Electronegativity Enhanced Strong Metal–Support Interaction in Ru@F–Ni₃N for Enhanced Alkaline Hydrogen Evolution

Abstract

Precious metals (Pt, Ir, Ru, and so on) and related compounds usually demonstrate superb catalytic activity for electrochemical hydrogen production. However, scarcity and stability are still challenges for hydrogen evolution reaction, even for single-atomic-site electrocatalysts. Herein, a fluorine (F) doping strategy is proposed to enhance the strong metal–support interaction between the F-doped Ni3N support and the loaded ruthenium (Ru) species. Via synergistically modulating both the Ru loading amount and F doping concentration, outstanding HER activity was achieved in Ru@F–Ni3N with an overpotential (η) of 115 mV at 100 mA cm–2, superior to the benchmark Pt/C (η = 201 mV). Density functional theory simulation in combination with X-ray photoelectron spectra and X-ray absorption spectroscopy characterizations convincingly demonstrate that, with the strongest electronegativity, F doping could effectively stabilize Ru atoms doped in the F–Ni3N substrate and simultaneously reduce the H bonding strength, which accelerated the desorption of H2. These findings provide a facile strategy to modulate both catalytic activities and stabilities of heteroatom-loaded catalytic materials.

Cation Vacancy Clusters in Ti3C2Tx MXene Induce Ultra‐Strong Interaction with Noble Metal Clusters for Efficient Electrocatalytic Hydrogen Evolution

“…The nearest neighbor peak is ascribed to Ru-F centered at 1.41 Å and Ru-O centered at 1.85 Å. [31] As for Ru 4 @Ti 3 C 2 T x -V S , the ligands of Ru cluster include both -O/-F terminal groups and the carbon atom exposed by the single Ti vacancy. Therefore, the nearest neighbor peak was deconvoluted by the components of Ru-C, Ru-F, and Ru-O paths.…”

Modulating Dominant Facets of Pt through Multistep Selective Anchored on WC for Enhanced Hydrogen Evolution Catalysis

“…The full-scan XPS survey spectrum verified the expected elements of W, C, Pt, and O in Pt–WC/CNT (Figure S10). Compared with 5% Pt/C (the two Pt 4f peaks of Pt 0 species at 71.2 and 74.5 eV) (Figure S11), the Pt 4f peaks of Pt–WC/CNT with low Pt load (0.66%, 0.33%, and 0.07%) had obvious positive shift (Figure f and Table S2), revealing that there is strong interaction between Pt and WC. − While the counterpart peaks of 3.62% and 2.05% Pt–WC/CNT did not shift significantly, suggesting that the surface Pt in Pt–WC/CNT is in the same state as that in Pt/C. This observation is extraordinary consistent with the crystal facet-oriented growth of the Pt in Pt–WC/CNT, indicating that the strong catalyst–support interaction between WC and Pt is crucial for the preferential growth of Pt (200) facet.…”

Quantifying the Two-Dimensional Driving Patterns of Chemisorbed Oxygen and Particle Size on NO Reduction Activity and Mechanism

“…Structure–activity relationships and reaction mechanisms are normally regulated by the structural − and electronic − properties of heterogeneous catalysts. Particle size of a catalyst plays a key role in optimizing these properties, ,− which is able to induce the electron perturbation/transfer and the (inverse) oxygen spill-over or activation via strong metal–support interaction (SMSI) or electronic metal–support interaction (EMSI), resulting in changes in the electronic properties and activation of oxygen species. ,,, Furthermore, the geometry and crystal plane exposure of active phase and defects of the lattice (bulk, face, linear, and point defects) can also be manipulated by the particle size .…”

“…Structure–activity relationships and reaction mechanisms are normally regulated by the structural − and electronic − properties of heterogeneous catalysts. Particle size of a catalyst plays a key role in optimizing these properties, ,− which is able to induce the electron perturbation/transfer and the (inverse) oxygen spill-over or activation via strong metal–support interaction (SMSI) or electronic metal–support interaction (EMSI), resulting in changes in the electronic properties and activation of oxygen species. ,,, Furthermore, the geometry and crystal plane exposure of active phase and defects of the lattice (bulk, face, linear, and point defects) can also be manipulated by the particle size . In particular, the latter would further affect the amounts of active sites and adjacent sites with optimized physicochemical properties, such as redox, coordination structures, and even electron configuration of coordination fields, − which makes active sites be able to stimulate reactant activation and improve the reaction rate with fewer coordination ligands .…”