Docking MOF crystals on graphene support for highly selective electrocatalytic peroxide production

Abstract

Tailoring the reaction kinetics is the central theme of designer electrocatalysts, which enables the selective conversion of abundant and inert atmospheric species into useful products. Here we show a supporting effect in tuning the electrocatalytic kinetics of oxygen reduction reaction (ORR) from four-electron to two-electron mechanism by docking metalloporphyrin-based metal-organic frameworks (MOFs) crystals on graphene support, leading to highly selective peroxide production with faradaic efficiency as high as 93.4%. A magic angle of 38.1° tilting for the co-facial alignment was uncovered by electron diffraction tomography, which is attributed to the maximization of π-π interaction for mitigating the lattice and symmetry mismatch between MOF and graphene. The facilitated electron migration and oxygen chemisorption could be ascribed to the supportive effect of graphene that disperses of the electron state of the active center, and ultimately regulates rate-determining step. Electronic Supplementary Material Supplementary material is available for this article at 10.1007/s12274-021-3382-3 and is accessible for authorized users.

Recent Advances and Future Perspectives of Transition Metal‐Supported Carbon with Different Dimensions for Highly Efficient Electrochemical Hydrogen Peroxide Preparation

“…used Co(NO 3 ) 2 ·6H 2 O as metal source and triglyceride (2‐chloropropyl) phosphate (TCPP) as an organic ligand to prepare MOF@NG catalysts by a solvothermal method. [ 146 ] The authors found that there was a torsion angle of ≈38° between the tetragonal lattice of the cobalt porphyrin MOF and the hexagonal lattice of graphene, which maximized their π‐π interaction, thereby mitigating the mismatch between the metal oxide and grapheme (Figure 16b). Accordingly, the selectivity and FE of the catalyst for H 2 O 2 preparation were 88.2% and 93.4%, respectively.…”

“…Reproduced with permission. [ 146 ] Copyright 2022, Springer. c) Schematic preparation, the yield, and FE of P‐Ni/MC/CP at different voltages.…”

“…b) Synthetic process, the yield, and faradaic efficiencies of catalysts. Reproduced with permission [146]. Copyright 2022, Springer.…”

Metal‐Organic Frameworks and Their Derivatives‐Based Nanostructure with Different Dimensionalities for Supercapacitors

“…Sustainable energy such as solar, wind, geothermal, ocean, and hydrogen energies have emerged as a major global trend today. [9][10][11] As known, the development of unconventional new energy sources cannot be separated from the continuous upgrading of energy storage technologies and equipments. [12][13][14][15] Among numerous emerging energy storage and conversion devices, supercapacitor is a nanoscale energy storage element constructed by using its polarized electrode materials and the ion layer adsorbed on its surfaces.…”

Pre-embedding an energetic metal–organic framework to create interconnected pore structures in nitrogen-doped carbon for green and effective hydrogen peroxide electrosynthesis

“…[8][9][10][11] The electrochemical 2e − ORR is a facile and green method of synthesizing H 2 O 2 without any negative byproducts. [12][13][14][15][16][17][18][19] The electrolyte flow typically carries O 2 to the active sites, where it is reduced to H 2 O 2 or H 2 O, corresponding to the 2e − and 4e − ORR pathways, respectively. [20][21][22][23][24][25] An electrocatalyst with high 2e − selectivity is highly required for the production of H 2 O 2 .…”