Catalysis Mediated by 2D Black Phosphorus Either Pristine or Decorated with Transition Metals Species

Abstract

Among the novel class of mono-elemental two-dimensional (2D) materials, termed Xenes, phosphorene is emerging as a great promise for its peculiar chemical and physical properties. This review collects a selection of the recent breakthroughs that are related to the application of phosphorene in catalysis and electrocatalysis. Noteworthy, thanks to its intrinsic Lewis basic character, pristine phosphorene turned out to be more efficient and more selective than other non-metal catalysts, in chemical processes as the electroreduction of nitrogen to ammonia or the alkylation of nucleophiles with esters. Once functionalized with transition metals nanoparticles (Co, Ni, Pd, Pt, Ag, Au), its catalytic activity has been evaluated in several processes, mainly hydrogen and oxygen evolution reactions. Under visible light irradiation, it has shown a great improvement of the activity, demonstrating high potential as a photocatalyst.

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

“…16,17 To date, the heterogeneous catalytic application of phosphorene hasn't been well investigated. 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.…”

Interlayer Coordination of Pd–Pd Units in Exfoliated Black Phosphorus

“…To date, great efforts have been made to modify the surface of BP. Though surface decoration with metal nanoparticles has been extensively developed, ,− only a few studies have addressed its reactivity with molecular fragments, mainly organic molecules . Some established protocols include edge functionalization with C 60 buckyballs, reductive activation with alkali metals followed by alkylation with iodides, surface functionalization with nitrenes, , and arylation with diazonium salts, , though the last has recently been questioned .…”

Unraveling the Role of Nickel Nanoparticles Functionalization in the Electronic Properties and Structural Features of 2D Black Phosphorene Exposed to Ambient Conditions

“…Since its discovery in 2014 exfoliated black phosphorus, named hereafter BP, has gained an increasing interest among bidimensional materials and semiconductors thanks to its exceptional physicochemical properties [1] . The surface decoration of BP with metal nanoparticles [2] has boosted its application in various fields such as photo‐ and electrocatalysis, [3] gas‐sensors, [4] energy storage and conversion, [5] and biomedicine [6] . To date, the main pitfall of BP remains its limited ambient stability, [7] as photoexcited electrons formed upon light exposure can be easily transferred to surface adsorbed O 2 molecules, giving rise to reactive O 2 − species which in turn easily break down the polyphosphorus layers resulting in the formation of P−O [8] .…”