Pt-CoOx nanoparticles supported on ETS-10 for preferential oxidation of CO reaction

In this paper we prepare bimetallic Pt-CoOx nanoparticles which are further supported in microporous titanosilicate ETS-10. This support has been previously demonstrated as a good candidate for this reaction in the presence of CO2 and H2O. The bimetallic nanoparticles and the supported catalysts containing different loadings of nanoparticles have been extensively characterized and tested in the PROX reaction. The characterization of the nanoparticles discarded the formation of a metallic alloy, although Co and Pt are intimately in contact in the nanoparticle as the HAADF-STEM images revealed. XPS confirmed that the calcined nanoparticles would consist of metallic platinum and cobalt and Pt oxides. The catalyst containing 1.4 wt.% of PtCo nanoparticles can achieve complete CO conversion in the temperature range 120–150 °C working at WHSV = 30 L h-1 g-1

In situ temperature measurements in microwave-heated gassolid catalytic systems. Detection of hot spots and solid-fluid temperature gradients in the ethylene epoxidation reaction

Infrared thermographic techniques have been used for the first time to determine real-time gas and solid temperatures, as well as gas- solid temperature gradients in microwave heated structured reactors. A special reactor vessel has been developed that allows direct observation of the catalyst under microwave heating, and an operating procedure is presented to obtain gas and solid apparent emissivities as a function of temperature. These values are thereafter used to calculate temperatures at any point in the gas and solid phases under reaction. The method has been used to obtain gas and solid temperatures during the ethylene epoxidation reaction carried out on a silver-copper oxide catalyst. The direct heating of the monolith walls produced a stable, large temperature gradient between the solid and the gas phase

Ethylene epoxidation in microwave heated structured reactors

In the present work we show the microwave-induced heating of monolithic reactors containing a thin-layered catalyst that exhibits a strong and selective heating susceptibility under microwave irradiation. The combination of microwave radiation and structured reactors has been successfully applied for the intensification of the selective oxidation of ethylene to ethylene oxide (epoxidation) while operating at lower power consumptions and with higher energy efficiencies than in conventional heating conditions. The microwave radiation selectively heats the catalyst and the monolith walls while maintaining a relatively colder gas stream thereby creating a gas/solid temperature gradient of up to ~70 °C at a reaction temperature of 225 °C. Moreover, the influence of different parameters such as the distribution of the catalyst onto the structured monoliths or the temperature measurement techniques employed to determine the heating profiles (Optic Fibers and/or IR thermography) have been also thoroughly evaluated to justify the obtained catalytic results

In-situ preparation of a highly accessible Pt/CNF catalytic layer on metallic microchannel reactors. Application to the SELOX reaction

A general method to prepare a catalytic coating on the surface of stainless steel microreactors has been developed. The catalytic support consists of a layer of randomly oriented, highly accessible carbon nanofibers (CNFs), directly grown on the surface of the channels by chemical vapor deposition (CVD) of ethanol. These CNFs are functionalized to acquire a positive charge before a solution containing metallic nanoparticles (Pt) is flown through the channels. The nanoparticles adhere to the surface of the CNFs thanks to electrostatic interactions. This process is carried out in-situ and the method can be easily adapted to larger scale production. These catalyst-coated microchannel reactors have been tested in the selective oxidation (SELOX) of CO in the presence of H2. The results were compared to those obtained in a conventional fixed bed reactor packed with Pt/CNTs. The microreactor clearly outperformed the fixed bed reactor at the same space velocity (WSHV = 2220 l/h gPt),), achieving total CO conversion at temperatures 50ºC lower

Nano-heaters: New insights on the outstanding deposition of dielectric energy on perovskite nanoparticles

It has been experimentally observed that, in some Mott nanomaterials, outstanding dielectric losses may appear at microwave frequencies, leading to a rapid increase of temperature. This often takes place in association with the insulator to metal transition (IMT) in these materials. However, when other materials with a similar structure and composition are subjected to the same intensity of microwave (MW) irradiation, the observed heating is minimal. Here we show that the electron dynamics of these materials are responsible for their different heating behaviour. More specifically, for LaCoO3 perovskite nanoparticles, the spin shifts causing the IMT are also responsible for the observed heating behaviour. Under suitable conditions, the intense absorption of MW radiation leads to extremely high heating rates, above 600 degrees per second. The insight gained from this study has been used to design a directly heated catalytic system (LaCoO3 perovskite nanoparticles on a MW-transparent cordierite monolith) capable to operate under a stable, significant solid-gas temperature gradient

High-radiance LED-driven fluidized bed photoreactor for the complete oxidation of n-hexane in air

This work presents a highly efficient photo-reactor configuration for VOC abatement. It consists of a fluidized bed made of commercial, easy to fluidize, transparent borosilicate glass beads coated with commercial TiO2 nanoparticles (0.15–2.3 wt% loadings). Herein, we demonstrate that the use of high-radiance/low consumption UV-LEDs as irradiation sources with a deeper light penetration under fluidizing conditions facilitates the photocatalytic response to achieve the complete oxidation of VOCs. The role of different parameters such as catalyst loading and irradiation power have been thoroughly studied and evaluated to maximize the full combustion of n-hexane. Under the high radiance (up to 2200 mW/cm2) conditions used the bed heats significantly (up to 190 °C), although this did not have an effect on the conversions reached, which depended solely on the wavelength and power used. The productivity of the photoreactor tested and the space velocity used were around 5.25 × 10-2 mol/g·h and 12000 h-1 respectively

Magnetic nanofibers for remotely triggered catalytic activity applied to the degradation of organic pollutants

This work reports on the fabrication and characterization of a novel type of electrospun magnetic nanofibers (MNFs), and their application as a magnetically-activable catalysts for degradation of organic pollutants. The magnetic stimulation capability for the catalytic action is provided by iron-manganese oxide (MnxFe2-xO4) magnetic nanoparticles (MNPs) embedded into electrospun polyacrylonitrile (PAN), which provides stability and chemical resistance. The MNPs (average size d = 40 ± 7 nm) were first obtained by a green and fast sonochemical route, and subsequently embedded into electrospun PAN nanofibers. The final MNFs showed an average diameter of 760 ± 150 nm, providing a superhydrophobic surface with contact angle (θc = 165°), as well as a considerable amount ( 50 % wt.) of embedded MNPs (Mn0.5Fe2.5O4), thermally stable up to temperatures of 330 °C. The catalytic Fe2+/3+/Mn2+/3+/4+ active centers on the MNPs of MNF’s surface could be remotely activated by alternating magnetic fields (AMF) to degrade the methyl blue (MB). Remarkable stability of the MNFs during heating under extreme pH conditions (3 80 %, after several cycles of reusing the same sample without any regeneration process. The capacity of these materials as a catalytic material with magnetic remote activation makes them appealing for those catalytic applications under conditions of darkness or restrained access, where photocatalytic reaction cannot be achieved

Escaping undesired gas-phase chemistry: Microwave-driven selectivity enhancement in heterogeneous catalytic reactors

Research in solid-gas heterogeneous catalytic processes is typically aimed toward optimization of catalyst composition to achieve a higher conversion and, especially, a higher selectivity. However, even with the most selective catalysts, an upper limit is found: Above a certain temperature, gas-phase reactions become important and their effects cannot be neglected. Here, we apply a microwave field to a catalyst-support ensemble capable of direct microwave heating (MWH). We have taken extra precautions to ensure that (i) the solid phase is free from significant hot spots and (ii) an accurate estimation of both solid and gas temperatures is obtained. MWH allows operating with a catalyst that is significantly hotter than the surrounding gas, achieving a high conversion on the catalyst while reducing undesired homogeneous reactions. We demonstrate the concept with the CO 2 -mediated oxidative dehydrogenation of isobutane, but it can be applied to any system with significant undesired homogeneous contributions

3D fractals as SERS active platforms: Preparation and evaluation for gas phase detection of G-nerve agents

One of the main limitations of the technique surface-enhanced Raman scattering (SERS) for chemical detection relies on the homogeneity, reproducibility and reusability of the substrates. In this work, SERS active platforms based on 3D-fractal microstructures is developed by combining corner lithography and anisotropic wet etching of silicon, to extend the SERS-active area into 3D, with electrostatically driven Au@citrate nanoparticles (NPs) assembly, to ensure homogeneous coating of SERS active NPs over the entire microstructured platforms. Strong SERS intensities are achieved using 3D-fractal structures compared to 2D-planar structures; leading to SERS enhancement factors for R6G superior than those merely predicted by the enlarged area effect. The SERS performance of Au monolayer-over-mirror configuration is demonstrated for the label-free real-time gas phase detection of 1.2 ppmV of dimethyl methylphosphonate (DMMP), a common surrogate of G-nerve agents. Thanks to the hot spot accumulation on the corners and tips of the 3D-fractal microstructures, the main vibrational modes of DMMP are clearly identified underlying the spectral selectivity of the SERS technique. The Raman acquisition conditions for SERS detection in gas phase have to be carefully chosen to avoid photo-thermal effects on the irradiated area