Electrified hydrocarbon-to-oxygenates coupled to hydrogen evolution for efficient greenhouse gas mitigation.

Chemicals manufacture is among the top greenhouse gas contributors. More than half of the associated emissions are attributable to the sum of ammonia plus oxygenates such as methanol, ethylene glycol and terephthalic acid. Here we explore the impact of electrolyzer systems that couple electrically-powered anodic hydrocarbon-to-oxygenate conversion with cathodic H2 evolution reaction from water. We find that, once anodic hydrocarbon-to-oxygenate conversion is developed with high selectivities, greenhouse gas emissions associated with fossil-based NH3 and oxygenates manufacture can be reduced by up to 88%. We report that low-carbon electricity is not mandatory to enable a net reduction in greenhouse gas emissions: global chemical industry emissions can be reduced by up to 39% even with electricity having the carbon footprint per MWh available in the United States or China today. We conclude with considerations and recommendations for researchers who wish to embark on this research direction.

Electrolytic conversion of carbon capture solutions containing carbonic anhydrase.

The electrolysis of carbon capture solutions bypasses energy-intensive CO2 recovery steps that are often required to convert CO2 into value-added products. We report herein an electrochemical flow reactor that converts carbon capture solutions containing carbonic anhydrase enzymes into carbon-based products. Carbonic anhydrase enzymes benefit CO2 capture by increasing the rate of reaction between CO2 and weakly alkaline solutions by 20-fold. In this study, we reduced CO2-enriched bicarbonate solutions containing carbonic anhydrase ("enzymatic CO2 capture solutions") into CO at current densities of 100 mA cm-2. This result demonstrated how to electrolyse enzymatic CO2 capture solutions, but the selectivity for CO production was two-thirds less than bicarbonate solutions without carbonic anhydrase. This reduction in performance occurred because carbonic anhydrase deactivated the catalyst surface. A carbon microporous layer was found to suppress this deactivation.

What would it take for renewably powered electrosynthesis to displace petrochemical processes?

Electrocatalytic transformation of carbon dioxide (CO2) and water into chemical feedstocks offers the potential to reduce carbon emissions by shifting the chemical industry away from fossil fuel dependence. We provide a technoeconomic and carbon emission analysis of possible products, offering targets that would need to be met for economically compelling industrial implementation to be achieved. We also provide a comparison of the projected costs and CO2 emissions across electrocatalytic, biocatalytic, and fossil fuel-derived production of chemical feedstocks. We find that for electrosynthesis to become competitive with fossil fuel-derived feedstocks, electrical-to-chemical conversion efficiencies need to reach at least 60%, and renewable electricity prices need to fall below 4 cents per kilowatt-hour. We discuss the possibility of combining electro- and biocatalytic processes, using sequential upgrading of CO2 as a representative case. We describe the technical challenges and economic barriers to marketable electrosynthesized chemicals.

Microwave Heating-Assisted Catalytic Dry Reforming of Methane to Syngas.

Natural gas is a robust and environmentally friendlier alternative to oil resources for energy and chemicals production. However, gas is distributed globally within shales and hydrates, which are generally remote and difficult reserves to produce. The accessibility, transportation, and distribution, therefore, bring major capital costs. With today's low and foreseen low price of natural gas, conversion of natural gas to higher value-added chemicals is highly sought by industry. Dry reforming of methane (DRM) is a technology pathway to convert two critical greenhouse gas components, CH4 and CO2, to syngas, a commodity chemical feedstock. To date, the challenges of carbon deposition on the catalyst and evolution of secondary gas-phase products have prevented the commercial application of the DRM process. The recent exponential growth of renewable electricity resources, wind and solar power, provides a major opportunity to activate reactions by harnessing low-cost carbon-free energy via microwave-heating. This study takes advantage of differences in dielectric properties of materials to enable selective heating by microwave to create a large thermal gradient between a catalyst surface and the gas phase. Consequently, the reaction kinetics at the higher temperature catalyst surface are promoted while the reactions of lower temperature secondary gas-phase are reduced.