Synthesis of dimethyl carbonate on single Cu atom embedded in N-doped graphene: Effect of nitrogen species

Han, Xiaoxia; Sun, Wei; Zhao, Chaofan; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Li, Zhong; Ren, Jun

doi:10.1016/j.mcat.2017.09.028

Cited by 16 publications

(23 citation statements)

References 85 publications

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“…The N 1s spectrum was deconvoluted into three peaks at 399.1 ± 0.3, 400.2 ± 0.3, and 401.2 ± 0.3 eV, corresponding to the pyridine-N, amino-N or pyrrole-N, and graphitic-N species, respectively . It can be seen from Table that the nitrogen content in the Cu@NG/C- x catalysts gradually decreased with increasing pyrolysis temperature, implying that unstable pyrrole-N and amino-N were converted into more stable pyridine-N and graphitic-N species . Previous studies have proven that the pyridine-N and graphite-N incorporated into the carbon framework can reduce the energy barrier of the reaction rate-determining step, while the presence of amino-N is not conducive to the formation of DMC .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, the existence of pyridine-N and graphite-N in the carbon support can reduce the reaction energy barrier of the CO insertion reaction. 49,58 Therefore, it can be seen that the presence of nitrogen species in the NG layer also contributed to the improved activity of the Cu@NG/C-700 catalyst in the oxidative carbonylation of methanol.…”

Section: Discussionmentioning

confidence: 99%

“…48 It can be seen from Table 3 that the nitrogen content in the Cu@NG/C-x catalysts gradually decreased with increasing pyrolysis temperature, implying that unstable pyrrole-N and amino-N were converted into more stable pyridine-N and graphitic-N species. 49 Previous studies have proven that the pyridine-N and graphite-N incorporated into the carbon framework can reduce the energy barrier of the reaction rate-determining step, while the presence of amino-N is not conducive to the formation of DMC. 49 Therefore, it can be seen that the Cu@NG/C-x catalysts with high pyridine-N and graphite-N content were beneficial to the oxidative carbonylation of methanol.…”

Section: Methodsmentioning

confidence: 99%

“…49 Previous studies have proven that the pyridine-N and graphite-N incorporated into the carbon framework can reduce the energy barrier of the reaction rate-determining step, while the presence of amino-N is not conducive to the formation of DMC. 49 Therefore, it can be seen that the Cu@NG/C-x catalysts with high pyridine-N and graphite-N content were beneficial to the oxidative carbonylation of methanol.…”

Section: Methodsmentioning

confidence: 99%

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Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Shi

Zhao

Quan

et al. 2021

Ind. Eng. Chem. Res.

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Wrapping metal nanoparticles (NPs) in graphene shells has emerged as a promising strategy to design highly active and stable catalysts. A facile direct co-pyrolysis approach was proposed to prepare a carbon-supported nitrogen-doped graphene-coated copper NP composite (Cu@NG/C) to catalyze the oxidative carbonylation of methanol to dimethyl carbonate (DMC) effectively. Compared with a carbon-supported copper catalyst (Cu/C) without graphene coating, the optimized Cu@NG/C-700 catalyst has a grain size of Cu NPs of around 15.2 nm with an NG layer thickness of ∼2.0 nm and exhibits high catalytic activity (DMC space time yield, 1881 mg·g–1·h–1) and excellent stability after five reaction cycles. The NG shell allows the diffusion of the reactant and product molecules while acting as a layer of protection to prevent leaching and agglomeration of Cu NPs. In addition, the introduction of nitrogen strongly increased the charge transfer carrier density and therefore promoted the absorption of CO on the active copper sites. The confinement effect of the NG wrapping layer markedly enhanced the catalytic performance of the copper cores in methanol oxidative carbonylation, which may have great potential in fabricating advanced carbon-supported metal catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Shi

Zhao

Quan

et al. 2021

Ind. Eng. Chem. Res.

Self Cite

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“…This is a method providing stable and active catalysts with a well-defined nanostructure to be used in different areas. As examples for recent applications of this technique in different fields are the synthesis of graphene-derived Cu-SACs for the reaction of oxidative carbonylation of methanol [49], and the synthesis of efficient electrocatalysts based on nanoporous holey graphene doped with both N and single-atom Mo [50].…”

Section: Chemical-vapor-deposition (Cvd)mentioning

confidence: 99%

Carbon-Based Materials for the Development of Highly Dispersed Metal Catalysts: Towards Highly Performant Catalysts for Fine Chemical Synthesis

et al. 2020

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Single-atom catalysts (SACs), consisting of metals atomically dispersed on a support, are considered as advanced materials bridging homogeneous and heterogeneous catalysis, representing the catalysis at the limit. The enhanced performance of these catalysts is due to the combination of distinct factors such as well-defined active sites, comprising metal single atoms in different coordination environments also varying its valence state and strongly interacting with the support, in this case porous carbons, maximizing then the metal efficiency in comparison with other metal surfaces consisting of metal clusters and/or metal nanoparticles. The purpose of this review is to summarize the most recent advances in terms of both synthetic strategies of producing porous carbon-derived SACs but also its application to green synthesis of highly valuable compounds, an area in which the homogeneous catalysts are classically used. Porous carbon-derived SACs emerge as a type of new and eco-friendly catalysts with great potential. Different types of carbon forms, such as multi-wall carbon nanotubes (MWCNTs), graphene and graphitic carbon nitride or even others porous carbons derived from Metal–Organic-Frameworks (MOFs) are recognized. Although it represents an area of expansion, experimentally and theoretically, much more future efforts are needed to explore them in green fine chemical synthesis.

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Green Synthesis of Dimethyl Carbonate from CO₂ and Methanol: New Strategies and Industrial Perspective

Raza¹,

Ikram

Guo

et al. 2022

Advanced Sustainable Systems

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Dimethyl carbonate (DMC) is a commonly used and environmentally sustainable chemical compound and intermediate in a variety of industrial applications. To date, several large‐scale industrial DMC synthesis routes have been developed, including methanol phosgenation, transesterification, and oxidative carbonylation of methanol. However, these manufacturing routes have several disadvantages, such as the use of hypertoxic phosgene as raw material, costly processing, and explosion risks. The most encouraging and ecofriendly path is the green production of DMC from CO2 and methanol. Various catalytic materials have been examined concerning their suitability for DMC synthesis. The issues of low yield and difficulty in tests have not been resolved fundamentally, which is caused by the inherent problems of the synthetic pathway and limitations imposed by thermodynamics. The search for more efficient production routes has driven the activation of CO2 via electro‐assisted synthesis as well as membrane reactors, which can isolate products in real‐time to maximize DMC yield. The green synthesis of dimethyl carbonate catalyzed by different catalysts including Zr/Ce/Cu‐based nanocomposites, organometallic compounds, heteropoly acid, ionic liquid, metal‐organic frameworks, etc, is discussed in detail. Further, the structure–activity relationships and insights into molecular activation and catalytic mechanisms, as well as the identification of active sites on catalysts are addressed.

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Synthesis of dimethyl carbonate on single Cu atom embedded in N-doped graphene: Effect of nitrogen species

Cited by 16 publications

References 85 publications

Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Carbon-Based Materials for the Development of Highly Dispersed Metal Catalysts: Towards Highly Performant Catalysts for Fine Chemical Synthesis

Green Synthesis of Dimethyl Carbonate from CO₂ and Methanol: New Strategies and Industrial Perspective

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Synthesis of dimethyl carbonate on single Cu atom embedded in N-doped graphene: Effect of nitrogen species

Cited by 16 publications

References 85 publications

Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Carbon-Supported Nitrogen-Doped Graphene-Wrapped Copper Nanoparticles: An Effective Catalyst for the Oxidative Carbonylation of Methanol

Carbon-Based Materials for the Development of Highly Dispersed Metal Catalysts: Towards Highly Performant Catalysts for Fine Chemical Synthesis

Green Synthesis of Dimethyl Carbonate from CO2 and Methanol: New Strategies and Industrial Perspective

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Product

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Green Synthesis of Dimethyl Carbonate from CO₂ and Methanol: New Strategies and Industrial Perspective