Dogmas and misconceptions in heterogeneous photocatalysis. Some enlightened reflections

In a recent article, Ollis analyzed heretofore reported photocatalyst kinetics of surface photochemical reactions that take place in heterogeneous systems and that rely heavily on the Langmuir-Hinshelwood (LH) kinetic model to interpret the experimental observations. This model assumes a fast adsorption/desorption equilibrium step and a subsequent slow surface step. His interesting analysis of the experimental results reported in 2000 by Emeline and co-workers, Xu and Langford, and Martyanov and Savinov prompted our reexamination of the LH kinetic model along with several other dogmas that continue to propagate in the heterogeneous photocatalytic landscape. This short article discusses some of these issues and reexamines certain misinterpretations. Specifically, we reexamine (1) the a priori assumed validity of the LH kinetic model in heterogeneous photocatalysis, (2) the recombination of photogenerated free charge carriers on the solid (metal oxide) photocatalyst by the band-to-band recombination pathway, and (3) the mistaken assertion that the kinetics of a heterogeneous photoreaction are either only first-order dependent or half-order dependent on photon flow (i.e., light irradiance).     

A novel liquid plasma AOP device integrating microwaves and ultrasounds and its evaluation in defluorinating perfluorooctanoic acid in aqueous media

A simplified and energy-saving integrated device consisting of a microwave applicator and an ultrasonic homogenizer has been fabricated to generate liquid plasma in a medium possessing high dielectric factors, for example water. The microwave waveguide and the ultrasonic transducer were interconnected through a tungsten/titanium alloy stick acting both as the microwave antenna and as the horn of the ultrasonic homogenizer. Both microwaves and ultrasonic waves are simultaneously transmitted to the aqueous media through the tungsten tip of the antenna. The microwave discharge liquid plasma was easily generated in solution during ultrasonic cavitation. The simple device was evaluated by carrying out the degradation of the perfluorooctanoic acid (PFOA), a system highly recalcitrant to degradation by conventional advanced oxidation processes (AOPs). PFOA is 59% degraded in an aqueous medium after only 90 s of irradiation by the plasma. Intermediates were identified by electrospray mass spectral techniques in the negative ion mode.     

Sonochemistry II.—Effects of ultrasounds on homogeneous chemical reactions and in environmental detoxification

Sonication of aqueous solutions causes cavitation in the liquid which results in the formation of H· and ·OH radical species that can be used to reduce or oxidize certain chemical compounds. This article focuses on the effect of ultrasounds in homogeneous reactions to examine the type of chemistry that ensues. It also deals with a rather novel method of using ultrasounds in combination with photochemical methods of inducing chemical reactions; this sonophotochemical technique remains to be explored and exploited. Finally, we examine and explore the potential utilization of ultrasounds to convert environmental hazardous substances into more benign substrates, or better still to mineralize organics into carbon dioxide.     

Photoinduced radical processes on the spinel (MgAl2O4) surface involving methane, ammonia, and methane/ammonia

The present study explored photoinduced radical processes caused by interaction of CH(4) and NH(3) with a photoexcited surface of a complex metal oxide: magnesium-aluminum spinel (MgAl(2)O(4); MAS). UV irradiation of MAS in vacuo yielded V-type color centers as evidenced by the 360 nm band in difference diffuse reflectance spectra. Interaction of these H-bearing molecules with photogenerated surface-active hole states (O(S)(-)?) yielded radical species which on recombination produced more complex molecules (including heteroatomic species) relative to the initial molecules. For the MAS/CH(4) system, photoinduced dissociative adsorption of CH(4) on surface-active hole centers produced ?CH(3) radicals that recombined to yield CH(3)CH(3). For MAS/NH(3), a similar dissociative adsorption process led to formation of ?NH(2) radicals with formation of NH(2)NH(2) as an intermediate product; continued UV irradiation ultimately yielded N(2). For the mixed MAS/CH(4)/NH(3) system, however, interaction of adsorbed NH(3) and CH(4) on the UV-activated surface of MAS yielded ?NH(2) and ?CH(3) radicals, respectively, which produced CH(3)-NH(2) followed by loss of the remaining hydrogens to form a surface-adsorbed cyanide, CN(S), species. Recombination of photochemically produced radicals released sufficient energy to re-excite the solid spinel, generating new surface-active sites and a flash luminescence (emission decay time at 520 nm, τ ~ 6 s for the MAS/NH(3) case) referred to as the PhICL effect.     

Sonochemistry I. Effects of ultrasounds on heterogeneous chemical reactions – a useful tool to generate radicals and to examine reaction mechanisms

Application of ultrasound to a system that contains at least one liquid phase produces microscopic bubbles in the liquid which undergo periodic expansions and contractions. Some of these microbubbles eventually destabilize and collapse violently, generating temperatures in the thousands of degrees Kelvin and pressures in the hundreds of atmospheres. This phenomenon, known as cavitational implosion, favors the production of free solvent radicals that react amongst themselves and with other substrates in the system. In addition, ultrasound accelerates reactions that involve single electron transfers but seems to have no effect on reactions that proceed via ionic mechanisms for reasons that remain unclear. In practical terms, ultrasound allows the synthesis of novel compounds as well as the improved preparations of standard compounds. Sonication is more than just more efficient stirring. The high temperatures produced on cavitation, both in the cavity and at the interface, could lead to molecular combustion of the substrate and of the solvent to form radical species which could then initiate reactions.     

Integrated Systems for Water Cleavage by Visible Light; Sensitization of TiO2 Particles by Surface Derivatization with Ruthenium Complexes

Irradiation of acidic (pH 2) solutions of RuL₃²⁺ 2Cl^? (L = diisopropyl 2,2′-bipyridine-4,4′ -dicarboxylate) in the presence of TiO₂ at 100°C leads to the loss of one bipyridyl ligand and the chemical fixation of RuL₂ at the surface of teh TiO₂ particles through formation of Ru-O-Ti bonds. These surface complexes are very stable and shift the absorption onset of TiO₂ beyond 600 mm. Efficient sensitization H₂-generation is achieved with this system beginning in the wave length domain between 590 and 665 nm. Preliminary water cleavage experiments with bifunctional TiO₂/Pt/RuO₂ redox catalyst are reported.     

Microwaves in advanced oxidation processes for environmental applications. A brief review

This review article focuses, albeit non-exhaustively, on the influence of microwave radiation on photoassisted processes often referred to as Advanced Oxidation Processes. In particular, we describe and illustrate the possible advantages of microwaves in TiO₂-assisted photodegradations and photomineralizations of various organic pollutants such as herbicides and endocrine disruptors, among others. Described are also various reactor configurations involving UV/visible radiation and microwaves, with the former being supplied either by traditional Hg lamps or alternatively by electrodeless lamps activated by microwaves. To place the use of microwaves on processes occurring in aqueous TiO₂ dispersions in perspective regarding environmental applications, we first introduce the various sources of pollutants and subsequently describe in brief the various advanced oxidation processes such as UV/peroxidation, UV/ozonation and the photo-Fenton process(es) in addition to direct photolysis either by sunlight or by artificial light sources.     

Microwave Flow Chemistry as a Methodology in Organic Syntheses,Enzymatic Reactions,and Nanoparticle Syntheses

Several studies have used microwaves as a heat source for carrying out various types of reactions employing circulation reaction vessels. The microwave flow chemical synthesis methodology is most appropriate in the use of microwaves in chemical syntheses. It can attenuate the problem of microwave heating (non‐uniform heating and penetration depth) and maximize the benefits (rapid heating and first temperature adjustments). In this brief review, we examine and explain some of the relevant features of microwave heating with applicative examples of the usage of microwave flow chemistry equipment in carrying out organic syntheses, enzymatic reactions, and (not least) nanoparticle syntheses.