Visible light-driven CO2 reduction by enzyme coupled CdS nanocrystals

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a Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom, Tel: +44-. 1865 272647 ...
Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011

SUPPLEMENTARY INFORMATION Visible light-driven CO2 reduction by enzyme coupled CdS nanocrystals# Yatendra S. Chaudhary,a,d Thomas W. Woolerton,a Christopher S. Allen,b Jamie H. Warner,b c c a 5 Elizabeth Pierce, Stephen W. Ragsdale and Fraser A. Armstrong* Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x a

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Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom, Tel: +441865 272647; *E-mail: [email protected] b Department of Materials, University of Oxford, 16 Parks Road, Oxford OX1 3PH, United Kingdom. c Department of Biological Chemistry, University of Michigan, Ann Arbor, Michigan 48109-0606,USA d Colloids and Materials Chemistry Department, Institute of Minerals and Materials Technology (CSIR), Bhubaneswar 751013, India

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calcined

as-synthesized 20

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Figure S1. The XRD patterns of as-synthesised CdS QDs and calcined CdS

Absorbance (au)

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Wavelength (nm) Figure S2. UV-vis absorption spectrum for CdS QDs

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Determination of the amount of CODH attached to CdS nanocrystals: To determine the amount of co-attached CODH, 10 mg of CdS nanocrystals was dispersed in 5 ml of 0.35 M MES buffer solution (pH 6) in a pressure vessel, and sonicated for 20 min to ensure the formation of a stable suspension. Then, 13.9 µl of 184 µM CODH I (2.56 nmol) was introduced into the CdS nanocrystals suspension, followed by gentle stirring for 20 min to allow coattachment. The CODH-CdS nanocrystals suspension was then subjected to ultra-centifugation. The resulting supernatant was filtered through a membrane filter to assist the removal of any remaining traces of CdS. The supenatant solutions for each sample were subjected to UV-vis spectroscopy, and these spectra were compared to that of a control enzyme solution which had not been exposed to nanocrystals but had otherwise been through an identical procedure. The amount of co-attached CODH was determined from the difference in absorbance at 280 nm. 1

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Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011

0.1

Absorbance (au)

Before co-attachment

After co-attachment

0.08 0.06 0.04 0.02 0 220

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Wavelength (nm) Figure S3. Representative UV-vis absorbance spectra for solutions of CODH I in MES buffer (0.51 μM CODH I, 0.35 M MES, pH 6) before and after coattachment of CODH I with CdS QDs

Area CO peak / Area CH4 peak

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3.0 2.5

y = 0.7078x + 0.0109

2.0 1.5 1.0 0.5 0.0 0.0

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% CO Figure S4. Calibration plot for GC quantification of CO against an internal CH4 standard. 10

CO produced (µmol)

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200 mM MES 500 mM MES 350 mM MES

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Time (h) Figure S5. The amount of CO produced versus time for CODH-QD assemblies with different concentrations of MES (pH 6, 20 °C)

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