Boron-Doped Activated Carbon Supports for Cobalt-Catalyzed Oxygen Evolution in Alkaline Electrolyte.

Activated carbons (ACs) are the most widely used and attractive support materials for electrocatalytic applications because of their significant surface areas, high electrical conductivities, and moderate affinities toward supported metal catalysts. However, the corrosive behavior of ACs at oxidative potentials causes an inevitable reduction in the active surface area of supported catalysts, resulting in the continuous deterioration of their electrocatalytic performance. Therefore, the introduction of corrosion-resistant durable catalyst supports is essential for sustainable and efficient electrocatalysis. Here, we modified ACs to obtain different boron (B)-doped structures via doping-temperature controls to investigate the corrosion resistance of B-doped ACs. With increasing doping temperature, the B-doped ACs exhibited a decreased defect density and enhanced crystallinity owing to the accelerating dopant-induced graphitization. We found that the substitution of B atoms into the carbon lattice improved the structural integrity of the carbon structure, and cyclic voltammetry (CV) tests suggested that the highly B-substituted structures caused electrochemical surface passivation against carbon corrosion. Moreover, B-doped ACs significantly contributed to the increase in loading mass of cobalt (Co)-based catalyst on them and the electrochemical durability toward the oxygen evolution reaction as catalyst-support hybrid. The B22 (B-doped AC obtained at a 2200 °C B-doping temperature)-supported Co catalyst with the lowest oxidation current exhibited a voltage change of 32 mV at a current density of 10 mA/cm2 (ΔEj=10) after 10,000 cycles, which was a factor of ∼7 higher cycle durability and stability than that of the conventional IrO2 catalyst (ΔEj=10 = 205 mV). Here, we propose that surface engineering by B-doping to improve the structural integrity of ACs is an attractive method for designing durable electrocatalytic support materials.

[1]  G. Henkelman,et al.  Template-assisted synthesis of single-atom catalysts supported on highly crystalline vanadium pentoxide for stable oxygen evolution , 2022, Chem Catalysis.

[2]  Y. Kim,et al.  Edgeless porous carbon coating for durable and powerful lead-carbon batteries , 2021, Carbon.

[3]  Cheol-Min Yang,et al.  Boron-Doped Edges as Active Sites for Water Adsorption in Activated Carbons. , 2021, Langmuir : the ACS journal of surfaces and colloids.

[4]  K. Yoon,et al.  Hierarchically Assembled Cobalt Oxynitride Nanorods and N-Doped Carbon Nanofibers for Efficient Bifunctional Oxygen Electrocatalysis with Exceptional Regenerative Efficiency. , 2021, ACS nano.

[5]  J. Tintner,et al.  Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering , 2021, Molecules.

[6]  S. Chan,et al.  Carbon corrosion mechanism and mitigation strategies in a proton exchange membrane fuel cell (PEMFC): A review , 2021 .

[7]  Shichun Mu,et al.  Ionothermal Route to Phase-Pure RuB2 Catalysts for Efficient Oxygen Evolution and Water Splitting in Acidic Media , 2020 .

[8]  W. Schuhmann,et al.  Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry , 2019, Angewandte Chemie.

[9]  F. Speck,et al.  Mechanisms of Manganese Oxide Electrocatalysts Degradation during Oxygen Reduction and Oxygen Evolution Reactions , 2019, The Journal of Physical Chemistry C.

[10]  P. Simon,et al.  A SAXS outlook on disordered carbonaceous materials for electrochemical energy storage , 2019, Energy Storage Materials.

[11]  Jin-Song Hu,et al.  Scalable Solid‐State Synthesis of Highly Dispersed Uncapped Metal (Rh, Ru, Ir) Nanoparticles for Efficient Hydrogen Evolution , 2018, Advanced Energy Materials.

[12]  M. Koper,et al.  Effect of Saturating the Electrolyte with Oxygen on the Activity for the Oxygen Evolution Reaction , 2018, ACS catalysis.

[13]  Avelino Corma,et al.  Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles , 2018, Chemical reviews.

[14]  Yongfeng Hu,et al.  Carbon Nanosheets Containing Discrete Co-Nx-By-C Active Sites for Efficient Oxygen Electrocatalysis and Rechargeable Zn-Air Batteries. , 2018, ACS nano.

[15]  H. Byon,et al.  Brush-Like Cobalt Nitride Anchored Carbon Nanofiber Membrane: Current Collector-Catalyst Integrated Cathode for Long Cycle Li-O2 Batteries. , 2017, ACS nano.

[16]  Xiangkai Kong,et al.  Two-dimensional boron-doped graphyne nanosheet: A new metal-free catalyst for oxygen evolution reaction , 2017 .

[17]  M. Döbeli,et al.  Direct Synthesis of Bulk Boron-Doped Graphitic Carbon , 2017 .

[18]  Jinqiu Zhou,et al.  An Efficient Bifunctional Electrocatalyst for a Zinc-Air Battery Derived from Fe/N/C and Bimetallic Metal-Organic Framework Composites. , 2017, ACS applied materials & interfaces.

[19]  Michael J. Zdilla,et al.  Effect of Interlayer Spacing on the Activity of Layered Manganese Oxide Bilayer Catalysts for the Oxygen Evolution Reaction. , 2017, Journal of the American Chemical Society.

[20]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[21]  Klaus Kern,et al.  Driving the Oxygen Evolution Reaction by Nonlinear Cooperativity in Bimetallic Coordination Catalysts. , 2016, Journal of the American Chemical Society.

[22]  Vishal M. Dhavale,et al.  Surface-Tuned Co3O4 Nanoparticles Dispersed on Nitrogen-Doped Graphene as an Efficient Cathode Electrocatalyst for Mechanical Rechargeable Zinc-Air Battery Application. , 2015, ACS applied materials & interfaces.

[23]  Y. Qu,et al.  Hollow Fluffy Co3O4 Cages as Efficient Electroactive Materials for Supercapacitors and Oxygen Evolution Reaction. , 2015, ACS applied materials & interfaces.

[24]  J. P. Olivier,et al.  Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) , 2015 .

[25]  Shihe Yang,et al.  Cobalt-embedded nitrogen doped carbon nanotubes: a bifunctional catalyst for oxygen electrode reactions in a wide pH range. , 2015, ACS applied materials & interfaces.

[26]  Yong Wang,et al.  In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. , 2015, Journal of the American Chemical Society.

[27]  Bing Sun,et al.  Graphene-Co3O4 nanocomposite as electrocatalyst with high performance for oxygen evolution reaction , 2015, Scientific Reports.

[28]  S. Kolesnikov,et al.  Study of the Effect of High-Temperature Treatment on Carbon-Carbon Composite Material Oxidation Resistance , 2014, Refractories and Industrial Ceramics.

[29]  A. Hellman,et al.  Analysis of porphyrines as catalysts for electrochemical reduction of O2 and oxidation of H2O. , 2014, Journal of the American Chemical Society.

[30]  A. Heinzel,et al.  Graphene as catalyst support: The influences of carbon additives and catalyst preparation methods on the performance of PEM fuel cells , 2013 .

[31]  Bo-Hye Kim,et al.  SiC/SiO2 coating for improving the oxidation resistive property of carbon nanofiber , 2010 .

[32]  J. Xie,et al.  Investigation of the Carbon Corrosion Process for Polymer Electrolyte Fuel Cells Using a Rotating Disk Electrode Technique , 2010, ECS Transactions.

[33]  Z. Xia,et al.  X-ray diffraction patterns of graphite and turbostratic carbon , 2007 .

[34]  Ado Jorio,et al.  General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy , 2006 .

[35]  Zhongwei Chen,et al.  Durability investigation of carbon nanotube as catalyst support for proton exchange membrane fuel cell , 2006 .

[36]  L. Radovic,et al.  Ab Initio Molecular Orbital Study on the Electronic Structures and Reactivity of Boron-Substituted Carbon , 2004 .

[37]  A. Ōya,et al.  Catalytic graphitization of carbons by borons , 1979 .

[38]  C. Lowell Solid Solution of Boron in Graphite , 1967 .

[39]  Hui Pan,et al.  Co single-atom anchored on Co3O4 and nitrogen-doped active carbon toward bifunctional catalyst for zinc-air batteries , 2020 .

[40]  M. Terrones,et al.  Correlation in structure and properties of highly-porous graphene monoliths studied with a thermal treatment method , 2016 .

[41]  Zhenhai Xia,et al.  A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. , 2015, Nature nanotechnology.

[42]  J. Miyawaki,et al.  Electrochemical surface oxidation of carbon nanofibers , 2011 .

[43]  Hubert A. Gasteiger,et al.  Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes , 2010 .

[44]  F. G. Emmerich Evolution with heat treatment of crystallinity in carbons , 1995 .

[45]  D. N. Buckley,et al.  The oxygen electrode. Part 6.—Oxygen evolution and corrosion at iridium anodes , 1976 .