Electrochemical valorization of captured CO: recent advances and future perspectives.

The excessive emission of CO has led to severe climate change, prompting global concern. Capturing CO and converting it through electrochemistry into value-added products represent promising approaches to mitigating CO emissions and closing the carbon cycle. Traditionally, these two processes have been performed independently, involving multiple steps, high energy consumption, and low efficiency.

NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu.

Copper-based materials exhibit significant potential as catalysts for electrochemical CO reduction, owing to their capacity to generate multicarbon hydrocarbons. The molecular functionalization of Cu electrodes represents a simple yet powerful strategy for improving the intrinsic activity of these materials by favoring specific reaction pathways through the creation of tailored microenvironments around the surface active sites. However, despite its success, comprehensive mechanistic insights derived from experimental techniques are often limited, leaving the active role of surface modifiers inconclusive.

Breaking Scaling Relationships in CO Reduction on Copper Alloys with Organic Additives.

Boundary conditions for catalyst performance in the conversion of common precursors such as N, O, HO, and CO are governed by linear free energy and scaling relationships. Knowledge of these limits offers an impetus for designing strategies to alter reaction mechanisms to improve performance. Typically, experimental demonstrations of linear trends and deviations from them are composed of a small number of data points constrained by inherent experimental limitations.

Selective CO Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface.

Electrochemical CO reduction over Cu could provide value-added multicarbon hydrocarbons and alcohols. Despite recent breakthroughs, it remains a significant challenge to design a catalytic system with high product selectivity. Here we demonstrate that a high selectivity of ethylene (55%) and C products (77%) could be achieved by a highly modular tricomponent copolymer modified Cu electrode, rivaling the best performance using other modified polycrystalline Cu foil catalysts.

Molecular enhancement of heterogeneous CO reduction.

The electrocatalytic carbon dioxide reduction reaction (CORR) addresses the need for storage of renewable energy in valuable carbon-based fuels and feedstocks, yet challenges remain in the improvement of electrosynthesis pathways for highly selective hydrocarbon production. To improve catalysis further, it is of increasing interest to lever synergies between heterogeneous and homogeneous approaches. Organic molecules or metal complexes adjacent to heterogeneous active sites provide additional binding interactions that may tune the stability of intermediates, improving catalytic performance by increasing Faradaic efficiency (product selectivity), as well as decreasing overpotential.

Molecular tuning of CO-to-ethylene conversion.

The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources. However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CORR) remains a challenge. Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity, and this has recently been explored for the reaction on copper by controlling morphology, grain boundaries, facets, oxidation state and dopants.

In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO Reduction to Ethylene.

Bridging homogeneous molecular systems with heterogeneous catalysts is a promising approach for the development of new electrodes, combining the advantages of both approaches. In the context of CO electroreduction, molecular enhancement of planar copper electrodes has enabled promising advancement towards high Faradaic efficiencies for multicarbon products. Besides, nanostructured copper electrodes have also demonstrated enhanced performance at comparatively low overpotentials.

Photo- and Electrochemical Valorization of Carbon Dioxide Using Earth-Abundant Molecular Catalysts.

The dramatic increase in anthropogenic carbon dioxide emissions in recent decades has forced us to look for alternative carbon-neutral processes for the production of energy vectors and commodity chemicals. Photo- and electrochemical reduction of CO are appealing strategies for the storage of sustainable and intermittent energies in the form of chemical bonds of synthetic fuels and value-added molecules. In these approaches, carbon dioxide is converted to products such as CO, HCOOH and MeOH through proton-coupled electron transfer reactions.

Progress on all ends for carbon-carbon bond formation through photoredox catalysis.

Dual role for catalysts: Novel routes for the generation of asymmetric stereocenters using photoredox catalysis were recently developed. Different chiral catalytic systems allowed new CC bonds to form in good yields and enantioselectivities using a mild methodology in which light is used as the energy source.

Recent advances in the application of chiral phosphine ligands in Pd-catalysed asymmetric allylic alkylation.

One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used.