electronic supplementary information (esi) production from … · production from alkaline...

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S1 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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Page 1: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

S1

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

Page 2: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S1 SEM images of Cu(OH)2 NRs precursor.

Page 3: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S2 XRD pattern of Cu(OH)2 NRs precursor.

Page 4: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S3 The effect of formaldehyde concentration on the rate of H2 evolution over CuO

NPs.

Page 5: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S4 The effect of reaction temperature on the rate of H2 evolution over CuO NPs.

Page 6: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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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.

Page 7: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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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.

Page 8: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S7 The effect of oxygen partial pressure on the rate of H2 evolution over Cu NPs.

Page 9: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S8 FT-IR spectra of the reduced Cu after 15 min of hydrogen evolution reaction.

Page 10: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S9 O 1s XPS spectra of the reduced Cu before and after reaction.

Page 11: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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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)

Page 12: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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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)

Page 13: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S12 The cycle performance of the CuO and Cu NPs catalyzes the hydrogen

production of alkaline formaldehyde solution.

Page 14: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S13 TEM images of CuO catalyst after reaction.

Page 15: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S14 XRD pattern of CuO catalyst after reaction.

Page 16: Electronic Supplementary Information (ESI) production from … · production from alkaline formaldehyde solution Shipan Liang,a Shuang Chen,a Ziwei Guo,a Zhuohuang Lan,a Hisayoshi

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Fig. S15 Cu 2p XPS spectrum of CuO catalyst after reaction.