Spontaneous Formation of Cu O-g-C N Core-Shell Nanowires For Photocurrent and Humidity Responses

Electronic Supplementary Material (ESI) for Nanoscale.
This journal is © The Royal Society of Chemistry 2015
Spontaneous formation of Cu2O–g-C3N4 core–shell

nanowires for photocurrent and humidity responses
Lixia Wang, Fei Zhao, Qing Han, Chuangang Hu, Lingxiao Lv, Nan Chen, and
Liangti Qu*
Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials;
Key Laboratory of Cluster Science, Ministry of Education of China;
School of Chemistry, Beijing Institute of Technology, Beijing 100081, China

Fig. S1 (a)The photograph of the prepared FTO electrode. (b) The magnified optical
microscope photograph of the white box area in (a). (c) The photograph of
Cu2O–g-C3N4 core–shell nanowires-coated FTO sensor. (d) The magnified optical
microscope photograph of the white box area in (c). Scale bars: (a, c), 5 mm; (b, d),
100 μm.
Fig. S2 Test arrangement. Flow F3 generates a constant saturated humidity, Flow F2
dilutes it and Flow F1 provides dry reference.
Fig. S3 The overlay chart of the elemental mapping images of C and Cu elements of
the prepared Cu2O–g-C3N4 core–shell nanowires. Scale bar: 50 nm.
Fig. S4 (a) HAADF image of the prepared Cu2O–g-C3N4 core–shell nanowires. The
red line in (a) is the position of the elemental line-scanning. (b) Elemental
line-scanning image of C, N, O and Cu elements, respectively. Scale bar: (a), 50 nm.
Fig. S5 EDS spectrum and the corresponding contents of C, N, O and Cu of
Cu2O–g-C3N4 core–shell nanowires. The peaks of Mo and Au are attributed to the Mo
micro-grid substrate used.
Fig. S6 EDS spectra and the corresponding contents of C, N, O and Cu of
Cu2O–g-C3N4 core–shell nanowires with different growth conditions. (a) 48 h and
(b) 144 h with 1 mg mL-1of O-functional g-C3N4 solution, (c) 96 h with 0.1 mg
mL-1of O-functional g-C3N4 solution, (d) 96 h with 0.3 mg mL-1of O-functional
g-C3N4 solution. The peaks of Mo and Au are attributed to the Mo micro-grid
substrate used.
Fig. S7 (a) Schematic description of the designed galvanic cell. Cu and Au foils was
used as the anode and inert platinum was used as the cathode. A salt bridge was used
to allow the flow of current. In the anode compartment, the electrolyte was 1 mol L-1
bluestone solution. In the cathode compartment, the electrolyte was O-functional
g-C3N4 solution with pH=6.5. Before measurements, the electrolytes were saturated
with nitrogen. Oxidation occurred at the anode and provided electrons (M → Mn++
ne-). O-functional g-C3N4 would accept the electrons and be reduced at the cathode (n
O-functional g-C3N4 + 2ne-+ 2nH+→ g-C3N4 +nH2O). (b) The cell (-) Cu|Cu2+||
O-functional g-C3N4| g-C3N4 (+) could generate a cell voltage of 156 mV. So,
according to the relationship between the thermodynamic function and the cell
voltage (ΔG=-nFE), the redox reaction between O-functional g-C3N4 and copper was
spontaneous. (c) The cell (-) Au|Au3+|| O-functional g-C3N4| g-C3N4 (+) only
generated a very small voltage (~ -7 mV) that might be caused by the concentration
potential and liquid junction potential. So, gold could not be used to reduce
O-functional g-C3N4.
Fig. S8 The SEM images of Cu2O−g-C3N4 core−shell nanowires kept still for 96 h
with different concentrations of O-functional g-C3N4 solution (a, b) 0.1 mg mL-1, (c, d)
0.3 mg mL-1. Scale bars: (a, c), 1 μm; (b, d), 100 nm.
In addition, When the concentration is 0.1 mg mL-1, Cu2O−g-C3N4 core−shell

nanowires has formed, but the amount was less. With increasing the concentration to
0.3 mg mL-1, there is almost no change of the structure of Cu2O−g-C3N4 core−shell
nanowires but more amouts appeared.
Fig. S9 The SEM images of Cu2O−g-C3N4 core−shell nanowires kept still for 96 h in
dark (a, b) and under illumination (c, d). Scale bars: (a, c), 1 μm; (b, d), 100 nm.
Given the excellent photocatalytic activity of g-C3N4 under visible light, the
illumination contrast experiments were conducted at identical experimental conditions
to explain further the reaction process. Compared with the long and thick nanowires
prepared under normal indoor lighting, short and thin nanowires formed on the
surface of Cu under totally dark condition, indicating the main drive force to
contribute the reaction should be oxidation-reduction between the O-functional
g-C3N4 and Cu, illumination only accelerating it. while the sample was irradiated
under a 300 W Xe lamp, flower-like nanoclusters formed on the surface of Cu foil
probably because the accelerating reaction between the O-functional g-C3N4 and Cu
under illumination caused the disorder stack of g-C3N4.
Fig. S10 The TEM of the contrast Cu2O nanowires. The inset is the magnified image
of of the Cu2O nanowires.
In accordance with the solution-grown condition at room temperature for

Cu2O−g-C3N4 core − shell nanowires, a similar process was choosed for the
preparation of the contrast Cu2O nanowires.1 The HRTEM image of the Cu2O
nanowires show interplanar spacing of 0.30 nm, consistent with the (110) lattice
planes of cubic-phase Cu2O, which is well matched with that in the XRD pattern
(Figure 2g (ii)). Scale bars: 0.2 μm; The inset, 5 nm.
Fig. S11 The TEM image of the g-C3N4. Scale bar: 100 nm.
Fig. S12 Current response of Cu2O−g-C3N4 core−shell nanowires-coated FTO
sensors to dynamic switches between dry air (0%) and different (75%−95%) RH at
30 °C for 100 cycles. The first 10 cycles in the figure were the first 10 cycles of the
100 cycles, the eleventh (11th) and twelfth (12th) cycles correspond to the 29th and
30th cycles of the 100 cycles, 13th and 14th cycles to the 49th and 50th cycles, 15th
(69th) ,16th (70th), 17th (99th) and 18th (100th).
Fig. S13 The enlarged image of the recovery process in the Fig. 6e.
References
[s1] A. Kargar, S. S. Partokia, M. T. Niu, P. Allameh, M. Yang, S. May, J. S. Cheung,
K. Sun, K. Xu and D. L. Wang, Nanotechnology, 2014, 25, 1.

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Electronic Supplementary Material (ESI) for Nanoscale.

This journal is © The Royal Society of Chemistry 2015

Spontaneous formation of Cu2O–g-C3N4 core–shell

Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials;

Key Laboratory of Cluster Science, Ministry of Education of China;

School of Chemistry, Beijing Institute of Technology, Beijing 100081, China

In addition, When the concentration is 0.1 mg mL-1, Cu2O−g-C3N4 core−shell

In accordance with the solution-grown condition at room temperature for

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