Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu 1 /graphene catalyst

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

doi:10.1016/j.apsusc.2017.07.002

Cited by 27 publications

(12 citation statements)

References 72 publications

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“…Single-step synthesis of dimethyl carbonate (DMC) has paid considerable attention to the research community in past two decades because of the utilization of CO 2 , which is a chief offender of the greenhouse effect [1][2][3]. Although various routes have been reported for the conversion of CO 2 to valuable chemicals, DMC was found to be a priority due to its remarkable properties and numerous applications [4,5]. The important feature of DMC is its utilization of CO 2 as a building block for useful organic chemicals by replacing conventional fossil fuels.…”

Section: Introductionmentioning

confidence: 99%

Direct Dimethyl Carbonates Synthesis over CeO2 and Evaluation of Catalyst Morphology Role in Catalytic Performance

et al. 2021

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In recent years, direct synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO2) has received considerable attention due to green and sustainable technology. Here, we report a production of DMC from major greenhouse gases and CO2 using various morphologies of cerium oxide (CeO2). Time-dependent synthesis of CeO2, with controlled morphology having various shapes including sphere, nanorods and spindle shape, along with its formation mechanism is proposed. The experimental results indicate the morphology of CeO2 was mostly dependent on the reaction time where crystal growth occurred through Ostwald ripening. The morphology, size and shape of CeO2 were observed using transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM).The crystallographic analysis using X-ray diffraction (XRD) shows cubic fluorite phase of CeO2 with crystallite size ~72.0 nm using the Debye–Scherrer equation. The nitrogen adsorption desorption technique suggested the formation of the highly mesoporous framework of CeO2 and the excellent surface area around 104.5 m2/g obtained for CeO2 spindles by Brunauer–Emmett–Teller (BET) method. The DMC synthesis reactions were studied over CeO2 catalyst with different morphologies. The results of catalytic reactions specify that the morphology of catalyst plays an important role in their catalytic performances, where spindle shape CeO2 was the most active catalyst producing of up to13.04 mmol of DMC. Furthermore, various dehydrating agents were used to improve the DMC production at optimized reaction parameters. The overall results reveal that the higher surface area and spindle shape of CeO2 makes it a useful, reusable catalyst for one-pot DMC synthesis.

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Section: Introductionmentioning

confidence: 99%

Direct Dimethyl Carbonates Synthesis over CeO2 and Evaluation of Catalyst Morphology Role in Catalytic Performance

et al. 2021

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“…The mechanism of methanol oxidative carbonylation over copper catalysts showed that the insertion of CO is the ratedetermining step for DMC formation; 58,59 therefore, the CO adsorption on the Cu@NG/C-x and Cu/C catalysts was examined. It is reported that a strong charge transfer ability is beneficial to the adsorption of gas molecules on the catalyst surface.…”

Section: Discussionmentioning

confidence: 99%

“…The mechanism of methanol oxidative carbonylation over copper catalysts showed that the insertion of CO is the rate-determining step for DMC formation; , therefore, the CO adsorption on the Cu@NG/C- x and Cu/C catalysts was examined. It is reported that a strong charge transfer ability is beneficial to the adsorption of gas molecules on the catalyst surface. ,− The EIS results showed that nitrogen doping reduced the impedance of the catalyst and enhanced the effective charge transfer; thus, it promoted the adsorption of the reactive CO gas molecules.…”

Section: Discussionmentioning

confidence: 99%

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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“…[ 35,159–162 ] Typically, heteroatom doping engineering is divided into two categories: non‐metal‐atom doping (such as N‐, B‐, O‐, S‐, and P‐doped materials) [ 33–35 ] and metal‐atom doping (such as single atom Pd, Au, Mo, Fe, Pt and Co‐doped materials). [ 44–49,163 ]…”

Section: Rational Design Strategies For Electrocatalystsmentioning

confidence: 99%

“…To date, various strategies have been developed to design nanomaterials for further improving the NRR performance, including heteroatom dopants, [ 33–35 ] interface engineering, [ 36 ] alloys, [ 37,38 ] facet engineering, [ 39,40 ] defects, [ 41–43 ] and the size effect [ 44–49 ] coupled with an optimized electrochemical reaction system. However, because the competing hydrogen evolution reaction (HER) and the by‐product N 2 H 4 formation, there is still a big gap facing N 2 fixation before it can move into future practical application, such as low FE and low yield rate.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances and Perspective on Electrochemical Ammonia Synthesis under Ambient Conditions

Zhang

Mei

et al. 2021

Small Methods

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Ammonia is an essential chemical for agriculture and industry. To date, NH3 is mainly supplied by the traditional Haber–Bosch process, which is operated under high‐temperature and high‐pressure in a centralized way. To achieve ammonia production in an environmentally benign way, electrochemical NH3 synthesis under ambient conditions has become the frontier of energy and chemical conversion schemes, as it can be powered by renewable energy and operates in a decentralized way. The recent progress on developing different strategies for NH3 production, including 1) classic NH3 synthesis pathways over nanomaterials; 2) the Mars‐van Krevelen (MvK) mechanism over metal nitrides (MNx); 3) reducing the nitrate into NH3 over Cu‐based nanomaterial; and 4) metal–N2 battery release of NH3 from LixM. Moreover, the most recent advances in engineering strategies for developing highly active materials and the design of the reaction systems for NH3 synthesis are covered.

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Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu 1 /graphene catalyst

Cited by 27 publications

References 72 publications

Direct Dimethyl Carbonates Synthesis over CeO2 and Evaluation of Catalyst Morphology Role in Catalytic Performance

Direct Dimethyl Carbonates Synthesis over CeO2 and Evaluation of Catalyst Morphology Role in Catalytic Performance

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

Recent Advances and Perspective on Electrochemical Ammonia Synthesis under Ambient Conditions

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