Versatile Graphene-Promoting Photocatalytic Performance of Semiconductors: Basic Principles, Synthesis, Solar Energy Conversion, and Environmental Applications
TL;DR: Graphene-semiconductor nanocomposites, considered as a kind of most promising photocatalysts, have shown remarkable performance and drawn signifi cant attention in the fi eld of photo-driven chemical conversion using solar energy, due to the unique physicochemical properties of graphene as discussed by the authors.
Abstract: Graphene-semiconductor nanocomposites, considered as a kind of most promising photocatalysts, have shown remarkable performance and drawn signifi cant attention in the fi eld of photo-driven chemical conversion using solar energy, due to the unique physicochemical properties of graphene. The photocatalytic enhancement of graphene-based nanocomposites is caused by the reduction of the recombination of electron-hole pairs, the extension of the light absorption range, increase of absorption of light intensity, enhancement of surface active sites, and improvement of chemical stability of photocatalysts. Recent progress in the photo catalysis development of graphene-based nanocomposites is highlighted and evaluated, focusing on the mechanism of graphene-enhanced photocatalytic activity, the understanding of electron transport, and the applications of graphene-based photocatalysts on water splitting, degradation or oxidization of organic contaminants, photoreduction of CO 2 into renewable fuels, toxic elimination of heavy metal ions, and antibacterial applications.
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TL;DR: It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.
Abstract: As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...
5,054 citations
TL;DR: This review for the first time summarizes all the developed earth-abundant cocatalysts for photocatalytic H2- and O2-production half reactions as well as overall water splitting.
Abstract: Photocatalytic water splitting represents a promising strategy for clean, low-cost, and environmental-friendly production of H2 by utilizing solar energy. There are three crucial steps for the photocatalytic water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic H2 and O2 evolution reactions. While significant achievement has been made in optimizing the first two steps in the photocatalytic process, much less efforts have been put into improving the efficiency of the third step, which demands the utilization of cocatalysts. To date, cocatalysts based on rare and expensive noble metals are still required for achieving reasonable activity in most semiconductor-based photocatalytic systems, which seriously restricts their large-scale application. Therefore, seeking cheap, earth-abundant and high-performance cocatalysts is indispensable to achieve cost-effective and highly efficient photocatalytic water splitting. This review for the first time summarizes all the developed earth-abundant cocatalysts for photocatalytic H2- and O2-production half reactions as well as overall water splitting. The roles and functional mechanism of the cocatalysts are discussed in detail. Finally, this review is concluded with a summary, and remarks on some challenges and perspectives in this emerging area of research.
1,990 citations
TL;DR: The formation of semiconductor composites comprising multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems as discussed by the authors, and a review summarizes the recent strategies to develop such composites, and highlights the most recent developments in the literature.
Abstract: The formation of semiconductor composites comprising multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems. This review summarizes the recent strategies to develop such composites, and highlights the most recent developments in the fi eld. After a general introduction into the different strategies to improve photocatalytic activity through formation of heterojunctions, the three different types of heterojunctions are introduced in detail, followed by a historical introduction to semiconductor heterojunction systems and a thorough literature overview. Special chapters describe the highly-investigated carbon nitride heterojunctions as well as very recent developments in terms of multiphase heterojunction formation, including the latest insights into the anatase-rutile system. When carefully designed, semiconductor composites comprising two or three different materials or phases very effectively facilitate charge separation and charge carrier transfer, substantially improving photocatalytic and photoelectrochemical effi ciency.
1,241 citations
TL;DR: The present review provides an overview and highlights recent state-of-the-art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation.
Abstract: Photocatalytic reduction of CO2 into hydrocarbon fuels, an artificial photosynthesis, is based on the simulation of natural photosynthesis in green plants, whereby O2 and carbohydrates are produced from H2 O and CO2 using sunlight as an energy source. It couples the reductive half-reaction of CO2 fixation with a matched oxidative half-reaction such as water oxidation, to achieve a carbon neutral cycle, which is like killing two birds with one stone in terms of saving the environment and supplying future energy. The present review provides an overview and highlights recent state-of-the-art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation. It specifically includes: i) band-structure engineering, ii) nanostructuralization, iii) surface oxygen vacancy engineering, iv) macro-/meso-/microporous structuralization, v) exposed facet engineering, vi) co-catalysts, vii) the development of a Z-scheme system. The challenges and prospects for future development of this field are also present.
1,201 citations
TL;DR: In this article, a critical review presents the recent advances and progress in the design and synthesis of various semiconductor photocatalytic technology that converts solar energy into chemical fuel has been widely studied.
Abstract: To solve the problem of the global energy shortage and the pollution of the environment, in recent years, semiconductor photocatalytic technology that converts solar energy into chemical fuel has been widely studied. Regarding semiconductor-based photocatalysts, CdS has attracted extensive attention due to its relatively narrow bandgap for visible-light response and sufficiently negative potential of the conduction band edge for the reduction of protons. Studies have shown that CdS-based photocatalysts possess excellent photocatalytic performance in terms of solar-fuel generation and environmental purification. This critical review presents the recent advances and progress in the design and synthesis of various CdS and CdS-based photocatalysts. The basic physical and chemical properties of CdS and the related growth mechanism have been briefly summarized. Moreover, the applications of CdS-based photocatalysts have been discussed such as in photocatalytic hydrogen production, reduction of CO2 to hydrocarbon fuels and degradation of pollutants. Finally, a brief perspective on the challenges and future directions for the development of CdS and CdS-based photocatalysts are also presented.
1,054 citations
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TL;DR: Monocrystalline graphitic films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands and they exhibit a strong ambipolar electric field effect.
Abstract: We describe monocrystalline graphitic films, which are a few atoms thick but are nonetheless stable under ambient conditions, metallic, and of remarkably high quality. The films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands, and they exhibit a strong ambipolar electric field effect such that electrons and holes in concentrations up to 10 13 per square centimeter and with room-temperature mobilities of ∼10,000 square centimeters per volt-second can be induced by applying gate voltage.
55,532 citations
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TL;DR: Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena can now be mimicked and tested in table-top experiments.
Abstract: Graphene is a rapidly rising star on the horizon of materials science and condensed-matter physics. This strictly two-dimensional material exhibits exceptionally high crystal and electronic quality, and, despite its short history, has already revealed a cornucopia of new physics and potential applications, which are briefly discussed here. Whereas one can be certain of the realness of applications only when commercial products appear, graphene no longer requires any further proof of its importance in terms of fundamental physics. Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena, some of which are unobservable in high-energy physics, can now be mimicked and tested in table-top experiments. More generally, graphene represents a conceptually new class of materials that are only one atom thick, and, on this basis, offers new inroads into low-dimensional physics that has never ceased to surprise and continues to provide a fertile ground for applications.
35,293 citations
26,456 citations
TL;DR: This study reports an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation and reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions.
Abstract: Quantum electrodynamics (resulting from the merger of quantum mechanics and relativity theory) has provided a clear understanding of phenomena ranging from particle physics to cosmology and from astrophysics to quantum chemistry. The ideas underlying quantum electrodynamics also influence the theory of condensed matter, but quantum relativistic effects are usually minute in the known experimental systems that can be described accurately by the non-relativistic Schrodinger equation. Here we report an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation. The charge carriers in graphene mimic relativistic particles with zero rest mass and have an effective 'speed of light' c* approximately 10(6) m s(-1). Our study reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions. In particular we have observed the following: first, graphene's conductivity never falls below a minimum value corresponding to the quantum unit of conductance, even when concentrations of charge carriers tend to zero; second, the integer quantum Hall effect in graphene is anomalous in that it occurs at half-integer filling factors; and third, the cyclotron mass m(c) of massless carriers in graphene is described by E = m(c)c*2. This two-dimensional system is not only interesting in itself but also allows access to the subtle and rich physics of quantum electrodynamics in a bench-top experiment.
18,958 citations
TL;DR: Graphene is established as the strongest material ever measured, and atomically perfect nanoscale materials can be mechanically tested to deformations well beyond the linear regime.
Abstract: We measured the elastic properties and intrinsic breaking strength of free-standing monolayer graphene membranes by nanoindentation in an atomic force microscope. The force-displacement behavior is interpreted within a framework of nonlinear elastic stress-strain response, and yields second- and third-order elastic stiffnesses of 340 newtons per meter (N m(-1)) and -690 Nm(-1), respectively. The breaking strength is 42 N m(-1) and represents the intrinsic strength of a defect-free sheet. These quantities correspond to a Young's modulus of E = 1.0 terapascals, third-order elastic stiffness of D = -2.0 terapascals, and intrinsic strength of sigma(int) = 130 gigapascals for bulk graphite. These experiments establish graphene as the strongest material ever measured, and show that atomically perfect nanoscale materials can be mechanically tested to deformations well beyond the linear regime.
18,008 citations