Supporting information. A Metal-Organic Framework-Derived Porous Cobalt Manganese Oxide Bifunctional

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1 Supporting information A MetalOrganic FrameworkDerived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid NaAir/Seawater Batteries Mari Abirami a,, Soo Min Hwang a,, *, Juchan Yang a, Sirugaloor Thangavel Senthilkumar a, Junsoo Kim a, WooSeok Go a, Baskar Senthilkumar a, HyunKon Song a, and Youngsik Kim a,b, * a School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), UNISTgil 50, Ulsan 44919, Republic of Korea b Energy Materials and Devices Lab, 4TOONE Corporation, UNISTgil 50, Ulsan 44919, Republic of Korea These authors contributed equally to this work. *Corresponding author: smhwang@unist.ac.kr (S.M. Hwang); ykim@unist.ac.kr (Y. Kim) S1

2 Figure S1. SEM image (a), XRD pattern (b), and TGA curve (c) of the Mn 3 [Co(CN) 6 ] 2 nh 2 O nanocubes, and SEM image of the CMO nanoparticles (d). The marks a and d in Fig. S1c correspond to 30 C and 430 C, respectively. S2

3 Figure S2. SAED (a) and FFT (b) patterns of the CMO sample. All the Debye rings of the SAED pattern and the FFT pattern (with a zone axis of [14 1 ] ) correspond to the tetragonal (Co,Mn)(Co,Mn) 2 O 4 phase (I41/amdS; PDF#180408). S3

4 Figure S3. N 2 sorption isotherms and size distribution graph (inset) of Mn 3 [Co(CN) 6 ] 2 nh 2 O nanocubes. The graph shows a typical type I isotherm and a bimodal pore size distribution. S4

5 Table S1. Comparison of the catalytic activities of cobaltmanganese oxide toward the ORR and OER with previous literatures. ORR activity OER activity Catalysts E onset (E 1/2 ) [V vs. RHE] ΔV * [V] E (η) ma cm 2 [V vs. RHE] Solution Ref. tco 1.3 Mn 1.7 O 4±δ (+CB) 0.86 (0.74) (0.46) 0.1 M NaOH 0.67 (0.49) (0.63) seawater (ph~8) This work Co 0.51 Mn 0.49 O/NCNT 0.96 (0.84) 1.57 (0.34) 1 M KOH S1 cmnco 2 O 4 /NrmGO 0.95 ~0.05 ~1.57 (~0.34) 1 M KOH cmnco 2 O 4 (+CB) ~0.85 ~ M KOH S2 tcomn 2 O 4 NWs(+CB) ~0.87 ~1.67 (~0.44) 0.1 M KOH S3 cmn 1.4 Co 1.6 O 4 (+CB) tmn 1.9 Co 1.1 O 4 (+CB) ~0.88 (0.75) ~0.90 ~0.07 ~ M KOH S4 ccomn 2 O 4 /C 0.95 (0.85) 0.01 ~1.78 (~0.55) ccomn 2 O 4 (+CB) 0.91 (0.73) M KOH S5 tcomn 2 O 4 (+CB) 0.86 (0.71) 0.10 cmnco 2 O 4 NFs(+CB) tcomn 2 O 4 NFs(+CB) 0.92 V 0.85 V 0.1 M KOH S6 dpmnco 2 O 4 /NrGO dpmnco 2 O 4 /CNT tcomn 2 O 4 /rgo 0.09 V vs. Ag/AgCl 0.11 V vs. Ag/AgCl ~ 0.5 V vs. Hg/Hg 2 SO ~0.72 V vs. Ag/AgCl ~0.79 V vs. Ag/AgCl E onset ~0.43 V vs. Hg/Hg 2 SO M KOH S7 0.1 M KOH S8 ΔV*: Voltage difference from the E onset of benchmark Pt/C used in the corresponding literatures E(η)**: measured potential and overpotential (vs. RHE) for OER at 10 ma cm 2 t, c, and dp represent tetragonal, cubic, and dual (mixed) spinel phases, respectively. (+CB) indicates using a mixture with carbon black nanoparticles. Part of the specific values (~***) was taken from the graphs in the literatures. S5

6 Figure S4. The initial chargedischarge voltage profiles of seawater batteries with the CMO catalyst at different current densities of ma cm 2. S6

7 Figure S5. Galvanostatic chargedischarge voltage profiles of the halfcell with the hard carbon electrode at 20 ma g 1 during 20 cycles. S7

8 Figure S6. XRD pattern (a) and XPS spectra of Co 2p (b), Mn 2p (c), and O 1s (d) of the CMO catalyst after 100 cycles. The bottom in (a) shows the reference XRD pattern of tetragonal (Co,Mn) 3 O 4 phase (JCPDS No ). The broad peaks (marked by *) were arose from the remnant carbon black powders attached on the catalyst powders. S8

9 References (S1) L., Xien; Park, M.; Kim, M. G.; Gupta, S.; Wang, X.; Wu, G.; Cho, J. Highperformance nonspinel cobalt manganese mixedoxidebased bifunctional electrocatalysts for rechargeable zinc air batteries. Nano Energy 2016, 20, (S2) Liang, Y. Y.; Wang, H. L.; Zhou, J. G.; Li, Y. G.; Wang, J.; Regier, T.; Dai, H. Covalent Hybrid of Spinel ManganeseCobalt Oxide and Graphene as Advanced Oxygen Reduction Electrocatalysts. J. Am. Chem. Soc. 2012, 134, (S3) Oh, D.; Qi, J.; Han, B.; Zhang, G.; Carney, T. J.; Ohmura, J.; Zhang, Y.; ShaoHorn, Y.; Belcher, A. M. M13 VirusDirected Synthesis of Nanostructured Metal Oxides for Lithium Oxygen Batteries. Nano Lett. 2014, 14, (S4) Lee, E.; Jang, J.H.; Kwon, Y.U. Composition Effects of Spinel Mn x Co 3 x O 4 Nanoparticles on Their Electrocatalytic Properties in Oxygen Reduction Reaction in Alkaline Media. J. Power Sources 2015, 273, (S5) Li, C.; Han, X.; Cheng, F.; Hu, Y.; Chen, C.; Chen, J. Phase and Composition Controllable Synthesis of Cobalt Manganese Spinel Nanoparticles towards Efficient Oxygen Electrocatalysis. Nat. Commun. 2015, 6, (S6) Jung, K.N.; Hwang, S. M.; Park, M.S.; Kim, K. J.; Kim, J.G.; Dou, S. X.; Kim, J. H.; Lee, J.W. OneDimensional ManganeseCobalt Oxide Nanofibres as BiFunctional Cathode Catalyst s for Rechargeable MetalAir Batteries. Sci. Rep. 2015, 5, 7665 (S7) Ge, X.; Liu, Y.; Goh, F. W. T.; Hor, T. S. A.; Zong, Y.; Xiao, P.; Zhang, Z.; Lim, S. H.; Li, B.; Wang, X.; Liu, Z. DualPhase Spinel MnCo 2 O 4 and Spinel MnCo 2 O 4 /Nanocarbon Hybrids fo r Electrocatalytic Oxygen Reduction and Evolution. ACS Appl. Mater. Interfaces 2014, 6, (S8) Wang, L.; Zhao, X.; Lu, Y.; Xu, M.; Zhang, D.; Ruoff, R. S.; Stevenson, K. J.; Goodenough, J. B. CoMn 2 O 4 Spinel Nanoparticles Grown on Graphene as Bifunctional Catalyst for LithiumA ir Batteries. J. Electrochem. Soc. 2011, 158, A1379 A1382. S9