Photoinduced loading of electron-rich Cu single atoms by moderate coordination for hydrogen evolution

Abstract

Single-atom catalysts offer maximal atom utilization efficiencies and high-electronegativity heteroatoms play a crucial role in coordinating reactive single metal atoms to prevent agglomeration. However, these strong coordination bonds withdraw electron density for coordinated metal atoms and consequently affect their catalytic activity. Herein we reveal the high loading (11.3 wt%) and stabilization of moderately coordinated Cu-P3 structure on black phosphorus support by a photochemical strategy with auxiliary hydrogen. Single-atom Cu sites with an exceptional electron-rich feature show the $$\triangle {G}_{{{{{{\rm{H}}}}}}*}$$ △ G H * close to zero to favor catalysis. Neighboring Cu atoms work in synergy to lower the energy of key water adsorption and dissociation intermediates. The reported catalyst shows a low overpotential of only 41 mV at 10 mA cm−2 and Tafel slope of 53.4 mV dec−1 for the alkaline hydrogen evolution reaction, surpassing both isolated Cu single atoms and Cu nanoclusters. The promising materials design strategy sheds light on the design and fabrication of high-loading single metal atoms and the role of neighboring single atoms for enhanced reaction kinetics.

Potent Charge‐Trapping for Boosted Electrocatalytic Oxygen Reduction

“…Moreover, N atom doping changes the electronic structure of the carbon atoms, in which pyridinic‐N profits the ORR process. [ 15 ] Meanwhile, planar defect sites also cause in‐plane transfer localization of charge, interfering with the local density π‐electrons and modulating electrocatalytic activity. Therefore, the construction of defect density with precisely controlled density and electron‐rich environments are used to investigate the extent of electronic influence under real applications.…”

Adjacent atomic cobalt sites anchored on carbon foam as a self-supporting electrode for efficient hydrogen evolution

“…This reveals that the electron state of the Co 1 /Co 2 atom increases and its ability to promote charge transfer is strengthened. 48,49 This electron-rich state may regulate the dorbital structure of the Co atom and then benet the binding with the reaction intermediate. The interaction between the intermediate and the metal atomic site of the catalyst can also be evaluated by the d-band center of the metal atomic site.…”

A rational design of functional porous frameworks for electrocatalytic CO2reduction reaction

“…Specifically, the tandem electrolyzers achieved an n-propanol FE of 15.9% together with the corresponding halfcell power conversion efficiency (CPE) of 19.3%. Hence, tandem With the development of Cu-based functional porous frameworks, an increasing number of unique linking types and active site configurations has been designed and obtained, which are suitable equally for the ECO 2 RR, such as Cu-based MOFs formed by Cu 3 clusters and imide linkers (Li et al 143 and Lan et al 144 ), bicentric Cu-porphyrin structure (Peng et al 145 ), metal-porphyrin linked mercurated graphynes (Wong et al 146 ), and Cu-P 3 sites with novel coordinated heteroatom species and a high single-atom density of 11.3 wt% (Wang et al 147 ), which provide abundant Cu-based catalysts with reference significance on adjustable active sites for an improved ECO 2 RR performance.…”