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.

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Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Organic Photoredox Catalysis

A phenomenological description, or “conceptual model,” of how direct-injection (DI) diesel combustion occurs has been derived from laser-sheet imaging and other recent optical data. To provide background, the most relevant of the recent imaging data of the author and co-workers are presented and discussed, as are the relationships between the various imaging measurements. Where appropriate, other supporting data from the literature is also discussed. Then, this combined information is summarized in a series of idealized schematics that depict the combustion process for a typical, modern-diesel-engine condition. The schematics incorporate virtually all of the information provided by our recent imaging data including: liquidand vapor-fuel zones, fuel/air mixing, autoignition, reaction zones, and soot distributions. By combining all these elements, the schematics show the evolution of a reacting diesel fuel jet from the start of fuel injection up through the first part of the mixing-controlled burn (i.e. until the end of fuel injection). In addition, for a “developed” reacting diesel fuel jet during the mixingcontrolled burn, the schematics explain the sequence of events that occurs as fuel moves from the injector downstream through the mixing, combustion, and emissions-formation processes. The conceptual model depicted in these schematics also gives insight into the most likely mechanisms for soot formation and destruction and NO formation during the portion of the DI diesel combustion event discussed.

A Conceptual Model of DI Diesel Combustion Based on Laser-Sheet Imaging*

. Although black carbon (BC) is one of the key atmospheric particulate components driving climate change and air quality, there is no agreement on the terminology that considers all aspects of specific properties, definitions, measurement methods, and related uncertainties. As a result, there is much ambiguity in the scientific literature of measurements and numerical models that refer to BC with different names and based on different properties of the particles, with no clear definition of the terms. The authors present here a recommended terminology to clarify the terms used for BC in atmospheric research, with the goal of establishing unambiguous links between terms, targeted material properties and associated measurement techniques.

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Recommendations for reporting "black carbon" measurements

Light absorption by aerosols contributes to solar radiative forcing through absorption of solar radiation and heating of the absorbing aerosol layer. Besides the direct radiative effect, the heating can evaporate clouds and change the atmospheric dynamics. Aerosol light absorption in the atmosphere is dominated by black carbon (BC) with additional, significant contributions from the still poorly understood brown carbon and from mineral dust. Sources of these absorbing aerosols include biomass burning and other combustion processes and dust entrainment. For particles much smaller than the wavelength of incident light, absorption is proportional to the particle volume and mass. Absorption can be calculated with Mie theory for spherical particles and with more complicated numerical methods for other particle shapes. The quantitative measurement of aerosol light absorption is still a challenge. Simple, commonly used filter measurements are prone to measurement artifacts due to particle concentration and modification of particle and filter morphology upon particle deposition, optical interaction of deposited particles and filter medium, and poor angular integration of light scattered by deposited particles. In situ methods measure particle absorption with the particles in their natural suspended state and therefore are not prone to effects related to particle deposition and concentration on filters. Photoacoustic and refractive index-based measurements rely on the heating of particles during light absorption, which, for power-modulated light sources, causes an acoustic signal and modulation of the refractive index in the air surrounding the particles that can be quantified with a microphone and an interferometer, respectively. These methods may suffer from some interference due to light-induced particle evaporation. Laser-induced incandescence also monitors particle heating upon absorption, but heats absorbing particles to much higher temperatures to quantify BC mass from the thermal radiation emitted by the heated particles. Extinction-minus-scattering techniques have limited sensitivity for measuring aerosol light absorption unless the very long absorption paths of cavity ring-down techniques are used. Systematic errors can be dominated by truncation errors in the scattering measurement for large particles or by subtraction errors for high single scattering albedo particles. Remote sensing techniques are essential for global monitoring of aerosol light absorption. While local column-integrated measurements of aerosol light absorption with sun and sky radiometers are routinely done, global satellite measurements are so far largely limited to determining a semi-quantitative UV absorption index.

Aerosol light absorption and its measurement: A review

Through numerical calculations we have investigated the possibility of developing soot diagnostics based on laser heating of the soot particles. Two strategies, one using the laser-modulated incandescence of the particles, and the other using direct detection of the evaporated C2 molecules, were examined. Both strategies can yield size distribution and volume fraction information provided the laser wavelength is near the graphite absorption band at 260 nm; otherwise, only volume fractions can be obtained.

Soot diagnostics based on laser heating

Spectrally separated fluorescence emissions from liquid and vapor diesel fuel can be obtained by adding an exciplex-forming molecule to the fuel. The exciplex emission dominates the condensed phase emission, while the monomer emission dominates the vapor phase emission. In particular with the naphthalene/tetramethyl-p-phenylene diamine system, the liquid and vapor phase emissions peak at 470 and 380 nm, respectively. Results for droplets at 110 and 250°C are presented.

Spectrally separated fluorescence emissions for diesel fuel droplets and vapor

The relaxed and spectroscopic energies of olefin triplets

Recent developments in time‐resolved photoacoustic calorimetry (PAC) are discussed. An equation is derived relating the amplitude of the maximum photoacoustic signal to parameters of a photoacoustic cell, to physical properties of the solvents, and to the energy deposited as heat. The equation is validated by a series of scaling experiments: it correctly correlates the dependence of the PAC signal on cell thickness, on energy deposition, and on solvent properties. The dominant sources of background signal have been determined and the background signal reduced substantially relative to previous work. It is now possible to measure energies and lifetimes of transients in solutions with optical densities as low as ∼5×10−4. Data are presented for the energy of 2‐cyclopentenone triplet, a transient for which interpretable PAC measurements were previously not possible. Its triplet energy is 73.1±1.1 kcal/mole. With reduced background and a faster digital storage oscilloscope, a quite short transient lifetime, 7....

Recent advances in photoacoustic calorimetry: Theoretical basis and improvements in experimental design

In a demonstration experiment, the vapor and liquid disiributions in a hollow-cone spray have been separately photographed using laser-excited fluoresent dopants which form organic exciplexes. In color photographs, the Fluorescence from the liquid appears blue-green and the fluorescence from the vapor appears purple. With high-speed black and while film, “stopped action” pictures of the liquid and/or vapor portions of the spray were obtained. This technique may lead to the development of real-lime visualization diagnostics For evaporating fuel sprays.

Lynn A. Melton

Papers

Soot diagnostics based on laser heating

Spectrally separated fluorescence emissions for diesel fuel droplets and vapor

The relaxed and spectroscopic energies of olefin triplets

Recent advances in photoacoustic calorimetry: Theoretical basis and improvements in experimental design

Vapor/Liquid Visualization for Fuel Sprays