Catalytic decomposition of NO2 over a copper-decorated metal–organic framework by non-thermal plasma

Xu, Shaojun; Han, Xue; Ma, Yujie; Duong, Thien D.; Lin, Longfei; Gibson, Emma K.; Sheveleva, Alena M.; Chansai, Sarayute; Walton, Alex; Ngo, Duc‐The; Frogley, Mark D.; Tang, Chiu C.; Tuna, Floriana; McInnes, Eric J. L.; Catlow, C. Richard A.; Hardacre, Christopher; Yang, Sihai; Schröder, Martin

doi:10.1016/j.xcrp.2021.100349

Cited by 10 publications

(10 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast, Cu/ZrO 2 , prepared through a similar method as for Cu/UiO-66 (Section S1.1), showed a much lower catalytic efficiency, with values of 90% and 26% for C NO 2 and S N 2 , respectively( Figure a and Table , Entry 7), indicating that the nature of atomically dispersed Cu sites within Cu/UiO-66 plays a crucial role in its observed activity. Although NTP-activated deNO x systems have been reported, − they generally suffer from poor catalytic efficiency, low TOF, and/or stability.…”

Section: Resultsmentioning

confidence: 99%

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Han

et al. 2021

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Metal–organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO 2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO 2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N 2 at a 97% conversion of NO 2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h –1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO 2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO 2 } adducts promoting the conversion of NO 2 to N 2 . This study will inspire the further design and study of new efficient single-atom catalysts for NO 2 abatement via detailed unravelling of their role in catalysis.

show abstract

Section: Resultsmentioning

confidence: 99%

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Han

et al. 2021

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

show abstract

“…In this regard, infrared spectroscopy is a suitable technique to characterize both chemical bonds and interactions in materials . In particular, Fourier-transform infrared spectroscopy (FTIR) has been used to assess the chemical modifications of the MOF-808 nodes with a variety of functional groups, including both organic and inorganic. , However, the most common use of this technique is the monitoring of signals associated with target functional groups characteristic of the new molecules added that are not present in the MOF framework itself. – Recently, FTIR combined with computational studies has been applied to assess the tuning of defect sites in Zr-MOFs with methoxy/ethoxy groups . However, there are numerous examples of MOF modification (i.e., aromatic carboxylate), where the added ligands are similar to the MOF linkers, thereby making FTIR data ambiguous and difficult to interpret.…”

Section: Introductionmentioning

confidence: 99%

Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr₆O₈ Metal-Organic Framework Nodes

Romero‐Muñiz

Castillo-Velilla

et al. 2022

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

The metal-organic framework MOF-808 contains Zr6O8 nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the Zr6O8 nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol–benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditions.

show abstract

“…A mixture of CH 4 and He (1 and 2% CH 4 diluted in He, 25 °C, 1 atm) at a total flow rate of 60 mL min –1 controlled by mass flow controllers was used as the feed gas. Prior to the NTP-assisted catalytic reaction, the catalysts were activated by heating at 150 °C under dynamic vacuum for 16 h. The desolvated sample (60 mg) was packed in a fixed-bed reactor , and treated at 80 °C for 1 h under a flow of He (60 mL min –1 ) to remove any residual water in the system. A gas mixture of CH 4 and He was then allowed to pass through the fixed-bed reactor to test the catalytic performance of each catalyst.…”

Section: Methodsmentioning

confidence: 99%

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Ma,

Han,

et al. 2023

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat –1 h–1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat –1 h–1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe–O(CH3)–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

show abstract

Catalytic decomposition of NO2 over a copper-decorated metal–organic framework by non-thermal plasma

Cited by 10 publications

References 48 publications

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr₆O₈ Metal-Organic Framework Nodes

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Contact Info

Product

Resources

About

Catalytic decomposition of NO2 over a copper-decorated metal–organic framework by non-thermal plasma

Cited by 10 publications

References 48 publications

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr6O8 Metal-Organic Framework Nodes

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Contact Info

Product

Resources

About

Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr₆O₈ Metal-Organic Framework Nodes