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1. Improving alkane dehydrogenation activity on γ-Al ₂ O ₃ through Ga doping

   https://doi.org/10.1039/d0cy01474e  

   Abdelgaid, Mona; Dean, James; Mpourmpakis, Giannis (November 2020, Catalysis Science & Technology)

   null (Ed.)

   Nonoxidative alkane dehydrogenation is a promising route to produce olefins, commonly used as building blocks in the chemical industry. Metal oxides, including γ-Al 2 O 3 and β-Ga 2 O 3 , are attractive dehydrogenation catalysts due to their surface Lewis acid–base properties. In this work, we use density functional theory (DFT) to investigate nonoxidative dehydrogenation of ethane, propane, and isobutane on the Ga-doped and undoped (100) γ-Al 2 O 3 via the concerted and stepwise mechanisms. We revealed that doping (100) γ-Al 2 O 3 with Ga atoms has significant improvement in the dehydrogenation activity by decreasing the C–H activation barriers of the kinetically favored concerted mechanism and increasing the overall dehydrogenation turnover frequencies. We identified the dissociated H 2 binding energy as an activity descriptor for alkane dehydrogenation, accounting for the strength of the Lewis acidity and basicity of the active sites. We demonstrate linear correlations between the dissociated H 2 binding energy and the activation barriers of the rate determining steps for both the concerted and stepwise mechanisms. We further found the carbenium ion stability to be a quantitative reactant-type descriptor, correlating with the C–H activation barriers of the different alkanes. Importantly, we developed an alkane dehydrogenation model that captures the effect of catalyst acid–base surface properties (through dissociated H 2 binding energy) and reactant substitution (through carbenium ion stability). Additionally, we show that the dissociated H 2 binding energy can be used to predict the overall dehydrogenation turnover frequencies. Taken together, our developed methodology facilitates the screening and discovery of alkane dehydrogenation catalysts and demonstrates doping as an effective route to enhance catalytic activity. 

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2. Tuning the electronic properties of the γ-Al ₂ O ₃ surface by phosphorus doping

   https://doi.org/10.1039/C9CP03105G  

   Acikgoz, Muhammed; Khoshi, M. Reza; Harrell, Jaren; Genova, Alessandro; Chawla, Rupali; He, Huixin; Pavanello, Michele (July 2019, Physical Chemistry Chemical Physics)

   Tuning the electronic properties of oxide surfaces is of pivotal importance, because they find applicability in a variety of industrial processes, including catalysis. Currently, the industrial protocols for synthesizing oxide surfaces are limited to only partial control of the oxide's properties. This is because the ceramic processes result in complex morphologies and a priori unpredictable behavior of the products. While the bulk doping of alumina surfaces has been demonstrated to enhance their catalytic applications ( i.e. hydrodesulphurization (HDS)), the fundamental understanding of this phenomenon and its effect at an atomic level remain unexplored. In our joint experimental and computational study, simulations based on Density Functional Theory (DFT), synthesis, and a variety of surface characterization techniques are exploited for the specific goal of understanding the structure–function relationship of phosphorus-doped γ-Al 2 O 3 surfaces. Our theoretical calculations and experimental results agree in finding that P doping of γ-Al 2 O 3 leads to a significant decrease in its work function. Our computational models show that this decrease is due to the formation of a new surface dipole, providing a clear picture of the effect of P doping at the surface of γ-Al 2 O 3 . In this study, we uncover a general paradigm for tuning support–catalyst interactions that involves electrostatic properties of doped γ-Al 2 O 3 surface, specifically the surface dipole. Our findings open a new pathway for engineering the electronic properties of metal oxides’ surfaces. 

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3. Tandem In ₂ O ₃ -Pt/Al ₂ O ₃ catalyst for coupling of propane dehydrogenation to selective H ₂ combustion

   https://doi.org/10.1126/science.abd4441  

   Yan, Huan; He, Kun; Samek, Izabela A.; Jing, Dian; Nanda, Macy G.; Stair, Peter C.; Notestein, Justin M. (March 2021, Science)

   Tandem catalysis couples multiple reactions and promises to improve chemical processing, but precise spatiotemporal control over reactive intermediates remains elusive. We used atomic layer deposition to grow In₂O₃over Pt/Al₂O₃, and this nanostructure kinetically couples the domains through surface hydrogen atom transfer, resulting in propane dehydrogenation (PDH) to propylene by platinum, then selective hydrogen combustion by In₂O₃, without excessive hydrocarbon combustion. Other nanostructures, including platinum on In₂O₃or platinum mixed with In₂O₃, favor propane combustion because they cannot organize the reactions sequentially. The net effect is rapid and stable oxidative dehydrogenation of propane at high per-pass yields exceeding the PDH equilibrium. Tandem catalysis using this nanoscale overcoating geometry is validated as an opportunity for highly selective catalytic performance in a grand challenge reaction. 

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4. DFT Analysis of Methane C−H Activation and Over‐Oxidation by [Cu ₂ O] ²⁺ and [Cu ₂ O ₂ ] ²⁺ Sites in Zeolite Mordenite: Intra‐ versus Inter‐site Over‐Oxidation

   https://doi.org/10.1002/cphc.202100580  

   Panthi, Dipak; Adeyiga, Olajumoke; Odoh, Samuel_O (October 2021, ChemPhysChem)

   Abstract Methane over‐oxidation by copper‐exchanged zeolites prevents realization of high‐yield catalytic conversion. However, there has been little description of the mechanism for methane over‐oxidation at the copper active sites of these zeolites. Using density functional theory (DFT) computations, we reported that tricopper [Cu₃O₃]²⁺active sites can over‐oxidize methane. However, the role of [Cu₃O₃]²⁺sites in methane‐to‐methanol conversion remains under debate. Here, we examine methane over‐oxidation by dicopper [Cu₂O]²⁺and [Cu₂O₂]²⁺sites using DFT in zeolite mordenite (MOR). For [Cu₂O₂]²⁺, we considered the μ‐(η²:η²) peroxo‐, and bis(μ‐oxo) motifs. These sites were considered in the eight‐membered (8MR) ring of MOR. μ‐(η²:η²) peroxo sites are unstable relative to the bis(μ‐oxo) motif with a small interconversion barrier. Unlike [Cu₂O]²⁺which is active for methane C−H activation, [Cu₂O₂]²⁺has a very large methane C−H activation barrier in the 8MR. Stabilization of methanol and methyl at unreacted dicopper sites however leads to over‐oxidation via sequential hydrogen atom abstraction steps. For methanol, these are initiated by abstraction of the CH₃group, followed by OH and can proceed near 200 °C. Thus, for [Cu₂O]²⁺and [Cu₂O₂]²⁺species, over‐oxidation is an inter‐site process. We discuss the implications of these findings for methanol selectivity, especially in comparison to the intra‐site process for [Cu₃O₃]²⁺sites and the role of Brønsted acid sites. 

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5. Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub‐ and Supercritical Methanol

   https://doi.org/10.1002/cnma.202400222  

   Parker, Julia; Santillan‐Jimenez, Eduardo; Harman‐Ware, Anne_E; Umenweke, Great_C; Heintz, Olivier; Caboche, Gilles; Crocker, Mark (December 2024, ChemNanoMat)

   Abstract The use of γ‐Al₂O₃‐supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni‐based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni‐5 wt.% Cu/Al₂O₃catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni⁰on the catalyst surface and, consequently, improved hydrogenation activity. The main monomers formed were propanol‐, propyl‐ and propenyl‐substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin. 

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