Europium-Magnesium-Aluminum-Based Mixed-Metal Oxides as Highly Active Methane Oxychlorination Catalysts.

Methane oxychlorination (MOC) is a promising reaction for the production of liquefied methane derivatives. Even though catalyst design is still in its early stages, the general trend is that benchmark catalyst materials have a redox-active site, with, e.g., Cu2+, Ce4+, and Pd2+ as prominent showcase examples. However, with the identification of nonreducible LaOCl moiety as an active center for MOC, it was demonstrated that a redox-active couple is not a requirement to establish a high activity. In this work, we show that Mg2+-Al3+-based mixed-metal oxide (MMO) materials are highly active and stable MOC catalysts. The synergistic interaction between Mg2+ and Al3+ could be exploited due to the fact that a homogeneous distribution of the chemical elements was achieved. This interaction was found to be crucial for the unexpectedly high MOC activity, as reference MgO and γ-Al2O3 materials did not show any significant activity. Operando Raman spectroscopy revealed that Mg2+ acted as a chlorine buffer and subsequently as a chlorinating agent for Al3+, which was the active metal center in the methane activation step. The addition of the redox-active Eu3+ to the nonreducible Mg2+-Al3+ MMO catalyst enabled further tuning of the catalytic performance and made the EuMg3Al MMO catalyst one of the most active MOC catalyst materials reported so far. Combined operando Raman/luminescence spectroscopy revealed that the chlorination behavior of Mg2+ and Eu3+ was correlated, suggesting that Mg2+ also acted as a chlorinating agent for Eu3+. These results indicate that both redox activity and synergistic effects between Eu, Mg, and Al are required to obtain high catalytic performance. The importance of elemental synergy and redox properties is expected to be translatable to the oxychlorination of other hydrocarbons, such as light alkanes, due to large similarities in catalytic chemistry.

Bifunctional Europium for Operando Catalyst Thermometry in an Exothermic Chemical Reaction.

Often the reactor or the reaction medium temperature is reported in the field of heterogeneous catalysis, even though it could vary significantly from the reactive catalyst temperature. The influence of the catalyst temperature on the catalytic performance and vice versa is therefore not always accurately known. We here apply EuOCl as both solid catalyst and thermometer, allowing for operando temperature determination. The interplay between reaction conditions and the catalyst temperature dynamics is studied. A maximum temperature difference between the catalyst and oven of +16 °C was observed due to the exothermicity of the methane oxychlorination reaction. Heat dissipation by radiation appears dominating compared to convection in this set-up, explaining the observed uniform catalyst bed temperature. Application of operando catalyst thermometry could provide a deeper mechanistic understanding of catalyst performances and allow for safer process operation in chemical industries.

A Ziegler-type spherical cap model reveals early stage ethylene polymerization growth versus catalyst fragmentation relationships.

Polyolefin catalysts are characterized by their hierarchically complex nature, which complicates studies on the interplay between the catalyst and formed polymer phases. Here, the missing link in the morphology gap between planar model systems and industrially relevant spherical catalyst particles is introduced through the use of a spherical cap Ziegler-type catalyst model system for the polymerization of ethylene. More specifically, a moisture-stable LaOCl framework with enhanced imaging contrast has been designed to support the TiCl4 pre-active site, which could mimic the behaviour of the highly hygroscopic and industrially used MgCl2 framework. As a function of polymerization time, the fragmentation behaviour of the LaOCl framework changed from a mixture of the shrinking core (i.e., peeling off small polyethylene fragments at the surface) and continuous bisection (i.e., internal cleavage of the framework) into dominantly a continuous bisection model, which is linked to the evolution of the estimated polyethylene volume and the fraction of crystalline polyethylene formed. The combination of the spherical cap model system and the used advanced micro-spectroscopy toolbox, opens the route for high-throughput screening of catalyst functions with industrially relevant morphologies on the nano-scale.

Favoring the Methane Oxychlorination Reaction over EuOCl by Synergistic Effects with Lanthanum.

The direct conversion of CH4 into fuels and chemicals produces less waste, requires smaller capital investments, and has improved energy efficiency compared to multistep processes. While the methane oxychlorination (MOC) reaction has been given little attention, it offers the potential to achieve high CH4 conversion levels at high selectivities. In a continuing effort to design commercially interesting MOC catalysts, we have improved the catalyst design of EuOCl by the partial replacement of Eu3+ by La3+. A set of catalytic solid solutions of La3+ and Eu3+ (i.e., La x Eu1-x OCl, where x = 0, 0.25, 0.50, 0.75, and 1) were synthesized and tested in the MOC reaction. The La3+-Eu3+ catalysts exhibit an increased CH3Cl selectivity (i.e., 54-66 vs 41-52%), a lower CH2Cl2 selectivity (i.e., 8-24 vs 18-34%), and a comparable CO selectivity (i.e., 11-28 vs 14-28%) compared to EuOCl under the same reaction conditions and varying HCl concentrations in the feed. The La3+-Eu3+ catalysts possessed a higher CH4 conversion rate than when the individual activities of LaOCl and EuOCl are summed with a similar La3+/Eu3+ ratio (i.e., the linear combination). In the solid solution, La3+ is readily chlorinated and acts as a chlorine buffer that can transfer chlorine to the active Eu3+ phase, thereby enhancing the activity. The improved catalyst design enhances the CH3Cl yield and selectivity and reduces the catalyst cost and the separation cost of the unreacted HCl. These results showcase that, by matching intrinsic material properties, catalyst design can be altered to overcome reaction bottlenecks.

Mechanistic Insights into the Lanthanide-Catalyzed Oxychlorination of Methane as Revealed by Operando Spectroscopy.

Commercialization of CH4 valorization processes is currently hampered by the lack of suitable catalysts, which should be active, selective, and stable. CH4 oxychlorination is one of the promising routes to directly functionalize CH4, and lanthanide-based catalysts show great potential for this reaction, although relatively little is known about their functioning. In this work, a set of lanthanide oxychlorides (i.e., LnOCl with Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho) and Er- and Yb-based catalysts were synthesized, characterized, and tested. All lanthanide-based catalysts can directly activate CH4 into chloromethanes, but their catalytic properties differ significantly. EuOCl shows the most promising catalytic activity and selectivity, as very high conversion levels (>30%) and chloromethane selectivity values (>50%) can be reached at moderate reaction temperatures (∼425 °C). Operando Raman spectroscopy revealed that the chlorination of the EuOCl catalyst surface is rate-limiting; hence, increasing the HCl concentration improves the catalytic performance. The CO selectivity could be suppressed from 30 to 15%, while the CH4 conversion more than doubled from 11 to 24%, solely by increasing the HCl concentration from 10 to 60% at 450 °C. Even though more catalysts reported in this study and in the literature show a negative correlation between the S CO and HCl concentration, this effect was never as substantial as observed for EuOCl. EuOCl has promising properties to bring the oxychlorination one step closer to an economically viable CH4 valorization process.