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Electrochemical CO reduction to multi-carbon products offers a carbon-negative approach to produce chemicals, but the intricate reaction pathways lead to a broad spectrum of products. Now it has been shown that alkali cations alter the mechanistic pathways that govern the reaction selectivity involved in the formation of hydrocarbons versus oxygenates.

Electrochemical CO/CO₂ reduction to multicarbon species represents an exciting approach to synthesize valuable products, but controllably linking three or more carbons remains a challenge. Now the pathway towards C–C coupling beyond two carbons has been shown using a probe reactant strategy to afford a 53% the selectivity towards C₃₊ oxygenates.

Acidic CO₂ electroreduction is carbon efficient but suffers from low energy efficiency and selectivity. Here an interfacial cation matrix is developed to enrich alkali cations and increase the local pH at a Cu–Ag catalyst surface, improving efficiency. A 45% CO₂-to-ethanol Faradaic efficiency and 15% energy efficiency for ethanol production are achieved.

The direct electrosynthesis of acetic acid from CO₂ typically has the drawback of CO₂ crossover. Now, a cascade approach for the electroreduction of CO₂ to CO, followed by CO to acetic acid, is reported in which off-target intermediates are destabilized, leading to an acetic acid Faradaic efficiency of 70%.

Current industrial methods of ethylene glycol production generate substantial CO₂ emissions. Here electrocatalytic ethylene-to-ethylene glycol conversion is coupled to electrochemical CO₂ capture, decreasing carbon intensity by an order of magnitude.

The electrocatalytic upgrading of CO₂/CO provides a promising route to produce carbon-neutral alcohols but suffers from product loss to crossover and dilution. Here, the authors report on a CO reduction electrolyzer that recovers over 85% of alcohol without dilution, which is then scaled to 800 cm².

Carbon dioxide (CO₂) electroreduction is a sustainable way to reduce the carbon footprint of producing carbon-based chemicals. This work analyses voltage distributions within CO₂ electrolysers, identifies the sources of inefficiencies and highlights opportunities for system optimization.

Reactive capture—integrating CO₂ capture and electrochemical valorization—improves energy efficiency by eliminating gas-phase CO₂ desorption. Here, authors design a redox-active polymeric network to boost the direct conversion of captured CO₂ to multicarbon products with CO₂-free gas product stream.

Tandem electrocatalysts are developed for acidic CO₂ electroreduction. The catalyst contains planar-copper for CO₂ reduction to CO, and a dual-copper-active-site layer for CO reduction to C₂₊ products. An ethanol Faradaic efficiency of 46% and a C₂₊ Faradaic efficiency of 91% are achieved in acidic electrolyte at 150 mA cm⁻².

Biomass is a renewable source of carbon that can be exploited to produce valuable chemicals and fuels. This Perspective discusses the electrochemical valorization of biomass, identifying specific chemical transformations in which the approach can excel.

This work regulates solid/liquid/gas triple-phase interface, facilitating site-selective protonation in carbon monoxide electroreduction. It achieves increased energy-efficiency in acetate production and contributes to the understanding of selectively controlling the electrosynthesis of a single product.

Enhancing the kinetics and selectivity of CO₂/CO electroreduction towards valuable multi-carbon products poses a scientific challenge and is imperative for practical applicability. Here the authors report that modifying copper catalysts with surface thiol ligands significantly improves acetate selectivity.

Oxygen reduction to hydrogen peroxide is a promising alternative to replace the energy-intensive anthraquinone process in industry. Now, the hydrogen peroxide electrosynthesis performance of a carbon-supported cobalt phthalocyanine catalyst is tuned via the introduction of oxygen functional groups to the support, which optimize the electronic structure of cobalt active sites.

Electrosynthesis of higher carbon products (C₄₊) in a high selectivity has not been achieved by the direct reduction of CO₂ or CO. Here, the authors use a cascade electrocatalysis–thermocatalysis approach to produce butane from CO with an overall selectivity of 43%.