Abstract“Graphitic” (g)‐C3N4 with a layered structure has the potential of forming graphene‐like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g‐C3N4 nanosheets with a thickness of around 2 nm can be easily obtained by a simple top‐down strategy, namely, thermal oxidation etching of bulk g‐C3N4 in air. Compared to the bulk g‐C3N4, the highly anisotropic 2D‐nanosheets possess a high specific surface area of 306 m2 g−1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in‐plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g‐C3N4 nanosheets have been remarkably improved in terms of •OH radical generation and photocatalytic hydrogen evolution.
Electronic structure intrinsically controls the light absorbance, redox potential, charge-carrier mobility, and consequently, photoreactivity of semiconductor photocatalysts. The conventional approach of modifying the electronic structure of a semiconductor photocatalyst for a wider absorption range by anion doping operates at the cost of reduced redox potentials and/or charge-carrier mobility, so that its photoreactivity is usually limited and some important reactions may not occur at all. Here, we report sulfur-doped graphitic C(3)N(4) (C(3)N(4-x)S(x)) with a unique electronic structure that displays an increased valence bandwidth in combination with an elevated conduction band minimum and a slightly reduced absorbance. The C(3)N(4-x)S(x) shows a photoreactivity of H(2) evolution 7.2 and 8.0 times higher than C(3)N(4) under lambda > 300 and 420 nm, respectively. More strikingly, the complete oxidation process of phenol under lambda > 400 nm can occur for sulfur-doped C(3)N(4), which is impossible for C(3)N(4) even under lambda > 300 nm. The homogeneous substitution of sulfur for lattice nitrogen and a concomitant quantum confinement effect are identified as the cause of this unique electronic structure and, consequently, the excellent photoreactivity of C(3)N(4-x)S(x). The results acquired may shed light on general doping strategies for designing potentially efficient photocatalysts.
A novel reduced melon photocatalyst with a bandgap of 2.03 eV developed here has a widened visible light absorption range and suppressed radiative recombination of photo-excited charge carriers due to the homogeneous self-modification with nitrogen vacancies. As a consequence, the reduced melon shows a much superior photocatalytic activity compared to the pristine melon in generating •OH radicals and degrading the organic pollutant Rhodamine B.
Vacancy defects can play an important role in modifying
the electronic
structure and the properties of photoexcited charge carriers and consequently
the photocatalytic activity of semiconductor photocatalysts. By controlling
the polycondensation temperature of a dicyandiamide precursor in the
preparation of graphitic carbon nitride (g-C3N4), we introduced nitrogen vacancies in the framework of g-C3N4. These vacancies exert remarkable effects on modifying
the electronic structure of g-C3N4 as shown
in UV–visible absorption spectra and valence band spectra.
Steady and time-resolved fluorescence emission spectra show that,
due to the existence of abundant nitrogen vacancies, the intrinsic
radiative recombination of electrons and holes in g-C3N4 is greatly restrained, and the population of short-lived
and long-lived charge carriers is decreased and increased, respectively.
As a consequence, the overall photocatalytic activity of the g-C3N4, characterized by the ability to generate •OH
radicals, photodecomposition of Rhodamine B, and photocatalytic hydrogen
evolution under both UV–visible and visible light, was remarkably
improved.
Narrowing the bandgap of wide-bandgap semiconductor photocatalysts (for instance, anatase TiO 2 ) by introducing suitable heteroatoms has been actively pursued for increasing solar absorption, but usually suffers from a limited thermodynamic/kinetic solubility of substitutional dopants in bulk and/or dopant-induced recombination centres. Here we report a red anatase TiO 2 microsphere with a bandgap gradient varying from 1.94 eV on its surface to 3.22 eV in its core by a conceptually different doping approach for harvesting the full spectrum of visible light. This approach uses a pre-doped interstitial boron gradient to weaken nearby Ti-O bonds for the easy substitution of oxygen by nitrogen, and consequently it substantially improves the nitrogen solubility. Furthermore, no nitrogen-related Ti 3+ was formed in the red TiO 2 due to a charge compensation effect by boron, which inevitably occurs in common nitrogen doped TiO 2 . The red anatase TiO 2 exhibits photoelectrochemical water splitting activity under visible light irradiation. The results obtained may shed light on how to increase high visible light absorbance of wide-bandgap photocatalysts.
We show that in contrast to conventional compound photocatalysts, α-sulfur crystals of cyclooctasulfur (S(8)) are a visible-light-active elemental photocatalyst. The α-S crystals were found to have the ability not only to generate ·OH radicals but also to split water in a photoelectrochemical process under both UV-vis and visible-light irradiation. Although the absolute activity obtained was low because of the large particle size and poor hydrophilicity of the α-S crystals studied, there is great potential for increasing the activity with the assistance of known strategies such as surface modification, nanoscaling, doping, and coupling with other photocatalysts.
Black phosphorus (BP) is a rapidly up and coming star in two‐dimensional (2D) materials. The unique characteristic of BP is its in‐plane anisotropy. This characteristic of BP ignites a new type of 2D materials that have low‐symmetry structures and in‐plane anisotropic properties. On this basis, they offer richer and more unique low‐dimensional physics compared to isotropic 2D materials, thus providing a fertile ground for novel applications including electronics, optoelectronics, molecular detection, thermoelectric, piezoelectric, and ferroelectric with respect to in‐plane anisotropy. This article reviews the recent advance in characterization and applications of in‐plane anisotropic 2D materials.
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