Phosphorene Supported Single‐Atom Catalysts for CO Oxidation: A Computational Study

Abstract

Single‐atom catalysts (SACs) have attracted extensive attention owing to their high catalytic activity. The development of efficient SACs is crucial for applications in heterogeneous catalysis. In this article, the geometric configuration, electronic structure, stabilitiy and catalytic performance of phosphorene (Pn) supported single metal atoms (M=Ru, Rh, Pd, Ir, Pt, and Au) have been systematically investigated using density functional theory calculations and ab initio molecular dynamics simulations. The single atoms are found to occupy the hollow site of phosphorene. Among the catalysts studied, Ru‐decorated phosphorene is determined to be a potential catalyst by evaluating adsorption energies of gaseous molecules. Various mechanisms including the Eley‐Rideal (ER), Langmuir‐Hinshelwood (LH) and trimolecular Eley‐Rideal (TER) mechanisms are considered to validate the most favourable reaction pathway. Our results reveal that Ru−Pn exhibits outstanding catalytic activity toward CO oxidation reaction via TER mechanism with the corresponding rate‐determining energy barrier of 0.44 eV, making it a very promising SAC for CO oxidation under mild conditions. Overall, this work may provide a new avenue for the design and fabrication of two‐dimensional materials supported SACs for low‐temperature CO oxidation.

Pd speciation on black phosphorene in a CO and C2H4 atmosphere: a first-principles investigation

“…4a) and is in reasonable agreement with the reported CO E ad over other Pd based SACs. 34,51 The adsorption of the first CO doesn't change the coordination of Pd significantly. The Pd atom is still in tetrahedral coordination with the CO standing 2.01 Å right above and CQO perpendicular to the lattice plane of bP (Pd 1 (CO) 1 , Fig.…”

“…18 Preformed Ag, Au, Ni, Pd and Pt nanoparticles were loaded onto few-layer phosphorene and the observed superior performance in gas sensing, selective hydrogenation, oxidation and photocatalysis was attributed to the metal/phosphorene contact. [19][20][21][22][23][24] Phosphorene based single atom catalysts (SACs) were also proposed to be efficient in the partial oxidation of methane, 25 electrocatalytic nitrogen, CO and CO 2 reductions, [26][27][28][29][30][31] hydrogenation, 32 CO oxidation, 33,34 oxygen reduction/evolution and hydrogen evolution, 35 etc. However, the reported approaches for the fabrication of phosphorene based SACs are still limited to the atomic layer deposition with the reaction of high energy precursors with the phosphorene support that may result in defective or doped phosphorene, and the wet chemistry approach through liquid phase reduction of precursors, but further treatment is required.…”

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

“…P-coordinated Ru and Rh single atoms showed electron-rich states too . Metal phosphides or black phosphorus (BP) containing surface P sites have been also extensively used as a support for the preparation of ADMCs. ,− For example, due to the relatively low electronegativity of BP and its buckled structure, robust zerovalent metal atoms can be well restricted in the vacancy sites of BP. Therefore, 2D BP served as an excellent support for the preparation of high-loading Pd and Pt via the ALD method.…”

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

“…The applicability of Pn as a support material was also suggested experimentally by the improved catalytic performance of metal nanoparticles (Pt, Ag, and Au) deposited on thin‐layered black phosphorus toward the oxygen reduction reaction (ORR) 74 . Furthermore, a large number of computational studies have presented the potential catalytic performance of metal‐doped Pn for electrochemical conversion, such as the nitrogen reduction reaction (NRR), 75–78 ORR, 79 OER, 79 thermal hydrogenation of small unsaturated molecule, 80 and low‐temperature CO oxidation 81 …”

“…74 Furthermore, a large number of computational studies have presented the potential catalytic performance of metal-doped Pn for electrochemical conversion, such as the nitrogen reduction reaction (NRR), [75][76][77][78] ORR, 79 OER, 79 thermal hydrogenation of small unsaturated molecule, 80 and low-temperature CO oxidation. 81 We herein present a systematic computational mechanistic study using periodic density functional theory (DFT) calculations to investigate the catalytic performance of single non-noble transition metal (Co) embedded in a Pn monolayer, Co@Pn, for CO oxidation. The cobalt was selected as an alternative species to noble metal SAC based on its earth abundance and the previously reported stability of Co-based SAC on the Pn monolayer.…”