Electronic Supplementary Material (ESI) for Journal of Materials Chemistry B. This journal is The Royal Society of Chemistry 2018 Electronic Supplementary Information Experimental 2.1 Chemicals and Materials Hydrochloric acid (HCl), sodium hydroxide (NaOH), D-glucose, L-ascorbic acid (AA), sodium chloride (NaCl), fructose (Fru), lactose (Lac), L-cysteine (L-Cys), Dopamine(DA), Urea and uric acid (UA) were purchased from the Aladdin Co. Ltd (Shanghai, China). Cu foam was gained from Shenzhen Lifeixin Environmental Protection Equipment Co. Ltd (110 ppi, 320 g m 2, 0.5 mm in thick). All reagents were of analytical grade and used without further purification. Varies concentrations of glucose solution were prepared by stepwise dilution with 0.1 M NaOH. All aqueous solutions were prepared with distilled water. 2.2 Preparation of the Cu 2 Se SPs/CF Electrode A piece of Cu foam (2 3 cm 2 ) was etched with diluted hydrochloric acid (HCl:H 2 O = 1:3) for about 5 min to remove impurities on the surface and washed with distilled water for several times. The cleaned copper foam was immerged into a 50 ml Teflon-lined stainless autoclave containing a certain concentration of NaHSe solution (40 ml). The autoclave was sealed and maintained at 120, 150, and 180 C for 5 h. The resulting material was washed with distilled water three times and dried in vacuum at 60 C, then giving the Cu 2 Se SPs/CF samples. 2.3 Characterizations XRD measurement was performed using a Bruker D8 advanced diffractometer with Cu K α radiation (40 kv, 40 ma). SEM measurements were performed on a
Hitachi S-4800 field emission scanning electron microscope at an accelerating voltage of 20 kv. TEM test was conducted on a HITACHI H-8100 electron microscopy (Hitachi, Tokyo, Japan) with an accelerating voltage of 200 kv. 2.4 Electrochemical Measurements Electrochemical measurements were carried out with an electrochemical analyzer (CHI 660E, Shanghai, Chenhua) in a typical three-electrode setup with Cu 2 Se SPs/CF or bare Cu foam as the working electrode, a platinum wire as the counter electrode and a Ag/AgCl as the reference electrode. The electrochemical performance of Cu 2 Se SPs/CF electrode for detection of glucose was investigated by the techniques of Cyclic Voltammetry and Amperometric i-t Curve. The geometric area of working electrodes was controlled as 0.5 0.5 cm 2 in all tests.
Fig. S1. The left is bare Cu foam and the right is Cu 2 Se SPs/CF.
Fig. S2. (a-c) The SEM images of Cu 2 Se/CF sample synthesized at 180 o C. (d-f) The SEM images of Cu 2 Se/CF sample synthesized at 150 o C. (g-i) The SEM images of Cu 2 Se/CF sample synthesized at 120 o C.
Fig. S3. The effect of different reaction temperatures on the catalytic performance of Cu 2 Se/CF samples.
Fig. S4. The effect of the ph of electrolyte on the catalytic performance of Cu 2 Se SPs/CF.
Fig. S5. (a) Amperometric measurements in the presence of 1.0 mm glucose in 0.1 M NaOH up to 15 days by one as-prepared Cu 2 Se SPs/CF electrode. (b) Amperometric measurements in the presence of 1.0 mm glucose in 0.1 M NaOH by six as-prepared Cu 2 Se SPs/CF electrodes. (3) Amperometric responses of Cu 2 Se SPs/CF to the successive addition of glucose in the low concentration range at 0.5 V vs. Ag/AgCl recorded for two times. (4) Corresponding linear calibration curve of the second recorded amperometric response.
Fig. S6. Amperometric measurements of reuse after detection of glucose in diluted serum samples recorded for four times.
Table S1. Comparison of the performance of Cu 2 Se SPs/CF with other previously reported superior transition-metal based glucose sensors. Material Cu 2 Se SPs/CF Linear Range (mm) 0.00025 0.237 0.237 0.687 0.837 2.237 LOD (μm) 0.25 Sensitivity (μa mm -1 cm -2 ) 18660 11010 2689 ITO/Ni/Cu 0.001 2 1 2530 1 Au/Ni multilayer NWs 0.00025 2.0 2.0 5.5 0.25 3372 1906 Ni-Fe/CFP 0.00005-0.2 0.05 7900 3 Cu foam 0.001-0.5 1 5850 4 Ref. This work 2 Co 3 O 4 /Au/FTO 0.0002 0.2 0.5 20 0.2 6000 5 IrO 2 @NiO NWs 0.0005 2.5 0.5 1439.4 6 Pt NiO/rGO 0.008 14.5 8 832.95 7 Cu/Cu 2 O nanohybrid 0.005 40 5 1434.12 8 Cu-Cu 2 O/TiO 2 0.1 2.5 100 4895 9 Cu@Cu 2 O NS-NWs 0.0007 2.0 0.7 1420.77 10 Cu 2 O/CF 0.001 1.4 1 5040 11 CuO NS/CC 0.005 2.515 5 4901.96 12 Cu 2 O PLNWs/CF 0.001 1.8 1 6680.7 13 Cu(OH) 2 /PGF 0.0012 6 1.2 3360 14 Cu 2 O/TNT 3.0 9.0 3000 14.56 15 NiCo 2 O 4 HR 0.0003 1.0 0.3 1685.1 16 NiO NS@NR/NF 0.00075-3.837 0.75 2739.5 17 CuCo 2 O 4 /PrGO-10 0.0005 3.354 0.5 2426 18 ammonia-doped-prgo/cuo 0.00025 6 0.25 1210 19 Cu x O/Ppy/rGO 0.1 10 100 \ 20
CuO/SG/GCE 0.1 10.5 100 1298.6 21 Ni 3 S 2 /MWCNT-NC 0.03 0.5 1 3345 22 Cu 2 S@MWCNT 0.01 1 10 \ 23 CuS MF/GCE 0.02 5.4 20 1007 24 NiCoS/TM 0.001 3.0 1 3291.5 25 NiS/ITO 0.005 0.045 5 7430 26 Ni 3 S 2 NS/Ni foam 0.005 3.0 5 6148 27 Ni 7 S 6 /GCE 0.005 3.7 5 271.8 28 CuS dendrite 0.001 4.9 1 8337 29 Cu 3 P NWs/CF 0.005 1 5 11450 30 Ni 2 P NS/CC 0.001 3.0 1 7792 31 NiCoP/TM 0.001 6 1 14586 32 CoP NW/TM 0.0005 1.5 0.5 5168.6 33 Cu 3 N NA/CF 0.001 2.0 1 14180 34 Co 3 N NW/TM 0.0001-2.5 0.1 3325.6 35 Fe 3 N-Co 2 N NW/CC 0.0001-1 0.1 4333.7 36 Co 2 N x /NG 0.01-4.75 10 1167 37 References (1) P. Salazar, V. Rico and A. R. González-Elipe, Sens. Actuators B Chem., 2016, 226, 436-443. (2) L. Qin, L. He, J. Zhao, B. Zhao, Y. Yin and Y. Yang, Sens. Actuators B Chem., 2017, 240, 779-784. (3) K. Palanisamy, M. Thandavarayan, M. Enrico, G. Srabanti, N.-J. Joanna and J.-N. Martin, Nanoscale, 2016, 8, 843-855. (4) L. Bie, X. Luo, L. Kang, D. He and P. Jiang, Electroanal., 2016, 28, 2070-2074. (5) Y. Su, B. Luo and J. Zhang, Anal. Chem., 2016, 88, 1617-1624. (6) J. Wang, L. Xu, Y. Lu, K. Sheng, W. Liu, C. Chen, Y. Li, B. Dong and H. Song, Anal. Chem., 2016, 88, 12346-12353. (7) L. Wang, X. Lu, C. Wen, Y. Xie, L. Miao, S. Chen, H. Li, P. Li and Y. Song, J. Mater. Chem. A, 2015, 3, 608-616. (8) X. Cheng, J. Zhang, H. Chang, L. Luo, F. Nie and X. Feng, J. Mater. Chem. B, 2016, 4, 4652-4656. (9) Q. Yang, M. Long, L. Tan, Y. Zhang, J. Ouyang, P. Liu and A. Tang, ACS Appl.
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