Efficient Discovery of Active, Selective, and Stable Catalysts for Electrochemical H₂O₂ Synthesis through Active Motif Screening

Abstract

Electrochemical reduction of O2 provides a clean and decentralized pathway to produce H2O2 compared to the current energy-intensive anthraquinone process. As the electrochemical reduction of O2 proceeds via either two-electron or four-electron pathway , it is thus essential to control the selectivity as well as to maximize the catalytic activity. Siahrostami et al. demonstrated a novel approach to control the reaction pathway by optimizing an adsorption ensemble to tune adsorption sites of reaction intermediates, and identified Pt-Hg catalysts from density functional theory (DFT) calculations and experimentally validated this catalyst (Nat. Mater. 2013, 12, 1137). Inspired by this concept, in this work, we apply a state-of-the-art high-throughput screening to develop O2 reduction catalyst for selective H2O2 production. Starting from Materials Project database, we evaluate activity, selectivity and electrochemical stability. To efficiently perform the screening, we introduce an active motif based approach which pre-screens unpromising materials and only performs DFT calculations for promising materials, which significantly reduce the number of the required calculations. We not only provide a list of promising candidates identified by DFT calculations, but also suggest element species to achieve high catalytic activity or H2O2 selectivity for future experimental attempts. Finally, we discuss a strategy for efficient future high-throughput screening using a machine learning pipeline consisting of a non-linear dimension reduction and a density-based clustering. File list (2) download file view on ChemRxiv active_motif_ORR.pdf (4.40 MiB) download file view on ChemRxiv active_motif_ORR_SI.pdf (3.41 MiB)

Selective, Stable, Bias‐Free, and Efficient Solar Hydrogen Peroxide Production on Inorganic Layered Materials

“…Because the 2e – and 4e – reactions share the same steps until the * OOH formation step (I), we focused on the free energy values of the subsequent (II) and (II') steps. [ 42 ] The G ( * O) values of the various Co configurations are 3.80 eV (1Co), 3.72 eV (2Co), 3.51 eV (3Co), and 3.45 eV (4Co), which were higher than the value corresponding to G (OOH – ) ( = 3.44 eV). The Co content increased as the value of free energy ( * O) decreased.…”

Screening and Understanding Lattice Silicon‐Controlled Catalytically Active Site Motifs from a Library of Transition Metal‐Silicon Intermetallics

“…Fortunately, high-throughput density functional theory (DFT) calculations are becoming powerful enough to quickly predict catalytic properties and speed up the search for novel catalysts. [6][7][8][9] The high-throughput screening of highperforming catalysts is often dependent upon the simple and efficient thermodynamic descriptor (e.g., hydrogen adsorption energy (ΔG H* ) for hydrogen-evolving electrocatalysts), [10][11][12][13] which requires DFT calculations of surface adsorption properties of key intermediate species on surface active sites. For a desirable catalyst with the optimized local atomic structures, their surface active sites could bind the key reaction intermediates neither too strongly nor too weakly (also known as Sabatier principle).…”

Composition Engineering of Amorphous Nickel Boride Nanoarchitectures Enabling Highly Efficient Electrosynthesis of Hydrogen Peroxide

“…[ 8–10 ] However, the oxygen reduction reaction (ORR) inherently bears the high tendency to undergo the four electron (4e − ) transfer to form H 2 O, which inevitably suppresses the formation of H 2 O 2 through two electron (2e − ) pathway. [ 11–14 ] In this regard, developing electrocatalysts with high 2e − ORR selectivity is vitally important for the efficient production of H 2 O 2 .…”

“…Herein, a composition engineering strategy is proposed to flexibly regulate the intrinsic activity of amorphous nickel boride nanoarchitectures for efficient 2e − ORR by oriented reduction of Ni 2+ with different amounts of BH 4 H 2 O 2 through two electron (2e − ) pathway. [11][12][13][14] In this regard, developing electrocatalysts with high 2e − ORR selectivity is vitally important for the efficient production of H 2 O 2 .…”