Bjorn Hasa

Ethylene glycol is a widely utilized commodity chemical, the production of which accounts for over 46 million tons of CO₂ emission annually. Here we report a paired electrocatalytic approach for ethylene glycol production from methanol. Carbon catalysts are effective in reducing formaldehyde into ethylene glycol with a 92% Faradaic efficiency, whereas Pt catalysts at the anode enable formaldehyde production through methanol partial oxidation with a 75% Faradaic efficiency. With a membrane-electrode assembly configuration, we show the feasibility of ethylene glycol electrosynthesis from methanol in a single electrolyzer. The electrolyzer operates a full cell voltage of 3.2 V at a current density of 100 mA cm⁻², with a 60% reduction in energy consumption. Further investigations, using operando flow electrolyzer mass spectroscopy, isotopic labeling, and density functional theory (DFT) calculations, indicate that the desorption of a *CH₂OH intermediate is the crucial step in determining the selectively towards ethylene glycol over methanol.

Mitigating nitrogen oxide (NO_x) emissions is critical to tackle global warming and improve air quality. Conventional NO_x abatement technologies for emission control suffer from a low efficiency at near ambient temperatures. Herein, we show an electrochemical pathway to reduce gaseous NO_x that can be conducted at high reaction rates (400 mA cm^–2) under ambient conditions. Various transition metals are evaluated for electrochemical reduction of NO and N₂O to reveal the role of electrocatalyst in determining the product selectivity. Specifically, Cu is highly selective toward NH₃ formation with >80% Faradaic efficiency in NO electroreduction. Furthermore, the partial pressure study of NO electroreduction revealed that a high NO coverage facilitates the N–N coupling reaction. In acidic electrolytes, the formation of NH₃ is greatly favored, whereas the N₂ production is suppressed. Additional mechanistic studies were conducted by using flow electrochemical mass spectrometry to gain further insights into reaction pathways. This work provides a promising avenue toward abating gaseous NO_x emissions at ambient conditions by using renewable electricity.

Electrifying chemical manufacturing using renewable energy is an attractive approach to reduce the dependence on fossil energy sources in chemical industries. Primary amines are important organic building blocks; however, the synthesis is often hindered by the poor selectivity because of the formation of secondary and tertiary amine byproducts. Herein, we report an electrocatalytic route to produce ethylamine selectively through an electroreduction of acetonitrile at ambient temperature and pressure. Among all the electrocatalysts, Cu nanoparticles exhibit the highest ethylamine Faradaic efficiency (~96%) at −0.29 V versus reversible hydrogen electrode. Under optimal conditions, we achieve an ethylamine partial current density of 846 mA cm⁻². A 20-hour stable performance is demonstrated on Cu at 100 mA cm⁻² with an 86% ethylamine Faradaic efficiency. Moreover, the reaction mechanism is investigated by computational study, which suggests the high ethylamine selectivity on Cu is due to the moderate binding affinity for the reaction intermediates.

The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts.

Operando mass spectrometry is a powerful technique to probe reaction intermediates near the surface of catalyst in electrochemical systems. For electrochemical reactions involving gas reactants, conventional operando mass spectrometry struggles in detecting reaction intermediates because the batch‐type electrochemical reactor can only handle a very limited current density due to the low solubility of gas reactant(s). Herein, we developed a new technique, namely flow electrolyzer mass spectrometry (FEMS), by incorporating a gas‐diffusion electrode design, which enables the detection of reactive volatile or gaseous species at high operating current densities (>100 mA cm⁻²). We investigated the electrochemical carbon monoxide reduction reaction (eCORR) on polycrystalline copper and elucidated the oxygen incorporation mechanism in the acetaldehyde formation. Combining FEMS and isotopic labelling, we showed that the oxygen in the as‐formed acetaldehyde intermediate originates from the reactant CO, while ethanol and n‐propanol contained mainly solvent oxygen. The observation provides direct experimental evidence of an isotopic scrambling mechanism.

Operando mass spectrometry is a powerful technique to probe reaction intermediates near the surface of catalyst in electrochemical systems. For electrochemical reactions involving gas reactants, conventional operando mass spectrometry struggles in detecting reaction intermediates because the batch‐type electrochemical reactor can only handle a very limited current density due to the low solubility of gas reactant(s). Herein, we developed a new technique, namely flow electrolyzer mass spectrometry (FEMS), by incorporating a gas‐diffusion electrode design, which enables the detection of reactive volatile or gaseous species at high operating current densities (>100 mA cm⁻²). We investigated the electrochemical carbon monoxide reduction reaction (eCORR) on polycrystalline copper and elucidated the oxygen incorporation mechanism in the acetaldehyde formation. Combining FEMS and isotopic labelling, we showed that the oxygen in the as‐formed acetaldehyde intermediate originates from the reactant CO, while ethanol and n‐propanol contained mainly solvent oxygen. The observation provides direct experimental evidence of an isotopic scrambling mechanism.

Invited for this month's cover picture are the groups of Alexandros Katsaounis at the Department of Chemical Engineering (University of Patras, Greece) and Costas Galiotis also at the same department and the Institute of Chemical Engineering Sciences (FORTH/ICE‐HT, Greece). The cover picture shows schematically the operation of a Proton Exchange Membrane fuel cell (PEMFC) under hydrogen feeding. The metallic phase of the electrodes (usually Pt and Ru) is usually dispersed on a carbon‐based support. Novel carbon materials (such as carbon nanotubes, biochar and graphene) are used in this study as alternative supports and compared with the state‐of‐the‐art Vulcan XC‐72. Read the full text of the Article at 10.1002/celc.201900566.