Surface Confinement of Atomically Thin Pt Nanoclusters on 2D δ‐Mon for Durable pH‐Universal Hydrogen Evolution

Abstract

Engineering precious metals’ sub‐nanometer cluster on 2D earth‐abundant supports provides a promising approach for the development of high‐efficient electrocatalysts in pursuit of green hydrogen. Herein, a novel solid phase deposition approach is demonstrated for the homogenous confinement of atomically thin Pt nanoclusters on 2D delta‐MoN as a viable catalyst for pH‐universal hydrogen evolution reaction. Notably, the optimized material (MoN‐5% Pt) exhibits excellent catalytic performance as evidenced by low overpotentials required, excellent mass activity exceeding 20 A mgPt−1 at 100 mV overpotential, and outstanding stability with negligible activity degradation. The enhanced performance is attributed to (1) novel nanostructure, constituting atomically thin Pt nanoclusters confined on 2D δ‐MoN substrate, thus rendering high atomic utilization and seamless surface mass transfer, and (2) influence of strong metal‐support interaction that effectively limits structural deformation and performance degradation. Theoretical simulations reveal that the strong metal‐support interaction induces substantial charge redistribution across the heterointerface, initiating an energy‐favorable multi‐active site microkinetics in which Pt atoms with an optimal hydrogen adsorption energy making way for enhanced H2 evolution, while Mo atoms situated at the heterointerface enhance water absorption/dissociation steps, enriching the catalytic surface with adsorbed hydrogen atoms.

Molten‐Salt Electrochemical Preparation of Co2B/MoB2 Heterostructured Nanoclusters for Boosted pH‐Universal Hydrogen Evolution

“…Hence, the minimumΔG H 2 O * of Co 2 B/MoB 2 suggests the heterointerface favors water adsorption for accelerated HER kinetics in alkaline and neutral medium. [54] Furthermore, the RDS of HER process is the conversion from the initial state to the transition state, for which the energy barriers of Co 2 B, MoB 2 and Co 2 B/MoB 2 are 2.06, 1.82, and 1.61 eV, respectively (Figure 5e). Meanwhile, the water molecule adsorbed at the Co sites of Co 2 B/MoB 2 exhibits the maximum Bader charge (Figure S41 and Table S8, Supporting Information).…”

Subnanometric Osmium Clusters Confined on Palladium Metallenes for Enhanced Hydrogen Evolution and Oxygen Reduction Catalysis

“…3−6 Thus far, platinum (Pt) is widely recognized as the gold standard for catalyzing the HER and ORR by virtue of close-to-optimal binding energies with oxygen and hydrogen, respectively. 4,7,8 Nevertheless, the extensive cost arising from resource scarcity, poor antipoisoning characteristics, and insufficient durability of Pt-based electrocatalysts render them impractical for use in large-scale applications and severely hamper the widespread adoption of these electro-conversion technologies. 9−12 Therefore, it is of great desire to rationally design cost-effective and durable Pt alternatives which can accelerate the HER and ORR efficiently.…”

“…Green energy technologies and electrochemical systems, such as water electrolyzers, fuel cells, and metal-air batteries, which are capable of driving efficient conversion, storage, and utilization of renewable energy, serve as one of the most promising ways to address the ever-increasing global energy demands and environmental crisis facing modern society. , Undoubtedly, the aforementioned sustainable energy initiatives hold tremendous merit, but significant penetration into the energy supply necessitates construct of high-performance electrocatalysts for driving the hydrogen evolution (HER) and oxygen reduction reactions (ORR), which primarily lie at the heart of these technologies. − Thus far, platinum (Pt) is widely recognized as the gold standard for catalyzing the HER and ORR by virtue of close-to-optimal binding energies with oxygen and hydrogen, respectively. ,, Nevertheless, the extensive cost arising from resource scarcity, poor antipoisoning characteristics, and insufficient durability of Pt-based electrocatalysts render them impractical for use in large-scale applications and severely hamper the widespread adoption of these electro-conversion technologies. − Therefore, it is of great desire to rationally design cost-effective and durable Pt alternatives which can accelerate the HER and ORR efficiently. − …”

“…The incorporation of In atoms was found to tailor the electronic structure of Pt, thereby relieving the overbinding of oxygen intermediates and making way for a favorable ORR reaction pathway. Besides, MoN-supported Pt NCs (MoN-5% Pt) were shown to demonstrate superior hydrogen evolution activity owing to strong metal support interactions (i.e., charge redistribution), and multiactive site mechanisms in which Mo sites located at the heterointerface aid in water adsorption/dissociation processes, while Pt atoms render optimal hydrogen adsorption . Indeed, the cluster-size dependent catalytic activity of various noble metals such as Ir, Ru, Pt, and their alloys have been extensively studied on supports including carbon-based materials, transition metal oxides and metal–organic frameworks, among others. − Thus, far, however, sub-nanometric clusters, with comparatively distinct physicochemical properties to that of single atoms or larger sized nanoparticles, represents a field that has been vastly underexplored in electrocatalysis.…”