The adsorption of CO2, H2CO3, HCO3− and CO32− on Cu2O (111) surface: First‐principles study

Wu, Huanwen; Zhang, Ning; Cao, Zhen; Wang, Hongming; Hong, Sheng

doi:10.1002/qua.23250

Cited by 34 publications

(16 citation statements)

References 66 publications

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“…Zn-Cu oxides are known from their use as photocatalysts for dye degradation 18, 19 . We expect that Zn and Cu oxides will also be an excellent photocatalyst for CO 2 reduction, due to the fact that CO 2 species are readily adsorbed on the surface sites of metal oxides 20, 21 . Guided by this inspiration, we are able to successfully grow Cu 2 O single-crystalline nanocubes on ZnO surfaces, generating a ZnO-Cu 2 O hybrid nanostructure with well-defined surface structures.…”

Section: Introductionmentioning

confidence: 99%

Colloidal zinc oxide-copper(I) oxide nanocatalysts for selective aqueous photocatalytic carbon dioxide conversion into methane

et al. 2017

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Developing catalytic systems with high efficiency and selectivity is a fundamental issue for photochemical carbon dioxide conversion. In particular, rigorous control of the structure and morphology of photocatalysts is decisive for catalytic performance. Here, we report the synthesis of zinc oxide-copper(I) oxide hybrid nanoparticles as colloidal forms bearing copper(I) oxide nanocubes bound to zinc oxide spherical cores. The zinc oxide-copper(I) oxide nanoparticles behave as photocatalysts for the direct conversion of carbon dioxide to methane in an aqueous medium, under ambient pressure and temperature. The catalysts produce methane with an activity of 1080 μmol gcat −1 h−1, a quantum yield of 1.5% and a selectivity for methane of >99%. The catalytic ability of the zinc oxide-copper(I) oxide hybrid catalyst is attributed to excellent band alignment of the zinc-oxide and copper(I) oxide domains, few surface defects which reduce defect-induced charge recombination and enhance electron transfer to the reagents, and a high-surface area colloidal morphology.

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Section: Introductionmentioning

confidence: 99%

Colloidal zinc oxide-copper(I) oxide nanocatalysts for selective aqueous photocatalytic carbon dioxide conversion into methane

et al. 2017

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“…In addition to the knowledge acquired from study of heterogeneous processes such as adsorption and reactions on the surfaces of mineral particles, aerosols could be helpful in reducing the concentration of carbon dioxide and other harmful pollutions in the atmosphere. Many reactions of carbon dioxide with mineral surfaces and metal oxides have been studied both experimentally and theoretically to obtain information of carbon dioxide adsorption and carbonation (Tai et al 2004;Baltrusaitis et al 2006Baltrusaitis et al , 2007Wang et al 2007;Pan et al 2008;Allen et al 2009;Pulido et al 2009;Hornebecq et al 2011;Kwon et al 2011;Sorescu et al 2012;Wu et al 2012;Ye et al 2012;Funk et al 2013;Hur et al 2013). It is well known that the presence of water could significantly lower the reaction barriers and stabilize the reaction product (Shih et al 1999;Nikulshina et al 2007;Baltrusaitis and Grassian 2010;Kvamme et al 2012;Fricker and Park 2013;Gao et al 2013;Yu and Balbuena 2013;Wang and Cao 2013).…”

Section: Introductionmentioning

confidence: 97%

Effect of water on carbonation of mineral aerosol surface models of kaolinite: a density functional theory study

et al. 2015

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Gas-solid interfacial phenomena always play a significant role in the multiphase process in atmospheric chemistry. The mineral aerosols have desirable interfacial reactivity on the carbonation of kaolinite. In addition, carbonation of kaolinite may play a role in carbon dioxide capture. It is not well-known about the mechanisms of this reaction. In this paper, the carbonation of kaolinite cluster models with or without water on the atomic scale is studied. We simulate the corresponding reaction paths and accurately calculate the transition states with the homologous enthalpies via using the density functional theory (DFT) method. The study shows that the reaction barriers are lowered down seriously with the existence of water. In addition, water can help stabilize the reaction regions thereby firming the structure of carbonated product.

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“…However, the efficiencies for methane production are extremely low and Pt will never be an economically viable catalyst for large scale CO2 conversion. Catalysts based on metallic Cu, oxide-derived Cu or Cu with mixed oxidation states have been demonstrated to reduce CO2 to useful molecules such as methane, methanol or ethanol [14][15][16][17][18][19][20][21][22][23] . Recent experimental work indicates the ability of nanocatalysts containing a mix of Cu + and Cu 2+ oxidation states and in oxide-like structures to drive CO2 reduction 1, 2, 10, 14-16, 18, 19, 22-25 .…”

Section: Introductionmentioning

confidence: 99%

“…Copper-based catalysts have been widely studied for CO2 activation and conversion 2,15,16,[18][19][20][21][22][24][25][26][27][28][29] and this includes Cu metal, oxide-derived Cu and mixed oxidation state Cu. There has also been a great deal of interest in modelling of the interaction of CO2 with copper oxides using density functional theory (DFT) as this would provide useful and important guidelines for further development of CO2 activation catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…There has also been a great deal of interest in modelling of the interaction of CO2 with copper oxides using density functional theory (DFT) as this would provide useful and important guidelines for further development of CO2 activation catalysts. Cu2O, with a Cu(I) oxidation state, and CuO, with a Cu(II) oxidation state, have emerged as potential candidates for the CO2 reduction reaction due to favourable band gap positions and widths 16 , and studies have focused on the interaction of CO2 molecules with various cuprous oxide surfaces and terminations 2,15,16,18,19,22 although issues still persist regarding their stability in solution. Wu et al studied the adsorption of CO2 at the Cu2O (111) surface in which oxygen vacancies were present 18 , and found that dissociative adsorption was thermodynamically unfeasible.…”

Section: Introductionmentioning

confidence: 99%

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CO2 Activation on Heterostructures of Bi2O3-Nanocluster Modified TiO2: Promoting the Critical First Step in CO2 Conversion

Nolan¹

2018

Preprint

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The conversion of CO2 to fuels is of significant importance in enabling the production of sustainable fuels, contributing to alleviating greenhouse gas emissions. While there are a number of key steps required to convert CO2, the initial step of adsorption and activation by the catalyst is critical. Well-known metal oxides such as oxidised TiO2 or CeO2 are unable to promote this step. In addressing this difficult problem, recent experimental work shows the potential for bismuth-containing materials to activate and convert CO2, but the origin of this activity is not yet clear. Additionally, nanostructures can show enhanced activity towards CO2. In this paper we present density functional theory (DFT) simulations of CO2 activation on heterostructured materials composed of extended rutile and anatase TiO2 surfaces modified with nanoclusters with Bi2O3 stoichiometry. These heterostructures show low coordinated Bi sites in the nanoclusters and a valence band edge that is dominated by Bi-O states. These two factors mean that supported Bi2O3 nanoclusters are able to adsorb and activate CO2. Computed adsorption energies lie in the range of -0.54 eV to -1.01 eV. In these strong adsorption modes, CO2 is activated, in which the molecule bends giving O-C-O angles of 126 - 130o and elongation of C-O distances up to 1.28 Å, with no carbonate formation. The electronic properties show a strong CO2-Bi-oxygen interaction that drives the interaction of CO2 to induce the structural distortions. Bi2O3-TiO2 heterostructures can be reduced to form Bi2+ and Ti3+ species. The interaction of CO2 with this electron-rich, reduced system can produce CO directly, reoxidising the heterostructure or form an activated carboxyl species (CO2-) through electron transfer from the heterostructure to CO2. These results highlight that a semiconducting metal oxide modified with suitable metal oxide nanoclusters can activate CO2, thus overcoming the difficulties associated with the difficult first step in CO2 conversion.

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The adsorption of CO₂, H₂CO₃, HCO₃⁻ and CO₃²⁻ on Cu₂O (111) surface: First‐principles study

Cited by 34 publications

References 66 publications

Colloidal zinc oxide-copper(I) oxide nanocatalysts for selective aqueous photocatalytic carbon dioxide conversion into methane

Colloidal zinc oxide-copper(I) oxide nanocatalysts for selective aqueous photocatalytic carbon dioxide conversion into methane

Effect of water on carbonation of mineral aerosol surface models of kaolinite: a density functional theory study

CO2 Activation on Heterostructures of Bi2O3-Nanocluster Modified TiO2: Promoting the Critical First Step in CO2 Conversion

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