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Optimizing Microenvironment of Asymmetric N,S-Coordinated Single-Atom Fe via Axial Fifth Coordination toward Efficient Oxygen Electroreduction

Journal Article · · Small
 [1];  [2];  [3];  [1];  [2];  [1];  [1];  [1];  [2];  [1]
  1. Nanchang University (China)
  2. Shanghai Jiao Tong University (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
+ Show Author Affiliations

We report single-atom catalysts (SACs) are attractive candidates for oxygen reduction reaction (ORR). The catalytic performances of SACs are mainly determined by the surrounding microenvironment of single metal sites. Microenvironment engineering of SACs and understanding of the structure–activity relation-ship is critical, which remains challenging. Herein, a self-sacrificing strategy is developed to synthesize asymmetric N,S-coordinated single-atom Fe with axial fifth hydroxy (OH) coordination (Fe-N3S1OH) embedded in N,S codoped porous carbon nanospheres (Fe-N/S-C). Such unique penta-coordination microenvironment is determined by cutting-edge techonologies aiding of systematic simulations. The as-obtained Fe-;N/S-C exhibits superior catalytic ORR activity, and showcases a half-wave potential of 0.882 V surpassing the benchmark Pt/C. Moreover, theoretical calculations confirmed the axial OH in Fe-N3S1OH can optimize 3d orbitals of Fe center to strengthen O2 adsorption and enhance O2 activation on Fe site, thus reducing the ORR barrier and accelerating ORR dynamics. Furthermore, Fe-N/S-C containing H2-O2 fuel cell performs a high peak power density of 512 mW cm-2, and Fe-N/S-C based Zn-air batteries show the peak power density of 203 and 49 mW cm-2in liquid and flexible all-solid-state configurations, respectively. This study offers a new platform for fundamentally understand the axial fifth coordination in asymmetrical planar single-atom metal sites for electrocatalysis.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangxi Province; German Research Foundation (DFG)
DOE Contract Number:
AC02-76SF00515; 52073137; 51763018; 21704038; 51761135114; 20202ZDB01009; 20192BCB23001
OSTI ID:
1889786
Journal Information:
Small, Vol. 18, Issue 2; ISSN 1613-6810
Publisher:
Wiley
Country of Publication:
United States
Language:
English

References (88)

Recent Developments of Microenvironment Engineering of Single‐Atom Catalysts for Oxygen Reduction toward Desired Activity and Selectivity August 2021
Bridge Bonded Oxygen Ligands between Approximated FeN 4 Sites Confer Catalysts with High ORR Performance June 2020
Tuning the Coordination Environment in Single-Atom Catalysts to Achieve Highly Efficient Oxygen Reduction Reactions December 2019
Single Cobalt Sites Dispersed in Hierarchically Porous Nanofiber Networks for Durable and High‐Power PGM‐Free Cathodes in Fuel Cells October 2020
Engineering Energy Level of Metal Center: Ru Single-Atom Site for Efficient and Durable Oxygen Reduction Catalysis November 2019
Turning main-group element magnesium into a highly active electrocatalyst for oxygen reduction reaction February 2020
Advanced Electrocatalysts with Single-Metal-Atom Active Sites November 2020
A Honeycomb‐Like Bulk Superstructure of Carbon Nanosheets for Electrocatalysis and Energy Storage May 2020
Construction of Highly Active Metal‐Containing Nanoparticles and FeCo‐N 4 Composite Sites for the Acidic Oxygen Reduction Reaction October 2020
Preferentially Engineering FeN 4 Edge Sites onto Graphitic Nanosheets for Highly Active and Durable Oxygen Electrocatalysis in Rechargeable Zn–Air Batteries November 2020
Sulfuration of an Fe-N-C Catalyst Containing Fe x C/Fe Species to Enhance the Catalysis of Oxygen Reduction in Acidic Media and for Use in Flexible Zn-Air Batteries October 2018
Multilayer stabilization for fabricating high-loading single-atom catalysts November 2020
Understanding the inter-site distance effect in single-atom catalysts for oxygen electroreduction July 2021
Pyrolysis-free polymer-based oxygen electrocatalysts January 2021
Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity June 2020
Two-Step Activated Carbon Cloth with Oxygen-Rich Functional Groups as a High-Performance Additive-Free Air Electrode for Flexible Zinc-Air Batteries December 2018
Molecular Control of Carbon‐Based Oxygen Reduction Electrocatalysts through Metal Macrocyclic Complexes Functionalization July 2021
Direct Growth of Carbon Nanotubes Doped with Single Atomic Fe–N 4 Active Sites and Neighboring Graphitic Nitrogen for Efficient and Stable Oxygen Reduction Electrocatalysis September 2019
Nanopore Confinement of Electrocatalysts Optimizing Triple Transport for an Ultrahigh‐Power‐Density Zinc–Air Fuel Cell with Robust Stability October 2020
High-performing commercial Fe–N–C cathode electrocatalyst for anion-exchange membrane fuel cells August 2021
Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell December 2018
Single‐Atom Iron Catalysts on Overhang‐Eave Carbon Cages for High‐Performance Oxygen Reduction Reaction March 2020
Engineering of Coordination Environment and Multiscale Structure in Single-Site Copper Catalyst for Superior Electrocatalytic Oxygen Reduction July 2020
Atomically Dispersed Fe–Heteroatom (N, S) Bridge Sites Anchored on Carbon Nanosheets for Promoting Oxygen Reduction Reaction January 2021
Hierarchically Porous Carbon Plates Derived from Wood as Bifunctional ORR/OER Electrodes February 2019
Intrinsic Electrocatalytic Activity Regulation of M–N–C Single‐Atom Catalysts for the Oxygen Reduction Reaction October 2020
Atomically dispersed nickel–nitrogen–sulfur species anchored on porous carbon nanosheets for efficient water oxidation March 2019
Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction June 2018
From Supramolecular Species to Self‐Templated Porous Carbon and Metal‐Doped Carbon for Oxygen Reduction Reaction Catalysts April 2019
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells March 2019
Single Fe Atom on Hierarchically Porous S, N‐Codoped Nanocarbon Derived from Porphyra Enable Boosted Oxygen Catalysis for Rechargeable Zn‐Air Batteries May 2019
Discovery of main group single Sb–N 4 active sites for CO 2 electroreduction to formate with high efficiency January 2020
MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions January 2020
Regulating the allocation of N and P in codoped graphene via supramolecular control to remarkably boost hydrogen evolution January 2019
Atomic Fe Dispersed on N-Doped Carbon Hollow Nanospheres for High-Efficiency Electrocatalytic Oxygen Reduction December 2018
Confining Sub‐Nanometer Pt Clusters in Hollow Mesoporous Carbon Spheres for Boosting Hydrogen Evolution Activity November 2019
Efficient Oxygen Reduction Reaction (ORR) Catalysts Based on Single Iron Atoms Dispersed on a Hierarchically Structured Porous Carbon Framework June 2018
In Situ Charge Exfoliated Soluble Covalent Organic Framework Directly Used for Zn–Air Flow Battery December 2018
Iron Single Atoms on Graphene as Nonprecious Metal Catalysts for High‐Temperature Polymer Electrolyte Membrane Fuel Cells March 2019
Co Nanoislands Rooted on Co–N–C Nanosheets as Efficient Oxygen Electrocatalyst for Zn–Air Batteries June 2019
Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination January 2020
Simultaneously Integrating Single Atomic Cobalt Sites and Co 9 S 8 Nanoparticles into Hollow Carbon Nanotubes as Trifunctional Electrocatalysts for Zn–Air Batteries to Drive Water Splitting March 2020
Mesoporous Nitrogen‐Doped Carbon‐Nanosphere‐Supported Isolated Single‐Atom Pd Catalyst for Highly Efficient Semihydrogenation of Acetylene June 2019
Engineering efficient bifunctional electrocatalysts for rechargeable zinc–air batteries by confining Fe–Co–Ni nanoalloys in nitrogen-doped carbon nanotube@nanosheet frameworks January 2020
Single-Atom Catalysts across the Periodic Table October 2020
Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions July 2020
Edge‐Rich Fe−N 4 Active Sites in Defective Carbon for Oxygen Reduction Catalysis March 2020
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction December 2017
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation September 2017
Self-Adjusting Activity Induced by Intrinsic Reaction Intermediate in Fe–N–C Single-Atom Catalysts August 2019
Cation-Exchange Induced Precise Regulation of Single Copper Site Triggers Room-Temperature Oxidation of Benzene June 2020
Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen‐Doped Carbons with Encapsulated Metal Nanoparticles January 2020
Controlled synthesis of FeNx-CoNx dual active sites interfaced with metallic Co nanoparticles as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries December 2020
Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement January 2020
Ultrathin Fe–N –C single-atom catalysts with bifunctional active site for simultaneous production of ethylene and aromatic chlorides February 2021
Versatile Strategy for Tuning ORR Activity of a Single Fe-N 4 Site by Controlling Electron-Withdrawing/Donating Properties of a Carbon Plane March 2019
A new steric tetra-imidazole for facile synthesis of high loading atomically dispersed FeN4 electrocatalysts February 2021
Revealing Isolated M−N 3 C 1 Active Sites for Efficient Collaborative Oxygen Reduction Catalysis October 2020
Dual-Shelled Multidoped Hollow Carbon Nanocages with Hierarchical Porosity for High-Performance Oxygen Reduction Reaction in Both Alkaline and Acidic Media July 2020
Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts September 2020
In situ nanoarchitecturing and active-site engineering toward highly efficient carbonaceous electrocatalysts May 2019
Molecular Design of Single‐Atom Catalysts for Oxygen Reduction Reaction February 2020
Atomic-level tuning of Co–N–C catalyst for high-performance electrochemical H2O2 production January 2020
Atomically Dispersed Iron-Nitrogen Species as Electrocatalysts for Bifunctional Oxygen Evolution and Reduction Reactions December 2016
Three-Dimensional Ordered Macroporous Metal–Organic Framework Single Crystal-Derived Nitrogen-Doped Hierarchical Porous Carbon for High-Performance Potassium-Ion Batteries July 2019
Realizing Ultrafast Oxygen Evolution by Introducing Proton Acceptor into Perovskites April 2019
Chemical vapour deposition of Fe–N–C oxygen reduction catalysts with full utilization of dense Fe–N4 sites June 2021
Two-Dimensional Core-Shelled Porous Hybrids as Highly Efficient Catalysts for the Oxygen Reduction Reaction April 2016
Covalent organic framework nanosheets: preparation, properties and applications January 2020
Fe L-Edge X-ray Absorption Spectroscopy of Low-Spin Heme Relative to Non-heme Fe Complexes:  Delocalization of Fe d-Electrons into the Porphyrin Ligand January 2007
Toward a mechanistic understanding of electrocatalytic nanocarbon June 2021
Identification of the Electronic and Structural Dynamics of Catalytic Centers in Single-Fe-Atom Material December 2020
Efficient Electrochemical and Photoelectrochemical Water Splitting by a 3D Nanostructured Carbon Supported on Flexible Exfoliated Graphene Foil November 2016
Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction August 2020
Zinc‐Mediated Template Synthesis of Fe‐N‐C Electrocatalysts with Densely Accessible Fe‐N x Active Sites for Efficient Oxygen Reduction January 2020
Edge-Functionalized Polyphthalocyanine Networks with High Oxygen Reduction Reaction Activity September 2020
A Zeolitic‐Imidazole Frameworks‐Derived Interconnected Macroporous Carbon Matrix for Efficient Oxygen Electrocatalysis in Rechargeable Zinc–Air Batteries June 2020
Unveiling the Axial Hydroxyl Ligand on FeN 4 C Electrocatalysts and Its Impact on the pH‐Dependent Oxygen Reduction Activities and Poisoning Kinetics April 2020
A rechargeable zinc-air battery based on zinc peroxide chemistry December 2020
Tailoring Electronic Structure of Atomically Dispersed Metal–N3S1 Active Sites for Highly Efficient Oxygen Reduction Catalysis May 2019
Cross‐Linked Polyphosphazene Hollow Nanosphere‐Derived N/P‐Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction July 2020
Stereodefined Codoping of sp-N and S Atoms in Few-Layer Graphdiyne for Oxygen Evolution Reaction April 2019
In Situ Pyrolysis Tracking and Real‐Time Phase Evolution: From a Binary Zinc Cluster to Supercapacitive Porous Carbon May 2020
Recent Insights into the Oxygen-Reduction Electrocatalysis of Fe/N/C Materials September 2019
Axial ligand effect on the stability of Fe–N–C electrocatalysts for acidic oxygen reduction reaction December 2020
Atomic Level Dispersed Metal–Nitrogen–Carbon Catalyst toward Oxygen Reduction Reaction: Synthesis Strategies and Chemical Environmental Regulation June 2020
Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts March 2019
Two-dimensional metallic tantalum ditelluride with an intrinsic basal-plane activity for oxygen reduction: A microkinetic modeling study June 2022

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microenvironment
oxygen electroreduction
penta-coordination
single-atom catalysts
Zn-air batteries