Closing the Loop: Unexamined Performance Trade-Offs of Integrating Direct Air Capture with (Bi)carbonate Electrolysis.

CO2 from carbonate-based capture solutions requires a substantial energy input. Replacing this step with (bi)carbonate electrolysis has been commonly proposed as an efficient alternative that coproduces CO/syngas. Here, we assess the feasibility of directly integrating air contactors with (bi)carbonate electrolyzers by leveraging process, multiphysics, microkinetic, and technoeconomic models. We show that the copresence of CO32- with HCO3- in the contactor effluent greatly diminishes the electrolyzer performance and eventually results in a reduced CO2 capture fraction to ≤1%. Additionally, we estimate suitable effluents for (bi)carbonate electrolysis to require 5-14 times larger contactors than conventionally needed contactors, leading to unfavorable process economics. Notably, we show that the regeneration of the capture solvent inside (bi)carbonate electrolyzers is insufficient for CO2 recapture. Thus, we suggest process modifications that would allow this route to be operationally feasible. Overall, this work sheds light on the practical operation of integrated direct air capture with (bi)carbonate electrolysis.

Process modeling, techno-economic assessment, and life cycle assessment of the electrochemical reduction of CO2: a review.

The electrochemical reduction of CO2 has emerged as a promising alternative to traditional fossil-based technologies for the synthesis of chemicals. Its industrial implementation could lead to a reduction in the carbon footprint of chemicals and the mitigation of climate change impacts caused by hard-to-decarbonize industrial applications, among other benefits. However, the current low technology readiness levels of such emerging technologies make it hard to predict their performance at industrial scales. During the past few years, researchers have developed diverse techniques to model and assess the electrochemical reduction of CO2 toward its industrial implementation. The aim of this literature review is to provide a comprehensive overview of techno-economic and life cycle assessment methods and pave the way for future assessment approaches. First, we identify which modeling approaches have been conducted to extend analysis to the production scale. Next, we explore the metrics used to evaluate such systems, regarding technical, environmental, and economic aspects. Finally, we assess the challenges and research opportunities for the industrial implementation of CO2 reduction via electrolysis.

Unidirectional Adsorption of Bifunctional 1,4-Phenylene Diisocyanide on the Ge(100)-2 × 1 Surface.

Adsorption of bifunctional organic molecules on semiconductor surfaces is important for surface modification; however, most bifunctional molecules previously studied have yielded mixtures of singly and dually tethered adsorbates. Here we report the adsorption of bifunctional 1,4-phenylene diisocyanide (PDI) on the Ge(100)-2 × 1 surface, in which singly bound adsorbates are selectively produced. As shown by polarized multiple internal reflection infrared spectroscopy experiments and density functional theory calculations, PDI adsorbates form a single C-dative bonding configuration through one of the isocyanide functionalities, retaining one unreacted isocyanide moiety per adsorbate. The angle of the molecular axis is ∼30° from the surface normal. The delocalized π* molecular orbital of the free molecule is also preserved upon adsorption. These results demonstrate the potential usefulness of isocyanide adsorbates as a means toward selective organic functionalization of semiconductor surfaces.