Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

Abstract

The family of bulk metal phosphorus trichalcogenides (APX3, A = M(II), M(I)(0.5)M(III)(0.5); X = S, Se; M(I), M(II), and M(III) represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functional theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe3, CdPSe3, Ag0.5Sc0.5PSe3, and Ag0.5In0.5PX3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag0.5Sc0.5PSe3 is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting.

Biological and environmental interactions of emerging two-dimensional nanomaterials

“…water splitting), 353 which suggests they may undergo photo-induced degradation or transformation in the environment. Similar to layered TMDs, these layered metal phosphorus trichalcogenides can undergo intercalation reactions 354–356 including cationic substitution-intercalation reactions, where a cation from the environment can replace and remove the original cation in the host lattice, leading to release of potential toxic ions such as Cu, Cd, Ni, or Co. 355, 357–359 …”

The stabilities and electronic structures of single-layer bismuth oxyhalides for photocatalytic water splitting

“…19 Xiang's group 20 predicted a stable 2D boron-carbon compound BC 3 which exhibits a semiconductor behavior. Moreover, Liu and co-workers 21 proposed that singlelayer metal phosphorus trichalcogenides are potential photocatalysts for overall water splitting. Inspired by these progressive achievements, we thus expect that single-layer BiOX could also be obtained through mechanical or chemical exfoliation strategies, and could exhibit highly efficient photocatalytic performance.…”

Metall‐Phosphor‐Trichalkogenide (MPCh3): von der Synthese zu aktuellen Energieanwendungen

“…Im vorliegenden Fall beobachtete man keine direkte Korrelation zwischen der Leitfähigkeit des Materials und seiner elektrokatalytischen Aktivität. [50][51][52][53] Klassischerweise wurden drei Verteilungstypen magnetischer Momente in Volumenkristallen von MPCh 3 -Verbindungen vorgeschlagen: [13] Ty pI ist gekennzeichnet durch parallele doppelte ferromagnetische Ketten, die antiferromagnetisch miteinander gekoppelt sind (CoPS 3 ,N iPS 3 ). Daneben ist auch ein Ladungstransfer zwischen rGO und FePSe 3 mçglich, der in der hochauflçsenden XPS am Komposit durch eine Tieffeldverschiebung des Fe 2p-Peaks angezeigt wird (Abbildung 3b).…”