Nitrogen-doped graphene supported copper catalysts for methanol oxidative carbonylation: Enhancement of catalytic activity and stability by nitrogen species

Shi, Ruina; Zhao, Jinxian; Liu, Shusen; Sun, Wei; Li, Haixia; Hao, Panpan; Li, Zhong; Ren, Jun

doi:10.1016/j.carbon.2018.01.011

Cited by 92 publications

(46 citation statements)

References 82 publications

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“…This result might seem contradictory to a number of reports showing enhanced stability of metal nanoparticles over N‐doped carbon supports. [ 25–27 ] First, we limit our conclusions to the case of tertiary nitrogen sites. Moreover, from Table 1 one can see that studied metals are indeed more stable on NDG than on pristine graphene.…”

Section: Resultsmentioning

confidence: 99%

Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

Jovanović

Mentus

Skorodumova

et al. 2020

Adv Materials Inter

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Single atom catalysts (SACs) present the ultimate level of catalyst utilization, which puts them in the focus of current research. Using density functional theory calculations, model SACs consisting of nine metals (Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) on four different supports (pristine graphene, N‐ and B‐doped graphene and graphene with single vacancy) are analyzed. Only graphene with a single vacancy enables the formation of SACs, which are stable in terms of aggregation and dissolution under electrochemical conditions. Reactivity of models SACs is probed using atomic (hydrogen and A = C, N, O, and S) and molecular adsorbates (AHx, x = 1, 2, 3, or 4, depending on A). Scaling relations between adsorption energies of A and AHx on model SACs are confirmed. However, the scaling is broken for CH3. There is also an evident scaling between adsorption energies of atomic and molecular adsorbates on metals SAs supported by pristine, N‐doped and B‐doped graphene, which originates from similar electronic structures of SAs on these supports. Using the obtained data, the authors analyze the hydrogen evolution on the model SACs. Only M@graphene vacancy systems (excluding Ag and Au) are stable under hydrogen evolution conditions in highly acidic solutions.

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Section: Resultsmentioning

confidence: 99%

Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

Jovanović

Mentus

Skorodumova

et al. 2020

Adv Materials Inter

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“…There are also numerous theoretical and experimental studies showing that a monovacancy site in N 3 ‐Gr is highly active to trap a TM atom or cluster, and exhibit outstanding catalytic performance in the CO oxidation. Recently, Cu and N codoped graphene sheets were synthesized and proven with an efficient catalytic activity in the oxidative carbonylation of methanol . The results have suggested that the presence of pyridinic‐N atoms is able to greatly increase the interaction between the Cu species and N‐Gr, which hinders the aggregation and clustering of Cu nanoparticles during reaction.…”

Section: Resultsmentioning

confidence: 99%

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

Esrafili

Mousavian

2018

Int J of Quantum Chemistry

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Using dispersion-corrected density functional theory (DFT) calculations, a single Cu adatom incorporated nitrogen-doped graphene (CuN 3 -Gr) is proposed as a new and highly active noble-metalfree catalyst for carbon monoxide (CO) oxidation reaction. According to our results, the Cu adatom can be stably anchored onto the monovavancy site of the nitrogen-doped graphene, and the resulting large diffusion barrier suggests that the metal clustering is avoided in CuN 3 -Gr. Three possible reaction mechanisms for CO oxidation (ie, Eley-Rideal, Langmuir-Hinshelwood, and termolecular Eley-Rideal) are systematically studied. It is found that the activation energy for the ratedetermining step of the termolecular Eley-Rideal mechanism is only 0.13 eV, which is much smaller than those of others. The results of this study may provide a useful guideline for the design of highly active and promising single-metal catalysts for the CO oxidation reaction based on graphene.

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“…These results suggested the successful immobilization of CuCl, and that there was a strong copper–ligand interaction between the phenanthroline ligand and Cu species. Previous results have suggested that the coordination effect of N groups could contribute to the activity and stability of Cu species in the oxidative carbonylation of methanol . Thus, it is not unreasonable to expect that the prepared solid could be a promising heterogeneous catalyst for the oxidative carbonylation of methanol due to its hierarchically porous structure, flexible framework, excellent swelling property, and strong copper–ligand interaction.…”

Section: Resultsmentioning

confidence: 99%

“…The superior catalytic activity of Cu@PCP‐Phen could be attributed to its hierarchically porous structure, flexible framework, excellent swelling property, and strong electron‐donating effect of N groups for copper species. The strong electron‐donating effect of N groups could contribute to the activity and stability of Cu species, and thus, achieving higher catalytic activity than commercial CuCl. The hierarchically porous structure, flexible framework, and excellent swelling property endow the Cu@PCP‐Phen catalyst with the characteristics of a quasi‐homogeneous catalyst, thus affording superior activity than surface‐immobilized CuCl/PS‐Phen catalyst.…”

Section: Resultsmentioning

confidence: 99%

Copper supported on phenanthroline‐functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

Lei

Leng

et al. 2019

Applied Organom Chemis

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Porous organic polymer has recently attracted tremendous interest because of its potential to combine the best features of homogeneous and heterogeneous catalysts. In this study, copper supported on phenanthroline‐functionalized porous polymer (Cu@PCP‐Phen) was prepared by a co‐polymerization method and used as a heterogeneous catalyst for dimethyl carbonate synthesis via the oxidative carbonylation of methanol. The catalyst was characterized by N2 adsorption, scanning electron microscopy, transmission electron microscopy, 13C solid‐state nuclear magnetic resonance, and X‐ray photoelectron spectroscopy, which suggested that it possessed a big surface area, hierarchical porous structure, and strong electron‐donating effect toward copper species. The Cu@PCP‐Phen catalyst showed high catalytic activity, which was significantly higher than those achieved with Cu‐based catalysts under similar reaction conditions. In addition, the catalyst can be easily separated and reused at least six times with only a slight decrease in activity. The salient features of this protocol are the simplicity in handling of the catalyst, high catalytic activity, excellent selectivity, low copper leaching, and good catalyst recyclability.

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Nitrogen-doped graphene supported copper catalysts for methanol oxidative carbonylation: Enhancement of catalytic activity and stability by nitrogen species

Cited by 92 publications

References 82 publications

Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

Copper supported on phenanthroline‐functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

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