The adsorption and dissociation of N2O on CuO(111) surface: The effect of surface structures

Suo, Wei; Sun, Song; Liu, Ningning; Li, Xiaojun; Wang, Yanji

doi:10.1016/j.susc.2020.121596

Cited by 14 publications

(4 citation statements)

References 49 publications

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“…Conversely, the 1%Cu-BEA possessing active Cu cations for N2O dissociation that generate αO exhibits a much higher level of N2O-ODHP activity relative to the 1%CuO-SiO2. As has also been reported on a theoretical level [22], the CuO exhibits a much high energy barrier (2.71 eV) for N2O dissociation, which indicates that it is very difficult to decompose N2O and produce α-O over CuO.…”

Section: N 2 O-odhp Activity Measurementsupporting

confidence: 73%

“…This finding shows that the lower N 2 O dissociation activity of CuO species probably constitutes one of the major reactions that leads to the extremely low N 2 O-ODHP activity of the 1%CuO-SiO 2 .Conversely, the 1%Cu-BEA possessing active Cu cations for N 2 O dissociation that generate αO exhibits a much higher level of N 2 O-ODHP activity relative to the 1%CuO-SiO 2 . As has also been reported on a theoretical level[22], the CuO exhibits a much high energy barrier (2.71 eV) for N 2 O dissociation, which indicates that it is very difficult to decompose N 2 O and produce α-O over CuO.As for the samples of 1%Fe-BEA and 1%Fe-ZSM-5, the nearly complete N 2 O conversion (~100%) can be achieved due to the superior N 2 O dissociation activity of Fe cations than those of the Cu cations[23], although this does lead to the ready overoxidation of C 3 H 8 into CO x (CO and CO 2 of 64.1 and 46.0%, respectively; see Figure7c). This finding shows that the Fe cations are active for N 2 O dissociation, although they suffer from the…”

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confidence: 76%

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Mechanistic Insight into the Propane Oxidation Dehydrogenation by N2O over Cu-BEA Zeolite with Diverse Active Site Structures

Liu

Dai

et al. 2023

Catalysts

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The present work theoretically investigated propane oxidation dehydrogenation by utilizing N2O as an oxidant (N2O-ODHP) over Cu-BEA with three different types of active site, including monomeric Cu ([Cu]+), dimeric Cu ([Cu−Cu]2+), and distant monomeric Cu sites ([Cu]+—[Cu]+). Energetically, we calculated that the monomeric [Cu]+ is favorable for the αH dehydrogenation step (∆E = 0.05 eV), which, however, suffers from high barriers of N2O dissociation and βH dehydrogenation steps of 1.40 and 1.94 eV, respectively. Although the dimeric [Cu−Cu]2+ site with a Cu—Cu distance of 4.91 Å is much more favorable for N2O dissociation (0.95 eV), it still needs to overcome an extremely high barrier (∆E = 2.15 eV) for βH dehydrogenation. Interestingly, the distant [Cu]+—[Cu]+ site with the Cu—Cu distance of 5.82 Å exhibits low energy barriers for N2O dissociation (0.89 eV) and ODHP steps (0.01 and 0.33 eV) due to the synergistic effect of distant [Cu]+. The microkinetic analyses quantitatively verified the superior activity of the distant [Cu]+—[Cu]+ site with a reaction rate being eight to nine orders of magnitude higher than those of the monomeric and the dimeric Cu sites, and this is related to its ready charge-transfer ability, as shown by the partial Density of State (PDOS) analysis and the static charge differential density analysis in this study. Generally, the present work proposes that the distance between the [Cu]+ sites plays a significant and important role in N2O-ODHP over the Cu-based zeolite catalyst and modulates Cu—Cu distance, and this constitutes a promising strategy for highly-efficient Cu-zeolite catalyst design for N2O-ODHP.

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Section: N 2 O-odhp Activity Measurementsupporting

confidence: 73%

supporting

confidence: 76%

Mechanistic Insight into the Propane Oxidation Dehydrogenation by N2O over Cu-BEA Zeolite with Diverse Active Site Structures

Liu

Dai

et al. 2023

Catalysts

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“…Given that the CuO bulk possesses an antiferromagnetic ground state, the spin was not restricted in the calculations [22,23]. According to the literature [24], the DFT semi-core pseudopot (DSPP) [25] was utilized for the treatment of Cu atoms so that the electron behavior of Cu atoms can be described more accurately. Additionally, to ensure precise depiction of the van der Waals (VDW) interactions, the DFT-D 3 method developed by Grimme et al [26] was employed for correction of dispersion forces.…”

Section: Methodsmentioning

confidence: 99%

Investigation on the Catalytic Cracking Mechanism of CuO on Dimethyl Sulfoxide (C2H6OS) and Surface Modification Effects: Insights from Density Functional Theory Calculations

et al. 2023

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To explore the catalytic cracking mechanism of CuO on oil shale and the catalytic activity of surface modifications of CuO on oil shale, dimethyl sulfoxide (C2H6OS) is used as a model molecule representative of organic sulfur compounds in oil shale, and the adsorption and dissociation behaviors of C2H6OS molecules on pure and OH pre-adsorbed CuO(111) surfaces were investigated by density functional theory calculations. The results indicate that C2H6OS selectively adsorbs at the Cusub sites via the S atom and decomposes through cleavage of the C–H bond prior to the breaking of the C-S bond on both surfaces. The presence of OH on the CuO(111) surface promoted the dissociation of C2H6OS. The energy barriers of dehydrogenation and desulfurization of C2H6OS on the OH pre-adsorbed CuO(111) surface were 20.0 and 19.3 kcal/mol, respectively, which are 41% and 49% lower than those on pure surfaces. The present results provide crucial guidance for the synthesis and improvement of high-performance pyrolysis catalysts specifically designed for oil shale applications. Additionally, they also present important data regarding to the thermal stability of C2H6OS in the presence of incompatible substances.

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“…As a conventional method, the adsorption process is characterized by its simplicity [7][8][9][10]; moreover, the adsorption serves as the initial step in catalysis and has been extensively investigated for gas separation and purification [11][12][13]. Among them, the chemical absorption method employs specific chemical solutions to react with the target gas, facilitating its separation from the gas.…”

Section: Introductionmentioning

confidence: 99%

Effect of Physico-Chemical Properties Induced by N, P Co-Doped Biomass Porous Carbon on Nitrous Oxide Adsorption Performance

Gong,

Liu,

Mou

et al. 2024

Sustainability

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The adsorption and enrichment of greenhouse gases on biomass porous carbon is a promising approach. Herein, a simple type of nitrogen and phosphorus co-doped biomass porous carbon (NPPC), which was derived from fast-growing eucalyptus bark, was reported via one-step method of carbonization and activation, and the nitrous oxide (N2O) adsorption performance and the adsorption mechanism of the NPPCs were also investigated. The results showed that NPPC-800-2 demonstrated a high specific surface area (1038.48 m2∙g−1), abundant micropores (0.31 cm3∙g−1), and enriched content of N and P (4.17 wt.% and 0.62 wt.%), which also exhibited a high N2O adsorption capacity of 0.839 mmol∙g−1. Moreover, the addition of N enhanced the surface polarity of carbon, thereby altering its pore structure. And P doping induced changes in the structural orientation of carbon, resulting in an increased presence of N-P functional groups. This finding reveals that the eucalyptus bark-based N and P co-doped porous carbon shows great potential for wide applications in N2O capture and provides effective guidance for the design and development of waste biomass adsorbent.

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The adsorption and dissociation of N2O on CuO(111) surface: The effect of surface structures

Cited by 14 publications

References 49 publications

Mechanistic Insight into the Propane Oxidation Dehydrogenation by N2O over Cu-BEA Zeolite with Diverse Active Site Structures

Mechanistic Insight into the Propane Oxidation Dehydrogenation by N2O over Cu-BEA Zeolite with Diverse Active Site Structures

Investigation on the Catalytic Cracking Mechanism of CuO on Dimethyl Sulfoxide (C2H6OS) and Surface Modification Effects: Insights from Density Functional Theory Calculations

Effect of Physico-Chemical Properties Induced by N, P Co-Doped Biomass Porous Carbon on Nitrous Oxide Adsorption Performance

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