Formation of Hierarchical Structure Composed of (Co/Ni)Mn-LDH Nanosheets on MWCNT Backbones for Efficient Electrocatalytic Water Oxidation
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1 Supporting Information Formation of Hierarchical Structure Composed of (Co/Ni)Mn-LDH Nanosheets on MWCNT Backbones for Efficient Electrocatalytic Water Oxidation Gan Jia, Yingfei Hu, Qinfeng Qian, Yingfang Yao, Shiying Zhang, Zhaosheng Li, *, Zhigang Zou Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, 22 Hankou Road, Nanjing , People's Republic of China, Hunan Key Laboratory of Applied Environmental Photocatalysis, Changsha University, Changsha, People s Republic of China *Corresponding author: Prof. Zhaosheng Li zsli@nju.edu.cn S-1
2 Figure S1. Typical FESEM images of Co 2 Mn-LDH/MWCNT (A), Co 3 Mn-LDH/MWCNT (B), Co 5 Mn-LDH/MWCNT (C) and Co 7 Mn-LDH/MWCNT (D). S-2
3 Figure S2. Typical FESEM images of Ni 2 Mn-LDH/MWCNT (A), Ni 3 Mn-LDH/MWCNT (B), Ni 5 Mn-LDH/MWCNT (C) and Ni 7 Mn-LDH/MWCNT (D). S-3
4 Table S1. EDS analysis results for the Co/Mn and Ni/Mn atomic ratios in CoMn-LDH/MWCNT and NiMn-LDH/MWCNT, respectively. Co 2 Mn-LDH/ MWCNT Co 3 Mn-LDH/ MWCNT Co 5 Mn-LDH/ MWCNT Co 7 Mn-LDH/ MWCNT Starting materials atomic ratios (Co : Mn) 2 : 1 3 : 1 5 : 1 7 : 1 EDS atomic ratios (Co : Mn) 2.54 : : : : 1 Ni 2 Mn-LDH/ MWCNT Ni 3 Mn-LDH/ MWCNT Ni 5 Mn-LDH/ MWCNT Ni 7 Mn-LDH/ MWCNT Starting materials atomic ratios (Ni : Mn) 2 : 1 3 : 1 5 : 1 7 : 1 EDS atomic ratios (Ni : Mn) 2.12 : : : : 1 S-4
5 Table S2 Co/Mn and Ni/Mn atomic ratios determined by ICP-AES Co 5 Mn-LDH/MWCNT (Co : Mn) Ni 5 Mn-LDH/MWCNT (Ni : Mn) Starting materials atomic ratios 5 : 1 5 : 1 As-prepared materials atomic ratios : : 1 S-5
6 Figure S3. TEM image of the hybrids in a relatively sparse fraction (red circle: MWCNT; blue circle: LDH nanoplates). S-6
7 Figure S4. TEM image of the Co 5 Mn-LDH nanoplatelets. S-7
8 Figure S5 HRTEM image of an individual Co 5 Mn-LDH nanocrystal. S-8
9 Figure S6. HRTEM image of an individual Ni 5 Mn-LDH nanocrystal. S-9
10 Figure S7. XRD patterns of the CoMn-LDH/MWCNT hybrids with different Co/Mn ratios. S-10
11 Figure S8. XRD patterns of the NiMn-LDH/MWCNT hybrids with different Ni/Mn ratios. S-11
12 Figure S9. Linear slope is equivalent to twice the double-layer capacitance (C dl ). Charging current density differences ( J = J a J c ) plotted as a function of the scan rate. The corresponding cyclic voltammograms obtained with CoMn-LDH/MWCNT hybrids loaded on RDEs in a capacitance current range of 0.25~0.35 vs. Hg/HgO at scan rates of 20, 40, 80, 120, 160 and 200 mv s -1. S-12
13 Figure S10. Linear slope is equivalent to twice of the double-layer capacitance (C dl ). Charging current density differences ( J = J a J c ) plotted as a function of the scan rate. The corresponding cyclic voltammograms obtained with NiMn-LDH/MWCNT hybrids loaded on RDEs in a capacitance current range of 0.25~0.35 vs. Hg/HgO at scan rates of 20, 40, 80, 120, 160 and 200 mv s -1. S-13
14 Table S3 Comparison of electrocatalytic performance of Co 5 Mn-LDH/MWCNT and Ni 5 Mn-LDH/MWCNT as well as some similar previously reported materials. Catalyst Material 10 ma cm -2 Ref. Co 3 O 4 /2.7Co 2 MnO 4 ~ 540 mv 1 MnCo 2 O 4 ~ 510 mv 2 CoMn 2 O 4 /N-rGO ~ 430 mv 3 dp-mnco 2 O 4 /CNT ~ 470 mv 4 CoMn-LDH ~ 325 mv 5 Co 3 O 4 /CNT ~ 380 mv 6 MCC-5-V72 ~ 420 mv 7 Ni 6 MnO 8 Not Reach 8 NiO/CNT ~ 360 mv 6 MnNiCoO 4 /N-MWCNT ~ 395 mv 9 h-co@ mv 10 Ni@[Ni( 2+/3+ )Co 2 (OH) 6 7 ] x 350 mv 11 NiCo 2 O 4 /CNTs 320 mv 12 MWCNTs/Ni(OH) mv 13 Co 5 Mn-LDH/MWCNT ~ 300 mv This Work Ni 5 Mn-LDH/MWCNT ~ 350 mv This Work S-14
15 The TOF value of Co 5 Mn-LDH/MWCNT and Ni 5 Mn-LDH/MWCNT was calculated according to the following equation: TOF = j A /(4 F m), where j is the current density obtained at a fixed overpotential in A cm -2, A is the surface area of the GC electrode (~ 0.07 cm -2 ), F is the Faraday efficiency (96485 C mol -1 ) and m is the number of moles of the electro-active elements in the electrocatalysts modified on the GC electrode. We calculated a TOF of ~ s 1, which was associated with Co 5 Mn-LDH/MWCNT at an overpotential of 350 mv in 1 M KOH, assuming that all the Co and Mn were involved in the electrochemical reaction. In addition, the TOF associated with Ni 5 Mn-LDH/MWCNT at an overpotential of 350 mv was ~ s -1. The table below shows the TOF value compared to those previously reported. Table S4 Comparison of TOF value of Co 5 Mn-LDH/MWCNT and Ni 5 Mn-LDH/MWCNT to some similar previously reported data. Catalyst TOF Ref. Co 5 Mn-LDH/MWCNT 350 mv ~ s -1 This work Ni 5 Mn-LDH/MWCNT 350 mv ~ s -1 This work NiFe/NF 400 mv ~ s NiFe/CNT 300 mv ~ s 1 15 NiCo 2.7 (OH) x 350 mv ~ s 1 16 Zn Co LDH 410 mv s 1 17 NG-CoSe mv ~ s α-ni(oh) mv ~ s S-15
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