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Electronic Supplementary Information (ESI)
In situ generated electron-deficient metallic copper as
the catalytically active site for enhanced hydrogen
production from alkaline formaldehyde solution
Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a
Hisayoshi Kobayashi,b Xiaoqing Yan,c Renhong Li,*a
a Department of Materials Engineering, College of Material and Textiles, Zhejiang Sci-
Tech University, Hangzhou 310018, China
b Emeritus Professor of Department of Chemistry and Materials Technology, Kyoto
Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
c Department of Chemistry, College of Science, Zhejiang Sci-Tech University,
Hangzhou 310018, China
Corresponding Author
*E-mail: [email protected]
Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2019
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Fig. S1 SEM images of Cu(OH)2 NRs precursor.
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Fig. S2 XRD pattern of Cu(OH)2 NRs precursor.
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Fig. S3 The effect of formaldehyde concentration on the rate of H2 evolution over CuO
NPs.
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Fig. S4 The effect of reaction temperature on the rate of H2 evolution over CuO NPs.
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Fig. S5 In–situ XRD analysis of Cu NPs measured in 1M Na2CO3 solution before, after
5 min and 15 min of hydrogen production reaction.
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Fig. S6 In–situ XRD analysis of CuO NPs measured in 1M Na2CO3 solution before,
after 5 min and 15 min of hydrogen production reaction.
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Fig. S7 The effect of oxygen partial pressure on the rate of H2 evolution over Cu NPs.
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Fig. S8 FT-IR spectra of the reduced Cu after 15 min of hydrogen evolution reaction.
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Fig. S9 O 1s XPS spectra of the reduced Cu before and after reaction.
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Fig. S10 (a) Optimized structures for Cu22-H2O (LM1). (b) Optimized structures for
O2 and H2O co-adsorption on Cu22 cluster (LM2). (c) Optimized structures for O2,
H2CO, and H2O co-adsorption on Cu22 cluster (LM3). (d) Optimized structures for
OOH-H2C(O)OH (LM4). (e) Optimized structures for O2-H2-HCOOH (LM5).
(a) (b) (c)
(d) (e)
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Fig. S11 (a) Optimized structures for Cu22O9-H2O (LM1). (b) Optimized structures for
co-adsorbed states of O2+H2O (LM2). (c) Optimized structures for co-adsorbed states
of O2+H2O+H2CO (LM3). (d) Optimized product structure for H2O dissociation.
(LM4). (e) Optimized structures for OOH-HCO. (f) Optimized product structure for
HCOOH formation. (g) Optimized structures for OOH+H. (h) Optimized structures for
O2+H2.
(a) (b) (c)
(d) (e) (f)
(g) (h)
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Fig. S12 The cycle performance of the CuO and Cu NPs catalyzes the hydrogen
production of alkaline formaldehyde solution.
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Fig. S13 TEM images of CuO catalyst after reaction.
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Fig. S14 XRD pattern of CuO catalyst after reaction.
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Fig. S15 Cu 2p XPS spectrum of CuO catalyst after reaction.