Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons

Abstract

The electrochemical reduction of CO to multi-carbon products has attracted much attention because it provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the efficiency of CO conversion to C products remains below that necessary for its implementation at scale. Modifying the local electronic structure of copper with positive valence sites has been predicted to boost conversion to C products. Here, we use boron to tune the ratio of Cu to Cu active sites and improve both stability and C-product generation. Simulations show that the ability to tune the average oxidation state of copper enables control over CO adsorption and dimerization, and makes it possible to implement a preference for the electrosynthesis of C products. We report experimentally a C Faradaic efficiency of 79 ± 2% on boron-doped copper catalysts and further show that boron doping leads to catalysts that are stable for in excess of ~40 hours while electrochemically reducing CO to multi-carbon hydrocarbons.

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO2 Reduction to Formate

“…Of important note, the commercial viability of CO 2 RR to different products depends on a series of factors including not only the market demand of the product, but also the material, manufacturing, and separation costs. Although it is intuitively more desirable to control the selectivity toward higher‐valued products such as ethylene, ethanol, acetate, n ‐propanol, or even C 4 products, recent technoeconomic analysis unambiguously points out that the two‐electron electrochemical CO 2 RR to CO or formic acid is the most economically viable, whereas those C 2 –C 4 products other than propanol are not even profitable . This is understandable because the electricity cost is the major contributor to the operation cost of CO 2 electrolyzer.…”

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst

“…Electrochemical carbon dioxide reduction is ap romising solution for renewable energy storage,chemical/fuel production, and managing the global carbon balance. [1] To achieve the CO 2 reduction reaction (CO 2 RR) at al ow overpotential with high selectivity,good stability,and large current density, numerous material systems have been investigated, [2] including carbon materials, [3] metals, [4] metal oxides, [5] metal sulfides, [6] and so on. [7] However,t he mechanism of CO 2 activation and conversion, such as the catalytically active site and reaction pathway,r emains elusive.S ingle-atom catalysts (SACs) offer potential platforms for exploring the CO 2 RR.…”

Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring

“…It is well‐known that the activity and selectivity of CO 2 RR catalysts strongly depend on the precise control of their structure, such as the content of defects, subsurface oxygen or Cu + species, the specific shape of the nanocrystals, or the surface composition and atomic ordering in bimetallic nanostructures . Previous experimental and theoretical studies demonstrated that Cu(100) is the most favorable crystal orientation for the C−C coupling process .…”