CoChat
Sign Up
Cited by 40Electrocatalysts for Energy ConversionAdvanced battery technologies researchCatalytic Processes in Materials Science

Nanowrinkled Carbon Aerogels Embedded with FeNx Sites as Effective Oxygen Electrodes for Rechargeable Zinc-Air Battery

Open access
He, Ting, Lu, Bingzhang, Chen, Yang, Wang, Yong, Zhang, Yaqiang, Davenport, John L., Chen, Alan P., Pao, Chih-Wen +8 more·2019·Research
DOI 10.34133/2019/6813585PMC PMC6944486
Open this paper in CoChat — free account

Abstract

Rational design of single-metal atom sites in carbon substrates by a flexible strategy is highly desired for the preparation of high-performance catalysts for metal-air batteries. In this study, biomass hydrogel reactors are utilized as structural templates to prepare carbon aerogels embedded with single iron atoms by controlled pyrolysis. The tortuous and interlaced hydrogel chains lead to the formation of abundant nanowrinkles in the porous carbon aerogels, and single iron atoms are dispersed and stabilized within the defective carbon skeletons. X-ray absorption spectroscopy measurements indicate that the iron centers are mostly involved in the coordination structure of FeN 4 , with a minor fraction (ca. 1/5) in the form of FeN 3 C. First-principles calculations show that the FeN x sites in the Stone-Wales configurations induced by the nanowrinkles of the hierarchically porous carbon aerogels show a much lower free energy than the normal counterparts. The resulting iron and nitrogen-codoped carbon aerogels exhibit excellent and reversible oxygen electrocatalytic activity, and can be used as bifunctional cathode catalysts in rechargeable Zn-air batteries, with a performance even better than that based on commercial Pt/C and RuO 2 catalysts. Results from this study highlight the significance of structural distortions of the metal sites in carbon matrices in the design and engineering of highly active single-atom catalysts.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.34133/2019/6813585

Cites

2 of 2 references verified0 citation errors · 0 not checkable

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • Single metal atom sites at micropores and nanowrinkles often entail an asymmetrical coordination shell compared to single atom sites on a basal plane.

    “More importantly, the single metal atom sites at the micropores and nanowrinkles often entail an asymmetrical coordination shell, as compared to single atom sites on a basal plane [44,47].”

    From Atomically dispersed ruthenium in carbon aerogels as effective catalysts for pH-universal hydrogen evolution reaction (2022) · cites this paper as [44]

    Section 2.2 reports that FeNx sites associated with nanowrinkle-induced defects have a distorted, nonplanar structure, unlike the normal planar FeNx sites used for comparison. This supports the nanowrinkle comparison, but the paper does not establish the same coordination-shell difference for sites at micropores or for single-metal sites generally. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • Carbon aerogels exhibit two main features, rich pores and abundant nanowrinkles, which can result in the formation of edged metal sites and Stone-Wale defected metal sites.

    “Generally, carbon aerogels exhibit two main features, rich pores and abundant nanowrinkles, which can result in the formation of edged metal sites and Stone-Wale defected metal sites [44].”

    From Atomically dispersed ruthenium in carbon aerogels as effective catalysts for pH-universal hydrogen evolution reaction (2022) · cites this paper as [44]

    The Results and Discussion (§2.1) describe the prepared carbon aerogel as porous and nanowrinkled, and §2.2 says nanowrinkles can form Stone–Wales-defect Fe sites. The paper does not identify edged metal sites as a product of the pores, and its findings concern the aerogels prepared in this study rather than carbon aerogels generally. (LLM, conf=0.85)

    Experimental — accuracy not yet measured

  • Carbon aerogels are a three-dimensional material with rich porosity and nanowrinkles.

    “Carbon aerogels are a three-dimensional (3D) material with rich porosity and nanowrinkles [43–46]”

    From Atomically dispersed ruthenium in carbon aerogels as effective catalysts for pH-universal hydrogen evolution reaction (2022) · cites this paper as [44]

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Cites

Flagged first, then by citations

Research works printed but not linked: 45

  1. [1]Ma L. Chen S. Pei Z. Single-site active iron-based bifunctional oxygen catalyst for a compressible and rechargeable zinc-air battery ACS Nano 2018 12 2 1949 1958 10.1021/acsnano.7b09064 2-s2.0-85042688683 29432686 · DOI
  2. [2]Zhu L. Zheng D. Wang Z. A confinement strategy for stabilizing ZIF-derived bifunctional catalysts as a benchmark cathode of flexible all-solid-state zinc-air batteries Advanced Materials 2018 30 4, article 1805628 10.1002/adma.201805268 2-s2.0-85053932387 30259586 · DOI
  3. [3]Liu Z.-Q. Cheng H. Li N. Ma T. Y. Su Y. Z. ZnCo2 O4 quantum dots anchored on nitrogen-doped carbon nanotubes as reversible oxygen reduction/evolution electrocatalysts Advanced Materials 2016 28 19 3777 3784 10.1002/adma.201506197 2-s2.0-84961820804 26996677 · DOI · Paper page
  4. [4]Wang X.-T. Ouyang T. Wang L. Zhong J. H. Ma T. Liu Z. Q. Redox-inert Fe3+ Ions in octahedral sites of Co-Fe spinel oxides with enhanced oxygen catalytic activity for rechargeable zinc-air batteries Angewandte Chemie 2019 131 38 13425 13430 10.1002/ange.201907595 31317625 · DOI
  5. [5]Li S. Cheng C. Zhao X. Schmidt J. Thomas A. Active salt/silica-templated 2D mesoporous FeCo-Nx-carbon as bifunctional oxygen electrodes for zinc-air batteries Angewandte Chemie, International Edition 2018 57 7 1856 1862 10.1002/anie.201710852 2-s2.0-85041074782 29266731 · DOI
  6. [6]He T. Xue H. Wang X. Architecture of CoNx single clusters on nanocarbon as excellent oxygen reduction catalysts with high-efficient atomic utilization Nanoscale 2017 9 24 8341 8348 10.1039/c7nr02165h 2-s2.0-85021793914 28593211 · DOI
  7. [7]He T. Wang X. Wu H. In situ fabrication of defective CoNx single clusters on reduced graphene oxide sheets with excellent electrocatalytic activity for oxygen reduction ACS Applied Materials & Interfaces 2017 9 27 22490 22501 10.1021/acsami.7b04667 28609106 · DOI
  8. [8]Lu B. Smart T. J. Qin D. Nitrogen and iron-codoped carbon hollow nanotubules as high-performance catalysts toward oxygen reduction reaction: a combined experimental and theoretical study Chemistry of Materials 2017 29 13 5617 5628 10.1021/acs.chemmater.7b01265 2-s2.0-85022323166 · DOI
  9. [9]Cheng H. Li M.-L. Su C.-Y. Li N. Liu Z. Q. Cu–Co bimetallic oxide quantum dot decorated nitrogen-doped carbon nanotubes: a high-efficiency bifunctional oxygen electrode for Zn-air batteries Advanced Functional Materials 2017 27 30, article 1701833 10.1002/adfm.201701833 2-s2.0-85021731718 · DOI · Paper page
  10. [10]Li D. Jia Y. Chang G. A defect-driven metal-free electrocatalyst for oxygen reduction in acidic electrolyte Chem 2018 4 10 2345 2356 10.1016/j.chempr.2018.07.005 2-s2.0-85054975719 · DOI · Paper page
  11. [11]Zang W. Sumboja A. Ma Y. Single Co atoms anchored in porous N-doped carbon for efficient zinc-air battery cathodes ACS Catalysis 2018 8 10 8961 8969 10.1021/acscatal.8b02556 2-s2.0-85052796218 · DOI
  12. [12]Peng Y. Lu B. Chen S. Carbon-supported single atom catalysts for electrochemical energy conversion and storage Advanced Materials 2018 30 48, article e1801995 10.1002/adma.201801995 2-s2.0-85052460947 30132997 · DOI
  13. [13]Xue H. He T. Chabu J. M. Iron single clusters anchored on N-doped porous carbon as superior trace-metal catalysts toward oxygen reduction Advanced Materials Interfaces 2018 5 7, article 1701345 10.1002/admi.201701345 2-s2.0-85041013853 · DOI
  14. [14]Peng Y. Lu B. Chen L. Hydrogen evolution reaction catalyzed by ruthenium ion-complexed graphitic carbon nitride nanosheets Journal of Materials Chemistry A 2017 5 34 18261 18269 10.1039/C7TA03826G 2-s2.0-85028719478 · DOI
  15. [15]Deng Y. Chi B. Li J. Atomic Fe-doped MOF-derived carbon polyhedrons with high active-center density and ultra-high performance toward PEM fuel cells Advanced Energy Materials 2019 9 13, article 1802856 10.1002/aenm.201802856 2-s2.0-85061595755 · DOI
  16. [16]Deng Q. Zhao J. Wu T. Chen G. Hansen H. A. Vegge T. 2D transition metal-TCNQ sheets as bifunctional single-atom catalysts for oxygen reduction and evolution reaction (ORR/OER) Journal of Catalysis 2019 370 378 384 10.1016/j.jcat.2018.12.012 2-s2.0-85060254722 · DOI
  17. [17]Wang X. Chen Z. Zhao X. Regulation of coordination number over single Co Sites: Triggering the efficient electroreduction of CO2 Angewandte Chemie 2018 130 7 1962 1966 10.1002/ange.201712451 29266615 · DOI
  18. [18]Deng Y. Chi B. Tian X. g-C3N4 promoted MOF derived hollow carbon nanopolyhedra doped with high density/fraction of single Fe atoms as an ultra-high performance non-precious catalyst towards acidic ORR and PEM fuel cells Journal of Materials Chemistry A 2019 7 9 5020 5030 10.1039/C8TA11785C 2-s2.0-85062297254 · DOI
  19. [19]Budarin V. Clark J. H. Hardy J. J. E. Starbons: new starch-derived mesoporous carbonaceous materials with tunable properties Angewandte Chemie 2006 118 23 3866 3870 10.1002/ange.200600460 16671136 · DOI · Paper page
  20. [20]De S. Balu A. M. van der Waal J. C. Luque R. Biomass-derived porous carbon materials: synthesis and catalytic applications ChemCatChem 2015 7 11 1608 1629 10.1002/cctc.201500081 2-s2.0-85027949962 · DOI
  21. [21]Sahiner N. Soft and flexible hydrogel templates of different sizes and various functionalities for metal nanoparticle preparation and their use in catalysis Progress in Polymer Science 2013 38 9 1329 1356 10.1016/j.progpolymsci.2013.06.004 2-s2.0-84882286794 · DOI
  22. [22]Lv C. Xu W. Liu H. 3D sulfur and nitrogen codoped carbon nanofiber aerogels with optimized electronic structure and enlarged interlayer spacing boost potassium-ion storage Small 2019 15 23, article 1900816 10.1002/smll.201900816 2-s2.0-85065043108 31021514 · DOI
  23. [24]Sun Z. Lv F. Cao L. Liu L. Zhang Y. Lu Z. Multistimuli-responsive moldable supramolecular hydrogels cross-linked by ultrafast complexation of metal ions and biopolymers Angewandte Chemie International Edition 2015 54 27 7944 7948 10.1002/anie.201502228 2-s2.0-84935035641 26012538 · DOI
  24. [25]Biswas B. Al-Hunaiti A. Räisänen M. T. Efficient and selective oxidation of primary and secondary alcohols using an iron(III)/phenanthroline complex: structural studies and catalytic activity European Journal of Inorganic Chemistry 2012 2012 28 4479 4485 10.1002/ejic.201200658 2-s2.0-84866714767 · DOI
  25. [26]Sun X. Hao G.-P. Lu X. High-defect hydrophilic carbon cuboids anchored with Co/CoO nanoparticles as highly efficient and ultra-stable lithium-ion battery anodes Journal of Materials Chemistry A 2016 4 26 10166 10173 10.1039/C6TA03098J 2-s2.0-84976530494 · DOI
  26. [27]Hao G.-P. Mondin G. Zheng Z. Unusual ultra-hydrophilic porous carbon cuboids for atmospheric-water capture Angewandte Chemie International Edition 2015 54 6 1941 1945 10.1002/anie.201409439 2-s2.0-85027924651 25522081 · DOI
  27. [28]Cho S. H. Park S.-M. Electrochemistry of conductive Polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy The Journal of Physical Chemistry B 2006 110 51 25656 25664 10.1021/jp0656781 2-s2.0-33846386472 17181203 · DOI
  28. [29]Lee H. J. Park S.-M. Electrochemistry of conductive polymers. 30. Nanoscale measurements of doping distributions and current-voltage characteristics of electrochemically deposited polypyrrole films The Journal of Physical Chemistry B 2004 108 5 1590 1595 10.1021/jp035766a · DOI
  29. [30]Zhu C. Shi Q. Xu B. Z. Hierarchically Porous M-N-C (M = Co and Fe) Single-Atom Electrocatalysts with Robust MNx Active Moieties Enable Enhanced ORR Performance Advanced Energy Materials 2018 8 29, article 1801956 10.1002/aenm.201801956 2-s2.0-85052817462 · DOI
  30. [31]Yang Y. Lun Z. Xia G. Zheng F. He M. Chen Q. Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst Energy & Environmental Science 2015 8 12 3563 3571 10.1039/C5EE02460A 2-s2.0-84948439006 · DOI
  31. [32]Wan G. Yu P. Chen H. Engineering single-atom cobalt catalysts toward improved electrocatalysis Small 2018 14 15, article 1704319 10.1002/smll.201704319 2-s2.0-85045403829 29504227 · DOI
  32. [33]Jiang R. Li L. Sheng T. Hu G. Chen Y. Wang L. Edge-site engineering of atomically dispersed Fe-N4 by selective C-N bond cleavage for enhanced oxygen reduction reaction activities Journal of the American Chemical Society 2018 140 37 11594 11598 10.1021/jacs.8b07294 2-s2.0-85053540875 30168714 · DOI · Paper page
  33. [34]Xia W. Mahmood A. Liang Z. Zou R. Guo S. Earth-abundant nanomaterials for oxygen reduction Angewandte Chemie International Edition 2016 55 8 2650 2676 10.1002/anie.201504830 2-s2.0-84958753178 26663778 · DOI
  34. [35]Jiang H. Liu Y. Li W. Li J. Co nanoparticles confined in 3D nitrogen-doped porous carbon foams as bifunctional electrocatalysts for long-life rechargeable Zn-air batteries Small 2018 14 13 10.1002/smll.201703739 2-s2.0-85041819258 29430832 · DOI
  35. [36]Liu S. Wang M. Sun X. Facilitated oxygen chemisorption in heteroatom-doped carbon for improved oxygen reaction activity in all-solid-state zinc-air batteries Advanced Materials 2018 30 4, article 1704898 10.1002/adma.201704898 2-s2.0-85037650479 29210474 · DOI
  36. [37]Wu X. Han X. Ma X. Morphology-controllable synthesis of Zn-Co-mixed sulfide nanostructures on carbon fiber paper toward efficient rechargeable zinc-air batteries and water electrolysis ACS Applied Materials & Interfaces 2017 9 14 12574 12583 10.1021/acsami.6b16602 2-s2.0-85017547446 28319373 · DOI
  37. [38]Niu W. Pakhira S. Marcus K. Li Z. Mendoza-Cortes J. L. Yang Y. Apically dominant mechanism for improving catalytic activities of N-doped carbon nanotube arrays in rechargeable zinc-air battery Advanced Energy Materials 2018 8 20, article 1800480 10.1002/aenm.201800480 2-s2.0-85045408300 · DOI
  38. [39]Fu K. Wang Y. Mao L. Rational assembly of hybrid carbon nanotubes grafted on the carbon nanofibers as reliable and robust bifunctional catalyst for rechargeable zinc-air battery Journal of Power Sources 2019 421 68 75 10.1016/j.jpowsour.2019.03.005 2-s2.0-85062656834 · DOI
  39. [40]Fan Y. Ida S. Staykov A. Ni-Fe nitride nanoplates on nitrogen-doped graphene as a synergistic catalyst for reversible oxygen evolution reaction and rechargeable Zn-air battery Small 2017 13 25, article 1700099 10.1002/smll.201700099 2-s2.0-85019447310 28509363 · DOI
  40. [41]Giannozzi P. Baroni S. Bonini N. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Journal of Physics: Condensed Matter 2009 21 39, article 395502 10.1088/0953-8984/21/39/395502 2-s2.0-70349568754 21832390 · DOI
  41. [42]Garrity K. F. Bennett J. W. Rabe K. M. Vanderbilt D. Pseudopotentials for high-throughput DFT calculations Computational Materials Science 2014 81 446 452 10.1016/j.commatsci.2013.08.053 2-s2.0-84888290366 · DOI · Paper page
  42. [44]Baroni S. de Gironcoli S. Dal Corso A. Giannozzi P. Phonons and related crystal properties from density-functional perturbation theory Reviews of Modern Physics 2001 73 2 515 562 10.1103/RevModPhys.73.515 2-s2.0-0035535380 · DOI
  43. [45]Li Y. Galli G. Electronic and spectroscopic properties of the hydrogen-terminated Si(111) surface from ab initio calculations Physical Review B 2010 82 4, article 045321 10.1103/PhysRevB.82.045321 2-s2.0-77956667847 · DOI
  44. [46]Tersoff J. Hamann D. R. Theory and application for the scanning tunneling microscope Physical Review Letters 1983 50 25 1998 2001 10.1103/PhysRevLett.50.1998 2-s2.0-18344373200 · DOI
  45. [47]Guillaume S.-O. Zheng B. Charlier J.-C. Henrard L. Electronic properties and STM images of doped bilayer graphene Physical Review B 2012 85 3, article 035444 10.1103/PhysRevB.85.035444 2-s2.0-84856413501 · DOI

Cited by

Sorted by citations

Authors
He, T., Lu, B., Chen, Y., Wang, Y., Zhang, Y., Davenport, J. L., Chen, A. P., Pao, C.-W., Liu, M., Sun, Z., Stram, A., Mordaunt, A., Velasco, J., Ping, Y., Zhang, Y., & Chen, S.
Affiliations
  • Central South University (CN)
  • University of California, Santa Cruz (US)
  • Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 1H9
  • National Synchrotron Radiation Research Center (TW)
Corresponding author
  • Zhang, Yi
  • Chen, Shaowei
ORCID
Venue
Research
Publisher
American Association for the Advancement of Science (AAAS)
Published
2019-01
Volume
2019
Pages
6813585-6813585
ISSN
2639-5274 (ISSN-L)
DOI
10.34133/2019/6813585
PMC
PMC6944486
OpenAlex
W2995458476
Cited by
40
References
2
Citations by year
2026: 4 · 2025: 6 · 2024: 4 · 2023: 3 · 2022: 11 · 2021: 6 · 2020: 5 · 2018: 1
FWCI
1.17
Type
journal article
Language
en
Open access
Licence
Locations
  • Research (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • eScholarship (California Digital Library) (submittedVersion)
  • eScholarship (California Digital Library) (submittedVersion, cc-by)
Funders
  • National Science Foundation (CHE-1900235, CHE-1710408)
  • Army Research Office (W911NF-17-1-0473)
  • China Scholarship Council (201806370027)
  • Hunan Provincial Science and Technology Plan Project (2017TP1001)
  • National Natural Science Foundation of China (21473257, 21773311, 21972169)
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Advanced battery technologies research
  • Physical Sciences › Materials Science › Materials Chemistry › Catalytic Processes in Materials Science
Keywords
single-atom catalysts, oxygen electrocatalysis, rechargeable zinc-air batteries, carbon aerogels, Stone-Wales defects, pyrolysis, hierarchical porous carbon

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review