Catalytic manganese oxide nanostructures for the reverse water gas shift reaction

He, Yulian; Yang, Ke R.; Yu, Ziwei; Fishman, Zachary S.; Achola, Laura A.; Tobin, Zachary M.; Heinlein, Jake A.; Hu, Shu; Suib, Steven L.; Batista, Victor S.; Pfefferle, Lisa D.

doi:10.1039/c9nr06078b

Title: Catalytic manganese oxide nanostructures for the reverse water gas shift reaction

Journal Article · 13 August 2019 · Nanoscale

DOI: https://doi.org/10.1039/c9nr06078b · OSTI ID:1598231

^[1]; Yang, Ke R. ^[2]; Yu, Ziwei ^[3];

^[2]; Achola, Laura A. ^[4]; Tobin, Zachary M. ^[4]; Heinlein, Jake A. ^[2];

^[2];

^[4]; Batista, Victor S. ^[2]; Pfefferle, Lisa D. ^[2]

Yale Univ., New Haven, CT (United States); Univ of Connecticut
Yale Univ., New Haven, CT (United States)
Nankai Univ., Tianjin (China)
Univ. of Connecticut, Storrs, CT (United States)

Understanding the fundamental structure–property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. In this paper, we develop efficient synthetic methods to prepare various MnO₂ structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO₂ 1D, 2D and 3D nanostructures are highly selective (100% CO₂ to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H₂/CO₂ feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO₂ morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K⁺ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO₂) and product (CO), ΔE = E_ads(CO₂) - E_ads(CO), is found to correlate linearly with the catalytic activity, implying a structure–function relationship. Lastly, the strong correlation found between E_ads(CO₂) - E_ads(CO), or more generally, E_ads(R) - E_ads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involving gas-solid interactions beyond the rWGS.

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Research Organization:: Univ. of Connecticut, Storrs, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Army Research Laboratory; Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: FG02-86ER13622

OSTI ID:: 1598231

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 35 Vol. 11; ISSN NANOHL; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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