Engineering topics
Rangarajan, Srinivas
Publications and source records attributed to Rangarajan, Srinivas.
Actively Learned Optimal Sustainable Operation of Plasma-Catalyzed Methane Bireforming on La 0.7 Ce 0.3 NiO 3 Perovskite Catalyst
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A Coverage Self-Consistent Microkinetic Model for Vapor-Phase Formic Acid Decomposition over Pd/C Catalysts
An iterative approach utilizing density functional theory (DFT, PW91-GGA)-informed mean-field microkinetic models and reaction kinetics experiments is used to determine the reaction mechanism and the active site for formic acid (HCOOH, FA) decomposition over a Pd/C catalyst. Models parametrized using DFT energetics on clean Pd(100) and Pd(111) required large corrections to the DFT energetics for capturing our experimental data. Further, both Pd(111) and Pd(100) models predicted a high coverage of adsorbed CO (CO*), inconsistent with the assumption of a clean surface at which the rate parameters for these models were calculated. To better represent the active site under reaction conditions and explicitly account for the presence of CO*, subsequent microkinetic models were formulated using DFT energetics that were calculated on partially (5/9 ML) CO*-covered Pd (111) and (100) facets. Upon parameter adjustment, the resultant 5/9 ML CO*-covered Pd(100) model, although consistent in terms of CO* coverage, was unable to capture the dehydration path measured in the experiments and was, therefore, deemed not to offer an accurate representation of the active site for FA decomposition over Pd/C. In contrast, a partially CO*-covered Pd(111) model was better at representing the catalytic active site, as in addition to being consistent in terms of CO* coverages, it required small adjustments of the DFT parameters to accurately capture the experimental data set (both dehydrogenation and dehydration). Our results suggest that the reaction occurs via the spectroscopically elusive carboxyl (COOH*) intermediate and that spectator CO*-assisted decomposition pathways play an important role under typical experimental conditions. In addition, our study highlights the importance of striving for coverage self-consistent microkinetic models and for including spectator-assisted mechanisms in order to develop an improved picture of the active site under reaction conditions.
A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS 2
The binding energy of hydrogen sulfide, ammonia, ethane, ethylene, butadiene, benzene, toluene, pyridine, pyrrole, and thiophene on the basal plane of the semi-conducting 2H-molybdenum sulfide (MoS 2 ) was calculated with the following flavors of Density Functional Theory (DFT): GGA-PW91, PBE-D3, vdW-DF, optPBE, optB86b, optB88, vdW-TS, and BEEF-vdW. The GGA-PW91 binding energies are negligible (<0.07 eV in magnitude) in all cases. The predictions with vdW-DF and PBE-D3 are the closest (error <0.05 eV) to the isosteric heats of adsorption calculated from reported temperature programmed desorption data for thiophene and butadiene. For all dispersion flavors examined here, the magnitude of the dispersion contribution to the binding energy increases linearly with the number of heavy atoms in the adsorbate, with each atom contributing 0.05 eV (BEEF-vdW) – 0.09 eV (optB88-vdW). Further, this implies that the calculated adsorption constants of molecules larger than acridine (i.e., comprising > 14 non-heavy atoms) can vary by more than four orders of magnitude at industrial conditions depending on the chosen method of dispersion correction. Further, dispersion effects fall off rapidly (>0.03 eV/ non-hydrogen atom/Å) as the adsorbate-surface distance increases.
Atomically Dispersed Tin-Modified $\gamma$-alumina for Selective Propane Dehydrogenation under H 2 S Co-feed
Developing an earth-abundant catalyst that is sulfur-tolerant, active, and highly selective is of great interest for valorizing natural gas streams containing sour gas. Here, a tin-modified alumina catalyst is reported that is stable and selective for propane dehydrogenation in the presence of percent quantities of H 2 S in the feed. In particular, Sn/Al 2 O 3 –S catalysts with 1.5–5% Sn content exhibit 98% selectivity with up to 16% conversion at 560 °C during the fourth cycle. Experimental and computational characterization shows that the active sites are the defect tricoordinated Al atoms. H 2 S pretreatment further modifies a portion of these sites via exchanging a neighboring oxygen atom with sulfur, thereby rendering them more active and selective. At low loadings, Sn is atomically dispersed and selectively binds to hydroxyl groups or oxygen atoms on Al 2 O 3 . This prevents the formation of original (unmodified) defect sites on Al 2 O 3 and improves overall selectivity. The activity and selectivity of the catalyst are heavily dependent on the chemical potential of sulfur and hydrogen because they influence both the relative concentration of the two types of sites and the overall reaction mechanism. Finally, the catalyst can be regenerated fully under a pure H 2 S stream, thereby precluding treatment under oxygen, which can lead to sintering.
Sulfur Tolerant Subnanometer Fe/Alumina Catalysts for Propane Dehydrogenation
A series of Al 2 O 3 -supported Fe-containing catalysts were synthesized by incipient wetness impregnation. The iron surface density was varied from 1 to 13 Fe atoms/nm 2 spanning submonolayer to above-monolayer coverage. Here, the resulting supported Fe-catalysts were characterized by N 2 physisorption, ex situ X-ray diffraction (XRD), X-ray pair distribution function (PDF), X-ray absorption spectroscopy (XAS), aberration corrected scanning transmission electron microscopy (AC-STEM) and chemically probed by hydrogen temperature-programmed reduction (H 2 -TPR). The results suggest that over this entire range of loadings, Fe was present as dispersed species, with only a very small fraction of Fe 2 O 3 aggregates, at the highest Fe loading in oxide phase. The in situ sulfidation of Fe/Al 2 O 3 resulted in the formation of a highly active and selective PDH catalyst. The highest activity with 52% propane conversion and ~99% propylene selectivity at 560 °C was obtained for the 6.4 Fe/Al 2 O 3 -S catalyst, suggesting that this is the highest amount of Fe that could be fully dispersed on the support in sulfided form. XRD and AC-STEM indicated the absence of any crystalline iron sulfide aggregates after sulfidation and reaction. H 2 -TPR results indicated that the amount of the reducible Fe sites in the sulfided catalyst remained constant above monolayer coverage, and increasing loading did not increase the number of reducible Fe sites. Consistent with these results, the reactivity per gram of catalyst showed no increase with Fe loading above monolayer coverage, suggesting that additional Fe remains conformal to the alumina surface.
On the structure sensitivity of and CO coverage effects on formic acid decomposition on Pd surfaces
Using density functional theory calculations, the Pd-catalyzed vapor-phase formic acid decomposition was studied, with a focus on the structure sensitivity and CO coverage effects. A comprehensive reaction network was developed on both the (111) and (100) facets of Pd, at CO coverages of 0 and 5/9 monolayer (ML). Pd(100) was determined to be more reactive than Pd(111) at both CO coverages. The introduction of 5/9 ML CO decreased the activity of both facets significantly, due to destabilization of the surface intermediates and transition states on the CO-decorated surfaces. Three reaction pathways were explored on the clean surfaces: the formate (HCOO) pathway, the carboxyl (COOH) pathway leading to the formation of CO 2 , and the COOH pathway leading to the formation of CO (COOH→CO). Based on the DFT-derived energetics alone, it appears that all three pathways contribute to the reaction on clean Pd, whereas the presence of 5/9 ML of CO inhibits the HCOO pathway on both facets and favors the COOH→CO pathway on the (111) facet, but the COOH→CO 2 one on the (100) facet. Moreover, at high CO coverages, alternative spectator CO-assisted adsorbate decomposition pathways were discovered, which could potentially play a role in formic acid decomposition on Pd catalysts under realistic reaction conditions.
Elucidating the origin of selective dehydrogenation of propane on γ-alumina under H2S treatment and co-feed
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Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis
Microkinetic modeling based on density functional theory (DFT) derived energetics is important for addressing fundamental questions in catalysis. The quantitative fidelity of microkinetic models (MKMs), however, is often insufficient to conclusively infer the mechanistic details of a specific catalytic system. Here, this can be attributed to a number of factors such as an incorrect model of the active site for which DFT calculations are performed, deficiencies in the hypothesized reaction mechanism, inadequate consideration of the surface environment under reaction conditions, and intrinsic errors in the DFT exchange-correlation functional. Despite these limitations, we aim at developing a rigorous understanding of the reaction mechanism and of the nature of the active site for heterogeneous catalytic chemistries under reaction conditions. By achieving parity between experimental and modeling outcomes through robust parameter estimation and by ensuring coverage-consistency between DFT calculations and MKM predictions, it is possible to systematically refine the mechanistic model and, thereby, our understanding of the catalytic active site in situ.
Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene
The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.