Termolecular Eley–Rideal pathway for efficient CO oxidation on phosphorene‐supported single‐atom cobalt catalyst

Abstract

Density functional theory calculations are conducted to examine the oxidation of CO on a single Co atom anchored on a two-dimensional phosphorene monolayer (Co@Pn). The stability of the Co adatom on the Pn monolayer was revealed by ab initio molecular dynamics simulations. Three plausible pathways for CO oxidation over Co@Pn were explored: Langmuir-Hinshelwood (LH), Eley-Rideal (ER), and the recently proposed termolecular Eley-Rideal (TER) mechanisms. The TER pathway has a relatively lower energy barrier for the rate-determining step (0.55) than those of the LH (0.81) and ER (0.70 eV) pathways. The efficiency of TER pathway can be interpreted by CO-promoted O 2 activation via the effective formation of a five-membered ring composed of two CO and one O 2 molecules. The results open a new avenue for developing phosphorene-supported non-noble transition metal single-atom catalysts for various catalytic applications.

Rise of atomically dispersed metal catalysts: Are they a new class of catalysts?

“…30,31 Accordingly, many reviews are now available, which are recommended to readers. [25][26][27][28][29][30][31][32][33][34][35][36] This account focuses on the unusual reactivities of atomically dispersed metal catalysts, which are hard to realize with homogeneous or heterogeneous catalysts. We present selective exemplars drawn from our own works as well as other prominent works: coke-resistant catalysts, thermally stable Os catalysts, reactivity-controllable catalysts, low-temperature conversion catalysts, and new chlorine evolution reaction (CER) catalysts.…”

“…Since these pioneering works, the field of atomically dispersed catalysts has blossomed in the past decade (Figure 1). 21–25 Their compositions have been broadened across the periodic table and they have demonstrated promise in a wide range of thermo‐, 26–28 photo‐, 29 and electro‐catalytic reactions 30,31 . Accordingly, many reviews are now available, which are recommended to readers 25–36 …”

Co(O)4(N)‐type single‐atom‐based catalysts and ligand‐driven modulation of electrocatalytic properties for reducing oxygen molecules

“…The presence of molecularly or atomically dispersed active species at surfaces leads the maximum utilization of the active species, and the strong coordination enables to preserve the active species during the electrochemical cycles. SABCs including the M‐N‐C (M = metal) type of active species, which are embedded into sp 2 carbon network, show excellent performance as electrocatalysts for various reaction 1,3,10,11 . Despite of numerous reports achieving uniformly dispersed active sites and excellent electrocatalytic activities, understanding the catalytic behaviors associated with electronic and steric environments around active sites will accelerate their practical applications.…”

“…SABCs including the M-N-C (M = metal) type of active species, which are embedded into sp 2 carbon network, show excellent performance as electrocatalysts for various reaction. 1,3,10,11 Despite of numerous reports achieving uniformly dispersed active sites and excellent electrocatalytic activities, understanding the catalytic behaviors associated with electronic and steric environments around active sites will accelerate their practical applications. Furthermore, development of cost-effective low-temperature process to produce M-N-C catalysts is required.…”

Constrained density functional theory calculations for estimation of forward and backward intermolecular charge transfer energy

“…Charge transfer (CT) is one of the most important concepts in chemical reactions, therefore, has received a great deal of interest in various chemistry fields such as solar cells, organic light-emitting diodes, and photoinduced reactions using photocatalysts. [1][2][3][4][5][6][7][8] For a general bimolecular donor (D)-acceptor (A) system, intermolecular CT can theoretically occur in two directions: from D to A and from A to D. CT excitation energy can be described with the sum of ionization potential (IP), electron affinity (EA), and Coulomb attractive interaction. Under the point charge model, the energy required for CT (E CT ) from D to A at long distance R can be written as follows [9][10][11] :…”