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.
We recently reported that Ag(3)PO(4) exhibits excellent photooxidative capabilities for O(2) evolution from water and organic dye decomposition under visible-light irradiation. However, very little is known about the shape and facet effects of Ag(3)PO(4) crystals on their photocatalytic properties. Herein we have developed a facile and general route for high-yield fabrication of single-crystalline Ag(3)PO(4) rhombic dodecahedrons with only {110} facets exposed and cubes bounded entirely by {100} facets. Moreover, studies of their photocatalytic performance have indicated that rhombic dodecahedrons exhibit much higher activities than cubes for the degradation of organic contaminants, which may be primarily ascribed to the higher surface energy of {110} facets (1.31 J/m(2)) than of {100} facets (1.12 J/m(2)).
Methane activation at moderate conditions and with good selectivity for value-added chemicals still remains a huge challenge. Here, we present a highly selective catalyst for the transformation of methane to methanol composed of highly dispersed iron species on TiO2. The catalyst operates under moderate light irradiation (close to one sun) and at ambient conditions. The optimised sample shows a 15% conversion rate for CH4 with an alcohol selectivity of over 97% (methanol selectivity over 90%) and a yield of 18 moles of alcohol per mole of iron active site in just three hours. XPS measurements with and without Xenon lamp irradiation, light intensity-modulated spectroscopies, photoelectrochemical measurements, XANES and EXAFS spectra, as well as isotopic analysis confirm the function of the major ironcontaining species, namely FeOOH and Fe2O3, which enhance charge transfer and separation, decrease the overpotential of the reduction reaction and improves selectivity towards methanol over CO2 production.
Photoelectrochemical (PEC) water splitting is a promising method for storing solar energy in the form of hydrogen fuel, but it is greatly hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Herein, a facile solution impregnation method is developed for growing ultrathin (2 nm) highly crystalline β-FeOOH nanolayers with abundant oxygen vacancies on BiVO photoanodes. These exhibited a remarkable photocurrent density of 4.3 mA cm at 1.23 V (vs. reversible hydrogen electrode (RHE), AM 1.5 G), which is approximately two times higher than that of amorphous FeOOH fabricated by electrodeposition. Systematic studies reveal that the excellent PEC activity should be attributed to their ultrathin crystalline structure and abundant oxygen vacancies, which could effectively facilitate the hole transport/trapping and provide more active sites for water oxidation.
Herein, we have developed a facile and general method for the high-yield fabrication of AgX/Ag(3)PO(4) (X = Cl, Br, I) core-shell heterostructures with an unusual rhombic dodecahedral morphology, which exhibit much higher photocatalytic activities, structural stabilities and photoelectric properties than pure Ag(3)PO(4) crystals in environment and energy applications.
Photocatalysis is a promising technology that can contribute to renewable energy production from water and water purification. In order to further develop the field and meet industrial requirements, it is imperative to focus on advancing high efficiency visible light photocatalysts, such as silver phosphate (Ag3PO4). This review aims to highlight the recent progress made in the field, focusing on oxygen production from water, and organic contaminant decomposition using Ag3PO4. The most important advances are discussed and explained in detail, including semiconductor-semiconductor junctions, metal-semiconductor junctions, exposing facet control, and fundamental understanding using advanced spectroscopies and computational chemistry. The review then concludes by critically summarising both findings and current perspectives, and ultimately how the field might best advance in the near future.
A strategy of reaction-environment modulation was employed to change the surface property of a semiconductor photocatalyst to enhance its photocatalytic performance. Surface alkalinization induced by a high alkalinity of the solution environment significantly shifted the surface energy band of a SrTiO(3) photocatalyst to a more negative level, supplying a strong potential for H(2)O reduction and consequently promoting the photocatalytic efficiency of H(2) evolution. This mechanism is also applicable for visible-light-sensitive La,Cr-codoped SrTiO(3) photocatalyst, which hence, could achieve a high apparent quantum efficiency of 25.6% for H(2) evolution in CH(3)OH aqueous solution containing 5 M NaOH at an incident wavelength of 425 ± 12 nm.
Efficient generation of active oxygen-related radicals plays an essential role in boosting advanced oxidation process. To promote photocatalytic oxidation for gaseous pollutant over g-CN, a solid-gas interfacial Fenton reaction is coupled into alkalinized g-CN-based photocatalyst to effectively convert photocatalytic generation of HO into oxygen-related radicals. This system includes light energy as power, alkalinized g-CN-based photocatalyst as an in situ and robust HO generator, and surface-decorated Fe as a trigger of HO conversion, which attains highly efficient and universal activity for photodegradation of volatile organic compounds (VOCs). Taking the photooxidation of isopropanol as model reaction, this system achieves a photoactivity of 2-3 orders of magnitude higher than that of pristine g-CN, which corresponds to a high apparent quantum yield of 49% at around 420 nm. In-situ electron spin resonance (ESR) spectroscopy and sacrificial-reagent incorporated photocatalytic characterizations indicate that the notable photoactivity promotion could be ascribed to the collaboration between photocarriers (electrons and holes) and Fenton process to produce abundant and reactive oxygen-related radicals. The strategy of coupling solid-gas interfacial Fenton process into semiconductor-based photocatalysis provides a facile and promising solution to the remediation of air pollution via solar energy.
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