Carbon-doped BN nanosheets for metal-free photoredox catalysis

Abstract

The generation of sustainable and stable semiconductors for solar energy conversion by photoredox catalysis, for example, light-induced water splitting and carbon dioxide reduction, is a key challenge of modern materials chemistry. Here we present a simple synthesis of a ternary semiconductor, boron carbon nitride, and show that it can catalyse hydrogen or oxygen evolution from water as well as carbon dioxide reduction under visible light illumination. The ternary B–C–N alloy features a delocalized two-dimensional electron system with sp2 carbon incorporated in the h-BN lattice where the bandgap can be adjusted by the amount of incorporated carbon to produce unique functions. Such sustainable photocatalysts made of lightweight elements facilitate the innovative construction of photoredox cascades to utilize solar energy for chemical conversion.

Graphitic Carbon Nitride Polymers toward Sustainable Photoredox Catalysis

“…[78][79][80][81][82][83][84][85][86][87][88][89][90] Tang and co-workers have constructed two parallel systems for overall water splitting (both H 2 and O 2 can be evolved in an ideal ratio of 2:1) with visible light by using g-C 3 N 4 with two different metal oxides,B iVO 4 and WO 3 . [78][79][80][81][82][83][84][85][86][87][88][89][90] Tang and co-workers have constructed two parallel systems for overall water splitting (both H 2 and O 2 can be evolved in an ideal ratio of 2:1) with visible light by using g-C 3 N 4 with two different metal oxides,B iVO 4 and WO 3 .…”

Photocatalytic water oxidation by layered Co/h-BCN hybrids

“…The hybridized phases of the two two-dimensional (2D) materials by atomic mixture of B, N, and C with broad composition ranges to create various layered semiconducting structures would produce new material functions complementary to graphene and h-BN, enabling a wide variety of electronic structures, applications and properties [28][29][30]. Such an emerging family of chemically inert and mechanically strong 2D materials practically allows the bandgap-engineered applications in heterogeneous photocatalysis by creating a medium-gap ternary semiconductor, in which the band gap, redox energy levels, p/n-type properties and surface acid-base chemistry can in principle be modulated by rational design and synthesis [31,32].A hexagonal boron carbon nitride (h-BCN) semiconductor was applied to intercalate cobalt ions to catalyze oxygen evolution reaction (OER) with light illumination, without using noble metals. The h-BCN with high specific surface area showed a strong chemical affinity towards metal ions due to the "lop-sided" densities characteristic of ionic B-N bonding, enabling the creation of metal/h-BCN hybrid layered structures with unique properties.…”

Green Synthesis of Lamellae Rhombohedra Boron Suboxide for Efficient Photoreduction Catalysis with Visible Light Response

“…Since the discovery of the Honda–Fujishima effect in the early 1970s, photocatalytic and photoelectrochemical (PEC) water splitting or CO 2 reduction on semiconducting materials have been envisioned as a promising strategy for converting solar energy to fuels, such as H 2 , CO, etc . In addition to common transition metal‐based photocatalysts, of particular recent interest are materials so called “metal‐free photocatalysts,” which mainly consist of graphitic carbon nitride (g‐C 3 N 4 ), boron carbide (B 4 C), boron arsenide (BAs), boron phosphide (BP), C‐doped boron nitride (C‐doped BN), and elemental photocatalysts, such as α‐S, β‐B, red P, and black P (Table S1, Supporting Information). Obviously, boron‐containing photocatalysts play a pivotal role in the family of “metal‐free photocatalyst.”…”