High‐Density Frustrated Lewis Pair for High‐Performance Hydrogen Evolution

Abstract

It is significant to develop catalysts with high‐density and adjacent frustrated Lewis pair (FLP) sites. Herein, a method is designed to construct FLPs on an intermetallic alloy (IMA) with regulable acidity and basicity by using the Mott–Schottky effect. By dint of the high‐density FLP site and suitable acidity and basicity on IMA, the fct‐PtCo@NC displays excellent hydrogen evolution reaction performance. The catalyst fct‐PtCo@NC, with high‐density FLP sites, exhibits a fast water adsorption and decomposition rate, which is derived from the synergistic effect of FLP‐acid sites and FLP‐base sites significantly reducing the energy barrier between the two processes. Due to the FLP‐base Pt site, fct‐PtCo@NC has the best binding energy of hydrogen intermediates, the H3O+ generated during the reaction can accumulate on it and form an acid‐like environment, and thus speed up the kinetics of the reaction. In comparison, the catalyst without FLP shows lower binding energy and the formation of H3O+ is not observed. This work opens a new horizon for the design of new‐style heterogeneous FLP catalysts and the catalysts with high‐density and adjacent FLP sites are expected to be used in a variety of multistep catalytic reactions.

Electrocatalysts Design Guided by Active Intermediates of Hydrogen Evolution Reaction

“…Wang's group prepared an intermetallic alloy (IMA) catalyst fct‐PtCo@NC with high‐density FLP sites and suitable acidity/basicity sites by adjusting the N doping amount of the supporting materials ( Figure 11 a). [ 135 ] The ultraviolet photoemission spectroscopy (UPS) tests, photoluminescence (PL) spectra, and X‐ray photoelectron spectroscopy (XPS) demonstrated the N doped carbon material as the support had a significant effect on tuning the electron density of PtCo IMA. Specifically, the electron‐deficient Co sites and electron‐rich Pt sites acted as FLP‐acid site and FLP‐base site, respectively.…”

“…Reproduced with permission. [ 135 ] Copyright 2022, Wiley‐VCH. c) The schematic illustration for the preparation of Pt@CoO x .…”

“…Copyright 2020, 2022, 2023, Wiley-VCH. Reproduced with permission [101,115,134,135,144]. Copyright 2012, 2020, 2021, 2022, Springer Nature.…”

Modulating the d‐Band Center Enables Ultrafine Pt3Fe Alloy Nanoparticles for pH‐Universal Hydrogen Evolution Reaction

“…[ 19–28 ] Additionally, the strong chemical bonding between Pt and M endows intermetallic alloys with much‐improved stability against the acid etching, which is in favor of their long‐term operation and recycling. Large amounts of intermetallic Pt–M alloys including Pt 3 Fe, [ 29 ] PtFe, [ 30 ] Pt 3 Co, [ 31,32 ] PtCo, [ 33,34 ] PtNi, [ 35 ] Pt 3 Ge, [ 36 ] PtRu, [ 37 ] PtSn, [ 38 ] and Pt 3 Ir [ 39 ] have been synthesized and researched as highly active electrocatalysts for HER. Due to the strong d–d orbital electronic interactions (e.g., the shift of the d‐band center ( ε d )), they often exhibit significantly enhanced HER activity compared to bare counterparts.…”

Competitive adsorption of oxygen-containing intermediates on ruthenium–tin solid-solution oxides for alkaline oxygen evolution

“…Herein, considering the identical cation valence, similar ionic radii, and analogous crystal structure of Sn and Ru oxides, 20 we aimed to incorporate Sn into RuO 2 to construct rutile ruthenium-tin solid-solution oxides. 21 More importantly, the incorporation of Sn, which is a highly oxophilic element with excellent *O adsorption capability, 22,23 mitigated the excessive adsorption of *O on Ru sites through competitive adsorption of *O between the Ru and Sn sites. Among the synthesized catalysts, Ru 0.6 Sn 0.4 O 2 , with optimized catalytic activity, only required a low overpotential of 245 mV to achieve a current density of 10 mA cm −2 , a low Tafel slope of 61.80 mV dec −1 , and an ultrahigh turnover frequency (TOF) of 0.3 s −1 at 245 mV, which were much lower values than those for commercial RuO 2 (311 mV at 10 mA cm −2 , Tafel slope of 66.64 mV dec −1 , TOF of 0.05 s −1 at 245 mV).…”