Carbon Dioxide Conversion to Methanol over Size-Selected Cu<sub>4</sub> Clusters at Low Pressures

Liu, Cong; Yang, Bing; Tyo, Eric C.; Seifert, Söenke; DeBartolo, Janae; Issendorff, Bernd von; Zapol, Peter; Vajda, Štefan; Curtiss, Larry A.

doi:10.1021/jacs.5b03668

Cited by 340 publications

(326 citation statements)

References 32 publications

Supporting

Mentioning

314

Contrasting

Unclassified

Order By: Relevance

“…This is not unexpected since formate is typically observed on CO 2 hydrogenation using Cu as catalysts. [60][61][62] Nevertheless, formate decomposition to the HCO intermediate is very unlikely since it is endothermic by 1.4 eV and HCOO hydrogenation towards formic acid or dioxymethylene (H 2 COO) ⎯as previous step of H 2 CO formation 26,56 ⎯ presents large energy barriers; 1.40 eV to H 2 COO formation. Clearly, reaction pathways via formate can be discarded and this species will at most behave as an spectator perhaps poisoning the surface.…”

Section: Computational Studymentioning

confidence: 99%

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

et al. 2016

View full text Add to dashboard Cite

The ever growing increase of CO 2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO 2 activation and conversion towards valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO 2 to CO with some subsequent selective hydrogenation towards methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo 2 C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO 2 conversion. A control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

show abstract

Section: Computational Studymentioning

confidence: 99%

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Therefore, more efforts have to be devoted, to develop more powerful catalysts for efficient CO 2 conversion to multi-carbon hydrocarbons and oxygenates. Reducing the structural features to sub-nanometre dimensions often significantly enhances the hydrogenation activity for metal catalysts and it even has been demonstrated to transform a non-catalytic active bulk counterpart into a highly active catalyst towards CO 2 reduction14151617. Separately, the introduction of additional defects in carbon nanostructures by heteroatom doping gives rise to activity toward CO 2 activation6781819.…”

mentioning

confidence: 99%

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

et al. 2016

View full text Add to dashboard Cite

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

show abstract

“…Cluster beam deposition is a new method to prepare heterogeneous catalysts for research and development, in which atomic clusters (nanoparticles) of tunable size typically below 10 nm are pre‐assembled into a beam and then deposited in a vacuum chamber onto the catalyst support . Potential advantages of the approach include the absence of solvent and effluent in the catalyst synthesis; control of cluster size, composition, and morphology; and the absence of ligands compared with colloidal routes .…”

Section: Introductionmentioning

confidence: 99%

Performance of Preformed Au/Cu Nanoclusters Deposited on MgO Powders in the Catalytic Reduction of 4‐Nitrophenol in Solution

Cai

Ellis

Yin

et al. 2018

Small

View full text Add to dashboard Cite

clusters (nanoparticles) of tunable size typically below 10 nm are pre-assembled into a beam and then deposited in a vacuum chamber onto the catalyst support. [1][2][3][4] Potential advantages of the approach include the absence of solvent and effluent in the catalyst synthesis; control of cluster size, composition, and morphology; and the absence of ligands compared with colloidal routes. [5][6][7][8] However, the technique is at an early stage, [9] most especially where catalytic behavior under realistic reaction conditions is concerned. Thus, there is an urgent need to validate the performance of this new class of nanomaterials in a series of model chemical transformations, and compare their behavior with catalysts prepared by more traditional and well-established routes. In this work, we report a first investigation of a solution phase transformation performed by nanoalloy catalysts prepared by cluster beam deposition.The discovery of the catalytic activity of gold (Au) nanoparticles for low-temperature oxidation of carbon monooxide (CO) provoked an explosion of interest in gold catalysis. [10,11] Au clusters can catalyze a range of reactions, for example, the water-gas shift reaction [12][13][14] and selective oxidation of carbon-carbon double bonds [15,16] and carbon-oxygen bonds. [17,18] The 4-nitrophenol The deposition of preformed nanocluster beams onto suitable supports represents a new paradigm for the precise preparation of heterogeneous catalysts. The performance of the new materials must be validated in model catalytic reactions. It is shown that gold/copper (Au/Cu) nanoalloy clusters (nanoparticles) of variable composition, created by sputtering and gas phase condensation before deposition onto magnesium oxide powders, are highly active for the catalytic reduction of 4-nitrophenol in solution at room temperature. Au/Cu bimetallic clusters offer decreased catalyst cost compared with pure Au and the prospect of beneficial synergistic effects. Energy-dispersive X-ray spectroscopy coupled with aberration-corrected scanning transmission electron microscopy imaging confirms that the Au/Cu bimetallic clusters have an alloy structure with Au and Cu atoms randomly located. Reaction rate analysis shows that catalysts with approximately equal amounts of Au and Cu are much more active than Au-rich or Cu-rich clusters. Thus, the interplay between the Au and Cu atoms at the cluster surface appears to enhance the catalytic activity substantially, consistent with model density functional theory calculations of molecular binding energies. Moreover, the physically deposited clusters with Au/Cu ratio close to 1 show a 25-fold higher activity than an Au/Cu reference sample made by chemical impregnation.Heterogeneous Catalysts

show abstract

Carbon Dioxide Conversion to Methanol over Size-Selected Cu₄ Clusters at Low Pressures

Cited by 340 publications

References 32 publications

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

Performance of Preformed Au/Cu Nanoclusters Deposited on MgO Powders in the Catalytic Reduction of 4‐Nitrophenol in Solution

Contact Info

Product

Resources

About

Carbon Dioxide Conversion to Methanol over Size-Selected Cu4 Clusters at Low Pressures

Cited by 340 publications

References 32 publications

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO2: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO2: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

Performance of Preformed Au/Cu Nanoclusters Deposited on MgO Powders in the Catalytic Reduction of 4‐Nitrophenol in Solution

Contact Info

Product

Resources

About

Carbon Dioxide Conversion to Methanol over Size-Selected Cu₄ Clusters at Low Pressures

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO₂: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability