A mathematical analysis of carbon fixing materials that grow, reinforce, and self-heal from atmospheric carbon dioxide

Parviz, Dorsa; Lundberg, Daniel J.; Kwak, Seon‐Yeong; Kim, Hyun-Ah; Strano, Michael S.

doi:10.1039/d1gc00965f

Cited by 3 publications

(2 citation statements)

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“…The presented reaction mechanism, comprising both CO 2 reduction and liquid product (formaldehyde) oxidation, is shown to fit well the activity and selectivity of the 12 distinct photocatalysts for CO 2 reduction. The calculated first order rate constants agree with previously reported kinetics for CO 2 reduction on TiO 2 -based catalysts84 (FigureS14). The lowest activity catalyst (platinummodified SnO 2 ) is shown with modified error bars, as this catalyst was the only one where no formate was detected.…”

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confidence: 90%

Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

et al. 2022

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Photocatalytic conversion of CO 2 to generate high-value and renewable chemical fuels and feedstock presents a sustainable and renewable alternative to fossil fuels and petrochemicals. Currently, there is a dearth of kinetic understanding to inform better catalyst design, especially at uniform reaction conditions across diverse catalytic species. In this work, we investigate 12 active, stable, and unique but common nanoparticle photocatalysts for CO 2 reduction at room temperature and low partial pressure in aqueous phase: TiO 2 , SnO 2 , and SiC deposited with silver, gold, and platinum. Our analysis reveals a single consistent chemical kinetic mechanism, which accurately describes the yield and selectivity of all single-carbon containing (C1) products obtained in spite of the diverse catalysts employed. Formaldehyde is predicted as the first product in the reaction network and we report, to the best of our knowledge, the highest selectivity to date toward formaldehyde during CO 2 photoreduction when compared against all other C1 products (∼80%) albeit at low CO 2 conversion (<0.5 μmol g cat −1 h −1 , <16.8 nmol m −2 h −1 ). Further, we observe a volcano-like relationship between the electron-transfer rate of a given photocatalyst for CO 2 reduction and the net rate at which reduced products are produced in the reaction mixture taking into account unfavorable product oxidation. We establish an empirical upper limit for the maximum rate of production of CO 2 reduction products for any nanoparticle photocatalyst in the absence of a hole-scavenging agent. These results form the basis for the design and optimization of the next generation of highly efficiency and active photocatalysts for CO 2 reduction.

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Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

et al. 2022

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“…The rate of this adsorption and accompanying conversion are analyzed in tandem in order to understand any limitations which this adsorption may present. Such adsorption-reaction analysis has been used to analyze other systems of greenhouse gas conversion within similar materials [6]. For a generic methane adsorbent, the rate of methane adsorption onto it can be modeled as a first-order process:…”

Section: Analytical Methodologymentioning

confidence: 99%

Mitigation of ventilation air methane (VAM) using novel methanotrophic coating materials: a technical analysis

Lundberg,

Kim,

Parviz

et al. 2023

Environ. Res. Lett.

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Ventilation Air Methane (VAM) is a potent greenhouse gas source originating from geological wells, current and extinct mineshafts and other terrestrial conduits venting methane to the atmosphere, contributing to global methane emissions and disproportionate warming potential. Herein, we introduce the concept of the methanotrophic material as an engineering solution. Such materials should be capable of converting methane at ambient temperatures and pressures to a binder product, capturing and permanently sequestering the methane while simultaneously restricting its further emission. While such materials are currently under research development, this goal is supported and facilities by the mathematical framework, introduced and used herein, to evaluate the ability to convert methane, using currently published activity data. We include a case study of the conversion of a characteristic stream of ventilation air methane (0.6% methane in air, 1.7⋅108 L hr-1 equivalent to 100,000 standard cubic feet per minute). We show that when appropriately designed, such systems require a surface coverage of less than 1,000 meters of mine tunnel length (equivalent to 20,000 m2 areal coverage) in order to reduce the methane emission from this stream by over 99%. Finally, we highlight formaldehyde as a reactive intermediate of methane oxidation which may itself be incorporated into these coating materials. As a component of binders and polymers already used ubiquitously in commercial products, this intermediate ultimately allows these systems to sequester the carbon from methane in a stable and solid form. The results presented here are easily extended to the treatment of other methane streams—either more concentrated or dilute—and the results herein will guide the design and development of a new class of carbon-negative materials.

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Impact of copper on activity, selectivity, and deactivation in the photocatalytic reduction of CO2 over TiO2

Nosrati-Ghods,

Teržan,

Finšgar

et al. 2024

Journal of Photochemistry and Photobiology A: Chemistry

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A mathematical analysis of carbon fixing materials that grow, reinforce, and self-heal from atmospheric carbon dioxide

Abstract: Carbon fixing materials are a new class of self-healing, self-reinforcing materials we have introduced that utilize ambient CO2 to chemically add to an ever extending carbon backbone. This class of...

Cited by 3 publications

References 68 publications

Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

Mitigation of ventilation air methane (VAM) using novel methanotrophic coating materials: a technical analysis

Impact of copper on activity, selectivity, and deactivation in the photocatalytic reduction of CO2 over TiO2

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A mathematical analysis of carbon fixing materials that grow, reinforce, and self-heal from atmospheric carbon dioxide

Abstract: Carbon fixing materials are a new class of self-healing, self-reinforcing materials we have introduced that utilize ambient CO2 to chemically add to an ever extending carbon backbone. This class of...

Cited by 3 publications

References 68 publications

Universal Kinetic Mechanism Describing CO2 Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

Universal Kinetic Mechanism Describing CO2 Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

Mitigation of ventilation air methane (VAM) using novel methanotrophic coating materials: a technical analysis

Impact of copper on activity, selectivity, and deactivation in the photocatalytic reduction of CO2 over TiO2

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Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts

Universal Kinetic Mechanism Describing CO₂ Photoreductive Yield and Selectivity for Semiconducting Nanoparticle Photocatalysts