The dehydration of lactic acid to produce acrylic acid is a renewable alternative to the mostly used production of acrylic acid from propene. In this review, the recent developments and state of the art for the dehydration of lactic acid to acrylic acid are presented and critically commented. The most recent publications on the topic are discussed inetail with respect to the observed catalysts and process performance data. Among the different catalysts developed, three main groups can be distinguished: zeolites, sulphates, and phosphates. The latter, especially hydroxyapatites, have recently attracted the attention of academics in particular. The three families of catalysts are discussed and the recent developments and technical drawbacks in the gas phase dehydration are reported.

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Noble metals-promoted tungstated oxides have been shown to be profitable in a wide variety of catalytic reactions of environmental interest but to be detrimental in the hydrogenation of aromatics. The origin of the deleterious effect of tungstates on the hydrogenation performance of noble metals is still being debated. To provide further insights into this, the location and the oxidation state of Rh were investigated as a function of the W surface density (0–10 W/nm2) of Rh/WO x –Ce0.62Zr0.38O2 (Rh/W–CZ) catalysts after high-temperature reduction. For that purpose, a thorough characterization of the oxide phases was performed through N2-sorption, X-ray diffraction, Raman spectroscopy, NO x temperature-programmed desorption, and X-ray photoelectron spectroscopy (XPS), whereas the metallic phases were characterized by low-temperature H2 chemisorption, XPS, N2 Fourier transform infrared spectroscopy and benzene hydrogenation. It was found that Rh deposited on both tungstates and CZ, and did not sinter with increasing W surface densities. The observed linear decrease in the Rh hydrogenation performance of the WO x -promoted Ce0.62Zr0.38O2 below pseudo monolayer coverage of CZ (4.8 W/nm2 CZ) was assigned to a strong metal support interaction effect between the Rh particles and the nonreducible underlying WO x phase, resulting in the formation of electron-deficient Rh species (Rh δ+ ).

One of the most interesting intermediates for the chemical industry is acrylic acid, which can be derived from lactic acid by catalytic dehydration in the gas phase. The realization of this reaction is complex due to a strong thermal activation leading to the formation of undesired by-products (acetaldehyde, propanoic acid…) as well as polymerization. We studied this reaction over hydroxyapatites modified by substitution of the hydroxyl groups by fluoride. This notably enabled increasing the selectivity to acrylic acid while reducing the formation of the undesired acetaldehyde. Introduction of fluoride induced a modification of the phosphate (PO 3− 4) groups. In the presence of water, fluoride prevented the formation of hydrogenophosphate species (HPO 2− 4), which are well-known acid sites responsible for the formation of acetaldehyde by decarboxylation/decarbonylation. Further, we evidenced an important impact of fluoride substitution on crystallinity, specific surface area and on the surface Ca/P ratio. This latter is known to be a key parameter to control the acidity and the basicity of the hydroxyapatites. Using FT-IR spectroscopy with propyne as a probe molecule, we could show that lactic acid was concertedly adsorbed on basic and acid sites, which might be at the origin of the observed superior performances.

The redox switching dynamics of poly(3,4-ethylenedioxythiophene) (PEDOT) in an acetonitrile solution and a room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmiTFSI), are investigated by means of potential step experiments. Redox switching can be viewed as a phase transition in which the nucleation and growth processes occur. We have developed a phenomenological model allowing the determination of the kinetic parameters. Two limiting cases are shown as follows: (i) a progressive and (ii) an instantaneous nucleation. In all cases, the growth process is described in terms of a self-exchange electron transfer reaction. We show that the mechanisms depend upon the medium. In acetonitrile, progressive nucleation and growth occur during oxidation (p-doping), whereas nucleation is instantaneous in the reduction of the PEDOT film. On the other hand, instantaneous nucleation and growth mechanisms are observed for both oxidation and reduction in EmiTFSI. The difference in the mechanisms results from the ionic exchange process associated with electron transfer and the initial structure of the film (open or compact). The influence of the applied potential on the dynamics is analyzed for both media.

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