Ammonia synthesis: The bellwether reaction in heterogeneous catalysis

This is a personal account of the Havreholm Conference with a choice of topics dealing with catalytic ammonia synthesis. Among the general concepts that were retained are: the rate determining step with rates of adsorption and desorption of nitrogen; the direct activated dissociative adsorption of N₂; the surface crystalline anisotropy of iron; the role of promoters in industrial iron based catalysts; and the atomic structure of the metallic surface on the industrial multiply promoted catalyst. Finally, a new isotope jump technique to measure an upper limit to the real turnover frequency is discussed.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Kinetic modeling of Fe‐BEA as NH3‐SCR catalyst—effect of phosphorous

The focus of this work is to investigate whether a previously developed microkinetic deactivation model for hydrothermally treated Fe‐BEA as NH₃‐SCR catalyst can be applied to describe chemical deactivation of Fe‐BEA due to phosphorous exposure. The model describes the experiments well for Fe‐BEA before and after phosphorous exposure by decreasing the site density, representing deactivation of sites due to formation of metaphosphates blocking the active iron sites, while the kinetic parameters are kept constant. Furthermore, the results show that the activity for low‐temperature selective catalytic reduction (SCR) is very sensitive to loss of active monomeric iron species due to phosphorous poisoning compared to high‐temperature SCR. Finally, the ammonia inhibition simulations show that exposure to phosphorous may affect the internal transport of ammonia between ammonia storage sites buffering the active iron sites, which results in a lower SCR performance during transient conditions. © 2014 American Institute of Chemical Engineers AIChE J, 61: 215–223, 2015     

Mechanistic insights into the structure‐dependent selectivity of catalytic furfural conversion on platinum catalysts

The effects of surface structures on the selectivity of catalytic furfural conversion over platinum (Pt) catalysts in the presence of hydrogen have been studied using first principles density functional theory (DFT) calculations and microkinetic modeling. Three Pt model surface structures, that is, flat Pt(111), stepped Pt(211), and Pt₅₅ cluster are chosen to represent the terrace, step, and corner sites of Pt nanoparticle. DFT results show that the dominant reaction route (hydrogenation or decarbonylation) in furfural conversion depends strongly on the structures (or reactive sites). Using the size‐dependent site distribution rule, our microkinetic modeling results indicate the decarbonylation route prevails over smaller Pt particles less than 1.4 nm while the hydrogenation is the dominant reaction route over larger Pt catalyst particles at T = 473 K and = 93 kPa. This is in good agreement with the reported experimental observations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3812–3824, 2015     

Formic acid decomposition on Au catalysts: DFT,microkinetic modeling,and reaction kinetics experiments

A combined theoretical and experimental approach is presented that uses a comprehensive mean‐field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self‐consistent, generalized gradient approximation (GGA‐PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO₂ + H₂) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is ≤4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1303–1319, 2014     

Microkinetic modeling as a tool in catalyst discovery

We propose a new approach for catalyst development that combines different scientific disciplines: experimental design, surface science, reaction kinetics and simulations with the objective of accelerating catalyst development. In this paper we present a study of the possibilities of using small data sets in microkinetic modeling, and studies of the required precision of temperature measurement.     

The dissociative adsorption of N2 on a multiply promoted iron catalyst used for ammonia synthesis: a temperature-programmed desorption study

The temperature-programmed desorption (TPD) of N₂ from a multiply promoted iron catalyst used for ammonia synthesis has been studied in a microreactor system at atmospheric pressure. From TPD experiments with various heating rates a preexponential factorA = 2 × 10⁹ molecules/site s and an activation energyE = 146 kJ/mol was derived assuming second-order desorption. The observed dependence of the TPD peak shapes on the heating rates indicated the influence of readsorption of N₂ in agreement with the results obtained for various initial coverages. Simulating the N₂ TPD curves using the model by Stoltze and Nørskov revealed that the calculated TPD curves were not influenced by the molecular precursor to desorption. However, the calculated rate of readsorption was found to be overestimated at high coverage compared with the experimental results. A coverage-dependent net activation energy for dissociative chemisorption (E*) was introduced as the simplest assumption rendering the dissociative chemisorption of N₂ activated at high coverage. The best fit of the experimental data yieldedE* = (–15+30) kJ/mol using only a single type of atomic nitrogen species. These findings are in satisfactory agreement with the parameters underlying the Stoltze-Nørskov model for the kinetics of ammonia synthesis as well as with the data reported for Fe(111) single crystal surfaces.     

Analysis of volume‐to‐surface ratio effects on methane oxidative coupling using microkinetic modeling

The effect of the volume‐to‐surface (V/S) ratio on the catalytic performance of a La–Sr/CaO catalyst in a fixed bed reactor under oxidative coupling of methane (OCM) conditions is investigated by adjusting the amount of diluent in the catalyst bed. It was observed experimentally that the catalyst activity, C₂ selectivity, and C₂H₄/C₂H₆ ratio are all favored at high V/S ratios. The total void volume, available in the intraparticle and the interstitial phase, was considered. A comprehensive OCM microkinetic model, explicitly distinguishing between these two phases, allowed accounting for the observed dependence of catalytic performance on V/S ratio. The major experimentally implemented variation in interstitial volume available for reaction, provoked also changes in radical concentration profiles in intraparticle phase. Given the high reaction rates occurring at this location, the experimentally observed effects with varying the V/S ratio, are attributed to concentration and, hence, reaction rate changes occurring mainly in the intraparticle phase. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2603–2611, 2018     

Strategy to improve catalytic trend predictions for methane oxidation and reforming

Computational catalysts screening is an increasingly popular technique, in which the mechanism from a known good catalyst is commonly adopted, parameterized from linear scaling relationships, and then used in a microkinetic model to identify other metal alloys with incrementally improved activity. This strategy, however, fails to identify truly novel catalysts that operate under nontraditional reaction conditions and exhibit alternative dominant reaction pathways. Using methane oxidation and reforming we investigated a series of O* and OH*‐assisted C‐H scission and C‐O bond formation pathways. Notably, for methane oxidation we discovered a second local optimum for O*‐assisted C‐H bond activation near Ag, which is inactive if only the direct C‐H scission route is considered. In light of the significant qualitative difference in the predicted catalytic trends when parallel mechanisms are allowed, we propose a minimum barrier assumption to rapidly screen for potentially important alternative pathways without the need for costly density functional theory simulations. © 2016 American Institute of Chemical Engineers AIChE J, 63: 66–77, 2017     

In situ adaptive tabulation for the CFD simulation of heterogeneous reactors based on operator‐splitting algorithm

In situ Adaptive Tabulation algorithm is applied to efficiently solve the chemical substep in the context of the simulation of heterogeneous reactors. A numerical strategy—specifically conceived for unsteady simulation of catalytic devices—has been developed and interfaced, in the context of the operator splitting technique, with the solution of the chemical substep, which requires 70–90% of the total computational time. The algorithm performances have been illustrated by considering a single channel of a honeycomb reactor operating the catalytic partial oxidation of methane and a methane steam reforming packed bed reactor. The application of in situ adaptive tabulation resulted in a speed‐up of the chemical substep up to ～500 times with an overall speed‐up of ～5–15 times for the whole simulation. Such reduction of the computation effort is key to make affordable fundamental computational fluid dynamics simulations of chemical reactors at a level of complexity relevant to technological applications. © 2016 American Institute of Chemical Engineers AIChE J, 63: 95–104, 2017