CO2 Electroreduction To Syngas With Tunable Composition In An Artificial Leaf.

Invited for this month's cover is the group of Javier Pérez-Ramírez at ETH Zürich, which collaborated with the group of Tsvetelina Merdzhanova at Forschungszentrum Jülich. The image shows how artificial leaves, able to recycle carbon dioxide into syngas of variable composition, could be integrated with chemical plants. The Research Article itself is available at 10.1002/cssc.202301398.

CO2 Electroreduction To Syngas With Tunable Composition In An Artificial Leaf.

Artificial leaves (a-leaves) can reduce carbon dioxide into syngas using solar power and could be combined with thermo- and biocatalytic technologies to decentralize the production of valuable products. By providing variable CO : H2 ratios on demand, a-leaves could facilitate optimal combinations and control the distribution of products in most of these hybrid systems. However, the current design procedures of a-leaves concentrate on achieving high performance for a predetermined syngas composition. This study demonstrates that incorporating the electrolyte flow as a design variable enables flexible production without compromising performance. The concept was tested on an a-leaf using a commercial cell, a Cu2 O:Inx cathodic catalyst, and an inexpensive amorphous silicon thin-film photovoltaic module. Syngas with CO : H2 ratio in the range of 1.8-2.3 could be attained with only 2 % deviation from the optimal cell voltage and controllable solely by catholyte flow. These features could be beneficial for downstream technologies such as Fischer-Tropsch synthesis and anaerobic fermentation.

Microfabrication Enables Quantification of Interfacial Activity in Thermal Catalysis.

A myriad of heterogeneous catalysts comprises multiple phases that need to be precisely structured to exert their maximal contribution to performance through electronic and structural interactions at their peripheries. In view of the nanometric, tridimensional, and anisotropic nature of these materials, a quantification of the interface and the impact of catalytic sites located there on the global performance is a highly challenging task. Consequently, the true origin of catalysis often remains subject of debate even for widely studied materials. Herein, an integrated strategy based on microfabricated catalysts and a custom-designed reactor is introduced for determining interfacial contributions upon catalytic activity assessment under process-relevant conditions, which can be easily implemented in the common catalysis research infrastructure and will accelerate the rational design of multicomponent heterogeneous catalysts for diverse applications. The method is validated by studying the high-pressure continuous-flow hydrogenation of CO and CO2 over Cu-ZnO catalysts, revealing linear correlations between the methanol formation rate and the interface between the metal and the oxide. Characterization of fresh and used materials points to the model catalyst preparation as the current challenge of the methodology that can be addressed through further development of nanotechnological tools.

Electrochemical Reduction of Carbon Dioxide to 1-Butanol on Oxide-Derived Copper.

The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n-propanol, but more complex C4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO2 to 1-butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency=0.056 %, j1-Butanol =-0.080 mA cm-2 at -0.48 V vs. RHE) and elucidate its formation mechanism. Electrolysis of possible molecular intermediates, coupled with density functional theory, led us to propose that CO2 first electroreduces to acetaldehyde-a key C2 intermediate to 1-butanol. Acetaldehyde then undergoes a base-catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion by the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1-butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO2 .

Nitride-Derived Copper Modified with Indium as a Selective and Highly Stable Catalyst for the Electroreduction of Carbon Dioxide.

The lack of efficient catalysts prevents the electrocatalytic reduction of carbon dioxide from contributing to the pressing target of a carbon-neutral economy. Indium-modified copper nitride was identified as a stable electrocatalyst selective toward CO. In2 O3 /Cu3 N showed a Faradaic efficiency of 80 % at 0.5 V overpotential for at least 50 h, in stark contrast to the very limited stability of the benchmark In2 O3 /Cu2 O. Microfabricated systems allowed to correlate activity with highly stable interfaces in indium-modified copper nitride. In contrast, fast diffusion of indium resulted in rapidly evolving interfaces in the case of the system based on oxide-derived Cu. A metastable nitrogen species observed by spectroscopic means was proposed as the underlying cause leading to the unchanging interfaces. This work reveals the stabilizing properties of nitride-derived copper toward high-performance multicomponent catalysts.