CoPi/BiVO4 Photocatalyst

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Presentation transcript:

CoPi/BiVO4 Photocatalyst Catherine Bridges and Connor Hayes

CoPi/BiVO4 & Water Oxidation Bismuth Vanadate (BiVO4) Monoclinic scheelite BiVO4 Photocatalytic Water Oxidation Cobalt Phosphate Cocatalyst Addition of CoPi increased activity by 7x Applications O2 Suarez, C; Hernadez, S; Russo, N. BiVO4 as photocatalyst for solar fuels through water splitting: A Short Review. Appl. Catal. A: Gen. 2014, 1-13. Yang, J; Wang, D; Han, H; Li, C. Roles of Cocatalysts in Photocatalysis and Photoelectrocatalysis. Acc. Chem. Res. 2013, 46, 1900-1909.

PEC Cell Water Oxidation 3 electrode system Xenon Lamp excites the photocatalyst Formation of O2 and photoanodic current occurred H+ reduction occurs at the counter electrode Jeon, T.; Choi, W.; Park, H.; Cobalt-phosphate complexes catalyze the photoelectrochemical water oxidation of BiVO4 electrodes. Phys. Chem. Chem. Phys. 2011, 13, 21392-21401. Wang, D; Li, R; Zhu, J; Shi, J; Han, J; Zong, X; Li, C. Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation CoCatalyst: Essential Relations between Electrocatalyst and Photocatalyst. J. Phys. Chem. 2012, 116, 5082-5089.

Preparation of CoPi/BiVO4 𝐵𝑖(𝑁 𝑂 3 ) 3 +𝑁 𝐻 4 𝑉 𝑂 3 →𝑩𝒊𝑽 𝑶 𝟒 Synthesis of BiVO4: 1:1 stoichiometric mixture of Bi(NO3)3 and NH4VO3 Coating onto FTO working electrode Formation and deposition of CoPi: 0.1M K3PO4 and 0.5mM CoCl2 CoPi Deposition BiVO4 FTO Electrode Jeon, T.; Choi, W.; Park, H.; Cobalt-phosphate complexes catalyze the photoelectrochemical water oxidation of BiVO4 electrodes. Phys. Chem. Chem. Phys. 2011, 13, 21392-21401.

Structure of Photocatalyst Monoclinic Scheelite BiVO4 Photocatalytic Molecular Cobaltate Clustered (MCC) CoPi Allows for CoIV oxidation state Kanan, M; Yano, J; Surendranath, Y; Dinca, M; Yachandra, V; Nocera, D. Structure and Valency of a Cobalt-Phosphate Water Oxidation Catalyst Determined by in Situ X-Ray Spectroscopy. J. Am. Chem. Soc., 2010, 132, 13692-13701. Suarez, C; Hernadez, S; Russo, N. BiVO4 as photocatalyst for solar fuels through water splitting: A Short Review. Appl. Catal. A: Gen. 2014, 1-13.

Mechanism of CoPi/BiVO4 Light excites an electron in BiVO4 CoPi donates its electron to BiVO4 Cobalt center’s oxidation state increases Process continues until Co(IV) is achieved Water oxidation occurs Kanan, M; Yano, J; Surendranath, Y; Dinca, M; Yachandra, V; Nocera, D. Structure and Valency of a Cobalt-Phosphate Water Oxidation Catalyst Determined by in Situ X-Ray Spectroscopy. J. Am. Chem. Soc., 2010, 132, 13692-13701. Zhong, D; Sujung, C; Gamelin, D. Near Complete Supression of Surface Recombination in Solar Photoelectrolysis by “Co-Pi” Catalyst-Modified W:BiVO4. J. Am. Chem. Soc. 2011, 133, 18370-18377.

XPS Spectra w/o CoPi = Bare BiVO4 S-ED = step wise electrodeposition S-PD = stepwise photodeposition S-ED (L) = stepwise electrodeposition after 12 hours S-ED on FTO = Bare CoPi Co peaks P peaks Jeon, T.; Choi, W.; Park, H. Cobalt-phosphate complexes catalyze the photoelectrochemical water oxidation of BiVO4 electrodes. Phys. Chem. 2011, 13, 21392-21401.

SEM images of Bare BiVO4 and CoPi/BiVO4 CoPi on BiVO4 Wang, D.; Li, R.; Zhu, J.; Shi, J.; Han, J.; Zong, X.; Li, C. Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation Cocatalyst: Essential Relations between Electrocatalyst and Photocatalyst. J. Phys. Chem. 2012, 116, 5082-5089.

O2 Evolution Capability Optimal CoPi Loading = 1.0% wt Wang, D.; Li, R.; Zhu, J.; Shi, J.; Han, J.; Zong, X.; Li, C. Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation Cocatalyst: Essential Relations between Electrocatalyst and Photocatalyst. J. Phys. Chem. 2012, 116, 5082-5089.

Comparison with other Cocatalysts 1 2 3 CoPi is da best 4 5 6 Wang, D.; Li, R.; Zhu, J.; Shi, J.; Han, J.; Zong, X.; Li, C. Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation Cocatalyst: Essential Relations between Electrocatalyst and Photocatalyst. J. Phys. Chem. 2012, 116, 5082-5089.

Summary The addition of the cocatalyst CoPi exponentially enhances the water oxidizing ability of the photocatalyst BiVO4. This combination is preferred because of its low toxicity, efficiency and availability (aka cheap). Coupling of this photocatalyst with a high yielding hydrogen evolver could potentially give the most efficient water splitting system.