Translating Tactics from Direct CO₂ Electroreduction to Electroorganic Coupling Reactions with CO₂

Abstract

Sustainable electrosynthesis technologies are rapidly developing stimulated by the drive for sustainable chemical manufacturing and the increasingly accessible renewable electricity prices. The electrochemical utilization of easily available feedstock, such as carbon dioxide (CO2), has attracted significant attention as it can additionally help closing the disrupted carbon cycle. While direct CO2 reduction has benefited from recent advancements in the catalyst, electrolyte and system design, developments in electrochemical coupling of CO2 with organic precursors to yield value‐added chemicals have been lagging behind due to the apparent disconnect between the direct CO2 reduction and the organic electrosynthesis communities. Currently, electrocarboxylation reactions require high operating voltages, show low current densities, limited selectivity towards target products and are associated with low atom economy due to the reliance on sacrificial anode dissolution. Advancing this indirect electrochemical CO2 utilization strategy will enable sustainable synthesis of valuable chemicals including non‐steroidal anti‐inflammatory drugs and precursors for plasticizers and commercially‐relevant polymers—all of which are currently produced with high carbon footprint and low atom economy. This perspective discusses the current state‐of‐the‐art in electroorganic synthesis with CO2 as a one‐carbon synthon and suggests several transferrable strategies from direct CO2 reduction breakthroughs to advance electrocarboxylation and bring it closer to industrial implementation.

Pathways of ammonia electrooxidation on nickel hydroxide anodes and an alternative route towards recycled fertilizers

“…This knowledge gap represents a promising opportunity for the growing electrosynthesis sector, as the oxidation of ammonia to nitrate at the anode can be coupled with a value-added process at the cathode, such as green hydrogen production (or hydrogen evolution reaction, HER) or electrochemical CO 2 reduction (CO 2 R) to fuels or valuable carboxylic acids. 29–32…”

Synthesis of α-Amino Acids via Electrochemical Fixation of CO2 to Imines Using Different Metal Cathodes

“…The electrochemical carboxylation of organic compounds has been extensively studied since the 1970s. 44 Despite the large number of papers and reviews published on this topic, [49][50][51][52][53][54][55][56] only a few of them studied the EC of organic imines. Two mechanisms were proposed in the literature for the EC of imines.…”

A comparative overview of the electrochemical valorization and incorporation of CO2 in industrially relevant compounds

“…[53][54][55][56] The electrochemical CO 2 reduction reaction (eCO 2 RR) is a highly promising approach since a wide variety of desired products are possible, such as carbon monoxide (CO), [57][58][59][60] formic acid (HCOOH), [61][62][63][64] methanol (MeOH), [65][66][67][68][69] methane (CH 4 ) [70][71][72] and even ethylene, [73][74][75][76] ethanol (EtOH) [77][78][79][80] and other C 2+ products. [81][82][83][84][85][86][87] Capturing a reactive intermediate of the eCO 2 RR with a second substrate creates structural motives ubiquitous in the chemical industry, [88][89][90] expanding the product scope significantly and highlighting the versatility of the eCO 2 RR. Owing to this large pool of high-value products and the sustainable benefits of eCO 2 RR, industrial viability is already being thoroughly investigated.…”