrates the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

A combination of density functional theory (DFT) and experiments with atomically size-selected Pt_n clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Pt_n size on the electrocatalytic activity of Pt_n (n = 1, 4, 7, and 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Pt_n size such that Pt₇/ITO and Pt₈/ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both the DFT and experiment find that hydrogen under-potential deposition (H_upd) results in Pt_n/ITO (n = 4, 7, and 8) adsorbing ∼2H atoms/Pt atom at the HER threshold potential, equal to ca. double the H_upd observed for Pt bulk or nanoparticles. The cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt₁/ITO, where H adsorption at the HER threshold potential is energetically unfavorable. The theory combines global optimization with grand canonical approaches for the influence of potential, uncovering the fact that several metastable structures contribute to the HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible Pt_nH_x/ITO structures to correctly predict the activity vs Pt_n size and applied potential. For the small clusters, spillover of H_ads from the clusters to the ITO support is significant, resulting in a competing channel for loss of H_ads, particularly at slow potential scan rates.

Subnano cluster catalysts, while highly promising due to unique activity, selectivity, and atom-efficiency, are limited in wider applications, as they are prone to deactivation via sintering. Even size-selection, which was previously shown to reduce sintering of nanoparticles, cannot reduce the sintering of highly fluxional subnano clusters due to their inherent isomeric diversity. Here, we use a combination of theory and experiment to show that Pt clusters on Al₂O₃ exhibit size-dependent sintering resistance. We furthermore show that Pt₄/Al₂O₃ and Pt₇/Al₂O₃ are "magic" sinter-resistant cluster sizes. Their stability is attributed to the greater degree of bulk-like crystallinity of the dominant isomers. In addition, we identify different spatial signatures characteristic of the sintering of clusters with differing sintering stabilities.

Deactivation via coking due to a lack of selectivity is a persistent problem for the longevity of Pt-based dehydrogenation catalysts. Ge as a promoter improves the exper- imental selectivity and stability of subnano Pt clusters. The origin of this improvement is self-limiting coking, to form a Pt4GeC2 cluster which is more stable and selective than the bare Pt4Ge cluster. In this paper we compare the dehydrogenation abilities of Pt4 and Pt4C2 with and Pt4Ge and Pt4GeC2 with DFT calculations in order to explore the origin of self-limiting coking in the presence of Ge. The unique stability of Pt4GeC2 is attributed to electron donation from Ge to the C2 atoms. This prevents the coke from drawing electrons from the Pt, which is the origin of deactivation via coking. Thus, we identify an electronic mechanism for coke deactivation and then use an electronically driven doping strategy to improve catalyst longevity. This differs from the common perception of coke deactivating via steric blocking of active sites.Furthermore, Pt4C2 and Pt4GeC2 show differences in kinetic accessibility of different isomers, which brings us into a new paradigm of sub-ensembles of isomers, where the dominant active sites are determined by kinetic stability under reaction conditions, rather than Boltzmann populations.

We report the size-dependent activity and stability of supported Pt_1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with size-dependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (≈2 H/Pt). An ensemble-based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. The stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.