Steering CO ₂ hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

Abstract

The conversion of CO2 into fuels and chemicals is an attractive option for mitigating CO2 emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO2 catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO2 hydrogenation behavior of the Ru surface, significantly enhancing the C2+ production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.

A critical review of technologies, costs, and projects for production of carbon-neutral liquid e-fuels from hydrogen and captured CO2

“…90 Other laboratory-scale advancements in preventing methanation include coating ruthenium with a thin layer of a porous plastic/polymer. 91,92…”

“…90 Other laboratory-scale advancements in preventing methanation include coating ruthenium with a thin layer of a porous plastic/polymer. 91,92 In the case of a two-step process for e-methanol production that also includes a high-temperature RWGS reactor (usually the case, as shown in Fig. 9), barium zirconate-based perovskite-type catalysts doped with Y, Zn, and Ce show stable performance; 93 Fig.…”

Perspective on Sorption Enhanced Bifunctional Catalysts to Produce Hydrocarbons

“…The chemical industry is one of the most significant contributors to GHG emissions due to conventional processes that rely on oil and fossil resources . A sustainable solution to maintain the chemical industry while reducing GHG emissions is using CO 2 as a potential feedstock for polymers, − chemicals, − and fuels. ,, Such a transition will use catalysts to provide a technologically practical solution for mitigating GHGs. While there are several thermo- and electro-catalytic CCU schemes, ,− the integration of heterogeneous catalysts with CO 2 -capture solid sorbents may be a viable solution capable of selectively removing CO 2 directly from air or flue gases.…”

“…Typical thermal CO 2 conversion schemes use renewable hydrogen from water electrolysis as a reductant to synthesize relevant building blocks like synthesis gas (CO, H 2 ), methane, and methanol. ,,,,,− Most research using an ICCU framework has traditionally focused on C 1 products. However, the development of ICCU that can capture and convert CO 2 to C 2 + hydrocarbons could be transformative.…”

Understanding the geometric and basicity effects of organic polymer modifiers on Ru/TiO2 catalysts for CO2 hydrogenation to hydrocarbons

“…1–4 Functionalizing catalysts with organic moieties, 5–10 especially those that possess Lewis basic character, such as organic amines, has thus proved to be a powerful tool to enhance CO 2 hydrogenation activity by electronic interactions of CO 2 with active sites and between organic ligands and reaction intermediates. 11–16 There has been overall less focus on the effect of organic moieties on C–C coupling and higher hydrocarbon production, mostly because most organic ligand modifiers are unstable at conditions that are relevant for C–C coupling, such as high temperature (220–320 °C) and pressure (10–30 bar). 7,13 Additionally, it is challenging to precisely control the spatial distribution of liner organic amines on catalyst surfaces, often leading to uncontrollable blocking of active sites, which will in turn affect the intrinsic activity of the resulting catalyst ensembles.…”