Balancing Mass Transfer and Active Sites to Improve Electrocatalytic Oxygen Reduction by B,N Codoped C Nanoreactors

Mass transfer is critical in catalytic processes, especially when the reactions are facilitated by nanostructured catalysts. Strong efforts have been devoted to improving the efficacy and quantity of active sites, but often, mass transfer has not been well studied. Herein, we demonstrate the importance of mass transfer in the electrocatalytic oxygen reduction reaction (ORR) by tailoring the pore sizes. Using a confined-etching strategy, we fabricate boron- and nitrogen-doped carbon (B,N@C) electrocatalysts featuring abundant active sites but different porous structures. The ORR performance of these catalysts is found to correlate with diffusion of the reactant. The optimized B,N@C with trimodal-porous structures feature enhanced O2 diffusion and better activity per heteroatomic site toward the ORR process. This work demonstrates the significance of the nanoarchitecture engineering of catalysts and sheds light on how to optimize structures featuring abundant active sites and enhanced mass transfer.

[1]  Zhenguo Huang,et al.  Fabrication of monodispersed B, N co-doped hierarchical porous carbon nanocages through confined etching to boost electrocatalytic oxygen reduction , 2022, Nano Research.

[2]  Xiangke Wang,et al.  Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications , 2022, Innovation (Cambridge (Mass.)).

[3]  Huajun Zheng,et al.  Edge-enriched N, S co-doped hierarchical porous carbon for oxygen reduction reaction , 2022, Chinese Chemical Letters.

[4]  Yali Cao,et al.  Using Anion‐Exchange to Induce the Formation of Edge Defects in CoNx to Enhance ORR Activity , 2022, ChemCatChem.

[5]  Baoxiang Peng,et al.  Recent advances in metal-organic-framework-based catalysts for thermocatalytic selective oxidation of organic substances , 2022, Chem Catalysis.

[6]  Lipeng Zhang,et al.  Boron, nitrogen co-doped carbon with abundant mesopores for efficient CO2 electroreduction , 2021 .

[7]  Xuting Li,et al.  Single-Atom-like B-N3 Sites in Ordered Macroporous Carbon for Efficient Oxygen Reduction Reaction. , 2021, ACS applied materials & interfaces.

[8]  G. Xiu,et al.  B,N-decorated carbocatalyst based on Fe-MOF/BN as an efficient peroxymonosulfate activator for bisphenol A degradation. , 2021, Journal of hazardous materials.

[9]  Yunhui Huang,et al.  Porous N, B co-doped carbon nanotubes as efficient metal-free electrocatalysts for ORR and Zn-air batteries , 2021 .

[10]  Xiaodong Chen,et al.  Facile Synthesis of Boron and Nitrogen Dual-Doped Hollow Mesoporous Carbons for Efficient Reduction of 4-Nitrophenol. , 2021, ACS applied materials & interfaces.

[11]  Tianyi Liu,et al.  Mesoscale Diffusion Enhancement of Carbon-Bowl-Shaped Nanoreactor toward High-Performance Electrochemical H2O2 Production. , 2021, ACS applied materials & interfaces.

[12]  Shu‐Hong Yu,et al.  Microchemical Engineering in a 3D Ordered Channel Enhances Electrocatalysis. , 2021, Journal of the American Chemical Society.

[13]  Xinyao Wang,et al.  Microenvironment and Nanoreactor Engineering of Single-Site Metal Catalysts for Electrochemical CO2 Reduction , 2021 .

[14]  Wenping Sun,et al.  2D Metal‐Free Nanomaterials Beyond Graphene and Its Analogues toward Electrocatalysis Applications , 2021, Advanced Energy Materials.

[15]  Yang Wang,et al.  Molecular Surgery at Microporous MOF for Mesopore Generation and Renovation. , 2021, Angewandte Chemie.

[16]  X. Lou,et al.  Exposing unsaturated Cu1-O2 sites in nanoscale Cu-MOF for efficient electrocatalytic hydrogen evolution , 2021, Science Advances.

[17]  Y. Yamauchi,et al.  Hollow Carbon-Based Nanoarchitectures Based on ZIF: Inward/Outward Contraction Mechanism and Beyond. , 2020, Small.

[18]  Jintao Zhang,et al.  A Defect‐rich N, P Co‐doped Carbon Foam as Efficient Electrocatalyst toward Oxygen Reduction Reaction , 2020 .

[19]  Yanli Zhao,et al.  Selective wet-chemical etching to create TiO2@MOF frame heterostructure for efficient photocatalytic hydrogen evolution , 2020 .

[20]  P. Shen,et al.  Revealing the dependence of active site configuration of N doped and N, S-co-doped carbon nanospheres on six-membered heterocyclic precursors for oxygen reduction reaction , 2020 .

[21]  X. Lou,et al.  Metal Atom‐Doped Co3O4 Hierarchical Nanoplates for Electrocatalytic Oxygen Evolution , 2020, Advanced materials.

[22]  Dan Zhao,et al.  A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries , 2020 .

[23]  T. Hyeon,et al.  Recent Advances in Electrochemical Oxygen Reduction to H2O2: Catalyst and Cell Design , 2020 .

[24]  Y. Yamauchi,et al.  Spatial-controlled etching of coordination polymers , 2020 .

[25]  Jingxiang Zhao,et al.  Optimal N-doped carbon defect configuration in 2D turbostratic carbon nanomesh for advanced oxygen reduction electrocatalysis. , 2020, Angewandte Chemie.

[26]  Q. Cai,et al.  Molecular‐Level Design of Pyrrhotite Electrocatalyst Decorated Hierarchical Porous Carbon Spheres as Nanoreactors for Lithium–Sulfur Batteries , 2020, Advanced Energy Materials.

[27]  Yanchun Li,et al.  Highly efficient electrosynthesis of hydrogen peroxide on a superhydrophobic three-phase interface by natural air diffusion , 2020, Nature Communications.

[28]  X. Lou,et al.  Metal-Organic Frameworks Based Electrocatalysts for the Oxygen Reduction Reaction. , 2020, Angewandte Chemie.

[29]  Yongchul G. Chung,et al.  Synergistic effect of metal-organic framework-derived boron and nitrogen heteroatom-doped three-dimensional porous carbons for precious-metal-free catalytic reduction of nitroarenes , 2019, Applied Catalysis B: Environmental.

[30]  Shaoming Huang,et al.  Bottom-up synthesis of MOF-derived hollow N-doped carbon materials for enhanced ORR performance , 2019, Carbon.

[31]  Li Xu,et al.  Boron and nitrogen co-doped graphene aerogels: Facile preparation, tunable doping contents and bifunctional oxygen electrocatalysis , 2018, Carbon.

[32]  Yadong Li,et al.  Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction , 2018, Advanced materials.

[33]  Shuang Li,et al.  Bifunctional Electrocatalysts for Overall Water Splitting from an Iron/Nickel-Based Bimetallic Metal-Organic Framework/Dicyandiamide Composite. , 2018, Angewandte Chemie.

[34]  T. Zhou,et al.  Cobalt Boron Imidazolate Framework Derived Cobalt Nanoparticles Encapsulated in B/N Codoped Nanocarbon as Efficient Bifunctional Electrocatalysts for Overall Water Splitting , 2018 .

[35]  Zheng Jiang,et al.  Bifunctional Nitrogen and Cobalt Codoped Hollow Carbon for Electrochemical Syngas Production , 2018, Advanced science.

[36]  Xian‐Ming Zhang,et al.  Co/CoO/C@B three-phase composite derived from ZIF67 modified with NaBH4 solution as the electrocatalyst for efficient oxygen evolution , 2018 .

[37]  Kui Shen,et al.  Nanoreactor of MOF-Derived Yolk–Shell Co@C–N: Precisely Controllable Structure and Enhanced Catalytic Activity , 2018 .

[38]  Xinchen Wang,et al.  Metal-Free Boron-Containing Heterogeneous Catalysts. , 2017, Angewandte Chemie.

[39]  Zhaoping Liu,et al.  Enhancing the pyridinic N content of Nitrogen-doped graphene and improving its catalytic activity for oxygen reduction reaction , 2017 .

[40]  Daoyong Chen,et al.  Multiheteroatom-Doped Porous Carbon Catalyst for Oxygen Reduction Reaction Prepared using 3D Network of ZIF-8/Polymeric Nanofiber as a Facile-Doping Template. , 2017, ACS applied materials & interfaces.

[41]  A. Mahmood,et al.  Metal–Organic Frameworks Derived Cobalt Phosphide Architecture Encapsulated into B/N Co‐Doped Graphene Nanotubes for All pH Value Electrochemical Hydrogen Evolution , 2017 .

[42]  Q. Fu,et al.  Catalysis under shell: Improved CO oxidation reaction confined in Pt@h-BN core–shell nanoreactors , 2017, Nano Reseach.

[43]  W. Xia,et al.  Hierarchical Cobalt Hydroxide and B/N Co-Doped Graphene Nanohybrids Derived from Metal-Organic Frameworks for High Energy Density Asymmetric Supercapacitors , 2017, Scientific Reports.

[44]  Jinhua Ye,et al.  Active Sites Implanted Carbon Cages in Core-Shell Architecture: Highly Active and Durable Electrocatalyst for Hydrogen Evolution Reaction. , 2016, ACS nano.

[45]  Kimoon Kim,et al.  Hydrolytic Transformation of Microporous Metal-Organic Frameworks to Hierarchical Micro- and Mesoporous MOFs. , 2015, Angewandte Chemie.

[46]  P. Ajayan,et al.  Nitrogen-Doped Graphene with Pyridinic Dominance as a Highly Active and Stable Electrocatalyst for Oxygen Reduction. , 2015, ACS applied materials & interfaces.

[47]  Jian Liu,et al.  Thermal conversion of core-shell metal-organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon. , 2015, Journal of the American Chemical Society.

[48]  J. Baek,et al.  BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. , 2012, Angewandte Chemie.

[49]  J. Gore,et al.  A study of catalytic hydrolysis of concentrated ammonia borane solutions , 2010 .

[50]  D. Goldsack,et al.  The viscosity of concentrated electrolyte solutions—III. A mixture law , 1977 .

[51]  Xinyao Wang,et al.  The structure–activity correlation of single-site Ni catalysts dispersed onto porous carbon spheres toward electrochemical CO2 reduction , 2022, Fuel.

[52]  J. Qiu,et al.  Ultrasound-Assisted Nitrogen and Boron Codoping of Graphene Oxide for Efficient Oxygen Reduction Reaction , 2019, ACS Sustainable Chemistry & Engineering.

[53]  T. Ma,et al.  Synthesis of Co–B in porous carbon using a metal–organic framework (MOF) precursor: A highly efficient catalyst for the oxygen evolution reaction , 2018 .

[54]  Lei Jiang,et al.  Highly Boosted Oxygen Reduction Reaction Activity by Tuning the Underwater Wetting State of the Superhydrophobic Electrode. , 2017, Small.

[55]  Controlling the Interfacial Charge Polarization of MOF-Derived 0D2D vdW Architectures as a Unique Strategy for Bifunctional Oxygen Electrocatalysis , 2022 .