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The electro-oxidative synthesis of valued chemicals offers to enhance the overall efficiency and economic viability of renewable electrosynthesis systems. Here, the authors use dopant-tuned catalysts to promote the electrosynthesis of dimethyl carbonate from CO and methanol via oxidative carbonylation.

Electrocatalytic reduction of CO₂ over copper can be made highly selective by ‘tuning’ the copper surface with adsorbed organic molecules to stabilize intermediates for carbon-based fuels such as ethylene

The production of higher alcohols is very valuable because of their high volumetric energy density. Now, Sargent, Sinton and co-workers report the design of copper nanoparticles with tailored nanocavities that promote n-propanol formation by the coupling of C2 and C1 intermediates inside the cavity.

Reconstruction of Cu catalysts under electrochemical CO₂ reduction conditions is a well-reported phenomenon. Here the reconstruction of bimetallic Cu–X catalysts is investigated to reveal the roles of atomic miscibility and intermediate binding on surface reconstruction and the resulting effects on product selectivity.

CO2 reduction rate shows a strong dependence on alkali metal cation identity but a unified molecular picture for underlying mechanism requires further investigation. Using advanced molecular simulations and experimental kinetic studies, here the authors establish a unified mechanism for cation-coupled electron transfer.

Efficiently producing multicarbon chemicals through electrochemical CO₂ reduction is essential for achieving economically feasible carbon neutrality. Here, the authors present molecularly enhanced CO₂-to-*CO conversion and *CO dimerization for high-rate ethylene production by nanoconfinement of ascorbic acid.

Controlling the reaction pathway in electrochemical CO₂ reduction for the selective production of hydrocarbons or oxygenates is challenging. Now, control over atomic immiscibility in Cu and Cu–Ag alloyed catalysts can steer CO₂ reduction products from ethylene towards ethanol.

It is challenging to realize doping and surface passivation simultaneously in colloidal quantum dot inks. Here Choi et al. employ a cascade surface modification approach to solve the problem and obtain record high efficiency of 13.3% for bulk homojunction solar cells based on these inks.

Copper is unique among CO₂ electrocatalysts owing to its ability to produce multicarbon products at high rates; however, achieving selectivity for specific products remains challenging. Here, Cu surfaces decorated with alkaline earth metal oxides are found to strongly favour alcohols over hydrocarbons.

CO₂-to-ethylene conversion using renewable electricity provides a sustainable route to produce valuable chemicals. Here, the authors report high ethylene activity of 215 mA cm⁻² and selectivity of 65% made possible by silica clusters in copper.

Surface reconstruction of electrocatalysts is an important issue for electroconversion of carbon dioxide to value-added chemical products. Here the authors address this issue by using copper nanoparticles protected by self-formed quasi graphitic carbon shell for stable CO2 to C2H4 conversion.

Converting CO2 and H2O into value-added chemical feedstocks and fuels offers a carbon neutral approach to tackling global energy and climate concerns. Here the authors report a metal supported single-atom catalytic site enabling the electrocatalytic reduction of CO2 to methane.

Producing ethanol from carbon dioxide, water, and renewable electricity offers a route to sustainable energy. Here, the authors enhance electrocatalytic activity for carbon dioxide reduction by tuning adsorbed hydrogen in a class of copper catalysts with oxide- and hydroxide-modified surfaces.

Catalysts for CO electroreduction have focused on Cu, and their main products have been C₂ chemicals. Here authors use the concept of asymmetric active sites to develop a class of doped Cu catalysts for C-C coupling, delivering record selectivity to n-propanol.

Electrochemical conversion of CO₂ into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Now, Sargent and co-workers present a cooperative catalyst design of molecule–metal interfaces to improve the electrosynthesis of ethanol from CO₂ by producing a reaction-intermediate-rich local environment.

Ethylene glycol is a commodity chemical with an annual consumption of 20 million tonnes. Its production generates 1.6 tonnes of CO₂ per tonne of ethylene glycol. To reduce these CO₂ emissions, the authors report a one-step electrochemical route to selectively convert ethylene to ethylene glycol at ambient temperature and pressure in aqueous media.

The electrocatalytic upgrading of CO to higher-value fuels provides a promising route to multi-carbon alcohol products. Here, the authors show that high alcohol selectivity and activity can be achieved by incorporating palladium in copper.

Electrochemical conversion of CO₂ into high-value products is attractive for lowering net carbon emissions. Lee et al. present the valorization of chemisorbed CO₂ to CO in an aqueous monoethanolamine electrolyte via tailoring of the electrochemical double layer, with 72% Faradaic efficiency at 50 mA cm^–2.

The electroreduction of CO₂ to ethanol could enable the clean production of fuels using renewable power. This study shows how confinement effects from nitrogen-doped carbon layers on copper catalysts enable selective ethanol production from CO₂ with a Faradaic efficiency of up to 52%.

The carbon dioxide reduction reaction can enable renewable energy storage by producing valuable products such as ethylene. This Perspective provides an overview of strategies that use molecular enhancement of heterogeneous catalysts to improve activity, efficiency and selectivity.