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Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO.


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Authors

Kuehnel, Moritz F 
Wakerley, David W 
Orchard, Katherine L 

Abstract

Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H2 g(cat)(-1) h(-1) with >99% selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7%. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO g(cat)(-1) h(-1) with >95% selectivity and 19.7±2.7% quantum yield. H2 and CO production was sustained for more than one week with turnover numbers greater than 6×10(5) and 3×10(6), respectively.

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Keywords

CdS, formic acid, hydrogen, photocatalysis, quantum dots

Journal Title

Angew Chem Int Ed Engl

Conference Name

Journal ISSN

1433-7851
1521-3773

Volume Title

54

Publisher

Wiley
Sponsorship
Engineering and Physical Sciences Research Council (EP/H00338X/2)
This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group, the EPSRC (EP/H00338X/2 to ER), the Isaac Newton Trust, the German Research Foundation (MFK), and the Advanced Institute for Materials Research-Cambridge Joint Research Centre (KLO). XPS spectra were obtained at the National EPSRC XPS User's Service (NEXUS) at Newcastle University, an EPSRC Mid-Range Facility.