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Toward Combined Carbon Capture and Recycling: Addition of an Amine Alters Product Selectivity from CO to Formic Acid in Manganese Catalyzed Reduction of CO₂.

ABSTRACT: Owing to the energetic cost associated with CO₂ release in carbon capture (CC), the combination of carbon capture and recycling (CCR) is an emerging area of research. In this approach, "captured CO₂," typically generated by addition of amines, serves as a substrate for subsequent reduction. Herein, we report that the reduction of CO₂ in the presence of morpholine (generating mixtures of the corresponding carbamate and carbamic acid) with a well-established Mn electrocatalyst changes the product selectivity from CO to H₂ and formate. The change in selectivity is attributed to in situ generation of the morpholinium carbamic acid, which is sufficiently acidic to protonate the reduced Mn species and generate an intermediate Mn hydride. Thermodynamic studies indicate that the hydride is not sufficiently hydritic to reduce CO₂ to formate, unless the apparent hydricity, which encompasses formate binding to the Mn, is considered. Increasing steric bulk around the Mn shuts down rapid homolytic H₂ evolution rendering the intermediate Mn hydride more stable; subsequent CO₂ insertion appears to be faster than heterolytic H₂ production. A comprehensive mechanistic scheme is proposed that illustrates how thermodynamic analysis can provide further insight. Relevant to a range of hydrogenations and reductions is the modulation of the hydricity with substrate binding that makes the reaction favorable. Significantly, this work illustrates a new role for amines in CO₂ reduction: changing the product selectivity; this is pertinent more broadly to advancing CCR.

SUBMITTER: Bhattacharya M

PROVIDER: S-EPMC7584391 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Rising CO2 emissions are responsible for increasing global temperatures causing climate change. Significant efforts are underway to develop amine-based sorbents to directly capture CO2 from air (called direct air capture (DAC)) to combat the effects of climate change. However, the sorbents' performances have usually been evaluated at ambient temperatures (25 °C) or higher, most often under dry conditions. A significant portion of the natural environment where DAC plants can be deployed experiences temperatures below 25 °C, and ambient air always contains some humidity. In this study, we assess the CO2 adsorption behavior of amine (poly(ethyleneimine) (PEI) and tetraethylenepentamine (TEPA)) impregnated into porous alumina at ambient (25 °C) and cold temperatures (-20 °C) under dry and humid conditions. CO2 adsorption capacities at 25 °C and 400 ppm CO2 are highest for 40 wt% TEPA-incorporated γ-Al2O3 samples (1.8 mmol CO2/g sorbent), while 40 wt % PEI-impregnated γ-Al2O3 samples exhibit moderate uptakes (0.9 mmol g-1). CO2 capacities for both PEI- and TEPA-incorporated γ-Al2O3 samples decrease with decreasing amine content and temperatures. The 40 and 20 wt % TEPA sorbents show the best performance at -20 °C under dry conditions (1.6 and 1.1 mmol g-1, respectively). Both the TEPA samples also exhibit stable and high working capacities (0.9 and 1.2 mmol g-1) across 10 cycles of adsorption-desorption (adsorption at -20 °C and desorption conducted at 60 °C). Introducing moisture (70% RH at -20 and 25 °C) improves the CO2 capacity of the amine-impregnated sorbents at both temperatures. The 40 wt% PEI, 40 wt % TEPA, and 20 wt% TEPA samples show good CO2 uptakes at both temperatures. The results presented here indicate that γ-Al2O3 impregnated with PEI and TEPA are potential materials for DAC at ambient and cold conditions, with further opportunities to optimize these materials for the scalable deployment of DAC plants at different environmental conditions.

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Toward Combined Carbon Capture and Recycling: Addition of an Amine Alters Product Selectivity from CO to Formic Acid in Manganese Catalyzed Reduction of CO₂.

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Toward Combined Carbon Capture and Recycling: Addition of an Amine Alters Product Selectivity from CO to Formic Acid in Manganese Catalyzed Reduction of CO2.

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OmicsDI is part of the ELIXIR infrastructure

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Toward Combined Carbon Capture and Recycling: Addition of an Amine Alters Product Selectivity from CO to Formic Acid in Manganese Catalyzed Reduction of CO₂.