Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation

Lehn, Jean-Maríe; Ziessel, Raymond

doi:10.1073/pnas.79.2.701

Cited by 334 publications

(186 citation statements)

References 26 publications

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“…Here, CoCl 2 was used as the catalytic site for CO 2 reduction with [Ru(bpy) 3 ]Cl 2 as PS (Fig. 7d) 88 . However, CoCl 2 has very low selectivity towards the reduction of CO 2 to CO, resulting from the reduction of water in the aqueous media to produce H 2 that is the main product in this system.…”

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon-trapped in a waste product-and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO 2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.A more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical industry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO 2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO 2 has steadily increased and nowadays CO 2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO 2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world's energy demand 1 . Obviously, there is an urgent need to control CO 2 emissions and develop efficient carbon capture systems. Although the extensive use of carbon dioxide for chemical production cannot solve this problem alone, CO 2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance, availability, nontoxicity and recyclability. As a result, valorization of CO 2 is currently receiving considerable and ever increasing attention by the scientific community 2-4 . However, activation and utilization of CO 2 is still problematic due to the fact that it is the most oxidized form of carbon, which is also thermodynamically stable and/or kinetically inert in certain desired transformations. Consequently, most of the known studies used highly reactive substrates and/or severe reaction conditions to activate CO 2 , limiting the application of such methods. In particular, the catalytic coupling of CO 2 with energy-rich substrates, such as epoxides and aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has drawn significant attention over the past decades. To create C-C bonds with CO 2 , the use of carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard reagents, as well as phenolates.

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Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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“…However, the single electron transfer to CO 2 occurs at potentials as negative as -1.9 V (Eq. (6)), which is highly endothermic because of the negative adiabatic electron affinity of CO 2 (Lehn and Ziessel, 1982;Freund and Roberts 1996;Indrakanti et al, 2009). The activation of CO 2 molecules in both gas and liquid phases and the formation of CO 2…”

Section: Typical Mechanismsmentioning

confidence: 99%

“…Many researchers now agree that this pathway is a multi-electron transfer (MET) process rather than a single electron transfer process; for the later, the electrochemical potential of -1.90 V precludes the likelihood of a single electron transport mechanism (Lehn and Ziessel, 1982;Yahaya et al, 2004). As shown in Scheme 1, various products could be formed based on MET photoreduction reactions (Eqs.…”

Section: Typical Mechanismsmentioning

confidence: 99%

Comparison of CO2 Photoreduction Systems: A Review

Wang

Soulis

Yang

et al. 2014

Aerosol Air Qual. Res.

143

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Carbon dioxide (CO 2 ) emissions are a major contributor to the climate change equation, and thus strategies need to be developed in order to reduce increases in CO 2 levels in the atmosphere. One of the most promising approaches is to convert CO 2 into useful products in engineered processes. The photocatalytic reduction of CO 2 into hydrocarbon fuels is a promising way to recycle CO 2 as a fuel feedstock by taking advantage of the readily available solar energy. This article reviews the basics of CO 2 photoreduction mechanisms, limiting steps, possible strategies to enhance photoreduction efficiency, and the state-of-the-art photocatalytic systems for CO 2 reduction. In particular, a comparison between different catalytic systems, including biological (plants and algae), inorganics (semiconductors), organics (molecular complexes), and hybrid (enzyme/semiconductors) systems is provided.

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“…The ΔG 0 values of all the reactions are highly positive, and make CO 2 reduction a highly endothermic process which is much more difficult to proceed at ambient temperature. The ΔG 0 values also indicate that the CO 2 reduction reactions can store more energy than the water splitting reaction [25,26].For reduction of CO 2 , the reaction by one electron to form CO 2 − radical is highly unfavorable due to the higher reduction potential of −1.9 V vs. normal hydrogen electrode (NHE). In addition, a large kinetic "overvoltage" for the one-electron reduction was required because of the structural differences between linear CO 2 and bent CO 2 − [15,26,27].…”

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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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Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation

Cited by 334 publications

References 26 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Comparison of CO2 Photoreduction Systems: A Review

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

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