Conversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems

doi:10.1016/S1872-2067(10)60209-4

Chinese Journal of Catalysis

Volume 32, Issues 6–8, 2011, Pages 879-890

https://doi.org/10.1016/S1872-2067(10)60209-4 Get rights and content

Abstract

Over the last several years, the need to find clean and renewable energy sources has increased rapidly because current fossil fuels will not only eventually be depleted, but their continuous combustion leads to a dramatic increase in the carbon dioxide amount in atmosphere. Utilisation of the Sun's radiation can provide a solution to both problems. Hydrogen fuel can be generated by using solar energy to split water, and liquid fuels can be produced via direct CO₂ photoreduction. This would create an essentially free carbon or at least carbon neutral energy cycle. In this tutorial review, the current progress in fuels' generation directly driven by solar energy is summarised. Fundamental mechanisms are discussed with suggestions for future research.

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Nano-sized Zeolitic imidazolate framework-67 (nZIF-67(Co)) were synthesized in water, and its metal centers partially exchanged with Nickel(II) and Manganese(II) centers to form bimetallic nZIF-67(Co/Ni) (25 % Ni²⁺) and nZIF-67(Co/Mn) (41 % Mn²⁺) respectively. This was achieved without altering the structural integrity of the sodalite (SOD) framework of the parent nZIF-67 and the metal oxidation states, as shown by Transmission Electron Microscope (TEM), Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS). The Co/Ni/Mn atomic composition, determined by XPS, was consistent with values obtained from Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES) and Energy-dispersive X-ray spectroscopy (EDS). Carbon dioxide (CO₂) adsorption studies showed that the uptake of nZIF-67 (39.3 cm³ g^-1) was enhanced by metal-exchange to 47.8 cm³ g^-1 (nZIF-67(Co/Mn) and 49.4 cm³ g^-1 (nZIF-67(Co/Ni), respectively. nZIF-67(Co), nZIF-67(Co/Ni) and nZIF-67(Co/Mn) was employed as catalysts in a solventless and co-catalyst free CO₂-epichlorohydrin coupling reaction and yielded cyclic chloropropene carbonate at low pressure (1 bar) and temperature (60 ^oC). nZIF-67(Co/Ni) performed the best, due to its larger surface area and the presence of nickel. These catalysts can be regenerated and re-used without appreciable loss in activity.
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Citation Excerpt :
Thus, the development of non-sulﬁde photocatalysts for efficient photocatalytic coupling of methanol to EG and H2 with high stability is urgent but extremely challenging. Metal oxide photocatalysts, such as titanium dioxide (TiO2), zinc oxide (ZnO), tungsten oxide (WO3), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), have been extensively studied for many photocatalytic reactions [24,26–31]. Most of the metal oxide photocatalysts showed higher stability than metal sulfide photocatalysts during the photocatalytic reactions processes [24,26–31].
Direct photocatalytic coupling of methanol to ethylene glycol (EG) is highly attractive. The reported photocatalysts for this reaction are all metal sulfide semiconductors, which may suffer from photocorrosion and have low stability. Thus, the development of non-sulﬁde photocatalysts for efficient photocatalytic coupling of methanol to EG and H₂ with high stability is urgent but extremely challenging. Herein, the first metal oxide photocatalyst, tantalum-based semiconductor, is reported for preferential activation of C−H bond within methanol to form hydroxymethyl radical (•CH₂OH) and subsequent C−C coupling to EG. Compared with other metal oxide photocatalysts, such as TiO₂, ZnO, WO₃, Nb₂O₅, tantalum oxide (Ta₂O₅) is unique in that it can realize the selective photocatalytic coupling of methanol to EG. The co-catalyst free nitrogen doped tantalum oxide (2%N-Ta₂O₅) shows an EG formation rate as high as 4.0 mmol g_cat⁻¹ h⁻¹, about 9 times higher than that of Ta₂O₅, with a selectivity higher than 70%. The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production. This catalyst also shows excellent stability longer than 160 h, which has not been achieved over the reported metal sulfide photocatalysts. Tantalum-based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.
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: This work was supported by the Engineering and Physical Sciences Research Council (EPSRC).

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SURVEY PAPERConversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems

Abstract

Biotechnol Adv

Fuel

Chem Phys Lett

Chemosphere

J Catal

Chem Phys Lett

Top Catal

Int J Hydrogen Energy

Catal Today

Chem Phys Lett

Appl Catal A

J Photochem Photobiol A

Chem Phys Lett

J Photochem Photobiol A

Electrochim Acta

J Catal

Catal Today

Solid State Ionics

J Catal

Chem Phys Lett

J Mol Catal

Catal Today

Appl Catal B

J Catal

Carbon

Appl Catal A

Sol Energy Mater Sol Cells

Coord Chem Rev

J Phys Chem Solids

Nature

Proc Natl Acad Sci USA

Annual Energy Review 2008

Chem Soc Rev

Environmental Research Letters

The Open Atmospheric Science Journal

Science

Chem Soc Rev

ACS Nano

Ind Eng Chem Res

ChemSusChem

Nature

J Chem Soc, Faraday Trans I

Chem Commun

J Am Chem Soc

Langmuir

J Phys Chem

Chem Commun

J Phys Chem

SURVEY PAPER
Conversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems