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In this work, we demonstrate two types of photo\u2010electrochemical cells (PECs) that photoreduce CO<jats:sub>2<\/jats:sub> directly to formate in aqueous solutions both in the presence and absence of external bias or additional electron sources. The photocathodes were either a CuFeO<jats:sub>2<\/jats:sub>\/CuO electrode or a bilayer of CdTe on NiO, whereas the photoanode was a bilayer of NiO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> on CdS. The PECs were characterized by using both electrochemistry and spectroscopy, and the products formed from CO<jats:sub>2<\/jats:sub> reduction were characterized and quantified by using <jats:sup>1<\/jats:sup>H\u2005NMR spectroscopy and ESI\u2010MS. In addition, an organohydride catalyst was tested in conjunction with the PECs, which not only showed a significant gain of 85\u2005times in CO<jats:sub>2<\/jats:sub> reduction (27\u2005\u03bc<jats:sc>m<\/jats:sc> formate without the catalyst, 2.3\u2005m<jats:sc>m<\/jats:sc> formate with it) compared to the NiO\/CdTe photocathode system but could also generate methanol under an external bias (10\u2005\u03bc<jats:sc>m<\/jats:sc>).<\/jats:p>","DOI":"10.1002\/cssc.201601105","type":"journal-article","created":{"date-parts":[[2016,10,24]],"date-time":"2016-10-24T05:25:04Z","timestamp":1477286704000},"page":"3188-3195","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Semiconductor\u2010Based, Solar\u2010Driven Photochemical Cells for Fuel Generation from Carbon Dioxide in Aqueous Solutions"],"prefix":"10.1002","volume":"9","author":[{"given":"Omer","family":"Yehezkeli","sequence":"first","affiliation":[{"name":"Department of Chemical and Biological Engineering University of Colorado  Boulder USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicholas M.","family":"Bedford","sequence":"additional","affiliation":[{"name":"Chemicals and Materials Division National Institute of Standards and Technology  Boulder CO USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eunsol","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of Colorado  Boulder USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ke","family":"Ma","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering University of Colorado  Boulder USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jennifer 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