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DOE OSTI · 2875653

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Dorneles de Mello, Matheus [University of Delaware, Newark, DE (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000265749421)·Ahmad, Mueed [Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook University, NY (United States)]·Lee, Dennis T. [Johns Hopkins University, Baltimore, MD (United States)] (ORCID:0000000219762852)·Dimitrakellis, Panagiotis [University of Delaware, Newark, DE (United States)]·Miao, Yurun [Johns Hopkins University, Baltimore, MD (United States)] (ORCID:0000000164298297)·Zheng, Weiqing [University of Delaware, Newark, DE (United States)]·Nykypanchuk, Dmytro [Brookhaven National Laboratory (BNL), Upton, NY (United States)]·Vlachos, Dionisios G. [University of Delaware, Newark, DE (United States)] (ORCID:0000000267958403)·Tsapatsis, Michael [University of Delaware, Newark, DE (United States); Johns Hopkins University, Baltimore, MD (United States); Johns Hopkins University, Laurel, MD (United States)] (ORCID:0000000156103525)·Boscoboinik, Jorge Anibal [University of Delaware, Newark, DE (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000250907079)
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Abstract

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

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IRRASZIF-8etchingmembranesmetal organic frameworksnon-thermal plasmaoxygenplasmaseparationssurface modification

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Dorneles de Mello, Matheus [University of Delaware, Newark, DE (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000265749421), Ahmad, Mueed [Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook University, NY (United States)], Lee, Dennis T. [Johns Hopkins University, Baltimore, MD (United States)] (ORCID:0000000219762852), Dimitrakellis, Panagiotis [University of Delaware, Newark, DE (United States)], Miao, Yurun [Johns Hopkins University, Baltimore, MD (United States)] (ORCID:0000000164298297), Zheng, Weiqing [University of Delaware, Newark, DE (United States)], Nykypanchuk, Dmytro [Brookhaven National Laboratory (BNL), Upton, NY (United States)], Vlachos, Dionisios G. [University of Delaware, Newark, DE (United States)] (ORCID:0000000267958403), Tsapatsis, Michael [University of Delaware, Newark, DE (United States); Johns Hopkins University, Baltimore, MD (United States); Johns Hopkins University, Laurel, MD (United States)] (ORCID:0000000156103525), Boscoboinik, Jorge Anibal [University of Delaware, Newark, DE (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000250907079). 2022-04-13. In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films. https://doi.org/10.1021/acsami.2c00259

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