Cristina E. Stere

SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths

Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.

Non-Thermal Plasma Activation of Gold-Based Catalysts for Low-Temperature Water–Gas Shift Catalysis

Abstract Non‐thermal plasma activation has been used to enable low‐temperature water‐gas shift over a Au/CeZrO4 catalyst. The activity obtained was comparable with that attained by heating the catalyst to 180 °C providing an opportunity for the hydrogen production to be obtained under conditions where the thermodynamic limitations are minimal. Using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), structural changes associated with the gold nanoparticles in the catalyst have been observed which are not found under thermal activation indicating a weakening of the Au−CO bond and a change in the mechanism of deactivation.

Probing the role of a non-thermal plasma (NTP) in the hybrid NTP catalytic oxidation of methane

Abstract Three recurring hypotheses are often used to explain the effect of non‐thermal plasmas (NTPs) on NTP catalytic hybrid reactions; namely, modification or heating of the catalyst or creation of new reaction pathways by plasma‐produced species. NTP‐assisted methane (CH4) oxidation over Pd/Al2O3 was investigated by direct monitoring of the X‐ray absorption fine structure of the catalyst, coupled with end‐of‐pipe mass spectrometry. This in situ study revealed that the catalyst did not undergo any significant structural changes under NTP conditions. However, the NTP did lead to an increase in the temperature of the Pd nanoparticles; although this temperature rise was insufficient to activate the thermal CH4 oxidation reaction. The contribution of a lower activation barrier alternative reaction pathway involving the formation of CH3(g) from electron impact reactions is proposed.

Non-thermal-plasma-activated de-NOx catalysis

The combination of non-thermal plasma (NTP) with catalyst systems as an alternative technology to remove NOx emissions in the exhaust of lean-burn stationary and mobile sources is reviewed. Several factors, such as low exhaust gas temperatures (below 300°C), low selectivity to N2 and the presence of impurities, make current thermally activated technologies inefficient. Various hybrid plasma–catalyst systems have been examined and shown to have a synergistic effect on de-NOx efficiency when compared with NTP or catalyst-alone systems. The NTP is believed to form oxygenated species, such as aldehydes and nitrogen-containing organic species, and to convert NO to NO2, which improves the reduction efficiency of N2 during hydrocarbon-selective catalytic reduction reactions. The NTP has been used as a pretreatment to convert NO to its higher oxidation states such as NO2 to improve NOx reduction efficiency in the subsequent processes, e.g. NH3-selective catalytic reduction. It has been applied to the lean phase of the NOx storage to improve the adsorption capacity of the catalyst by conversion of NO to NO2. Alternatively, a catalyst with high adsorption capacity is chosen and the NTP is applied to the rich phase to improve the reduction activity of the catalyst at low temperature. This article is part of a discussion meeting issue ‘Providing sustainable catalytic solutions for a rapidly changing world’.

Unraveling the H2 Promotional Effect on Palladium-Catalyzed CO Oxidation Using a Combination of Temporally and Spatially Resolved Investigations

The promotional effect of H2 on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H2. In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H2 was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H2 promotes the Langmuir–Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H2. This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect.