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Journal ArticleDOI

Novel BiOCl–C3N4 heterojunction photocatalysts: In situ preparation via an ionic-liquid-assisted solvent-thermal route and their visible-light photocatalytic activities

01 Dec 2013-Chemical Engineering Journal (Elsevier)-Vol. 234, pp 361-371
TL;DR: In this paper, a novel BiOCl-C3N4 heterojunction was synthesized through an ionic-liquid-assisted solvent-thermal method, through which a highly dispersed heterointerface was formed with almost no loss of C 3N4, which increased the visible light photocatalytic activity 3.3-fold relative to that of a sample of a mechanically mixed counterpart of this composition.
About: This article is published in Chemical Engineering Journal.The article was published on 2013-12-01. It has received 274 citations till now. The article focuses on the topics: Photocatalysis & Visible spectrum.
Citations
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Journal ArticleDOI
TL;DR: The photo-catalytic applications of g-C3N4 -based photocatalysts in the fields of water splitting, CO2 reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non-noble-metal coc atalysts, and Z-scheme heterojunctions.
Abstract: Semiconductor-based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g-C3N4) for visible-light photocatalytic water splitting, g-C3N4 -based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g-C3N4 -based photocatalysts, including the fabrication and nanostructure design of pristine g-C3N4 , bandgap engineering through atomic-level doping and molecular-level modification, and the preparation of g-C3N4 -based semiconductor composites. Also, the photo-catalytic applications of g-C3N4 -based photocatalysts in the fields of water splitting, CO2 reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non-noble-metal cocatalysts, and Z-scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g-C3N4 -based photocatalysts are highlighted.

2,868 citations

Journal ArticleDOI
TL;DR: In this paper, the fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the design considerations of g-C3N4-based photocatalysts are summarized, including their crystal structural, surface phisicochemical, stability, optical, adsorption, electrochemical, photoelectrochemical and electronic properties.

2,132 citations

Journal ArticleDOI
TL;DR: The enhanced performance of g-C(3)N(4)-based nanocomposites has been widely employed in environmental and energetic applications such as photocatalytic degradation of pollutants, photoc atalytic hydrogen generation, carbon dioxide reduction, disinfection, and supercapacitors.
Abstract: Graphitic carbon nitride (g-C3N4), as an intriguing earth-abundant visible light photocatalyst, possesses a unique two-dimensional structure, excellent chemical stability and tunable electronic structure. Pure g-C3N4 suffers from rapid recombination of photo-generated electron–hole pairs resulting in low photocatalytic activity. Because of the unique electronic structure, the g-C3N4 could act as an eminent candidate for coupling with various functional materials to enhance the performance. According to the discrepancies in the photocatalytic mechanism and process, six primary systems of g-C3N4-based nanocomposites can be classified and summarized: namely, the g-C3N4 based metal-free heterojunction, the g-C3N4/single metal oxide (metal sulfide) heterojunction, g-C3N4/composite oxide, the g-C3N4/halide heterojunction, g-C3N4/noble metal heterostructures, and the g-C3N4 based complex system. Apart from the depiction of the fabrication methods, heterojunction structure and multifunctional application of the g-C3N4-based nanocomposites, we emphasize and elaborate on the underlying mechanisms in the photocatalytic activity enhancement of g-C3N4-based nanocomposites. The unique functions of the p–n junction (semiconductor/semiconductor heterostructures), the Schottky junction (metal/semiconductor heterostructures), the surface plasmon resonance (SPR) effect, photosensitization, superconductivity, etc. are utilized in the photocatalytic processes. Furthermore, the enhanced performance of g-C3N4-based nanocomposites has been widely employed in environmental and energetic applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation, carbon dioxide reduction, disinfection, and supercapacitors. This critical review ends with a summary and some perspectives on the challenges and new directions in exploring g-C3N4-based advanced nanomaterials.

1,382 citations

Journal ArticleDOI
TL;DR: In this article, a review of the fundamental aspects of photocatalysis as a pollution remediation strategy is presented, followed by an introduction to graphitic carbon nitride as a photocatalyst, preparation strategies and its properties, and a comprehensive and critical discussion of the various most recent developments towards enhancing the visible light photocatalytic properties of g-C 3 N 4 for pollution alleviation.
Abstract: Engineering photocatalytic materials for renewable energy generation and environmental decontamination has always been a very exciting prospect to counter the global energy demands and pollution challenges. Graphitic carbon nitride (g-C 3 N 4 ), a polymeric, metal-free semiconductor with a mild band gap (2.7 eV) has become hot-spot in various scientific exploits such as environmental pollution mitigation, energy generation and storage, organic synthesis, sensors, etc. These applications exploit the interesting properties of g-C 3 N 4 such as good visible light absorption, graphene-like structure, good thermal and chemical stability and photocatalytic properties. In this review we begin with an overview of the fundamental aspects of photocatalysis as a pollution remediation strategy. This is followed by an introduction to graphitic carbon nitride as a photocatalyst, preparation strategies and its properties. Subsequently, a comprehensive and critical discussion of the various most recent developments towards enhancing the visible light photocatalytic properties of g-C 3 N 4 for pollution alleviation, selected results and important photocatalytic degradation mechanisms, is given. Summary remarks and future perspective conclude the review.

920 citations

Journal ArticleDOI
TL;DR: In this article, a critical review summarizes recent progress in designing and tuning new bismuth oxyhalide materials to boost solar energy conversion, including structural engineering, defect control, interface engineering, solid solutions, inner coupling, and heterojunction construction.

386 citations

References
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Journal ArticleDOI
TL;DR: It is shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor.
Abstract: The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.

9,751 citations

Journal ArticleDOI
15 Dec 1995-Science
TL;DR: In this paper, the carrier collection efficiency and energy conversion efficiency of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives.
Abstract: The carrier collection efficiency (ηc) and energy conversion efficiency (ηe) of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives. Composite films of poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) and fullerenes exhibit ηc of about 29 percent of electrons per photon and ηe of about 2.9 percent, efficiencies that are better by more than two orders of magnitude than those that have been achieved with devices made with pure MEH-PPV. The efficient charge separation results from photoinduced electron transfer from the MEH-PPV (as donor) to C60 (as acceptor); the high collection efficiency results from a bicontinuous network of internal donor-acceptor heterojunctions.

9,611 citations

Journal ArticleDOI
TL;DR: 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 the excellent photoreactivity of C(3)N(4-x)S(x), which may shed light on general doping strategies for designing potentially efficient photocatalysts.
Abstract: 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.

1,762 citations

Journal ArticleDOI
TL;DR: In this article, the behavior of semiconducting electrodes for photoelectrolysis of water is examined in terms of the physical properties of the semiconductor and the photocurrent is described using a simple Schottky barrier.
Abstract: The behavior of semiconducting electrodes for photoelectrolysis of water is examined in terms of the physical properties of the semiconductor. The semiconductor‐electrolyte junction is treated as a simple Schottky barrier, and the photocurrent is described using this model. The approach is appropriate since large‐band‐gap semiconductors have an intrinsic oxygen overpotential which removes the electrode reaction kinetics as the rate‐limiting step. The model is successful in describing the wavelength and potential dependence of the photocurrent in WO3 and allows a determination of the band gap, optical absorption depth, minority‐carrier diffusion length, flat‐band potential, and the nature of the fundamental optical transition (direct or indirect). It is shown for WO3 that minority‐carrier diffusion plays a limited role in determining the photoresponse of the semiconductor‐electrolyte junction. There are indications that the diffusion length in this low carrier mobility material is determined by diffusion‐controlled bulk recombination processes rather than the more common trap‐limited recombination. It is also shown that the fundamental optical transition is indirect and that the band‐gap energy depends relatively strongly on applied potential and electrolyte. This effect seems to be the result of field‐induced crystallographic distortions in antiferroelectric WO3.

1,758 citations

Journal ArticleDOI
TL;DR: Graphene and graphitic carbon nitride composite photocatalysts were prepared by a combined impregnation−chemical reduction strategy involving polymerization of melamine in the presence of graphene oxide (precursors) and hydrazine hydrate (reducing agent), followed by thermal treatment at 550 °C under flowing nitrogen as mentioned in this paper.
Abstract: Graphene and graphitic carbon nitride (g-C3N4) composite photocatalysts were prepared by a combined impregnation−chemical reduction strategy involving polymerization of melamine in the presence of graphene oxide (precursors) and hydrazine hydrate (reducing agent), followed by thermal treatment at 550 °C under flowing nitrogen. The resulting graphene/g-C3N4 composite photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, UV−visible spectrophotometry, nitrogen adsorption, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and photoluminescence spectroscopy. The transient photocurrent response was measured for several on−off cycles of intermittent irradiation. The effect of graphene content on the rate of visible-light photocatalytic hydrogen production was studied for a series of graphene−graphitic carbon nitride composite samples containing Pt as a cocatalyst in methanol aqueous solutions. This study shows that graphene sheets a...

1,660 citations