Spontaneous Dissociation of CO2 to CO on Defective Surface of Cu(I)/TiO2–x Nanoparticles at Room Temperature

Liu, Lianjun; Zhao, Cunyu; Li, Ying

doi:10.1021/jp300932b

Cited by 284 publications

(270 citation statements)

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“…The surface oxygen vacancies play very important roles in governing the adsorption, activation and dissociation of CO 2 , which provide not only an electronic charge (Ti 3+ ) but also the sites for the adsorption of oxygen atoms from CO 2 [283]. It was even demonstrated that CO 2 − species, generated upon an electron attachment to CO 2 , are spontaneously dissociated into CO on defective Cu(I)/TiO 2−x at room temperature even in the dark [283].…”

Section: Important Factors Affecting Co 2 Activationmentioning

confidence: 99%

“…It was even demonstrated that CO 2 − species, generated upon an electron attachment to CO 2 , are spontaneously dissociated into CO on defective Cu(I)/TiO 2−x at room temperature even in the dark [283]. Indrakanti et al [249] performed the excited-state ab initio calculations of CO 2 adsorbed on clusters from the (010), (101), and (001) anatase surface planes.…”

Section: Important Factors Affecting Co 2 Activationmentioning

confidence: 99%

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Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel

et al. 2014

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The shortage of fossil fuels and the disastrous pollution of the environment have led to an increasing interest in artificial photosynthesis. The photocatalytic conversion of CO 2 into solar fuel is believed to be one of the best methods to overcome both the energy crisis and environmental problems. It is of significant importance to efficiently manage the surface reactions and the photo-generated charge carriers to maximize the activity and selectivity of semiconductor photocatalysts for photoconversion of CO 2 and H 2 O to solar fuel. To date, a variety of strategies have been developed to boost their photocatalytic activity and selectivity for CO 2 photoreduction. Based on the analysis of limited factors in improving the photocatalytic efficiency and selectivity, this review attempts to summarize these strategies and their corresponding design principles, including increased visible-light excitation, promoted charge transfer and separation, enhanced adsorption and activation of CO 2 , accelerated CO 2 reduction kinetics and suppressed undesirable reaction. Furthermore, we not only provide a summary of the recent progress in the rational design and fabrication of highly active and selective photocatalysts for the photoreduction of CO 2 , but also offer some fundamental insights into designing highly efficient photocatalysts for water splitting or pollutant degradation. INTRODUCTIONThe shortage of the energy supply and the problem of disastrous environmental pollution have been recognized as two main challenges in the near future [1]. It is a better way to efficiently and inexpensively convert solar energy into chemical fuels by developing an artificial photosynthetic (APS) system because solar fuels are high density energy carriers with long-term storage capacity. The most important and challenging reactions in APS-the photocatalytic water splitting into H 2 and O 2 (water reduction and oxidation) [2][3][4] and photoreduction of CO 2 to solar fuel, such as CH 4 and CH 3 OH [5,6] have been extensively studied since the photocatalytic water splitting on TiO 2 electrodes was discovered by Honda and Fujishima in 1972 [7]. The photocatalytic reduction of CO 2 by means of solar energy has attracted growing attention in the recent years, which 1 State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China 2 College of Science, South China Agricultural University, Guangzhou 510642, China 3 Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia * Corresponding author (email: jiaguoyu@yahoo.com) is also believed to be one of the best methods to overcome both global warming and energy crisis [8]. However, it is also generally thought that photocatalytic CO 2 reduction is a more complex and difficult process than H 2 production due to preferential H 2 production and low selectivity for the carbon species produced [9,10]. The progress achieved in the photoreduction of CO 2 is still far behind that in wate...

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Section: Important Factors Affecting Co 2 Activationmentioning

confidence: 99%

Section: Important Factors Affecting Co 2 Activationmentioning

confidence: 99%

Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel

et al. 2014

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“…In addition to theoretical calculations (Markovits et al, 1996;Pan et al, 2009;He et al, 2010;Indrakanti et al, 2011;Pipornpong et al, 2011;Rodriguez et al, 2012), various microscopic (e.g., scanning tunneling microscopy (STM)) (Lee et al, 2011;Sutter et al, 2011) and spectroscopic (e.g., diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), electron paramagnetic resonance (EPR)) (Schilke et al, 1999;Ulagappan and Frei, 2000;Wu and Huang, 2010;Dimitrijevic et al, 2011;Yang et al, 2011;Liu et al, 2012a;Shkrob et al, 2012) studies have been conducted to understand the steps associated with CO 2 adsorption, activation, and dissociation. These steps are found to be significantly affected by crystal phases (e.g., anatase, rutile), surface acidic-basic sites (e.g., hydroxyl group), defect disorders (e.g., oxygen vacancy (V O )), co-adsorbates (e.g., H 2 O), and electronic structure (e.g., charge transport) of TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

Understanding the Reaction Mechanism of Photocatalytic Reduction of CO2 with H2O on TiO2-Based Photocatalysts: A Review

Liu

2014

Aerosol Air Qual. Res.

Self Cite

316

217

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Recently, there has been an increasing interest in the research of photocatalytic reduction of CO 2 with H 2 O, an innovative way to simultaneously reduce the level of CO 2 emissions and produce renewable and sustainable fuels. Titanium dioxide (TiO 2 ) and modified TiO 2 composites are the most widely used photocatalysts in this application; however, the reaction mechanism of CO 2 photoreduction on TiO 2 photocatalysts is still not very clear, and the reaction intermediates and product selectivity are not well understood. This review aims to summarize the recent advances in the exploration of reaction mechanism of CO 2 photoreduction with H 2 O in correlation with the TiO 2 photocatalyst characteristics. Discussions are provided in the following sections: (1) CO 2 adsorption, activation and dissociation on TiO 2 photocatalyst; (2) mechanism and approaches to enhance charge transfer from photocatalyst to reactants (i.e., CO 2 and H 2 O); and (3) surface intermediates, reaction pathways, and product selectivity. In each section, the effects of material properties are discussed, including TiO 2 crystal phases (e.g., anatase, rutile, brookite, or their mixtures), surface defects (e.g., oxygen vacancy and Ti 3+) and material modifications (e.g., incorporation of noble metal, metal oxide, and/or nonmetal species to TiO 2 ). Finally, perspectives on future research directions and open issues to be addressed in CO 2 photoreduction are outlined in this review paper.

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“…Particularly in the case of gas/solid reactions, these deposited metals generate new catalytic sites. For example, isolated surface Cu + sites on TiO 2 promoted CO 2 photodissociation to CO [73], and surface Fe 3+ cations enhanced maleic acid photooxidation [74]. Metal cations like Cu, V, or Cr loaded onto TiO 2 during the sol-gel procedure raised NO photooxidation because it enhanced adsorption [75].…”

Section: Change Of Tio 2 Surface Speciationmentioning

confidence: 99%

Surface-Modified Photocatalysts

Minero

2013

The Handbook of Environmental Chemistry

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The surface properties of TiO 2 play a very important role in determining photocatalytic reaction efficiencies because heterogeneous photocatalytic reactions take place on the surface. Various parameters such as composition, phase structures, surface hydroxyl group, particle size, crystallinity, surface defects, and adsorbates or surface complexes play a key role. TiO 2 surfaces have been actively modified through manipulating the above parameters to enhance the photocatalytic performance. Here the main effects that influence the surface electron transfer are reported.

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Spontaneous Dissociation of CO₂ to CO on Defective Surface of Cu(I)/TiO_2–x Nanoparticles at Room Temperature

Cited by 284 publications

References 40 publications

Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel

Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel

Understanding the Reaction Mechanism of Photocatalytic Reduction of CO2 with H2O on TiO2-Based Photocatalysts: A Review

Surface-Modified Photocatalysts

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