Molecule-Enhanced Electrocatalysis of Sustainable Oxygen Evolution Using Organoselenium Functionalized Metal–Organic Nanosheets

Abstract

Remolding the reactivity of metal active sites is critical to facilitate renewable electricity-powered water electrolysis. Doping heteroatoms, such as Se, into a metal crystal lattice has been considered an effective approach, yet usually suffers from loss of functional heteroatoms during harsh electrocatalytic conditions, thus leading to the gradual inactivation of the catalysts. Here, we report a new heteroatom-containing molecule-enhanced strategy toward sustainable oxygen evolution improvement. An organoselenium ligand, bis(3,5-dimethyl-1H-pyrazol-4yl)selenide containing robust C−Se−C covalent bonds equipped in the precatalyst of ultrathin metal−organic nanosheets Co-SeMON, is revealed to significantly enhance the catalytic mass activity of the cobalt site by 25 times, as well as extend the catalyst operation time in alkaline conditions by 1 or 2 orders of magnitude compared with these reported metal selenides. A combination of various in situ/ex situ spectroscopic techniques, ab initio molecular dynamics, and density functional theory calculations unveiled the organoselenium intensified mechanism, in which the nonclassical bonding of Se to O-containing intermediates endows adsorption-energy regulation beyond the conventional scaling relationship. Our results showcase the great potential of moleculeenhanced catalysts for highly efficient and economical water oxidation.

Co−Co Dinuclear Active Sites Dispersed on Zirconium‐doped Heterostructured Co9S8/Co3O4 for High‐current‐density and Durable Acidic Oxygen Evolution

“…[36][37][38] The wavelet transform (WT) was further conducted to reveal the EXAFS oscillations for Co K-edge. In the WT analysis, the CoÀ Co DASs/ZCC also showed the obvious intensity feature assigned to CoÀ O bonds, which was consistent with reference Co 3 O 4 , [39,40] further revealing the existence of Co 3 O 4 species in catalysts (Figure 2d-f). The above XAFS fitting results also found that the slightly elongated CoÀ O bonds (1.95 Å) of CoÀ Co DASs/ZCC with longer interatomic distance owing to the formation of SÀ CoÀ O HGBIs (Figure 2g), compared with bulk Co 3 O 4 (1.91 Å).…”

“…The above XAFS fitting results also found that the slightly elongated CoÀ O bonds (1.95 Å) of CoÀ Co DASs/ZCC with longer interatomic distance owing to the formation of SÀ CoÀ O HGBIs (Figure 2g), compared with bulk Co 3 O 4 (1.91 Å). [36,39] The relatively elongated distance was also very beneficial to enhance the stability. [35] Furthermore, the symmetric dual Co sites with appropriate atomic distances ( � 2.80 Å) were beneficial to facilitating OÀ O radical coupling for two active site OER process under…”

Trimetallic-organic framework/MXene composite as an oxygen evolution reaction electrocatalyst with elevated intrinsic activity

“…), their widespread application is restricted, requiring the development of other electrocatalysts free of noble metals, such as transition-metal oxides or hydroxides. 5 Transition-metal-based oxides, chalcogenides, 6–8 hydroxides, phosphides, double perovskites, metal–organic frameworks (MOFs) 9,10 and their composites with carbon (graphene, carbon nanotubes, etc. ) have been developed through extensive scientific investigations.…”

Electrocatalysts for the oxygen evolution reaction: mechanism, innovative strategies, and beyond

“…[1][2][3][4][5] A common feature of all these systems is that the cathode region undergoes a reduction reaction while the anode region experiences an oxygen evolution reaction (OER). [6][7][8][9][10] However, the sluggish and multi-step proton-coupled electron transfer process of the OER plays a decisive role, especially in electrocatalytic water-splitting systems. [11][12][13][14][15][16] Water splitting is considered a straightforward, environmentally friendly, and cost-effective approach to hydrogen production instead of hydrocarbon reforming or cracking.…”

“…1–5 A common feature of all these systems is that the cathode region undergoes a reduction reaction while the anode region experiences an oxygen evolution reaction (OER). 6–10…”