Modification of heterogeneous photocatalysts for selective organic synthesis
05 Mar 2018-Catalysis Science & Technology (The Royal Society of Chemistry)-Vol. 8, Iss: 5, pp 1229-1250
TL;DR: In this article, a concept is proposed that the performance of these catalysts is directly determined by the degrees of participation of various photo-induced active species, which can be selectively controlled by modifying the compositions, crystalline structures, electronic structures and surface structures of the photocatalysts.
About: This article is published in Catalysis Science & Technology.The article was published on 2018-03-05. It has received 52 citations till now.
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TL;DR: In this article, a review of the fundamental understanding of the reactive oxygen species involved in photocatalytic organic oxidations and furthermore, the general mechanisms of a few crucial oxidation reactions is presented.
Abstract: Most organic compounds are conventionally synthesized under high temperature and elevated pressure, resulting in significant energy consumption and wastage. Heterogeneous photocatalytic oxidation has the potential to provide a green route for the synthesis of the majority of industrially important chemicals. The major limiting factor affecting the efficiency of photocatalytic organic synthesis is the lack of high selectivity; therefore, substantial effort has been devoted to solving this problem. Responding to this fast-moving progress, this review gives an overview of the fundamental understanding of the reactive oxygen species involved in photocatalytic organic oxidations and furthermore, the general mechanisms of a few crucial oxidation reactions. The focus of this critical review is on the discussion of diverse strategies to improve the selectivity of high value chemicals, including band engineering, metal loading, hybrid materials, and defect engineering, with the primary aim of highlighting the catalyst design protocols based on the reaction mechanism. Finally, the difficulties and challenges of developing highly selective oxidation photocatalysts are comprehensively discussed in order to help direct the focus of future research.
154 citations
TL;DR: In this paper, the most relevant literature related to the use of metal oxide semiconductors as photocatalysts to light induce organic reactions, including oxidations, C-C and C-heteroatom bond formations.
121 citations
TL;DR: In this paper, the authors discuss current advances in cooperative photoredox reaction systems that integrate CO2 valorization with organics upgrading based on heterogeneous photocatalysis, and the ongoing challenges and prospects in this area are critically discussed.
Abstract: Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way to increase the energy supply and reduce greenhouse gas emissions. However, the conventional reaction system for CO2 photoreduction with pure H2 O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, or cost-ineffective atom economy. A recent surge of developments, in which photocatalytic CO2 valorization is integrated with selective organic synthesis into one reaction system, indicates an efficient modus operandi that enables sufficient utilization of photogenerated electrons and holes to achieve the goals for sustainable economic and social development. In this Review we discuss current advances in cooperative photoredox reaction systems that integrate CO2 valorization with organics upgrading based on heterogeneous photocatalysis. The applications and virtues of this strategy and the underlying reaction mechanisms are discussed. The ongoing challenges and prospects in this area are critically discussed.
106 citations
TL;DR: In this paper, a photocatalytic H2 evolution by water splitting coupled with biomass derived 5-(hydroxymethyl) furfural (HMF) oxidation to a more valued platform chemical, 2,5-diformylfuran (DFF), under visible light using porous carbon nitride (SGCN) for the first time.
Abstract: In this study, we have demonstrated photocatalytic H2 evolution by water splitting coupled with biomass derived 5-(hydroxymethyl) furfural (HMF) oxidation to a more valued platform chemical, 2,5-diformylfuran (DFF), under visible light using porous carbon nitride (SGCN) for the first time. Simultaneously, a H2 production rate of 12 μmol h−1 m−2 was obtained with a DFF yield of 13.8% with >99% selectivity after 6 h under visible light. The selectivity of DFF was maintained >99% even after longer runs (48 h) with an improved DFF yield of 38.4% and H2 production rate of 36 μmol h−1 m−2. In addition, a H2 production rate of 6.2 μmol h−1 m−2 with 0.15 light-to-fuel efficiency (LFE) and DFF (7.2% yield) were obtained under natural sunlight after 6 h. Thus, this study describes an effective way to utilize both photogenerated electrons and holes for simultaneous H2 production by water splitting and biomass derived HMF oxidation to DFF, respectively, under natural sunlight.
80 citations
TL;DR: The state-of-the-art progress on heterojunction based on 2D materials is reviewed, including the photocatalysis principles using 2D heterojunctions, the categories of 2Dheterojunctions and their applications in different photocatalytic reactions, and the theoretical studies of the 2D homojunctions.
Abstract: Two-dimensional (2D) photocatalysts have attracted considerable research interest in the past decades due to their unique optical, physical and chemical properties. Constructing 2D/2D heterojunctions with large interface area has been considered as an effective approach to enhance the transfer rate and the separation efficiency of the charge carriers, leading to dramatic increase in the photocatalytic performance of the photocatalysts. Here, the state-of-the-art progress on heterojunctions based on 2D materials is reviewed, including the photocatalysis principles using 2D heterojunctions, the categories of 2D heterojunctions and their application in different photocatalytic reactions, and the theoretical studies of the 2D heterojunctions. Moreover, the advantages and disadvantages of the 2D heterojunctions are also discussed. Finally, the ongoing challenges and opportunities for the future development of 2D photocatalysts with built-in heterojunctions are proposed.
62 citations
References
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TL;DR: The conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.
Abstract: A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light.
Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.
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Figure 1
Ruthenium polypyridyl complexes: versatile visible light photocatalysts.
6,252 citations
TL;DR: In plasmonics, the metal nanostructures can serve as antennas to convert light into localized electric fields (E-fields) or as waveguides to route light to desired locations with nanometer precision through a strong interaction between incident light and free electrons in the nanostructure.
Abstract: Coinage metals, such as Au, Ag, and Cu, have been important materials throughout history.1 While in ancient cultures they were admired primarily for their ability to reflect light, their applications have become far more sophisticated with our increased understanding and control of the atomic world. Today, these metals are widely used in electronics, catalysis, and as structural materials, but when they are fashioned into structures with nanometer-sized dimensions, they also become enablers for a completely different set of applications that involve light. These new applications go far beyond merely reflecting light, and have renewed our interest in maneuvering the interactions between metals and light in a field known as plasmonics.2–6
In plasmonics, the metal nanostructures can serve as antennas to convert light into localized electric fields (E-fields) or as waveguides to route light to desired locations with nanometer precision. These applications are made possible through a strong interaction between incident light and free electrons in the nanostructures. With a tight control over the nanostructures in terms of size and shape, light can be effectively manipulated and controlled with unprecedented accuracy.3,7 While many new technologies stand to be realized from plasmonics, with notable examples including superlenses,8 invisible cloaks,9 and quantum computing,10,11 conventional technologies like microprocessors and photovoltaic devices could also be made significantly faster and more efficient with the integration of plasmonic nanostructures.12–15 Of the metals, Ag has probably played the most important role in the development of plasmonics, and its unique properties make it well-suited for most of the next-generation plasmonic technologies.16–18
1.1. What is Plasmonics?
Plasmonics is related to the localization, guiding, and manipulation of electromagnetic waves beyond the diffraction limit and down to the nanometer length scale.4,6 The key component of plasmonics is a metal, because it supports surface plasmon polariton modes (indicated as surface plasmons or SPs throughout this review), which are electromagnetic waves coupled to the collective oscillations of free electrons in the metal.
While there are a rich variety of plasmonic metal nanostructures, they can be differentiated based on the plasmonic modes they support: localized surface plasmons (LSPs) or propagating surface plasmons (PSPs).5,19 In LSPs, the time-varying electric field associated with the light (Eo) exerts a force on the gas of negatively charged electrons in the conduction band of the metal and drives them to oscillate collectively. At a certain excitation frequency (w), this oscillation will be in resonance with the incident light, resulting in a strong oscillation of the surface electrons, commonly known as a localized surface plasmon resonance (LSPR) mode.20 This phenomenon is illustrated in Figure 1A. Structures that support LSPRs experience a uniform Eo when excited by light as their dimensions are much smaller than the wavelength of the light.
Figure 1
Schematic illustration of the two types of plasmonic nanostructures discussed in this article as excited by the electric field (Eo) of incident light with wavevector (k). In (A) the nanostructure is smaller than the wavelength of light and the free electrons ...
In contrast, PSPs are supported by structures that have at least one dimension that approaches the excitation wavelength, as shown in Figure 1B.4 In this case, the Eo is not uniform across the structure and other effects must be considered. In such a structure, like a nanowire for example, SPs propagate back and forth between the ends of the structure. This can be described as a Fabry-Perot resonator with resonance condition l=nλsp, where l is the length of the nanowire, n is an integer, and λsp is the wavelength of the PSP mode.21,22 Reflection from the ends of the structure must also be considered, which can change the phase and resonant length. Propagation lengths can be in the tens of micrometers (for nanowires) and the PSP waves can be manipulated by controlling the geometrical parameters of the structure.23
2,421 citations
TL;DR: The detection methods and generation mechanisms of the intrinsic reactive oxygen species (ROS) in photocatalysis were surveyed comprehensively and the major photocatalyst used in heterogeneous photocatalytic systems was found to be TiO2.
Abstract: The detection methods and generation mechanisms of the intrinsic reactive oxygen species (ROS), i.e., superoxide anion radical (•O2–), hydrogen peroxide (H2O2), singlet oxygen (1O2), and hydroxyl radical (•OH) in photocatalysis, were surveyed comprehensively. Consequently, the major photocatalyst used in heterogeneous photocatalytic systems was found to be TiO2. However, besides TiO2 some representative photocatalysts were also involved in the discussion. Among the various issues we focused on the detection methods and generation reactions of ROS in the aqueous suspensions of photocatalysts. On the careful account of the experimental results presented so far, we proposed the following apprehension: adsorbed •OH could be regarded as trapped holes, which are involved in a rapid adsorption–desorption equilibrium at the TiO2–solution interface. Because the equilibrium shifts to the adsorption side, trapped holes must be actually the dominant oxidation species whereas •OH in solution would exert the reactivity...
2,249 citations
TL;DR: This review gives a concise overview of the all-solid-state Z-scheme photocatalytic systems, including their composition, construction, optimization and applications, which have a huge potential to solve the current energy and environmental crises facing the modern industrial development.
Abstract: The current rapid industrial development causes the serious energy and environmental crises. Photocatalyts provide a potential strategy to solve these problems because these materials not only can directly convert solar energy into usable or storable energy resources but also can decompose organic pollutants under solar-light irradiation. However, the aforementioned applications require photocatalysts with a wide absorption range, long-term stability, high charge-separation efficiency and strong redox ability. Unfortunately, it is often difficult for a single-component photocatalyst to simultaneously fulfill all these requirements. The artificial heterogeneous Z-scheme photocatalytic systems, mimicking the natural photosynthesis process, overcome the drawbacks of single-component photocatalysts and satisfy those aforementioned requirements. Such multi-task systems have been extensively investigated in the past decade. Especially, the all-solid-state Z-scheme photocatalytic systems without redox pair have been widely used in the water splitting, solar cells, degradation of pollutants and CO2 conversion, which have a huge potential to solve the current energy and environmental crises facing the modern industrial development. Thus, this review gives a concise overview of the all-solid-state Z-scheme photocatalytic systems, including their composition, construction, optimization and applications.
1,949 citations
TL;DR: It is considered more feasible that the rate-deter-mining step is the cleavage of the C-H bond at the R-carbon atom, and the active site consists of an ensemble of metallic Auatoms and a cationic Au.
Abstract: ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au
1,784 citations