Restructuring of Cu-based Catalysts during CO Electroreduction: Evidence for the Dominant Role of Surface Defects on the C2+ Product Selectivity.

CO is the key reaction intermediate in the Cu-catalyzed electroreduction of CO2 to products containing C-C bonds. Herein, we investigate the impact of the particle size of CuO precursors on the direct electroreduction of CO (CORR) to C2+ products. Flame spray pyrolysis was used to prepare CuO particles with sizes between 4 and 30 nm. In situ synchrotron wide-angle X-ray scattering (WAXS), quasi-in situ X-ray photoelectron spectroscopy, and transmission electron microscopy demonstrated that, during CORR, the CuO precursors transformed into ∼30 nm metallic Cu particles with a crystalline domain size of ∼17 nm, independently of the initial size of the CuO precursors. Despite their similar morphology, the samples presented different Faradaic efficiencies (FEs) to C2+ products. The Cu particles derived from medium-sized (10-20 nm) CuO precursors were the most selective to C2+ products (FE 60%), while those derived from CuO precursors smaller than 10 nm displayed a high FE to H2. As the oxidation state, the particle and the crystallite sizes of these samples were similar after CORR, the differences in product distribution are attributed to the type and density of surface defects on the metallic Cu particles, as supported by studying electrochemical oxidation of the reduced Cu particles during CV cycling in combination with synchrotron WAXS. Cu particles derived from <10 nm CuO contained a higher density of more under-coordinated defects, resulting in a higher FE to H2 than Cu particles derived from 10 to 30 nm CuO. Bulk oxidation was most prominent and stable for Cu particles derived from medium-sized CuO, which indicated the more disordered nature of their surface compared to Cu particles derived from 30 nm CuO precursors and their lower reactivity compared to Cu particles derived from small CuO. Cu particles derived from <10 nm CuO initially displayed intense redox behavior, quickly fading during subsequent CVs. Our results evidence the significant restructuring during the electrochemical reduction of CuO precursors into Cu particles of similar size. The differences in CORR performance of these Cu particles of similar size can be correlated to different surface structures, qualitatively resolved by studying surface and bulk oxidation, which affect the competition between CO dimerization to yield C2+ products and undesired H2 evolution.

Structure Sensitivity of CO2 Hydrogenation on Ni Revisited.

Despite the large number of studies on the catalytic hydrogenation of CO2 to CO and hydrocarbons by metal nanoparticles, the nature of the active sites and the reaction mechanism have remained unresolved. This hampers the development of effective catalysts relevant to energy storage. By investigating the structure sensitivity of CO2 hydrogenation on a set of silica-supported Ni nanoparticle catalysts (2-12 nm), we found that the active sites responsible for the conversion of CO2 to CO are different from those for the subsequent hydrogenation of CO to CH4. While the former reaction step is weakly dependent on the nanoparticle size, the latter is strongly structure sensitive with particles below 5 nm losing their methanation activity. Operando X-ray diffraction and X-ray absorption spectroscopy results showed that significant oxidation or restructuring, which could be responsible for the observed differences in CO2 hydrogenation rates, was absent. Instead, the decreased methanation activity and the related higher CO selectivity on small nanoparticles was linked to a lower availability of step edges that are active for CO dissociation. Operando infrared spectroscopy coupled with (isotopic) transient experiments revealed the dynamics of surface species on the Ni surface during CO2 hydrogenation and demonstrated that direct dissociation of CO2 to CO is followed by the conversion of strongly bonded carbonyls to CH4. These findings provide essential insights into the much debated structure sensitivity of CO2 hydrogenation reactions and are key for the knowledge-driven design of highly active and selective catalysts.

Carbon dioxide and nitrate co-electroreduction to urea on CuOxZnOy.

Urea is a commonly used nitrogen fertiliser synthesised from ammonia and carbon dioxide using thermal catalysis. This process results in high carbon dioxide emissions associated with the required amounts of ammonia. Electrocatalysis provides an alternative method to urea production with reduced carbon emissions while utilising waste products like nitrate. This manuscript reports on urea synthesis from the electroreduction of nitrate and carbon dioxide using CuOxZnOy electrodes under mild conditions. Catalysts with different ratios of CuO and ZnO, synthesised via flame spray pyrolysis, were explored for the reaction. The results revealed that all the CuOxZnOy electrocatalyst compositions produce urea, but the efficiency strongly depends on the metal ratio composition of the catalysts. The CuO50ZnO50 composition had the best performance in terms of selectivity (41% at -0.8 V vs RHE) and activity (0.27 mA/cm2 at -0.8 V vs RHE) towards urea production. Thus, this material is one of the most efficient electrocatalysts for urea production reported so far. This study systematically evaluates bimetallic catalysts with varying compositions for urea synthesis from carbon dioxide and nitrate.

Pt/CeO2 as Catalyst for Nonoxidative Coupling of Methane: Oxidative Regeneration.

Direct nonoxidative coupling is a promising route for methane upgrading, yet its commercialization is hindered by the lack of efficient catalysts. Pt/CeO2 catalysts with isolated Pt species have attracted an increasing amount of interest in recent years. Herein, we studied the catalytic role and evolution of isolated Pt centers on CeO2 prepared by flame spray pyrolysis under the harsh reaction conditions of nonoxidative methane coupling. During the reaction at 800 °C, the isolated Pt sites sinter, leading to a loss of the ethylene and ethane yield. The agglomerated Pt can be redispersed by using an in situ regeneration strategy in oxygen. We found that isolated Pt centers are able to activate methane only at the initial reaction stage, and the CePt5 alloy acts as the active phase in the prolonged reaction.

Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction.

The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this type of promotion are not well understood. Here, we study the interaction of Ca2+ with reaction intermediates and products formed during the MTH reaction. Using transient kinetic and spectroscopic tools, we find strong indications that the selectivity differences between Ca/ZSM-5 and HZSM-5 are related to the different local environment inside the pores due to the presence of Ca2+. In particular, Ca/ZSM-5 strongly retains water, hydrocarbons, and oxygenates, which occupy as much as 10% of the micropores during the ongoing MTH reaction. This change in the effective pore geometry affects the formation of hydrocarbon pool components and in this way directs the MTH reaction toward the olefin cycle.

Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO2 Catalysts.

Aiming at knowledge-driven design of novel metal-ceria catalysts for automotive exhaust abatement, current efforts mostly pertain to the synthesis and understanding of well-defined systems. In contrast, technical catalysts are often heterogeneous in their metal speciation. Here, we unveiled rich structural dynamics of a conventional impregnated Pd/CeO2 catalyst during CO oxidation. In situ X-ray photoelectron spectroscopy and operando X-ray absorption spectroscopy revealed the presence of metallic and oxidic Pd states during the reaction. Using transient operando infrared spectroscopy, we probed the nature and reactivity of the surface intermediates involved in CO oxidation. We found that while low-temperature activity is associated with sub-oxidized and interfacial Pd sites, the reaction at elevated temperatures involves metallic Pd. These results highlight the utility of the multi-technique operando approach for establishing structure-activity relationships of technical catalysts.