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Journal ArticleDOI

A metal-free polymeric photocatalyst for hydrogen production from water under visible light

01 Jan 2009-Nature Materials (Nature Publishing Group)-Vol. 8, Iss: 1, pp 76-80
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.

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Citations
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Journal ArticleDOI
TL;DR: Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting and its Applications d0 Metal Oxide Photocatalysts 6518 4.4.1.
Abstract: 2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

6,332 citations

Journal ArticleDOI
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

Journal ArticleDOI
27 Feb 2015-Science
TL;DR: The design and fabrication of a metal-free carbon nanodot–carbon nitride (C3N4) nanocomposite is reported and its impressive performance for photocatalytic solar water splitting is demonstrated.
Abstract: The use of solar energy to produce molecular hydrogen and oxygen (H2 and O2) from overall water splitting is a promising means of renewable energy storage. In the past 40 years, various inorganic and organic systems have been developed as photocatalysts for water splitting driven by visible light. These photocatalysts, however, still suffer from low quantum efficiency and/or poor stability. We report the design and fabrication of a metal-free carbon nanodot-carbon nitride (C3N4) nanocomposite and demonstrate its impressive performance for photocatalytic solar water splitting. We measured quantum efficiencies of 16% for wavelength λ = 420 ± 20 nanometers, 6.29% for λ = 580 ± 15 nanometers, and 4.42% for λ = 600 ± 10 nanometers, and determined an overall solar energy conversion efficiency of 2.0%. The catalyst comprises low-cost, Earth-abundant, environmentally friendly materials and shows excellent stability.

3,553 citations

Journal ArticleDOI
TL;DR: This article reviews state-of-the-art research activities in the field, focusing on the scientific and technological possibilities offered by photocatalytic materials, and highlights crucial issues that should be addressed in future research activities.
Abstract: Semiconductor photocatalysis has received much attention as a potential solution to the worldwide energy shortage and for counteracting environmental degradation. This article reviews state-of-the-art research activities in the field, focusing on the scientific and technological possibilities offered by photocatalytic materials. We begin with a survey of efforts to explore suitable materials and to optimize their energy band configurations for specific applications. We then examine the design and fabrication of advanced photocatalytic materials in the framework of nanotechnology. Many of the most recent advances in photocatalysis have been realized by selective control of the morphology of nanomaterials or by utilizing the collective properties of nano-assembly systems. Finally, we discuss the current theoretical understanding of key aspects of photocatalytic materials. This review also highlights crucial issues that should be addressed in future research activities.

3,265 citations

Journal ArticleDOI
TL;DR: This review attempts to summarize the recent progress in the rational design and fabrication ofheterojunction photocatalysts, such as the semiconductor-semiconductor heterojunction, the semiconductors-metal heterojunctions, the silicon-carbon heteroj junction and the multicomponent heteroj conjunction.
Abstract: Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many strategies have been developed in the past few decades and the most widely used one is to develop photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction and the multicomponent heterojunction. The photocatalytic properties of the four junction systems are also discussed in relation to the environmental and energy applications, such as degradation of pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a summary and some perspectives on the challenges and new directions in this exciting and still emerging area of research.

3,013 citations

References
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Journal ArticleDOI
TL;DR: In this paper, the most efficient catalysts were found to be IrO2, Co3O4, RuO2 and NiCo2O4 and Mn2O3 for the fourelectron oxidation of water to O2 under photochemical conditions.
Abstract: Metal oxides, in the form of dispersed powders, have been tested as potential catalysts for the four-electron oxidation of water to O2 under photochemical conditions. The most efficient catalysts were found to be IrO2, Co3O4, RuO2, NiCo2O4, Rh2O3 and Mn2O3 and, in particular, high activity was observed with IrO2. Comparison of the oxide structure with its observed rate of O2 generation under standard conditions has allowed formulation of a few general requisites for an effective catalyst. Samples of iridium oxide deposited onto the surface of a second (inert) oxide were tested for their O2-evolving capability. The efficiency of the system depended markedly upon the nature of the support. Materials that favour formation of small deposits of iridium oxide (e.g. ZnO, MgO, TiO2) are the best supports, whilst O2 production is almost completely inhibited with acidic supports. Many metal oxides can be prepared in the form of hydrates of variable composition. These materials also function as O2-evolving catalysts, the efficiency of the process depending upon any thermal pretreatment. This finding is explained in terms of changes in structure and composition of the oxide that occur upon heating.

505 citations


Additional excerpts

  • ...As a first trial, we thus attempted to introduce RuO 2 , which is well known as a good oxidation catalyst for O 2 evolutio...

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Journal ArticleDOI
TL;DR: The stoichiometric splitting of water into H2 and O2 (H2/O2 = 2) under visible light irradiation took place for the first time using a mixture of Pt-WO3 and Pt-SrTiO3 (Cr-Ta-doped) photocatalysts and an IO3-/I- shuttle redox mediator.

426 citations

Journal ArticleDOI
30 Apr 1993-Science
TL;DR: In this article, a structural model and a determination of the manganese oxidation states based on x-ray absorption spectroscopy was presented, and the salient features, in both higher plants and cyanobacteria, are a pair of di-mu-oxo bridged manganous binuclear clusters linked by a mono-muoxo bridge, one proximal calcium atom, and one halide.
Abstract: In the photosynthetic evolution of oxygen, water oxidation occurs at a catalytic site that includes four manganese atoms together with the essential cofactors, the calcium and chlorine ions. A structural model and a determination of the manganese oxidation states based on x-ray absorption spectroscopy are presented. The salient features, in both higher plants and cyanobacteria, are a pair of di-mu-oxo bridged manganese binuclear clusters linked by a mono-mu-oxo bridge, one proximal calcium atom, and one halide. In dark-adapted samples, manganese occurs in oxidation states (III) and (IV). Data from oriented membranes display distinct dichroism, precluding highly symmetrical structures for the manganese complex.

390 citations

Journal ArticleDOI
01 Jan 1981-Nature
TL;DR: In this article, a bifunctional redox catalyst composed of RuO2 and Pt co-supported on colloidal TiO2 particles is used for water decomposition by visible light illumination.
Abstract: A bifunctional redox catalyst, composed of Pt and RuO2 co-deposited on a colloidal TiO2 carrier, is a highly potent mediator for water decomposition by visible light1. The system contains apart from the sensitizer (Ru(bipy)2+3) an electron relay—methylviologen. The latter is reduced on light excitation, and the photoreaction is coupled with catalytic steps2 generating H2 and O2 from water. To rationalize the surprisingly high efficiency of this photoredox system, we proposed a mechanism involving species adsorbed at the TiO2 surface. This led us to explore sensitizers which through suitable functionalization show an enhanced affinity for adsorption at the particle–water interface. We describe here the performance of electron relay-free systems capable of efficiently decomposing water into H2 and O2 under visible light illumination. A bifunctional redox catalyst composed of RuO2 and Pt co-supported on colloidal TiO2 particles is used. The only other component present is a sensitizer. Amphiphilic surfactant derivatives of Ru(bipy)2+3 exhibit extremely high activity in promoting the water cleavage process. Adsorption of the sensitizer at the TiO2 particle–water interface and electron ejection into the TiO2 conduction band are evoked to explain the observations. Exposure to UV radiation leads to efficient water cleavage in the absence of sensitizer.

353 citations