A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

Abstract

Red phosphorus is a promising photocatalyst with wide visible‐light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]‐oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h−1 from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]‐oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.

A general-purpose machine-learning force field for bulk and nanostructured phosphorus

“…2). Whilst most of the work on 2D phases is currently focused on phosphorene, Schusteritsch et al suggested to exfoliate Hittorf's P to give "hittorfene" 73 , and very recently Hittorf-based monolayers 11 and nanostructures 14 were indeed experimentally realised. It is therefore of interest to ask whether this exfoliation can be described by a force field for P, especially as the process involves more complex structures, making the routine application of DFT + MBD more computationally costly than for phosphorene.…”

“…White P, known since alchemical times, is formed of weakly bound P 4 molecules 2 , red P is an amorphous covalent network [3][4][5] and black P can be exfoliated to form monolayers, referred to as phosphorene 6,7 , which have promise for technological applications 8 . Other allotropes include Hittorf's violet and Ruck's fibrous forms, consisting of cage-like motifs that are covalently linked in different ways [9][10][11] , P nanorods and nanowires [12][13][14] and a range of thus far hypothetical allotropes [15][16][17][18] . Finally, liquid P has been of fundamental interest due to the observation of a first-order transition between low-and high-density phases [19][20][21] .…”

Hierarchically Structured Allotropes of Phosphorus from Data‐Driven Exploration

“…The application relevance of black phosphorus is most clear in light of its monolayer, phosphorene , but other allotropes are being actively studied as well. For example, monolayer violet phosphorus, dubbed hittorfene , was suggested as a direct‐band gap two‐dimensional (2D) material, and subsequently such samples were indeed experimentally realized, as were nanowires of the same allotrope . Fibrous phosphorus is built from similar tubular fragments as Hittorf's form but exhibits a different extended structure; yet other tubular allotropes can be formed by de‐intercalation from phosphorus‐rich CuI adducts .…”

Modification of g‐C3N4 Photocatalyst with Flower‐like ReS2 for Highly Efficient Photocatalytic Hydrogen Evolution

“…The peak at binding energies of 284.80 eV is related to adventitious C [27] . The peaks of binding energies at 286.25 eV and 288.18 eV are attributed to sp 3 carbon(C−N) in the edges of tri‐s‐triazine unit and sp 2 ‐hybridized carbon (N−C=N), respectively [28] . The C 1s spectra of 3 % ReS 2 /g‐C 3 N 4 presents three peaks originating from C−N (286.10 eV), N−C=N (288.27 eV) and adventitious C (284.80 eV) with similar binding energy positions as g‐C 3 N 4 .…”