Supporting Information. for Water Splitting. Guangxing Zhang, Jie Yang, Han Wang, Haibiao Chen, Jinlong Yang, and Feng Pan

Similar documents
Supporting Information for. Highly active catalyst derived from a 3D foam of Fe(PO 3 ) 2 /Ni 2 P for extremely efficient water oxidation

Bioinspired Cobalt-Citrate Metal-Organic Framework as An Efficient Electrocatalyst for Water Oxidation

Supplementary Information for. High-performance bifunctional porous non-noble metal phosphide catalyst for overall

Supporting information

Supporting Information. Cobalt Molybdenum Oxide Derived High-Performance Electrocatalyst

Supporting Information. Electronic Modulation of Electrocatalytically Active. Highly Efficient Oxygen Evolution Reaction

bifunctional electrocatalyst for overall water splitting

Honeycomb-like Interconnected Network of Nickel Phosphide Hetero-nanoparticles

Co-vacancy-rich Co 1 x S nanosheets anchored on rgo for high-efficiency oxygen evolution

Supporting Information

Supporting Information

Formation of Hierarchical Structure Composed of (Co/Ni)Mn-LDH Nanosheets on MWCNT Backbones for Efficient Electrocatalytic Water Oxidation

Revelation of the Excellent Intrinsic Activity. Evolution Reaction in Alkaline Medium

Supporting Information. Bi-functional Catalyst with Enhanced Activity and Cycle Stability for. Rechargeable Lithium Oxygen Batteries

Supporting Information. Direct Observation of Structural Evolution of Metal Chalcogenide in. Electrocatalytic Water Oxidation

Carbon-encapsulated heazlewoodite nanoparticles as highly efficient and durable electrocatalysts for oxygen evolution reactions

Supplementary Figure 1. (a-b) EDX of Mo 2 and Mo 2

Lotus root-like porous carbon nanofiber anchored with CoP nanoparticles as all-ph hydrogen evolution electrocatalysts

Interconnected Copper Cobaltite Nanochains as Efficient. Electrocatalysts for Water Oxidation in Alkaline Medium

Magnesiothermic synthesis of sulfur-doped graphene as an efficient. metal-free electrocatalyst for oxygen reduction

Photo of the mass manufacture of the Fe-rich nanofiber film by free-surface electrospinning technique

η (mv) J (ma cm -2 ) ma cm

Supporting Information

Engineering NiS/Ni 2 P Heterostructures for Efficient Electrocatalytic Water Splitting

Boosting the hydrogen evolution performance of ruthenium clusters. through synergistic coupling with cobalt phosphide

Bimetallic Thin Film NiCo-NiCoO as Superior Bifunctional Electro- catalyst for Overall Water Splitting in Alkaline Media

Hexagonal-Phase Cobalt Monophosphosulfide for. Highly Efficient Overall Water Splitting

Dominating Role of Aligned MoS 2 /Ni 3 S 2. Nanoarrays Supported on 3D Ni Foam with. Hydrophilic Interface for Highly Enhanced

Supporting Information

Supporting Information

Phytic Acid-Assisted Formation of Hierarchical Porous CoP/C Nanoboxes for Enhanced Lithium Storage and Hydrogen Generation

Supporting Information

Supporting Information for:

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

Supporting Information

High Salt Removal Capacity of Metal-Organic Gel Derived. Porous Carbon for Capacitive Deionization

Supporting Information. MOF Templated Nitrogen Doped Carbon Stabilized Pt-Co Bimetallic

Three-Dimensional Honeycomb-Like Cu 0.81 Co 2.19 O 4. Nanosheet Arrays Supported by Nickel Foam and. Their High Efficiency as Oxygen Evolution

Electronic Supplementary Information

Metal Organic Framework-Derived Metal Oxide Embedded in Nitrogen-Doped Graphene Network for High-Performance Lithium-Ion Batteries

A Scalable Synthesis of Few-layer MoS2. Incorporated into Hierarchical Porous Carbon. Nanosheets for High-performance Li and Na Ion

Supporting Information. Engineering Two-Dimensional Mass-Transport Channels

Supporting Information

Supporting Information for

In-Situ Fabrication of CoS and NiS Nanomaterials Anchored on. Reduced Graphene Oxide for Reversible Lithium Storage

Cloth for High-Efficient Electrocatalytic Urea Oxidation

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires. by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts

Self-Growth-Templating Synthesis of 3D N,P,Co-Doped. Mesoporous Carbon Frameworks for Efficient Bifunctional

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing , China

Supporting information for. The development of cobalt hydroxide as a bifunctional catalyst for oxygen. electrocatalysis in alkaline solution.

Supporting Information

Metal free and Nonprecious Metal Materials for Energy relevant Electrocatalytic Processes. Shizhang Qiao ( 乔世璋 )

Flexible Asymmetrical Solid-state Supercapacitors Based on Laboratory Filter Paper

Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction

Ni-Mo Nanocatalysts on N-Doped Graphite Nanotubes for Highly Efficient Electrochemical Hydrogen Evolution in Acid

Supporting Information. Co 4 N Nanosheets Assembled Mesoporous Sphere as a Matrix for Ultrahigh Sulfur Content Lithium Sulfur Batteries

Supporting Information

An Advanced Anode Material for Sodium Ion. Batteries

Hierarchical MoO 2 /Mo 2 C/C Hybrid Nanowires for High-Rate and. Long-Life Anodes for Lithium-Ion Batteries. Supporting Information

Pomegranate-Like N, P-Doped Nanospheres as Highly Active Electrocatalysts for Alkaline Hydrogen Evolution

Supporting Information. Metal-Organic Frameworks Mediated Synthesis of One-Dimensional Molybdenum-Based/Carbon Composites for Enhanced Lithium Storage

Supporting Information for

Metal-Organic Framework Derived Iron Sulfide-Carbon Core-Shell Nanorods as a Conversion-Type Battery Material

Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin , PR China

Carbon Quantum Dots/NiFe Layered Double Hydroxide. Composite as High Efficient Electrocatalyst for Water

Tuning the Shell Number of Multi-Shelled Metal Oxide. Hollow Fibers for Optimized Lithium Ion Storage

Self-assembled pancake-like hexagonal tungsten oxide with ordered mesopores for supercapacitors

Electronic Supplementary Information

B-site doping effects of NdBa 0.75 Ca 0.25 Co 2 O 5+δ double perovskite catalysts for oxygen evolution and reduction reactions

Hydrothermally Activated Graphene Fiber Fabrics for Textile. Electrodes of Supercapacitors

Supplemental Information. In Situ Electrochemical Production. of Ultrathin Nickel Nanosheets. for Hydrogen Evolution Electrocatalysis

Supporting Informantion

One-Step Facile Synthesis of Cobalt Phosphides for Hydrogen Evolution Reaction Catalyst in Acidic and Alkaline Medium

Supporting Information

Supporting information

Electronic Supplementary Information

Trifunctional Ni-N/P-O-codoped graphene electrocatalyst enables

Multicomponent (Mo, Ni) metal sulfide and selenide microspheres with empty nanovoids as anode materials for Na-ion batteries

Fabrication of Metallic Nickel-Cobalt Phosphide Hollow Microspheres for. High-Rate Supercapacitors

Self-Supported Three-Dimensional Mesoporous Semimetallic WP 2. Nanowire Arrays on Carbon Cloth as a Flexible Cathode for

Science and Technology, Dalian University of Technology, Dalian , P. R. China b

Oxygen Vacancy Induced Bismuth Oxyiodide with Remarkably. Increased Visible-light Absorption and Superior Photocatalytic.

Electronic Supplementary Information

Electronic Supplementary Information

Supporting Information

Supporting Information

Supporting Information

Reviewers' Comments: Reviewer #1 (Remarks to the Author)

Supporting information

Electronic Supplementary Information

Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery

One-pot synthesis of bi-metallic PdRu tripods as an efficient catalyst for. electrocatalytic nitrogen reduction to ammonia

Cobalt Ferrite bearing Nitrogen Doped Reduced. Graphene Oxide Layers Spatially Separated with. Electrocatalyst

Scalable Preparation of Hierarchical Porous Activated Carbon/graphene composite for High-Performance Supercapacitors

Electronic Supplementary Information

Journal of Materials Chemistry A ELECTRONIC SUPPLEMENTARY INFORMATION (ESI )

Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with. Gui-Xiang Huang, Chu-Ya Wang, Chuan-Wang Yang, Pu-Can Guo, Han-Qing Yu*

Achieving Stable and Efficient Water Oxidation by Incorporating NiFe. Layered Double Hydroxide Nanoparticles into Aligned Carbon.

Atomic H-Induced Mo 2 C Hybrid as an Active and Stable Bifunctional Electrocatalyst Supporting Information

Engineering of Hollow Core-Shell Interlinked Carbon Spheres for Highly Stable Lithium-Sulfur Batteries

Transcription:

Supporting Information Co 3 O 4-δ Quantum Dots as a Highly Efficient Oxygen Evolution Reaction Catalyst for Water Splitting Guangxing Zhang, Jie Yang, Han Wang, Haibiao Chen, Jinlong Yang, and Feng Pan School of Advanced Materials, Shenzhen Graduate School, Peking University, Shenzhen 518055, People s Republic of China *Corresponding authors: yangjl@pkusz.edu.cn, panfeng@pkusz.edu.cn. S1

Figure S1. (a) SEM image of mesoporous Co 3 O 4 nanosheets; (b) N 2 sorption isotherms and (c) BJH pore size distribution of mesoporous Co 3 O 4 nanosheets. S2

Figure S2. (a) Full XPS spectra; Binding energy at (b) Li 1s, (c) Co 2p and (d) O 1s for the Co 3 O 4-δ QDs with different cycles and Co 3 O 4 nanosheets. S3

Figure S3. EDLC curves of (a) Co 3 O 4 nanosheets, (b) Co 3 O 4 nanosheets@ni foam, and (c) Co 3 O 4-δ -QDs-20 th cycle respectively with different scan rates. Figure S4. Faraday efficiency test. (a) Water drainage device; (b) Comparison of the measured amount of O 2 and the theoretical amount calculated based on 100% Faradaic efficiency. Constant current of 20 ma cm -2 was used in the experiment. S4

Figure S5. TEM images of the Co 3 O 4-δ -QDs-20 th cycle after OER: (a) Nanosheet morphology consisted of quantum dots; (b) Lattice spacing with the quantum dots. Figure S6. Full XPS spectra for the Co 3 O 4-δ -QDs-20 th cycle before and after OER, as well as Co 3 O 4 nanosheets, inset is binding energy at Li 1s. S5

Figure S7. Nyquist plots for the different galvanostatic cycle Co 3 O 4-δ measured at 1.5 V vs. RHE during the OER at 25 C. 100 80 ir corrected η vs. RHE (V) 0.0 0.1 0.2 0.3 0.4 1.65 Co3O4 nanosheets@ni foam Co3O4 sheet@ni foam Current Density (ma cm -2 ) 60 40 20 ir corrected E vs. RHE (V ) 1.60 1.55 1.50 47.1 mv/dec 20 40 60 80 100 Log (i ma cm -2 ) 0 1.2 1.3 1.4 1.5 1.6 1.7 ir corrected E vs. RHE (V) Figure S8. LSV curves of Co 3 O 4 nanosheets@ni foam at 1 mv s -1 in O 2 -saturated 1 M KOH solution, inset was the Tafel plot of Co 3 O 4 nanosheets@ni foam. S6

Figure S9. Cyclic voltametry curves with scan rate from 3 to 40 mv s -1 for (a) Co 3 O 4 nanosheets and (b) Co 3 O 4-δ -QDs-20 th cycle. Figure S10 Figure S10. Extrapolation of (a) q* Total and (b) q* Outer for different galvanostatic cycle of Co 3 O 4-δ. Table S1. Electrochemical parameters obtained for different galvanostatic cycle of Co 3 O 4-δ. S7

Table S2. Detailed comparison of OER activity for the Co 3 O 4 serials catalysts reported in recent years. Catalysts η@10 ma Tafel slope Mass loading Electrolyte Substrate Ref., year cm -2 (V) (mv dec -1 ) (mg cm -2 ) Co 3O 4 NS 0.33 58 0.25 1 M KOH CNF This work Co 3O 4 NS@Ni Foam 0.31 47 0.25 1 M KOH Ni foam This work Co 3O 4-δ-QDs-20 th cycle 0.27 39 0.25 1 M KOH CNF This work Co 3O 4/N-rmGO 0.31 67 0.17 1 M KOH GC (s1, 2011) Co 3O 4 CuCo 2O 4 0.427 / 0.12 1 M KOH GC (s2, 2013) Ordered Meso-Co 3O 4 0.476 / 0.13 1 M KOH Au foil (s3, 2013) Co 3O 4/GR 0.375 67 / 0.1 M KOH ITO (s4, 2013) Au/Co 3O 4 0.37 60 0.064 0.1 M KOH GC (s5, 2014) N-CG-CoO 0.34 71 0.18 1 M KOH GC (s6, 2014) Co 3O 4/C-NA* 0.22 61 0.2 0.1M KOH Cu foil (s7, 2014) Meso-Co 3O 4 NWs 0.37 72 0.136 1 M KOH GC (s8, 2014) Graphene-Co 3O 4 0.31 49 0.04 1 M KOH GC (s9,2014) CoMn LDH 0.32 43 0.142 1 M KOH GC (s10,2014) Hierarchical CoO x 0.29 75 0.136 1 M KOH GC (s11,2015) Crystalline Co 3O 4 0.3 65 0.04 0.1 M KPi. GC (s12,2015) Co 3O 4 Flakes 0.31 48 0.04 1 M KOH GC (s13,2015) CoO x@cn 0.26 85 1 1 M KOH GC (s14,2015) Rhombus Co 3O 4 0.27 62 / 1 M KOH ITO (s15,2015) Co@ Co 3O 4/NC 0.41 54 0.21 0.1 M KOH GC (s16,2016) Plasma-Engraved Co 3O 4 0.30 68 / 0.1 M KOH Ti foil (s17,2016) Reduced Co 3O 4 0.38 73 0.08 0.1 M KOH GC (s18,2016) CuCo 2O 4/NrGO 0.36 64 0.14 1 M KOH GC (s19,2016) rgo Co 3O 4 YSNC 0.41 85 0.08 0.1 M KOH GC (s20,2016) CoO@N/S-CNF 0.30 95 0.08 0.1 M KOH GC (s21,2016) CoP NS/C 0.277 85.6 0.71 1 M KOH CNF (s22,2016) S8

References (s1) Liang, Y.; Li, Y.; Wang, H.; Zhou, J.; Wang, J.; Regier, T.; Dai, H. Co₃O₄ Nanocrystals on Graphene as a Synergistic Catalyst for Oxygen Reduction Reaction. Nat. Mater. 2011, 10, 780-786. (s2) Grewe, T.; Deng, X.; Weidenthaler, C.; Schüth, F.; Tuysüz, H. Design of Ordered Mesoporous Composite Materials and Their Electrocatalytic Activities for Water Oxidation. Chem. Mater. 2013, 25, 4926-4935. (s3) Tüysüz, H.; Yun, J. H.; Khan, S. B.; Asiri, A. M.; Yang, P. Mesoporous Co 3 O 4 as an Electrocatalyst for Water Oxidation. Nano Res. 2013, 6, 47-54. (s4) Suryanto, B. R.; Lu, X.; Zhao, C. Layer-by-Layer Assembly of Transparent Amorphous Co 3 O 4 Nanoparticles/Graphene Composite Electrodes for Sustained Oxygen Evolution Reaction. J. Mater. Chem. A 2013, 1, 12726-12731. (s5) Zhuang, Z.; Sheng, W.; Yan, Y. Synthesis of Monodispere Au@Co 3 O 4 Core-Shell Nanocrystals and Their Enhanced Catalytic Activity for Oxygen Evolution Reaction. Adv. Mater. 2014, 26, 3950-3955. (s6) Mao, S.; Wen, Z.; Huang, T.; Hou, Y.; Chen, J. High-Performance Bi-Functional Electrocatalysts of 3D Crumpled Graphene Cobalt Oxide Nano-Hybrids for Oxygen Reduction and Evolution Reactions. Energy Environ. Sci. 2014, 7, 609-616. (s7) Ma, T. Y.; Dai, S.; Jaroniec, M.; Qiao, S. Z. Metal-Organic Framework Derived Hybrid Co 3 O 4 -Carbon Porous Nanowire Arrays as Reversible Oxygen Evolution Electrodes. J. Am. Chem. Soc. 2014, 136, 13925-13931. (s8) Wang, Y.; Tong, Z.; Jiang, K.; Da, P.; Zheng, G. Reduced Mesoporous Co 3 O 4 Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes. Adv. Energy Mater. 2014, 4, 1400696. (s9) Zhao, Y.; Chen, S.; Sun, B. Graphene-Co 3 O 4 Nanocomposite as Electrocatalyst with High Performance for Oxygen Evolution Reaction. Sci. Rep. 2015, 5, 7629-7629. (s10) Song, F.; Hu, X. Ultrathin Cobalt Manganese Layered Double Hydroxide Is an Efficient Oxygen Evolution Catalyst. J. Am. Chem. Soc. 2014, 136, 16481-16484. (s11) Wang, Y.; Jiang, K.; Zhang, H. Heterostructures: Bio Inspired Leaf Mimicking Nanosheet/Nanotube Heterostructure as a Highly Efficient Oxygen Evolution Catalyst. Adv. Sci. 2015, 2, 1500003. (s12) Bergmann, A.; Martinez-Moreno, E.; Teschner, D. Reversible Amorphization and the S9

Catalytically Active State of Crystalline Co 3 O 4 during Oxygen Evolution. Nat. Commun. 2015, 6, 8625. (s13) Chen, S.; Zhao, Y.; Sun, B. Microwave-Assisted Synthesis of Mesoporous Co 3 O 4 Nanoflakes for Applications in Lithium Ion Batteries and Oxygen Evolution Reactions. ACS Appl. Mater. Interfaces 2015, 7, 3306-3313. (s14) Jin, H.; Wang, J.; Su, D. In Situ Cobalt-Cobalt Oxide/N-doped Carbon Hybrids as Superior Bifunctional Electrocatalysts for Hydrogen and Oxygen Evolution. J. Am. Chem. Soc. 2015, 137, 2688-2694. (s15) Zhang, X.; Zhang, J.; Wang, K. Co Doping-Induced, Rhombus-Shaped Co 3 O 4 Nanosheets as an Active Electrode Material for Oxygen Evolution. ACS Appl. Mater. Interfaces 2015, 7, 21745-21750. (s16) Aijaz, A.; Masa, J.; Rösler, C. Co@Co 3 O 4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode. Angew. Chem. Int. Ed. 2016, 55, 4087-4091. (s17) Xu, L.; Jiang, Q.; Xiao, Z. Plasma-Engraved Co 3 O 4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction. Angew. Chem. Int. Ed. 2016, 55, 5277-5281. (s18) Ghanem, M. A.; Al-Mayouf, A. M.; Arunachalam, P. Mesoporous Cobalt Hydroxide Prepared Using Liquid Crystal Template for Efficient Oxygen Evolution in Alkaline Media. Electrochim. Acta 2016, 207, 177-186. (s19) Bikkarolla, S. K.; Papakonstantinou, P. CuCo 2 O 4 Nanoparticles on Nitrogenated Graphene as Highly Efficient Oxygen Evolution Catalyst. J. Power Sources 2015, 281, 243-251. (s20) Wu, Z.; Sun, L. P.; Yang, M. Facile Synthesis and Excellent Electrochemical Performance of Reduced Graphene Oxide Co 3 O 4 Yolk-Shell Nanocages as a Catalyst for Oxygen Evolution Reaction. J. Mater. Chem. A 2016, 4, 13534-13542. (s21) Liu, T.; Guo, Y. F.; Yan, Y. M. CoO Nanoparticles Embedded in Three-Dimensional Nitrogen/Sulfur Co-Doped Carbon Nanofiber Networks as a Bifunctional Catalyst for Oxygen Reduction/Evolution Reactions. Carbon 2016, 106, 84-92. (s22) Chang, J.; Liang, L.; Li, C. Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Catalysts for a Water Electrolysis Cell and the Origin for Cell Performance Degradation. Green Chem. 2016, 18, 2287-2295. S10